JPH05201712A - Linear-cahin phosphorus material - Google Patents

Abstract

(57) [Summary] [Constitution] The formula MP _x (where M is 1) attached to the support.
A solid film of one or more metals, and P is one or more pnictides). [Effect] A solid film of a phosphorus material having a novel form useful as a semiconductor can be obtained.

Description

Detailed Description of the Invention

[0001] Technical Field The present invention is a chain (catenated) phosphor material, its manufacture and use, and to semiconductor devices and other devices using the same. These materials include high phosphorus polyphosphides (ie, phosphides in which the polymer properties are maintained), alkali metal polyphosphides,
It relates to monoclinic phosphorus and novel forms of phosphorus. Vapor transfer is used to produce bulk, thick and thin film crystalline, polycrystalline and amorphous phosphorus and polyphosphite materials. Flash vapor and chemical vapor deposition are used to produce thin films.
For the production of crystalline and polycrystalline polyphosphides,
Utilizes condensed phase technology. Diffusion doping is used to increase the conductivity of these materials. A rectifying bond is formed on the material by a suitable metal contact. The film material can be used as an optical coating. Powdered crystalline and amorphous materials can be used as flame retardant fillers. Crystalline materials, especially fibrous morphologies, can be used as the reinforced high tensile strength component.

Prior Art Over the last few decades, the use of semiconductors has been constantly expanding in application and increasing in importance. For example, silicon-based semiconductors have been generally successful in providing a variety of useful devices such as PN junction rectifiers (diodes), transistors, silicon controlled rectifiers (SCRs), photovoltaic cells, photosensitive diodes, and the like. However, the production of crystalline silicon is expensive and due to the ever-increasing demand for semiconductors across a growing range of applications, it is possible to correspondingly expand the range of useful semiconductor materials available. Has been requested.

Useful semiconductors of the present invention have about 1-3 eV.
(More specifically 1.4-2.2 eV) energy band gap greater than 5 (more specifically 100-
10,000) photoconductivity ratio, about 10 ^-5 to 10 ^-12 (ohm-cm) ^-1 (more specifically 10 ^-8 to 10 ^-9 (ohm-
cm) ^-1 ) conductivity and chemical and physical stability under ambient use conditions. Thus, many materials can be semiconducting in the sense that they are not pure metals or pure insulating materials, but only semiconducting materials that meet these criteria are useful semiconductors in connection with the present invention. Can be thought of as

Given the current demand to develop alternative non-petroleum based energies, the ability of semiconductors to also effectively and efficiently convert solar energy to electrical potential when the semiconductor also exhibits effective photovoltaic properties. , The potential commercial utility of semiconductors is significantly increased. From an economic point of view, amorphous semiconductors, especially in the form of thin films,
It is preferable to the single crystal form due to the potentially low manufacturing costs. Also, amorphous semiconductors have superior electrical qualities to polycrystalline forms of the same materials used in many semiconductor devices.

In the semiconductor industry, new semiconductor materials that are more useful than crystalline silicon are being researched. In the field of non-silicon crystals, semiconductor compounds,
For example, GaAs, GaP, and InP single crystals are in commercial use. Many other semiconductor materials have been used for specialized purposes. For example, Cd
S and selenium are used as photoconductors in many xerographic devices.

In this application, a semiconductor device is one in which the device uses electrical contacts, ie, is an electronic device, or is a non-electronic device, such as a photoconductor for use in xerography, a phosphorescent material, a phosphor in a cathode ray tube. Etc. means a device containing semiconductor material, whether or not. Although some of the known forms of phosphorus have been described as semiconducting, many are unstable, highly oxidative and reactive, and all known forms of phosphorus are useful. It has not been effectively used as a semiconductor.

The Group III-V materials, gallium phosphide and indium phosphide, are bound tetrahedrally and are thus clearly distinguished from the compounds disclosed herein, as noted below. .. Moreover, their semiconductivity is not dominated by phosphorus-to-phosphorus bonds, ie the main conduction path is not phosphorus-to-phosphorus bonds. Others disclosed hydrous phosphorus having a structure similar to black phosphorus and having semiconductivity.

Considerable research on high phosphorus polyphosphides has been reported by H. K. G. phone. Schnelling (von
Schnering). According to various reports from this group, the highest phosphorus-containing polyphosphide compounds they produced are crystalline MP ₁₅ (M = 1a group metal). These polyphosphides are produced by heating a mixture of metal and phosphorus in a closed ampoule. phone.
Schnelling reports that, based on their structure, polyphosphides are classified as valence compounds in the classical sense, which means that these compounds are insulators or semiconductors, i.e., metals. is not.

Monoclinic phosphorus, also called Hittorf phosphorus, is produced from yellow phosphorus and lead according to the prior art as follows: 1 g yellow phosphorus and 30 g lead in a sealed tube. Heat slowly to 630 ° C. to melt and hold at that temperature for a short time. The solution is then cooled to 520 ° C. at a rate of 10 ° C./day for 11 days and then rapidly cooled to room temperature. Then it is electrolyzed in a solution of 2 kg of acetic acid in 8 l of 6% acetic acid and phosphorus is collected in a sight glass placed under the anode. Substantially square tubular crystals, about 0.2 x 0.2 x 0.05 mm, are thus obtained.

The structure of this prior art monoclinic phosphorus is
Determined by Thurn and Krebs. The crystal consists of two layers of pentagonal tubes of phosphorus, all of the tubes are parallel, therefore all other pairs of phosphorus layers of all pentagonal tubes, all of the tubes in the second pair of layers are parallel. However, the tubes in the second pair of layers are perpendicular to the tubes in the first pair of layers. The spatial groups of crystals, and the bond angles and bond distances were measured by Jerry Do
See the prior art summary in the section "Phoaphorus", nabue, "The Structure of the Elementa", 1974.

The electronic properties of Hittorf's phosphorus crystals are:
Not reported. Due to the small size of crystals, their electronic properties cannot be easily determined. The production of high-purity electronic grade phosphorus according to the prior art is very complicated and time consuming, and therefore electronic grade phosphorus is very expensive. The prior art also indicates the need for the use of stable phosphorus compounds as flame retardants. The crystalline form has additional utility as a reinforcing material in plastics, glass and other materials.

[0012]

DISCLOSURE OF THE INVENTION We have discovered a group of alkali metal polyphosphide materials having useful semiconductor, optical, and mechanical properties. Useful Semiconductor Properties "Polyphosphide"
Means a material with a large proportion of phosphorus-to-phosphorus bonds predominating. By "useful semiconductor" is meant not only that the conductivity is between that of an insulator and a metal, but also of many useful properties: -stability-structure of elastic material-band of useful range. Gap (typically 1 to 2.5
eV) -High intrinsic resistance, but ability to be doped-Excellent photoconductivity-Efficient luminescence-Ability to form rectifying junctions-At relatively low temperatures (for semiconductors) by scalable methods Ability to Form-Ability to Form as a Thin Film of Large Area Phosphorus-Ability to Form as Ductile Fibers These polyphosphides are an independent group of materials that possess all of these characteristics.

Preservation of Utility in Multiple Forms It is equally important that useful properties remain essentially constant over a wide range of chemical compositions and physical forms (crystalline and amorphous). According to our knowledge,
Polyphosphides are the only semiconductors in which the desired polycrystalline-like properties are preserved in an amorphous form. This has major technical implications because the amorphous form is at least more modifiable, and is often essential for large scale applications such as photovoltaics, large area displays, and electrostatic copy machines. Is.

However, to date, the problem with using amorphous semiconductors is that they are not readily formed as stable single-phase materials. And the amorphous form loses some of the highly desirable features of its crystalline counterpart, even when forced. The major known semiconductor (silicon) has a tetrahedral coordination in its crystalline form. Attempts to make it amorphous (to make amorphous Si) are known to involve breaking tetrahedral bonds, leaving dangling bonds that break useful semiconducting properties. Pure amorphous Si is not useful, unstable, and brittle. Attempts to saturate dangling bonds with hydrogen or fluorine have been only partially successful.

Central Role of Structure The preservation of useful properties of the many forms of polyphosphides is a direct result of the structure of the material, which is a unique property of phosphorus, especially the large number of phosphorus. We believe that the three phosphorus-to-phosphorus covalent bonds at the site are enabled by its ability to form a predominant polymer.

In the crystalline form, polyphosphides of the type MP ₁₅ (where M = Li, Na, K, Rb, Cs) are formed by a phosphorus skeleton consisting of parallel tubes with a pentagonal cross section. It has a structured structure. These phosphorus tubes are joined by PMP crosslinks, as shown in FIGS. See the building blocks for this skeleton of MP ₁₅ atoms as P ₈ (formed by two rigid units of P ₄ ) and MP ₇ (formed by the association of rigid units of MP ₃ and P ₄ ). You can

Using the building blocks or populations described above, Kosyakov has been reviewed by Russ.
In ian Chemical Review, 48 (2), 1979) it was shown theoretically that these phosphide compounds could be processed by using them as polymeric materials and their basic building blocks as monomers. Therefore, in principle, it is possible to construct a large number of atomic skeletons with the same phosphorus skeleton.

In our research, by various techniques described later, MP ₁₅ crystal and also type [MP ₇ ] _a [P
₈ ] _b, where b is much larger than a, we have synthesized. These "fibers", "whiskers" or compounds rich novel phosphorus originally observed as a "ribbon" will be referred to as in this study MP _x (where x is much greater than 15). These low metal content materials are suitable for thick films of polycrystalline fibers (10
Manufactured by vapor transfer as large balls (greater than 1 micron) and amorphous (greater than 1 cm ³ ). Polycrystalline fibers exhibit the same morphology as KP ₁₅ whiskers.

The first MP _x we have found (where x is 1
The structural skeleton of the crystalline material is much larger than
The phosphorus skeleton, which is similar to the phosphorus skeleton of ₁₅ compounds, accounts for the major proportion. These crystalline materials MP ₁₅ and MP _x (x
We have found that the useful electrical and optical properties of (much greater than 15) are similar. Therefore, the properties of these materials are dominated by the PP covalent bond with a number of phosphorus skeletons whose coordination number is somewhat less than three. Surprisingly, the useful electro-optical properties of these materials are essentially conserved for MP ₁₅ and MP _x (x is much greater than 15) crystalline materials and their amorphous counterparts. We also found that.

Unlike previously known materials, it is a dimensionally rigid structure and is elastic in the following sense. The crystal symmetry of polyphosphite is very low (triclinic). It is believed that when transitioning from a crystalline form to an amorphous form, low symmetry materials can be accompanied by an increase in the structural disorder that characterizes the amorphous state. There is no strong tetrahedral bond (coordination number 4) tearing as in silicon. This is because phosphorus has a much lower coordination number than silicon and can accept much greater structural disorder without creating pendant bonds. Polyphosphides are polymeric in nature. An amorphous structure of the polymer is produced which has no apparent X-ray diffraction peaks, which has a longer range of local order (loc) than can be achieved by ordinary amorphous semiconductors.
al order). In a structural sense, this gradual onset of amorphousness is believed to be the reason for the preservation of desirable crystalline properties in amorphous polyphosphides.

Distinction from Known Useful Semiconductors The composition and structure of this group of polyphosphides are clearly distinguished from all known useful semiconductors: Group 4a (crystalline Si, amorphous Si; H, etc.) 3a-5a (III-V) (GaAs, GaP, InP, etc.) 2b-6a (II-VI) (CdS, CdTe, HgCdTe)
Etc.) Chalcogenides (Aa ₂
Se ₃ ) 1b-3a-6a (CuInSe ₂ ) Differentiation with known forms of phosphorus Alkaline polyphosphides (MP _x , M = Li, N
a, K, Rb, Ca: where x = 15 and much larger than 15) are rich in phosphorus. Nevertheless,
Their structure (parallel pentagonal tubes) and their properties (stability, bandgap, conductivity, photoconductivity) make them all known phosphorus materials (black phosphorus, white phosphorus / yellow phosphorus, red phosphorus, And purple phosphorus / Hittorph's phosphorus). The structural relationships between these various forms are discussed below.

Most of our work was carried out to clarify this aspect of phosphorus itself. Our current uses are summarized below. 1. Amorphous P or Red Phosphorus Amorphous red phosphorus is a general term for all amorphous forms of red phosphorus, usually produced by heat treatment of white phosphorus.

2. This microcrystalline form of purple phosphorus red phosphorus is produced by an extended heat treatment from a pure feed of white phosphorus or amorphous red phosphorus. 3. P structurally crystalline forms of red phosphorus are identical purple phosphorus Hittorufu. Hittorf's P is produced in the presence of a large excess. Despite this, "Hit Ruff's Rin" and "Purple Rin"
Are often used interchangeably. The crystal structure consists of parallel bilayers of pentagonal tubes, with adjacent bilayers perpendicular to each other in a monoclinic cell. Hittorf's phosphorus crystals are slightly larger (approximately 1) than purple phosphorus crystallites.
00 micron).

4. Large crystals, which are essentially isomorphic to the two types of monoclinic phosphorus on large crystals (number
mm) is described here. These new crystals are vapor phase (Vapor T
It is manufactured by a range port (VT) process. The inclusion of alkali is clearly essential for the formation of large crystals. Analysis confirms the presence of alkali (500-2000 ppm) in these large crystals of phosphorus.

5. Twisted Fiber Phosphorus The crystalline form of phosphorus described herein is produced by VT treatment of an amorphous phosphorus feed. It is believed to have a near isomorphic structure to polycrystalline MP _x "ribbons". The Role of Metals: Why Phosphorus Is Not Enough The many allotropic forms of elemental phosphorus are evidence for the diversity and complexity of binding and structure that can be obtained with phosphorus. We lack a detailed, comprehensive model of how alkali metals behave exactly, but alkali metals can stabilize phosphorus, resulting in the potential for a single, unique structure. A large number of extensive data have been drawn showing that one can choose from a set of structures.

In the absence of at least some alkali metal, the following undesirable phenomena occur: A. Phosphorus is unstable (eg white phosphorus). B. To the extent that a known single phase can become its phosphorus, it can only do so at elevated temperatures, and its size is limited to microcrystalline (eg, purple phosphorus) or C.I. At high pressure (eg black phosphorus).

D. In the absence of alkali metal in the feed, the MP _x form of the structure is not formed by vapor transfer.
Rather, it gives us the twisted phosphorus fibers we discovered. This crystal is metastable and the structure is well defined as shown by our X-ray, Raman and photoluminescence data. The presence of alkali metals in the vapor transport favors all parallel untwisted phases. It also favors monoclinic large crystals of phosphorus at different temperatures, which we have found.

The major role of the structure, not the composition, as the determining property is that KP _x (where x is much greater than 15) is essentially the property of KP ₁₅ , but monoclinic. It becomes clear by noting that it has a property (bandgap, photoluminescence, Raman spectrum) that is slightly different from that of phosphorus. It is clear that even very small amounts of alkali metals can serve to select stable phases. But how do non-alkali metals work? Krebs
2b-4a-P ₁₄ (2b = Zn, Cd, Hg and 4a =
We reported non-alkali polyphosphides with a tubular structure consisting of Sn, Pb).

The pure hypothesis is that these materials form a tubular structure because the elements of group 4a are amphoteric and may occupy the P site instead. P ₁₅ based on the ionization energy of the alkali metal
The effective electron affinities of the frameworks can be calculated, all of which are below 5.1 eV. Then, other compositions, for example, it is possible to calculate the effective ionization potential for 2b-4a-P ₁₄ compound. All of the aforementioned Krebs materials have an "effective ionization degree" of 4.8 eV or less.

Useful Properties Our major early discovery was that KP ₁₅ whiskers (single crystals) are stable semiconductors, have a bandgap (1.8 eV) equivalent to red light, and are efficient light sources. It was to show conductivity and photoluminescence. These are semiconductor properties with potential applications in electronics and optics. Whiskers of other alkaline MP ₁₅ materials also have these properties (M = Li, Na, Rb, C
s).

In order to achieve those potentials, the materials had to be manufactured in the appropriate size and configuration for making and testing the device. However, we have recognized that crystal habits do not aid in the growth of large, single crystals that do not include crystallographic "twinning". Large, twin-free single crystals are the basis of almost all semiconductor devices today. Polycrystalline materials are less desirable. Because, even when individual crystals are large enough, the presence of crystal boundaries serves to destroy some undesired properties because of the physical and chemical discontinuities associated with such boundaries. To do. Therefore, we turned our attention to the amorphous form we found.

Useful amorphous semiconductors, whether used as junction devices such as photovoltaic cells or as coatings in electrostatographic machines, are either
External reasons (cost, ease of manufacture, and application requirements)
And intrinsic reasons (materials in a massive amorphous state)
Has generally been made as a thin film. We have discovered (by vapor transport) that KP ₁₅ can be made as a stable amorphous thin film. (This cannot be done with silicon: amorphous Si is not stable, but single crystal Si is stable.) Stable, bulk, and thin film amorphous KP _x
(X is much larger than 15) can also be made by vapor transfer.

There is evidence that these polyphosphides are otherwise unusual. MP of these materials
The useful properties of ₁₅ and MP _x (x is much greater than 15) are similar in their crystalline morphology and their amorphous counterparts, as shown in Tables XVI and XVII below. Amorphous thin film K that does not require bonding
Applications that utilize P ₁₅ can be easily considered (eg, electrostatography). In fact, high resistivity (almost 10 ⁸ ~
10 ⁹ ohm-cm) is one advantage for applications in systems that do not include such junctions.

All electronic and optoelectronic devices require the formation of some bonds in or with materials that provide a sharp discontinuity in the potential energy experienced by charge carriers. This requires doping to reduce the resistance of the material. We have found that Ni diffused into KP ₁₅ serves to reduce the resistance of the material by several orders of magnitude. Surface analysis revealed that the diffusion of Ni from the solid state (KP ₁₅ deposited on the Ni layer) followed a normal diffusion pattern during the film growth process.

It has Ni as the back contact and the diffuser and another metal as the top contact, eg C.
The geometry of the device with u, Al, Mg, Ni, Au, Ag and Ti leads to the formation of the bond. The current-voltage (I-V) characteristics of the junction were measured using the contact portion on the upper surface of these. The capacitance-voltage (CV) characteristic of the junction is A
It was measured using the contact part on the upper surface of 1 and Au. The data show a double formation with a highly resistive layer near the top contact.

The high resistance layer is the undoped portion of the KP ₁₅ film resulting from the doping procedure of the present invention. A small photovoltaic effect (microamp current under short circuit conditions) was observed. Synthesis of Polyphosphides Described below is the method we found to produce polyphosphides with varying composition and morphology.

A. Condensed Phase (CP) Synthesis This refers to isothermal heating, soaking (heating at a fixed temperature), and cooling of the starting feed in a minimum volume vessel. Crystalline and massive polycrystalline M
The production of P _15. B. A single source vapor transfer synthesis (1S-VT) starting reactant feed is placed in one section of an evacuated tube. This tube heats to a temperature Tc above Td, where Td represents the temperature in the other areas of the tube where the material precipitates from the vapor. Crystalline MP ₁₅ : crystalline, polycrystalline (lumps and thin films) and amorphous bulky high x MP _x : monoclinic phosphorus: star-shaped fibers: and twisted-fiber phosphorus are produced. It

C. 2 source vapor transfer synthesis (2S-VT) evacuated chamber feed source feed components
Physically separate at the distance of the precipitation zone between the feeds. Two
The two sources are heated above the deposition zone (at least to obtain amorphous material: see below). The precipitation zone is not the coldest in the system and is not required, but the colder areas should not be able to trap more than one component. 2S-VT was the first method used to make thin film amorphous KP ₁₅ . M
Polycrystalline and amorphous thin films of P ₁₅ and polycrystalline films and agglomerates of amorphous large x, MP _x
Is manufactured.

D. The melt quench feed was sealed and heated in an evacuated tube (isothermally if possible) to a temperature above the "melting point" determined by the endotherm observed in the DTA experiment, at which temperature for some time Hold. The tube is then removed from the furnace and cooled rapidly. CsP ₇ was manufactured.

