JPH01726A - Deposited film formation method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of the Invention The present invention relates to a method suitable for forming a carbon-containing deposit (I+2).

[Prior Art] For example, ion beam evaporation method, R)I plasma CVD method, microwave plasma CVD method 1 reactive sputtering method is used to form die V mont gJIFI.

The ion plate ink method, the photo-CVD method, the tungsten wire filament method, and the like have been tried, and among these, it has been reported that a diamond thin film was successfully synthesized by the microwave plasma CVD method and the tungsten wire filament method.

To form diamond thin LiQ using these methods, hydrocarbons (C114, C2116, etc.) and 1
A mixed gas with No. 12 is introduced into a film forming space for forming a deposited film on the substrate-H, and microwave plasma is generated, or a tank wire filament placed near the substrate is heated to red-hot carbonization. Radicals are generated by the decomposition of hydrogen and 112, and these radicals reach the surface of the substrate and deposit a film.

In this case, the conditions for the deposited film to become a diamond film are as follows: the concentration of hydrocarbons is 1% or more, the substrate temperature is 700°C to 1%.
000°C.

However, the deposited films formed by these methods contain a graphite structure in addition to the tire mont structure, which deteriorates the properties of the film.

This is due to the fact that hydrocarbons are used as raw materials.
Because the agglomeration reaction in the gas phase is active, and because hydrocarbon radicals that adhere to the deposition surface do not diffuse over the deposition surface for 4 minutes, they do not necessarily adhere to sites with low potency or roughness. It is conceivable that because the diamond particles adhere randomly and without a diamond structure, it becomes easier to form a structure other than a diamond structure.

Furthermore, since hydrocarbons and H2 are activated by the same activation means, it is difficult to control the amount of radicals from both, 3IfH.

For this reason, only the amount of radicals can be optimized, making it difficult to perform film formation operations and improve film properties.

[Invention or Problems to be Solved] The present invention aims to solve the above-mentioned conventional problems and provide a deposited film forming method that can efficiently form carbon-containing deposited II films such as diamond thin films with high purity. It has been done.

The present invention is also suitable for increasing the area of the film while improving the characteristics of the formed film, IO#J film speed, reproducibility, and uniform film quality, improving the productivity of the film, and mass production. Contribution that can be easily achieved! ! This was done to provide a method for forming the structure.

[Step to Solve the Problems] The method for forming a deposited film provided by the present invention uses an active compound generated from a compound containing carbon and halogen in a film forming space for forming a deposited film on a substrate. A seed and an active species generated from a film-forming raw material that chemically interacts with the active species are separately introduced, and heated to form the active species of the fourth, fifth, and sixth periods of the periodic table. By reacting with a catalyst of a metal or metal compound selected from the group of elements,
The method is characterized in that a deposited film is formed on the substrate.

In the unreleased +51 method, instead of generating plasma in the film forming space for forming the deposited film, a heated metal catalyst is used to excite the film forming raw material gas and cause it to react, so the deposited film that is formed is There is substantially no effect on T4 due to etching effects or other abnormal discharge effects.

One of the differences between the method of the present invention and the conventional deposited film forming method is that
The method is to use a compound containing carbon and halogen as a raw material. The active species generated from this compound are weakly reactive, so reactions in the gas phase can be suppressed. In addition, the reactivity on the film-forming surface is also weak.

Radicals can be widely diffused over the film-forming surface and adhere to the most stable sites. As a result 1, for example, a deposited carbon film having only a diamond structure can be easily formed.

Another difference between the method of the present invention and conventional film forming methods is that active species activated in advance in a space different from the film forming space (hereinafter referred to as the decomposition space) are used. This makes it possible to dramatically improve the properties compared to conventional film formation methods, and in addition, it is possible to further lower the substrate temperature during deposition film formation, making it possible to achieve stable film quality.
Membranes can be provided industrially in large quantities at low cost.

In the present invention, the active species from the decomposition space introduced into the film forming space has a lifespan of 0.01 seconds or more, more preferably 0.1 seconds or more, from the viewpoint of productivity and ease of handling. is selected and used as desired. At least one of these active species (A) and (B) constitutes the main component constituting the deposited film formed in the film forming chamber. Also, the active species (A) and (B)
are separately introduced into the film forming space from the decomposition space and selected from the heated elements of the fourth period, fifth period, and sixth period of the periodic table. Chemical interaction between the active species (A) and the active species (Is) is promoted by the action of the metal catalyst.

In the present invention, the compound containing carbon and halogen introduced into the decomposition space is, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon are replaced with halogen atoms. is 1, for example, CuY2u+
Chain halogenated carbon, CvY, represented by t (u is an integer of 1 or more, Y is F, C1, Or, and summer)
2v (v is an integer of 3 or more, Y has the above meaning.)
Cyclic silicon halide, CuH, YV (u and Y have the above meanings. x+y=2u or 2u+
It is 2. ), and the like.

For example, CF4. (CF2)S, (CF2)
6゜(CF,),, C2F,, (::lF,l,
C11F+, C112F2. CCl2 (CC12)5
゜CRra+ (L:Brz)s+ 02CI6.
Examples include those that are gaseous or can be easily gasified, such as C2CIJ-J.

