JPS61276972A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve the electrical, optical and mechanical characteristics of the resulting film by introducing a compound contg. Ge and halogen and active species of a compound contg. carbon into a film forming space and by applying electric discharge energy to bring them into a reaction. CONSTITUTION:Active species are produced from a compound contg. carbon for film formation. The compound interacts chemically with a compound contg. Ge and halogen such as a compound represented by a formula GeuY2u+2 (where u is an integer of >=1 and Y is F, Cl, Br or I). The active species and the compound contg. Ge and halogen are introduced into a film forming space, where they are brought into a chemical reaction by applying electric discharge energy to form a deposited film on a substrate.

Description

Detailed Description of the Invention [Technical field to which the invention pertains] The present invention relates to a deposited film containing germanium and carbon, particularly a functional film, particularly a semiconductor device, a photosensitive device for electrophotography, and a line sensor for image input. The present invention relates to a method for forming an amorphous or crystalline deposited film for use in imaging devices, photovoltaic devices, and the like.

[Description of prior art]

Conventionally, semiconductor devices, photosensitive devices for electrophotography,
Several types of carbon-containing amorphous germanium (hereinafter simply referred to as ra-GeCJ) films have been proposed as element members for use in image input line sensors, imaging devices, photovoltaic devices, etc. is attached to practical use. In addition to the 1a-GeC film, several other methods have been proposed for forming the a-GeC film, including vacuum evaporation, ion blating, so-called CVD, plasma CVD, and photoCVD. Among them, the plasma CVD method has been put into practical use as the most suitable method and is generally widely used.

By the way, conventional a-QeC films are produced by, for example, plasma CVD.
Although the products obtained by this method are said to be satisfactory for the time being because they have many methods for expressing properties, they still lack the electrical, optical, photoconductive properties, and repeatability required for the establishment of a solid product. There is still a long way to go to solve the problem of satisfying all of the following points: fatigue resistance, usage environment characteristics, stability over time, durability, and homogeneity. It is in a certain state.

The reason for this is that the desired a-GeC film is not something that can be achieved by a simple layer deposition operation, and that skilled ingenuity is required in particular process operations, as well as the materials used. The part where it is exposed is thick.

By the way, for example, in the case of the so-called CVD method, C-based and G-based
After diluting the e-type gas material, so-called impurities are mixed in and then thermally decomposed at a high temperature of 500 to 650°C, so precise process operations and control are required to form the desired a-GeC film. However, it is extremely difficult to consistently obtain homogeneous a-GeC film products with the desired characteristics as described above, and therefore industrial The scale is 116.

Even with the plasma CVD method, which is generally widely used as the optimal method described above, there are some problems in process operation and problems in equipment investment. Regarding process operations, the conditions are as described above (CVI)
It is more complicated than the conventional method, and it is extremely difficult to make it into a film. That is, for example, there are already many parameters when considering the interrelationships among the substrate temperature, the flow rate and flow rate ratio of the introduced gas, the structure of the high-frequency electric shock absorber electrode during layer formation, the structure of the reaction vessel, the pumping speed, and the plasma generation method. In addition to these parameters, there are also other parameters, and in order to obtain the desired product, it is necessary to select the exact Hiko parameters, and since these parameters are strictly selected, there are If one of the constituent factors, especially plasma, becomes unstable, the formed film will be severely affected and cannot be used as a product. As for the equipment, as mentioned above, strict parameter selection is required, so the structure naturally becomes complex, and if the scale and type of equipment changes, the design must be able to accommodate the carefully selected parameters. Must. For these reasons, although the plasma CVD method is considered to be the most suitable method at present, it is difficult to achieve the desired a-G
Mass production of eC films requires a large amount of equipment investment, and the process control items for mass production are many and complex, the process control tolerance is narrow, and equipment adjustments are delicate. Therefore, there are problems such as the end result being a product that is quite expensive.

! On the other hand, the various devices mentioned above have become diversified, and the requirements for element materials, that is, the various characteristics mentioned above, are generally satisfied and are appropriate for the target object and use, and in some cases, There is a social demand for a steady supply of stable a-GeC film products with a large area at low cost, and there is a strong need for the development of methods and equipment to meet this demand. The situation is -5.

These also apply to other element members such as silicon nitride films, silicon carbide films, and silicon oxide films.

[Purpose of the invention]

The present invention solves all of the above-mentioned problems and satisfies the above-mentioned requirements regarding conventional element members and manufacturing methods thereof used in semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, imaging devices, photovoltaic elements, etc. The purpose is to meet the following criteria.

