JPH0750685B2 - Deposited film formation method - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a deposited film containing silicon, particularly a functional film, particularly a semiconductor device, a photosensitive device for electrophotography,
The present invention relates to a method for forming a non-single crystalline silicon-containing deposited film such as an amorphous or polycrystalline material used in a line sensor for image input, an imaging device, a photovoltaic element, and the like.

[Description of Prior Art]

Conventionally, semiconductor devices, photosensitive devices for electrophotography,
Amorphous silicon containing several kinds of germanium (hereinafter simply referred to as "a-Si") as an element member used for an image input line sensor, an imaging device photovoltaic element, and the like.
It is written as "Ge". ) Membranes have been proposed, some of which have been put to practical use. Along with such a-SiGe films, some methods for forming such a-SiGe films have been proposed, such as a vacuum vapor deposition method, an ion plating method, a so-called CVD method, a plasma CVD method, an optical CVD method, and the like. Among them, the plasma CVD method is put to practical use as an optimum method and is generally widely used.

By the way, conventional a-SiGe films, for example, those obtained by the plasma CVD method are said to be rich in characteristics and satisfactorily exhibited, but even then, they are required to firmly establish the product. Electrical, optical, photoconductive characteristics, fatigue resistance characteristics after repeated use, points of use environment characteristics, stability and durability over time, and further all points of homogeneity are satisfied, It is in a state where there is still a way to solve the problem.

The cause is not that the target a-SiGe film can be obtained by a simple layer deposition operation, not to mention the material to be used, but requires skillful ingenuity in the process operation in particular. However, it is big.

Incidentally, for example, in the case of the so-called CVD method, Ge-based and Si-based
Since the so-called impurities are mixed after diluting the system gas material and then pyrolyzed at a high temperature of 500 to 650 ° C., precise process operation and control are required for forming a desired a-SiGe film. Therefore, the apparatus becomes complicated and the cost is considerably high. However, it is extremely difficult to homogenize the apparatus and constantly obtain an a-SiGe film product having the above-mentioned desired characteristics. That is, it is difficult to adopt on an industrial scale.

Further, even in the plasma CVD method which is generally widely used as the optimum method described above, there are some problems in process operation and also problems in capital investment. Regarding the process operation, the conditions are more complicated than the above-mentioned CVD method, and it is difficult to generalize it.
That is, for example, the substrate temperature, the flow rate and flow rate of the introduced gas, the pressure at the time of layer formation, the high frequency power, the electrode structure, the structure of the reaction vessel, the exhaust speed, and the parameters of the mutual system of the plasma generation method have already been examined. There are many parameters, and there are other parameters,
A rigorous selection of parameters is required to obtain the desired product, and because of the rigorous selection of parameters, one of the constituents, especially it is the plasma, is unstable. In any case, the formed film is significantly adversely affected and cannot be realized as a product. As for the device, since the strict selection of parameters is required as described above, the structure naturally becomes complicated, and it is designed so that it can correspond to the individually selected parameters if the device scale and type change. Must. From these things, plasma CV
Regarding the D method, although it is considered to be the most suitable method so far, from the above, if the desired a-SiGe film is to be quantified, a large capital investment is required for the device,
However, since there are many and complicated process control items for mass production, the process control allowable range is narrow, and the device adjustment is delicate, the problem is that the cost of the product will be considerably high in the end. There is.

On the other hand, the above-mentioned various devices have been diversified, and element members therefor, that is, satisfying the requirements such as the above-mentioned various characteristics as a whole and corresponding to the application target and application,
In some cases, it is a social requirement that a stable a-SiGe film product with a large area can be constantly supplied at a low cost. There are situations where development is eagerly awaited.

The same applies to other element members such as a silicon nitride film, a silicon carbide film, and a silicon oxide film.

[Object of the Invention]

The present invention solves the above-mentioned problems and solves the above-mentioned problems with respect to conventional element members used for semiconductor devices, electrophotographic photosensitive devices, image input line sensors, imaging devices, photovoltaic devices, etc. The purpose is to satisfy.

That is, the main object of the present invention is that electrical, optical, and photoconductive properties are substantially always stable without depending on almost any use environment, have excellent light fatigue resistance, and are repeatedly used. Even in such a case, it is an object of the present invention to provide a uniform and improved a-SiGe film element member which does not cause a deterioration phenomenon, has excellent durability and moisture resistance, and does not cause a problem of residual potential.

Another object of the present invention is to improve various characteristics of a film to be formed, film formation rate, reproducibility, and uniformize and homogenize film quality, and to increase the area of the film, thereby improving productivity of the film. The above-mentioned improved a- which can be easily improved and mass-produced.
It is to provide a new manufacturing method of a SiGe film element member.

