JPH10319450A - Light control element, organic thin film element and method of manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both of high third-order nonlinear susceptibility and fast response rate by producing an electric field of an intensity lower than the intensity required to cause the phase transition of a light-controlling layer in an light- controlling element. SOLUTION: A first electrode layer 2, first insulating layer 3, light-controlling layer 4, second insulating layer 5, second electrode layer 6 are successively formed on one principal face of a substrate 1. The electrode layers 2, 6, insulating layers 3, 5 and light-controlling layer 4 are formed in such a manner that the principal plane of each layer is parallel to each other. The element is equipped with a means to apply an external electric field of an intensity lower than the intensity necessary to cause the phase transition of the light-controlling layer 4. Relating to this light-controlling element, charge transfer excitons are induced by applying an external electric field of an intensity lower than the intensity necessary to cause the phase transition of the light-controlling layer 4. By introducing the signal light into the light-controlling layer 4 held between the insulating layer pair and by irradiating the light-controlling layer 4 with controlling light, the output light can be controlled.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an optical control device, and more particularly to an all-optical control device capable of controlling the output of an optical signal using light.

[0002] The present invention also relates to an organic thin-film element having functions of controlling electric or optical signals, storing and transmitting information, and the like.

[0003]

2. Description of the Related Art In the near-term advanced information society, for example, it is required to transmit and process ultra-large capacity information exceeding terabits per second at high speed, high accuracy, and high efficiency. At present, it is considered that such a very large amount of information is transmitted and processed in the trunk backbone system. However, in the 21st century, the amount of information has been further increased, and even in the subscriber system. It is fully expected that transmission and processing of such a very large amount of information will be performed.

[0004] However, the processing speed of currently widely used electronic systems is limited to 50 gigabits per second, so that it is not possible to cope with the above-mentioned transmission and processing of very large amounts of information. Therefore, in the future,
It is anticipated that the importance of optical systems far exceeding electronic systems will increase in information transmission and processing capabilities.

In an optical system, an optical control element for realizing ultra-high-speed modulation / demodulation, that is, an all-optical (all-optical) optical device for controlling an optical signal using light.
Light control elements are important. This light-light control element has no band limitation due to the CR product of a circuit such as an electronic circuit, and is capable of ultra-high speed modulation / demodulation control. Further, the light-light control element has an advantage that output light can be used as it is as control light or signal light in the next step.

Therefore, when an optical system is constructed using an optical-optical control element as an optical gate element, an optical logic element, an optical bistable element, an optical pulse control element, etc., the signal processing speed due to the use of an electronic circuit. From the decline of
It is possible to transmit and process information at ultra-high speed,
Further, an optical computer can be realized.

[0007] In controlling an optical signal using such light, the nonlinear optical effect plays an important role.
A change in a refractive index or a change in an absorption coefficient depending on light intensity, which is called a next-order nonlinear optical effect, has attracted attention as a basic principle for performing light-light control.

In the third-order nonlinear optical effect, the relationship between the light intensity I and the refractive index n and the relationship between the light intensity I and the absorption coefficient α are represented by a linear refractive index, a nonlinear refractive index, a linear absorption coefficient, and a nonlinear absorption coefficient. Are n ₀ , n ₂ , α ₀ , and α ₂ , respectively, as shown in the following equations.

N = n ₀ + n ₂ · I α = α ₀ + α ₂ · I As is clear from these equations, in order to obtain a large change in the optical characteristics with low intensity light, it is necessary to use n ₂ or α _{2 Two}
Requires high nonlinearity. It is 3 that controls these
The second-order nonlinear susceptibility χ ⁽³⁾ .

Research on materials exhibiting such a third-order nonlinear optical effect has been conducted on the following three material systems: a semiconductor ultrafine particle system, a semiconductor superlattice system, and an organic π-electron material system.

When a direct transition type semiconductor is used as a material of the semiconductor superlattice system, it is expected that a large nonlinear optical response can be obtained due to a band filling effect. When GaAs / AlAs is used as the direct transition semiconductor, a third-order nonlinear susceptibility χ ⁽³⁾ as high as 5 × 10 ⁻² esu can be obtained with MQW.

However, in a semiconductor superlattice-based material, such an extremely large third-order nonlinear susceptibility χ
⁽³⁾ can be obtained, but the response speed is dominated by the recombination lifetime of the photoexcited carriers, so that the essential response speed is low (the lifetime of the excited carriers is on the order of nsec). Therefore, in order to increase the response speed, it has been studied to increase the surface recombination speed. However, there is a problem that an ultra-high-speed response equal to or lower than the psec level, in particular, the repetition response speed cannot be increased.

In the case of a semiconductor fine particle material, by setting the particle diameter to 10 nm or less, the surface recombination speed can be increased, and a high response speed of several tens ps can be obtained. However, as investigated for CdS _x Se _1-x doped glass and the like, the third-order nonlinear susceptibility χ ⁽³⁾
Is about 10 ⁻⁹ to 10 ⁻⁸ esu, and a high third-order nonlinear susceptibility χ ⁽³⁾ has not been obtained.

Further, in the organic π-electron material, since the nonlinear response is caused by pure electron polarization of π-electrons, a response speed as high as fsec is obtained.
However, regarding the third-order nonlinear susceptibility χ ⁽³⁾ , even the highest polydiacetylene-based paratoluenesulfonic acid ester derivative χ ⁽³⁾ = 8 × 10 ^-10 e
su and extremely small.

Regarding the light control element using this organic π-electron material, since the origin of the nonlinearity is pure electron polarization of π electrons, it is necessary to increase the third-order nonlinear susceptibility χ ^(3). Attempts have been made to extend the conjugation length of π electrons by using one-dimensional π-conjugated polymers such as polydiacetylene, trans-polyacetylene, and polyarylenevinylene, and cyclic π-conjugated compounds such as phthalocyanine. However, with this method, it is difficult to dramatically increase nonlinearity.

Further, the organic π-electron material has a very low third-order nonlinear susceptibility as described above. Therefore, in a light control element using an organic π-electron material, it is necessary to irradiate extremely high intensity light to induce a desired optical change. However, irradiation with such high-intensity light causes a problem that the material is damaged by light and heat, and a new thermal effect is generated.

Therefore, there is a demand for a light control element which simultaneously realizes a high third-order nonlinear susceptibility and a high response speed.

Further, in recent years, there has been an increasing interest in molecular electronics for realizing a device having a new function not available in conventional devices by utilizing physical properties inherent in organic molecules or organic crystals. Up to now, researches for applying to a second-order nonlinear optical element using an organic molecule, an electric switching element, an injection type light emitting element, a solar cell, an optical information recording medium and the like have been actively conducted.

All of these are intended to further improve the properties and manufacturing costs by using an organic material, the properties found in inorganic materials. On the other hand, as an example of a physical property phenomenon found only in an organic molecular system, a charge transfer phenomenon occurring in a certain kind of organic complex crystal has also attracted attention.

Among the organic materials, the ionization potential is small, electrons are supplied to other molecules, and the donor molecules themselves tend to be positive ions, and the electron affinity is large. There is an acceptor molecule that easily becomes a negative ion. It is well known that a compound called a charge transfer complex is formed between these two molecules. For example, a compound of perylene and tetracyanoquinodimethane (TCNQ) is a compound composed of neutral molecules. On the other hand, the compound of tetramethylphenylenediamine (TMPD) and TCNQ is an ionic compound in which the respective molecules are positive and negative. It is also known that a compound of tetrathiafulvalene (TTF) and chloranil (CA) exhibits a neutral-ionic transition due to a change in temperature or pressure (JB Tor).
lance et al. : Phys. Rev .. Let
t. , 46, 253 (1981)).

An important point in applying such a charge transfer phenomenon in an organic molecule as an operating principle of an electric element or an optical element is that charge transfer can be caused efficiently and efficiently by an electric field or light. That is. Recently, interesting results have been reported on the electrical properties of charge transfer complexes (Yoshinori Tokura et al .: Autumn 1988,
Proceedings of the Physical Society of Japan, 3a-S4-1, 3a-S4-2, 3
a-S4-3 and others; Tokura et al. : P
hysica 143B, 527 (1986)). Here, in an alternately stacked complex crystal in which a donor molecule and an acceptor molecule are stacked with their molecular surfaces facing each other, the anisotropy of the relative dielectric constant is high, and the relative dielectric constant in the stacking direction is 100 to 1000. Extremely high, 10 ³ to 10 ⁴ V
It has been reported that non-linear electric conduction and switching characteristics are observed under an electric field on the order of / cm. As a cause, it is considered that an ionic drain thermally or electrically generated in the neutral crystal or a neutral domain in the ionic crystal dynamically moves due to an electric field.

Although this phenomenon is related to the neutral-ionic transition, it is a very local change, and the entire crystal is not macroscopically changed. At present, a macroscopic neutral-ionic transition by an electric field or light has not been realized.

In order to cause a macroscopic neutral-ionic transition by an electric field in the charge transfer complex, the direction of the electric field in the device and the direction of the stacking axis of the donor molecule and the acceptor molecule must coincide. Very important. In order to realize a device utilizing the characteristics of organic molecules, not only the size such as the film thickness and the structural uniformity in the film, but also the molecular arrangement in the order of one molecule in the film and the neighboring molecules are required. It is very important to control the mutual arrangement and molecular orientation between them.

In recent years, Langmuir-Bl has been used as one method for producing an ultrathin film in which the molecular orientation and arrangement are controlled.
The oddt (LB) method is receiving attention. this is,
This is a method in which monomolecular films formed on the water surface are accumulated one by one on a substrate to produce the same or different superlattice films. However, in reality, there is a problem that the packing state and uniformity of the molecules in the film developed on the water surface are poor, and the monomolecular film structure is disturbed when the molecules are accumulated on the substrate. For this reason, it has not yet reached a level at which a superlattice thin film in which the molecular orientation between the entire film or the accumulated layers is controlled can be formed. In order to improve the film forming technique by the LB method, it is necessary to design a molecule suitable for the LB method and to establish a synthesis technique thereof.

On the other hand, as a technique which does not require a special molecular design and can be easily applied to most organic molecules, studies on a vacuum deposition method have been actively conducted. However, in the vacuum deposition method, since the molecular deposition source is once gasified and reagglomerated, the supply speed of gasified molecules, the balance of the speed of diffusion and crystallization of molecules attached to the substrate surface, the balance between the adsorbed molecules and the substrate surface. It is expected that the film structure and molecular orientation will be variously changed depending on the interaction with.

In the studies on conventional organic vapor deposition films, studies have been made on the growth process and molecular orientation of thin films on various substrates, mainly for long-chain hydrocarbon-based linear molecules and flat molecules such as phthalocyanine. As a substrate,
Single crystal alkali halide and single crystal metal for evaluation by electron microscope and electron beam diffraction; Quartz for optical evaluation; Si single crystal for electrical evaluation; Are mainly used. Regarding the deposition conditions, there are many examples in which the effects of the substrate temperature and the deposition rate were examined. Vincett et al. In the United States report that a uniform continuous film can be formed by setting the substrate temperature to 1/3 of the boiling point of the vapor deposition material in absolute temperature regardless of the type of the vapor deposition material and the substrate. However, it is extremely difficult to control the orientation of an organic thin film to be deposited on an arbitrary substrate only by appropriately adjusting the deposition conditions.

The following studies are known on the effect of a substrate on the molecular orientation of an organic thin film deposited thereon. (1) Karl of West Germany and others
It is reported that molecular planes of a few molecular layers of perylenetetracarboxylic dianhydride deposited on a single crystal surface are oriented parallel to the substrate surface. (2) Originally, in the study of phthalocyanine vapor-deposited films using molecular beam deposition, even under conditions where only a discontinuous film could be formed by ordinary high-vacuum vapor deposition, the deposition rate was about 0.1 nm / min under ultra-high vacuum. It is reported that by setting the conditions very slow, it is possible to form a uniform continuous film and a film whose molecular plane is oriented parallel to the substrate surface. In this study, a layered compound MoS ₂ is used as a substrate based on the concept of Van der Waals epitaxy in order to avoid lattice mismatch between the substrate and the deposited organic crystal. (3) Harada et al. Report that molecular planes of a few molecular layer pentacene vapor-deposited film formed on a graphite substrate are oriented parallel to the substrate surface.

As described above, although various studies have been made on the formation of a thin film by the vacuum evaporation method, it is not the situation that the controlling factors of the film structure and the molecular orientation are unified.

On the other hand, the present inventors have made intensive studies by focusing on the interaction between the substrate and the vapor deposition molecules. As a result, they have found that a uniform continuous film can be easily formed if the deposition conditions are optimized using a highly oriented graphite substrate. In addition, it was presumed that the orientation effect obtained on the highly oriented graphite substrate was based on the dispersion force between the substrate and the π-electron compound molecule.