E. A small amount of the feed in the form of flash-evaporated powder was fed into the RF-heated susceptor under a slight flow of argon, which gave about 800
Keep above ℃. Inside the susceptor, the material is passed through a tortuous path where it is theoretically forced into contact with the hot surface. This is intended to vaporize the feed rapidly and completely so that the composition of the resulting vapor stream is identical to that of the powder being injected. The vapor stream is directed to the evacuated chamber where it impinges on the cooler surface, producing condensed product material. An amorphous film was produced.

F. Chemical Vapor Deposition (CVD) Generally, this is the manufacture of a material by mixing two (or more) vaporized components that must undergo some type of chemical reaction to produce a product. Means that. In our practice, K and P ₄ were melted upright into a furnace where they were rapidly evaporated and carried by an argon stream to a downstream, cooler reaction chamber where the combined stream condensed Produces the material of the thing. CVD
Means the meaning of these methods, which can be scaled up and doped in situ. That is, simultaneous synthesis and doping of materials is possible.

G. Molecular Flow Deposition (MFD) This is 2S-VT and molecular beam epitaxy (MBD).
E) is a multi-source evaporative transfer technique that induces. An independently heated source was used and the evaporated seeds were treated with 2S.
-Arriving at the support (also independently heated) at a controlled rate that cannot be achieved with VT. Deposition occurs in an evacuated chamber, which has in-situ monitoring for deposition (2S-VT does not have this). The chamber can be sealed or continuously evacuated to control pressure.

KP ₁₅ Materials A wide variety of different polymorphs and compositions of polyphosphide materials were initially produced in our study. However, for potentially useful semiconductor applications, the focus of our work has shifted from single crystalline materials to amorphous materials-bulk or large area thin films.

Of all MP ₁₅ materials, KP ₁₅ is K
A unique crystalline higher polyphosphide (x is 7 or greater) compound that exists for the -P system. (By contrast, other alkali metals have x = 7 or x = 1.
1 compound, ie, CsP ₇ , NaP ₇ , RbP ₁₁
Can be formed). KP ₁₁ and KP ₇ do not form as compounds. For this reason, K-P systems are easier to control than other alkali metal-P systems that many compounds can form.

Furthermore, from the results of our experimental research,
Whenever K + P is vaporized by any means and transferred to a zone where the temperature is appropriately low in the proper ratio ([P] / [K] is greater than 15), amorphous K is used.
It is clear that P ₁₅ forms. By this observation,
The temperature is low enough to prevent crystallization of KP ₁₅ and x
We mean that KP _{x, which} is much greater than 15, is not high enough to prevent precipitation.

Based on this belief, it can be seen that all synthetic methods operate on the same general principle. Each method simply used different means to control the evaporation of the source or to control the deposition. A system of two sources (2S-VT,
CVD and MFD) are particularly useful because they allow independent control of important variables. Based on the above considerations, thin film amorphous KP ₁₅ was selected as our loading composition for the development of useful semiconductor materials.

In a general investigation of the properties of the polyphosphides, ca. 1 cm long potassium polyphosphide whiskers were prepared by single source evaporation transfer. When studying the properties of this material, the crystal was KP ₁₅ determined by X-ray diffraction of the single crystal. It was also discovered that these crystals are semiconductors. 1.8 eV when measuring the radiation at 4 ° K under the illumination of an argon laser
Photoluminescence with energies of was observed, thus indicating that the material may have a bandgap within this energy range.

Later, the leads were attached with silver paint to measure the conductivity of these whiskers. To see if the lead was actually attached to a very small crystal, it was observed under a microscope while measuring the conductivity. Surprisingly, when the crystal was moved in the microscope and the illumination was changed, the conductivity changed dramatically. 10
A photoconductivity ratio of 0 was measured and the illuminated conductivity of the whiskers was about ^10-8 (ohm-cm) ^-1 . In order to establish whether the whiskers have a band gap, we next measured the wavelength dependence of the photoconductivity, the wavelength dependence of the optical absorption, and the temperature dependence of the conductivity of the whiskers. These measurements, along with the photoluminescence measurements at 4 ° K, established that whiskers have a bandgap of approximately 1.8 eV. Thus, KP ₁₅ crystalline whiskers were established to be potentially useful semiconductors.

During the manufacture of the evaporative transfer of the KP ₁₅ whiskers,
An amorphous film formed inside the quartz tube. This amorphous film also has a band gap of about 1.8 eV and about 1
It was found to have a photoconductivity ratio of about 00. Similar to the whiskers, this amorphous film is almost 10 ^-8 (ohm-
It had an electrical conductivity of cm) ^-1 . Thus, it was established that it was also a potentially useful semiconductor.

The use that time, whether produced as large crystals such as silicon that is used to KP ₁₅ in semiconductor manufacturing, manufacture reproducibly a film of polycrystalline or non-crystalline KP _15, the semiconductor manufacturing Whether you can
And the question of complete characterization of materials produced by vapor transfer and similar materials that may have the same useful properties, arose to the inventors.

After a number of evaporative transfer experiments, polycrystalline and amorphous materials were produced by vapor transfer heating a single source of potassium and phosphorus and condensed on the other end of the closed tube. It was surprisingly found that the material is not KP ₁₅ but KP _x , which appears to range from about 200 to about 10,000 as measured by wet analysis.

Thereafter, and also in a single-source evaporative transfer, MP ₁₅ was initially deposited as the most stable polyphosphide because of the affinity of phosphorus for potassium or alkali metal for that substance. Unexpectedly, I did. If phosphorus is present in excess, a new form of phosphorus will precipitate. (MP _x , where x is 15
Much larger. ) Phosphorus this novel form, KP ₁₅
It has the same electronic quality as, and is useful as a semiconductor.

In the course of research, we sought to form thin films of polycrystalline and amorphous KP ₁₅ , and other alkali metal analogs that could not be formed by single source vapor transport. We devised an evaporation transfer method of two sources (classified sources) in which alkali metal and phosphorus are separated and heated separately. By controlling the temperature of the separated intermediate deposition zone, thin films of MP ₁₅ (where M is an alkali metal) were made in polycrystalline and amorphous forms. This technique also employs a new form of thin film of polycrystalline phosphorus material and thick film of amorphous phosphorus material, and the formula MP _x, where M is an alkali metal and x is much greater than 15. Has led to the production of other materials that are likely polymer-like.

We also propose to use flash evaporation, chemical vapor deposition and to use molecular flow deposition for the synthesis of these materials. Use MP _x as the formula for all polyphosphides. As noted below, for useful semiconductors, x can range from 7 to infinity. Known alkaline polyphosphides have the formula MP ₇ , MP ₁₁ and MP ₁₅ . We have found that there is probably a polymeric morphology with the formula MP _x , where x is much greater than 15.

Also during these studies, a single source evaporative transfer controlled the deposition temperature constant over a large area,
Improved over the prior art by allowing it to form large area thick films and boules of polycrystalline and amorphous MP _x, where x is much greater than 15. .. Large amounts of crystalline and polycrystalline MP ₁₅ (where M is an alkali metal) were prepared by isothermally heating stoichiometric ratios of alkali metal and phosphorus together. This condensed phase method is a very good MP _x (where x is 7 to 1) for use in single source vapor transfer.
Range of 5). Heated in a condensed phase manner to a temperature preferably near 100 ° C.,
This is facilitated by premixing and grinding the alkali metal and phosphorus together in a ball mill. This ball milling surprisingly produces a relatively stable powder.

All of the parallel tube polyphosphides have a bandgap of approximately 1.8 eV, a photoconductivity ratio of much greater than 5, (measured ratios of 100 to 10,000).
0), and 10 ⁻⁸ to 10 ⁻⁹ (ohm-cm)
^-It has a conductivity as low as ^-1 . It is noted that these materials in amorphous form formed in the presence of alkali metal, namely the alkali polyphosphides MP _x, where x is much larger than 6, have substantially the same quasi-conducting properties. As we have found, we conclude that the local order of amorphous materials is substantially the same throughout all parallel pentagonal tubes.

In all polysulphides, the three phosphorus-to-phosphorus [homatomic] covalent bonds in the majority of the phosphorus moieties occupy a major proportion of the other bonds present and provide a conductive pathway, and All of them have semiconductor properties. The covalent bonds of the phosphorus atoms are used in cartonations, all of which provide the predominant conduction paths and parallel local order in these materials, providing excellent semiconducting properties. 3 phosphorus atoms
Value, and cartonations form a helix or tube with a channel-like cross section. Alkali metal atoms, when present, join the cartonations together. Atomic species other than phosphorus, especially trivalent species capable of forming bonds of three covalently similar atoms, will also form semiconductors.

Thus, a novel form of phosphorus and its method of preparation: amorphous and polycrystalline MP _x solid films and methods and apparatus for its preparation: metal poly- METHODS AND APPARATUS FOR PRODUCING PHOSPHIDES: METHODS AND APPARATUS FOR PRODUCING HIGH PHOSPHORUS POLYPHOSFIDES BY MULTIPLE SEPARATED SOURCE TECHNOLOGIES: METHODS FOR PRODUCING MP ₁₅ BY CONCENTRATED PHASES IN POLYCRYSTALLINE FORM AND Device; bandgap greater than 1 eV and 1
Semiconductor device consisting of a group of polyphosphides of 7 or more phosphorus atoms covalently bonded together in a pentagonal tube having a photoconductivity ratio of 00 to 10,000: MP _x, where M is an alkali metal And x is greater than 6), and a bandgap greater than 1 eV and 1
Semiconductor device made of a material having a photoconductivity ratio of 00-10,000: a high proportion of catenated
It is formed from covalently bonded trivalent atoms, preferably phosphorus, consisting of a layer of chained atoms in which the chained atoms are joined together by a number of covalent bonds, the local order of which is parallel in each layer. A semiconductor device in which the layers are parallel to each other and the cartonations are preferably pentagonal tubes; the devices comprising an alkali metal and said cartonation structure, the number of consecutive covalent chain bonds making such materials semiconducting. A semiconductor device sufficiently larger than the number of non-chain bonds;
Formed of a compound of at least two chain units, each unit having at least 7 covalently bonded chain atoms,
A semiconductor device, preferably having a phosphorus skeleton and having an alkali metal that conductively couples the skeleton of one unit to the skeleton of another unit; a bonding device; a method of forming such a semiconductor device; We have invented a method of doping a semiconductor device; a method of applying an electric current and generating an electric potential using such a device.

Therefore, we have discovered a whole class of materials that are useful semiconductors, and one member of this class was one that we originally manufactured or appropriately characterized,
And while other members of this class were manufactured in the prior art, their useful semiconductor properties were unknown until our discovery and invention. All of these materials have a bandgap in the range of 1-3 eV, preferably 1.4-2.2 eV, most preferably about 1.8 eV. Their photoconductivity ratio is greater than 5 and is actually in the range 100-10,000. Their conductivity ranges from 10 ^-5 to 10 ^-12 (ohm-cm) ^-1 and is 10
It is about ^-8 (ohm-cm) ^-1 .

Those skilled in the art will readily appreciate that the alkali metal component M of a suitable trivalent "ide" having the formula MY _x, which is capable of forming polyphosphides, or covalent bonds of similar atoms, is , A metal that mimics the binding behavior of any number of alkali metals (or alkali metals) in any proportion, without changing the basic pentagonal tubular structure and thus without significantly affecting the electronic semiconductor properties of the material. Combination).

Furthermore, we have discovered and invented a doping method in which the material of the present invention is doped with iron, chromium and nickel to increase conductivity. Joining is Al, A
Manufactured using u, Cu, Mg, Ni, Ag, Ti, wet silver paint and point pressure contact. Incorporation of arsenic into polyphosphite (all parallel tubes) has also been shown to increase conductivity.

These doping methods are also part of our invention and discoveries. The semiconductor materials and devices of the present invention have a wide variety of applications. These include photoconductors, such as those in photocopying devices;
Photoemissive diodes; Transistors, diodes and integrated circuits; Photovoltaic applications; Metal oxide semiconductors; Light sensing applications; Phosphors exposed to photon or electron excitation; and other suitable semiconductor applications. Included.

In the course of our work, we also produced, for the first time, large crystals of monoclinic phosphorus. These crystals were produced from the vapor transfer technique using an MP ₁₅ feed or a mixture of M and P (M / P) in varying ratios. Surprisingly, these large crystals of monoclinic phosphorus contain significant amounts of alkali metals (50
0 to 2000 ppm was observed). Under the same conditions,
These crystals cannot grow without the presence of alkali metals in the feed.

Two crystal habits were observed for these large crystals of phosphorus. One crystal habit was identified as a truncated pyramidal crystal as shown in FIG. These crystals are difficult to cleave. The other morphology is platelet-like crystals, which are cleavable as shown in FIG. The largest crystal we have produced with the crystal habit shown in Fig. 39 is 4 x 3 mm.
× 2 mm (height). The largest crystals we have produced with the crystal habit shown in FIG. 40 are 4 mm square and 2 mm thick.

Crystals are metallic when viewed in reflection and deep red when viewed in transmission. Chemical analysis shows that the crystals contain somewhere between 500 and 2000 ppm of alkali metal. Their powder X-ray diffraction pattern, Raman spectrum and differential thermal analysis are all in agreement with the hitherto phosphorus of the prior art. The photoluminescence of the crystals grown in the presence of cesium in FIG. 41 and of the crystals grown in the presence of rubicium in FIG. 42 show peaks at 4019 and 3981 cm ⁻¹ , which indicates that this monoclinic system Figure 4 shows a bandgap of about 2.1 eV for phosphorus at room temperature.

These crystals serve as phosphorus sources; as optical rotators in the red and infrared parts of the spectrum (they are birefringent); for the growth of 3-5 materials such as indium phosphide and gallium phosphide. It can be used as a support. We grew and precipitated the star-shaped fibrous crystals shown in Figures 44 and 45 from the same feed at slightly lower temperatures. Also, we have shown that by vapor transport, an allotrope of phosphorus crystals, that is, FIG.
The twisted fibers of phosphorus shown in FIG. Polyphosphides can be used as flame retardants and reinforcing fillers in plastics, glass and other materials. Twisted tubes and star-shaped fibers may be of particular value in reinforcing composites because of their ability to mechanically entangle with surrounding materials. Platelet-like crystals would be of particular value in the thin sheet materials for which glass flakes are currently used.

The film material of the present invention has chemical stability,
Due to its flame retardant and optical properties it can be used as a coating. The purpose is therefore an object of the present invention the invention is to provide a useful semiconductor material of a novel class. Another object of the present invention is to
It is to provide a novel method and apparatus for producing polyphosphides. Yet another object of the present invention is to provide stable high phosphorus materials and methods and apparatus for making same. Another object of the present invention is to provide a novel form of phosphorus, and a method and apparatus for making it. Yet another object of the present invention is to provide dopants and methods for doping such materials. Still another object of the present invention is to provide a semiconductor device using the above material. Another object of the invention is to provide large crystals of monoclinic phosphorus. Yet another object of the invention is to provide high purity phosphorus. Another object of the invention is to provide new semiconductor materials. Yet another object of the invention is to provide a birefringent material for use in the red and infrared parts of the spectrum. Yet another object of the present invention is to provide a method of making a material of the above character. Another object of the invention is to provide such a method which is more convenient and less costly than the prior art. Another object of the invention is to provide coating materials, fillers, reinforcing materials and flame retardants. Other objects of the invention will in part be obvious and will in part appear hereinafter. Accordingly, the invention is exemplified in one or more of the inventive steps illustrated in the methods described below and the relationship of such steps with respect to each other, the compositions described below.
Compositions having properties, properties, and constituents and component relationships, features illustrated in the articles described below, manufactured articles having properties and element relationships, and composition and arrangement features of parts illustrated in the devices described below. Including a device consisting of. The scope of the invention is set forth in the claims.

The present invention will now be described with reference to the accompanying drawings for a further understanding of its nature and purpose. DESCRIPTION OF THE PREFERRED EMBODIMENTS The high phosphorus polyphosphides MP ₁₅ (where M is an alkali metal) high phosphorus material, and the novel forms of phosphorus formed, are crystalline, polycrystalline or otherwise. And all are believed to have similar local regularity. We believe that in crystalline and amorphous MP ₁₅ , this local order takes the form of elongated phosphorus tubes with a pentagonal cross section as shown in FIGS. 4, 5 and 6. All of the pentagonal tubes are generally parallel on a local scale, and in MP ₁₅ , the pentagonal phosphorus bilayers are joined together by interstitial alkali metal atoms. Many, if not most, of the alkali metal atoms are lost in the novel forms of phosphorus of the present invention. However, one novel form of phosphorus formed in the presence of very small amounts of alkali metal atoms grows from vapor deposition in the same form as MP ₁₅ . In one experiment discussed later, at least one form of which is shown to be due to growth of new features on the layer of MP _15. MP ₁₅ is a template that organizes phosphorus in the same structure (t
can act as an (employee). All of these materials with all parallel pentagonal phosphorus tubes were found to have band gaps on the order of 1.4-2.2 eV, almost 1.8 eV. Photoconductivity ratio is 1
The range is from 00 to 10,000. Thus, MP ₇ ~
All high phosphorus alkali metal polyphosphides from MP ₁₅ and more complex morphology and mixed polymers of M ₁₅ , and the novel phosphorus (MPx,
X is much greater than 15) is a useful semiconductor material when it has a pentagonal tube structure that is all parallel and stable, and is a useful semiconductor material, unless it includes an element that acts as a trap. Form boundaries.

In all of these materials with all parallel pentagonal tubular structures, our study shows that a large number of consecutive covalent phosphorus-to-phosphorus bonds in a number of tubes that is substantially greater than the number of other bonds. Have been shown to provide primary electrical conduction paths for electrons and holes, thus providing excellent semiconductor properties. Moreover, in our opinion, the presence of alkali metals in the feed, even when present in trace amounts in the novel form of phosphorus,
It was discovered that the growth of this material was accelerated and its morphology maintained the same structural and electronic properties as KP ₁₅ or monoclinic phosphorus, depending on the precipitation conditions.

The group of semiconductor members of the present invention has the formula MP
_x , where M is an alkali metal of Group 1a, and x is the atomic ratio of phosphorus to metal, and x is at least 7.
It consists of high phosphorus phosphides represented by. The most suitable metal elements of group 1a are Li, Na, K, Rb and Cs, although francium is probably also suitable, but it is rare and not included in the known synthesis of MP _x and is radioactive. High phosphorus polyphosphides in which M included Li, Na, K, Rb or Cs were formed and tested.

The presently defined polyphosphide compounds of the present invention must contain an alkali metal. Some of the new forms of phosphorus must be formed in the presence of small amounts of alkali metal, even in unmeasurable amounts. However, other metals must be present in small amounts, eg as dopants or impurities.

KP ₁₅ and, as we will see, a new form of phosphorus was first synthesized as follows. Referring to FIG. 1, the two temperature zone furnace 10 comprises an outer sleeve 12, preferably constructed of iron. The outer sleeve 12 is wrapped with a thermal barrier coating 14 which may be made of asbestos cloth. The furnace was constructed in our laboratory factory.

As the reaction component 36 in the furnace 10, P / K having a molar ratio of about 12 was used. As in one example, 5.5 g of red phosphorus and 0.6 g of potassium were placed in a quartz tube 32 under nitrogen. Prior to loading, phosphorus was repeatedly washed with acetone and air dried. However, this wash is optional, as is the choice of solvent. After feeding the reactants 36, the tube 32 was evacuated to, for example, 10 ⁻⁴ Torr, sealed, and then placed in the furnace 10. The tube 32 was placed in the furnace at a slight tilt. The power supplied to the conductors 24 and 26 is adjusted so that the heating zone 28 to the heating zone 3
The temperature gradient to 0 was, for example, 650 ° C to 300 ° C. The tilt of the furnace 10 described above was used to position the light-reflecting component 36 in the higher temperature heating zone.

After maintaining the furnace 10 for a sufficient period of time under these conditions, for example approximately 42 hours, the power to the conductors 24 and 26 was shut off and the tube 32 was cooled. When ambient temperature was reached, tube 32 was cut open under a nitrogen atmosphere and the contents of tube 32 removed. The contents were washed with CS ₂ to remove natural substances, leaving approximately 2.0 g of stable product. This gave a yield of approximately 33%.