In other words, the main object of the present invention is to have electrical, optical, and photoconductive properties that are virtually always stable regardless of the usage environment, to have excellent light fatigue resistance, and to be able to be used repeatedly. It is an object of the present invention to provide an a-GeC film element member that does not cause deterioration even under conditions of high temperature, has excellent durability and moisture resistance, and has a uniform and improved uniformity that does not cause the problem of residual potential. .

Another object of the present invention is to improve the characteristics of the formed film, the film formation speed, the reproducibility, and the quality of the film, while also making it suitable for increasing the area of the film. The object of the present invention is to provide a novel manufacturing method for an improved AiGeC membrane element member described in AiI, which can easily achieve a single production of membrane productivity.

[Structure of the invention]

The object of the present invention is to form a film that chemically interacts with a compound containing germanium and nitrogen in a film formation space for forming a deposited film on a substrate. and active species generated from carbon-containing compounds for
This is accomplished by applying discharge energy to these to cause a chemical reaction, thereby forming a deposited film on the substrate.

The method of the present invention involves discharging a compound containing all germanium and nitrogen in the coexistence of active species generated from a carbon-containing compound for film formation that chemically interacts with the compound. The method of the present invention forms a desired deposited film by causing all of these chemical interactions to occur, or by further promoting and amplifying them, by applying energy. The deposited film, which can be formed with a discharge energy lower than that of the conventional method, is extremely unlikely to be adversely affected by etching effects or other adverse effects such as abnormal discharge effects.

Further, the method of the present invention can be a more stable CVD method by arbitrarily controlling the atmospheric temperature of the film forming space and the substrate temperature as desired.

Further, in the method of the present invention, in addition to discharge energy, light energy and/or thermal energy can be used in combination, if desired. Light energy can be applied to the entire substrate using an appropriate optical system, or can be selectively applied to only desired areas, so that the formation position and thickness of the deposited film on the substrate can be controlled. etc. can be easily controlled. Further, as the thermal energy, thermal energy converted from light energy can also be used.

One of the points that distinguishes the method of the present invention from conventional CVD methods is that it uses activated species that have been activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). As a result, it is possible to dramatically increase the film formation speed of the conventional CVD method, and in addition, it is possible to further lower the substrate temperature during deposited film formation, resulting in stable film quality. The deposited film can be provided industrially in large quantities at low cost.

In the method of the present invention, the carbon-containing compound, which is a raw material for forming a deposited film, is activated in the activation space to produce an active compound. Then, the generated active species are introduced from the activation space into the film forming space, and a deposited film is formed in the film forming space.

Therefore, the constituent elements of the active species constitute the entire deposited film formed in the film forming space. In the method of the present invention, active species are selected and used as desired, and from the viewpoint of productivity and ease of handling, those with a lifetime of 0.1 seconds are usually used. ,
It is more preferable to use a time of 1 second or more, most preferably 10 seconds or more.

Further, the compound containing germanium and halogen used in the method of the present invention is introduced into the film forming space, excited by the action of discharge energy, and chemically interacts with the above-mentioned active species that are simultaneously introduced from the activation space to the film forming space. It has the effect of promoting the formation of a deposited film by interacting with each other and, for example, imparting energy or causing a chemical reaction.

Therefore, the constituent elements of the compound containing germanium and halogen may be the same as the constituent elements of the deposited film to be formed, or may be different.

It is preferable that the carbon-containing compound for forming a deposited film used in the method of the present invention is already in a gaseous state or is in a gaseous state before being introduced into the activation space. For example, when using a liquid compound, a suitable vaporizer can be connected to the compound supply source to vaporize the compound before introducing it into the activation space. Examples of carbon-containing compounds include chain or cyclic saturated or unsaturated hydrocarbon compounds whose main constituent atoms are carbon and hydrogen, and one or more halogens, sulfur, etc. or 2a! Among the organic compounds having all of the above constituent atoms, organosilicon compounds containing hydrocarbon groups, and organosilicon compounds having a bond between silicon and carbon, those in a gaseous state or those that can be easily vaporized are used. That's nice.

Among these, examples of hydrocarbon compounds include carbon atoms of 1 to
5 saturated hydrocarbons, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, etc. Specifically, saturated hydrocarbons include methane (CH4), ethane (02
H6), propane (C3H8), n-butane (n C
4HIO), pentane (C!1HI2), ethylene hydrocarbons include ethylene (C2H4), propylene (also C3I), butene-1 (C4H11), butene-2
(C4H8), isobutylene (C4H8), pentene (
C5HIO), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (CsH4)
, butyne (C4, Ha), and the like.

As the halogen-substituted hydrocarbon compound, at least 1 kF of hydrogen, which is a constituent of the above-mentioned hydrocarbon compound,
Compounds in which C1% Br and I are substituted can be mentioned, and compounds in which F and C1 are substituted with hydrogen are particularly effective.