Based on this, a method of forming a molecular orientation control layer by a thin film having a graphite-like skeleton on a substrate, and further focusing on the fact that the dispersion force depends on the electron polarizability of the substrate surface atoms, We tried to improve the method of specifying the polarizability of

However, it is actually difficult to control and form such a molecular orientation control layer on an arbitrary substrate, and this has been a major obstacle to the development of an organic thin film element using an oriented crystal thin film.

As described above, in order to optimize the characteristic function of the organic thin film, a thin film structure in which the molecular orientation with respect to the substrate surface is controlled or a thin film structure in which the crystal axis orientation in the thin film is controlled is formed. There is a need to.

However, in order to enable such molecular orientation control, a flat outermost surface at the molecular size level is prepared irrespective of the surface irregularities of the substrate body, and an outermost surface having high molecular orientation controllability is prepared. It is required to establish the technology to do it.

[0034]

SUMMARY OF THE INVENTION It is a first object of the present invention to provide a light control element which simultaneously realizes a high third-order nonlinear susceptibility and a high response speed.

A second object of the present invention is to provide a material and a material for a substrate main body.
It is an object of the present invention to provide an organic thin film element that can control the structure and molecular orientation of an organic thin film regardless of its shape and can be practically used as an optical element, an electronic element, and the like.

A third object of the present invention is to control the structure and molecular orientation of an organic thin film irrespective of the material and shape of a substrate main body, and to be used practically as an optical element or an electronic element. It is an object of the present invention to provide a method for producing an obtained organic thin film element.

[0037]

SUMMARY OF THE INVENTION The present invention comprises, first, a substrate; a first electrode layer formed on the substrate;
A first insulator layer formed on the first electrode layer; a light control layer including an electron donating organic compound and an electron accepting organic compound formed on the first insulator layer; A second insulator layer formed on the first layer, a second electrode layer formed on the second insulator layer, and the light control layer, wherein the light control layer undergoes a phase transition. Means for applying an external electric field of less than the required intensity, and providing a light control element that induces charge transfer excitons by application of an external electric field of less than the required intensity.

The present invention secondly comprises a support layer, a molecular orientation control layer composed of an amorphous organic film provided on the support layer, and a π-electron molecule provided on the molecular orientation control layer. A crystalline organic thin film formed by a vacuum deposition method at a growth rate of 100 Å / min or less and having a thickness of 1
Provided is an organic thin film element having a molecular layer of not less than 2000 Å.

Thirdly, the present invention provides a semiconductor substrate having a source,
An insulating film, a molecular orientation control film made of an amorphous organic thin film, a gate electrode and a π
It has a laminated structure including a crystalline organic thin film composed of electronic molecules. The crystalline organic thin film is formed at a growth rate of 100 Å / min or less by a vacuum deposition method, and has a thickness of at least one molecular layer and 2,000. Provided is an organic thin-film element having a thickness of Å or less.

Fourth, the present invention provides a molecular orientation control layer composed of an amorphous organic film formed on the surface of a support layer.
Provided is a method for manufacturing an organic thin film element, which comprises forming a crystalline organic thin film having a thickness of at least one molecular layer and not more than 2000 Å at a growth rate of 0 Å / min or less.

[0041]

DESCRIPTION OF THE PREFERRED EMBODIMENTS First, a light control element of the present invention will be described.

The light control element of the present invention basically includes a substrate, a first electrode layer formed on the substrate, a first insulator layer formed on the first electrode layer, A light controlling layer including an electron donating organic compound and an electron accepting organic compound formed on the first insulating layer, a second insulating layer formed on the light controlling layer, and a second insulating layer A second electrode layer formed on the layer; and a means for applying, to the light control layer, an external electric field less than the intensity required for the light control layer to undergo phase transition. In this light control element, a charge transfer exciton is induced by applying an external electric field less than the intensity required for the light control layer to undergo a phase transition.

The intensity of the external electric field is preferably less than the intensity required for the light control layer to undergo a phase transition and is in the range of 1/10 ⁴ or more of the intensity.

Signal light can be incident on the light control layer.

The signal light can be controlled by applying an external electric field less than the intensity required for the light control layer to undergo phase transition. Preferably, the output intensity of the signal light is controlled by control light irradiation means. Control light is applied to the light control layer.

The light control layer contains an electron-donating organic compound and an electron-accepting organic compound, and is preferably an alternately laminated charge transfer complex in which an electron-donating organic compound and an electron-accepting organic compound are alternately laminated. Consists essentially of crystals. When the layered charge-transfer complex crystal is used, a neutral-ionic phase transition occurs when a predetermined electric field is applied.

It is preferable that at least one of the first and second insulator layers has optical transparency. When any one of the insulator layers has a light-transmitting property, signal light can be transmitted through the insulator layer and incident on the light control layer.

The signal light can be incident on the light control layer from a direction parallel to the main surface of the substrate.

In the light control element of the present invention, at least one of between the first insulator layer and the light control element and between the second insulator layer and the light control element has a molecular orientation control. Layers can be provided. By using the molecular orientation control layer, it is possible to take advantage of the characteristics of an organic thin film having high crystallinity, and to obtain an organic thin film element utilizing anisotropy of physical properties in a crystal axis direction.

The molecular orientation control layer is preferably composed of an amorphous organic film, more preferably an organic film having molecules having a steroid skeleton.

Further, the molecular orientation control layer has a structure in which different kinds of amorphous organic films are laminated, and preferably contains at least one amorphous organic film having molecules having a steroid skeleton.

Hereinafter, the light control element of the present invention will be described with reference to the drawings.

FIG. 1 is a cross-sectional view of a light control element according to one embodiment of the present invention.

In this figure, reference numeral 1 denotes a substrate, and a first electrode layer 2 and a first electrode layer 2 are formed on one main surface of the substrate 1.
The insulator layer 3, the light control layer 4, the second insulator layer 5, and the second electrode layer 6 are sequentially laminated. The main surfaces of the electrode layers 2 and 6, the insulator layers 3 and 5, and the light control layer 4 are arranged so as to be parallel.

Examples of the substrate used in the light control element of the present invention include a transparent substrate made of a transparent dielectric such as glass, quartz, and oxide. Also,
A substrate having no light transmittance, such as a semiconductor such as Si or a metal such as Al, can also be used. These substrates are selected according to the driving method of the light control element.

The first and second electrode layers used in the light control element of the present invention are transparent electrodes such as ITO, ZnO and SnO ₂ and electrodes made of metals such as Al, Au, Ag and Pt. is there. Alternatively, a conductive polymer film such as polypyrrole, polyaniline, or polythiophene can be used. These electrodes are selected according to the driving method of the light control element, and both the first and second electrode layers can be formed of a transparent electrode or an electrode made of a metal, one of which is a transparent electrode and the other of which is a metal. It is also possible to use an electrode composed of Although an electrode plate made of metal can be used as the above-mentioned substrate, it is usually formed on an insulating substrate as a thin film having a thickness of 20 Å to 2000 Å.

The first and second electrode layers used in the light control element of the present invention may have their respective opposing surfaces having light reflectivity. These electrode layers have their main surfaces arranged in parallel so as to be mirrors of a Fabry-Perot resonator.

The first and second insulator layers used in the light control element of the present invention are made of insulating organic compounds such as succinonitrile, polymethyl methacrylate (PMMA), polyimide, polystyrene, and polysilane; SrTi
It is preferable to be formed of an insulator such as a metal oxide such as O ₃ and SiO ₂ and an organic film having a steroid skeleton.

The insulator layer preferably has a function as a molecular orientation control layer. This molecular orientation control layer is used for controlling the molecular orientation of the light control layer.

The insulator layer is preferably made of a material having a high dielectric constant so that a voltage can be effectively applied to the light control layer. Examples of such an insulator include a ferroelectric substance, and it is preferable to use a material having a relative dielectric constant of 10 or more, such as SrTiO ₃ or PbTiO ₃ .

In the light control element of the present invention, the signal light is introduced into the light control layer sandwiched between the pair of insulator layers, and the light control layer is irradiated with the control light to control the output light. Is performed. Here, the signal light is light whose output is controlled by the element of the present invention.
nm to 2000 nm, intensity 0.01 MW / cm ² -1
00 MW / cm ² . Further, the control light is light for controlling the optical properties of the light control layer.
0 nm to 2000 nm, intensity 0.01 MW / cm ² to
It is 1 GW / cm ² . These signal light and control light are
The light control layer may be separately irradiated, or signal light may be used as control light.

When signal light is introduced and outputted to the light control layer in a direction parallel to the main surface of the substrate without passing through the insulator layer, the insulator layer does not need to have optical transparency. However, when signal light is transmitted through the insulator layer and introduced into the light control layer, or when output light is transmitted through the insulator layer and output from the light control layer, the insulator layer has light transmittance. There is a need. The light transmittance of such an insulator layer is usually controlled so that the reflectance is 50% or less.

As the light control layer of the light control element of the present invention,
An alternately stacked charge transfer complex crystal in which an electron donating organic compound as a donor molecule and an electron accepting organic compound as an acceptor molecule are alternately stacked can be used.

The abbreviations, compound names and chemical formulas of donor molecules and acceptor molecules used in the light control element layer according to the present invention are shown below.

