JPS61236114A - Method for formation of deposition film - Google Patents

Abstract

PURPOSE:To enable to form a film at a high speed without maintaining a substrate at a high temperature by a method wherein germanium, halogen and the activating species formed by the carbon-containing compound for formation of a film are introduced, and they are chemically reacted by projecting photoenergy. CONSTITUTION:The intermediate layer 12 is constituted by the amorphous film containing germanium atoms, hydrogen atoms and/or halogen atoms, and carbon atoms as constituent atoms, and the P-type impurities such as boron and the like, for example, or the N-type impurities such as phosphorus and the like are contained as the material with which electric conductivity is controlled. When the intermediate layer 12 and a photosensitive layer 13 are formed continuously, active species formed by the compound containing germanium and halogen, and the carbon-containing compound for formation of a film, are introduced into the film forming vacant space as the raw material for the formation of the intermediate layer 12, a chemical reaction is generated by projecting photoenergy on the above-mentioned materials, and a deposition film is formed on the substrate.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention relates to a deposited film containing germanium and carbon, especially a functional film, especially a semiconductor device, a photosensitive device for electrophotography, a line sensor for image processing, and an imaging device. device,
The present invention relates to a method suitable for forming an amorphous or crystalline deposited film for use in photovoltaic devices and the like.

[Prior art]

For example, to form a deposited film such as an amorphous silicon film,
Vacuum deposition method, plasma CVD method.

CVD methods, reactive sputtering methods, ion blating methods, photo-CVD methods, and the like have been tried, and in general, plasma CVD methods are widely used and commercialized.

Deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility.
In terms of mass production, there is room to further improve the overall characteristics.

The reaction process in forming an amorphous silicon deposited film by the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, which often has a significant negative effect on the deposited film. Moreover,
The actual situation is that parameters unique to each device must be selected for each device, and therefore it is difficult to generalize manufacturing conditions. On the other hand, in order to develop an amorphous silicon film that fully satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. There is.

However, depending on the application of the deposited film, it is possible to satisfy the requirements of large area, uniform film thickness, uniform film quality, and high speed A.
Since it is necessary to achieve mass production with reproducibility using M, the formation of amorphous silicon deposited films using the plasma CVD method requires a large amount of capital investment in mass production equipment, and the management items for mass production are also complicated. As a result, the permissible management range has become narrower and the adjustment of equipment has become more delicate, so these have been pointed out as issues that should be respected in the future. On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to provide a deposited film with practically usable characteristics.

In the formation of amorphous silicon films such as HA, there is a strong desire to develop a method of forming amorphous silicon films that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity. The same can be said of other functional films, such as silicon nitride films, silicon carbide films, and fermented silicon films.

The present invention eliminates the above-mentioned drawbacks of the plasma CVD method and provides a new deposited film forming method that does not rely on conventional forming methods.

[Object of the invention and summary of disclosure]

The purpose of the present invention is to improve the properties, growth rate, and reproducibility of the film to be formed, and to make the film uniform in quality, while also being suitable for large-area films, improving film productivity, and mass production. An object of the present invention is to provide a method for forming a deposited film that can easily achieve the following.

The above purpose is to create an active substance that is generated by a compound containing germanium and halogen and a carbon-containing compound for film formation that chemically interacts with the compound containing germanium and halogen in the film formation space for forming a deposited film on a substrate. This is achieved by the deposited film forming method of the present invention, which is characterized in that a deposited film is formed on the substrate by introducing seeds and irradiating them with light energy to cause a chemical reaction.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film forming space for forming a deposited film, a compound containing germanium and halogen coexists with active species generated from a carbon-containing compound for film forming. By applying light energy to these components, chemical interactions are caused, promoted, or amplified. Therefore, the deposited film that is formed is free from etching effects or other adverse effects such as abnormal discharge effects. You will not receive any.