[Structure of Invention]

The above-mentioned object of the present invention is to provide a compound containing germanium and halogen in a film formation space for forming a deposited film on a substrate, and a silicon-containing compound for film formation, which chemically interacts with the compound, This is achieved by forming a deposited film on the substrate by introducing the active species generated by the above and reacting them with discharge energy to cause a chemical reaction.

In the method of the present invention, a compound containing germanium and a halogen is replaced with a compound containing germanium and a halogen, and a silicon containing film for film formation that chemically interacts with the compound is used instead of the conventional method in which discharge energy such as plasma is applied to a material for forming a deposited film In the presence of active species generated from the compound, by causing discharge energy to act on these, a chemical interaction due to these is caused, or further promoted or amplified, to obtain a desired deposited film. In the method of the present invention, it is possible to form a film with a lower discharge energy as compared with the conventional method, and the deposited film formed by the method of the present invention has an etching action, or It is extremely unlikely to be adversely affected by other effects such as abnormal discharge.

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.

Furthermore, the method of the present invention can optionally use light energy and / or heat energy in addition to the discharge energy. The light energy can be applied to the entire substrate by using an appropriate optical system, or can be selectively and selectively applied to only a desired portion.
It is possible to easily control the formation position and the film thickness of the deposited film on the substrate. Further, as the heat energy, heat energy converted from light energy can also be used.

One of the differences between the method of the present invention and the conventional CVD method is that
Since the activated species that are previously activated in a space different from the film formation space (hereinafter referred to as an activation space) are used, this can dramatically increase the film formation speed compared to the conventional CVD method. In addition, it is possible to further lower the substrate temperature at the time of forming the deposited film, and it is possible to industrially provide a large amount of the deposited film with stable film quality at low cost.

In the method of the present invention, the silicon-containing compound as the deposited film forming raw material is activated in the activation space to generate active species. Then, the generated active species is introduced from the activation space into the film formation space to form a deposited film in the film formation space. Therefore, the constituents of the active species constitute the constituents of the deposited film formed in the film formation space.
In the method of the present invention, the active species are appropriately selected and used as desired, but from the viewpoint of productivity and easiness of handling, the life is usually 0.1 seconds or more, but It is more preferable to use one having a duration of 1 second or longer, and optimally 10 seconds or longer.

Further, the compound containing germanium and halogen used in the method of the present invention is introduced into the film formation space, excited by the action of discharge energy, and introduced into the film formation space from the activation space at the same time as the aforementioned active species and chemical compounds. In the system, an action of accelerating the formation of a deposited film is exhibited by causing a physical interaction to give energy or cause a chemical reaction, for example.

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

It is preferable that the silicon-containing compound used as the material for forming a deposited film used in the present invention is already in a gas state or in a gas state before being introduced into the activation space. For example, when a liquid compound is used, an appropriate vaporizer can be connected to the compound supply system to vaporize the compound and then introduce the compound into the activation space.

As the silicon-containing compound, silicon, hydrogen, halogen,
Alternatively, silanes and halogenated silanes having a hydrocarbon group bonded thereto can be used.

Particularly, chain-like and cyclic silane compounds, compounds obtained by substituting a part or all of hydrogen atoms of the chain-like and cyclic silane compounds with halogen atoms, and the like are preferable.

Specifically, for example, SiH ₄ , Si ₂ H ₆ , Si ₃ H ₈ , Si ₄ H ₁₀ , Si ₅ H
₁₂ , Si ₆ H ₁₄ , etc. SipH ₂ p ₊₂ (p is 1 or more, preferably 1 to
It is an integer of 15, more preferably 1-10. ) Linear silane compound, SiH ₃ SiH (SiH ₃ ) SiH ₃ , SiH ₃ SiH
(SiH ₃ ) Si ₃ H ₇ , Si ₂ H ₅ SiH (SiH ₃ ) Si ₂ H ₅ etc.SipH ₂ p
A branched chain silane compound represented by ₊₂ (p has the above-mentioned meaning), and a part or all of hydrogen atoms of these linear or branched chain silane compounds are substituted with halogen atoms. Compound, Si ₃ H ₆ , Si ₄ H ₈ , Si ₅ H ₁₀ , Si ₆ H ₁₂
Such as SiqH ₂ q (q is 3 or more, preferably an integer of 3 to 6), some or all of the hydrogen atoms of the cyclic silane compound are replaced with other cyclic silanyl groups and / or Compounds substituted with a chain silanyl group, examples of compounds in which some or all of the hydrogen atoms of the above-mentioned silane compounds are substituted with halogen atoms are SiH ₃ F, SiH ₃ Cl, SiH ₃ B
r, SirHsXt such as SiH ₃ I (X is a halogen atom, r is 1 or more, preferably 1 to 10, more preferably an integer of 3 to 7,
s + t = 2r + 2 or 2r. And a halogen-substituted chain or cyclic silane compound represented by the formula (1). These compounds may be used alone or in combination of two or more.