The halogen substituting hydrogen may be one type or two or more types in one compound.

Examples of the organosilicon compound used in the present invention include organosilane and organohalogensilane.

Organosilane and organohalogensilane each have the general formula; RnSiH4□+ RrnSiX4-m (wherein, R: alkyl group, aryl group,
r, I, n=1. ．． 2, 3, 4, m=1. ．． 2.3
), and typical examples include alkylsilanes, arylsilanes, alkylhalogensilanes, and arylhalogensilanes.

Specifically, as organochlorosilane, trichloromethylsilane CH35iCt
3dichlorodimethylsilane (CHs)
2 S 1c12 chlorotrimethylsilane
(CH3) s S icl trichloroethylsilane C2H5S 1ce3 dichlorodiethylsilane (C2H5) 2 S ic4 organochlorofluorosilane includes chlordifluoromethylsilane CH35IF2Ct dichlorofluoromethylsilane CH35iFCt2 chlorofluorodimethylsilane (CH3) 25iFc
tChlorethyldifluorosilane C2H,5i
F2CA dichloroethylfluorosilane C2H
65iFC12 Chlordifluoroglopyrsilane
C3H75iF2Ct dichlorofluoropropylsilane C5H7S 1FCt2 Organosilane is Tetramethylsilane (CH3)4S
l Ethyltrimethylsilane (CH3)3
SIC2■5 trimethylpropylsilane
(CH3)3SiC3H7 triethylmethylsilane
CH35j(C2H5)B-13= Tetraethylsilane (C2H5)4
As Si organohydrogenosilane, methylsilane CH35iH3
Dimethylsilane (CH3) 2
S i H2 trimethylsilane
(CHs)ssiH diethylsilane
(C,,H,)2S iH,.

Triethylsilane (C2H5)
s S iH tripropylsilane
(C3H7) s SiH diphenylsilane
(C6H5)2SIH2 Organofluorosilane includes trifluoromethylsilane CH35iF3
Difluorodimethylsilane (CHs)2s
iF2 Fluorotrimethylsilane (CHs
)sSiF ethyltrifluorosilane C2
H5S iF3 diethyldifluorosilane
(C2H5)2SIF2 triethylfluorosilane
(C2H5) 3S IF trifluoropropylsilane (C3H7) S i F3 organobromosilane includes bromotrimethylsilane (CHs)3S
iBrdibromdimethylsilane (CH3
)25iBr2, and other organopolysilanes include hexamethyldisilane C(CHs)s
Si:)2hexapropyldisilane [
(CJT7)3Si)2 etc. can also be used.

One type of these compounds may be used, or two or more types may be used in combination.

In the method of the present invention, the compound containing germanium and halogen introduced into the film-forming space is, for example, a chain or cyclic germanium hydride compound in which some or all of the hydrogen atoms are replaced with halogen atoms. Specifically, for example, a chain halogenated compound represented by Geu"2u-1-2 (' is an integer of 1 or more, Y is at least one element selected from F, C11Br, and Germanium, Ge, cyclic germanium halide represented by Y2v (v is an integer of 3 or more, Y has the meaning described above), GeuHxYy (u and Y have the meaning described above)
+X+y=2t+ or 2u+2. ), and the like.

Specifically, for example, GeF4, (cep'2)a, (G
eF2)6, (GeF2)4, Ge2 F6, Ge3F
8, GeHF3, GeHBr3, GeCl4, (GeC
4)5. GeBr4, (GeBr, ), Ge2C
1a, Ge2Br6, GeHCl3, GeHBr3, G
Examples include those that are in a gaseous state or can be easily gasified, such as eH3 and Ge2Ct3F3.

Further, in the method of the present invention, in addition to the compound containing germanium and a halogen, a compound containing silicon and a halogen and/or a compound containing carbon and a halogen can be used in combination.

As the compound containing silicon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically,
For example, 5iuY2u+2 (U is an integer greater than or equal to 1, Y is F
At least one element selected from lCL, Br, and (1). ) chain silicon halide, 5iv
Y2v (v is an integer of 3 or more, Y has the above-mentioned meaning.

) Cyclic silicon halide, 5luHxYy (
U and Y have the meanings given above. X y = 2u or 2u+2. ) and chain or cyclic compounds represented by the following formulas.

Specifically, for example, 5IF4, (SjF2)5, (SIF
2:)e, (SiF2)+, Si2F6, Si3F8,
SiHF3, SI H2F2, S'C'4, (S
ICt2)6, SiBr4, (SiBr2)5, S 1
2 CLa, 5i2Br6, Si HCt3.5iHB
Examples include those in a gaseous state or those that can be easily gasified, such as rs, 5tHIa, and 5i2C4F3.