Using this form of synthesis, the resulting products of the various phases occur at well-defined locations within tube 32 as illustrated in FIG. A dark gray to black residue 40 with a yellow and colored film 42 typically formed at the extreme end of hot zone 30 where reaction component 36 was initially located. Moving along the tube 32 in the direction of decreasing temperature, a black or purple film deposit 42 of polycrystalline material is then present. Next to the film deposit 42, there is a sudden dark ring of crystals 44, and crystals 4
In the immediate vicinity of 4 is a transparent zone, in which whiskers 46 grow. A highly reflective coating or film deposit 48 is present at the bottom of tube 32 at the beginning of cold zone 28. Above the film deposit 48, a dark red film deposit 50 optionally occurs depending on the temperature maintained in this zone. The deposits 48 and 50 are polycrystalline materials, amorphous materials or mixtures thereof, depending on the reaction components and temperature. At the very end of the cold zone 28, a deposit of lumps or films of amorphous material.

Due to the presence of a continuous temperature gradient from the hot zone to the cold zone of the reaction tube shown in FIGS. 1 and 2, the nature of the material that precipitates is actually from a high quality crystalline whisker to polycrystalline or amorphous. The quality changes continuously. The three-zone furnace shown in FIG. 3 was configured to handle the reaction to deposit a large area of uniform layer material. As embodied here, a three zone furnace 5
4 is essentially the same as the furnace 10 shown in FIG. 1, and the furnace 54 consists of an outer iron sleeve 56, a tube 60 and a reaction tube 58. For the sake of simplicity, the asbestos exterior of outer sleeve 56 and tube 58 have been omitted from FIG. The furnace 54 is distinguished from the furnace 10 in that the tube 58 is much longer than the tube 32, preferably as long as 48 cm. Furthermore, the furnace 54 has its three distinct heating zones 6
2, 64 and 66 are associated and these zones can be individually controlled to create a more defined thermal gradient along tube 60. The tube 60 and the reaction tube 58 are tilted toward the heating zone to keep the reaction component 36 in place in such a way that the tube 60 is removed from the asbestos block 6.
It can be supported by 8 and 70.

Very good quality manufacture of KP ₁₅ whiskers was obtained using temperature fixed points of 550, 475 and 400 ° C. in heating zones 62, 64 and 66, respectively. In addition, the bulky deposits generated in the furnace 10 are sublimed when loaded into the inner sleeve 60 of the furnace 54 and reheated with the temperature gradient shown above to form films 48-52 illustrated in FIG. It was found that a film deposit was formed that resembled a deposit, but only with high zone temperatures of at least 400-475 ° C.

The unit cell structural information for the KR ₁₅ crystals produced according to the method described above was obtained by single crystal X-ray diffraction data and collected using an automated diffractometer. A fibrous single crystal with a diameter of 100 microns was selected and attached to glass fiber. The structure was determined by a direct method with a total of 2,544 independent reflections. All atoms were searched by electron diagram and differential Fourier synthesis.

Typical needle crystals were examined by high magnification scanning electron microscopy (SEM). The resulting SEN picture of the cross section of the needle-like crystals showed that the needle-like crystals were clearly composed of dense fibrils rather than hollow tubes. Significant twins of whiskers crystals are also shown in FIGS. 7 and 8.
Is observed for the micrograph of KP ₁₅ in. The diameter of the primary fibrils of whiskers is approximately 0.1 to
It is estimated to be 0.2 microns. Large fibrils appear to have microstructures consisting of parallel lamellas approximately 500 angstroms thick.

From the initial crystal purification studies, the stoichiometry of the potassium phosphide compound studied appears to be KP ₁₅ . The phosphorus atom skeleton of this compound is formed from identical unit tubes with a pentagonal cross section. The tube is one-dimensional along the axial direction of the needle crystal. The phosphorus tubes are parallel to each other. In the simplest description, the separated phosphorous tube bilayers are connected by a layer of potassium atoms.
The K atom is at least partially ionically bound to the P atom, as judged by the interatomic distance. The cross section of the whiskers is shown in FIG.

More specifically, each potassium site is associated with a rigid unit of 15 consecutive phosphorus atoms having the structure shown in FIG. In this stiffness unit, all but one phosphorus atom is bonded to three other phosphorus atoms. The other phosphorus atoms are connected as shown in FIG. 5, and the missing bond is bonded to the potassium atom. Thus, the potassium atom appears to attach the tubular phosphorus unit through the missing PP bridge. In the structures studied, potassium was 3.6A and 2.99, respectively.
It has a phosphorus atom as the closest neighbors at a distance of A and 2.76A. The distance of P-P is 2.13A-2.
58A. The bond angle in the phosphorus chain is from 87 ° to
The angle is 113 °, and the average is 102 °.

Arsenic forms a layered structure with an average angle of 98 °, which is not known to be a useful semiconductor.
Black phosphorus has a similar structure and an average bond angle of 96 °. Trivalent atoms capable of forming three bonds within the range of 87 ° to 113 ° and at an average of 98 ° or more can form a chain structure like MP _x . When the bond is covalent, the material can be expected to have the same electronic properties as MP _x .

The crystal lattice parameters and atomic positions obtained for crystalline KP ₁₅ are listed in Table I.

[0084]

[Table 1]

The highest achievable symmetry in structural configuration on the space group P ₁ is
It is a centrosymmetric P ₁ space with stoichiometry given by KP ₁₅ . The corresponding X-ray powder diffraction data for KP ₁₅ polycrystalline material with copper illumination is shown in FIG. this is,
The d intervals with corresponding X-ray densities are shown.

Similar X-ray powder diffraction data were obtained for whiskers and crystals of MP ₁₅ (where M = Li, Na, K, Rb).
And Cs). In all these isomorphic compounds, the structural scaffold can be seen as being formed from parallel pentagonal phosphorus tubes. These tubes are joined by P-M-P bridges.

The stiffness unit for this type of construction is P ₄
And it is an MP _3. Building blocks for framework atoms may be viewed as [P ₄ -MP _3] or [MP _7]. Therefore, a [MP _7] +2 [P _4] → [P ₄ -MP ₇ -P _4], which represents the basic structure MP _15.

Of course, one of the building blocks in such a compound can be present in a much larger amount than the other. For example, in the case of MP _x , [M
There may be P ₇ ] and [P ₈ ] building blocks, each of which may be present in a to b ratio. In such a case, MP _x is [MP ₇ ] _a
It can be represented in the form of [P ₈ ] _b , where mathematically x = (7a + 8b) / (a).

The compounds can have b much larger than a and can also have the same basic structural framework.
This type of polymer-like tubular structure will result in "fibers" or whiskers of type MP _x, where x is much greater than 15. Type MP _x (where M is Li, Na,
Whiskers and polycrystalline "fibers" (K, Rb or Cs, and x is greater than 1000) were observed to crystallize at low temperatures (about 400 ° C) using vapor transfer techniques. The X-ray powder diffraction data for these materials are virtually identical. KP _x under copper lighting
The data for (where x is much larger than 15) is shown in FIG.

The structure described above can be compared with other structures based on phosphorus tubes of pentagonal cross section. The KP ₁₅ compound has the same isomorphic structure as LiP ₁₅ , NaP ₁₅ , RbP ₁₅ , and CsP ₁₅ . Other alkali metals appear to play the same role as K. From the structural data, we conclude that a large number of compounds could be formed which would be based on the building blocks of tubes of pentagonal cross section. It has also been discovered that in phosphorus materials, at least in part, the phosphorus atom can be replaced with other pnictides, such as As, Bi or Sb. Substitutions up to 50% are possible without adversely affecting the basic structure of the high phosphorus polyphosphides.

It was found to have the same structure as crystalline KP ₁₅ as shown by XRD powder diffraction finger analysis. The various MP _x compounds synthesized are shown in Table II.

[0092]

[Table 2]

As mentioned above, it was initially found that the crystalline whiskers produced with the apparatus of FIGS. 1, 2 and 3 were MP ₁₅ . However, analyzes for polycrystalline and amorphous materials show that these materials have MP ₁₅
It shows that it has the same semiconducting property as that of MP _{200 to} MP
_{It has} a widely varying stoichiometric ratio of _10,000 and, surprisingly, the treatment of temperature in the three zone furnace illustrated in FIG. 3 produces MP ₁₅ in an amorphous form. Let's Therefore, it is necessary to greatly refine the methods of producing these materials and to invent a novel two-source vapor transfer device in order to effectively produce polycrystalline and amorphous MP ₁₅ materials. Is. Very large x materials currently considered phosphorus novel forms also precipitate a first MP _15, followed by cutting the alkali metal source, due to that only phosphorus vapor deposition of phosphorus is present, Manufactured by this method. Furthermore, M
The condensed phase method of studying the molar feed of P _x (where x is 7-15) materials has been extensively studied. In this method, the stoichiometric mixture was heated isothermally to react and then cooled. A wide variety of MP _x materials were produced in this way, which were crystalline or polycrystalline powders.

The methods used to synthesize the high phosphorus materials, the methods of measuring the electro-optical properties, and the proof that they are useful semiconductors are described below. Production of stable high phosphorus materials from a single source by vapor transfer technology
Adding granulated Introduction sufficient energy into the system at a suitable temperature to generate vapor species, techniques to produce the product by condensation or precipitation of this steam is referred to as "vapor transport". In the following discussion, the expression "single source" technique is further applied when the source materials are held in intimate contact and heated together to about the same temperature.

Phon. Schnelling (von Schn
The morphology described by Ering) was essentially a single source vapor transfer technique, but the feed sometimes consisted of separate ampoules of metal and phosphorus heated to about the same temperature. However, the flow of vapor species into the deposition zone was effectively the same as when the metal and phosphorus were first mixed. More specifically, in a single source vapor transfer, the vapor species are first combined at high temperature and then precipitated at low temperature.

The technique developed by us applied to the production of alkali metal polyphosphides and von. The difference from the method of schnelling is explained below. This developed technology is based on crystalline metal polyphosphides of type KP ₁₅ ;
Low alkali metal content polyphosphides, polycrystalline materials of the type KP _x (where x is much greater than 15); Amorphous phosphorus is produced more selectively and effectively.

The present invention covers several categories: feed type, feed ratio, tube length and geometry, and temperature gradient profile. The temperature-dependent product precipitation relationships we have discovered and improved temperature control methods for selectively producing the desired product are illustrated in the following examples. General Method Alkali metal and red phosphorus are sealed in a quartz tube at reduced pressure (about 10 ⁻⁴ Torr). The atomic ratio of the two elements is P / M =
5/1 to 30/1, with a range of 15 to 1 for most common feeds. The elements are generally ball milled together and then loaded into a quartz tube. Milling is carried out for at least 40 hours using stainless steel balls and mills. The mill is usually heated to 100 ° C. during milling to help disperse the metal in the red phosphorus powder.

Milling brings the two elements into intimate contact in a manner that is as homogeneous as possible. The product of milling is generally a finely divided powder that is easy to handle in a dry box and can be stored without appreciable deterioration. Compared to the stability of the ingredients, especially the alkali metals, the powder
Remarkably stable when exposed to air and humidity. For example, adding water directly to the powder will only burn the material irregularly and on a small scale.

Single Crystal, Polycrystalline and Amorphous Material of MP ₁₅
A mixture of the manufacturing elements (alkali metal and red phosphorus) between quartz
(Fig. 3), length approx. 50 cm x diameter 2.5 cm, decompressing inside (1
^{Seal at} < ^0-4 Torr). Tube 58 is supported inside the heating chamber of a Lindberg model 24357 three zone furnace in one of two ways. One method uses a second quartz tube 60 as a support piece, which is held in the chamber away from the heating element and held by asbestos blocks 68 and 70, which causes the joined tubes to be placed at an angle and to react. Allow ingredients to stay in the hottest zone. Another method (FIG. 14) is to use a woven tape 136 support construction, which is a 1 inch (2.54 cm) wide strip of the reaction tube, wrapped around the reaction tube. Fill a circular cross section.
The woven tape can be made from various materials: asbestos, Fiberfrax (from Carborundum Company) or woven glass. The latter is preferred primarily due to safety and performance criteria. The implications of using two different methods are described below.

The reaction components are propelled into products by supplying energy to the system via the resistance element of the furnace. When a sufficiently high temperature is applied to the reaction components while the other parts of the tube are held at a suitably low temperature, the product precipitates or condenses from the vapor species. The temperature difference that drives this so-called "vapor transfer" synthesis is achieved in three zone furnaces by selecting different set point temperatures for the individually controlled heating elements.

Method 1. See FIG. Contains reaction components 5
The 0 cm tube is held by a second quartz tube in a 61 cm long heating chamber. Using a thermal gradient with a set point treatment of 3 generally results in a linearly decreasing gradient. That is, the slope of the gradient ΔT / d, where T is the temperature and d is the length along the chamber, is approximately constant between the centers of the two outer heating elements. This linear gradient applied across the length of the tube serves to clearly separate the various product materials formed in the reaction. The product has a characteristic pattern of reduced precipitation temperature: dark purple to black polycrystalline film; a ring of lumps of crystals; "single"
It occurs in crystals or whiskers; red films in the form of small crystals, polycrystalline; and dark gray amorphous materials at the coldest temperatures.

In a series of experiments, the amorphous material is
It has been shown that if the coldest temperature is above about 375 ° C, it will form in these sealed tubes. Similarly, the generation of red polycrystalline material causes a minimum temperature of 450
It will be greatly reduced by keeping above ℃.
It was also found that polycrystalline MP ₁₅ would not form in a single source device. The polycrystalline and amorphous materials formed are all large x materials with x much greater than 15.

Method 2. The woven tape holder not only positions the reaction tubes, but also serves as an effective barrier to heat transfer between the three heating zones.
These barriers cause a sharp temperature drop between zones but give a flat gradient in the central zone. As a result, the temperature profile is gradual, so that the product can be selectively produced by adjusting the precipitation temperature to an appropriate range.

A. Determining the precipitation temperature of the product In the report of von Schnelling, which produces KP ₁₅ single crystals (whiskers), "6
The elements-potassium and red phosphorus-were heated in a "temperature gradient" of "00/200 ° C". Furthermore, the crystal is "30
He states that it forms at 0-320 ° C. The furnace used was clearly a single element furnace in which the gradient was caused by heat loss from one end of the tube protruding from the furnace.

In a first refinement of this procedure, a three-zone furnace with independently controlled heating elements and a heating chamber 61 cm in length (Lindburgh 54357 three-zone furnace), as shown in FIG. Was used to apply and control the gradient. By supporting a reaction tube extending to a length of approximately 52 in the second open quartz tube and supporting the second quartz tube with an asbestos block, a generally linear temperature gradient ΔT /
d was almost constant between the centers of the two outer heating elements. The power to these elements comes from Lindberg 5974.
4-A type control console (Control
Controlled by the Console), this console used three independent SCR-proportional band controllers to maintain the selected temperature on a manually set thumb wheel.

The linearly decreasing gradient applied over the length of the reaction tube served to clearly separate the various product materials that formed in the reaction. The product has a reduced temperature characteristic pattern of precipitation: a dark purple to black polycrystalline film; a ring of lumps of crystals; a single crystal or "whisker"; a small film of a red film in the polycrystalline form; and It occurs in dark gray amorphous materials at the coldest temperatures.

Example 1 As shown in FIG. 3, for a synthetic heating chamber length of 61 cm, heating embedded in refractory material in separate cylindrical sections of lengths 15.3 cm, 30.6 cm and 15.3 cm. A component, Lindberg Model 54357, three zone furnace was used in this example. The chamber diameter is 8
It was cm. Control thermocouple (not shown), length 61cm
And were located at approximately 7.0, 30.5 and 53.5 cm along.

The ends of the heating chamber were stoppered with glass wool to minimize heat loss from the furnace. A quartz tube having a length of 60 cm and a diameter of 4.5 was held in the heating chamber with an asbestos block at a slight angle. The quartz reaction tube has a round bottom and is 49 cm in length and 2.5 cm in diameter.
The diameter was reduced to 10 cm in length and 1.0 cm in diameter. 6.51g of red phosphorus and 0.62g under an atmosphere of dry nitrogen
g potassium was placed in a tube. The phosphorus to metal atom-to-atom ratio was 13.3 to 1. Phosphorus was reagent grade (JT Baker). The tube was evacuated to 10 ^-4 Torr and sealed by melting the addition tube a few cm from the thick part of the tube so that the total length was 51.5 cm. The sealed tube was placed in a three zone furnace as described above and the three zone set point temperatures were 650 ° C, 450 ° C and 300 ° C over 5 hours and held there for a further 164 hours. The power was turned off and the furnace was allowed to cool to ambient temperature at the furnace's own cooling rate. The tube was cut open in a glove bag under an atmosphere of dry nitrogen. The product consisted of crystalline, polycrystalline and polycrystalline forms.

Table III lists the different process parameters used in some other experiments, along with the type of product observed in each experiment. Prior to cutting and opening, the tubes from the first three experiments were inspected for some product along the tube location: dark ring of lumps of crystallites, and initiation of a red polycrystalline film. . Whiskers were always observed between these two points. These positions were later related to the temperature along the gradient created by the set points described. These data are listed in Table IV.

[0110]

[Table 3]

[0111]

[Table 4]

The information from these two tables was used to establish the relationship between temperature and product type. Single crystals of KP ₁₅ appear to form over a temperature range of about 40 ± 10 ° C., the center of that range varying from experiment to experiment, but at about 465-475 ° C. Similarly, the onset of precipitation of the red polycrystalline material appears to be about 450 ± 10 ° C. Finally, the amorphous material precipitated even when the recent temperatures were around 350 ° C. When the temperature was raised to 400 ° C, no amorphous material was observed. (Experiments using this temperature were ultimately terminated because the reaction tube broke before the product could actually be harvested, but this temperature-product relationship for amorphous materials suggests a more advanced technique. Proved in later experiments). An upper limit for precipitation of amorphous material of about 375 ° C. was used, assuming values in the middle range. The pressure in the heated tube was not measured.

B. Suitable for growing single crystals (whiskers)
Knowledge of the morphology relationships of precipitation temperatures in Tables III and IV of temperature gradients was used to explore improvements in synthetic techniques that could increase product type selectivity. A method was studied to ensure that the temperature profile in the furnace increasing the area of the tube surface was within the appropriate temperature range for the desired product. Several available materials with low thermal conductivity and easy to handle form were examined for use as barriers to heat transfer in the furnace. Woven asbestos tape has been shown to be a suitable product for supporting reaction tubes and creating complex gradients. This gradient consists of flat or isothermal temperature zones separated by a steep drop or gradient zone (across the barrier). These so-called "step-like" profiles were applied in all subsequent examples in an attempt to obtain the specific product in the highest yield.

Another improvement that facilitated obtaining a reproducible temperature profile from experiment to experiment was to fill the gaps in the walls of the heating chamber with a more solid ceramic type material. In an early experiment, put a glass wool plug on the end,
This suppressed heat loss, but was not very efficient. There was a large cylindrical gap in the chamber wall. Because the furnace actually holds the process tube along its length and is designed for flow-through applications rather than closed systems, as is practiced in these methods.

A specific example of promoting the growth of larger single crystals at higher yields (in both percent product formation and absolute yield) is illustrated in the following examples. These results were in fact achieved. Example II A Lindberg Model 54357 three-zone furnace identical in design and size to that of Example 1 was also used in this example. The elements were propelled by a similar, manually set 594744-A control console. The end of the heating chamber was plugged with a refractory ceramic-like material to minimize heat loss from the furnace. The reaction tube was supported in the heating chamber by two rings of woven asbestos tape. One of these was located between 16 and 19 cm and the other between 42 and 45 cm along the chamber. This placed the two rings completely inside the central heating compartment, in the immediate vicinity of the joint of the central element and the joint of the two outer compartments. The ring was constructed so that the tube was held at a slight angle. The rings served to insulate the heating zones from each other by acting as barriers to heat transfer.