In the present invention, as the compound containing germanium and halogen to be introduced into the film formation space, for example, a compound obtained by substituting a part or all of hydrogen atoms of a chain or cyclic germanium hydride compound with a halogen atom can be used. For example, GeuY ₂ u ₊₂ (u is an integer of 1 or more, Y is F, C
It is at least one element selected from l, Br and I. ) Chain germanium halide represented by GevY ₂ v
(V is an integer of 3 or more, and Y has the above-mentioned meaning), and the chain is represented by GeuHxYy (u and Y have the above-mentioned meaning. X + y = 2u or 2u + 2). Examples include a ring-shaped or cyclic compound.

Specifically, for example, GeF ₄ ,, (G ₂ F ₂ ) ₅ ,, (GeF ₂ ) ₆ ,, (Ge
F ₂ ) ₄ , Ge ₂ F ₆ , Ge ₃ F ₈ , GeHF ₃ , GeH ₂ F ₂ , GeCl ₄ , (GeCl ₂ ) ₅ , Ge
_{Br 4, (GeBr 2) 5} , Ge 2 Cl 6, Ge 2 Br 6, GeHCl 3, GeHBr 3, GeHI 3, G
Examples thereof include those in a gas state such as e ₂ Cl ₃ F ₃ or those that can be easily gasified.

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

As the compound containing silicon and halogen, for example, a compound obtained by substituting a part or all of hydrogen atoms of a chain or cyclic silane compound with a halogen atom can be used. Specifically, for example, SiuY ₂ u ₊₂ (U is an integer of 1 or more, Y is F,
It is at least one element selected from Cl, Br and I. ) Chain silicon halide represented by SivY ₂ v
(V is an integer of 3 or more, and Y has the above-mentioned meaning), and a chain represented by SiuHxYy (u and Y have the above-mentioned meaning; x + y = 2u or 2u + 2). Examples include a ring-shaped or cyclic compound.

Specifically, for example, SiF ₄ ,, (SiF ₂ ) ₅ ,, (SiF ₂ ) ₆ ,, (Si
F ₂ ) ₄ , Si ₂ F ₆ , Si ₃ F ₈ , SiHF ₃ , SiH ₂ F ₂ , SiCl ₄ (SiCl ₂ ) ₅ , SiB
r ₄ , (SiBr ₂ ) ₅ , Si ₂ Cl ₆ , Si ₂ Br ₆ , SiHCl ₃ , SiHBr ₃ , SiHI ₃ , Si
Examples thereof include those in a gas state such as ₂ Cl ₃ F ₃ or those that can be easily gasified.

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

As the compound containing carbon and halogen, for example, a compound obtained by substituting a part or all of hydrogen atoms of a chain or cyclic hydrocarbon compound with a halogen atom can be used, and specifically, for example, CuY ₂ u ₊₂ (u is an integer of 1 or more, Y is
It is at least one element or two or more elements selected from F, Cl, Br and I. ) A chain carbon halide represented by
Cyclic silicon halide represented by CvY ₂ v (V is an integer of 3 or more, Y has the above-mentioned meaning) and CuHxYy (u and Y have the above-mentioned meaning; x + y = 2u or 2u + 2). Examples thereof include the chain or cyclic compounds shown.

Specifically, for example, CF ₄ , (CF ₂ ) ₅ ,, (CF ₂ ) ₆ ,, (CF ₂ ) ₄ ,, C
₂ F ₆ , C ₃ F ₈ , CHF ₃ , CH ₂ F ₂ , CCl ₄ (CCl ₂ ) ₅ , CBr ₄ , (CBr ₂ ) ₅ , C
Examples thereof include those in a gas state such as ₂ Cl ₆ , C ₂ Br ₆ , CHCl ₃ , CHBr ₃ , CHI ₃ , and C ₂ Cl ₃ F ₃ or which can be easily gasified.

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

Furthermore, the compound containing germanium and halogen (or the compound containing silicon and halogen and / or
Or a compound containing carbon and halogen), if necessary, other germanium compounds such as germanium simple substance, hydrogen, halogen compounds (for example, F ₂ gas, Cl ₂ gas, gasified Br ₂ , I ₂ etc.), etc. Can also be used together.