These silicon-containing compounds may be used alone or in combination of two or more.

Further, as the compound containing carbon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound is substituted with kenorogen atoms is used, and specifically, for example, CuY2u+2(11 is an integer greater than or equal to 1, Y is F, ct.

It is at least one element selected from 13r and 1. ) Chain-like rogenated carbon, C, ￥2゜(
V is an integer of 3 or more, and Y has the meaning described above. ), CuHxYy (u and Y
has the meaning described above.

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

Specifically, for example, CF, , (CF2 )5, (CF2
)6, (CF2)4.02F',,C,F8,CHF3
, CH2F2, CCZ4 (CC4)5, CBr, , (
cnr2), C2Cto, C2Br6, CHCL3,
Examples include those that are in a gaseous state or can be easily gasified, such as CHBr3, CHI3, C2C1, F3.

These carbon-containing compounds may be used alone or in combination of two or more.

Furthermore, in addition to the above-mentioned compounds containing germanium and halogen, germanium-containing compounds such as germanium alone, hydrogen, halogen compounds (for example, F2 gas,
Ct2 gas, gasified Br2, (2), etc.) can also be used in combination.

In the present invention, as a method for generating all active species in the activation space, microwave, R
Activation energy such as electrical energy such as F, low frequency, or DC, thermal energy such as heater heating or infrared heating, or optical energy such as laser light is used.

In the activation space, excitation energy such as heat, light, or electricity is applied to the carbon-containing compound to generate active species.

In the method of the present invention, the ratio between the amount of active species generated from the above-mentioned carbon-containing compound for forming a deposited film and the amount of the above-mentioned compound containing germanium and halogen, which is introduced into the film-forming space, is determined. It is determined as desired depending on the membrane conditions, the type of active species, etc., but is preferably 10:1 to 1:10.
(introduction flow rate ratio) is appropriate, more preferably 8:2
A ratio of ~4:6 is desirable.

In the method of the present invention, the above-mentioned deposited film forming compounds that can generate active species include, in addition to carbon-containing compounds, silicon-containing compounds, hydrogen gas, and halogen compounds (
For example, F2 gas, Ct2 gas, gasified Br2, ■2
), helium, argon, neon, and other inert gases may also be used. When using multiple of these chemicals, they can be mixed in advance and introduced into the activation space in a gaseous state, or they can be introduced into separate activation spaces and activated individually. You can also do that.

As the silicon-containing compound introduced into the activation space for forming the deposited film, use all of the silanes in which silicon is bonded with hydrogen, nitrogen, or hydrocarbon groups, and the silanes containing rosogenide. I can do it. Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with halogen atoms.

Specifically, for example, SiH4, Si2TTa%
S j3H8, S 14HIO1S 15H12,51
Linear silane compounds represented by Si, T (2p-1-2 (p is an integer of 1 or more, preferably 1 to 15, more preferably 1 to 10) such as 6HI4, 5iH3Si■l
(5iH3) SiH3, S 1H3S iH(S 1
T(3)S 13H7,5i2H5SiH(SiH3)
81, B2 p+ 2 (p has the above-mentioned meaning) such as 5i2IT5, a branched chain silane compound, a part or all of the hydrogen atoms of these linear or branched chain silane compounds Compound substituted with kethalogen atom, S13 mountain, Si4■■8.5i5H,. ,
A cyclic silane compound represented by 5i9H29 (, is an integer of 3 or more, preferably from 3 to 6) such as Examples of compounds substituted with groups and/or chain silanyl groups, compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are substituted with halogen atoms,
i′H3F1SiH3Ct, 5iHsBr, 5
5irH8X such as iH3T, (X is a halogen atom, r is an integer of 1 or more, preferably 1 to 10, more preferably 3 to 7, s + t = 2r + 2 or 2r) halogen-substituted linear or cyclic silane Compounds, etc. These compounds may be used alone or in combination of two or more.

The deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. As the impurity element to be used, as an n-type impurity, elements of group ⅠA of the periodic table, such as B1At, Ga, In1T/
Examples of suitable n-type impurities include Group V A (7) elements of the periodic table, such as P and As1S.
B, Bi, etc. are mentioned as suitable ones, but especially B
, Qa.

P% sb etc. is optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical characteristics.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under deposited film forming conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to select Such compounds include PH3, P2H4, PF
3, PF5, PCl5, A8H3% A8F3% A8
F5%, AsCA3, SbH3, SbF5.5in3
．． BF,, BC4, BB rs, B2 Ha s
B4HIO, P5H9, B5HII, BaH+o%
Examples include B6HI2 and htct3. One type of compound containing an impurity element may be used, or two or more types may be used in combination.