Furthermore, in JJ, in addition to the active species generated by decomposing the compound containing carbon and halogen,
Active species generated by decomposing compounds containing silicon and halogen can be used in combination. As the compound containing silicon and halogen, for example, a compound in which some or all of the hydrogen atoms of a chain or cyclic silane compound are replaced with halogen atoms is used, and specifically, for example, S! u
Z2u or 2 (U is an integer greater than or equal to 1, Z is F, CI, B
r, and I. ) chain silicon halide, S! Cyclic silicon halide represented by vZav (V is an integer of 3 or more, Z has the above-mentioned meaning),
s;uu,z, (u and Z have the above meanings.

X+y=2u or 2u+2. ), and the like.

Specifically, for example, SiF+, (SiF2)s, (S
! P2) an(SiF2)<, 5iJs, Si, 3
Fs, 5iHFi, 5ill□F,, 5iC14゜(Si(:12)s, 5iBr,, (SiBr2)
,, Gaseous such as 5i2Cla+ 5i2CI3F3! The answer to A is whether it can be easily gasified.

In order to generate active species, in addition to compounds containing carbon and halogen (and compounds containing silicon and halogen), if necessary, other silicon compounds such as silicon cloth, hydrogen, and halogen compounds (e.g. F2 gas, C1 gas, gasified Br2.L, cap), etc. can be used in combination.

The film-forming raw material gas used in the method of the present invention includes hydrogen gas and/or saturated hydrocarbons having 1 to 5 carbon atoms, and ethylene hydrocarbons having 2 to 5 carbon atoms. , acetylenic hydrocarbons with carbon'pj2 to 4, etc.
Specifically, saturated hydrocarbons include methane (CIL),
Ethane (C2116), propane Cct++a), n
-butane (n Gjlto), pentane (Csll+
2) As the ethylene hydrocarbon, ethylene (ct
n4), propitz:/ (CAL), butene-1 (
C4H6), Buty:/-2(C4H6), Isobuty L
/ :/ (C, +ll5), pentene (Csll+2
), acetylene hydrocarbons include acetylene (C
'211. ), methylacetylene (CiN4), silane ((:, +116), etc., and gases such as CH3F, CH:ICI, etc. in which some of the H of these is replaced with halogen, or Si and H as constituent atoms. 5itln.

5i2Ha, Si:+lla and 5iH3(:l,
Hydrogen-rich halogenated silanes such as SiH3F and 5iH3Br.

G e Ha and Ge1 whose constituent atoms are Ge and H
Halogenated germane containing a large amount of hydrogen such as lzC1, Ge1liF, Ge113Br, or ammonia (NH:l), hydrazine (11
2N N I+ 2 ), hydrogen azide (N!lz),
Ammonium azide (NHJz) # can be gaseous or gasified. Nitrogen hydride or the like is used as necessary.

In addition to these film-forming raw material gases, inert gases such as helium, argon, and neon, or depending on the film to be formed, N2.02, F2, C
+a, Br2.12, etc. can also be added.

When using multiple of these raw material gases, they can be mixed in advance and introduced into the activation space, or they can be separately supplied from independent sources and then introduced into the activation chamber. It can also be introduced.

In the present invention, as a method for generating active species between one decomposition chamber, the discharge energy,
Excitation energy such as thermal energy or light energy is used.

Active species are generated by adding decomposition energy such as heat, light, or electric discharge to the above-mentioned decomposition space.

In the present invention, active species (B
) is determined as desired depending on the deposition conditions, the type of active species, etc., but preferably Zoo: 1
'~1:too (introduction flow rate ratio) is appropriate, and more preferably lO:1~l:ioo.

It is also possible to dope the deposited film formed by the method of the invention with impurity elements. The impurity elements to be used include, as p-type impurities, elements of group A of the periodic table, such as B, AI, Ga, and In.

TI'5 is mentioned as a suitable one, and n-type impurity and 1
For example, P is an element of Group V A of the Table of Contents.

As, Sb, Ri, etc. are preferred, and especially fA, Ga, P, Sb, etc. are most suitable.

The concentration of impurities to be doped is determined as appropriate depending on the atmospheric and optical characteristics to be applied.

As a compound containing such an impurity element as a component, a compound that is in a gaseous state at room temperature and normal pressure, or at least a gaseous state under deposited film formation conditions, and that can be easily vaporized with an appropriate vaporization device should be selected. Delicious. Such compounds include PII+.

P2114. PF:l, PF5. r'cIyu,
As11. , AsFff, AsF5. AsCl
3.5bll, SbF5,5illi, RF3.
RC13, BRr+, 82116184Hto,
85119. B511++, t1611+o, R6
113g, AlCl:+ or (Cl7), AI
, ((:H*):+Ga, Kasa's organic metals, etc.) Compounds containing impurity elements can be used even if one type is used.
It may be used in combination with seeds.

In order to introduce a compound containing an impurity element as a component into the film forming space, it must be mixed with the film forming raw material gas or the raw material gas for creating active species, etc., or introduced from multiple independent gas supply sources. It is also possible to introduce each of these raw material gases individually.

The catalyst used in the present invention selected from the elements of the 4th period, 5th period, and 6th period of the periodic table should be selected from those that are difficult to mix into the deposited film due to sputter linking, sublimation, scattering, etc. It is also desirable to use these °C
When activating, it is necessary to choose activation conditions that do not easily cause contamination.

Examples of such materials include metals, alloys, metal oxides, and metal chlorides of elements in the 4th, 5th, or 6th period of the periodic table, and among these, ■, ■ , ■, transition metals belonging to groups ■, in some cases 1. Non-transition total dielectric materials of the n and m groups or oxides thereof can be suitably used.

Specifically, for example, Ti, Nd, Cr, Mo,
W, Fe.