Donor molecule aniline [D-1] N-methylaniline [D-2] N, N-dimethylaniline [D-3] PD: p-phenylenediamine [D-4] ClPD: 2-chloro-p- Phenylenediamine [D-
5] ClMePD: 2-chloro-5-methyl-p-phenylenediamine [D-6] DCLPD: 2,5-dichloro-p-phenylenediamine [D-7] DMePD: 2,5-dimethyl-p-phenylenediamine [D-8] DAD: diaminodulene [D-9] TMPD: N, N, N ′, N′-tetramethyl-PD
[D-10] N, N-DMePD: N, N-dimethyl-PD [D-1
1] 1,5-dimethylnaphthalene [D-12] 1,8-dimethylnaphthalene [D-13] benzidine [D-14] TMB: 3,3 ′, 5,5′-tetramethylbenzidine [D-15] NNN'N'-TMB: N, N, N ', N'-tetramethyl-benzidine [D-16] DAP: 1,6-diaminopyrene [D-17] TMDAP: N, N, N', N ' -Tetramethyl-DA
P [D-18] phenazine [D-19] M ₂ P: 5,10-dimethyl-5,10-dihydrophenazine [D-20] E ₂ P: 5,10-diethyl-5,10-dihydrophenazine [ _{D-21] Pr 2 P:} 5,10- dipropyl-5,10-dihydro-phenazine [D-22] HMP: 5- methyl-5,10-dihydrophenazine _{[D-23] M 6 P} : 5,10- Dihydro-2,3,5,7,8,1
0-hexamethylphenazine [D-24] PTZ: phenothiazine [D-25] N-MePTZ: N-methylphenothiazine [D-2]
6] ClPTZ: 2-chlorophenothiazine [D-27] TDAE: tetrakis (dimethylamino) ethylene ferrocene [D-28] dimethylferrocene [D-29] decamethylferrocene [D-30] nickelocene decamethylnickelocene cobaltene TTF : Tetrathiafulvalene [D-31] DMTTF: 2,6-dimethyltetrathiafulvalene [D-32] TMTTF: tetramethyltetrathiafulvalene [D-31]
33] DPhTTF: 2,6-diphenyltetrathiafulvalene [D-34] DPhDMTTF: 2,6-diphenyl-3,7-dimethyltetrathiafulvalene [D-35] DBTTF: dibenzotetrathiafulvalene [D-3]
6] OMTTF: octamethylenetetrathiafulvalene [D
-37] HMTTF: hexamethylenetetrathiafulvalene [D
-38] TTC ₁ TTF [D-39] TTeC ₁ TTF [D-40] TSF: Tetraselenafulvalene [D-41] TMTSF: Tetramethyltetraselenafulvalene [D
-42] HMTSF; hexamethylenetetraselenafulvalene [D-43] HMTTeF: hexamethylenetetratellurafulvalene [D-44] TTT: tetrathiatetracene [D-45] TST: tetraselenatetracene [D-46] BTP : Tetraphenylbithiopyralidene [D-47] naphthalene anthracene phenanthrene pentacene pyrene penylene azulene acenaphthene carbazole acridine (acceptor molecule) BQ: p-benzoquinone [A-1] R ¹ R ² R ³ R ⁴ BQ (R ^{1 to} R ⁴ = H, Me, Cl,
Br, I, F, CN) [A-2] R 1 BQ: (R 1 = Me, Cl, Br) [A-3] MeBQ ClBQ BrBQ R 1 R 2 BQ: 2-R 1 -5-R 2 −BQ (R ¹ , R ²
= Me, Cl, Br) [A-4] Me ₂ BQ Cl ₂ BQ ClMeBQ Br ₂ BQ BrMeBQ 2-R ¹ -6 -R ² -BQ (R ¹ , R ² = Me, Cl,
Br) [A-5] 2,6-Cl ₂ BQ 2,6-Br ₂ BQ 2,6-Me ₂ BQ Cl ₃ BQ: 2,3,5-trichloro-p-benzoquinone [A-6] CA: Chloranyl [A-7] BA: Blomanyl [A-8] IA: Iodanyl [A-9] FA: Fluoranyl [A-10] DDQ: 2,3-dicyano-5,6-dichloro-p-benzoquinone [A- 11] Me ₄ BQ: tetramethyl-p-benzoquinone [A-1
2] o-BQ: o-benzoquinone [A-13] o-CA: o-chloranyl [A-14] o-BA: o-bromanyl [A-15] NQ: naphthoquinone [A-16] R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ NQ [A-17] R ¹ R ² NQ: 2-R ¹ -3-R ² -NQ (R ¹ , R ²
= Cl, CN) [A- 18] Cl 2 NQ: 2,3- dichloro naphthoquinone (CN) ₂ NQ: 2,3- dicyano naphthoquinone-AQ: 9,10-anthraquinone ^{[A-19] R 1 R} 2 R 3 R ⁴ R ⁵ R ⁶ AQ [A-20] TCNQ: Tetracyanoquinodimethane [A-21] R ¹ R ² R ³ R ⁴ TCNQ [A-22] R ¹ TCNQ: 2-R ¹ -TCNQ (R ¹ = Me, OM
e, F, Cl, Br) [A-23] MeTCNQ (OMe) TCNQ FTCNQ ClTCNQ BrTCNQ R 1 R 2 TCNQ: 2-R 1 -5-R 2 -TCNQ (R
¹ , R ² = Me, Et, Pr, OMe, F, Cl, B
r, I) [A-24 ] Me 2 TCNQ Et 2 TCNQ Pr 2 TCNQ (OMe) 2 TCNQ F 2 TCNQ Cl 2 TCNQ Br 2 TCNQ I 2 TCNQ ClMeTCNQ BrMeTCNQ IMeTCNQ F 4 TCNQ [A-25] TCNNQ: tetracyano - 1,4-naphthoquinodimethane [A-26] R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ TCNNQ [A-27] TCNAQ: tetracyano-9,10-anthraquinodimethane [A-28] R ¹ R ² R ³ R ⁴ R ⁵ TCNAQ [A-29] TNAP: tetracyano-2,6-naphthoquinodimethane [A-30] F ₆ TNAP [A-31] TCNDQ [A-32] F ₈ TCNDQ [A -33] DCNQI: dicyanoquinone diimine ^{[A-34] R 1 R} 2 R 3 R 4 DCNQI [A-35] R 1 DC QI: 2-R ¹ - dicyanoquinone diimine ^{(R 1 = Me, Cl,} Br) [A-36] MeDCNQ
I: 2-methyldicyanoquinonediimine ClDCNQI: 2-chlorodicyanoquinonediimine BrDCNQI: 2-bromodicyanoquinonediimine R ¹ R ² DCNQI: 2-R ¹ -5-R ² -DCNQI
(R ¹ , R ² = Me, Cl, Br) [A-37] DMeDCNQI: 2,5-dimethyldicyanoquinonediimine ClMeDCNQI: 2-chloro-5-methyldicyanoquinonediimine DCDDCNQI: 2,5-dichlorodicyano Quinone diimine BrMeDCNQI: 2-bromo-5-methyldicyanoquinone diimine Br ₂ DCNQI: 2-dibromodicyanoquinone diimine Cl ₄ DCNQI: 2,3,5,6-tetrachlorodicyanoquinone diimine F ₄ DCNQI: 2 , 3,5,6-tetrafluorodicyanoquinonediimine DCNNQI: dicyano-1,4-naphthoquinonediimine [A-38] R ¹ R ² R ³ R ⁴ R ⁵ R ⁶ DCNNQI [A-39] DCNAQI: dicyano -1,4-Naphthoquinone diimine [A-40] R ¹ R ² R ³ R ⁴ R ⁵ DCNAQI [A-41] TNB: 1,3,5-trinitrobenzene [A-42] TNF: 2,4,7-trinitro-9-fluorenone [A-43] DTF: 2,4,7 -Trinitro-9-fluorenylidenemalononitrile [A-44] TENF: 2,4,5,7-tetranitro-9-fluorenone [A-45] DTENF: 2,4,5,7-tetranitro-9-fur Olenylidenemalononitrile [A-46] TCNE: Tetracyanoethylene [A-47] HCBD: Hexacyanobutadiene [A-48] HCNB: Hexacyanobenzene [A-49] TCNB: Tetracyanobenzene [A-50] DCNB: Dicyano Benzene [A-51] PMDA: pyromellitic dianhydride [A-52]

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[0066]

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[0067]

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[0068]

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[0069]

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[0070]

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[0071]

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[0073]

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[0074]

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[0075]

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The following table shows examples of combinations of these donor molecules and acceptor molecules.

[0079]

[Table 1]

[0080]

[Table 2]

[0081]

[Table 3]

[0082]

[Table 4]

[0083]

[Table 5]

[0084]

[Table 6]

[0085]

[Table 7]

[0086]

[Table 8]

[0087]

[Table 9]

[0088]

[Table 10]

[0089]

[Table 11]

Crystals composed of a combination of the donor molecule and the acceptor molecule exemplified in the above table can be used in a neutral charge transfer complex having a small charge transfer amount and an ionic charge having a large charge transfer amount when no external field is applied. Contains charge transfer complexes. In general, the charge transfer state of the layered charge transfer complex is determined by the ionization energy of the constituent molecules and the Madelung energy of the ionic crystal.

The present inventors have found that the ionization energy can be controlled by mixing crystals having different charge transfer states to form a mixed crystal.
No. 7666, by making the crystal ultra-thin and changing the number of molecules that contribute to Madelung energy,
It discloses that Madelung energy can be controlled.

Therefore, even if the crystal composed of a combination of the donor molecule and the acceptor molecule exemplified in the above table forms an ionic charge transfer complex when no external field is applied, the light control element of the present invention can be used. It can be used for

The thickness of the light control layer formed as described above varies depending on the material forming the device.
10 angstrom to 1 μm. In addition, a set of donor molecules and acceptor molecules is usually stacked in the thickness direction of the light control layer in the order of several to several thousand.

The light control element of the present invention described above usually has a first electrode layer, a first insulator layer, a light control layer, a second insulator layer, and a second electrode layer formed on a substrate. It is formed by sequentially laminating in order. The electrode layer and the insulator layer can be formed by a method such as a vacuum evaporation method, a sputtering method, a plasma polymerization method, a CVD method, and a spin coating method.
The light control layer can be formed by a method such as a vacuum evaporation method, a solution deposition method, and an LB method.

Hereinafter, the driving principle of the light control element of the present invention will be described.

Among organic compounds, a donor molecule (D) which has a small ionization potential, supplies electrons to other molecules and becomes a positive ion by itself, and has a high electron affinity and accepts electrons from other molecules There is an acceptor molecule (A) that becomes a negative ion by itself. These molecules are selected appropriately
In the mixed and stacked crystals, a compound called a charge transfer complex is formed that is stabilized by resonance between a state in which electrons move from the donor molecule to the acceptor molecule to form a bond (charge transfer state) and a non-bonded state. It is well known.

For example, in a crystal in which perylene and tetracyanoquinodimethane (TCNQ) are stacked, each molecule is in a state in which the ratio of non-bonded states is high, that is, a neutral state charge transfer complex. However, in a crystal in which tetramethylphenylenediamine (TMPD) and TCNQ are stacked, electrons are transferred from TMPD to TCNQ, and each molecule enters a resonance state in which the ratio of charge transfer states is high, that is, an ionic state. Therefore, an ionic charge transfer complex is formed.

It is known that, in a certain crystal, the above-described charge transfer state changes according to the applied amount of an external field. JB Torrance et al., Phys. Rev. Lett., 4
6, 253 (1981), a crystal in which tetrathiafulvalene (TTF) and chloranil (CA) are laminated is a phase transition between a neutral state and an ionic state (NI transition) due to changes in temperature and pressure. Is reported to occur.

It has been reported that such NI transition may be caused by an external field other than temperature and pressure. For example, Y. Tokura et al., Physica. 143B, 527
(1986) reports that the electric conductivity changes nonlinearly by applying an electric field of about 10 ³ to 10 ⁴ V / cm to the neutral complex. Also, S. Koshihara et al.
Phys. Rev. B 42, 6853 (1990) reports that ionic or neutral domains can be injected by intensely irradiating a neutral or ionic complex with light.

However, the above-mentioned state change due to application of an electric field or light irradiation is microscopic, and does not mean that the entire crystal is macroscopically changed. That is, these state changes are generated in a one-dimensionally arranged DA chain such as DADADADADA ^.
- DADA ... as in, locally D ⁺ A ^- only exciton like are formed.

In the case where a macroscopic change or a similar change over the entire crystal is caused by irradiating light and intensely exciting, that is, when causing photoinduced transition, it is necessary to irradiate very high intensity light. Therefore, when the output of incident light is simply controlled by light irradiation / non-irradiation as a light control element, by irradiating very strong light,
The problem of crystal degradation and other thermal effects occurs.

[0102] More recently, in microscopic state change by light irradiation described above, a plurality (n) pieces of D ⁺ A ^- charge transfer excitons like are aggregated, verified experimentally that the bound state is present Was done. For example, in an anthracene-pyromellitic acid dianhydride (PMDA) crystal, when two or three charge transfer excitons approach in a stacked chain of a donor molecule and an acceptor molecule, each charge transfer excitation having an electric dipole is caused. The bound state is enabled by the electrostatic interaction of the child.

Such an agglomerated state of excitons is called an “exciton n-string state” and significantly increases optical nonlinearity in response to light due to a giant oscillator effect. In addition, under the situation where such a giant oscillator effect appears, the life of excitons becomes extremely short,
There is a possibility that a very fast response speed can be obtained.

The state change of the crystal due to the application of the electric field described above is considered to be a state in which a large number of charge transfer excitons are aggregated, and the NI transition is caused by the charge transfer excitons, as shown in FIG. It is considered that the agglomeration density increases and the ground state is reversed between the neutral state and the ionic state.

Referring to FIG. 2, the N
The I transition will be described.

As shown in this figure, when the electric field strength E is 0, both the donor molecule D and the acceptor molecule A are in a neutral state. However, when the electric field strength E is increased, excitons D ⁺ A ^- are generated and aggregated, and an ionic state is locally formed. When the electric field strength E further increases, the ionic state D ⁺ A
^{When −} is more stabilized, that is, when the electric field strength E reaches the value E _c required for the phase transition, all the DAs become D ⁺
A ^- was changed to, it is the NI transition occurs.

FIG. 3 is a graph showing the relationship between the electric field intensity E and the third-order nonlinear susceptibility χ ⁽³⁾ in the NI transition. As shown in this graph, immediately before the electric field strength E reaches E _c, the maximum value of the third-order nonlinear susceptibility chi ⁽³⁾ is obtained.

Therefore, the light control layer is made of a crystal composed of donor molecules and acceptor molecules, and the light control layer is made of E _c
By constantly applying an electric field less than the intensity required to reach and controlling the optical properties of the light control layer by light irradiation, without causing deterioration of the crystal by irradiating strong light, It is possible to obtain a high third-order nonlinear susceptibility and a high response speed.

In this case, as the electric field strength E increases, 3
Since the non-linear susceptibility increases, the intensity of the control light can be reduced. The electric field strength E is expressed as E _c × 10 ⁻⁴ ≦ E <
It is preferably E _c, more preferably, 0.1E
_c ≦ E <E _c However, when the electric field strength E is E _c
When the value exceeds 3, a neutral-ionic transition occurs and the ionic ground state is established, so that the charge transfer exciton effect cannot be used.

FIG. 4 is a graph showing the relationship between the input light intensity and the output light intensity when a predetermined voltage is applied to the optical bistable light control element according to one embodiment of the present invention.

As shown in this graph, a light control element in which the refractive index and the absorption coefficient of the light control layer are in two stable states with respect to an input light of a certain intensity is called an optical bistable element. It is used as any optical modulation element such as an element, an optical pulse waveform shaping / limiter element, a differential amplifier element, an optical transistor, and a logic element.

The control of the signal light output in the light control element of the present invention is performed by applying a voltage to the light control layer and irradiating light as described above. The present inventors and S. Tanaka et al.
In ys. Rev. B52, 1549 (1995), it is necessary to apply a strong electric field of 10 ⁶ V / cm or more in order to bring a crystal in a state very close to the phase transition point to a state immediately before the NI transition occurs. Some things are revealed by simulation.