The substance for introducing impurities can be introduced into the film forming space directly in a gaseous state, or mixed with the above-mentioned compound containing germanium and halogen, or after being introduced into the activation space and activated. It can also be introduced into the film forming space.

In order to activate the impurity-introducing substance, the above-mentioned activation energy for generating active species can be appropriately selected and employed. The active species generated by activating the impurity introduction substance are mixed with the above-mentioned active species in advance, or introduced alone into the film forming space.

Next, the content of the method of the present invention will be explained in detail using typical examples of electrophotographic imaging members and semiconductor devices.

FIG. 1 is a schematic diagram for explaining an example of the structure of a photoconductive member as a typical electrophotographic image forming member obtained by the method of the present invention.

A photoconductive member 10 shown in FIG. 1 can be applied as an electrophotographic image forming member, and has an intermediate layer 12 provided as necessary on a support 11 for the photoconductive member.
, and a photosensitive layer 13.

In manufacturing the photoconductive member 10, the intermediate layer 12 or/and
and the photosensitive layer 13 can be created by the method of the present invention. Further, the photoconductive member 10 may include a protective layer provided to chemically and materially protect the surface of the photosensitive layer 13, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical withstand pressure. , these layers can also be created by the method of the present invention.

Even if the support 11 is conductive! ! Alternatively, it may be electrically insulating.

Examples of the conductive support include NiCr, stainless steel,
At, CrlMo, Au, Ir, NblTa
%V1Ti, Pt, Pd and other metals or alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose, acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, and holamide, glass, ceramic, and paper. .

Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, there is NiCr on its surface.

At%Cr, Mo, Au, ■r1Nb%Ta, V1
Ti.

pt, Pds In20s) 5no2,
If conductive treatment is performed by providing a spanning film such as ITO (In2O5 + 5nO2), or if it is a synthetic resin film such as polyester film, NiCr %kl
s Ag s Pbs Z” sNl % Au%
Cr, Mo, ■r%Nb, 'l'a, V%
It is treated with a metal such as T1% PT using vacuum evaporation, electron beam evaporation, sputtering, etc., or it is laminated with the metal, and its surface is subjected to conductive treatment. The shape of the support can be any shape, such as a cylinder, a belt, or a plate. The shape of the photoconductive member 10 shown in FIG. 1 can be determined as appropriate depending on the purpose and desire. , an endless belt or cylindrical shape would make the car heavier.

The intermediate layer 12 completely effectively blocks the inflow of carriers into the photosensitive layer 13 from the side of the support 11, and also prevents carriers generated in the photosensitive layer 13 by irradiation with electromagnetic waves and moving toward the side of the support 11. It has a function of easily allowing the photocarrier to pass from the side of the photosensitive layer 13 to the side of the support 11.

This intermediate layer 12 contains germanium atoms, hydrogen atoms (H)
and/or...an amorphous film containing rogen atoms (X) and carbon atoms as constituent atoms [hereinafter referred to as r a-GeC
(H, X, Si) Written as J. ], and
For example, boron (B) is a substance that controls electrical conductivity.
It contains p-type impurities such as phosphorus (P) or n-type impurities such as phosphorus (P).

In the method of the present invention, B contained in the intermediate layer 12
The content of the conductivity-dominant substance such as , P, etc. is preferably as follows:
1×10−3 to 5×104atO104atO, preferably 0.5 to I×lo'atomiccp
pm1 optimum is 1-5 x 103103ato pp
It is desirable to set it to m.

If the components of the intermediate layer 12 are similar or the same as those of the photosensitive layer 13, the formation of the photosensitive layer 13 can be performed four times in succession following the formation of the intermediate layer. In that case, the raw materials for forming the intermediate layer include a compound containing germanium and a halogen, a gaseous carbon-containing compound, and if necessary, a silicon-containing compound, hydrogen, a halogen compound, an inert gas, and an impurity element. Active species generated by activating the gas etc. of the compound containing;
All of them are introduced separately or mixed as necessary into the film forming space where the support 11 is installed, and discharge energy is applied to the coexistence atmosphere of the introduced germanium- and halogen-containing compounds and active species. In particular, an intermediate layer 12 is formed on the support 11.

The thickness of the intermediate layer 12 is preferably 3×10”~
10μ, more preferably 4 x 10"-3~8
It is desirable that μ is optimally set to 3×10” to 5 μ.

The photosensitive layer 13 is made of amorphous silicon [hereinafter referred to as ra-8i (
It is written as H, X, Ge, C) J. ] or amorphous germanium (hereinafter referred to as r a-G
e (H,X.

C) Marked as J. ], and has both the charge generation function of generating all photocarriers by laser beam irradiation and the charge transport function of transporting the charges.