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

Furthermore, excitation energy is applied uniformly or selectively to the raw material that has reached the vicinity of the substrate, but if optical energy is used, the entire substrate is irradiated using an appropriate optical system to form a deposited film. Alternatively, it is possible to selectively control and irradiate only the desired area to form a partially deposited film, or use a resist etc. to irradiate only a predetermined graphic area to form a deposited film. It is advantageously used because it has the convenience of being able to be formed.

One of the points that differs from the conventional CVD method is that the wood-based method uses active species that have been activated in advance in a space different from the film-forming space (hereinafter referred to as activation space).

This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and also to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

In addition, the active species in the present invention is a species that has the effect of promoting the formation of a deposited film by chemically interacting with a compound containing germanium and a halogen, for example, by imparting energy or causing a chemical reaction. Therefore, the active species may include constituent elements constituting the deposited film to be formed, or may not include such constituent elements.

In the present invention, the active species from the activation space introduced into the film forming space has a lifetime of (1 second or more, more preferably 1 second or more, optimally) from the viewpoint of productivity and ease of handling. A length of 10 seconds or more is selected and used as desired.

The carbon-containing compound for forming a deposited film used in the present invention is preferably in a gaseous state before being introduced into the activation space, or is preferably introduced in a gaseous state, for example, a liquid compound. When using a compound supply system, an appropriate vaporizer can be connected to the compound supply system 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, organic compounds whose main constituent atoms are carbon and hydrogen, and one or more constituent atoms such as halogen and sulfur, and carbonized Among organosilicon compounds having a hydrogen group as a constituent and organosilicon compounds having a bond between silicon and carbon, those in a gaseous state or those that can be easily vaporized are preferably used.

Among these, 1 as a hydrocarbon compound, for example, 1 carbon number
~5 saturated hydrocarbons, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylenic hydrocarbons having 2 to 4 carbon atoms, etc. Specifically, saturated hydrocarbons include methane (CH4), ethane (C2H6), Propane (CsHe), n-Buta 7 (n
-C4H1o), penta7 (C5H12), and ethylene hydrocarbons include ethylene (C2H4), propylene (C3H6), and butene-1 (C4H8).

Butene-2 (C4H8), Isobutylene (C4H8)
, pente 7 (CsHto), acetylene (C2H2), methylacetylene (C
3H4), butyne (C4Hs), and the like.

As the halogen-substituted hydrocarbon compound, at least one of the hydrogens that are constituents of the hydrocarbon compound described above is F,
Compounds substituted with CM, Br, I can be mentioned,
Particularly effective are compounds in which hydrogen is substituted with F or C1.

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

Examples of the organosilicon compounds used in the present invention include organosilanes and organohalogensilanes.

Organosilane and organohalogensilane each have the general formula; Rn5iH4-H, RmSfX4-m (however,
R: alkyl group, aryl group HX: F, C1, Br, I
@n=1,2,3.4am=1.2.3) Representative examples include alkylsilanes, arylsilanes, alkylhalogensilanes, and arylhalogensilanes.

Specifically, as organochlorosilane, trichloromethylsilane CH35iCJ
L3 dichlorodimethylsilane (CH3
) 251cJ12 Chlortrimethylsilane
(CH3)3Sicjl trichloroethylsilane
C2H55iCfL3 dichlorodiethylsilane (C2H5)2SiC12 organochlorofluorosilane.

Chlordifluoromethylsilane CH35iF2
C1 dichlorofluoromethylsilane CH35i
FCJ12 Chlorfluorodimethylsilane (C
H3) 2S i FCfL Chlorethyldifluorosilane CC2H3)Si F2C1 Dichloroethylfluorosilane C2H55iFC2 Chlorodifluoropropylsilane CC3H75iF2
c dichlorofluoropropylsilane C3H75i
FC42 organosilane is tetramethylsilane (CH3)
4S i Ethyltrimethylsilane (C
H3) 3SiC2H5 trimethylpropylsilane
(CH3)3SiC3H7 triethylmethylsilane CH35i (C2H5)3tetraethylsilane (C2H5)4S
As organohydrogenosilane.