Therefore, the stacking direction of these molecules is controlled so that the direction of the electric field matches the stacking direction of the donor molecules and the acceptor molecules in the crystal, and a voltage is efficiently applied to these molecules. Is preferred. This can be achieved, for example, by providing a molecular orientation control layer for controlling the molecular orientation in the light control layer between the insulator layer provided on the substrate side and the light control layer.

As described above, the light control element of the present invention controls the optical characteristics of the light control layer by irradiating the control light with a predetermined voltage applied. Thereby, the optical characteristics of the light control layer can be controlled. In this case, it is possible to control the optical characteristics of the light control layer with a slight change in voltage.

FIG. 5 is a cross-sectional view of a light control element according to another embodiment of the present invention.

The light control element shown in FIG. 5 has substantially the same structure as the light control element shown in FIG. 1, except that a molecular orientation control layer 7 is provided between the insulator layer 3 and the light control layer 4. Is different. The molecular orientation control layer preferably has a flat surface at the molecular level in order to make the stacking direction of the donor molecules and the acceptor molecules in the light control layer uniform. In addition, in order to control the stacking direction of the molecules, it is preferable to form the molecular orientation control layer using a material that causes strong intermolecular interaction with the molecules. Examples of such a molecular orientation control layer include an organic amorphous film and a layered compound having a structure similar to graphite.

When such a molecular orientation control layer is provided, the lamination direction of the donor molecules and the acceptor molecules in the light control layer can be controlled in a direction perpendicular to the main surface of the substrate.
An electric field can be effectively applied to the crystal.

The characteristics of the molecular orientation control layer used in the present invention will be further described below.

The light control layer having an element function according to the present invention comprises:
It is characterized by having a crystal structure, and further targets ultrathin films from one molecular layer. Therefore, the most fundamentally required property is that the molecular orientation control layer itself has no structure and the surface is flat at the molecular size level.

For example, a π-electron-based molecule has a plate-like shape, and when a strong interaction is received from the substrate, as many of the atoms constituting the molecule as possible approach the substrate, that is, are oriented in parallel. This seeks to obtain high stabilizing energy. Therefore, most simply, in order to form a one-molecule two-dimensional crystal of parallel alignment molecules, it is essential that the surface of the base on which the organic thin film used as the light control layer is formed is flat at the molecular size level. You can see that. This situation is the same when the thickness of the organic thin film is increased. Therefore, in order to form a crystalline thin film with controlled molecular orientation on a substrate having an arbitrary surface structure, a molecular orientation control layer that realizes a flat surface structure at the molecular level is formed between the organic thin film and the substrate. Being provided is an effective means.

The organic amorphous film is known to have such a flat structure at least with respect to the surface structure from studies of organic EL devices and the like, and is easy to form on an arbitrary substrate. Is very effective for producing a practical device.

However, the molecular orientation control layer is not simply required to have a flat surface structure, but a surface-intermolecular interaction such that the molecular orientation can be controlled on the surface of the molecular orientation control layer. It is necessary to have characteristics.
That is, the molecular orientation control layer must have not only an amorphous structure but also a chemical element on the outermost surface in contact with the crystalline organic thin film, which can control the molecular orientation of the crystalline thin film. This is a unique point of view of the present invention, which is different from the conventional organic thin film laminating technique on an organic amorphous film.

As described above, when a plate-shaped thin film of parallel-aligned π-electron molecules is formed, as described above, a strong interaction occurs between the thin film forming molecules and the molecules forming the thin film.
It is necessary to control the outermost surface of the amorphous molecular orientation control layer. Conversely, when forming a thin film in which the plate-like molecules are oriented with respect to the substrate surface, the amorphous molecular orientation control layer is formed so that the intermolecular cohesion becomes larger than the substrate-molecule interaction. It becomes necessary to control the surface.

Means for strengthening the interaction are to increase the number of atoms (groups) having a high electron polarizability near the surface of the amorphous organic film so as to increase the induced dipole in order to increase the dispersion force. For example, a method in which an aromatic ring or a polycyclic aromatic group is arranged on the surface, or the surface has conductivity is effective.

Conversely, as a means for weakening the interaction, as many atoms (groups) having a low electron polarizability as possible are arranged near the surface of the amorphous organic film so that the induced dipole does not increase. Derived groups consisting of atoms with low electronic polarizability, such as methyl, carboxyl, ketone, alcohol, amino, and fluorine-containing groups, are introduced at the outermost contour of the amorphous molecule so that the polycyclic aromatic groups do not appear on the outermost surface. It is effective to do.

The amorphous organic film used in the present invention includes:
It may be either a low molecular weight or a high molecular weight. Materials used for the low molecular weight amorphous organic film include Alq3, OXD, OXD-S, and Diamin.
e, BNIBPC, TDAB, TPTTA, TDP, T
TPAE, TDATA, DPH, PPCP, and TCT
And amorphous organic molecules such as A.

The structural formula of the above-mentioned amorphous organic molecule is shown below.

[0128]

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[0129]

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[0130]

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[0131]

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[0132]

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[0133]

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[0134]

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[0135]

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[0137]

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[0140]

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[0141]

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[0142]

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[0143]

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[0144]

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As for the polymer amorphous organic film, there are many polymers having an irregular structure, ie, an atactic polymer or a copolymer polymer having an amorphous structure. Specifically, polystyrene,
Examples include polymethyl methacrylate and styrene butadiene synthetic rubber. Many of polymers having a branched structure or a crosslinked structure also show an amorphous structure, and examples thereof include vulcanized rubber and phenolic resin. Further, from the viewpoint of the polarizability of constituent atoms, Si-based polymers, that is, polysilane materials are more effective materials than C-based polymers, and the main chain of polysilane is oriented parallel to the substrate surface, and the main chain and the outermost surface It is important that the distance be as close as possible. From the viewpoint that induced polarization is easily generated between molecules constituting the crystalline thin film, it is also effective to use conductive polymers such as polypyrrole, polyaniline, and polythiophene having conductivity.

Further, when it is necessary to apply an electric field of a functional crystalline organic thin film layer in application to an electronic element, it is preferable that the organic amorphous film has surface flatness and insulating properties. In order to apply a strong electric field to the functional film at a voltage as low as possible, it is preferable that such an insulating film is as thin as possible. For this reason, it is preferable to form organic amorphous molecules having a constant molecular weight capable of forming an ultrathin film by an evaporation method or the like. As a molecule constituting the organic film having such characteristics, for example, a molecule having a steroid skeleton is given.

The amorphous organic film of these molecules can form a laminated structure composed of different types of amorphous organic films in combination with the above-mentioned low molecular weight and high molecular weight amorphous organic films. When sufficient heat resistance cannot be obtained with low molecular amorphous film alone, the heat resistance is improved by using a polymer amorphous film with high heat resistance in combination with an orientation control film having such a laminated structure. can do. Heat resistance is important when performing the electrode forming process.

The molecules having a steroid skeleton include the following molecules.

[0149]

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Cholesterol

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Β-estradiol benzoate

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Methyl hyodeoxycholate

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Methylcholate

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Pregnenolone

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Methylandrostenediol

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Β-estradiol

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Estriol

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Cholic acid

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Estrone Hereinafter, application examples of the light control element of the present invention will be described.

The light control element of the present invention can be used, for example, as an optical Kerr cell, a waveguide element, an optical bistable element, an etalon, and the like described below.

FIG. 6 shows the configuration of an optical shutter using the light control element of the present invention.

In FIG. 6, reference numerals 61 and 62 indicate polarizers. These polarizers 61 and 62 are arranged to face each other such that their main surfaces are parallel and their polarization directions are orthogonal. Between the polarizer 61 and the polarizer 62, the light control element of the present invention is an optical card.
It is arranged as a cell 63 and forms an optical shutter 64.

When a predetermined voltage is applied to the optical Kerr cell 63 and the control light 66 is irradiated, an anisotropy occurs in the refractive index of the crystal constituting the light control layer. The signal light 65 becomes elliptically polarized by passing through the optical Kerr cell 63. Therefore, irradiation of control light 66 /
By controlling the non-irradiation, the on / off of the output light 67 output from the polarizer 62 can be controlled.

An element that controls the phase of a light wave propagating through a waveguide by using a change in the refractive index in the waveguide and performs optical modulation is called a waveguide element, and is a Mach-Zehnder interferometer type waveguide element. Sex coupler type waveguide elements and the like are known.

FIG. 7 shows the principle of a Mach-Zehnder interferometer type waveguide device using the light control device of the present invention.

In the waveguide element shown in FIG. 7, the signal light 71 is split into signal lights 72 and 73,
After passing through the branches 74 and 75, the light beams 2 and 73 are superimposed again and output as output light 76. Further, the branches 74 and 75 of the waveguide element are constituted by the light control element of the present invention, and a difference in refractive index can be generated between the respective branches.

Normally, a predetermined voltage is applied to one of the branches 74 and 75, for example, the branch 74. However, at this time, there is no difference in the refractive index between the respective branches, and the signal light 72 and the signal light 7
3 are synthesized so as to have the same phase.

When control light having a predetermined intensity is irradiated on the waveguide element, the refractive index of the branch 74 changes nonlinearly, and the difference between the refractive indexes of the branches 74 and 75 according to the control light intensity is changed. Occurs. As a result, a large phase difference occurs between the signal light 72 and the signal light 73, and the intensity of the output light 76 decreases.

FIG. 8 shows the principle of a directional coupler type waveguide element using the light control element of the present invention.

In the waveguide device shown in FIG. 8, two arms 81 and 82 are arranged close to and parallel to each other.
The signal light 83 incident on the arm 8 is output as an output light 84 by the arm 8.
2 output.

The arms 81 and 82 are constituted by the light control element of the present invention. Usually, a predetermined voltage is applied to these arms 81 and 82, and a non-linear change in the refractive index occurs. Absent. That is, the arm 81 and the arm 8
2 is mode-matched, so that the signal light 83
The transition from 1 to the arm 82 is complete.

However, when the control light is applied to the arm 81, the refractive index of the arm 81 changes non-linearly, and a large difference occurs between the refractive indexes of the arm 81 and the arm.
As a result, the mode matching is broken, the light transition is incomplete,
The intensity of the output light 84 decreases.

FIG. 9 shows the principle of an etalon using the light control element of the present invention.

In this figure, the light control element of the present invention is used as an etalon 91, and a signal light 92 enters from one main surface of the etalon 91 and is output from the other main surface of the etalon 91. . Since the refractive index changes according to the control light intensity, the wavelength of the light wave propagating in the medium is modulated. As a result, the intensity of the multiple reflection composite wave output from the output side,
That is, the output light intensity changes. This etalon is suitable for use in an optical integrated circuit, a two-dimensional image processing element, or the like because the size of the element can be significantly reduced as compared with the waveguide element.

EXAMPLES Examples of the light control element of the present invention will be described below.

Example 1-1 A light control element was manufactured by the following method.

First, an aluminum film was formed as an electrode layer on a quartz substrate having a thickness of 2 mm so as to have a reflectance of 0.9 and a thickness of 150 Å. On this aluminum film, an SrTiO ₃ film having a relative dielectric constant of 200 was formed as a dielectric layer to a thickness of 500 angstroms by a vacuum evaporation method.
₃ An amorphous film of tetratriphenylaminoethylene (TTPAE) is formed on the film as a molecular orientation control layer.
It was formed to a thickness of 0 Å by a vacuum evaporation method.

Next, using tetramethylbenzidine (TMB) as a donor molecule and tetracyanoquinodimethane (TCNQ) as an acceptor molecule, a 200 Å-thick TMB is formed on the molecular orientation control layer by a vacuum deposition method. A light control layer comprising a -TCNQ complex was formed.
On this light control layer, polymethyl methacrylate (PMMA) having a thickness of 200 Å as an insulator layer and an aluminum film having a reflectivity of 0.9 and a thickness of 150 Å as an electrode layer are sequentially vacuum-deposited. The light control element was manufactured by the method. This light control element is used as an etalon.

For this device, the third-order nonlinear susceptibility and response speed of the device were examined by the following methods.

First, an electrostatic voltage of 10 V was applied to this device to form an electric field having an intensity of 1.0 × 10 ⁶ V / cm in the light control layer. A pulse laser beam having a wavelength of 1400 nm, 1 MW / cm ² , and 500 fs was irradiated as control light and signal light perpendicularly to the light control layer of the device, and the intensity of output light was measured. I got

As shown in FIG. 10, this device shows optical bistability. Off (low transmission state) of this element
The switching time from on to off (high transmission state), ie from the neutral state to the ionic state, is 700 fs, and the switching time from on to off is 800 fs.
Met. In the low transmission state, the ratio of the output light intensity to the input light intensity was 0.1, whereas in the high transmission state, the ratio of the output light intensity to the input light intensity increased to about 0.4.