Ni, Go, Rh, Pd, Mn, Ag, Z
n, (:d, W, Ta, PL, Pd-Ag, Ni
-Cr, TiO2, NiO, 705, PdClt, R
Examples include hCl:++TiCl4.

In addition to resistance heating by directly applying electricity to the catalyst material, activation conditions include a method in which the catalyst is packed in a quartz tube or the like and indirectly heated from the outside using an electric furnace, an infrared furnace, etc.

The shape of the catalyst can be selected from among granules, fine metal particles attached to a porous carrier, filaments, meshes, tubes, and honeycombs, so that precursors and/or active species can be It is possible to change the cross-sectional area of the formation, control the reaction between the precursor and the active species, and create a uniform deposited film.

Next, the present invention will be explained by giving a typical example of an electrophotographic image forming member formed by the method of the present invention.

FIG. 1 and FIGS. 2(a) and 2(b) are schematic diagrams for explaining an example of the configuration of a typical photoconductive member obtained by the present invention.

In these figures, the reference numeral 11 indicates a photoconductive layer, the reference numeral 23 indicates a charge transport layer, 22 a charge generation layer, 1
2 and 24 are supports, 21 is a surface layer, and 25 is a charge barrier! L
It is a layer.

The film mainly composed of charge transport layer 23 may be amorphous or may contain at least a part of a crystal structure such as a diamond structure, but the Raman spectrum of 1333 cm- If there is a carbonaceous film constituting the charge transport layer or a film close to diamond polycrystalline containing a large amount of perfect diamond structure, it is desirable to at least partially contain a structure characterized by Stokes lines in the region containing '. The charging property, sensitivity, surface hardness, durability, etc. of an electrophotographic photoreceptor can be improved.

In addition, carbonaceous films may be colored depending on the film formation conditions, but regardless of whether the resulting film is amorphous or crystalline, the flow rate of fluorine, hydrogen, or other halogen element molecules during film formation is Coloring can be reduced by increasing the ratio.

The carbonaceous film constituting the charge transport layer 23 is doped with atoms belonging to Group Ⅰ or Group V of the periodic table as semiconductor impurities to improve its characteristics! I can do it. Such doping with Group 1 or Group V atoms increases the chargeability when the electrophotographic photoreceptor of the present invention is used with positive or negative charging, improves the sensitivity, and has the effect of lowering the residual potential (71). There is.

This is due to the doping of these atoms in the charge transport layer 23.
This is thought to be due to a change in the concentration of charge carriers or a change in the transportability of charge carriers. Since this change is relatively gradual, it is easy to control. The amount of these atoms added is preferably in the range of 5 ppm or more and 5 atomic % or less, and more preferably in the range of 50 ppm or more and 5 atomic % or less. These conditions will be described in more detail in the Examples. Atoms belonging to Group 1 include B, AI,
Examples include Ga, In, and TI. Group V elements include N, P, and ^S.

Sb and Bi k are listed as I'f. manufacturing stability,
In terms of cost and effectiveness, N, P, B, AI, etc. are particularly desirable.

The thickness of the charge transport layer 23 can be appropriately selected depending on the conditions of use, etc., but it is preferably IJLm or more and 1 or more and 10 or more, and if it is less than 17Lm, a satisfactory visual image density may not be obtained by ordinary developing methods. This is because if it exceeds 1100p, the residual potential will be too large, which may cause problems in the time required for film formation, adhesion to the support, etc. A more preferable range between the layers is 5 gm or more and 4150 gm or less. In this range, the usage conditions are not only easy to use, but also the image density tends to be higher even if the film thickness is thinner than that of conventional photoreceptors, which is advantageous for reducing manufacturing costs.

When the carbon-based film of the electrophotographic photoreceptor of the present invention is used as the charge transport layer, the charge generation layer 22 may have any conventionally known structure as long as it has photoconductivity6.
For example, examples include a film with a thickness of about 0.5 to 201 Lm mainly composed of A-9i:II formed by plasma CVD, and a film further containing Ge and C1. According to the present invention, such charge injection from the charge generation layer to the charge transport layer can be performed satisfactorily.

In the above example, a carbon-based film with excellent charge transport ability and high electrical resistance (reciprocal of electrical conductivity), which was prepared under the conditions described in the example below, is used as the charge transport layer. Therefore, the charge generation layer 22 can have a lower resistance than that in conventional electrophotographic photoreceptors. Specifically, for example, the electrical resistance value may be about IQ-100 cm or less. Therefore, it becomes possible to use materials that have been difficult to use due to their high photoconductivity but low resistance, and extremely high sensitivity can be obtained.

Furthermore, when the carbon-based film of the present invention is used as the photoconductive layer shown in FIG.
It is preferable that it is ΩC irises-1.

The supports 12 and 24 of the electrophotographic photoreceptor of the present invention are supports and may be made of an insulator or a conductor as long as the mechanical strength of C is satisfied. The sides of the bodies 12 and 24 that contact the photosensitive layer are preferably treated to be conductive. Examples of the conductive support include AI and Fe.

Ni. Stainless steel, Sn, Zn, Cr, Mo, Ti,
Metals such as Ta, W, Au, Ag, Pt, Si, Ge,
Graphite etc. can be used. The surface of the conductive support may be coated with a conductive substance other than the support metal for the purpose of improving the adhesion of the photosensitive layer or for other purposes. Insulating supports include polyester, polyurethane, polycarbonate, polystyrene, polyamide, and PEi.
In addition to organic polymers, inorganic materials such as glass and ceramics can also be used. The size and shape of the support can be freely selected depending on the intended use of the electrophotographic photoreceptor of the present invention.
Anything can be used, such as a small card-like object that can fit in the palm of your hand, a cylindrical object, or a belt-like object.