The thickness of the photosensitive layer 13 is preferably 1 to 100 microns, more preferably 1 to 80 microns, and most preferably 2 to 50 microns.

The photosensitive layer 13 is made of non-doped a5i (H, X, Ge, C
) or a-Ge (H, Alternatively, the intermediate layer 1 may contain a substance.
If the actual amount of the substance controlling the conduction properties contained in 2 is large, the substance controlling the conduction properties of the same polarity may be contained in an amount much smaller than the amount.

When the photosensitive layer 13 is formed by the method of the present invention, it is formed in the same manner as the intermediate layer 12 described above. That is, a compound containing germanium and a halogen or a compound containing silicon and a halogen, an active species generated from a carbon-containing compound for forming a deposited film, an inert gas as necessary, and a compound gas containing an impurity introducing substance as a component. etc. are introduced into the film forming space where the support 11 is installed, and discharge energy is applied to form the photosensitive layer 13 on the intermediate layer 12 formed on the support 11.

Furthermore, if desired, as a surface layer on this photosensitive layer,
An amorphous deposited film containing carbon and silicon as constituent atoms can be formed, and in this case also, the film can be formed by the method of the present invention in the same manner as the intermediate layer and photosensitive layer.

FIG. 2 is a schematic diagram illustrating a typical example of a PIN type diode device using an a-8i deposited film doped with an impurity element prepared by the method of the present invention.

In the figure, 21 is a base, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an n-type semiconductor layer 24, an i-type semiconductor layer 2
5. Consisting of a p-type semiconductor layer 26. 28 is a conductive wire connected to an external electric circuit device.

These semiconductor layers are a5i(H,X), a-8i
It is composed of C(H,X), a-8iGeC(H,X), etc.

Although the method of the present invention can be applied to the production of any layer, the conversion efficiency can be particularly improved by producing the 26 semiconductor layers using the method of the present invention.

The base 21 may be conductive, semiconductive, or electrically insulating. Base body 21
is conductive, the thin film electrode 22 may be omitted. Examples of the semiconductive substrate include Si,
Examples include semiconductors such as Qe, QaAs, ZnO, and ZnS. The thin film electrode 22.27 is made of, for example, NiCrs.
At% Cr% MosAu, Ir, Nb
, Ta, V, Ti, Pts Pd11n203,
It can be obtained by forming a thin film of SnO2, 1TO (2n203+5nO2), etc. on the substrate 21-1- by processing such as vacuum evaporation, electron beam evaporation, or sputtering.

The layer thickness of the electrode 22.27 is preferably 3×10 to 5×
10"y=, but more preferably 10"~5×
It is desirable to set it to 103X.

In order to make the film body constituting the semiconductor layer n-type or p-type as necessary, during layer formation, a layer in which n-type impurity or p-type impurity, or both impurities are entirely formed, is added. It is formed by doping in a controlled amount.

When forming n-type, i-type, and p-type semiconductor layers, any one or all of these semiconductor layers can be formed by the method of the present invention. In other words, a compound containing germanium and halogen or further silicon and
・Introduce compounds containing rogens. -! f. Separately, a carbon-containing compound in a gaseous state, or a silicon-containing compound and, if necessary, an inert gas and a gas of a compound contained as an impurity elemental sound component are excited by activation energy, respectively. The activated species are decomposed to produce each active species, and each of them is introduced into the film forming space where the substrate 21 is installed, either separately or mixed as appropriate. Next, discharge energy is applied to these to form them. By applying discharge energy, chemical interaction is caused in the compound containing germanium and halogen and the active species introduced into the film forming space, or is further promoted or amplified to form a deposited film on the substrate 21. urge n-type and p-type
The thickness of the semiconductor layer of the mold is preferably 102~], O'X
The weight of the vehicle is more preferably within the range of 3 x 102 to 2 x 103.

Further, the layer thickness of the i-type semiconductor layer is preferably 5 x 102 ~
It is desirable to set it in the range of 10'X, more preferably 103 to 104 days.

〔Example〕

Hereinafter, the present invention will be explained in more detail according to examples.
The present invention is not limited to these.

Example 1 Using the apparatus shown in Fig. 3, i
Germanium and carbon-containing amorphous deposited films of type, p-type, and n-type were formed.

In FIG. 3, 101 is a film forming chamber, in which a desired substrate 103 is placed on a substrate support stand 102-42.

104 is a heater for basic heating;
4 is used when heating the substrate 104 before the film forming process or annealing the formed film after forming the film in order to further improve the characteristics of the formed film, and supplies power through the conductive wire 105. Causes fever.

Reference numerals 106 to 109 denote gas supply sources, which are provided depending on the type of gas of the carbon-containing compound and the compound containing hydrogen, a halogen compound, an inert gas, and an impurity element, which are used as necessary. If one of these raw material compounds is used in a liquid state under standard conditions, an appropriate vaporization device is provided.