Example 1-2 A light control element was manufactured in the same manner as in Example 1-1 except that the thickness of the first and second electrode layers was set to 50 Å and the reflectance was set to 0.3. . An electrostatic voltage was applied to the device to cause a phase transition. As a result, it was found that a phase transition occurs when a voltage of 20 V and an electric field having an intensity of 2 × 10 ⁶ V / cm are formed.

A laser light having a wavelength of 540 nm and an intensity of 0.5 MW / cm ² was incident as signal light perpendicular to the light control layer of the device, and the light of the device was applied by applying / non-applying a voltage of 25V. The response speed when the optical characteristics of the control layer were controlled was examined. As a result, the switching time from off to on was 50 psec, and the switching time from the charge transfer state to the non-coupling state was 65 psec.

In the uncoupled state, the ratio of the output light intensity to the input light intensity was 0.60, whereas in the charge transfer state, the ratio of the output light intensity to the input light intensity was 0.10.
It was about 62.

Comparative Example 1-1 Using the device manufactured in Example 1-1, the wavelength was 1400 nm perpendicular to the light control layer without applying a voltage.
Pulsed laser light having an intensity of 1 MW / cm ² and 500 fs was irradiated. As a result, no bistability of the light control layer occurred.

When the intensity of the laser light was increased, a bistable operation of the light control layer was slightly confirmed when the intensity was 1 GW / cm ² .

As in Example 1-1, when a predetermined voltage was applied to the light control layer and control light and signal light were used, excellent third-order nonlinear susceptibility and response speed switching were observed. Similar effects were obtained even when the film thickness and the reflectance were changed as in Example 1-2. However, when no voltage is applied as in Comparative Example 1-1, the bistable operation is not observed unless the intensity of the laser beam is considerably increased.

Example 1-3 A light control element was manufactured in the same manner as in Example 1-1, except that the thickness of the light control layer was changed to 100 Å.

In this device, the thickness of the light control layer is smaller than that of the device manufactured in Example 1-1. For this reason, the state of the complex crystal constituting the light control layer becomes closer to the phase transition boundary due to the decrease of the Madelung energy gain in the ionic state, and accordingly, the excitation wavelength of the charge transfer exciton decreases from 1400 nm to 1550 nm. And shifted to the lower energy side.

A static voltage of 5 V was applied to the device, and the wavelength was 1550 nm and the intensity was 1 MW perpendicular to the light control layer.
A pulse laser beam of 500 fs / cm ² was irradiated as control light and signal light, and the intensity of output light was measured. As a result, a hysteresis curve showing optical bistability was obtained.

The switching time from off to on of this element was 500 fs, and the switching time from on to off was 650 fs.

Example 1-4 As a light control layer, chloromethyl paraphenylenediamine (ClMePD) -dimethyldicyanoquinodiimine (D
MeDCNQI) and dimethylparaphenylenediamine (DMePD) -DMeDCNQI using a complex mixed crystal in which the respective molar ratios were adjusted to be 3: 7,
Except that it was formed with a thickness of 100 angstroms,
A light control element was manufactured in the same manner as in Example 1-1.

A static voltage of 5 V was applied to the device, and a wavelength of 1000 nm and an intensity of 0.8 were measured perpendicularly to the light control layer.
A pulse laser beam of MW / cm ² and 500 fs was irradiated as control light and signal light, and the intensity of output light was measured while changing the intensity of input light. As a result, a hysteresis curve showing optical bistability was obtained.

The switching time from off to on of this element was 650 fs, and the switching time from on to off was 730 fs.

Example 1-5 An electrostatic voltage of 10 V was applied to the light control element manufactured in Example 1-1, and the wavelength was set to 1300 n perpendicular to the light control layer.
m, an intensity of 0.1 MW / cm ² laser light is incident as signal light, and the light control layer is irradiated with the signal light in an area where the signal light is irradiated.
A pulse laser beam having a wavelength of 1000 nm, an intensity of 0.8 MW / cm ² , and 500 fs was irradiated as control light from an oblique direction to the light control layer, and the intensity of output light was measured. As a result, a hysteresis curve showing optical bistability was obtained.

The switching time from off to on of the device was 700 fs, and the switching time from on to off was 800 fs.

Example 1-6 An aluminum film was formed as an electrode layer so as to have a reflectivity of 0.4 and a thickness of 50 Å, and tetrathiafulvalene (T) was used as a donor molecule.
TF) using chloranil (CA) as the acceptor molecule to a thickness of 150 Å and TTF-C
A light control element was produced in the same manner as in Example 1-1, except that a light control layer made of the A complex was formed. This element is a planar light control element that does not use internal multiple reflection unlike an etalon because the reflectance of the electrode layer is low.

A static voltage of 10 V was applied to the device, and the wavelength was 1550 nm and the intensity was 1 M perpendicular to the light control layer.
A pulse laser beam of W / cm ² and 500 fs was irradiated as control light and signal light, and the intensity of output light was measured. As a result, a hysteresis curve showing optical bistability was obtained.

The switching time from off to on of this element was 650 fs, and the switching time from on to off was 800 fs.

Example 1-7 The light control element fabricated in Example 1-1 was irradiated with a pulse laser beam having a wavelength of 540 nm and an intensity of 1 MW / cm ² perpendicular to the light control layer. The modulated rectangular voltage was applied in a range of 0 V to 30 V. As a result, in a voltage range of 20 V or less, the element is in a low transmission state,
In the above voltage range, the element was in a high transmission state, and an optical pulse modulation signal synchronized with the modulation of the voltage signal could be obtained.

Example 1-8 The light control device shown in FIG. 11 was manufactured by the following method.

First, a quartz substrate 11 having a thickness of 2 mm and a length in a direction parallel to the substrate surface of 20 mm × 20 mm, respectively.
An aluminum film as an electrode layer 112
It was formed with a thickness of 0 Å.

On this electrode layer 112, an SrTiO ₃ film having a relative dielectric constant of 200 is formed as a dielectric layer 113 to a thickness of 500 angstroms by a vacuum evaporation method.
TT as a molecular orientation control layer 117 on the rTiO ₃ film
An amorphous film of PAE was formed to a thickness of 250 angstroms by a vacuum evaporation method.

Next, by using TTF as a donor molecule and CA as an acceptor molecule, a light control layer 114 made of a TTF-CA complex with a thickness of 150 Å is formed on the molecular orientation control layer 117 by a vacuum evaporation method. Formed. On this light control layer 114, PMMA is formed as an insulator layer 115 to a thickness of 200 angstroms to form an electrode layer 1
An aluminum film having a thickness of 500 angstroms as No. 16 was sequentially formed by a vacuum evaporation method. The electrode layer 116 was formed at the center of the substrate 111 with a length of 10 mm and a width of 5 mm.

On the substrate 111 on which the electrode layers and the like are stacked as described above, a pair of prisms 118 and 119 are disposed so as to be located at both ends in the longitudinal direction of the electrode layer 116, respectively. A light control element used as a slab waveguide element was manufactured.

A static voltage of 5 V is applied to this element, and a wavelength of 1550 nm and an intensity of 0.1 MW are output from the prism 118.
/ Cm ² pulsed laser light is incident as signal light, and the wavelength is 1400 nm and the intensity is 1 MW from the prism 119.
/ Cm ² was irradiated as pulsed control laser light, and the intensity of output light was measured. As a result, at the time of irradiation with the control light, the output of the signal light was completely shut off.

The waveguide element is turned from on to off.
The switching time from off to on was 700 fs, and the switching time from off to on was 800 fs.

Example 1-9 An optical control element used as a grating-coupled slab waveguide element shown in FIG. 12 was manufactured.

The element shown in FIG. 12 has substantially the same configuration as the element shown in FIG. 11, except that gratings 128 and 129 are provided instead of the prisms 118 and 119.

A static voltage of 5 V was applied to this element, and a wavelength of 1550 nm and an intensity of 0.
A pulse laser beam of 1 MW / cm ² is made incident as signal light, and a wavelength of 1400 nm is obtained from the grating 129.
Pulse laser light having an intensity of 1 MW / cm ² was irradiated as control light, and the intensity of output light was measured. As a result, at the time of irradiation with the control light, the output of the signal light was completely shut off.

The waveguide element is turned from on to off.
The switching time from off to on was 700 fs, and the switching time from off to on was 800 fs.

Example 1-10 The light control element produced in Example 1-8 was irradiated with a pulse laser beam having a wavelength of 540 nm and an intensity of 0.1 MW / cm ² from one of the prisms, and modulated at 1 GHz. A rectangular voltage was applied in a range of 0 V to 30 V. As a result, in a voltage range of 20 V or less, the element is in a low transmission state,
In the above voltage range, the element was in a high transmission state, and an optical pulse modulation signal synchronized with the modulation of the voltage signal could be obtained.

Example 1-11 A directional coupler type waveguide device shown in FIG. 13 was manufactured by the following method.

First, after patterning on the quartz substrate 131, arms 132 and 133 made of 7059 glass were formed by sputtering. These arms 13
The width and height of 2,133 are 2 μm and 0.2 μm, respectively. Also, the arm 132 and the arm 133
Are formed with gaps in which the light control elements 134 and 135 are disposed, respectively.

Next, an aluminum film was formed as an electrode layer so as to have a thickness of 500 angstroms, using a mask, in each of the gap portions of the arms 132 and 133. On this aluminum film, an SrTiO ₃ film having a relative dielectric constant of 200 was formed as an insulator layer to a thickness of 500 Å by a vacuum evaporation method.
TTPAE on the rTiO ₃ film as a molecular orientation control layer
Of the amorphous film of 250 angstrom thickness,
It was formed by a vacuum evaporation method.

Using TMB as a donor molecule and TCNQ as an acceptor molecule on the molecular orientation control film formed as described above, a 500 Å-thick TMB-type film was formed on the molecular orientation control layer by vacuum evaporation. TCN
A light control layer made of a Q complex was formed. On these light control layers, an aluminum layer having a thickness of 200 angstroms of PMMA as an insulator layer and a thickness of 500 angstroms as an electrode layer is sequentially laminated by a vacuum evaporation method, and the light control element portions 134 and 135 are formed. Was formed, and a directional coupler type waveguide element 136 was manufactured.

A voltage of 30 V is applied only to the light control element section 134 of the directional coupler type waveguide element 136 manufactured as described above, and pulse light having a wavelength of 1550 nm and 500 fs is input from the input section 137 of the arm 132. Was irradiated with varying intensity. As a result, when the intensity is less than 1 MW / cm ^{2, the} output light is output from the output unit 138 of the arm 133, but when the intensity is 1 MW / cm ² or more, the output light is output from the output unit 138 of the arm 133. Arm 13
2 was output only from the output unit 139.

The switching time from the non-coupling state to the charge transfer state of this waveguide element was 1.4 ps, and the switching time from the charge transfer state to the non-coupling state was 2.1 ps.

Example 1-12 A Mach-Zehnder waveguide device shown in FIG. 14 was manufactured by the following method.

First, waveguides 142 and 145 and branches 143 and 144 made of 7059 glass are formed on a quartz substrate 141 by patterning and sputtering so that the width and height are 2 μm and 0.2 μm, respectively. did. Also, branches 143 and 144 include
A gap in which the light control elements 146 and 147 are arranged is formed.

Next, an aluminum film was formed as an electrode layer in a gap portion of each of the branches 143 and 144 by using a mask so as to have a thickness of 500 angstroms. On this aluminum film, an SrTiO ₃ film having a relative dielectric constant of 200 was formed as an insulator layer to a thickness of 500 Å by a vacuum evaporation method.
TTPAE on the rTiO ₃ film as a molecular orientation control layer
Of the amorphous film of 250 angstrom thickness,
It was formed by a vacuum evaporation method.

A light control layer having a thickness of 500 angstroms was formed on the molecular orientation control layer by vacuum evaporation using TMB as a donor molecule and TCNQ as an acceptor molecule. On the light control layer, an aluminum layer having a thickness of 200 angstroms of PMMA as an insulator layer and a thickness of 500 angstroms as an electrode layer is sequentially laminated by a vacuum deposition method, and the light control element portions 146 and 147 are formed. The directional coupler type waveguide element 148 was formed.

Only the light control element section 146 of the directional coupler type waveguide element 148 manufactured as described above has a voltage of 30V.
And a wavelength of 1550 n from the waveguide 142 is applied.
Irradiated with pulse light of 500 fs while changing the intensity. As a result, when the intensity was less than 1 MW / cm ^2, output light was output from the waveguide 145, but the intensity was 1 MW / cm ^2.
In the case of cm ² or more, no output light was output from the waveguide 145.