Methylsilane CH35iH
3dimethylsilane (CH3)
2S i H2 trimethylsilane
(CH3) 3 S i H diethylsilane
(C2Hs)2SiH2Triethylsilane (C2H5)3S iH
Tripropylsilane (C3H7)
3S iH diphenylsilane (
C6H5)2S iH2 Orcanofluorosilane is trifluoromethylsilane CH35iF3
Cyfluorodimethylsilane (CH3)
2S i F2 fluorotrimethylsilane
(CH3) 3 S i F Ethyltrifluorosilane C2H55iF3 Diethyldifluorosilane (C2H5) 2S iF2 Triethylfluorosilane (C2H5) 3 S
tF trifluoropropylsilane (C
3H7) S i F3 organobromosilane includes bromotrimethylsilane (CH3)3
SiBrdibromdimethylsilane (CH
3) 25iBr2, etc., and other organopolysilanes include hexamethyldisilane ((CH3)
3S i) as 2-organodisilane.

Hexamethyldisilane ((CH3)
3Si) 2hexapropyldisilane
((C3H7)3Si)2 etc. can also be used.

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

In the present invention, as the compound containing germanium and halogen introduced into the film forming space, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic germanium hydride compound is replaced with a halogen atom is used. for,
For example, a chain germanium halide GevY2v (v is an integer of 3 or more, Y has the above-mentioned meaning.) Cyclic halide, rumanium, G
Examples include chain or cyclic compounds represented by e 11 HX Y y (U and Y have the above-mentioned meanings. x+y=2U or 2u+2).

Specifically, 1, for example, aeF4. (GeF2)5, (G
eF2)s, (GeF2)4, Ge2Fe, Ge
3Fs, Ge) IF3. GeH2F2゜GeCIa,
(GeCI2)ei, GeBr4゜(GeBr2)
5, Ge2C1B, Ge2Bre, GeHcJl
3, GeHBr3, GeHI3.

Examples include those that are in a gaseous state or can be easily gasified, such as Ge2CI3F3.

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 in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used. Specifically, for example, S i 11 Y 2u+2 (u is Chained silicon halide represented by 5iyY2v (v is an integer of 3 or more, Y is an integer of 3 or more, Y is the above-mentioned meaning) Cyclic silicon halide, S i
u8)(Yy (u and Y have the above meanings. x
y=2u or 2u+2. ), and the like.

Specifically, for example, SiF4. (SiF2)5゜(SiF
2) s, (SiF2)4.5t2F6゜5i3FB,S
iHF3.5jH2F2゜5iC14(SiC12)5
．． SiBr4゜(SiBr2)5,5i2C1s,5i
2Br6. S: HCl3. S: HBr3. S:HI3,
Examples include those in a gaseous state or those that can be easily gasified, such as 5i2C13F3.

These silicon 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 replaced with a halogen atom is used. Specifically, for example, CuY2u+2 (u is 1 An integer greater than or equal to Y, F, CI.

It is at least one element selected from Br and I. ) Chain I＼ rogenated carbon, CVY2V (
V is an integer of 3 or more, and Y has the meaning described above. ), C11HxYy (u and Y have the above-mentioned meanings.xy=2u or 2u+2
It is. ) Examples of the chain-like compound represented by ) include cyclic compounds.

271, for example, CF4, (CF2)5 for weight.

(CF2)6. (CF2)4. C2F6. C3FB,
CHF3, CH2F2. CC14(CC12)s+C
Br4. (CBr2)5. C2C1e, C2Br5. C
HCl3. Examples include those that are in a gaseous state or can be easily gasified, such as CHI3°C2Cl3F3.