In the case of the electrophotographic photomaterial shown in FIG. 2(a), it is usually desirable to provide a surface layer 21. In particular, when the charge generation layer 22 is A-3 i:H, the surface layer 21 It is desirable to have a The surface layer 21 can be made of various materials as long as it is transparent to some extent in the visible light range and has low electrical conductivity.For example, A-3iC formed by plus 7CVD.
(If), A-3iN(H), or the like may also be used. Further, a layer mainly composed of carbon that can be used for the charge transport layer 23 may be used, and in that case, it is desirable that the optical band gap is preferably 2, OcV or more. The electrical conductivity and fluorine content are not particularly limited as long as they satisfy the characteristics required for the surface layer 21. Furthermore, the surface layer 21 may contain hydrogen or other halogen elements in addition to C and Si. The halogen element may be contained only near the free surface of the surface layer, or may have a concentration gradient from the surface to the sea surface with the charge generation layer 22.

In the case of the electrophotographic photoreceptor shown in FIG. 2(b), it is preferable to provide a charge injection blocking layer 25 between the 'It charge generation layer 22 and the support 24. This further improves charging ability and further prevents defects in image quality. As the charge injection blocking layer 25, A-3i(H,X) doped with impurities by plasma CVD can be used. @When using the light body with positive charging, the charge injection blocking layer 25 is py! li, n when used with negative charge
It's best to dope the mold. If the p-type is to be used, use B, a group II atom such as AI, or if the n-type is to be made, use N or P.

Group V atoms such as As are suitable as Dobbinck materials.

3]〉4 is a PIN using an a-C deposited film doped with an impurity element produced by carrying out the method of the present invention
1 is a schematic diagram showing a typical example of a type diode device.

In the figure, 31 is a substrate, 32 and 37 are thin film electrodes, 33 is a semiconductor film, an n-type a-9i (H, X) layer 34, an i-type a-8i (It, X) layer or a-3i :Ge(It,X
) layer 35. It is composed of a p-type a-C(H,X) layer 36. 38 is a conductive wire connected to an external electric circuit device.

As the base 31, a conductive, semiconductive, or electrically insulating material is used. If the base 31 is conductive, the thin film electrode 32 may be omitted. Examples of the semiconductive substrate include Si and Ge.

Examples include semiconductors such as GaAs, ZnO, and ZnS. @
For example, the membrane electrodes 32.37 include NiCr, AI
, Cr, Mo.

＾u, Ir, Nb, Ta, V, Ti, Pt
, Pd, +n201+SnO2, ITO(In
It is obtained by applying a thin film such as tOi + SnO, ) to the substrate 31.1 by vacuum evaporation, electric T-beam evaporation, or sputtering process. A thin film having a center area of 32.37 is preferably 30 to 5×10, more preferably 10 to 5×10.

PIN type diode, thin film electrode 33 or 37 when the device is used as a solar cell or a light sensing device
At least one of them must be transparent or translucent.

To form the a-3i (H,

By the plasma glow discharge decomposition method of Si, 111g or a mixed gas of SiF4 and H2, or by the method of plasma glow discharge decomposition of Si, 111g or a mixed gas of SiF4 and H2, or by the method of plasma glow discharge decomposition of Si, 111g or a mixed gas of SiF4 and H2, or by the method of plasma glow discharge decomposition of Si, 111g or a mixed gas of SiF4 and H2.
Active species (A) generated by decomposing a compound containing silicon and halogen described in 869 in an activation space
It is generated by decomposing a film-forming chemical substance that chemically interacts with the active species (^) in a separate activation space.

The film can be formed by separately introducing the active species (B) and causing a chemical reaction.

In addition, in order to form an n-type a-3i layer, at the time of layer formation,
It is formed by mixing an n-type impurity-containing gas with a source gas.

To form a p-type a-C (It, The activated active species generated by decomposing the gas of the compound containing impurity elements as components in the activation space are introduced into the film forming space, and the introduced compound containing carbon and halogen is classified as The substrate 3 is activated by the catalytic action of a mesh-like or honeycomb-like member made of metals from the period to the sixth period, and chemically reacts with the active species introduced from the activation space.
A deposited film is formed on 1. n-type a-3i (!l,
) and the layer thickness of the p-type a-C(II,X) layer,
Preferably 50-104 people, more preferably 200-2
A range of 000 people is desirable.

Further, the thickness of the i-type a-3i (H,X) layer is preferably 500 to 104, more preferably 1000 to
A range of 10,000 people is desirable.

In addition, in order to take advantage of the characteristic of a-C (!I, to form.

No. 41A is an example of an apparatus for depositing a carbon film by the deposition method of the present invention.

In FIG. 4, 101 is a film forming chamber, and a desired substrate 103 is all placed on a substrate support stand 102 inside.

104 is a heater for heating the substrate;
4 is used when heating the base 105, and a conductive wire 105
Power is supplied through the device and generates heat.

A thermoelectric element 106 monitors the substrate surface temperature and feeds back the result to the heater 104 to maintain the desired temperature.

107.111 and 118 are gas supply pipes, which contain raw material gas for active species generation, gas for film formation, inert gas used as necessary, and the type of gas for compounds containing impurity elements as components. Established accordingly. If these gases are used in liquid form, an appropriate vaporization device is provided.