The quartz reaction tube (FIG. 3) has a round bottom and a length of 4
8 cm x 2.5 cm diameter, thin addition tube 162, length 1
It was as thin as 0 cm x 1.0 cm. Under an atmosphere of dry nitrogen, 5.47 g of red phosphorus and 0.50 g of potassium were placed in the tube. The atomic to atomic ratio of phosphorus to metal is
It was 15.1. Phosphorus was 99.9999% pure. Potassium was 99.95% pure. Tube 1
The tube was evacuated to 0 ^-4 Torr and the addition tube was sealed by melting at a few cm from the thick part of the tube to a total length of 52 cm. The sealed tube was placed in the three zone furnace described above and the temperature at the set points of the three zones was brought to 600 ° C, 475 ° C and 450 ° C over 4 hours and held there for a further 76 hours. Power was turned off at once for all three zones to cool the furnace to ambient temperature at the furnace's inherent cooling rate. The tube was cut and opened in a glove bag under a dry nitrogen atmosphere. The product consisted of crystalline and polycrystalline forms.

Processing parameters for many other such experiments → See N for data on the above examples
10 from the experiment) are listed in Table V.

[0118]

[Table 5]

In all of these experiments, crystalline and polycrystalline forms were obtained. The yield of single crystals was always higher than in Example 1. The polycrystalline material was always in the form of a film deposited on the cold end of the tube, usually confined to the last approximately 10 cm of the tube, but there was usually some overlap with the single crystal. The single crystals from these experiments have the same structure as KP ₁₅ determined from XRD data, X
It was characterized by a line powder diffraction pattern. Wet chemical analysis of crystals has been difficult to obtain with great accuracy because the crystals are stable and this material requires extreme conditions for aging for analysis. (Table VI for analytical data below
II-XI).

Polycrystalline films were also characterized by X-ray powder diffraction and wet methods. The film showed varying crystallinity and the diffractogram resembled that of KP ₁₅ in some planes, but was distinctly different in others. In addition, wet analysis, in combination with flame emission spectroscopy, has an alkali metal content in the ppm range (ie 10
Less than 00ppm, often less than 500ppm)
, And the P / K ratio is about 200 /
It was in the range of 1 to about 5000/1.

For the growth of polycrystalline and amorphous materials
After successfully improving the production of a suitable thermal gradient single crystal material, a similar series of experiments was carried out using a three zone furnace and asbestos ring, and the polycrystalline material and non-crystalline material observed in earlier experiments Suitable for selectively producing crystalline material,
A stepwise thermal gradient was found.

These initial experiments suggested the temperature required to obtain the desired product. What we are going to show is how to optimize these products. Table VI shows the type of profile used and the products observed.

[0123]

[Table 6]

The first experiment, the subject of Example III, was just an iterative experiment of the temperature range used in Example I, with the linearly decreasing slope being converted here into a stepwise slope. Not surprisingly, all product types were found, with some variation in amount compared to those in compartment A. When the coldest temperature was raised to 400 ° C., no amorphous material was present, as expected, as in the second experiment in Table VI. However, when the temperature of the central compartment was 425 ° C, almost two-thirds of the inside of the tube was covered with polycrystalline film, and only a small number of whiskers were present, which means that the film was produced almost exclusively. Means that.

In the third and fourth experiments, the coldest temperature was kept at 350 ° C. (sufficiently cold for the amorphous material to form in the first experiment) and the temperature in the central zone was 375 ° C. and 350 ° C. However, the amorphous material was not formed in a large amount at all. Instead,
Both monocrystalline and polycrystalline materials were present in large quantities over fairly short spaces in the tube, and at best only a thin film of amorphous material could form in the remainder of the tube. The same phenomenon was observed in the next two experiments, but in one experiment there was a distinctly thin amorphous film. Apparently most vapor species condense in polycrystalline and single crystalline forms, and there is no significant vapor migration to regions cold enough to form amorphous forms.

EXAMPLE III A Lindberg 54357 three-zone furnace identical in design and size to that of Example I was also used in this example. The element was similarly driven by the same manually set Lindberg Model 59744-A control, console. The end of the heating chamber was capped with a refractory material to minimize heat loss from the furnace. The reaction tube was supported by two rings of woven asbestos tape. One of the rings was placed along the chamber between 16 and 19 cm and the other between 42 and 45 cm. This placed both rings completely inside the central heating zone, just adjacent to the junction of the central element and the two outer zones. The ring was constructed so that the tube was held at an angle. The ring also served to insulate the heating zones from each other by acting as a barrier to heat transfer.

The quartz reaction tube had a round bottom, a length of 48 cm × a diameter of 2.5 cm, and a thin addition tube having a length of 10 cm × a width of 1.0 cm, and was tapered. Under an atmosphere of dry nitrogen, 5.95 g red phosphorus and 0.50 g potassium were charged to the tube. The atomic ratio of phosphorus to metal was 15. Phosphorus was 99.9999% pure. Potassium is 99.
It was 95% pure. Evacuate the tube to 3 × 10 ^-4 Torr,
And a few cm from the thick part of the tube so that the total length is 51 cm
At that point the addition tube was sealed by melting. The sealed tube was placed in 3 zones as described above. Temperature gradient at 600 ° C, 465 ° C and 350 ° C over 1 hour
C. and held there for 72 hours. The elements were then turned off simultaneously and the furnace cooled to ambient temperature at its own cooling rate. The tube was cut open in a glove bag in a dry nitrogen atmosphere. The product consisted of single crystals, polycrystalline films and amorphous materials.

D. Amorphous polyphosphide cylinder
In order to obtain large quantities of amorphous material, it is necessary to improve the methods already used, as is evident from the experiments described in the production section C of the report. It was found that, in contrast to thin films, suitable conditions for growth must be confined to smaller spaces than previously allowed in order to obtain the material in the form of lumps. This was to keep only the very end of the tube below approximately 375 ° C. This was achieved in principle by the use of thermal barriers. However, if the formation conditions for other materials, namely single-crystal MP ₁₅ or polycrystalline MP _x (where x is much larger than 15) are also present over a large area of the tube, these materials will "trap" for vapor species. It was recognized that it would act as ". Therefore, it is necessary to prevent the formation of other materials. This was accomplished by raising the temperature of the central zone to a level that was too high for the formation of polycrystalline or single crystals. The only area where these materials were then forced was through the area of the thermal barrier where a sudden temperature drop occurred.

Further refinements of this procedure were investigated as shown by the following examples and other experiments summarized in Table VII below. The first is Honeywell
ell) The DCP7000 Digital Control Program was used to activate the heating elements. This allowed pre-programming of temperature changes so that reproducible processing could be performed from experiment to experiment. Both controlled heating and cooling could be achieved, eliminating tube breaks and white phosphorus formation. The latter, when quenching the tube and phosphorus vapor condenses as P _4, was often occurred. This is why the material often seemed to be reactive. This reactivity could often be removed by dipping the material in a solvent that dissolves white phosphorus. A second improvement is 300-490-50 across the tube from the metal / phosphorus source to the deposition zone prior to vapor transfer.
The routine was to apply a 0 ° C. “inverted gradient”. This cleared the deposition zone of the material and may have affected the nucleation process.

To date, the most important improvement has been the redesign of the tube. Instead of a long tube with a diameter of 2.5 cm, which is almost uniform, shorten the body of the tube to about 30-32 cm and
Lengthen the 0 cm addition tube 160 (Fig. 2) to approximately 5
It was sealed so that 7 cm remained as an effective space inside the tube. When the latter compartment was placed in zone 3 and a vapor transfer gradient was applied, this compartment became filled with solid bulky cylinders of increasing length due to improved production conditions. ..

Example IV A Lindberg Model 5437 three-zone furnace identical in design and size to that of Example I was used in this example. However, the element is Honeywell DCP-
Promoted by a 7700 Digital Control Programmer. The programmer pre-programmed the process so that it could be performed in a reproducible manner.

The end of the heating chamber was plugged with a waterproof material to reduce the heat loss from the furnace. The reaction tube was supported by two rings of asbestos tape. The ring was constructed so that the tube was held at a small angle. The ring also served to insulate the heating zones from each other. The quartz reaction tube had a round bottom, was 33 cm in length × 2.5 cm in diameter, and was thin into a thin addition tube 160 of 20 cm in length × 1.0 cm in width. Ball was milled under dry nitrogen atmosphere at 7.92 g and charged with 15: 1 atomic to atomic ratio of the feed into the tube, and the tube was 1 ×.
It was evacuated to 10 ⁻⁴ Torr and sealed by melting the addition tube 10 cm from the thick part so that the total length was 43 cm. The sealed tube was placed in a three zone furnace by using the woven barrier described above.

Using a 6-49 cm tube, one thermal barrier placed at 16-19 cm, the other thermal barrier at about 38-40 cm, and 300 hours for 10 hours using a Honeywell programmer. , 490,500 ° C. “Reversal barrier” was applied. After cooling the furnace at its own cooling rate, the tube was moved and laid between 12 and 55 cm. The thermal barrier was also repositioned and laid down at 18.5-21.0 cm and 44.5-47 cm. The programmer then propelled the gradient to 600,485,300 ° C. for 64 hours. The programmer then ramped the tube through a controlled cooling sequence to 180,190,200 ° C and held there for 4 hours. The furnace was then allowed to cool to ambient temperature at its own cooling rate.

The tube was cut open under an atmosphere of dry nitrogen and 4.13 g of solid, 2-3 cm long, homogeneous, amorphous ball was recovered from addition tube 160 (FIG. 3). The results of some other experiments are shown in Table VII.

[0135]

[Table 7]

[0136]

[Table 8]

As the results show, the yield of material depends on the feed,
That is, it is largely independent of ball-milled feed or pre-reacted condensed phase product. However, there was a clear dependence on the P / M ratio. The higher the relative amount of metal in the feed, the lower the yield of material. When the amorphous material is essentially phosphorus, this reflects the lower vapor pressure of phosphorus above the metal-phosphorus feed, the higher the metal content, therefore the slower the growth rate for the same thermal conditions. Become.

Table VIII contains some analytical results for the amorphous balls produced. It shows the potassium content measured by the wet method. It also exhibits minor constituents shown to be present by flame emission spectroscopy.

[0139]

[Table 9]

Tables IX, X and XI are analytical data obtained by the wet method for products from vapor transfer synthesis. P / M ratios in the tables are atomic ratios unless otherwise noted.

[0141]

[Table 10]

[0142]

[Table 11]

[0143]

[Table 12]

[0144]

[Table 13]

Metal Polyphosphite by Two Source Technology
Preparation of the Polyphosphides The polyphosphides were prepared in two basically different types of equipment. These devices are identified herein as two sources or separate sources. This is because both types of equipment separate metal and phosphorus and heat them independently on either side of the deposition zone. All examples were performed on the K-P system.

In the first method, as shown in FIG.
A supply of phosphorus and potassium is held at both ends of a sealed quartz tube 100. The tube is exposed to the temperature profile as shown in Figure 12 achieved by using a three zone furnace. This profile heats up the independent feed as compared to the central zone between the two components. In this central zone, the vaporized components combine to form KP ₁₅ precipitation products in the form of a film on the reactor walls. In a second apparatus (more fully described in Example V below), a substantial area, shown at 102, is maintained at room temperature outside a three-zone furnace 104, as shown in FIG. This compartment contains the device of the stopcock 106 and the ball joint 108 used to achieve the low pressure at which the reaction is to be carried out. This alternative sealing technique, which requires low temperatures in this part, allows for rapid and non-destructive charging of a glass "boat" that holds the phosphorus and metal sources. The boat 112 (see FIG. 15) also has a glass support 114 (FIG. 14) on which the film is to be deposited.
Designed to hold metal on. The shape of these films / supports is as described below.
Serves as an initial starting point for the design of the device.

The outer compartment of the furnace provides a cold trap for the vapor species. Specifically, phosphorus is charged into the zone closest to the outer compartment and is deposited in large quantities in the outer compartment, generally as a highly self-sustaining white form. Due to the presence of this trap, the vapor pressure requirements of this system are very different from the fully heated system described above. It can be said that the temperature conditions that effectively produce the desired product in the first device are not suitable for the second device. Suitable conditions for the latter are
It was not decided independently.

Example V In a quartz tube 100 of 54 cm in length and 2.5 cm in diameter having a neck of 10 cm in length and 1.0 cm in diameter shown in FIG.
Phosphorus and potassium are charged under dry nitrogen conditions into the ends of the tube at an atom-to-atom ratio of 15: 1. Potassium (9
9.95% purity), first a small piece total weight 0.28g
The tube was then vertically oriented and charged by dropping it into cup 118. Then melt these pieces,
Re-solidify in cup. Then phosphorus (99.9999)
%) To the tube. A 3.33 g piece was easily handled around cup 118. The tube is then sealed at 5 × 10 ⁻⁵ Torr by melting neck 116.

The tube is then placed in three zones of Lindberg 54357-S and laid centrally between the three zones. 6, 12 and 6 inches (15.2, 3
543 with a zone length of 0.5 and 15.2 cm)
Unlike the 57, this S has 8, 8 and 8 inches (2
0.3, 20.3 and 20.3 cm). Two sheets of woven asbestos tape wrapped helically around the tube held the tube at the junction of zones 1 and 2 and zones 2 and 3. These tapes not only supported the tubes, but also insulated the central zone from higher temperatures than the outer zones. A schematic representation of the resulting temperature profile is shown in FIG. Using Honeywell DCP-7700 Digital Control Programmer,
Promote 3 heating zones through appropriate heating period 4
A 50, 300, 450 ° C. gradient was applied, held there for 72 hours, then cooled to ambient temperature via a 15 hour cooling sequence.

The material formed in the tube was analyzed by the following procedure. First, in a dry nitrogen atmosphere, the tube was cut into seven tube sections of approximately equal length with a silicon carbide saw. Pieces of film present in the compartment (typically 1
0 micron and above) were removed and individually examined by X-ray diffraction techniques. The rest of each compartment was analyzed by the wet method.

The P / M ratio of the precipitates present for the compartments is shown in FIG. For the central zone where T is approximately 300 ° C., the composition of the mass is approximately 14/1, which is within the accuracy of the method used to identify the material as KP ₁₅ . In addition, an X-ray powder diffraction pattern for a material found to have a P / K of about 14 is revealed, which matches that of KP ₁₅ from a single whisker or bulk polycrystalline material. I showed that. In addition, the diffraction pattern showed that both polycrystalline and amorphous material were present in a ratio of about 1: 1 as evidenced by the broad peaks.

Example VI The equipment used in this example was modified with respect to that of Example V. The quartz tube 119 was fitted with "nozzles" 120 and 122, separating the two end chambers from the central chamber (see Figure 16). Molten potassium (0.47 g, 99.95% pure) was added to the outer chamber designated K under dry nitrogen conditions and resolidified. The addition tube 124 was then melted and sealed. Then phosphorus (5.58 g, 99.9999)
% Purity) to the other outer chamber, designated P, and the entire apparatus evacuated and at 1 × 10 ^-5 Torr, the second addition tube
It was sealed by melting of 6. The phosphorus to potassium ratio for this system was 15 atoms to 1 atom.

The closed tube 119 was 41 cm long and was located in the center of three consecutive 20.3 cm zones of a Lindberg Model 5435-7S three zone furnace. Two thermal barriers (TB) of woven asbestos tape helically wrapped around the tube held the tube at the junction of zones 1 and 2 and zones 2 and 3. In addition to retaining the tubes, they insulated the central zone from the higher temperatures of the outer zone. Honeywell DCP-7700
Type digital control programmer,
Three heating zones were propelled to a gradient of 500, 355 and 700 ° C throughout the warming period. (Phosphorus was 500 ° C and potassium was 700 ° C. We chose the temperature in the central zone to be 300 ° C, but the heat leakage from the side chambers is central because of the limited thermal insulation properties of the woven tape The temperature of the zone was raised to a level of 355 ° C.) This gradient was held for 80 hours and then followed by a 24 hour cooling sequence.

When the tube 119 was opened by cutting it with a silicon carbide saw under dry nitrogen conditions, the nozzle 122 between the potassium zone K and the central zone was clogged with a material that looked like multifilamentary KP _15. became. Central zone is a thin, pale red film; a thicker, dark red film;
And several relatively large, single crystal system balls. The two largest pieces are each about 4 cm long x 1 cm wide,
The maximum thickness was about 4 mm. One side of each strip was relatively flat, but the other side was convex, associated with growth to the inside of the circular reaction tube.

Wet analysis of this material showed a very low potassium content, less than 60 ppm by mass analysis. Electron spectroscopy (ESCA) for chemical analysis
Indicated that the potassium content of this material decreased sharply outward from the tube wall where the material first deposited. 100
In Angstrom, the PK ratio was about 50. When measured by ESCA, the PK ratio on the final deposited surface was about 1000. X-ray diffraction studies have shown that the material is amorphous.

Example VII 0.19 g of molten potassium (9
9.95% purity) was placed in one of the outermost compartments 128 (5 cm long) of a Pyrex boat 112 (FIG. 15). The metal was resolidified. Two glass supports 114 (see Figure 14, each about 7.5 cm long x 1 cm wide) are laid end-to-end with a central compartment 1 of length 15.3 cm.
30 was filled. Next, 1.36 g of phosphorus (99.99)
99% pure, obtained from Johnson Matthey) was added to the outer compartment 132 on the opposite side of the boat. Phosphorus is in the form of particles of mixed size and is easy to pour into compartment 1
Fill the bottom of 32. Pyrex divider 113
Keeps P and K and the support from slipping in the boat 112. The 35 cm long boat 112 is then carefully slid into the Pyrex reaction chamber 134 of 60 cm length × 2.5 cm diameter of FIG. 14 where the compartment 128 with potassium in contact with the round bottom is at the end of chamber 136. To close. A Buta-N O-ring, size 124, was then installed in the O-ring joint 102 and a Teflon stopcock 106 (obtained from Chemback Inc.) was screwed in tightly. In the vacuum line, the stop cock 106 is reopened to open the chamber.
Evacuated to × 10 ^-4 torr. Then the stopcock was closed again and the reaction chamber was sealed.

The reaction chamber was placed in a three-zone furnace of Lindberg 54357-S type. As shown in FIG.
Two woven glass tapes 137 and 139 spirally wrapped the tube to support the chamber at the junction of zones 1 and 2 and zones 2 and 3. These tapes, which form the thermal barrier (TB), were set to lie exactly in the central zone. A third spirally wound tape 138 was used to support and insulate the device as it exited the furnace heating chamber. Cylindrical stopper 140 made of ceramic-like material
Was used to suppress heat loss from the furnace opening at the other end of the chamber.

This arrangement of equipment allows compartment 138 of the boat 112 containing potassium to lie in the third heating zone and compartment 130 containing the support to lie in the central or second heating zone. And a section 132 of the boat containing phosphorus is laid in the first heating zone. It also causes a large segment of equipment outside the furnace to reach ambient temperature.

A Honeywell DCP7700 Digital Control Programmer was used to propel the three heating zones throughout the warming period, during which the temperature was 100, 150 and 100 ° C. in the phosphorus, support and potassium zones, respectively. became.
Then, as quickly as possible (approximately 18 minutes), ramp up to 50
It was propelled to 0,300,400 ° C and kept there for about 8 hours. The furnace is then run at its own speed, 100, 100,
The profile was 100 ° C. and took about 10 hours. The furnace was then brought to room temperature.

Tube 134 was removed from the furnace. The outer compartment of the furnace contained white, yellow, and yellow-red material deposits, all of which were phosphorous of possibly varying polymerization stages.
The phosphorus heating zone contained no material, while the potassium zone contained a variety of materials with colors ranging from yellow brown, yellow and orange. The latter extended slightly into the central zone, otherwise the central zone was covered with a dark film through one-half of its length following the potassium zone, which film transmitted red light. The other half of this zone contained no material. The apparatus was opened under dry nitrogen conditions, the Pyrex boat 112 was removed, and the red film covered glass support was removed from the boat and placed in a tightly closed bottle for later analysis. (Phosphorus deposits in the exposed section of the tube generally burned violently when the rest of this material was exposed to ambient conditions, but those closest to the phosphorus source did not show such reactivity. The material present in was very reactive when exposed to moisture. This material generally burns violently due to the evolution of hydrogen, which apparently undergoes reduction of water.) Further examples are listed in Table XII.