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

Furthermore, in addition to this compound, other germanium-containing compounds such as simple germanium, hydrogen, and halogen compounds (for example, F2 gas) may be added as necessary.

C12 gas, gasified Br2. I2 etc.) can be used in combination.

In the present invention, methods for generating active species in the activation space include microwave, R
Activation energy such as electricity such as F, low frequency, DC, electrical energy, thermal energy such as heater heating, infrared heating, and light energy is used.

Activated species are generated by adding excitation energy such as heat, light, electricity, etc. in the activation space to the above.

In the present invention, a compound containing germanium and halogen is introduced into the film forming space, and a deposit is introduced into the activation space.
The ratio of the amount to the active species generated from the carbon-containing compound for film formation is determined as desired depending on the film forming conditions, the type of active species, etc., but is preferably lO:1 to 1:10 (introduction flow rate ratio). is suitable, more preferably 8:2 to 4:6
It is desirable that this is done.

In the present invention, in addition to the carbon-containing compound, a silicon-containing compound for forming a deposited film that generates active species, hydrogen gas, or a halogen compound (for example, F
2 gas, CI2 gas, gasified Br2, I2, etc.), helium, inert gas such as argon, neon, etc. can also be used in 711 by introducing into the activation space. 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. .

As a silicon-containing compound for forming a deposited film.

Silanes and halogenated silanes in which hydrogen, halogen, or hydrocarbon groups are bonded to silicon can be used. Particularly suitable are chain and cyclic silane compounds, and compounds in which part or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with /\logen atoms.

Specifically, for example, 5tH4, S i 2H6, S
i 3) (8, S i 4HIO, S i 5H12,
Linear silane compounds represented by 5iPH2F+2 (P is an integer of 1 or more, preferably 1-15, and more preferably 1-10) such as 5i6H14, 5iH3SiH (
SiH3)SIH3゜S 1H3S iH(S 1H3
)S t3) 17°-5i2H5SiH(SiH3)S
A chain silane compound having a branch represented by 5ipH2p+2 (p has the above-mentioned meaning) such as i2H5, and a part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with a halogen atom. substituted compounds,
5i3H6, 5i4H8, S i 5) (to, S
i 6H12 etc. (1) A cyclic silane compound represented by S i qH2 (1 (q is an integer of 3 or more, preferably 3 to 6), in which some or all of the hydrogen atoms of the cyclic silane compound are replaced by other Examples of compounds substituted with cyclic silanyl groups and/or chain silanyl groups, and compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are substituted with halogen atoms include SiH3F, 5iH3C1, 5iH3Br, 5i
H3I etc.cy)SirHsXt (X is a halogen atom,
r is 1 or more, preferably 1 to lO1, more preferably 3 to
An integer of 7, 3+t=2r+2 or 2r. ) and halogen-substituted linear or cyclic silane compounds. These compounds may be used alone or in combination of two or more.

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. The impurity elements to be used include, as p-type impurities, elements of group Ⅰ A (7) of the periodic table, such as B, AI, and Ga.
, In.

Preferred examples include TI, and examples of n-type impurities include elements of group V A of the periodic table, such as P, As, Sb,
Preferred examples include Bi, but especially B and Ga.
, P, Sb, etc. are optimal. The amount of impurity to be doped is determined as appropriate 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. Such compounds which are preferably selected include PH3, P2H4, PF
3, PF5, PC13, AsH3, AsF3.

AsF5. AsCl3. SbH3, SbF5゜5i)(
3, BF3. BCl3, BBr3.

B2H6, B4H10, B5H9, B5H11゜B6H
10, B8H12, AlCl3, etc. The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity-introducing substance may be introduced into the film forming space directly in a gaseous state or mixed with the compound containing carbon and halogen, or it may be activated in an activation space and then introduced into the film forming space. You can also. In order to activate the impurity-introducing substance, the above-mentioned activation energy can be appropriately selected and employed. The active species (P N) generated by activating the impurity introduction substance are:

It is mixed with the active species in advance or introduced into the film forming space independently.