108 and 119 are activation chambers for generating active species. 109 and 120 are energy sources for generating active species. 112 is a catalyst made of molybdenum molded into a honeycomb shape, and is supplied with electricity via a conductive wire 113.
I get a fever. Raw material gas for generating active species supplied from gas introduction pipes 107 and 118 is activated by activation energy sources 109 and 120 in activation chambers 108 and 119, and the generated active species are passed through the introduction pipes. It is introduced into the film forming chamber 101 through 110 and 121.

112 is a metal catalyst composed of elements from period 4 to period 6 of the periodic table, molded into a honeycomb shape or filament shape, and is supplied with electricity through a conductor 113.
I get a fever. 114 is a gas pressure gauge.

Further, in FIG. 1, 116 is an exhaust valve, and 115° and 117 are exhaust pipes.

(Example 1) Using the film forming apparatus shown in FIG. 4, a quartz glass substrate 103 on which an amorphous carbon film was formed by the following procedure was placed on a support stand 102. The substrate was heated to about 300°C.

Evacuate the inside of the film forming chamber 1O1 using an exhaust device to reduce the temperature to about 10-6
The pressure was reduced to 7 orr. Next, a conducting wire 11 is attached to a honeycomb-shaped molybdenum 112 as a catalyst placed in the film forming chamber 101.
3, and make it red hot. Gas supply pipe 107
H2 gas 50 sec, or P113 gas or B211. Gas (all 1000pp■Hydrogen gas dilution)
11□ gas la flow rate 80 sec mixed with 3 sec
- was introduced into the activation chamber 119. The activation chamber 119 is made of a quartz glass tube. A microwave plasma generator is installed around the quartz tube. Plasma is generated in the quartz glass tube by applying microwave as an activation energy source 120, and 2 gas, B 2 II r, gas, PH gas, is decomposed, and .H radical, B11.
, generates pHv radicals and injects t&
was introduced into the membrane chamber.

On the other hand, the activation chamber 108 is filled with 0 solid grains and heated with an electric furnace as the activation energy source 109.
Maintain the temperature at 00°C to make C a red-hot state, and introduce the inlet pipe 107 there.
40 sec of CF4 gas from a cylinder (not shown)
By blowing in CF' radicals are generated as active species, and the CF' radicals are introduced into J
JIi was introduced into the membrane chamber 101. While maintaining the pressure in the film forming chamber 101 at 0.5 Torr, each gas was flowed for about 60 minutes while maintaining the above conditions, and undoped or doped i-type and N-type and P-type carbon were formed on the quartz substrate. A membrane was formed. The thickness of each film was approximately 5,000. As a result of Raman spectroscopy,
I-type, N-type, and P-type films are all 1600cm-', 1360c
There was a broad peak at m-', indicating that it was amorphous. Eight liters per model of the obtained i-type, N-type, p5 carbon
When the dark conductivity of the i-type carbon film was measured using a comb-shaped gap electrode, it exceeded the measurement limit, and σ< l 0-
It was 14S 7cm. In addition, the dark conductivities of the N-layer and P-type carbon films are ~l10-6SeC and ~1O-7S/, respectively.
The conductivity types determined by cII thermoelectromotive force were N-layer and P-type, respectively.

(Example 2) A PIN type diode shown in FIG. 3 was manufactured using the apparatus shown in FIG. 4.

First, 1000 ITO films were mounted on a quartz glass substrate using a spouter device, and then placed on a support stand 102 in a film forming chamber lot. After that, after reducing the pressure to 10-6 Torr,
A conductive wire 1 is connected to a filament-shaped metal catalyst 112 made of Ta.
13 to make it red hot. Further, the temperature of the substrate 103 was set to 250° C. by a heater 104 embedded in the support base 102. After the surface temperature of the base 103 reaches a certain desired temperature, 305 ccs of C, F6 gas is introduced from the gas introduction pipe 107 into the activation space 10B made of a quartz glass tube.The area around the quartz glass tube is activated. A microwave plasma generation furnace is installed as an energy source 109, and plasma can be generated in the quartz glass tube by applying microwaves. Apply 300W microwave to generate plasma,
CF...''(n<3) radicals were generated, and the CF-radicals were introduced into the film forming chamber lot via the radical transport pipe 110.

In addition, from the transport pipe 118, R21t diluted to 1000111111 with R2 and gas at 80 sccm are transferred to the activation chamber 119.
A microwave electric field of 500 W was applied to generate ・H radicals.

BH, radicals were generated. The generated radicals were introduced into the film forming chamber 101. The pressure inside the film forming chamber 101 was set to 0.5 T.
The valve 116 was adjusted to 7A so that it was orr.

While maintaining the state described in L, let each raw material gas flow for about 5 minutes,
Approximately 300 p-type amorphous carbon films were formed on ITO.

After that, the power supply to the Ta filament is stopped, and after the temperature of the filament has sufficiently decreased, S
iF, gas 205 ec- was introduced into the activation space 108 made from a quartz glass tube. A 200W microwave was applied to generate plasma in the quartz glass tube, and 5iFn"
(n≦3) Generates radicals and radical transport pipe 110
5iFn'' radicals were introduced into the film-forming chamber lot through the.