In the present invention, in order to generate active species in the activation space, in consideration of each condition and device, microwave,
Electric energy such as RF, low frequency, DC, etc., heat energy by heater heating, infrared heating, etc., and activation energy such as light energy are used. That is, active species are generated by applying excitation energy such as heat, light, and discharge to the above-mentioned silicon-containing compound in the activation space.

In the present invention, the ratio of the amount of the compound containing germanium and halogen introduced into the film forming space and the amount of the active species generated from the silicon-containing compound may be appropriately set according to the film forming conditions, the type of the active species, etc. Decided, but preferably 10: 1 to 1:10
(Inlet flow rate ratio) is appropriate, and more preferably
8: 2 to 4: 6 is preferable.

In the method of the present invention, in addition to the silicon-containing compound as the above-described film-forming compound that generates active species in the activation space, hydrogen gas, a halogen compound (for example, F ₂ gas, Cl ₂ gas, gasified Br ₂ , I ₂ etc.), an inert gas such as helium, argon, or neon may be introduced into the activation space and used. When using a plurality of these compounds for film formation, they can be mixed in advance and introduced into the activation space, or these chemical substances for film formation can be individually supplied from independent sources. Alternatively, they can be introduced into the activation spaces, or can be introduced into the independent activation spaces and activated individually.

The deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. Preferable examples of the impurity element to be used include p-type impurities such as elements of Group A group A, such as B, Al, Ga, In and Tl, and n-type impurities include periodic elements. The elements of Group V in Table V, such as P, As, Sb, Bi, etc., can be mentioned as suitable ones, but B, Ga, P, Sb, etc. are particularly suitable. The amount of impurities to be doped is appropriately determined according to desired electrical / optical characteristics.

As the substance containing such an impurity element as a component (impurity introducing substance), a compound that is in a gas state at room temperature and atmospheric pressure, or is a gas at least under the conditions for forming a deposited film, and can be easily vaporized by an appropriate vaporizer. Is preferably selected.

Examples of such _{compounds, PH 3, P 2 H 4} , PF 3, PF 5, PCl 3, As
_{H 3, AsF 3, AsF 5} , AsCl 3, SbH 3, SbF 5, SiH 3, BF 3, BCl 3, BBr 3, B 2
_{H 6, B 4 H 10,} B 5 H 9, B 5 H 11, B 6 H 10, B 6 H 12, AlCl 3 and the like. The compound containing an impurity element may be used alone or in combination of two or more.

The substance for introducing impurities may be introduced into the film formation space directly in a gas state or mixed with the compound containing germanium and halogen, or may be activated in the activation space and then formed into a film. It can also be introduced into space.

In order to activate the substance for introducing impurities, the above-mentioned activation energy for generating active species can be appropriately selected and employed. The active species (PN) generated by activating the substance for introducing impurities is premixed with the active species, or is introduced alone into the film formation space.

Next, the content of the method of the present invention will be described with a typical example of an electrophotographic imaging member and a semiconductor device as specific examples.

FIG. 1 is a schematic view for explaining a constitutional example of a photoconductive member as a typical electrophotographic image forming member obtained by the present invention.

The photoconductive member 10 shown in FIG. 1 can be applied as an electrophotographic image forming member, and includes an intermediate layer 12 and a photosensitive layer, which are provided on the support 11 for the photoconductive member as necessary. It has a layer structure composed of the layer 13.

In making the photoconductive member 10, the intermediate layer 12 and / or the photosensitive layer 13 can be made by the method of the present invention.
Further, the photoconductive member 10 is a protective layer provided for chemically and physically protecting 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. If these are present, these layers can also be prepared by the method of the present invention.

The support 11 may be either conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel, Al, Cr, Mo, Au, Ir, Nb, Ta, V, T
Examples thereof include metals such as i, Pt, and Pd, or alloys thereof.

Examples of the electrically insulating support include polyester, polyethylene, polycarbonate, cellulose acetate,
Examples thereof include films or sheets of synthetic resin such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene and polyamide, glass, ceramics and paper.
It is preferable that at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is provided on the side of the surface subjected to the dielectric treatment.

For example, glass is NiCr, Al, Cr, Mo, Au, I on the surface.
Conductive treatment by providing a thin film of r, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ + SnO ₂ ) or synthesis of polyester film NiC for resin film
r, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt and other metals are processed by vacuum evaporation, electron beam evaporation, sputtering etc. A lamination process is performed, and the surface is subjected to a conductive process. The shape of the support can be any shape such as a cylindrical shape, a belt shape, a plate shape, or the like. The shape can be appropriately determined depending on the use and desire. For example, in the case of continuous high speed copying, if the photoconductive member 10 of FIG. 1 is used as an electrophotographic image forming member. It is desirable that the endless belt or the cylinder is used.