Next, the present invention will be described with reference to typical examples of electrophotographic image forming members formed by the method of the present invention.

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 present invention.

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

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13 can be created by the method of the present invention. Furthermore, the photoconductive member 10 may include a protective layer provided to chemically or 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. If so, these can also be created by the method of the present invention.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, AI, Cr, and Mo.

Au, Ir, Nb, Ta, V, Ti, Pt.

Fully flexible materials such as Pd or alloys thereof may be used.

Polyester is used as the electrically insulating support.

Films or sheets of synthetic resins such as polyethylene, polycarbonate 9 cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are commonly used.

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, its surface is NiCr.

Al, Cr, Mo, Au, Ir, Nb, Ta.

V, Ti, Pt, Pd, In2O3,5n02゜I
If it is conductive treated by providing a thin film such as TO (I n203 + 5n02), or if it is a synthetic resin film such as polyester film, NiCr, AI, A
g, Pb, Zn, Ni.

Au, Cr, Mo, Ir, Nb, Ta, V.

The surface is treated with a metal such as Ti or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal to make the surface conductive. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined depending on the needs.1 For example, the photoconductive member 10 in FIG. If used as a member, in the case of continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape.

For example, a photosensitive layer 13 is applied to the intermediate layer 12 from the side of the support 11.
This effectively prevents the inflow of carriers into the photosensitive layer 13 and causes the photocarriers to flow from the side of the photosensitive layer 13 to the side of the support 11, which is generated in the photosensitive layer 13 by the irradiation of electromagnetic waves and moves toward the side of the support weight 1. It has the function of allowing easy passage.

This intermediate layer 12 contains germanium atoms, hydrogen atoms (H)
and/or an amorphous film containing halogen atoms (X) and carbon atoms (hereinafter referred to as a-GeC (H,
X, Si)), and contains an n-type impurity such as boron (p-type impurity such as B5 or phosphorus CP) as a substance that controls electrical conductivity.

In the present invention, the content of substances governing conductivity such as B and P contained in the intermediate layer 12 is preferably o,
Desirably, the range is oot~5X104 atomic ppm, more preferably 0.5~1X11X104ato ppm, and optimally 1~5X103 atomic ppm.

When the intermediate layer 12 has similar or the same constituent components as the photosensitive layer 13, the photosensitive layer 13 is formed following the formation of the intermediate layer 12.
The process can be carried out continuously up to the formation of . In that case, as raw materials for forming the intermediate layer, a compound containing germanium and a halogen, a gaseous carbon-containing compound, a silicon-containing compound, hydrogen, a halogen compound, an inert A gas and active species generated by activating a gas of a compound containing an impurity element as a component are prepared separately or mixed as necessary, and the support 11 is installed. The intermediate layer 12 may be formed on the support 11 by introducing the active species into two spaces and irradiating the active species with light energy in an atmosphere in which each introduced active species coexists.

The thickness of the intermediate layer 12 is preferably 30 to 10 layers, more preferably 40 to 8 layers, and optimally 50 to 5 layers.

The photosensitive layer 13 is made of, for example, amorphous silicon whose base material is silicon atoms and, if necessary, constituent atoms such as hydrogen, halogen, germanium, etc.
, Ge, C) or amorphous germanium a-Ge (H, It has both a charge generation function and a charge transport function to transport the charge.

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

The photosensitive layer 13 is made of non-doped a-Si (H.

X,Ge,C) layer or a-Ge'(H,X,C)
However, if desired, the intermediate layer 12 may contain a substance that controls conduction characteristics with a polarity different from that of the substance that controls conduction characteristics (for example, n-type), or a substance with the same polarity. If the actual amount of the substance that governs the conduction properties of the intermediate layer 12 is large, it may be contained in a much smaller amount than the actual amount.