Further, 30 sccm of R2 gas and 30 sccm of Ar gas were introduced into the activation space 119 from the gas introduction pipe 118. The activation space 119 is made of a quartz glass tube like the activation space 108, and a microwave plasma generating furnace is similarly installed around it as an activation energy source 120, and microwaves can be applied thereto. As a result, plasma can be generated. A microwave of 300 W was applied to generate plasma to generate atomic hydrogen radicals, which were introduced into the film forming chamber via the transport pipe 121. A vacuum valve 116 placed in the middle of the exhaust pipe was adjusted to maintain the pressure in the film forming chamber at 0.5 Torr. It was left in this state for 40 minutes. As a result, about 6000 undoped a-3i films were formed on the p-type a-C film. After that, P flood gas is mixed into the R2 gas so that the concentration ratio is 4oopp■, and about 40%
0 Ny! A fia-3i film was deposited. After that, 8g of gas was evaporated by the stack ring method using about 500 people onto a sample on which ITO/p-type a-Cv/non-doped a-si film/N-type a-3i film was formed on quartz glass. As a result, ITO/p-type a-C film/I-type a was deposited on a quartz substrate.
-s: A PIN diode made of WAlN type aN layer 8t film/Ag was formed.

A M l 100 of the formed 1'IN diode
The photoelectric conversion efficiency under mW/cm2 is pJ! where the P layer was created using the same method as the N layer (that is, it was created by mixing BzHa gas instead of PH3 gas). ! ! An improvement of about 25% was observed compared to a PIN diode using an a-3i film.

(Example 3) Using the film forming apparatus shown in Fig. 4, the following procedure was used to form a diamond Q film.
ll! 2 was formed. After using a 5i ((1) wafer puff-polished with diamond paste of 1/4 mm diameter as a substrate and installing it on a support stand 102, the inside of the film forming chamber lot was evacuated using an exhaust gas 9'a. , about 10 −6 Tor
The pressure was reduced to r.

By the heater 104 embedded in the support stand 102,
The temperature on the substrate 103 was set at 600'C. In addition, power is supplied to a filament-shaped tungsten 112 as a catalyst placed near the base 103 via a conductive wire 113.
Become red-hot.

11□ Gas 405ccI118 from gas supply pipe 118:
It was introduced into the activation chamber 119 and a microwave power of 800 W was applied to generate H radicals. The generated H radicals were introduced into the film forming chamber. In addition, CF2 gas was introduced into the reaction chamber 108 from the quartz glass tube at a rate of 15 sec through the gas supply pipe 107.The microwave plasma generating furnace as the activation energy source 109 was installed around the quartz reaction chamber 108, and the microwave was heated at 300W. CFn', (n≦3)
Radicals such as the following were generated and introduced into the film forming chamber 101 via the radical transport pipe 110. The pressure in the film forming chamber 101 was set to 30 T.
It was adjusted by the exhaust valve 116 so that

When this result was left for about 2 hours, a carbon film with a thickness of about 2.0 JL111 was deposited on the 5i (Ill) substrate.

When the created carbon film was examined by Raman spectroscopy, it was found to be 1332c.
There was a sharp peak at m-'. In addition, spout-like diffraction of (Ill) was observed in electron beam diffraction, indicating that it was a diamond thin film. SEM of generated diamonds
Observation of the image revealed that an extremely high quality diamond thin film with grains of i7p-m or more had been formed.

Example 4 Using the apparatus shown in FIG. 5, a drum-shaped electrophotographic image forming member having the layer structure shown in FIG. 1 was prepared by the following operations.

In the 5th UA, 440 is a film forming chamber, 421 is a compound gas introduction pipe for detecting carbon and halogen, 422 is an activation chamber, 4
23 is an activation energy source, 426 is an active species introduction tube.
In the first part, 431 is a mesh-like metal catalyst, 432 is a cylindrical substrate, 433 is an infrared lamp for heating the cylindrical substrate, and 434 is a reflecting plate. Also, 427.428 is H
2 gas introduction pipes, 435 and 436 are activation chambers, 43
7°438 is FI:l'l: conversion energy source, 429.
430 t-1 This is a transport tube for active species and has a shape in which the diameter widens toward the discharge port. 424 is an exhaust pipe.

An AI cylinder base 432 was installed in the film forming chamber 440. The film forming chamber 440 is evacuated to approximately 1× by a vacuum evacuation device (not shown).
It was evacuated to 107'Torr. Using molybdenum mesh as a metal catalyst, AI cylinder base 432 and about 1
They were placed in a circular pattern with a distance of cs. Molybdenum mesh 431 was heated to red heat by applying electricity.

The AI cylinder was rotated.

In addition, the infrared lamp 433 was turned on to heat the surface temperature of the ^11 portion 432 to about 300°C.

When the substrate temperature reaches a steady state of the desired temperature, 200 scc of CF4 gas is introduced into the Si through the gas introduction pipe 421.
F4 was introduced into an activation chamber 422 made of a quartz glass tube. A microwave plasma generation furnace is installed around the activation chambers 422, 435, and 436 as activation energy sources 423 and 437, and 438, and plasma is generated in the activation chamber 422 by applying microwaves. It can be caused. Apply 800W microwave and CF
, the SiF4 gas was decomposed to generate radicals such as CFn and SiFm (n, m<3). The generated radicals were introduced into the film forming chamber through the active species introduction pipe 426. In addition, H2 gas s is supplied from the gas introduction chambers 427 and 428.
o o sccm activation chambers 435, 436,
Microwave power tooow was applied to generate H radicals, which were introduced into the film forming chamber in a uniform flow from the discharge portions 429 and 430.

When this state was maintained for about 30 minutes, an electrophotographic photoreceptor made of SiCv and having a thickness of about 6 pm was formed in the shape of an A1 cylinder.