The intermediate layer 12 effectively blocks the inflow of carriers from the side of the support 11 into the photosensitive layer 13, and is generated in the photosensitive layer 13 by the irradiation of electromagnetic waves and moves toward the side of the support 11. It has a function of easily allowing the photo-carrier to pass from the side of the photosensitive layer 13 to the side of the support 11.

The intermediate layer 12 is an amorphous silicon germanium (hereinafter, referred to as “a-SiGe (H, X) having a silicon atom and a germanium atom as a base material, and optionally containing a hydrogen atom (H) and / or a halogen atom (X). )), And as a substance that controls electrical conductivity, for example, p-type impurities such as boron (B) or n-type impurities such as adjacent (P) are contained.

In the present invention, the amount of the substance such as B or P contained in the intermediate layer 12 that controls the conductivity is usually 1 × 10 ^−3.
To 5 × 10 ⁴ atomic ppm, more preferably 5 × 10 ^-1
~ 1 × 10 ⁴ atomic ppm, optimally 1-5 × 10 ³ atomic p
pm is preferred.

When the constituents of the intermediate layer 12 and the photosensitive layer 13 are similar or the same, the formation of the intermediate layer 12 and the formation of the photosensitive layer 13 can be continuously performed. In that case, as a raw material for forming the intermediate layer, a compound containing germanium and halogen, a silicon-containing compound in a gas state, and if necessary, hydrogen, a halogen compound, a gas of a compound containing an inert gas and an impurity element as a component. And the like, and the active species generated by activating, etc., are introduced into the film formation space in which the support 11 is installed separately or by appropriately mixing them as necessary, and by applying discharge energy. The intermediate layer 12 may be formed on the support 11.

The thickness of the intermediate layer 12 is preferably 3 × 10 ^{−3 to} 10 μ, more preferably 4 × 10 ^{−3 to} 8 μ, and most preferably 5 × 10 ^{−3 to} 5 μ.

The photosensitive layer 13 is made of, for example, silicon as a matrix, and if necessary, amorphous silicon having hydrogen, halogen, germanium or the like as a constituent atom (hereinafter, referred to as “a-Si (H, X, Ge)”) or germanium. And amorphous as-germanium (hereinafter referred to as “a-Ge (H, X)”) whose constituent atoms are hydrogen, halogen, etc. It has both a charge generating function of generating a charge and a charge transporting function of transporting the charge.

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

The photosensitive layer 13 is composed of non-doped a-Si (H, X), but if desired, has a conductivity characteristic of a polarity (for example, n-type) different from that of the substance contained in the intermediate layer 12 that governs the conductivity characteristics. It may contain a controlling substance, or the intermediate layer 12
When the actual amount of the substance that controls the conduction characteristic is large, the substance that controls the conduction characteristic of the same polarity may be contained in a smaller amount than that.

When the photosensitive layer 13 is formed by the method of the present invention,
This is performed in the same manner as in the case of the intermediate layer 12. That is, a compound containing germanium and a halogen or a compound further containing silicon and a halogen, an active species generated from a silicon-containing compound for film formation, an inert gas if necessary, and a gas of a compound containing an impurity element as a component. Are introduced into the film forming space where the support 11 is installed, and discharge energy is used to form the photosensitive layer 13 on the intermediate layer 12 formed on the support 11.

FIG. 2 is a schematic diagram showing a typical example of a PIN diode device using an a-SiGe deposited film doped with an impurity element, which is manufactured by the method of the present invention.

In the figure, 21 is a substrate, 22 and 27 are thin film electrodes, and 23 is a semiconductor film, which is composed of an n-type semiconductor layer 24, an i-type semiconductor layer 25, and a p-type semiconductor layer 26. Reference numeral 28 is a lead wire connected to an external electric circuit device.

The substrate 21 may be conductive, semi-conductive, or electrically insulating. If the substrate 21 is conductive, the thin film electrode 22 may be omitted. As the semiconductive substrate, for example, Si, Ge, GaAs, ZnO, Z
Examples include semiconductors such as nS. The thin film electrodes 22 and 27 are, for example, N
iCr, Al, Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO
It can be obtained by providing a thin film such as (In ₂ O ₃ + SnO ₂ ) on the substrate by a process such as vacuum deposition, electron beam deposition, sputtering and the like. The layer thickness of the electrodes 22 and 27 is preferably 30 to 5
It is desirable to set it to x10 ⁴ Å, more preferably 10 ^{2 to} 5 x 10 ³ Å.