In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, a compound containing germanium and halogen is introduced into the film forming space, as in the case of the intermediate layer 12.
In addition, active species are generated separately and introduced into the film forming space.

Furthermore, if desired, an amorphous deposited film containing carbon and silicon as constituent atoms can be formed as a surface layer on this photosensitive layer. This can be carried out in the same manner as in the method of the present invention.

FIG. 2 is a schematic diagram showing a typical example of a PIN type diode device using an a-Ge deposit doped with an impurity element, which is manufactured by carrying out 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 25,
It is composed of a p-type semiconductor layer 26. 28 is a conductive wire connected to an external electric circuit device.

The present invention can be applied to the production of any one of the semiconductor layers 24, 25, and 26, but in particular, by producing the semiconductor layer 26 by the method of the present invention, the conversion efficiency can be increased. When the semiconductor layer 26 is created by the method, the semiconductor layer 26 is made of, for example, an amorphous material (hereinafter rA- S 1G
ec (H,X)J).

As the base 21, a conductive, semiconductive, or electrically insulating material is used. If the 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 Ge, GaAs, ZnO, and ZnS. For example, the thin film electrodes 22.27 include NiCr, A
I, Cr, Mo, Au, Ir.

Nb, Ta, V, Tt, PL, Pd, In2O3,5n
02, ITO (In203+5n02), or the like is provided on the substrate 21 by a process such as vacuum evaporation, electron beam evaporation, or sputtering. Electrode 22.
The layer thickness of 27 is preferably 30 to 5 x 104 people,
More preferably, the number is 100 to 5 x 103 people.

In order to make the film constituting the semiconductor layer n-type or p-type as necessary, a layer containing n-type impurities, p-type impurities, or both impurities among impurity elements is added during layer formation. It is formed by a city that controls the amount of doping inside.

When forming n-type, i-type, and p-type semiconductor layers by the method of the present invention, any one layer or all of the layers can be formed by the method of the present invention. In addition, separately from this, a gaseous jffH carbon-containing compound, a silicon-containing compound, and, if necessary, a compound gas containing an inert gas and an impurity element as components are activated. They are excited and decomposed by energy to produce each active species, which are introduced separately or appropriately mixed and introduced into the film forming space where the support 11 is installed, and are chemically activated by using light energy. A deposited film is formed on the support ill by causing, promoting or amplifying the chemical interaction.

The thickness of the n-type and p-type semiconductor layers is preferably 10
A range of 0 to 104 people, more preferably 300 to 2000 people is desirable.

Further, the thickness of the i-type semiconductor layer is preferably 50
A range of 0 to 104 people, more preferably 1000 to 1000 people, is desirable.

A specific example of the present invention is shown below.

Example 1 Using the apparatus shown in Figure 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, and a desired substrate 103 is placed on a substrate support stand 102 inside.

104 is a heater for heating the substrate;
04 is used when heat-treating the substrate 103 before film formation or when performing a 7-ring treatment to further improve the properties of the film formed after film formation.During film formation, the heater 1
04 is not driven.

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. When using a liquid compound in a standard state among these raw material compounds, an appropriate vaporization device is provided. Gas supply sources 106 to 10 in the diagram
The symbol 9 with a added is a branch pipe, b is added with a flow meter, C is added with a pressure gauge that measures the pressure on the high pressure side of each flow meter, and d or e with H is added. This valve is used to adjust the flow rate of each gas.

123 is an activation chamber for generating active species, and around the activation chamber 123 is provided a microwave plasma generator 122 that generates activation energy for generating active species.

The raw material gas for generating active species CB) supplied from the gas introduction pipe 110 is activated in the activation chamber 123, and the generated active species are introduced into the film forming chamber lot through the introduction pipe 124.

111 is a gas pressure gauge. In the figure, 112 is a compound supply source containing germanium and halogen, and an inlet pipe 11.3
The film is introduced into the film forming chamber 101 through the film forming chamber 101 .