When the obtained electrophotographic photoreceptor was set in an experimental electrophotographic copying machine and its electrophotographic properties were measured, it showed good charging properties and photosensitivity. Subsequently, when it was negatively charged and developed with toner through imagewise exposure, a high-quality image was obtained.

When images were formed continuously, it was found that the drum had much better durability and stability against temperature, humidity, etc. than the conventional a-3i drum.

Example 5 Using the apparatus shown in FIG. 5, a drum-shaped electrophotographic image forming member having the layer structure shown in FIG. 2(a) was prepared by the following operations.

An AI cylinder base 432 was installed in the film forming chamber 440. The film forming chamber 440 is heated to about 1X 1O-6 using a vacuum evacuation device.
After exhausting to Torr, electric current was applied to the molybdenum mesh 431 to heat it to red heat. The AI cylinder was rotated.

The infrared lamp 433 was turned on, and the surface temperature of the AI substrate 432 was heated to about 300°C.

When the substrate temperature reached a steady state of a desired temperature, OF gas was introduced from the gas introduction pipe 421 into the activation chamber 442 of the quartz/glass tube portion for 250 sec+s. A microwave plasma generation furnace is installed around the activation chamber 422 as an activation energy source 423, and plasma can be generated in the activation chamber 422 by applying microwaves. Apply 800W microwave to decompose CF and gas, CFn'', (n≦3)
generated radicals such as The generated radicals were introduced into the film forming chamber through the active species introduction pipe 426.

In addition, 112 gas 5005 from gas introduction pipes 427 and 428
scs, I'lF: l gas (diluted to 1% with l gas) was introduced into the activation chambers 435, 436, and microwaves of 1000 W were applied to generate H radicals and BF3 radicals. The generated H radicals were introduced into the film forming chamber through the discharge portions 429 and 430 in a uniform flow. At this time, the internal pressure of the film forming chamber was adjusted to I Torr.

When this state was maintained for about 30 minutes, a charge transport layer 23 made of a C film having a thickness of about 6 JLm was formed in an A1 cylinder shape.

Next, the introduction of the gas to which the microwave was applied was stopped, and the power supply to the molybdenum filament 431 was stopped to prevent damage to the film forming chamber.
After sufficiently exhausting to about x 10”” Torr, SiF4 gas is introduced from the gas introduction pipe 421 to 1000 m.

sccm, gas introduction pipes 427, 428] 12 gases are introduced at 100 sccm into the activation chambers 435, 436, and microwave power of 300 W and 400 W is applied, respectively, to generate plasma and generate 5iFn and H radicals. did.

The generated 5iFn radicals and H radicals were each introduced into the film forming chamber. At this time, the internal pressure of the film forming chamber was set to 0.3 Torr.
I adjusted it so that Furthermore, the surface temperature of the At base cylinder remained at 300°C. This state was maintained for 5 minutes, and a layer of 5,000 thick a-
A charge generation layer 22 made of 3i:H(F) was formed.

Next, the application of microwaves and the introduction of gas were stopped, and the film forming chamber was again evacuated to I.times.10-' Torr, and then the molybdenum filament 431 was energized to become red-hot. The surface temperature of the At base cylinder remained at 300°C. CF gas at 300 sccm was introduced into the activation chamber 435 through the gas introduction pipe 421, and a microwave power of 500 W was applied to generate plasma. CFn was introduced into a radical film forming chamber. At the same time, the gas introduction pipe 427.
and from 428 (2) Gas was introduced into the activation chamber at a flow rate of 000 secg, and microwaves 1KW were applied to generate H radicals.

The generated H radicals were introduced into the film forming chamber. The internal pressure of the film forming chamber was adjusted to 0.6 Torr.

This state was maintained for about 3 minutes, and a surface protective layer 21 made of a diamond-like carbon thin film having a thickness of 1000 wafers was formed on the charge generation layer 22. After introducing gas, applying microwaves, energizing the metal catalyst, and turning off the infrared lamp, the vacuum is broken with the μ roller when the substrate has cooled down sufficiently, as shown in Figure 2 (a).
An AI cylinder on which an electrophotographic photoreceptor having the structure was formed was taken out.

The characteristics of the electrophotographic photoreceptor thus obtained were measured in the same manner as in Example 1, and it showed excellent characteristics, and was also far superior in durability and environmental resistance than the existing a-3i photoreceptor. Ta.

Example 6 Using the apparatus shown in Fig. 6, the second
A drum-shaped electrophotographic image forming member having the layer structure shown in Figure (b) was prepared. A1 cylinder base 43 is placed in the film forming chamber 440.
2 was installed. The film forming chamber 440 is heated to approximately I by a vacuum evacuation device.
After evacuation to X 10-'Torr, the molybdenum mesh 431 was heated to red heat by applying electricity. A
I rotated the cylinder.

The infrared lamp 433 was turned on, and the surface temperature of the AI substrate 432 was heated to about 300°C.

When the substrate temperature reaches the desired steady state, from the gas introduction pipe 421, OF, gas 50 sec + a, N
1 sccm of o gas is sent to the activation chamber 422 of the quartz glass tube section.
It was introduced in A microwave plasma generation furnace is installed around the activation chamber 422 as an activation energy source 423, and plasma can be generated in the activation chamber 422 by applying microwaves. 300
Apply W microwave to decompose CF and gas, and CFn
”, (n≦3). The generated radicals were introduced into the film forming chamber through the active species introduction pipe 426.