Note 3 with ai attached to the gas supply sources 106 to 109 in the figure.
3 The one marked with "b" is a branch pipe, the one marked with "b" is a flow meter, the one marked with "C" is a pressure gauge that measures the pressure on the high pressure side of each flow meter, and d or e.
7f is the pulp for adjusting the flow rate of each gas. 123 is an activation chamber for generating active species;
A microwave plasma generator 122 is provided around the activation chamber 123 to generate activation energy for generating active species. The raw material gas for active species generation supplied from the gas introduction pipe 110 is activated in the activation chamber 123, and all the generated active species are introduced into the film forming chamber 10 through the introduction pipe 124.
Introduced within 1. ] 11 is a gas pressure gauge.

In the figure, 112 is a source of a compound containing germanium and halogen, and a to e attached to the reference numeral 112 indicate the same as in the case of 106 to 109 described above. Compounds containing germanium and haloken are introduced into the inlet pipe 113.
The film is introduced into the film forming chamber 101 through the film.

Reference numeral 117 denotes a discharge energy generating device, and a quad electrode 117 for high frequency introduction of a matching box 117a.
It is equipped with b.

In the figure, 120 is an exhaust pulp and 121 is an exhaust pipe.

Base made of polyethylene terephthalate film 103
Place it on the support stand 102, and use the exhaust system to remove the film forming chamber 1.
01 was evacuated and the pressure was reduced to approximately 10 Torr.

From the gas supply cylinder 106, CI-T, gas, or this and PH3 gas''!, or B2H6 gas (also 10
00 ppm diluted hydrogen gas) and 40 SCCM were added to the activation chamber 12 through the gas introduction pipe 110' (z).
It was introduced in 3. CH4 gas and the like introduced into the activation chamber 123 were activated by the microwave plasma generator 122 to form hydrogenated carbon active species, active hydrogen, etc., which were then introduced into the film forming chamber 101 through the introduction pipe 124. .

On the other hand, supply source], 1.2. ．． 1: GeF4 gas was introduced into the film forming chamber 1 through the introduction pipe 116.

The internal pressure in the film forming chamber 101 is maintained at fr: 0.4 Torr, and plasma is applied by the discharge energy generator 117 to form a non-doped or doped germanium and carbon-containing amorphous deposited film (thickness: 70 mm).
0A) k was formed. Deposition speed is 34 A/s
ec de tsu 7'v.

Next, the obtained non-doped or p-type germanium and carbon-containing amorphous deposited film sample was placed in a vapor deposition tank, and a comb-shaped At gap electrode (
After forming a gap length of 250 μm and a gap length of 1J5 mm, the dark current was measured at an applied voltage of 10 V, the dark conductivity σdi was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2 to 4 Linear CH6, C2■-■4, or C2 instead of CH4
A germanium and carbon-containing amorphous deposited film was formed in the same manner as in Example 1 except that 2) was used.

The dark conductivity of each sample was completely measured and the results are shown in Table 1.

From Table 1, it was found that according to the method of the present invention, germanium and carbon-containing amorphous films with excellent electrical properties can be obtained, and germanium and carbon-containing amorphous films that are sufficiently doped can also be obtained. .

Example 5 Using the apparatus shown in Fig. 4, the first
A drum-shaped electrophotographic image forming member having a layer structure as shown in the figure was prepared.

In FIG. 4, 201 is a film forming chamber, 202 is a compound supply source containing germanium and halogen, 206 is an introduction pipe, and 207
is a motor, 208 is a heating heater used in the same manner as 104 in Fig. 3, 209.210 is a blowing pipe, 211
212 is an At cylindrical base, 212 is an exhaust pulp, 213 to 216 are thick phase gas supply sources similar to 106 to 109 in FIG. 1, and 21721 is a gas introduction pipe. .

The film-forming chamber 2 is suspended from an At cylindrical base 2]-1, with 208 heating heaters installed inside it, and a motor 2.
07 to allow rotation. Reference numeral 218 denotes a discharge energy generating device, which includes a matching box 218a, a cathode electric machine 21.8b for introducing high frequency, and the like.

First, G e F gas is introduced from the supply source 202 into the pipe 20
6, it was introduced into the film forming chamber 201.

On the other hand, introduction tube 2] 7-1. , l:suC■■4 and 5i2H
Gases 8 and 2 were introduced into the activation chamber 220. The introduced C) T, +, 5t2H6% H2 gas is subjected to activation treatment such as plasma generation by a microwave plasma generator 220 in the activation chamber 219, and hydrogenated carbon active species, silicon hydride active species and activated Hydrogen, introduction pipe 2
] 7-2 and was introduced into the film forming chamber 2. At this time, impurity gases such as PH3 and B2H6 were also introduced into the activation chamber 219 for activation, if necessary.