Reference numeral 117 denotes a light energy generating device, for example, a mercury lamp, a xenon lamp, a charcoal gas laser, an argon ion laser, an excimer laser, or the like.

Light 118 directed from the optical energy generating device 117 to the entire substrate 103 or a desired portion of the substrate 103 using an appropriate optical system irradiates the active species and the compound containing germanium and halogen flowing in the direction of the arrow 119. , the irradiated compound and active species chemically react with each other to cause A to be applied to the entire substrate 103 or a desired portion thereof.
-G e C(H,X) deposited film is formed. Also in the figure,
120 is an exhaust valve, and 121 is an exhaust pipe.

First step, base 1 made of polyethylene terephthalate film
03 was placed on the support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device to obtain a pressure of about 10-11 iTorr. CH4 gas or this and PH3 gas or B2H6 gas (both 11000p) from the gas supply pump 106
(p hydrogen gas dilution) 403CCMi combined gas was introduced into the activation chamber 123 via the gas introduction pipe 110.

The CH4 gas etc. introduced into the activation chamber 123 are activated by the microwave plasma generator 122 to become hydrogenated carbon active species, activated hydrogen, etc., and are converted into hydrogenated carbon active species, activated hydrogen, etc. through the introduction pipe 124. etc. were introduced into the film forming chamber 101.

On the other hand, GeF4 gas is introduced into the pipe 1 from the supply 1i112.
13, and introduced into the film forming chamber lot.

The internal pressure in the film forming chamber IO1 was kept at 0.6 Torr, and the temperature was increased to 1K.
The substrate was irradiated perpendicularly from a WXe lamp to form an amorphous deposited film (thickness: 700 nm) containing undoped or doped gelatinium and arsenic carbon. The film formation rate was 21 people/sec.

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 AI gap electrode (gap length 250, width 5 mm) was formed at a vacuum degree of 1 O-5 Torr. The dark current was measured at an applied voltage of 10 V, the dark conductivity σd was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2-4 Linear C2H6, C2H4, or C2H instead of CHa
An amorphous deposited film containing gel yanilum and carbon was formed in the same manner as in Example 1 except that 2 was used. The dark conductivity was measured and the results are shown in Table 1.According to the present invention, an amorphous film containing germanium and carbon can be obtained, and a fully doped amorphous film containing germanium and carbon can 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, and 202 is a compound supply source containing germanium and halogen.

206 is an introduction pipe, 207 is a motor, 208 is a heating heater used similarly to 104 in FIG. 3, 209, 21
0 is a blowing pipe, 211 is an Al cylinder-shaped base, 2
12 indicates an exhaust valve. Also, 213 to 21
6 is a raw material gas supply source similar to 106 to 109 in FIG. 1, and 217-1 is a gas introduction pipe.

An Al cylindrical substrate 211 is suspended in the film forming chamber 201, a heating heater 208 is provided inside the substrate, and a motor 20 is installed.
7 so that it can be rotated.

218 is a light energy generating device.

Light 219 is irradiated onto a desired portion of All cylinder 211 .

GeF4 gas is introduced from the supply source 202 through the introduction pipe 206,
It was introduced into the film forming chamber 201.

On the other hand, from the introduction pipe 217-1, CH4, 5t2H6 and H2
Each gas was introduced into the activation chamber 220.

The CH4, Si2H6, and H2 gases introduced are activated in the activation chamber 2.
20, the microwave plasma generator 221 undergoes an activation process such as plasma generation to form hydrogenated carbon active species, silicon hydride active species, and activated hydrogen, which are then introduced into the inlet pipe 2.
It was introduced into the film forming chamber 201 through 17-2. At this time, impurity gases such as PH3 and B2H6 were also introduced into the activation chamber 220 and activated.