Also, H2 gas 50sec from gas introduction pipe 427.428
mBJ6 gas at 0.45secg+ in the activation chamber 435.
437, a microwave of 800 W was applied to generate H radicals and BHy radicals, and the generated radicals were introduced into the film forming chamber in a uniform flow from the discharge parts 429 and 430. At this time, the internal pressure of the film forming chamber was set to 0.8 Tor.
I adjusted the 3I to make it r.

When this state was maintained for about 2 minutes, a charge blocking layer 25 made of a C film having a thickness of about 300 mm was formed in the shape of a cylinder.

Next, the microwave application gas is stopped, the power supply to the molybdenum filament 431 is stopped, and the film forming chamber is turned on again.
After sufficiently evacuation to about X 10-'Torr, SiF and gas 101005e are introduced from the gas introduction pipe 421, and H2 gas is introduced at 100 sccm from the gas introduction pipe 427.428.
They were each introduced into activation chambers 435 and 436, and microwave power of 300 W and 400 W was applied, respectively, to generate plasma and generate 5iFn and H radicals. The generated 34gn radicals and H radicals were each introduced into the film forming chamber. At this time, the internal pressure of the film forming chamber was adjusted to 3i to 0.3 Torr.

Further, the surface temperature of the AI base cylinder remained at 300°C. This state was maintained for 5 minutes, and the charge blocking layer 2
A charge generation layer 22 made of a-3i:II(F) having a thickness of 5,000 yen was formed on top of the sample. Next, the application of microwaves and the introduction of gas were stopped, and the film forming chamber was heated again to I
'After exhausting torr, molybdenum filament 4
31 was energized and made red hot. The surface temperature of the AI base cylinder remained at 300°C. Gas introduction pipe 4
21, CF and gas 400 SCC11 were introduced into the film forming chamber, and microwave power of 1200 W was applied to generate plasma. CFn radicals were introduced into the film forming chamber. At the same time, H2 from the gas introduction pipes 427 and 428
Activation chamber 435,4 due to counterfeiting of gas 4000 scc+s
36, and a microwave of 1 kW was applied to generate H radicals. The generated H radicals were introduced into the film forming chamber.

*The internal pressure of the membrane chamber was adjusted to 1.0 Torr.

This state was maintained for about 25 minutes, and a charge transport layer 21 made of a diamond-shaped carbon thin film having a thickness of 51 Lm was formed on the charge generation layer 22. Introducing the gas, applying microwaves, energizing the metal catalyst, and turning off the infrared lamp. Once the substrate has cooled down sufficiently, the vacuum is broken, as shown in Figure 2 (b).
To form an electrophotographic photoreceptor with the structure of! I took out the cylinder.

When the characteristics of the electrophotographic photoreceptor thus obtained were measured in the same manner as in Example 1, it showed excellent characteristics, and its durability and environmental resistance were far superior to that of the existing a-3i photoreceptor. was.

[Effects of the Invention] According to the carbon film deposition method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and the substrate is maintained at a high temperature. High-speed film formation is possible without any problems. In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. can do. Furthermore, labor saving and activation efficiency can be improved due to the use of a catalyst when generating the front shell and/or active species generation, and therefore, the consumption efficiency of the raw material gas used can be greatly improved. This enables mass production at low cost. Further, the low temperature treatment has the effect of shortening the process.

Furthermore, by using the carbon film obtained in the present invention, P
A significant increase in the conversion efficiency of the IN diode is obtained. Further, by using the present invention in an electrophotographic photoreceptor, it is possible to obtain an electrophotographic photoreceptor with excellent electrophotographic properties, environmental resistance, and durability significantly increased compared to existing electrophotographic photoreceptors.

In the present invention, the diamond fJJI
Since 8I can be obtained, it is possible to coat a thin film of diamond on almost any substrate.

[Brief explanation of the drawing]

FIG. 1 and FIG. 2 are schematic diagrams for explaining a configuration example of an electrophotographic image forming member manufactured using the method of the present invention,
Ru. FIG. 3 is a schematic diagram for explaining a configuration example of a PIN diode manufactured using the method of the present invention. FIG. 4 and FIG. 5m are schematic diagrams for explaining the configuration of an apparatus for carrying out the method of the present invention used in Examples, respectively. 11--Photoconductive layer 12--Substrate 21--Surface layer 22--Charge generation layer 23--Charge transport layer 24--Substrate 25--Charge blocking layer 31-- Substrate 32.37... Thin film electrode 34... N-type semiconductor layer 35... i2u\-conductor layer 36... P-type semiconductor layer lot, 440... Film forming chamber 108.422... Activation Chamber 103.432--Substrate 112.431--Metal Catalyst Drawing Book 1, Figure 2 ((1) (b) 3rd Figure 4, Figure 5 (G) Figure 5 ( b) Hand Itosashi Neichi Official Book (Method) % Formula % l, Indication of the case Japanese Patent Application No. 1983-73615 2, Name of the invention Deposited film forming method 3, Person making the amendment Relationship to the case Patent applicant name Name (Zoo) Canon Co., Ltd. 4, Agent Address: 40 Mori Building, Toranomon, 5-13-1, Toranomon, Minato-ku, Tokyo Name (6538) Patent Attorney: Minoru Yamashita -° 5. Date of Amendment Order
-1- Submit a separate engraving specification, engraving drawings, and power of attorney.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, active species generated from a compound containing carbon and halogen, and active species generated from a film forming raw material that chemically interacts with the active species. , respectively, and reacted with a heated metal or metal compound catalyst selected from the group of elements in the fourth period, fifth period, and sixth period of the periodic table. A deposited film forming method characterized by forming a deposited film on top.