While maintaining the internal pressure in the film forming chamber 201 at 8 Torr,
Plasma generated by the discharge energy generator 218 was applied.

The A7 cylindrical base 211 was rotated, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust pulp 212.

The photosensitive layer 13 was formed in this manner, but in order to form the intermediate layer 12, the introduction tube 217 was used prior to forming the photosensitive layer 13.
A mixed gas of -1 and H2/B2H6 (B2I (6 gas is 0.2%) in terms of capacity) was introduced, and other than that, the film thickness was 200OA.
The intermediate layer 12 was formed so as to have the following properties.

Comparative Example 1 GeF4 and C■ 14.512H6, H2 and B2H,]
A film-forming chamber with the same configuration as the film-forming chamber 201 was equipped with a 13.56 MH2 high-frequency device using each gas '6.
An electrophotographic image forming member having the layer structure shown in FIG. 1 was generally formed by a plasma CVD method.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 5 and Comparative Example 1.

Example 6 A PIN type diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3 using C)14 as the carbon-containing compound.

First, the polyethylene naphthalate film 21 on which the ITO film 22 of 100 OA was deposited was placed on a support stand, and the ITO film 22 of 100 OA was deposited.
After reducing the pressure to −6 Torr, the introduction tube 1 was
GeF4 gas was introduced into the film forming chamber 1.01 from No. 13.

Furthermore, 5i3IL gas and PH3 gas (diluted with 11000 pp hydrogen gas) were each introduced into the activation chamber 123 for activation.

Next, this activated gas is introduced into the film forming chamber 1 through the introduction pipe 124, and the pressure inside the film forming chamber is increased to k 0.3 To.
7'cn type a-8iGe (H,
A film 24 (thickness: 700 A) was formed.

Next, except for completely stopping the introduction of PH3 gas, the n-type a-5
Non-doped a-8iQe (H,
was formed.

Then CI soil gas, 82H along with 5i3H6 gas.

A gas (1,000 ppm hydrogen gas dilution) was introduced, and an ip-type carbon-containing a-8iGe (H,
)' was formed. Furthermore, an At electrode 27 having a thickness of 103× was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

I- of the diode element thus obtained (area 1 ca)
The V characteristics were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

Even when the light is irradiated, light is introduced from the substrate side,
Light irradiation intensity AMT (approx. 1.OOrn W/aA)
and the conversion efficiency is 7.9% or more"-1 open end voltage 0.9]V,
A short circuit radio wave of 9°7 mA/cJ was obtained.

Examples 7 to 9 C2)T, respectively, instead of CH4 as carbon-containing compounds
], Example 6 except that C2■■4 or C2H2 minutes were used.
In the same manner as in Example 6, a PIN type diode similar to that made in Example 6 was fabricated.

This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

Table 3 shows that according to the method of the present invention, carbon-containing a
-8iGe (IT,X)PIN type diode (l
I knew it would happen.

[Summary of effects of the invention]

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible. In addition, reproducibility in film formation is improved, making it possible to improve film quality and uniformity of film quality, and it is advantageous for a large area ratio of the film, making it easier to improve film productivity and mass production. be able to.

Furthermore, since it is possible to form a film with low discharge energy as excitation energy, it is possible to form a film even on a substrate with poor heat resistance, for example. The low-temperature treatment has the effect of shortening the process.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining a configuration example of a PIN diode manufactured using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the method of the present invention used in Examples, respectively. 10... Electrophotographic image forming member 11... Support 1
2... Intermediate layer 13... Photosensitive layer 21... Base 22. 27... Thin film electrode 24... N-type semiconductor layer 25... Mold semiconductor layer 26... P-type semiconductor layer 28 ... Conductor wire 1 old, 201 ... Film forming chamber 11
2.202...Germanium and 7-chlorogen k tr
Compound supply source 123.219...Activation chamber 106.107.108.109.213.214.2
15.216...Gas supply source 103.211...Base 117, 218...Discharge energy generation device 102
...Substrate support stand 104.208...Substrate heating heater 105...
Conductor 110.113.124.206.217-1.21?
-2...Introduction pipe 111...Pressure gauge 120.212...Exhaust valve 121...Exhaust pipe 1.22.220...Activation energy generator 20
9.210...Blowout pipe 207...Motor-50=

Claims (1)

[Claims] A compound containing germanium and halogen and an active species generated from a carbon-containing compound for film formation that chemically interacts with the compound are placed in a film formation space for forming a deposited film on a substrate. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing these materials and applying discharge energy to cause a chemical reaction.