The switching time from the non-coupling state to the charge transfer state of the waveguide element was 1.6 ps, and the switching time from the charge transfer state to the non-coupling state was 2.5 ps.

Next, the organic thin film device of the present invention will be described.

In the organic thin film element of the present invention, an amorphous organic film preferably used in the above-mentioned light control element and a molecule having a steroid skeleton more preferably used as a light control element can be used as a molecular orientation control layer.

The organic thin film element of the present invention basically has a laminated structure including a molecular orientation control layer made of an amorphous organic film and a crystalline organic thin film made of π-electron molecules on a support layer. The crystalline organic thin film is formed by a vacuum deposition method at a growth rate of 100 Å / min or less, and has a film thickness of not less than one molecular layer and not more than 2000 Å.

Further, the method of the present invention is used for manufacturing such an organic thin film element, and prepares a support layer having a molecular orientation control layer formed of an amorphous organic film on the surface thereof. And 10 by vacuum evaporation
A crystalline organic thin film having a film thickness of not less than 1 molecular layer and not more than 2000 angstrom is formed at a growth rate of 0 angstrom / min or less, wherein the support layer is a layer supporting the molecular orientation control layer. That means. The support layer can be provided adjacent to the molecular orientation control layer depending on the use of the organic thin film element and the desired configuration. A typical example is a substrate, but the substrate is not limited to this, and a layer suitably used for an organic thin film element, such as an insulating layer and a crystalline organic thin film, is selected. When a layer other than the substrate is provided as a support layer,
Further, a substrate can be provided as a lower layer. At this time, any other layer can be provided between the support layer and the substrate.

According to a first preferred embodiment of the organic thin film element of the present invention, a low molecular weight dye molecule having an aromatic ring in the outermost shell of its molecular structure is used for a molecular orientation control layer comprising an amorphous organic thin film. Can be. As a result, a high dispersive force can be generated between the π-electron molecules forming the crystalline organic thin film formed on the molecular orientation control layer due to the high polarizability of the π-electrons nonpolarized in the aromatic ring. Becomes possible,
An organic thin film element utilizing characteristics of an organic thin film having high crystallinity and utilizing anisotropy of physical properties in a crystal axis direction can be obtained.

Further, according to the second preferred embodiment of the organic thin film element of the present invention, a polysilane derivative having a structure in which the main chain of polysilane is oriented parallel to the substrate surface is added to the molecular orientation control layer composed of an amorphous organic thin film. Can be used. By using a silicon polymer chain having an electron polarizability higher than that of carbon as the orientation control layer, the orientation control layer and the crystalline and π-electron molecules constituting the organic thin film can be formed more efficiently than when a carbon-based polymer is used. As a result, it is possible to produce an organic thin film element utilizing the characteristics of an organic thin film having high crystallinity and utilizing anisotropy of physical properties in the crystal axis direction.

According to the third preferred embodiment of the organic thin film device of the present invention, an organic thin film substantially composed of a molecule having a steroid skeleton can be used as a molecular orientation control layer formed of an amorphous organic thin film. As a result, an organic amorphous having insulating properties as well as surface flatness can be obtained. Such an insulating film can be formed thin. Therefore, it is possible to apply a strong electric field with an applied voltage as low as possible.

According to a fourth preferred embodiment of the organic thin film element of the present invention, as a molecular orientation control layer composed of an amorphous organic thin film, a molecule having a structure in which different kinds of amorphous organic films are laminated, and having a steroid skeleton. Can be used. A laminate including at least one organic thin film substantially consisting of When sufficient heat resistance cannot be obtained with low molecular amorphous film alone, the heat resistance is improved by using a polymer amorphous film with high heat resistance in combination with an orientation control film having such a laminated structure. can do. Heat resistance is important when performing the electrode forming process.

Further, according to the fifth preferred embodiment of the organic thin film element of the present invention, a structure in which thin films of different kinds of organic molecules are stacked can be applied as the crystalline organic thin film composed of π-electron molecules. As a result, it is possible to generate a charge transfer effect at a hetero interface between different kinds of organic molecules, a generation of a contact potential distribution, and a confinement effect of carriers and excitons due to generation of the potential barrier, and an organic thin film having a novel function. An element can be obtained.

According to the sixth preferred embodiment of the organic thin film element of the present invention, an organic charge transfer complex crystal can be applied as a crystalline organic thin film composed of π-electron molecules. As a result, it is possible to use the device as a device function having a phase transition phenomenon, anisotropic electric conductivity, and high nonlinear optical characteristics characteristic of the charge transfer complex, and to obtain an organic thin film device having a novel function. it can.

According to the seventh preferred embodiment of the organic thin film element of the present invention, a crystalline organic thin film having a light modulation function or an optical information recording function based on a nonlinear optical effect can be used. Due to the high nonlinear optical susceptibility and ultra-high-speed photoresponsiveness of organic π-electron molecules, light absorption (reflection) characteristics sensitive to molecular electronic structure and molecular aggregation structure, or high-speed electron transfer between molecules. This makes it possible to utilize the photolithographic effect or the hole burning phenomenon with high responsiveness, and can be used for an organic thin film element for optical modulation and an optical information recording medium.

According to an eighth preferred embodiment of the organic thin film device of the present invention, a pair of insulators is provided on both sides of a laminate of a molecular orientation control layer composed of an amorphous organic film and a crystalline organic thin film composed of π-electron molecules. A layer and a pair of electrodes can be provided. By providing the pair of insulator layers, a strong electric field can be effectively applied to the organic thin film, and an organic thin film element utilizing control of the electronic state of the organic thin film by the electric field can be obtained.

According to the ninth preferred embodiment of the organic thin film element of the present invention, a crystalline organic thin film having a function of generating photovoltaic power or photocurrent by light irradiation can be used. Thereby, an organic thin film element that can be used for a photodetector and a photovoltaic cell can be obtained.

According to the tenth preferred embodiment of the organic thin film element of the present invention, an insulating film, a molecular orientation control film made of an amorphous organic thin film, a gate electrode, and a π-electron are formed in a channel region between a source and a drain region of a semiconductor substrate. It has a laminated structure including a crystalline organic thin film composed of system-based molecules, and the crystalline organic thin film is 100 Å /
The organic thin film element is formed at a growth rate of not more than 1 minute and has a film thickness of not less than 1 molecular layer and not more than 2000 angstroms. Such an organic thin film element can be used as a field effect transistor.

According to the present invention, the structure and molecular orientation of the organic thin film can be controlled regardless of the material and shape of the substrate body, and an organic thin film element that can be practically used as an optical element, an electronic element, or the like can be obtained. can get.

Next, a specific example of the structure of the organic thin film element according to the present invention will be described.

The organic thin film device of the present invention basically has at least one layer of an organic thin film having a device function on a support layer such as a substrate. 15 to 17 show an example of the structure of the organic thin film element of the present invention.

The organic thin-film device shown in FIG. 15 is obtained by sequentially forming an amorphous organic film 152 and an organic thin film 3 having an element function on a substrate 151.

In the organic thin film element shown in FIG. 16, an amorphous organic film 152, a first organic thin film 153 having an element function, and an amorphous organic film 152 and a second organic thin film 154 having an element function are sequentially formed on a substrate 151. It is a laminated type organic thin film element.

In the organic thin film device shown in FIG. 17, an organic thin film 153 having an element function is sequentially formed on a substrate 151 on which a first electrode 155, a first insulating layer 156, and an amorphous organic film 152 are formed. And the second insulating layer 15
7 shows an organic thin-film element provided with a back electrode 158 as a second electrode.

In the present invention, as shown in FIGS. 15 to 17, a molecular orientation control layer composed of an amorphous organic film is formed on an arbitrary base surface. Such an orientation control layer can be formed by a vacuum evaporation method, a spin coating method, a coating method, a sputtering method, an LB method, or the like.

Here, it is preferable that the thickness of the orientation control layer formed as a base of the organic thin film is not less than one molecular layer and not more than 1000 angstroms. In other words, it is sufficient that the thickness is about the reach of the interaction acting between the orientation control layer and the thin film molecules. If the thickness is more than necessary, the applied voltage and the optical transmission characteristics of the device will be lost. . The reaching distance is not uniform depending on the type of interaction, but the thickness of the molecular orientation control layer is sufficient if a few molecular layers are sufficient if the dispersive force is main, and if a long-range force such as electrostatic force is used, It is about 100 to 1000 angstroms.

In the present invention, the organic thin film refers to a crystalline thin film of π-electron molecules. The π-electron molecule refers to a molecule having some π bonds in a molecule such as an unsaturated hydrocarbon and an aromatic compound. Polydiacetylene and condensed polycyclic aromatic molecules are representative thereof.

In order to form a crystalline thin film composed of the π-electron molecules on the molecular orientation control layer, it is very important to control the growth conditions of the thin film. In a deposition method under a normal vacuum degree (10 ⁻⁶ to 10 ⁻⁷ Torr) as reported previously, in order to attach film molecules to a substrate against a back pressure,
A fairly fast deposition rate, for example, 1000 Angstroms / min, was required. However, the growth of a thin film under such a condition is a growth condition for promoting self-aggregation between molecules, and in many cases, the grown film has an aggregate structure of polycrystalline grains. In order to avoid such a film growth, the conditions under which the film growth proceeds at an extremely low speed using ultra-high vacuum conditions are prepared, and the crystal structure is formed in accordance with the substrate-molecule interaction or the intermolecular interaction. It is necessary to allow the film growth to progress while assembling.

As such a film growth condition, it is considered that the film growth rate is desirably 100 Å / min or less. At this time, the degree of vacuum is preferably higher than 10 ^-9 Torr, and if it is lower than 10 ^-8 Torr, the above-described effect of the back pressure appears, and it tends to be difficult to reduce the deposition rate of the organic molecules.

Although the optimum thickness of the crystalline thin film composed of the π-electron molecules varies depending on the device function, it is sufficient for the device function to be exhibited, and in the case of an electronic device, unnecessary voltage and In order to prevent loss of current and, in the case of an optical element, loss such as absorption, there is generally a certain upper limit of the film thickness. It is desirable that the thickness be not less than 1 layer and not more than 1000 angstroms, more preferably not less than 1 molecular layer and not more than 2000 angstroms.

The material of the substrate body is not particularly limited.
Examples thereof include a semiconductor (including a circuit and a junction formed), a dielectric, and quartz.

In the case where an electrode is formed on a substrate as in the organic thin film element shown in FIG. 17, examples of the material include metal, ITO, and organic conductive materials. In the case of an element to which a voltage is applied, if an insulating layer is provided on the electrode as shown in FIG. 17, a strong electric field can be effectively applied to the organic thin film. That is, in general, when the electric field applied to the organic thin film is increased, the current flowing through the organic thin film is greatly increased, which adversely affects the structure of the organic thin film. In contrast, if an insulating layer is provided between the electrode and the organic thin film, the current flowing through the organic thin film does not increase even if a strong electric field is applied, and the strong electric field is effectively applied to the organic thin film. it can. An oxide such as SiO ₂ , SrTi
An oxide such as O ₃ , a ferroelectric material, an organic polymer, or the like is used. In particular, in order to apply an electric field with an organic thin film,
It is preferable to use an insulating material having a relative dielectric constant of 10 or more, for example, a ferroelectric substance such as SrTiO ₃ .

Further, in the present invention, the organic thin film may be composed of an alternately laminated charge transfer complex in which donor molecules and acceptor molecules are laminated with their molecular surfaces facing each other. Specific examples of such a layered charge transfer complex include phenothiazine-TCNQ, tetradiaminopyrene-TCNQ, TTF-chloranil, TTF-fluoranyl, dibenzene TTF-TCNQ, diethyldimethyltetraselenafulvalene-diethyl TCNQ, Diaminopyrene-fluoranyl, TTF-dichlorodicyanobenzoquinone, perylene-tetracyanoethylene, perylene-TCNQ, TTF-dinitrobenzene,
Perylene-chloranil, pyrene-tetracyanoethylene, pyrene-chloranil, anthracene-chloranil,
Numerous complexes including hexamethylbenzene-chloranil, naphthalene-tetracyanoethylene, anthracene-pyromellitic dianhydride, anthracene-tetracyanobenzene, phenanthrene-pyromellitic dianhydride and the like can be mentioned.

When the thickness of the organic thin film containing both the donor molecule and the acceptor molecule is large, the effective electric field applied to the film is reduced by the electric field generated by the carriers generated in the film. However, if the film thickness is less than the Debye length (about 30 nm), it becomes possible to screen the electric field generated by the carriers. In addition, when the complex is ionic, the contribution of the Madelung energy term in the complex stabilization energy is reduced by making the film thickness thin, and the complex is transferred to neutral. For this reason, the charge transfer state of the complex can be set to a neutral state close to the transition boundary condition. Therefore, the neutral-ionic transition can be efficiently realized in a low electric field.