[0161]

[Table 14]

There are restrictions on the manufacturing conditions for the dark film that transmits red light. The temperatures in the two source zones are given in Table XI.
With a slight reduction, as in I, Experiment No. 49, the amount of material formed drops dramatically, as evidenced by the length of the precipitate. Similarly, two 5's that are the same below that
The subtle differences between the performance characteristics of the 4357S three-zone furnace require a slightly elevated phosphorus source temperature in the second furnace (B) (see experiments No. 50, 51 and 52). ). Raising the temperature of the phosphorus source to 550 ° C gives excellent results and raising it to 525 ° C gives better results.

Materials from experiments Nos. 46, 47 and 48 were scanned electron microscopy and electron diffraction analysis (SEM-EDA).
Analysis by method X) revealed that the material was KP ₁₅ film as thick as 6-7 microns, and amorphous with a structure not visible in this microscope. Summary of vapor transfer conditions The features of the product type control process are as follows: 1) use of a three zone furnace for more uniform temperature control, 2) extended pipe length, 3) temperature gradient. Use of a thermal barrier for control, 4) use of a hot plug at the end of the furnace, and 5) use of an extended narrow addition tube to obtain a cylindrical ball.

The range of conditions for one vapor transfer is as follows: 1) the temperature range of the reaction zone from 650 to 550 ° C .; 450
Cold zone temperature range of ~ 300 ° C. 2) The precipitation temperature for a single crystal of KP ₁₅ is 465-47.
It was found to be in the range of median value of 5 ° C ± 25 ° C.

3) The deposition temperature for polycrystalline films was found to be in the range of about 455 ° C to 375 ° C. 4) Deposition temperature of the amorphous form of the new form of phosphorus from about 375 ° C to at least 300 ° C. (Lower temperatures have not been studied to date) The range of conditions for vapor transfer of the two sources is to form a bulk KP ₁₅ material (apparatus of FIG. 11); phosphorus, temperature of 450 ° C., Potassium 450 ° C., and precipitation zone 300 ° C .; precipitate was a thick film of mixed polycrystalline and amorphous KP ₁₅ ; bulk amorphous K
P _x (where x is much greater than 15, a novel form of phosphorus,
16 apparatus): Phosphorus 500 ° C., potassium 700 ° C. and precipitation zone 355 ° C. The K source became clogged and the precipitate was bulk amorphous KP _x ; for films of amorphous KP ₁₅ (apparatus in FIG. 14) phosphorus 500 ° C., potassium 400 ° C. and support 300 ° C.

For thin films of KP ₁₅ , the phosphorus source can be raised to 525 ° C. and amorphous KP _{15 is} still formed. When the phosphorus source temperature is lowered to 475 ° C., the system does not produce KP ₁₅ . The temperature of the potassium source is 375 ° C
When reduced to, this system does not produce KP ₁₅ . The temperature of the support can be raised to 315 ° C and the system still produces KP ₁₅ but not at 325 ° C.

Large amount of polycrystalline gold by “synthesis of condensed phase”
Preparation of genus polyphosphides Alkali metal polyphosphides of MP ₁₅ , MP ₇ and MP ₁₁ do not form in the physical state suitable for developing their useful semiconducting properties, but It can be easily produced in an amount of 1 g or more by a technique called synthesis. Prior to using this technique, the reaction components were generally intimately connected by a ball milling procedure. The more elements Dekaguramu, based on the dry nitrogen conditions, atoms to the atomic ratio of the desired metal to phosphorus, for example, the MP ₁₅ P
/ M15 into a ball mill. The closed mill was then run for 40 hours or more to grind the ingredients into a well-mixed, homogeneous, free-flowing powder. The mill was generally heated to about 100 ° C. for about 20 hours of milling.
This is done to increase the fluidity of the metal components during milling.

A portion of the milled mixture, typically 10
Transfer over g to a quartz ampoule under dry nitrogen conditions. The size of the ampoule depends on the amount of feed to be treated,
Diameter 2.5cm x Length 6.5cm ~ Diameter 2.5cm x Length 25
The range is cm. The tube is sealed at reduced pressure (generally less than 10 ⁻⁴ Torr). The reaction is carried out by exposing the tube to increasing temperatures under isothermal conditions until the temperature reaches 500 or 525 ° C. By isothermal conditions is meant that the entire material is always at about the same temperature as possible to prevent vapor transfer from hot or cold conditions that can result in heterogeneous products. The maximum soaking temperature is maintained for a substantial period of time during which time a powdery polycrystalline or crystalline product is formed. 72 typical soaking times
It's time. The longer the reaction or soaking time, the more crystalline product is obtained (as evidenced by the crystal size, the sharpness of the X-ray powder diffraction lines, etc.). The heat tube is also cooled to ambient temperature after a cooling period (10 hours). Slow cooling is not required for the reaction, but to prevent tube breakage due to the difference in the thermal coefficients of the product and the quartz ampoule.

Both the heating and cooling periods are relatively long (longer than 10 hours) and are at intermediate temperatures (eg 2
It was observed that it is best to soak at (00, 300, 400, 450 ° C.) for 4 to 6 hours.
Failure to follow these slow heating or cooling often caused the reaction tubes to explode. However,
The product of the condensed phase reaction was the same as in slow cooling, except that a small amount of residual phosphorus was white phosphorus rather than red phosphorus.

Example VII 19.5 g of a ball-milled mixture of reagent grade phosphorus and potassium in an atom to atom ratio of 15 to 1 was added to a length of 8 cm x
6.5cm in length taper to 1.0cm in diameter x 2.5 in diameter
A quartz tube of cm was placed under dry nitrogen conditions. The tube was sealed at reduced pressure (1 × 10 ^-4 Torr) by melting a thin section approximately 1 cm from its thick section.

This tube was supported in the central zone of a Lindberg 54357 three-zone furnace by a second quartz tube or liner, the latter supported by an asbestos block at the radial center of the heating chamber. The heating elements of the three zone furnace were driven by a Honeywell DCP-7700 Digital Control Programmer. The programmer was able to pre-program and implement the process in a reproducible manner. Using this programmer, the reaction tubes were exposed to the following temperatures for the indicated times: 100 ° C., 1 hour; 450 ° C., 6 hours; 500.
℃, 18 hours; 525 ℃, 72 hours; 300 ℃, 2 hours; and 200 ℃, 4 hours (all three zones controlled to the same temperature, the central zone is highly isothermal, the temperature across this zone Was less than 1 ° C).

After the furnace was brought to ambient temperature at the inherent cooling rate of the soup, the reaction tube was removed from the furnace. Under dry nitrogen conditions,
A quartz ampoule was cut open with a silicon carbide saw and a dark purple polycrystalline mass was collected. The composition of a sample of this material was analyzed. Wet analysis gave a P / K ratio of about 14.2: 1. This is an accuracy of about 6% of the theoretical value of 15: 1. Products from similar experiments with K / P ₁₅ feeds fall within the same range of values, as shown in Table XIII.

[0173]

[Table 15]

In addition, several samples from different experiments were analyzed morphologically. XRD for these materials
The powder diffraction pattern was in good agreement with that obtained from the single crystal KP ₁₅ produced by the vapor transfer method described above. Morphological analysis was performed for other metal-phosphorus systems as shown in the table. Comparing the XRD data of these materials with each other and with those obtained for single crystals, it was established that the products were similar in nature. That is, they all have essentially the same covalently bound phosphorus pentagonal tubes.

Milling Metal and Red Phosphorus Using ball milling, red phosphorus and Group 1a and 5
A homogeneous, intimately contacted mixture with a Group a metal was prepared. The milled product is relatively stable in air and is a convenient starting material for the condensed phase and single source vapor transfer techniques described above. Their stability is
It shows that the polyphosphides formed at least partially during milling.

It has been demonstrated that the Group 1a metals (excluding lithium) are easily milled with red phosphorus. The ease of milling was more pronounced for metals with lower melting points, typically rubidium. M / P ratio of group 1a is 1/1
The problem arises when changing from 5 to 1/7. With increasing metal content, the feed generally agglomerates significantly on the walls of the ball mill. Conveniently, the agglomerated product can be easily scraped from the mill, ground and passed through a 12 mesh screen. Lithium and arsenic are difficult to mill by standard ball milling methods because of their high hardness and melting point.

In the first experiment, reagent grade metal and reagent grade phosphorus were used. Here, only high purity metal (99.999% purity) and red phosphorus (99.9999% purity) obtained from Johnson Matthey are used. A. Standard Ball Milling This was originally the method of choice for the alkali metal / P system. However, stronger grinding methods (cold milling and vibration milling) were used for other Group 5a metals.

The stainless steel ball mill was made "in-house" and, as shown in FIG. 17, an inner diameter of 4.5 inches (11.4 cm) x a height of 6 inches (15.2 cm) x. Wall thickness 1/4 inch (0.64 cm)
It consists of a cylinder 150 of dimensions The top of myril is
It has an inner flange 151 that receives a Viton O-ring. The upper part 154 of stainless steel is screw 1
It is held in place by a rod 155 fastened by 56.

One mill has a smooth inner wall. The second mill had three baffles welded onto the wall from top to bottom. These baffles act as lifters for spheres and reagents, making grinding efficient. 50-6 in total
A reagent feed of less than 0 g is desirable. In the initial experiments, 1/4 inch (0.64 cm) stainless steel balls were used. Since then, 1/4 inch (0.64 cm) and 1
Better results have been obtained with a mixture of / 8 inch (0.32 cm) stainless steel balls.

Cold Milling (−196 ° C.) This was accomplished using a Spex Freezer Mill (available from Spex Industries, Inc., Metchen, NJ). Due to equipment limitations, only small amounts (2-3 g) can be milled in a single operation, but this can be done rapidly at liquid nitrogen temperatures (minutes). Thus, this technique can grind hard and high melting point metals such as lithium and arsenic. These metals can then be ground together with red phosphorus in a rotating ball mill or a vibrating ball mill.

Vibration Milling This device (Vibratom) is manufactured by TEMA (TEM).
A, Inc, Cincinnati, Ohio). This is essentially ball milling, but instead of using a rotary motion, it produces an isomorphic vibration, similar to a paint shaker. The mill has an inner diameter of 1/4 inch (0.64 cm) x height of 3.5 inches (8.9 cm) x thickness of 1/8 inch (0.32 cm).

This mill contains no baffles. This mill was used for milling difficult-to-mill elements such as As. Milling time There has been some variation here. Generally, the period of thermal milling is 40 hours or more, but 100 hours or less.
To some extent, this was determined by the milling system. The time required for Cs and Rb systems having a low melting point is short.

Milling Temperature This is at ambient temperature, or the mill is externally heated to approximately 100 ° C. with a heating lamp. Ambient temperatures have low melting points such as Cs (28.7 ° C) and Rb (38.9 ° C)
Suitable for. Application of an external heating lamp at 75-100 ° C. for 3-4 hours was performed using Na (97.8 ° C.) and K (6
It was certainly beneficial to the system (3.7 ° C). Heating to 100 ° C is not worth it for Li (108.5 ° C). We conclude that the stable product is the result of milling molten alkali metal and phosphorus.

K / P ₁₅ Ball Milling Example IX (Table XIV, Ref No. 88) Containing 884 g of 1/4 inch (0.64 cm) stainless steel balls under nitrogen in a dry box. , Stainless steel ball mill without baffles, 6.14g
(0.157 mol) of 99.95% pure K (obtained from United Minerals and Chemicals Company) and 72.95 g (2.36 mol) of 99.9.
Supplied 999% pure red phosphorus (obtained from Johnson Matthey Chemicals). The mill was sealed and rotated on a roll station for a total of 71 hours. 4 hours 1 by directing the surface of this mill to a heating lamp
Heated to 00 ° C. The mill contents were discharged into a 12 mesh sieve and pan in a dry box. No product agglomeration was observed. Steel balls were separated from the product on a sieve. A total of 76.4 g of a black powder product was obtained.

Cs / P ₇ Ball Milling Example X (Table XIV, Ref No. 115) 450 g 1/4 inch (450 g) and 450 g 1/8 inch under nitrogen in a dry box. (0.3
2.12 g (0.0912 moles) of 99.98% pure Cs (obtained from Alfa / Ventron Corporation) and 19.77 in a baffled stainless steel ball mill containing 2 cm) of stainless steel balls.
g (0.638 mol) of 99.999% pure red phosphorus (obtained from Johnson Matthey Chemicals) was fed. The mill was sealed and rotated on a roll station at ambient temperature for 46.5 hours. When the mill was opened in a dry box (no external heat source was used), almost total agglomeration of the product was observed on the mill wall. The material was scraped with a spatula and discharged into a 12 mesh sieve and dish. The large mass of product was then ground through a sieve. A total of 27.8 g of product was collected in the dish.

The results of milling various metals with red phosphorus are summarized in Table XIV. As mentioned above, these materials are surprisingly stable.

[0187]

[Table 16]

[0188]

[Table 17]

[0189]

[Table 18]

[0190]

[Table 19]

[0191]

[Table 20]

The materials obtained from these techniques were crystals or whiskers designated x; solid polycrystalline mass designated B;
Solid thin film designated TF; solid amorphous designated B and TF; and bulk powder from condensed phase synthesis designated B ^* . Synthesis of MP ₁₅ crystalline material has been described above with reference to FIGS. 7-10 FIG. As shown in Table XV, M ₁₅ material polycrystalline and amorphous was only produced in the form of a thin film.

Polycrystalline and thin films of KP _x (x is much greater than 15) were obtained by vapor transport (one source and two sources). These polycrystalline thin films nucleate on the glass support (or glass wall) and show a dense packing of parallel whiskers growing perpendicular to the support. SEM micrograph of such material,
18, 19 and 20 show a large physical separation between KP _x whiskers.

These polycrystalline thin films are formed at a low temperature from around 455 ° C. to 375 ° C. where the amorphous phase begins to form. Wet chemistry, XRD and EDAX analyzes on these materials constantly show that x is much greater than 15 (typically greater than 1000). A fingerprint of a typical powder XRD diagram of crystalline MP _x (x is much greater than 15) is shown in FIG.

As shown in Table XV, the amorphous MP _x material can be formed in the form of lumps (balls) by vapor transfer techniques. These balls may be formed by the narrow end 160 of tube 32 (FIGS. 1 and 2), the narrow end 162 of tube 58 in FIG.
Formed as a piece of material in zone 2 of 6. These materials show no X-ray diffraction peaks. The XRD powder diagram was used in our study to characterize the amorphousness of the materials obtained by these techniques. These amorphous MP _x materials (where x is much larger than 15)
It was cut, lapped and polished by conventional semiconductor technology for wafer processing. This is fact 50-50
It is a material containing 0 ppm or less of M, a new form of phosphorus.

The resulting large x KP _x amorphous wafer or support has been shown to have useful semiconductor properties and has almost the same electro-optical response as KP ₁₅ whiskers. Therefore, the local order of all MP _x materials (where x = 15 or much greater than 15) (when solidified in the presence of alkali metal) exhibits substantially the same local order throughout its spread. Concludes. This local order is an all-parallel pentagonal tube of phosphorus.

A large amorphous x KP _x material with a mirror-finished surface was prepared for electro-optical evaluation. Routine surface preparation of these amorphous materials involves some processing steps such as cutting, embedding, lapping, polishing and chemical etching. Surface processing damage induced during such processing steps is known to affect the electro-optical performance of semiconductor materials. Therefore, attention was focused on the evaluation techniques and processing steps that lead to the "damage free" surface. The following processing steps have been found suitable for producing high quality mirror finished surfaces.

High x KP _x embedded balls from Table VII (length 1-2 cm) were cut at a minimum pressure with a slow diamond saw. Almost 1 for each wafer
Sliced to a thickness of mm. Then bromine / wafer
Immersed in HNO ₃ solution. The thickness of each wafer was reduced by approximately 50 microns by this chemical etch in order to adequately remove the cut damage. The wafer was then washed and inspected for inclusions and voids. The large x KP _x material appeared void free.

A standard low temperature braze (melting point about 80 ° C.) was used to mount a large x KP _x wafer on the polishing block. The wafer is then spun at 50 rpm for 2
Laminated individually with 400-600 SiC grit at intervals of minutes using distilled water as a lubricant at a weight of 50 g / cm ² until a smooth surface was obtained. The final polishing step was carried out on Texmet cloth at 50 rpm and 50 g / cm ^{2 for} 1 hour with a 3 micrometer diamond formulation and lapping oil as extender. This polishing step is followed by an additional 15 minute polishing step at 5 rpm and 50 g /
Performed on a microcloth at a weight of cm ² with a slurry of 0.05 micrometer gamma alumina suspension in distilled water. All procedures are sound bath (son
meticulous during each cleaning step and subsequent washing and drying.

The samples produced by this technique have a high quality finished surface. The final polishing step was performed on a standard metallograph, Buehler polishing device. Chemical etching plays a major role in wafer manufacturing, surface treatment, preliminary equipment preparation, metallization and equipment fabrication.

There are numerous reports that cover the chemistry and practical aspects of etching processes. However, most information about a particular etchant is widely dispersed throughout the scientific literature. Should be useful in the selection of etching methods associated with these high amorphous x materials,
I tried to collect essential information. Particular attention was paid to the etching procedures and methods used to prepare the surface. G
We have found that some of the etching solutions and procedures currently used for aP and InP are applicable, but have different etching rates.

The following etching solutions were selected and tested: 5-10% Br ₂ for general etching and polishing, 95-90% CH ₃ OH-1 for high quality surface polishing only. % Br _2, 99% of CH ₃ OH (approximately 1 micron / min) - 5 wt% of NaOCl solution for chemical polishing - 1 HCl for removal of machining damage after cutting and lapping: 2HNO ₃ (1 % of Br ₂₎ - 1 HCl for removal of surface layer: 2HNO _3.

Several samples were prepared for optical absorption. Using the above technique, slice both sides of a large x material amorphous wafer to a thickness of about 0.5 mm,
There was polish. Both side surfaces of a reference sample of GaP and GaAs crystals were also polished, and the band gap was measured by optical absorption. An etching technique was developed to reveal the microstructure and thin small areas to a thickness of 0.2 mm for optical absorption.

Several solutions were selected and tested. The best chemical solution is 6.0 g of potassium hydroxide, 4 g of red potassium ferric anion and 70 ml of distilled water.
It was found to be a mixture at ° C. It takes less than 60 seconds before the etching pattern appears. This solution is very stable and can be used with reproducible etching rates.

After embedding, cutting, and polishing, the
Some samples of amorphous KP _x (x is much larger than 15) from VII and VIII were etched. Typical microstructures appeared 30 seconds after this chemical etching process. FIG. 21 shows amorphous balls of large x material grown by single source vapor transfer (Table VII, reference N).
o. 28) is a 360x photomicrograph of an etching pattern for a surface cut perpendicular to the axis, showing well-defined domains of a few microns in size (dom).
shows the honeycomb microstructure with ain). These honeycomb microstructures are characteristic of the etching pattern for materials with a two-dimensional atomic framework (eg parallel tubes).

FIG. 22 shows an etching pattern of 360 for a surface cut perpendicular to the axis of growth of an amorphous, large x material grown by vapor transfer of two sources in Example VI. It is a double microscopic photograph. Figure 23
Is a 720X photomicrograph of the same surface as shown in FIG. FIG. 24 is a photomicrograph at 360 × of the etched surface, perpendicular to the surface shown in FIGS. 22 and 23, showing the etching pattern characteristic of tubular packing.

Thus, all of the MP _x materials of the present invention, in which M is an alkali metal and x is much larger than 15, that is, the amount of alkali metal is as low as 50 ppm, are all parallel to each other in local order. It is concluded from the available evidence to have all parallel pentagonal phosphorus tubes either in the form of MP ₁₅ (in the form of MP ₁₅ ) or in doubly alternating vertical layers (monoclinic phosphorus).

The charge of high phosphorus materials from the vapor transfer of one source.
Child optical properties single crystal whiskers, the films and the ball of the polycrystalline film and the amorphous were performed electro-optic characterization. The characterization is (1) optical measurements on samples that do not rely on electrical contacts (absorption limit, photoluminescence) (2) electrical measurements on simple linear behaviors (conductivity, temperature-dependent conductivity, (Wavelength dependence of photoconductivity, conductivity type)
(3) Consists of electrical measurements with a non-linear or rectifying contact with a metal indicating a semiconducting behavior.