In order to make the film body forming the semiconductor layer n-type or p-type as necessary, when forming the layer, n-type impurities or p-type impurities of impurity elements, or both impurities are added to the layer to be formed. It is formed by controlling the amount and doping.

Any one of n-type, i-type and p-type a-SiGe (H, X) layers 1
One to all can be formed by the method of the present invention. That is, a compound containing germanium and halogen and a compound containing silicon and halogen are introduced into the film formation space. Separately from this, a silicon-containing compound, which is a chemical substance for film formation, introduced into the activation space, and, if necessary, an inert gas and a gas of a compound containing an impurity element as components are activated respectively. Excited by energy and decomposed to generate respective active species, which are introduced separately or appropriately mixed and introduced into the film formation space in which the support 11 is installed.
By causing discharge energy to act on the compound and the active species introduced into the film formation space, a chemical interaction is caused, or further promoted or amplified, and the support 11
A deposited film is formed on top. n-type and p-type a-SiGe
The layer thickness of (H, X) is preferably in the range of 10 ² to 10 ⁴ Å, more preferably 3 × 10 ² to 2 × 10 ³ Å. The layer thickness of i-type a-SiGe (H, X) is preferably 5 × 1.
It is desirable that the range is 0 ² to 10 ⁴ Å, more preferably 10 ³ to 10 ⁴ Å.

In addition, the p-type of the PIN diode device shown in FIG.
The object of the present invention can be achieved by forming at least one of the i-type semiconductor layer and the n-type semiconductor layer by the method of the present invention. By forming by the method of the present invention,
The conversion efficiency can be improved.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1 Using the apparatus shown in FIG.
Type, p-type and n-type a-SiGe (H, X) deposited films were formed.

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

Reference numeral 104 denotes a heater for heating the substrate. The heater 104 is used when the substrate 103 is heat-treated before the film formation process or after the film formation is annealed to further improve the characteristics of the formed film. The power is supplied through the conducting wire 105 to generate heat. The substrate heating temperature is not particularly limited, but when it is necessary to heat the substrate, it is preferably 30 to 450 ° C, more preferably 50 to 350 ° C in carrying out the method of the present invention. desirable.

106 to 109 are gas supply sources, silicon-containing compounds,
Further, it is provided depending on the types of hydrogen, halogen compounds, inert gas, gas of a compound containing an impurity element as a component, and the like, which are used as necessary. When using a liquid form of these raw material compounds in the standard state, an appropriate vaporizer is provided.

In the figure, reference numerals of gas supply sources 106 to 109 are indicated by a, a branch pipe, b by a flow meter, c by a pressure gauge for measuring the pressure on the high pressure side of each flow meter, and d. Alternatively, a valve denoted by e is a valve for adjusting each gas flow rate. 123 is an activation chamber for generating active species, and a microwave plasma generator 122 for generating activation energy for generating active species is provided around the activation chamber 123. A raw material gas for active species generation supplied from the gas introduction pipe 110 is activated in the activation chamber 123, and the generated active species is introduced into the film formation chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge.

In the figure, 112 is a supply source of a compound containing germanium and halogen, and a to e attached to the reference numeral 112 are 106 to 10
The same thing as the case of 9 is shown.

The compound containing germanium and halogen is introduced into the film formation chamber 101 through the introduction pipe 113.

Further, in the case of forming a film body having Si or the like as a constituent atom in addition to Ge, a supply source (not shown) similar to 112 is separately provided and a compound containing silicon and halogen is introduced into the film formation chamber 101. be able to.

Reference numeral 117 denotes a discharge energy generating device, which is provided with a matching box 117a, a high frequency introducing cathode electrode 117b, and the like.

The discharge energy from the discharge energy generator 117 is
The compound acts on the compound containing germanium and halogen and the active species flowing in the directions of arrows 116 and 119, and the reacted compound reacts with the compound containing germanium and halogen, and the active species are chemically reacted with each other. , X) to form a deposited film. Further, in the figure, 120 is an exhaust valve and 121 is an exhaust pipe.

First, a substrate 103 made of polyethylene terephthalate film
Was placed on the support base 102, the inside of the film forming chamber 101 was evacuated using an exhaust device, and the pressure was reduced to about 10 ⁻⁶ Torr. Using gas supply source 106 Si ₅ H ₁₀ gas 150 SCCM, or this and PH ₃ gas or
A gas mixed with 50 SCCM of B ₂ H ₆ gas (each diluted with 1000 ppm hydrogen gas) was introduced into the activation chamber 123 through the gas introduction pipe 110. The Si ₅ H ₁₀ gas or the like introduced into the activation chamber 123 is activated by the microwave plasma generator 122 into activated silicon hydride or the like, and the activated silicon hydride or the like is formed through the introduction pipe 124. It was introduced into the membrane chamber 101.