Hereinafter, the operation principle of one example of the organic thin film device according to the present invention will be described more specifically.

(A) Display Element The display element basically includes a transparent electrode 155, an insulating layer 156, an orientation control layer 152, an organic thin film 153, an insulating layer 157, and a transparent substrate 151 as shown in FIG. It has a structure in which the back electrode 158 is sequentially formed. In this display element, an electric field is applied to the organic thin film from the electrodes, whereby the alternately layered charge-transfer complex constituting the organic thin film transitions from neutral to ionic, and the light absorption wavelength changes. Can be obtained. In the present invention, by providing the orientation control layer, the orientation of the organic molecules constituting the organic thin film formed thereon becomes good, and the luminous efficiency can be improved.

(B) Field Effect Transistor (FET) A basic structure in which a gate insulating film, an orientation control layer, an organic thin film, and a gate electrode are sequentially formed on a channel region between source and drain regions formed on the surface of a semiconductor substrate. Have. In this FET, when the gate voltage is gradually increased, the alternating stack type charge transfer complex that forms the organic thin film at a certain voltage transitions from neutral to ionic, and the drain current increases rapidly. Is shown. In the present invention, by providing the orientation control layer, the orientation of the organic molecules constituting the organic thin film formed thereon becomes good, and a large output can be obtained.

Further, in any of the elements, if the structure shown in FIG. 16 is applied and a plurality of organic thin films are laminated to form a superlattice structure, a multi-value display function or a switching function can be obtained.

Hereinafter, the organic thin film device according to the present invention will be described in detail with reference to examples.

Example 2-1 On a Si substrate 151, a film thickness of about 50 n was formed by a vacuum evaporation method.
A molecular orientation control layer 152 having an amorphous structure of m OXD-S4 molecules was formed. Thereafter, an organic thin film 153 made of anthracene molecules is formed from an anthracene crystal powder at 10 ° C. in an atmosphere of about 1 × 10 ⁻⁹ Torr at a growth rate of 10 Å / min to a thickness of 200 Å. An organic thin film element having the structure shown in FIG.

The molecular orientation of the anthracene thin film was evaluated in situ by infrared spectroscopy. As a result, it was found that anthralene formed a thin film by orienting its planar molecular plane parallel to the surface.

Comparative Example 2-1 A film thickness of about 50 n was formed on a Si substrate 151 by a vacuum evaporation method.
A molecular orientation control layer 152 having an amorphous structure of m OXD-S4 molecules was formed. Thereafter, the organic thin film 153 comprising anthracene molecules is grown to a thickness of 1000 Å at a growth rate of 1000 Å / min in an atmosphere of about 1 × 10 ⁻⁷ Torr while heating the anthracene crystal powder to a temperature of 50 ° C. Forming, FIG.
An organic thin film element having the structure shown in FIG.

In situ evaluation of the molecular orientation of the anthracene thin film by infrared spectroscopy revealed that anthracene formed a thin film with a plurality of crystal orientations. From these results, it was found that the crystal structure was not controlled in this example. Further, as a result of observing the surface structure with a scanning electron microscope, it was found that the anthracene thin film had a polycrystalline structure.

Example 2-2 A film thickness of about 50 nm was formed on a Si substrate 151 by a vacuum evaporation method.
The molecular orientation control layer 152 having an amorphous structure of OXD-S4 was formed to a thickness of about 50 nm. Thereafter, the organic thin film 153 made of TCNQ molecules is
While heating the crystal powder to a temperature of 60 ° C., about 1 × 10 ⁻⁹
An organic thin film element having a structure as shown in FIG. 15 was formed in a Torr atmosphere at a growth rate of 10 angstroms / min to a thickness of 100 angstroms.

In-situ evaluation of the molecular orientation of the TCNQ thin film by infrared spectroscopy revealed that the TCNQ formed a thin film with its planar molecular plane oriented parallel to the surface.

Example 2-3 A film thickness of about 50 n was formed on a Si substrate 151 by a vacuum evaporation method.
A molecular orientation control layer 152 having an amorphous structure of m OXD-S4 molecules was formed. Then, the charge transfer complex T
The organic thin film 153 made of TF-chloranil was
While heating the chloranil crystal powder to a temperature of 50 ° C., it is formed at a growth rate of 20 Å / min in an atmosphere of about 1 × 10 ⁻⁹ Torr to a film thickness of about 100 Å, and a structure as shown in FIG. Was obtained.

The molecular orientation of the complex thin film was evaluated by infrared spectroscopy. As a result, it was found that both TTF and chloranil formed a crystalline complex thin film with their planar molecular faces oriented parallel to the surface. .

Example 2-4 A film having a thickness of about 50 was formed on a glass substrate 151 by vacuum evaporation.
A molecular orientation control layer 152 having an amorphous structure of OXD-S8 molecules of nm was formed. Thereafter, the organic thin film 153 made of TCNQ molecules is heated to a temperature of 60 ° C. at a growth rate of 10 Å / min to a thickness of 100 Å in an atmosphere of about 1 × 10 ⁻⁹ Torr. Formed.

As a result of evaluating the molecular orientation of the TCNQ thin film by infrared spectroscopy, it was found that the TCNQ formed a thin film with its planar molecular plane oriented parallel to the surface.

Example 2-5 A film having a thickness of about 50 n was formed on a Si substrate 151 by a vacuum evaporation method.
A molecular orientation control layer 152 having an amorphous structure of m TCTA molecules was formed. Then, the charge transfer complex TTF
The organic thin film 153 made of chloranil is heated to about 1 × while heating the TTF-chloranil crystal powder to a temperature of 50 ° C.
Approximately 100 Å was formed at a growth rate of 20 Å / min in an atmosphere of 10 ⁻⁹ Torr.

The molecular orientation of the complex thin film was evaluated by infrared spectroscopy. As a result, it was found that both TTF and chloranil formed thin films with their flat molecular surfaces oriented parallel to the surface.

Example 2-6 A molecular orientation control layer 152 having a polystyrene amorphous structure with a thickness of about 50 nm was formed on a Si substrate 1 by vacuum evaporation. Thereafter, the TCNQ crystal powder is heated to a temperature of 60 ° C. at a growth rate of 10 Å / min.
In an atmosphere of about 1 × 10 ⁻⁹ Torr, 100 Å was formed. The molecular orientation of the TCNQ thin film was evaluated by infrared spectroscopy. As a result, it was found that the TCNQ formed a thin film with its planar molecular plane oriented parallel to the surface.

Example 2-7 A film thickness of about 50 n was formed on a Si substrate 151 by a vacuum evaporation method.
A molecular orientation control layer 152 having an amorphous structure of polymethylphenylsilane of m was formed. Then, TCN
The organic thin film 153 composed of Q molecules is heated at a growth rate of 10 Å / min in an atmosphere of about 1 × 10 ⁻⁹ Torr while heating the TCNQ crystal powder to a temperature of 60 ° C.
An organic thin film element formed to a thickness of 0 Å and having a structure as shown in FIG. 15 was obtained.

As a result of evaluating the molecular orientation of the TCNQ thin film by infrared spectroscopy, it was found that the TCNQ formed a thin film with its planar molecular plane oriented parallel to the surface.

Example 2-8 On a Si substrate 151, a molecular orientation control layer 152 made of amphiphilic phenol-substituted polysilane (methyl (m-hydroxyphenyl) polysilane) (the main chain of the polysilane was (Parallel orientation). Then, T
The organic thin film 153 made of CNQ molecules is heated to about 1 × 10 ⁻⁹ Torr while heating the TCNQ crystal powder to a temperature of 60 ° C.
An organic thin-film element having a thickness of 100 Å was formed at a growth rate of 10 Å / min in an atmosphere of r to obtain an organic thin-film element having a structure as shown in FIG.

As a result of evaluating the molecular orientation of the TCNQ thin film by infrared spectroscopy, it was found that the TCNQ formed a thin film with its planar molecular plane oriented parallel to the surface.

Example 2-9 ClO ₄ ⁻ was formed on an ITO substrate 151 by electrolytic polymerization.
A molecular orientation control layer 152 having an amorphous structure of polypyrrole and having a film thickness of about 50 nm using as a dopant ion was formed. Thereafter, an organic thin film 15 made of TCNQ molecules is used.
3 was formed in a thickness of 100 Å at a growth rate of 10 Å / min in an atmosphere of about 1 × 10 ⁻⁹ Torr while heating the TCNQ crystal powder to a temperature of 60 ° C.

The molecular orientation of the TCNQ thin film was evaluated by infrared spectroscopy. As a result, it was found that the TCNQ formed a thin film with its planar molecular plane oriented parallel to the surface.

Example 2-10 A molecular orientation control layer 152 having an amorphous structure of OXD-S8 molecules having a thickness of about 50 nm was formed on a glass substrate by a vacuum evaporation method. Then, while heating the TCNQ crystal powder to a temperature of 60 ° C. in an atmosphere of about 1 × 10 ⁻⁹ Torr, the organic thin film 153 made of TCNQ molecules is heated to 1 × 10 ⁻⁹ Torr.
100 Å was formed at a growth rate of 0 Å / min.

Further, a molecular orientation control layer 152 having an amorphous structure of OXD-S8 molecules having a film thickness of about 50 nm was formed in the same manner again by the vacuum evaporation method. Thereafter, the organic thin film 154 made of perylene molecules is heated to about 1 × 10
^In an atmosphere of ^-9 Torr, 50 Å was formed at a growth rate of 5 Å / min to obtain an organic thin film device having a structure as shown in FIG.

The molecular orientation of the TCNQ thin film and the perylene thin film was evaluated by infrared spectroscopy. As a result, it was found that each molecule formed a thin film by orienting its planar molecular plane parallel to the surface.

Example 2-11 On a quartz substrate 151, an ITO transparent electrode 155 having a thickness of 400 nm and an insulating layer 156 made of SrTiO ₃ having a thickness of 150 nm were formed.

On top of this, a film thickness of about 50 was formed by vacuum evaporation.
A molecular orientation control layer 152 having an amorphous structure of TCTA molecules of nm was formed.

Thereafter, the organic thin film 153 comprising the charge transfer complex TTF-chloranil was heated to about 1 × 10 ⁻⁹ Torr while heating the TTF-chloranil crystal powder to a temperature of 50 ° C.
In an atmosphere of r, about 100 angstroms were formed at a growth rate of 20 angstroms / min.

In situ evaluation of the molecular orientation of the TTF-chloranil thin film by infrared spectroscopy revealed that TTF-chloranil formed a thin film with its tabular molecular plane oriented parallel to the surface. .

Further, an insulating layer 157 made of polyisobutyl methacrylate having a thickness of 20 nm,
An m thin Au translucent electrode 158 was formed, and an organic thin film element having a display function as shown in FIG. 17 was produced.

This display element exhibited a pale yellow color when no voltage was applied, but turned red at about 50 V when a voltage was applied.

Example 2-12 In the same manner as in Example 2-1, a molecular orientation control layer 152 having an amorphous structure of OXD-S4 molecules having a thickness of about 50 nm was formed on a quartz substrate 151 by a vacuum evaporation method. Thereafter, an organic thin film 153 made of anthracene molecules was formed at a growth rate of 2 angstroms / min to a thickness of 10 angstroms to obtain an organic thin film element having a structure shown in FIG.

The molecular orientation of the anthracene thin film was evaluated in situ by infrared spectroscopy. As a result, it was found that the anthracene thin film was formed by orienting its planar molecular plane parallel to the surface.

Further, as a result of evaluating the crystallinity by the low-speed electron diffraction method, it was found that a two-dimensional crystal lattice was formed. This thin film was cooled to the liquid He temperature, and the third-order nonlinear susceptibility χ ⁽³⁾ was evaluated by nonlinear spectroscopy.
A large value of 0 ^-5 esu was obtained. According to this value, the thin film was examined for optical bistability by applying two laser beams of control light and signal light. As a result, hysteresis was observed in the optical input-optical output curve, and the switch on / off time was 1 picosecond. It turned out to be on the order of seconds.

Embodiment 2-13 FIG. 18 is a schematic diagram showing an example of a configuration of an n-channel type field effect transistor (FET) according to the present invention.

An SiO ₂ insulating film is formed in the channel region between the source and drain regions on the Si substrate, and source / drain electrodes 52 and 53 are formed on the SiO ₂ insulating film.
A substrate 41 provided with a gate electrode 51 on a Si substrate was prepared. A molecular orientation control layer 152 having an amorphous structure of OXD-S4 molecules having a thickness of about 50 nm was formed on the SiO ₂ insulating film by a vacuum evaporation method. Thereafter, an organic thin film 153 consisting of C _60, while heating the C ₆₀ to a temperature of 300 ° C., in an atmosphere of about 1 × 10 ^-9 Torr, to of 20 Å / min growth rate, film thickness of 200 Angstroms Then, an n-channel type field effect transistor (FET) as shown in FIG. 18 was formed.