From the above data, all the materials produced have electrical criteria for useful semiconductors, that is, they all have an energy bandgap of 1 to 3 eV: 10 ⁻⁵ to 10 ⁻¹² (ohm). -Cm) ^-1 conductivity: 10
We expected to have a photoconductivity ratio of 0-10,000 and physical stability under ambient use conditions.
The measurements were carried out on the following devices: (1) Absorption limit-Zeiss two-beam IR and visible spectrophotometer photoluminescence-Low temperature (4 ° K) cryostat and laser excitation (2) Conduction -2 blow and 4 probe measurements Temperature-dependent conductivity-300 ° K to 55 in evacuated room
0 ° K photoconductivity-using a light source of almost 100 mW / cm ² wavelength-dependent photoconductivity-light source of Xe lamp and monochromator conductivity type-thermoelectric power measurement using thermal probe and cold probe (3) wetness A silver paint was used to form a temporary bond to the material and a photovoltaic open circuit voltage of 0.2 V was measured under illumination.

The metal and pressure contacts forming the bond are:
The current-voltage characteristics were evaluated with a Tektronix curve tracer. Data for samples from the wide range of materials studied are provided in Tables XVI, XVII, XVIII.
And XIX. Table XVI summarizes the basic physical, chemical and electro-optical properties of sample material, KP _x (x is much greater than 15 to 15), of various physical forms and chemical compositions.

[0211]

[Table 21]

Table XV shows the first of various compositions and physical forms.
The property of group a (alkali metal) polyphosphides is shown. Electro-optical properties are metals (Li, Na, K, Rb, C
s): physical form-crystalline, polycrystalline, amorphous (ball or film): and chemical composition (x = 15 or 15).
(Much larger) is observed.

[0213]

[Table 22]

Table XVIII summarizes the properties of mixed polyphosphides and that those formed from mixed alkali metals do not change their properties; partial substitution of As at the P site is possible and resistance , And possibly the bandgap (ie, substitutional doping).

[0215]

[Table 23]

Table XIX summarizes the materials and properties obtained from the different starting feed ratios. The best properties are obtained with materials having a P to K starting feed ratio of about 15 (ie between 10 and 30). Below 10 the yield decreases and above 30 the physical properties of the amorphous balls begin to deteriorate.

[0217]

[Table 24]

All of these materials, whatever their form, have a bandgap of 1 to 3 eV, especially 1.4 to 2.2 eV. Because 1.4 eV is the lowest photoconductivity we measured and 2.2 eV is the estimated band gap of red phosphorus. As the data further show, the bandgap of these best modes is approximately 1.8 eV. Plus, 100 of them
The surprisingly high photoconductivity ratio of ~ 10,000 indicates that they are very good semiconductors.

Bulk amorphous MP _x balls obtained by single source vapor transfer in a three zone furnace with a composition of doping x much greater than 15 were produced by cutting, lapping, polishing and etching. Can be processed into high quality mirror-finished wafers with a radius of about 0.5 cm.

Electrical measurements can be performed on these samples with different geometric arrangements of electrical contacts to accurately measure the bulk conductivity of the material. The measurements of 2 and 4 probes confirmed that the bulk conductivity of these materials was 10 ⁻⁸ to 10 ⁻⁹ (ohm-cm) ⁻¹ . This conductivity is too low for this material to form sharp junctions with rectifying properties. Therefore,
It was our aim to find a foreign element (doping agent) that affects the conduction mechanism in this material and increases its conductivity. As is typical of other amorphous materials, the presence of small amounts of impurities in this material has no effect on conductivity, indicating a Fermi level of the midgap above room temperature, We have found a unique behavior with activation energies equal to approximately half the bandgap. As shown in this, the electron wave function (electronic) of PP coupling is shown.
A strong perturbation of the wave function is required to modify conductivity and conductivity type.

Two methods are adopted, namely, (1) A
Substitution of s or Bi into the P site and (2) diffusion of the allogeneic element into the amorphous matrix. In the first method, K / Aa ₂ / P ₁₅ has As incorporated into the matrix. The conductivity increases by two orders of magnitude (Table XVIII) and the material remains n-type. In the second method, many common diffusing agents (eg Cu, Zn, Al, In, G
a, Kl) was tried with vapor, liquid and solid phase diffusion with no success. Surprisingly, Ni, then Fe
Diffusion of Cr and Cr from the solid phase was successful. For example, N
A layer of i was deposited by vacuum evaporation onto the well-prepared surface of a high x KP _x wafer. After annealing for several hours, Ni was found to diffuse into the support by about 0.5 micrometer and conductivity increased by 5 orders of magnitude. Conduction is still n-type.

More specifically, Varian (Varia)
n) 1500 Å Ni was deposited on the wafer under 10 ⁻⁶ Torr in a resistance-heated vacuum evaporator. Seal the sample in an evacuated Pyrex tube and
Heated at 50 ° C. for 4 hours. The upper Ni layer was removed. Conductivity measured by the two-probe method is 10 ⁻⁸ to 10
^It showed an increase to values greater than ^-4 . An electron spectrophotometric (ESCA) depth profile for the chemical analysis of the sample shows a diffusion depth of 0.4 micrometers and the chemical bond of Ni is Ni, ie It was shown to be free Ni in the material. Ni
, Overlaps with the electron wavefunction in the PP matrix and affects conduction (movement). The Ni temperature is greater than about 1 atom%.

A coplanar evaporated gold top contact or a dry silver paint forms an ohmic contact to the doped layer. Variable of diffusion temperature is 350 ℃ for Ni diffusion
Indicates that is optimal. The diffusion time variable follows the diffusion equation (diffusion depth is proportional to the square root of time) and 3
1500 Angstroms of Ni heated at 50 ° C. for 60 hours exhibited a diffusion depth of 1.5 micrometers as measured by ESCA. 350 ° C is the maximum temperature at which amorphous material can be exposed.

The diffusion of Ni can also be carried out from the liquid phase, eg from the Ni—Ga melt, or from the vapor phase, eg from the Ni carbonyl gas. In addition, Fe and C
It was found that r behaves similarly in the above procedure. For example, cut wafers from bulky, large amorphous x-balls obtained by single-source vapor transfer, and evaporate 500 angstroms of iron onto them.
It was then allowed to diffuse in the wafer for 16 hours at 350 ° C. Applying two pressure probes to the doped material, Tektronix
x) A completely non-linear characteristic was obtained on the curve.

On another wafer of large x material,
Evaporate 300 Å of nickel and 200 Å of iron, then heat the wafer at 350 ° C.
Heated for 16 hours. An aluminum contact with a thickness of 2000 angstrom and a radius of 1 mm was then deposited and the current-voltage characteristics were measured between the aluminum points with a Tektronix curve tracer, again obtaining a completely non-linear characteristic.

500 Å of Nichrome was deposited on another wafer of large x material produced by single source vapor transfer and then heated to 350 ° C. for 16 hours for diffusion. Then, two aluminum spots having a radius of 1 mm and a thickness of 2000 angstrom were vapor-deposited on the wafer, and completely non-linear characteristics were measured between the two aluminum spots.

Thus, nickel, iron and chromium are useful for reducing conductivity in these materials, and the ability to perform bonding on low conductivity materials with wet silver paint, pressure contacts and aluminum contacts, To be concluded. Ni, Fe having an occupied electronic level outside d or f that can overlap the level of phosphorus
Other elements in addition to Cr and Cr affect the conductivity in these materials, for example forming p-type materials, and p for solid state devices.
It is expected that the / n junction can be formed.

[0228] Amorphous high recovery with vapor transfer from two sources.
Materials of the type 2 material were produced by this method and the properties of these materials were investigated. 1) Amorphous bulk KP _x (Example VI), where x is approximately equal to 50 on one side and x is much greater than 15 on the other side. Surface analysis confirms the hypothesis of the template effect, which in this case is very strong. The surface of the cut and polished sample is of very high quality, has few defects and voids, and has a uniform etching pattern.

The conductivity was 10 ^-10 (ohm-cm) ^{-1 as} measured by two probe techniques. The photoconductivity ratio under illumination of 100 mV / cm ² is greater than 10 ³ . The photoconductivity peak is approximately 1.8 eV, which indicates a band gap of that level. As the data show, the PP bond has electrical and optical properties for this material and Table XVI, XVII, XVI.
It dominates the properties in II and XIV, and its strong photoconductivity is consistent with a highly diminished level of pendant binding.

2) KP ₁₅ amorphous thin film (Table) deposited with a metal layer for back contact to the thin film.
XII, ref. No. 47). The successful deposition of thin films of KP ₁₅ offers the opportunity to manufacture many forms of thin film equipment. The thin film of amorphous KP ₁₅ deposited by the two-source transfer technique has a thickness of approximately 0.5 micrometers over an area of 3 cm ² . The film is uniform, and the surface roughness does not exceed 2,000 Angstroms. This film is chemically stable. FIG. 25 is a 2000X photomicrograph of the surface of one of these KP ₁₅ films. The adhesion to the support is very good. Quantitative analysis of this film was performed by scanning electron microscopy (SEM) and energy dispersive X-ray (EDAX).
The measurement was performed using The composition of this film is KP
It was found to match ₁₅ nominal compositions. This uniform composition, homogeneous, pinhole-free surface provides uniform electro-optical properties across the film.

From the ability of Ni to diffuse into massive amorphous KP _x , Ni film 172 was applied to glass support 17
26, the amorphous KP
The back contact for ₁₅ layers 174 was formed. Ni acts as a back contact and a diffuser. ESCA and S
The EM profile shows that Ni diffuses well into KP ₁₅ film 174 at a rate of 200 Å / hr during the KP ₁₅ growth process.

More specifically, 1500 Å of Ni 172 was deposited by vapor deposition onto glass slide 170 at 10 ⁻⁶ Torr. A portion of the Ni surface is then masked with a Ta mask to form material free areas for electrical contacts. 2 micrometer phosphorus KP ₁₅ 174
Are deposited on Ni film 172 by a two source device. The composition of this composition was identified to be KP ₁₅ , which is amorphous and contains more than 1% Ni diffused into the film.

Pressure contacts were applied to the top surface of the KP ₁₅ film by an electric probe. Two lead wires were connected to the Tektronix curve tracer 176 from the back contact and the pressure contact on the upper surface, and the current-voltage characteristics were observed. The advancing characteristics of the commutation pressure contact junction are shown in FIG.
7 shows a junction with a barrier height of 5 eV and a current in the mA range.

As shown in FIG. 28, a Cu contact 178 having a radius of 2 mm is formed on the amorphous layer 182 of KP ₁₅ by vacuum evaporation.
Deposited on top surface 180 (grown on Ni layer 184 deposited on glass support 186 by two-source technique). The Tektronix curve tracer 176 was connected as shown and the fully advanced reverse bias junction curve shown in Figure 29 was measured. Thus, this indicates that Cu forms a bond with these materials.

Subsequently, similar metal dots were deposited as top contacts to reduce the leakage current effect at the edges of the contacts. Area 10 ⁻³ cm ² top contacts and 10 ⁻⁵ cm ² top contacts were deposited by mechanical masking in a vacuum evaporator. The IV characteristics shown in FIG. 31 are observed using Cu, Au, and Al top contacts. They appear in each case as two back-to-back diode breakdown voltages. A similar curve shows Ni, T as the top contact.
Obtained using i, Mg and Ag.

The most significant difference is that after applying 10V to this device, the Au contacts change the IV characteristics. This IV characteristic is asymmetrical, as shown in FIG. 32, and a more ohmic contact is
After this "formation", it is formed at the Au interface. This "formation" is constantly observed with Au, and occasionally with Ag and Cu top contacts. This "forming" does not permanently affect the device, but it reappears whenever a voltage is applied. Heating this device to 300 ° C. does not affect this phenomenon. -20
Cooling to ℃ results in a very sharp IV characteristic (Fig. 3).
3).

"Formation" appears to be the breakdown of the high resistance layer that remains between the diffused portion of the device and the top contact.
The capacitance-voltage (CV) characteristics shown in FIGS. 34, 35 and 36 point in the same direction. The top contacts of Al and Au have the C-V characteristics of a dual diode, but in the case of Au contacts, they transform into a single diode behavior. Assuming a dielectric constant of approximately 10, approximately 10
Carrier concentrations of ¹⁶ and carrier mobilities of approximately 10 ^{-2 to 1} cm ² / volt · sec can be induced. The frequency dependence of capacitance and resistance in Figure 37 can be used to model multiple junctions, which can be formed in such structures with graded diffusion profiles in the active material. In addition, poor bulk material quality (low density) and rough surface morphology give complex observations.
Nonetheless, the ability to form a bond on a thin film KP _{15 from} two amorphous sources was demonstrated.

Some of the above phenomena, such as "formation" using a top contact of Au, was observed with flash evaporated thin films deposited on Ni. This film is not pure KP ₁₅ , but has very good quality. In this case, C-V dependence is not seen. Very thin devices have excellent light responsiveness, and when illuminated with visible light, under short circuit conditions then a small current (1
0 ^-6 amps) is pulled out.

A thin film of KP ₁₅ made by the CVD technique will produce similar behavior when it is thick enough. It turned out to be a short when it was too thin. The formation of junctions with these materials shows that they can be used to form PN junctions, short key diodes, or metal oxide (MOS) devices.

By using the above classes of doping agents, the material can be converted to P-type conduction and thus be useful in the full range of semiconductors. Photoconductivity ratios were obtained in all of these by forming a semiconductor device consisting of the material of the invention and a means for electrically connecting it attached to it. This means consisted of two single electrodes 80 and 82 attached to the material illustrated in FIG.

More specifically, for a MP ₁₅ single crystal, two steel strips 80 and 82 were adhesively attached to a glass support 84. A sample 86 of KP ₁₅ made according to the technique described above was cross-linked at one end across strips 80 and 82 and attached thereto by silver paint 88. An electrometer 9 is attached to the other end of the strips 80 and 82.
0 is attached and an electric potential is introduced to KP ₁₅ , which causes KP ₁₅
Measure ₁₅ resistance.

The resulting device of FIG. 30 and similar devices using other materials have established that the high phosphorus materials of the present invention can be used to control current flow, at least as a photosensitive resist. Further, the material of the present invention is 4
It shows the luminescence properties with an emission peak at 1.8 eV at a temperature of ° K and the luminescence at ambient temperature.

Production of Large Crystal Single Crystal System P It was found that large crystal single crystal phosphorus can be produced using rubidium RbP ₁₅ . Diameter 10 mm x Inner Diameter 6 mm x 5.0 cm
0.62g of RbP ₁₅ sample was vacuum sealed in the quartz tube of
Placed vertically in crucible furnace and exposed to temperature gradient
The P ₁₅ feed was maintained at 552 ° C while maintaining the top of the tube at 539 ° C. After heating for about 22 hours, open the tube and open a truncated pyramid-shaped single crystal phosphorus single crystal with a helicopter size of about 3.0 mm (cold).
Got in the area.

Large crystal single-crystal phosphorus has Rb and P
It was also found that it could be prepared from a mixture (RbP ₁₅ ) in an atomic ratio of 1:15 with. Large cesium and sodium monoclinic single crystals were also produced by vapor transfer with CsP ₁₅ or NaP ₁₅ formed in the condensed phase process of the present invention. In each experiment, approximately 0.5 g of the appropriate alkali metal polyphosphide was added to a length of 8.9 cm.
It was vacuum-sealed in a quartz tube (10 mm outer diameter × 6 mm inner diameter).
The tube was then exposed to a temperature gradient such that the alkali metal polyphosphide feed was maintained at 558 ° C while maintaining the top of the tube at 514 ° C. 48 hours later,
Large, monoclinic, deep-red crystalline overlapping square platelets were formed from the CsP ₁₅ feed.

The morphology of monoclinic phosphorus crystals grown from CaP ₁₅ and NaP ₁₅ condensed phase feeds appears to be very similar, ie, overlapping square platelets. This is in symmetry with the truncated pyramidal habit of monoclinic phosphorus crystals grown from the RbP ₁₅ feed. Larger crystals of monoclinic phosphorus also have Cs / P ₁₁ maintained at high temperatures,
It was found that it can be produced from a mixture of Cs / P ₁₁ and Cs / P ₁₅ .

Potassium Using a similar method, KP ₁₅ in condensed phase, and K / P ₃₀
Crystals of monoclinic phosphorus were prepared from a mixture of K / P ₁₂₅ and K / P ₁₂₅ . Experiments were carried out using lithium lithium / phosphorus feed. However, large crystal monoclinic phosphorus could be produced from this material under similar conditions.

Effect of Temperature The nature of the alkali metal present does not appear to be important, but the temperature at which the feed is maintained is clearly very important for crystal growth. In the case of Cs / P ₁₁ ball milled system, large crystals feed 555 ° C.
Manufactured in an experiment in which the temperature was maintained at 554 ° C. However, large single crystal system crystals did not form in the experiments where the feed was held at 565 ° C and 545 ° C.

Referring to FIG. 38, using a preferred apparatus, a 0.6 g sample of RbP ₁₅ produced by the condensed phase method was vacuum sealed in a glass tube 270 having an outer diameter of 12 mm × an inner diameter of 6 mm × a length of 8 cm. The top is a flat glass surface with a diameter of 16 mm 2
Sealed at 72. The filling pipe 274 has a restraint portion 276 that is sealed after being supplied and exhausted. The tube was exposed to a temperature gradient to maintain a flat surface 272 on the top of the tube at 462 ° C, while maintaining the feed at the bottom of the tube at 550 ° C. 1
After heating for 40 hours, approximately half of the original feed was transferred to a flat surface.

The button-like balls obtained were torn and inspected. It consisted of perfectly uniform pale red fibers-not the desired large crystalline monoclinic phosphorus. Figures 44 and 45 are SEM micrographs of this product at 200x and 1000x, respectively. The SEM micrographs of Figures 44 and 45 were clearly surprising. Each "fiber" consists of a bundle of long platelets, which are joined together so that they look like a star when viewed from the end. Thus, this material is very different in appearance from the "twisted tube" (see below) made by vapor transfer from a 99.9999% red phosphorus feed.

The condensation temperature to form large crystalline monoclinic phosphorus will be in the range 500-560 ° C. Further, as experiments show, the preferred condensation temperature is about 539.
℃. The feed must be heated to a temperature above 545 ° C and below 565 ° C, as indicated previously. In the present invention, the preferred range is 550 to 560 ° C,
About 555 ° C gives the best results.

Compositional Effects Monoclinic phosphorus was prepared from feeds with a P to alkali metal ratio of 11 to 125. However, a ratio of about 15 seems to be most effective. Monoclinic liquid condensed from vapor in the presence of alkali metals.
Characteristics of emissions Figure 39 shows a phosphorus prismatic monoclinic prepared from RBP ₁₅ feed a micrograph of 50 times. These crystals are difficult to cleave. Similar crystals are made from a feed that uses sodium as the alkali metal. 4x3
Crystals as large as × 2 mm were produced.

FIG. 40 is an 80X photomicrograph of monoclinic phosphorus crystals made from a ball-milled mixture of Cs / P ₁₁ These platelets were easily cleaved to form mica-like sheets. Become. Similar crystals can be produced from a K / P ₁₅ feed. The side is as large as 4mm, and the thickness is 2
mm of this crystal habit was produced. The crystal was determined to be birefringent. When placed in a crossed polariser in a polarizing microscope, the crystal rotates the light and allows a portion of the light to pass through. Thus, the crystal can be used as a birefringent device, for example as an optical rotator in the red and infrared parts of the spectrum.

Chemical analysis shows that the crystals are 500 to 2000.
Containing ppm of alkali metal. Crystals are produced in as little as 22 hours, as opposed to 11 days in the prior art method of producing Hittorf's phosphorus. The powder X-ray diffraction patterns of these crystals are in agreement with those of the prior art Hittorf phosphorus.

The photoluminescence spectra shown in FIGS. 41 and 42 were obtained using an argon laser Raman spectrophotometer. A broad peak at 1.91 eV is clearly observed and the half-width is about 0.29 eV.
This means that the bandgap at room temperature is about 2.0 eV.
Is shown. The spectra of FIG. 41 were taken with a monoclinic system of phosphorus prepared in the presence of cesium, while the spectra of FIG. 42 were taken with a monoclinic system of phosphorus condensed in the presence of rubidium.