On the other hand, GeF ₄ gas from the supply source 112 is passed through the introduction pipe 113,
It was introduced into the film forming chamber 101.

In this way, while maintaining the internal pressure in the film forming chamber 101 at 0.4 Torr, the plasma from the discharge device is caused to act on the non-doped or doped a-SiGe (H, X) film (film thickness 700
Å) formed. The film formation rate was 25Å / sec.

Then, the obtained undoped or p-type a-SiGe
The (H, X) film sample was placed in a vapor deposition tank, and after forming a comb-type Al gear gap electrode (gear length 250μ, width 5mm) at a vacuum degree of 10 ^-5 Torr, dark current was measured at an applied voltage of 10 V and the dark current was measured. Conductivity σd
Then, the film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2 to 4 Similar to Example 1 except that linear Si ₄ H ₁₀ gas, branched Si ₄ H ₁₀ gas, or H ₆ Si ₆ F ₆ gas was used instead of Si ₅ H ₁₀ gas. An a-SiGe (H, X) film was formed according to the method and procedure.

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

From the results shown in Table 1, a formed by the method of the present invention
It has been found that the -SiGe (H, X) film has excellent electrical characteristics and is sufficiently doped.

Fifth Embodiment Using the device shown in FIG. 4, the first operation is performed as follows.
A drum-shaped electrophotographic image forming member having a layer structure as shown in the drawing was prepared.

In FIG. 4, 201 is a film forming chamber, 202 is a compound supply source containing germanium and halogen, 206 is a compound introduction tube containing germanium and halogen, 207 is a motor, and 208 is 10 in FIG.
A heating heater used in the same manner as in 4, 209 and 210 are blowing pipes, 211 is an Al cylindrical base, and 212 is an exhaust valve. Further, 213 to 216 are source gas supply sources similar to 106 to 109 in FIG. 3, and 217-1 is a gas introduction pipe.

An Al cylinder-shaped substrate 211 is hung in the film forming chamber 201, a heater 208 is provided inside the substrate 211, and a motor 207 can rotate the substrate. Reference numeral 218 is a discharge energy generator, which is a matching box 218a and a cathode electrode 21 for high frequency introduction.
Equipped with 8a etc.

First, GeF ₄ gas from the supply source 202 is passed through the introduction pipe 206, and then the film formation chamber
Introduced to 201.

On the other hand, Si ₂ H ₆ gas and H ₂ gas are introduced from the introduction pipe 217-1 into the activation chamber.
It was introduced in 219. The introduced Si ₂ H ₆ gas and H ₂ gas are subjected to activation treatment such as plasma conversion by the microwave plasma generator 220 in the activation chamber 219 to obtain activated silicon hydride, and a film is formed through the introduction pipe 217-2. Introduced into room 201.
At this time, if necessary, impurity gases such as PH ₃ and B ₂ H ₆ were also introduced into the activation chamber 219 for activation.

While maintaining the internal pressure in the film formation chamber 201 at 0.4 Torr, the discharge device 218
To activate the plasma.

The Al cylindrical substrate 211 was heated to 200 ° C. by the heater 208, held and rotated, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust valve 212.

Although the photosensitive layer 13 was formed in this manner, in the case of forming the intermediate layer 12, prior to the formation of the photosensitive layer 13, H ₂ / B ₂ H ₆ (B ₂ H ₆ The photosensitive layer 13 was the same as the photosensitive layer 13 except that a mixed gas containing 0.2% of gas was introduced. The thickness of the obtained intermediate layer was 2000Å.

Comparative Example 1 A film forming chamber having the same structure as the film forming chamber 201 was prepared by using each gas of SiF ₄ gas, Si ₂ H ₆ gas, H ₂ gas and B ₂ H ₆ gas.
An image forming member for electrophotography having a layer structure shown in FIG. 1 was formed by a general plasma CVD method equipped with a high frequency device of MHz.

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

Example 6 The PIN diode shown in FIG. 2 was produced by using the apparatus of FIG. 3 using Si ₃ H ₆ as the silicon-containing compound.

First, a polyethylene naphthalate film 21 having a 1000 Å ITO film 22 deposited thereon was placed on a support and the pressure was reduced to about 10 ⁻⁶ Torr. Then, in the same manner as in Example 1, a GeF ₄ gas was formed from the introduction tube 113. Introduced into room 101.

Further, each of Si ₂ H ₆ gas, H ₂ gas, and PH ₃ gas (diluted with 1000 ppm hydrogen gas) was introduced into the activation chamber 123 to be activated.