As a result of evaluating the field-effect mobility of this FET, a value of 0.15 cm ² / V · sec was obtained.

Embodiment 2-14 FIG. 19 is a diagram showing an example of the structure of a photodiode according to the present invention.

A molecular orientation control layer 152 having an amorphous structure of OXD-S4 molecules having a thickness of about 50 nm was formed on the ITO substrate 151 by a vacuum evaporation method. Then, an organic thin film 153 composed of copper phthalocyanine molecules is
The phthalocyanine powder was formed at a growth rate of 50 angstroms / min in an atmosphere of about 1 × 10 ⁻⁹ Torr to a thickness of 200 angstroms while being heated to a temperature of 330 ° C.

As a result of in-situ evaluation of the molecular orientation of the thin film by infrared spectroscopy, it was found that TCNQ formed a thin film with its planar molecular plane oriented parallel to the surface.

By forming an upper electrode on this thin film, a photodiode element as shown in FIG. 19 was formed.
When this device was irradiated with light of 500 nm, a photocurrent was obtained with an external quantum efficiency of 30%.

As is clear from Examples 2-1 to 2-14, in the organic thin film device of the present invention, the controllability of the orientation of the organic molecules in the organic thin film is remarkably improved. For example, an element for controlling the neutral-ionic transition of the charge transfer complex organic thin film by voltage can be formed on a glass / ITO substrate suitable for a display element, and the phase transition can be efficiently caused. As described above, it is possible to form an organic thin film on an arbitrary substrate while controlling the optimal molecular orientation or crystal orientation, so that an electronic element, a display element, an optical information recording medium,
Practical application of nonlinear optical elements can be expected. Therefore, the organic thin film element of the present invention has an extremely large industrial value.

Next, an example using an amorphous organic thin film made of a molecule having a steroid skeleton will be described.

Example 2-15 Except that a molecular orientation control layer having an amorphous structure of cholic acid was formed instead of the molecular orientation control layer having an amorphous structure of OXD-S4 molecules, the same procedure as in Example 2-2 was carried out. When an organic thin film element was obtained by the above method, a better evaluation was obtained.

Example 2-16 The procedure of Example 2-3 was repeated, except that a molecular orientation control layer having an amorphous structure of cholic acid was used instead of the molecular orientation control layer having an amorphous structure of OXD-S4 molecules. When an organic thin film element was obtained, a better evaluation was obtained.

Example 2-17 Example 2-17 was repeated except that a molecular orientation control layer having an amorphous structure of methyl cholate was formed instead of the molecular orientation control layer having an amorphous structure of OXD-S8 molecule.
When an organic thin-film element was obtained in the same manner as in No. 3, a better evaluation was obtained.

Example 2-18 Instead of forming a molecular orientation control layer having a polypyrrole amorphous structure with a film thickness of about 50 nm using ClO ₄ ⁻ as a dopant ion by electrolytic polymerization, amorphous cholic acid was formed by vapor deposition. An organic thin film device was obtained in the same manner as in Example 2-9, except that a molecular orientation control layer having a structure was formed. As a result, even better evaluation was obtained.

Example 2-19 The procedure of Example 2-10 was repeated, except that a molecular orientation control layer having an amorphous structure of cholic acid was formed instead of the molecular orientation control layer having an amorphous structure of OXD-S8 molecule. When an organic thin film element was obtained by the above method, a better evaluation was obtained.

Example 2-20 Instead of the molecular orientation control layer having an amorphous structure of TCTA molecules, a molecular orientation control layer having an amorphous structure of cholic acid was formed to obtain an organic thin film element. In the same manner as in Example 2-11, except that an insulating layer made of cholic acid having a thickness of 50 nm and an insulating layer made of polyisobutyl methacrylate having a thickness of 20 nm were formed instead of the insulating layer made of polyisobutyl methacrylate, An organic thin-film element having the following was obtained, and a better evaluation was obtained.

Example 2-21 The procedure of Example 2-12 was repeated, except that a molecular orientation control layer having an amorphous structure of cholic acid was formed instead of the molecular orientation control layer having an amorphous structure of OXD-S4 molecules. When an organic thin film element was obtained by the above method, a better evaluation was obtained.

Example 2-22 The procedure of Example 2-13 was repeated, except that a molecular orientation control layer having an amorphous structure of cholic acid was formed instead of the molecular orientation control layer having an amorphous structure of OXD-S4 molecules. When an n-channel field-effect transistor was obtained, better evaluation was obtained.

Example 2-23 The procedure of Example 2-14 was repeated, except that a molecular orientation control layer having an amorphous structure of cholic acid was formed instead of the molecular orientation control layer having an amorphous structure of OXD-S4 molecules. As a result, a better evaluation was obtained.

[0309]

According to the present invention, a high third-order non-linear susceptibility, a high response speed, and a high-order nonlinear susceptibility can be obtained by forming an electric field in the light control element having an intensity smaller than that required for the light control layer to undergo phase transition. Can be realized at the same time. In addition, this makes it possible to realize an optical modulation element such as an ultra-high-speed optical switching element, an optical logic element, and the like, and also allows the element to be miniaturized. Further, an optical logic element having a two-dimensional parallel processing function, An optical computer or the like can be constructed.

Further, according to the present invention, the material and
Regardless of the shape, the structure and molecular orientation of the organic thin film can be controlled, and an organic thin film element that can be practically used as an optical element, an electronic element, or the like can be obtained.

[0311]

[Brief description of the drawings]

[0312]

FIG. 1 is a cross-sectional view illustrating an example of a light control element of the present invention.

[0313]

FIG. 2 is a diagram showing NI transition of a crystal due to application of an electric field.

[0314]

FIG. 3 is a graph showing the relationship between the electric field strength and the third-order nonlinear susceptibility χ ⁽³⁾ in the NI transition.

[0315]

FIG. 4 is a graph showing a relationship between input light intensity and output light intensity in the optical bistable element according to the present invention.

[0316]

FIG. 5 is a sectional view showing another example of the light control element of the present invention.

[0317]

FIG. 6 is a diagram illustrating a configuration of an optical shutter using the light control element of the present invention.

[0318]

FIG. 7 is a diagram for explaining the principle of a Mach-Zehnder interferometer type waveguide device using the light control device of the present invention.

[0319]

FIG. 8 is a view for explaining the principle of a directional coupler type waveguide element using the light control element of the present invention.

[0320]

FIG. 9 is a view for explaining the principle of an etalon using the light control element of the present invention.

[0321]

FIG. 10 is a graph showing a relationship between an incident light intensity and an output light intensity in the light control element according to the first embodiment of the present invention.

[0322]

FIG. 11 is a schematic sectional view showing a light control element according to a sixth embodiment.

[0323]

FIG. 12 is a schematic cross-sectional view illustrating a light control element according to a seventh embodiment.

[0324]

FIG. 13 is a schematic view illustrating a directional coupling type waveguide element according to an eighth embodiment.

[0325]

FIG. 14 is a schematic diagram illustrating a Mach-Zehnder waveguide device according to a ninth embodiment.

[0326]

FIG. 15 is a schematic view showing an example of the structure of the organic thin film element of the present invention.

[0327]

FIG. 16 is a schematic view showing another example of the structure of the organic thin film element of the present invention.

[0328]

FIG. 17 is a schematic view showing still another example of the structure of the organic thin film element of the present invention.

[0329]

FIG. 18 is a schematic view showing still another example of the structure of the organic thin film element of the present invention.

[0330]

FIG. 19 is a schematic view showing another example of the structure of the organic thin film element of the present invention.

[0331]

[Description of sign]

 2 ... electrode layer 3 ... first insulator layer 4, 114, 134, 135 ... light control layer 5 ... second insulator layer 6 ... second electrode layer 7, 117, 152 ... molecular orientation control layer 41 ... Substrate 51 ... Gate electrode 52 ... Source electrode 53 ... Drain electrode 61,62 ... Polarizer 63 ... Optical Kerr cell 64 ... Optical shutter 66 ... Control light 67,76,84 ... Output light 71,72,73,83,92 ... Signal light 74, 75, 143, 144 ... Branch 81, 82, 132, 133 ... Arm 91 ... Etalon 111, 131, 141, 151 ... Quartz substrate 112, 116 ... Electrode layer 113, 115, 156, 157 ... Insulator Layers 118, 119 Prisms 128, 129 Gratings 134, 135 Optical control elements 136, 148 Directional coupler type waveguide element 137 Input section 138 Output 142 and 145 ... guide 146, 147 ... optical control device 154 ... organic thin film 155 ... transparent electrode 158 ... semi-transparent electrode

Claims (19)

[Claims] A first electrode layer formed on the substrate; a first insulator layer formed on the first electrode layer; and a first electrode layer formed on the first electrode layer. A light control layer including the formed electron donating organic compound and the electron accepting organic compound, a second insulator layer formed on the light control layer, and a light control layer formed on the second insulator layer. A second electrode layer, and means for applying, to the light control layer, an external electric field having a strength less than that required for the light control layer to undergo a phase transition. An optical control element for inducing charge transfer excitons. 2. The light control device according to claim 1, wherein a signal light is incident on the light control layer. 3. The light control element according to claim 2, further comprising control light irradiation means for irradiating the light control layer with control light for controlling the output intensity of the signal light. 4. The light control layer is substantially composed of an alternately stacked charge transfer complex crystal in which the electron donating organic compound and the electron accepting organic compound are alternately stacked, and is formed by applying a predetermined electric field. The light control element according to claim 1, wherein a ionic-ionic phase transition occurs. 5. The light control device according to claim 1, wherein at least one of the first and second insulator layers has light transmittance. 6. The light control element according to claim 2, further comprising: means for causing signal light to enter the light control layer from a direction parallel to the main surface of the substrate. 7. An alignment control film is further provided between at least one of the first insulator layer and the light control layer and between at least one of the second insulator layer and the light control layer. The light control element according to claim 1, wherein: 8. The light control device according to claim 7, wherein the alignment control film is formed of an amorphous organic film. 9. The organic thin film element according to claim 8, wherein the molecular orientation control layer made of the amorphous organic thin film contains a molecule having a steroid skeleton. 10. The organic thin film element according to claim 8, wherein the molecular orientation control layer made of the amorphous organic thin film contains a low molecular dye molecule having an aromatic ring in the outermost shell of the molecular structure. . 11. The organic thin film element according to claim 8, wherein the molecular orientation control layer formed of the amorphous organic thin film includes a polysilane derivative having a structure in which a main chain of polysilane is oriented parallel to a substrate surface. . 12. The organic thin film element according to claim 8, wherein the molecular orientation control layer made of the amorphous organic thin film has a structure in which different kinds of amorphous organic films are stacked. 13. A support layer, a molecular orientation control layer composed of an amorphous organic film provided on the support layer, and a crystalline organic thin film composed of π-electron molecules provided on the molecular orientation control layer. The crystalline organic thin film is formed by a vacuum deposition method at a growth rate of 100 Å / min or less, and has a thickness of at least one molecular layer and no more than 2 molecular layers.
An organic thin-film device having a thickness of not more than 000 angstroms. 14. The organic thin film element according to claim 13, wherein the crystalline organic thin film made of the π-electron-based molecule has a structure in which thin films of different kinds of organic molecules are stacked. 15. The organic thin film device according to claim 13, wherein the crystalline organic thin film made of the π-electron-based molecule is made of an organic charge transfer complex crystal. 16. The support layer is a first insulating layer,
A first electrode layer provided on the first insulating layer, a second insulating layer provided on the crystalline organic thin film made of the π-electron molecule, and a second insulating layer provided on the second insulating layer. The organic thin-film element according to claim 13, further comprising a second electrode layer. 17. The organic thin film element according to claim 13, wherein the crystalline organic thin film has a function of generating photovoltaic power or photocurrent by light irradiation. 18. A laminated structure including an insulating film, a molecular orientation control film composed of an amorphous organic thin film, a gate electrode, and a crystalline organic thin film composed of π-electron molecules in a channel region between source and drain regions of a semiconductor substrate. An organic thin film element, wherein the crystalline organic thin film is formed by a vacuum deposition method at a growth rate of 100 Å / min or less, and has a film thickness of 1 molecular layer or more and 2000 Å or less. 19. A molecular orientation control layer comprising an amorphous organic film formed on the surface of a support layer is prepared, and one or more molecular layers are formed on the amorphous organic film by a vacuum deposition method at a growth rate of 100 Å / min or less. A method for manufacturing an organic thin film element, comprising forming a crystalline organic thin film having a thickness of 2000 Å or less.