The Raman spectrum of FIG. 43 was taken using monoclinic phosphorus crystals formed in the presence of rubidium. Peaks 280, 282, 283, 284 and 28
5 is wave number 285, 367, 465, 483 and 529
Exists in. Evaporated spots of about 25 micrometers in diameter were deposited on monoclinic large phosphorus crystals (from Rb / P ₁₅ source) for electrical measurements. The resistance of this crystal was 10 ⁻⁶ ohms to 10 ⁷ ohms and was virtually independent of crystal geometry and contact size. This reflects surface resistance.

These crystals can be used as supports for depositing 3-5 materials such as indium phosphide or gallium phosphide. They can be used as emitters in light emitting displays, semiconductors, lasers, and as starting materials in other semiconductor devices. The presence of alkali metals in the twisted fibrous phosphorus feed appears to be important in the production of large crystal monoclinic phosphorus. Attempts were made to produce large monoclinic phosphorus single crystals from red phosphorus with a purity of 99.9999% by imitating the conditions that were effective with various alkali metal / phosphorus systems. This attempt failed. No monoclinic phosphorus was produced. For example, a 0.6 g sample of 99.9999% pure red phosphorus was heated to 552 ° C. in a vertically positioned quartz tube of 10 mm outer diameter × 6 mm inner diameter in an evacuated and sealed tube. The temperature gradient between the bottom and top of a 2.75 inch (7.0 cm) long tube was 43 ° C. After heating for 24 hours, more than half of the feed was transferred to the upper third of the tube where balls formed.

It was surprisingly found that the balls consist entirely of red fibrous material. Several long fibers (approximately 1.5 mm) were present in the vapor space at the bottom of the ball. When the deep red fibers were examined microscopically, they were twisted. The XRD data for this fibrous material was found to be consistent with the data initially obtained for polycrystalline KP _x, where x is much greater than 15.
Figure 46 is a 500X SEM micrograph of these fibers.

Differential thermal analysis (DTA) data were similar to those obtained for the polycrystalline large x material. The first heat plot is 62 for two DTA measurements.
It consisted of a single endotherm at 2 ° C (average). Second
The heat plot consisted of a single endotherm at 599 ° C in both cases. The DTA data initially obtained for the polycrystalline large x material show that the first heat single absorption (614 ° C.) and the second heat single absorption (590 ° C.)
Was made of. Thus, the fibrous phosphorus made from 99.9999% red phosphorus and the polycrystalline large x material were substantially similar.

Flash Evaporation Flash evaporation has been successfully used to form stable thin films on glass and nickel coated glass substrates. The flash evaporator is shown in FIG.
Generally indicated by. It consists of a glass cylinder 304 connected via a tube 306 to a vacuum system (not shown). Argon is supplied to the inlet 308 of the supply pipe 310. For 3
Fill 12 with KP ₁₅ powder formed by the condensed phase method.
It is agitated by a vibrator, generally indicated at 314, and picked up by an argon flow, generally at 316, through a venturi. It then flows into reactor 304 and pipe 317.
And enters the steel susceptor 318. This susceptor is RF
Coil 318 heats to a temperature of at least 900 ° C. to vaporize KP ₁₅ . At the end of tube 316, FIG.
Nozzles are formed by combining a plurality of small tubes, generally designated 320 in FIG. 41, having a plurality of small orifices 321 as shown in FIG. Tubes 317 and 320 are alumina and tube 320 is held within the end of tube 317 by magnesium oxide cement 322.

Upon evaporation, KP ₁₅ dissociates into its constituents, and this evaporation is carried by the argon gas through orifice 321. Film is cold support 3
Precipitates on 24. The support can be heated by a hot wire 326 that is powered by electrical connection 328. Alumina tube 317 has an outer diameter of 0.25 inch (0.64 cm) and an inner diameter of 0.125 inch (0.318 cm). Tube 328
Has an outer diameter of 0.0625 inch (0.159 cm) and a length of 0.
25 has an outer diameter of 0.064 cm) and a diameter of 0.06
It has four 25-inch (0.159 cm) through holes.

This apparatus is operated under a reduced pressure of 0.1 to 0.5 mmHg. Amorphous films up to 1 micron thick can be formed in experiments up to 15 minutes. At the end of the experiment, the support 324 is 200 to 3 depending on whether it starts at room temperature or is initially preheated to 200 ° C.
It reaches a temperature of 00 ° C. Chemical vapor deposition A thin film of KP ₁₅ was produced by chemical vapor deposition.

A typical chemical vapor deposition reactor is shown in FIG. It is made of Pyrex. The reaction chamber 401 is a tube having an inner diameter of 26 mm and a length of 27.0 cm, and a tube having an inner diameter of 6.0 mm and a length of 30.0 cm serving both as a thermowell and a support holder is located in the center of the reaction chamber 401.
Vent tube 404 allows for continuous removal of the gas exhaust stream. It is attached to a trap (not shown) that removes unreacted phosphorus before exhausting the stream into air. The vent pipe 404 and the O-ring collar 403 are attached via an O-ring joint 405 having an inner diameter of 2.0 cm. Reaction chamber 401 is located in a resistance furnace, generally indicated at 406.

The molten or phosphorus is melted by a piston pump (not shown) through a capillary tube 407 having an inner diameter of 1.0 mm and an evaporation chamber 40.
Put in 8. The molten phosphorus is vaporized in the evaporation chamber 408 by an argon flow injected into the evaporation chamber 408 through an inlet pipe 409 having an inner diameter of 6.0 mm. A gaseous phosphorus / argon stream enters the reaction chamber through nozzle 410. Nozzle 41
0 has an opening of 4.0. Evaporation chamber 408 is located in a resistance furnace, generally indicated at 411.

The gas mixture of potassium and argon was weighed and measured from the inlet tube 412 having an inner diameter of 6.0 mm to the reaction chamber 40.
Enter 1. Shroud of potassium / argon flow (shr
Pure argon, acting as aud), enters the system through a tube 413 with an internal diameter of 6.0 mm. The potassium / argon stream and the pure argon stream enter the reaction chamber 401 at 414. The potassium / argon and pure argon lines (412, 413) are located in a resistance furnace, generally indicated at 415.

The support 416 is located on the thermowell 402. The temperature of the support 416 is measured by a thermocouple 417 located on the thermowell 402 just below the support 416. The furnaces 406, 411 and 415 are maintained at the proper temperature during operation. The gaseous reactant flow enters in reaction chambers 410 and 414. The exhaust gas mixture leaves the reaction chamber via vent pipe 404. The desired film is formed on the support 416.

The support is maintained at a temperature of 310 to 350 ° C. and kept in a chamber at a temperature of ± 2 ° C. In a typical experiment, 1.24 g phosphorus and 0.13 g potassium are fed into the reactor over 2 hours. The total argon flow rate is maintained at 250 ml / min during the experiment. A number of experiments were performed in which phosphorus / argon and potassium / argon were fed to the reactor simultaneously. Phosphorus / argon flow is almost 2
The temperature was maintained at 90 ° C and the potassium / argon flow was maintained at approximately 410 ° C. The calculated atomic ratio of the reaction components in the reactor was approximately 15 P / K. In a typical experiment, the liquid phosphorus feed rate was 0.34 ml / hr.

Amorphous KP ₁₅ films were prepared using a nickel coated glass support. The film is about 0.3
The thickness was mm. Using a 1.0 hour run time, the film produced had a composition of nominal KP ₁₅ . The thickness of this film depended on the position of the characteristic support in the reactor. The film was inspected by SEM and was very uniform.

Purification of Phosphorus 50 g of Atomergic phosphorus, "99.95% pure", was exposed to a gradient of 450-300 ° C for 75 days. After this noticeably very long time, 21% of the material remained and 60% of the feed became an amorphous lumpy deposit.

According to the previous analysis, Atomagic phosphorus was less than 99.90% pure, probably 99.80% phosphorus.
, The main impurities were aluminum, calcium, iron, magnesium, sodium and silicon (all above 0.01%, some as high as 0.05%). The cost of this material is about $ 220 / kg. In comparison, "90%" phosphorus obtained from Alpha Bentron is $ 17 / pound ($ 37.5 / kg).

The results of flame emission spectroscopy on the three materials produced by the above treatments are summarized in Table XX.

[0271]

[Table 25] Material A was a dark brown material that remained through the feed zone and did not undergo vapor transfer. The material indicated as Material B is mainly located at 450 ° C. in the feeding zone.
It was a light colored material of a hard ball that did not evaporate due to the slightly lower temperature. Material C was an amorphous ball in the cold zone.

Apparently, most of the impurities in the feed remained in Material A in fairly concentrated amounts. High levels of impurities reduce the vapor pressure of phosphorus at a given temperature. Material impurity levels mirror the values for the initial feed. Ball material C is a fairly pure material, with sodium being the major observed contaminant. Summing up the contaminants at the highest indicated level, the purity level of this material is, at worst, 99.997.
%. The cost of a comparable material available as 99.999% P from commercial sources is about $ 1,800 / kg.

As is apparent, the above method is a cost effective method for highly purifying red phosphorus. Reinforced Materials The use of phosphorus compounds as flame retardants is well known. The alkali metal-containing phosphorus material disclosed herein can be used for such purpose because of its highly stable property.

The materials disclosed herein in the form of fibers and plates, such as fibrous KP ₁₅ and KP _x (where x
44), phosphorus with plate-like monoclinic phosphorus habit, phosphorus in the form of twisted tubes, and FIG.
And the star material of Figure 45 can all be used as a reinforcing additive material for plastics and glass. Twisted tube fibers and star fibers are of particular value because they can mechanically interlock with the matrix of the composite material.

Coatings As mentioned above, many of the materials disclosed herein are highly stable, amorphous coatings with excellent adhesion to metals and glass. KP ₁₅ amorphous film is particularly stable and provides excellent adhesion to metals and glass. Thus, they can be used as corrosion resistant coatings on metals and as optical coatings on glass.

A suitable infrared optical component, such as a coating of approximately 1000 Å on germanium, is transparent to infrared but absorbs visible light.
Such coatings, when combined with coatings of other materials with different optical indices, can be used to form antireflection coatings on infrared optics.

Other experiments have shown that MP _x materials can be deposited on copper, aluminum and molybdenum as films with good adhesion. The film is ductile, non-porous, polymeric and not brittle. Thus, the materials shown herein can be used as coatings and thin films.

Industrial Applications As mentioned above, a completely new class of high phosphorus anti-materials has been disclosed. These semiconductors consist of covalently bonded atoms in a chain, where the chain covalent bonds serve as the main conduction paths in the material. Chain atoms form parallel columns as a local ordering that occupies a major proportion. Preferably the atoms are trivalent and have bonds that allow tubular, helical or channel-like columns. The columns can be joined by atoms of one or more different elements bound to two or more chain columns.

We have disclosed certain high phosphorus mixed pnictide semiconductor materials of this class. These include high-phosphorus polyphosphides of the formula MP _x , where x is in the range 7 to 15 and completely novel materials for which x is much greater than 15-for all practical purposes. In contrast, pure phosphorus is included. These materials can be characterized as containing groups of 7 or more atoms organized into pentagonal tubes. They are the formula M
P _x , where x is greater than 6, and they can be characterized as being composed of phosphorus with a molar ratio of phosphorus to other atomic components greater than 6; Is a high phosphorus, consisting of phosphorus atoms whose phosphorous atoms at virtually all local orders are joined together by a number of covalent PP bonds organized into layers of all parallel pentagonal tubes. It can be characterized as a material. They can be characterized as alkali metal-containing polyphosphides, in which the number of consecutive covalent phosphorus-to-phosphorus bonds is significantly higher than the number of non-phosphorus-to-phosphorus bonds, making the material semiconducting. They have a skeleton of at least 7 covalently bound phosphorus atoms associated with at least one alkali metal atom,
The alkali metal atoms can be characterized as bridging the phosphorus skeleton of one unit with the phosphorus skeleton of another unit; they have the formula MP _x , where M is an alkali metal and x Is at least 7).

These materials can be further characterized by having a bandgap of greater than 1 eV, especially 1.4-2.2 eV, and for the best material we have found about 1.8 eV. They are,
It can be characterized by having a photoconductivity ratio greater than 5, and more particularly in the range 100-10,000.

These materials are composed of major trivalent atomic species; similar atoms (homatomi) formed by the major species.
c) bonds; the covalent nature of these bonds; the coordination number of the material slightly less than 3; the polymeric nature of the material; the presence of one or more alkali metals that mimic the bond between the alkali metal and the main species. Formation of material below; all parallel pentagonal parallel tubes in KP ₁₅ -like material in crystal form, paired parallel intersecting layers in monoclinic phosphorus, or twisted fibrous phosphorus Can be further characterized by: all-parallel twisted tubes in; amorphous films and balls that retain electronic quality; and methods of making them; and other qualities that will be apparent in the above description.

The amorphous material we have discovered is KP
_It retains ₁₅ electronic qualities, an all-parallel pentagonal tube structure, and theoretically, at least, it is clear that its structure is maintained on a local scale in our amorphous materials. However, we do not want to be bound by any particular theory regarding this. In particular, the claims are broadly and implicitly construed as covering all aspects of our invention, regardless of what is later admitted to contradict our stated theories and hypotheses. Should be.

We have disclosed bonding devices, photoconductive (resist) devices, photovoltaic devices and emitters made from these materials. It has been reached the conclusion that substantially all groups of atomic species having an occupied outer electronic level of d or f can be used if the atomic 9 size is suitable, ie a drag-reducing doping agent, ie We have disclosed nickel, chromium and iron.

We have disclosed drag reducing dopants that can be used in place of arsenic, indicating that all Group 5 metals can be used. We disclose a bonder, which has Ni, diffused Ni back contacts and Cu, Al, Mg, Ni, Au, Ag and Ti top contacts. We have disclosed novel forms of phosphorus, twisted fibrous phosphorus and monoclinic phosphorus, which are pentagonal tubes with all local regularities substantially parallel. These new forms of phosphorus were formed by vapor deposition. All parallel, monoclinic morphologies require the presence of alkali metal during precipitation.

MP ₁₅ (where M is an alkali metal)
The amorphous and polycrystalline forms of All of the materials for all parallel pentagonal tubes, for example MP _x wafers, where x is much larger than 15, novel forms of phosphorus, KP ₁₅ amorphous thin films and KP _x. Various semiconductor devices were constructed from the amorphous thin film of.

We have disclosed the production of metal polyphosphides and two novel forms of phosphorus by a controlled two temperature single source technique. A method of making high phosphorus materials by vapor transfer of two sources has been disclosed. A method for producing high purity phosphorus has been disclosed. Disclosed is a method for producing crystalline and amorphous forms of MP _x, where x is 7-15, by the condensed phase method.

Chemical vapor deposition, flash evaporation and molecular flow deposition have been disclosed. The industrial applications of semiconductor materials and devices we have discovered are obvious and encompass the full range of semiconductor applications. Crystalline materials can be used as reinforcing fibers and flakes in plastics, glass and other materials. The materials of the present invention can be used as coatings on metals, glass and other materials. The coating protects the support from flame, oxidation or chemical attack. The coating can be used to transmit infrared radiation and absorb visible radiation. The coating, along with other materials, can be used as an antireflection coating on infrared optics. The material can be used as flame retardant filler and coating. Monoclinic phosphorus can be used as an optical rotatory substance.

Thus, as will be appreciated, unless otherwise noted, crystalline material was used to mean single crystalline and polycrystalline materials. Amorphous is distinguished from single crystal and polycrystalline and means to X-ray diffraction is amorphous. All Periodic Tables are in The Handbook of Chemistr
y and Physics (Handbook of Chemistry and Physics), CRC Pres
s Inc., Boca Raton Florida, 60th edition, see the table printed inside the front cover. Alkali metals have been identified therein, where they are Group 1a, and pnictides are Group 5a. All ranges stated herein include their limits.

Semiconductors These refer to devices that use semiconductor materials. In particular, the semiconductor device has a zero-dullaffey surface and an emitter, regardless of how it is excited.
As well as photoconductors, photovoltaics, junctions, transistors, integrated circuits and the like.

[Brief description of drawings]

FIG. 1 is a partial cross-sectional view of a single source vapor transfer device according to the present invention.

2 is a diagrammatic view of a portion of the vapor transfer device of FIG.

FIG. 3 is a diagram of another single source vapor transfer device in accordance with the present invention.

FIG. 4 is a computer diagram from X-ray diffraction data of phosphorus atoms in MP ₁₅ (where M is an alkali metal).

FIG. 5 is a computer plot from X-ray diffraction data of KP ₁₅ cross-sections showing how the covalent bonds of the phosphorus atoms of FIG. 4 form a pentagonal tubular structure.

FIG. 6 is a computer diagram from X-ray diffraction data of a longitudinal section of KP ₁₅ .

FIG. 7 is a micrograph of KP ₁₅ crystal whiskers.

FIG. 8 is a micrograph of KP ₁₅ crystal whiskers.

FIG. 9 is a powder X-ray diffraction chart of crystalline KP ₁₅ .

FIG. 10 is a powder X-ray diffraction chart of crystalline KP _x, where x is much larger than 15.

FIG. 11 is a diagram of an experimental reaction tube for vapor transfer of two sources according to the present invention.

FIG. 12 is a temperature versus length plot for the reaction tube of FIG.

13 is a P-to-K ratio diagram of the reaction product in the reaction tube of FIG.

FIG. 14 is a schematic diagram of an apparatus for dual source vapor transfer in accordance with the present invention.

15 is a diagrammatic view of one of the elements of the device shown in FIG.

FIG. 16 is a diagrammatic view of another reaction tube for the transfer of two sources according to the present invention.

FIG. 17 is a diagram of a ball mill according to the present invention.

FIG. 18 is a scanning electron microscope (SEM) of a film showing the crystalline morphology of the novel form of phosphorus MP _x, where x is much larger than 15.

FIG. 19 is a scanning electron microscope (SEM) of a film showing the crystalline morphology of the novel form of phosphorus MP _x, where x is much larger than 15.

FIG. 20 is a scanning electron microscope (SEM) of the film showing the crystalline morphology of the novel form of phosphorus MP _x, where x is much larger than 15.

FIG. 21 is a photomicrograph of such an xMP _x etched amorphous surface synthesized by single source vapor transfer according to the present invention.

FIG. 22 is a photomicrograph of such an xMP _x etched amorphous surface synthesized by vapor transfer of two sources according to the present invention.

FIG. 23 is a micrograph of the same surface shown in FIG.

FIG. 24 is a photomicrograph of an etched surface perpendicular to the surface shown in FIGS. 22 and 23.

FIG. 25: Surface S on top of an amorphous thin film of KP ₁₅ synthesized by vapor transfer of two sources according to the present invention.
It is an EM micrograph.

FIG. 26 is a sectional view of a partial diagram illustrating the formation of a bond according to the present invention.

FIG. 27 is an illustration of an oscilloscope screen in the experiment shown in FIG. 26.

FIG. 28 is a partial cross-sectional view illustrating the formation of a bond according to the present invention.

29 is an illustration of an oscilloscope screen for the experiment shown in FIG. 28. FIG.

FIG. 30 is a diagram of a photosensitive resistor according to the present invention.

FIG. 31 is a screen illustration of an oscilloscope showing the activity of the junction by the device according to the invention.

FIG. 32 is a screen illustration of an oscilloscope showing the activity of the junction by the device according to the invention.

FIG. 33 is a screen illustration of an oscilloscope showing the activity of the junction by the device according to the invention.

FIG. 34 is a plot of capacitance versus applied potential in a bonding device according to the present invention.

FIG. 35 is a plot of capacitance versus applied potential in a bonding device according to the present invention.

FIG. 36 is a plot of capacitance vs. applied potential in a bonding device according to the present invention.

FIG. 37 is a plot of capacitance and resistance as a function of frequency of applied potential for a device according to the present invention.

FIG. 38 is a preferred form diagram of a sealed ampoule used to form monoclinic phosphorus according to the present invention.