Next, the activated gas was introduced into the film forming chamber 101 through the introduction pipe 124. While maintaining the internal pressure in the film forming chamber 101 at 0.4 Torr, plasma was applied by a discharge device to form an n-type a-SiGe (H, X) film 24 (film thickness 700Å) doped with P.

Next, except that the introduction of PH ₃ gas was stopped, n-type a-SiGe
Undoped a-SiGe in the same way as for (H, X) film
A (H, X) film 25 (film thickness 5000Å) was formed.

Next, B ₂ H ₆ gas (diluted with 1000 ppm hydrogen gas) together with H ₂ gas, and a p-type a-SiGe (H, X) film 26 (film thickness 700 Å) doped with B under the same conditions as n type otherwise Formed.
Furthermore, a 1000 Å film thickness of Al is formed on this p-type film by vacuum deposition.
The electrode 27 was formed to obtain a PIN diode.

IV of the diode device (area: 1 cm ² ) thus obtained
The characteristics were measured and the rectification characteristics and the photovoltaic effect were evaluated.
The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, light is introduced from the substrate side, and the conversion efficiency is 8.2% or more at the light irradiation intensity AMI (about 100 mW / cm ² ).
An open circuit voltage of 0.95 V and a short circuit current of 10.1 mA / cm ² were obtained.

Examples 7 to 9 Instead of Si ₃ H ₆ gas as a silicon compound, linear Si ₄ H _{10 was used.}
A PIN diode similar to that produced in Example 6 was produced in the same manner as in Example 6 except that gas, branched Si ₄ H ₁₀ gas, or H ₆ Si ₆ F ₆ gas was used. The rectifying characteristics and the photovoltaic effect of this sample were evaluated, and the results are shown in Table 3.

From Table 3, according to the method of the present invention, a-SiGe having better optical and electrical characteristics than those by the conventional method is obtained.
It has been found that a (H, X) PIN diode can be obtained.

[Outline of Effects of Invention]

According to the deposited film forming method of the present invention, desired electrical, optical, photoconductive and mechanical properties of the formed film are improved, and high-speed film formation is possible. In addition, the reproducibility in film formation is improved, the film quality can be improved and the film quality can be made uniform, and it is advantageous for increasing the area of the film, and it is possible to easily achieve improvement in film productivity and mass production. be able to. Furthermore, for example, when a film can be formed on a substrate having poor heat resistance, the process can be shortened by the low temperature treatment, and the effect is exhibited.

[Brief description of drawings]

FIG. 1 is a schematic view for explaining a constitutional example of an electrophotographic image forming member manufactured by using the method of the present invention. FIG. 2 is a schematic diagram for explaining a configuration example of a PIN diode manufactured by using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of the apparatus for carrying out the method of the present invention used in the examples. 10 ... Electrophotographic image forming member 11 ... Support 12 ... Intermediate layer 13 ... Photosensitive layer 21 ... Substrate 22, 27 ... Thin film electrode 24 ... N-type semiconductor layer 25 ... i-type semiconductor layer 26 ...... P-type semiconductor layer 28 …… lead wire 101,201 …… deposition chamber 112,202 …… compound source containing germanium and halogen 123,219 …… activation chamber 106,107,108,109,213,214,215,216 …… gas source 103,211 …… substrate 117,118 …… discharge energy generator 102 ... Base support 104,208 ... Heater for heating base 105 ... Conductor 110,113,124,206,217-1,217-2 ... Introduction pipe 111 ... Pressure gauge 120,212 ... Exhaust valve 121 ... Exhaust pipe 122,220 ... Activation energy generator 209,210 …… Blowout tube 207 …… Motor

Front page continuation (72) Inventor Isamu Shimizu 2-41-21 Fujigaoka, Midori-ku, Yokohama-shi, Kanagawa (56) Reference JP-A-59-90923 (JP, A)

Claims (1)

[Claims] 1. A linear or branched structure represented by the general formula Si _p H _{2p + 2} (p is an integer of 2 to 6) is formed in a film formation space for forming a deposited film on a substrate. silane compound, or the general formula Si _p H _{2p + 2 (p} is a is an integer from 2 to 6) a silane compound having a straight瑳状or branched represented by, or the general formula Si
A cyclic silane compound represented by _q H _2q (q is an integer of 3 to 6), or an active species generated by decomposing H ₆ Si ₆ F ₆ and a chemical interaction with the active species. GeF
_{4. A} method for forming a deposited film, characterized in that ₄ and ₄ are separately and simultaneously introduced, and discharge energy is applied to these to form a deposited film on the substrate.