FIG. 39 is a micrograph of monoclinic phosphorus crystals according to the present invention.

FIG. 40 is a micrograph of monoclinic phosphorus crystals according to the present invention.

41 is a diagram of the photoluminescence response of monoclinic phosphorus crystals according to the present invention. FIG.

42 is a diagram similar to FIG. 6 of the photoluminescence of monoclinic phosphorus crystals according to the present invention.

FIG. 43 is a Raman spectrum of monoclinic phosphorus according to the present invention.

FIG. 44: SEM of another novel form of phosphorus according to the present invention
It is a micrograph.

FIG. 45: SEM of another novel form of phosphorus according to the present invention
It is a micrograph.

FIG. 46: S of yet another novel form of phosphorus according to the invention
It is an EM micrograph.

FIG. 47 is a side view of a flash evaporation device according to the present invention.

48 is a cross-sectional view taken along line 48-48 of FIG. 47.

49 is a cross-sectional view taken along line 49-49 of FIG. 48.

FIG. 50 is a diagram of a chemical vapor deposition device according to the present invention.

[Explanation of symbols]

10 ... Furnace of two temperature zones 14 ... Insulation coating 24 ... Conductor 26 ... Conductor 28 ... Heating zone, cold zone 30 ... Heating zone, hot zone 32 ... Quartz tube 36 ... Reactive component 40 ... Dark gray or black residue 42 ... Film deposits 44 ... Crystals 46 ... Whiskers 48 ... Film deposits 50 ... Film deposits 52 ... Agglomerates or film deposits of an amorphous material 54 ... Three-zone furnace 58 ... Reaction tube 60 ... tube 62 ... heating zone 64 ... sample 88 ... silver paint 90 ... potentiometer 100 ... quartz tube heating zones 66 ... heating zone 68 ... asbestos blocks 70 ... asbestos blocks 80 ... electrode 82 ... electrode 84 ... glass substrate 86 ... KP ₁₅ 102 ... Substantial division 104 ... Three-zone furnace 112 ... Boat 113 ... Pyrex's Divider 114 ... Glass support 119 ... Quartz tube 120 ... Nozzle 122 ... Nozzle 124 ... Addition tube 126 ... Second addition tube 128 ... Outermost compartment 130 ... Central compartment 132 ... Outer compartment 134 ... Pyrex reaction chamber 136 ... Chamber 137 ... Woven glass tape 138 ... Tape 139 ... Woven glass tape 140 ... Plug 150 ... Cylinder 160 ... Narrow end 162 ... Addition tube 170 ... Glass support 172 ... Ni film 174 ... Amorphous KP ₁₅ layer 178 ... Cu contact 180 ... Top surface 182 ... Amorphous layer of KP ₁₅ 184 ... Ni layer 186 ... Glass support 270 ... Glass tube 272 ... Flat glass surface 302 ... Flash evaporation device 304 ... Glass cylinder 306 ... Tube 308 ... Inlet 310 ... Supply tube 312 ... for storage 318 ... copper susceptor 324 ... support 328 ... Electrical connection 401 ... Reaction chamber 405 ... O-ring joint 406 ... Resistance furnace 407 ... Capillary 408 ... Evaporation chamber 409 ... Inlet tube 410 ... Nozzle 411 ... Resistance furnace 412 ... Inlet tube 413 ... Tube 414 ... Potassium / argon flow and Pure argon flow 415 ... Resistance furnace 416 ... Support 417 ... Thermocouple

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[Procedure amendment]

[Submission date] June 1, 1992

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be amended] Claims

[Correction method] Change

[Correction content]

[Claims]

[Procedure 3]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction content]

Considerable research on high phosphorus polyphosphides has been reported by H. K. G. phone. Schnelling (von
Schnering). According to various reports from this group, the highest phosphorus-containing polyphosphide compounds they produced are crystalline MP ₁₅ (M = 1a group metal). These polyphosphides are produced by heating a mixture of metal and phosphorus in a closed ampoule. phone.
Schnelling reports that, based on their structure, polyphosphides are classified as valence compounds in the classical sense, which means that these compounds are insulators or semiconductors, i.e., metals. is not. The report by Schnelling et al. Above includes:
Mu. HGvon Schnering and H. Schmidt, "KP ₁₅ , A New Pota
ssium Polyphosphide ", Angew.Chem., Int.Ed. 6, p.35
6, 1967. HGvon Schnering, "Catenation of Phosphorus Atom.
s ", Homoatomic Rings, Chains Macromolecules, Main-G
roup Elements, Chapter 14, pp.317-348, edited by
ALRheingold, Elsevier Scientific Publishing Co.,
Amsterdam, 1977. HGvon Schnering, M. Whittmann, R. Nesper; "Dithor
ium UndecaphosphideTh ₂ P ₁₁ , A Polyphosphide with a
One-dimensional Superstructure Generated by a Perio
dic Change in the Covalent Bonds ", J. Less-Common M
et., vol.76, No.1-2, 213-226, Dec / 1980. H. Schmidt, "Chemistry and Structural Chemistry of
the Polyphosphides of Alkaline Metals, The Crystal
line Structures of KP ₁₅ , RbP ₁₁ , and CsP ₁₁ ", Disser
tation. Westfalische Wilhelms University Munster,
1970, Germany.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0067

[Correction method] Change

[Correction content]

The film material of the present invention has chemical stability,
Due to its flame retardant and optical properties it can be used as a coating. The purpose is therefore an object of the present invention the invention is to provide a useful semiconductor material of a novel class. Another object of the present invention is to
It is to provide a novel method and apparatus for producing polyphosphides. Yet another object of the present invention is to provide stable high phosphorus materials and methods and apparatus for making same. Another object of the present invention is a novel form.
Provide phosphorus in a state, and method and apparatus for manufacturing the same
It is to be. Another object of the invention is the monoclinic phosphorus.
Is to provide large crystals. Yet another object of the invention is to provide high purity phosphorus. Another object of the invention is to provide new semiconductor materials. Yet another object of the invention is to provide a birefringent material for use in the red and infrared parts of the spectrum. Yet another object of the present invention is to provide a method of making a material of the above character. Another object of the invention is to provide such a method which is more convenient and less costly than the prior art. Another object of the invention is to provide coating materials, fillers, reinforcing materials and flame retardants. Other than the present invention
The purpose is partly clear, and partly later
It will be clear. The scope of the present invention is claimed.
It is described in.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical display location C30B 29/10 7821-4G 29/62 Z 7821-4G U 7821-4G H01L 21/208 T 7353- 4M 29/28 8728-4M 31/04 31/0248 (72) Inventor Christian Gabriel Mikul United States, New York, Ossining, Edgewood Road 15 (72) Inventor Rosalie Shachiter United States, New York, Flashing, One Hundred and Seven Tee Third Street 75-14 (72) Inventor John Andrew Bowman Riverside Place, Dobbs Ferry, New York, USA 26 (72) Inventor Paul Mordecai Laker United States, Ili Neu, Chicago, N. Albany Street 7521

Claims (98)

[Claims] 1. The formula MP _x (where M
Is one or more metals, and P is one or more pnictides). 2. Phosphorus atoms are joined together by a number of covalent phosphorus-to-phosphorus bonds to form a substantially pentagonal tubular array of bound phosphorus atoms, the local ordering of the phosphorus being substantially throughout. A novel form of solid phosphorus material defined by said tubular array wherein all of the axes are generally parallel to one another. 3. The formula MP _x , wherein M is one or more alkali metals and P is predominantly phosphorus, but may include one or more other pnictides, And x is greater than 15), a stable solid material. 4. A high phosphorus material formed as a deposition product of vapor transfer from a vaporized source of phosphorus vapor and vapors of one or more metals. 5. A high phosphorus polyphosphide film material formed by chemical vapor deposition. 6. A high phosphorus polyphosphide film material formed by flash evaporation. 7. A semiconductor device formed from a material of atoms, wherein substantially all of the atoms of the species throughout have a covalent bond consisting of three similar atoms. 8. A semiconductor device substantially formed from the material of claim 2. 9. Substantially all of the covalent bonds in the material are contained in the cartonation of the atoms, and the covalent bonds provide the major conduction paths in the material, the material being substantially 1. The semiconductor device according to claim 7, which has a bandgap within a range of 0.4 to 2.2 eV. 10. Substantially all of the covalent bonds in the material are contained in the cartonation of the atoms, and the covalent bonds provide the predominant conduction path in the material, the material being substantially 100. The semiconductor device according to claim 7, having a photoconductivity ratio in the range of ˜10,000. 11. A method of chemical vapor deposition of high phosphorus polyphosphide material comprising flowing separate vaporized vapor streams of phosphorus and alkali metal over a condensing support. 12. A flash evaporation method comprising flowing material through a heated susceptor to evaporate it. 13. A material made by ball milling together one or more alkali metals and one or more pnictides. 14. The vapor transfer produces two heated and separated sources of phosphorus and one or more metals, and a separated deposition zone having a substantially constant temperature over an extended zone. Provided and formula MP
5. The high phosphorus material of claim 4 of the formula _{x wherein} M is one or more metals and P is predominantly phosphorus, but can contain one or more pnictides. .. 15. A method of forming substantially pure phosphorus by depositing phosphorus by vapor transfer onto a support of metal polyphosphite. 16. A second controlled temperature zone for heating one or more metals and phosphorus in a controlled temperature zone and having a substantially constant temperature over an extended area thereby. A method for producing a metal polyphosphide material, which comprises depositing metal phosphide from supplied steam. 17. The formula MP _x , wherein M and P consist of heating together and then cooling them to room temperature.
Is one or more metals and P is phosphorus). 18. A) containing a phosphorus-to-phosphorus bond and containing an alkali metal atom bound to said phosphorus atom, wherein the number of consecutive covalent phosphorus-to-phosphorus bonds is non-conducting in order to render the material semiconducting. Providing a material comprising polyphosphide as at least one component thereof, which is sufficiently greater than the number of phosphorus-to-phosphorus bonds, and b) means for electrically contacting said material for use as a semiconductor. A method of forming a semiconductor device, the method comprising the steps of: 19. A) consisting of at least two polyphosphide units, at least as one component thereof, each unit having a skeleton of at least 7 covalently bonded phosphorus atoms, said units comprising at least one alkali metal Associated with an atom, the alkali metal atom conductively bridges the phosphorus skeleton of one unit with the phosphorus skeleton of another unit, and the material has a band gap predominantly determined by the phosphorus-phosphorus bond Forming a material, and b) attaching to the material a means for electrically connecting the material to the material for use as a semiconductor. 20. A) a polyphosphide of the formula MP _x , wherein M is an alkali metal and x is the atomic ratio of P to M, and x is at least 7; Preparing a material containing as a component and having a bandgap of energy in the range of 1-3 eV,
And b) a method of forming a semiconductor device comprising the step of attaching to the material a means for electrically communicating with the material for using the material as a semiconductor. 21. The material of claims 1-11, 13, 14, 16, 17, and 1 wherein the material comprises a single alkali metal.
The invention according to any one of 8 to 20. 22. The method of claim 1, wherein the material comprises at least two different alkali metals.
The invention according to any one of 16, 17, and 18 to 20. 23. In the material, at least 7 phosphorus atoms are bound to another phosphorus atom for each metal atom in the material.
The invention according to any one of 4, 16, 17 and 18-22. 24. The invention of claim 23, wherein 15 phosphorus atoms are attached to each other phosphorus atom for each metal atom in the material. 25. The invention of claim 24, wherein there are at least 500 phosphorus atoms for each metal atom in the material. 26. The material is of the formula [MP ₇ ] _a [P ₈ ] _b
(In the formula, b: a is the atomic ratio of [P ₈ ] to [MP ₇ ])
23. The invention of claim 22 defined by: 27. The polyphosphide has the formula MP _x , and x is substantially equal to 15.
The invention according to any one of 0, 13, 14, 16, 17 and 18 to 26. 28. The polyphosphide has the formula MP _x , and x is greater than 14;
The invention according to any one of 3, 14, 16, 17 and 18 to 26. 29. The invention according to any one of claims 1-10, 13, 14, 16, 17 and 18-26, wherein x is in the range of 7-15. 30. The method according to claim 1, wherein the metal is Li.
The invention according to any one of 0, 13, 14, 16, 17 and 18 to 29. 31. The method according to claim 1, wherein the metal is Na.
The invention according to any one of 0, 13, 14, 16, 17 and 18 to 29. 32. The method of claim 1, wherein the metal is K.
The invention according to any one of 0, 13, 14, 16, 17 and 18 to 29. 33. The method according to claim 1, wherein the metal is Rb.
The invention according to any one of 0, 13, 14, 16, 17 and 18 to 29. 34. The method according to claim 1, wherein the metal is Cs.
The invention according to any one of 0, 13, 14, 16, 17 and 18 to 29. 35. The method of claim 2, 7-1, wherein at least six-sevenths of said atoms have exclusively three similar atom bonds.
The invention according to any one of 0 and 18 to 20. 36. The invention of claim 35, wherein at least 14/15 of said atoms have a bond of 3 similar atoms. 37. The ratio of atoms of said species having bonds of like atoms is much greater than 14/15.
The invention described. 38. The material of claim 2, 11, 1 characterized by a tubular strut structure in its local order.
The invention according to any one of 3, 14, 16, 17 and 18 to 26. 39. The invention of claim 38, wherein the tubular structures in the local sequence are all substantially parallel. 40. The invention according to claim 38 or 39, wherein the atoms of the main component of the material are trivalent. 41. The strut structure, when viewed from one end,
41. The invention according to any of claims 38-40, which is channel-like. 42. The strut structure, when viewed from one end,
42. The invention according to any of claims 38-41, which is a pentagon. 43. The invention of any of claims 40-42, wherein the atom is one or more pnictides. 44. The invention according to any of claims 38-43, wherein the atom is primarily phosphorus. 45. The semiconductor device of any of claims 7-10, wherein the atomic bonds are spaced at an angle greater than 98 ° on average. 46. The semiconductor device according to claim 45, wherein the angle is in the range of 87 ° to 109 °. 47. 1 other than the atoms of the cartonation
11. The semiconductor device of claim 9 or 10, wherein additional atoms of species or more different elements are bound between two or more of the cartonations. 48. The additional atom forms a conduction path between the cartonations to which they are attached.
7. The semiconductor device according to 7. 49. The semiconductor device according to claim 47, wherein the cartonations at each local degree of regularity are substantially parallel to each other. 50. The method of claim 1, wherein the material is formed as a product deposited by vapor transfer from a separate source of phosphorus and alkali metal in a deposition zone.
The invention according to any one of 14, 16 to 20 and 37 to 49. 51. The invention of any of claims 7-10, 18-20, 35-37 and 43-49, wherein substantially the major portion of said atoms is phosphorus. 52. The atomic ratio of phosphorus to metal is substantially 50 or more, as defined in claim 3, 4, 5, 11, 14, 16, 1.
The invention according to any one of 7, 18 to 21, 26, 30 to 34, 50 and 51. 53. The invention according to claim 52, wherein the atomic ratio is substantially 200 or more. 54. The invention according to claim 53, wherein the atomic ratio is substantially 1,000 or more. 55. The invention according to claim 54, wherein the amount of the metal is 1,000 ppm or less. 56. The material of claims 1-11, wherein the material has a bandgap substantially in the range of 1-3 eV.
14, 16, 17, 18-25, 35-37 and 45
The invention according to any one of to 49. 57. The invention of claim 56, wherein the material has a bandgap of substantially 1.4 to 2.2 eV. 58. The invention of claim 57, wherein the material has a bandgap of substantially 1.8 eV. 59. The material of claim 1, wherein the material has a photoconductivity ratio in the range of 100 to 10,000.
The invention according to any one of 6, 17, 18 to 25, 35 to 37, 45 to 49 and 56 to 58. 60. The material of any of claims 1-11, 14, 16, 17, and 18-5 is formed of a single crystal.
9. The invention according to any one of 9. 61. The material of claim 1, wherein the material is polycrystalline.
The invention according to any one of to 11, 14, 16 to 59. 62. The material of claim 1, wherein the material is amorphous.
The invention according to any one of to 11, 14, 16 to 59. 63. The material is in the form of a thin film,
The invention according to any one of claims 1 to 11, 14, 16, 18 to 59, 61 and 62. 64. The invention of claim 63, wherein the thin film is deposited on a glass support. 65. The invention of claim 63, wherein the thin film is deposited on a metal support. 66. The semiconductor device of any of claims 7-10 and 45-49, further defined as including a junction. 67. The joint comprises Cu, Al, Mg, Ni,
67. The semiconductor device according to claim 66, comprising a metal selected from the group consisting of Au, Ag and Ti. 68. The joint metal is Ni.
The semiconductor device described. 69. The semiconductor device according to claim 7, wherein said material is doped with atoms of another pnictide. 70. The semiconductor device according to claim 69, wherein the pnictide is As. 71. The material of claims 7-10, 45-49, wherein the material is doped by diffusing therein a metal having an occupied external f or d electron level.
67. The semiconductor device according to any one of 66 and 66. 72. The semiconductor device according to claim 71, wherein the doping agent is selected from the group consisting of nickel, iron and chromium. 73. A metal contact portion is included, and the contact portion is C
7. A composition selected from the group consisting of u, Al, Mg, Ni, Au, As and Ti, 7 to 10, 45 to 49 and 6.
The semiconductor device according to any one of 6 to 72. 74. The invention according to any one of claims 1 to 10, 11, 13, 14, 16 and 17, wherein the metal is an alkali metal. 75. The invention of claim 74, wherein at least 7 phosphorus atoms are attached to every other phosphorus atom for each metal atom in the material. 76. The invention of claim 75, wherein at least 15 phosphorus atoms are attached to each other phosphorus atom for each metal atom in the material. 77. The invention of claim 76, wherein the ratio of phosphorus atoms to metal atoms in the material is at least 500: 1. 78. The metal is Li, Na or K,
Claims 35 to 37, 45 to 49, 56 to 59, 66 to 7
The invention according to any of 3 and 74 to 77. 79. The alloy of claim 35, wherein the metal is Rb.
37, 45-49, 56-59, 66-73 and 74
77. The invention according to any of 77. 80. The method of claim 35, wherein the metal is Cs.
37, 45-49, 56-59, 66-73 and 74
77. The invention according to any of 77. 81. The material is LiP _x , NaP _x or K.
4. P _x , and x is at least 7.
The invention according to any one of 5 to 37, 45 to 49, 56 to 59, 66 to 73 and 74 to 77. 82. The material is RbP _x , and x
Is at least 7, 35-37, 45-4
The invention according to any one of 9,56 to 59, 66 to 73 and 74 to 77. 83. The material is CsP _x , and x
Is at least 7, 35-37, 45-4
The invention according to any one of 9,56 to 59, 66 to 73 and 74 to 77. 84. The material of claims 56-5, wherein the material has a bandgap substantially in the range of 1-3 eV.
The invention according to any one of 9, 66 to 73 and 74 to 83. 85. The material of claim 8, wherein the material has a bandgap substantially in the range of 1.4 to 2.2 eV.
Invention of 4. 86. The invention of claim 85, wherein the material has a bandgap of substantially 1.8 eV. 87. The material of any of claims 56-59, 66-7, wherein the material has a photoconductivity ratio in the range of 100-10,000.
The invention according to any of 3 and 74-83. 88. The flowable material comprises phosphorus.
The method described in 2. 89. The flowable material comprises an alkali metal,
89. The method of claim 12 or 88. 90. A material produced by the method of claim 88 or 89. 91. The material of claim 90 in the form of a thin film. 92. is further defined as being polycrystalline,
The material according to claim 91. 93. Further defined as being amorphous.
The material according to claim 91. 94. A crystalline MP _x, wherein M is an alkali metal, or one or more other metals similar to an alkali metal bond, P is phosphorus, and x is 7 or more. A) for strengthening composite materials. 95. The reinforcing material according to claim 94, wherein M is an alkali metal. 96. The method according to claim 14 or 95, wherein x is 15.
Reinforcement material as described. 97. The material of any of claims 94-96, wherein the material is embedded in glass. 98. A material according to any of claims 94-96, wherein said material is embedded in a plastic material.