The atmospheric pressure inside the film forming chamber 201 was maintained at 1.0 Torr.
A KWXe lamp 218 irradiates light perpendicularly to the circumferential surface of the An cylinder 211-shaped substrate.

The A1 cylinder 211 was rotated, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust valve 212. In this way, the photosensitive layer 13 was formed.

Further, the intermediate layer 12 is connected to the introduction pipe 217 before the photosensitive layer 13.
-1 to H2/B2H6 (B2H6 gas in volume % is 0.
A mixed gas of 2%) was introduced, and a film was formed to a film thickness of 2,000 yen.

Comparative Example 1 A film forming chamber with the same configuration as the film forming chamber 201 was prepared using GeF4 and each gas of CH4, Si2H6, H2 and B2H6, and a general plasma CVD method was carried out using a 13.56 MHz high frequency device. In this manner, an electrophotographic image forming member having the layer structure shown in FIG. 1 was formed.

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 Using CH4 as a carbon compound and the apparatus shown in Fig. 3,
A PIN type diode shown in FIG. 2 was manufactured.

First, a polyethylene naphthalate film 21 on which too much ITo@22 was vapor-deposited was placed on a support stand. Place,
After reducing the pressure to 1O-6 Torr, Ge
F4 gas was introduced into the film forming chamber 101. Also S i 2H
6 gas and PH3 gas (diluted with 1000 ppm hydrogen gas) were introduced into the activation chamber 123 for activation. Then,
This activated gas is introduced into the film forming chamber 1 through the introduction pipe 113.
0.01, and the pressure inside the film forming chamber was reduced to 0.01. P-doped n-type A-SiGe (H,
0 people) was formed.

Next, the n-type a-3 except that the introduction of PH3 gas was stopped.
Tenon doping (7) A-S i Ge (H, X) M2S (film thickness s
o o o, entered) was formed.

Next, along with Si2H6 gas, CH4 gas and B2Hs
(4 volumes of 1000 ppm hydrogen gas) P-type carbon-containing a-S 1G doped with B under the same conditions as the n-type except that
An eC(H,X) film 26 (700 mm thick) was formed. Furthermore, on this p-type film, a film thickness of too much A is added by vacuum evaporation.
A t-electrode 27 was formed to obtain a PIN type diode.

I of the diode element thus obtained (area ICm2)
-V characteristics were measured, and rectification characteristics and photovoltaic effects were evaluated. The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, when light is introduced from the substrate side and the light irradiation intensity is AMI (approximately 100 mW/cm2), the conversion efficiency is 8.1% or more, the open circuit voltage is 0, 96 V, and the short circuit current is 1.
0.2 mA/cm2 was obtained.

Examples 7-9 C2H6 instead of CH4 as carbon compound.

A PIN type diode similar to that in Example 6 was manufactured in the same manner as in Example 6 except that C2H4 or C2H2 was used. 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 present invention, carbon-containing a-S iGe (H
, X) It was found that a PIN type diode can be obtained.

〔Effect 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 without maintaining the substrate at a high temperature. becomes. In addition, reproducibility in film formation is improved, making it possible to improve film quality and uniform modification, and is advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. can do. Furthermore, since light energy is used as excitation energy in the film forming space, 1, for example, 1
Substrate with poor heat resistance.

Effects such as being able to form a film even on the substrate -L, which is easily affected by plasma etching, and shortening the process through low temperature treatment are exhibited.

[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 an example of the configuration of a PIN diode manufactured using the method of the present invention. FIGS. 3 and 4 are configurations of an apparatus for carrying out the method of the present invention used in Examples, respectively. FIG. 2 is a schematic diagram for explaining. 10---One electrophotographic imaging member, 1i---One substrate, 12---One intermediate layer, J3---One photosensitive layer, 21---One substrate, 22.27---Thin film. electrode. 24---n type semiconductor layer, 25---i type semiconductor layer, 26---p type semiconductor layer. 10 L, 201----1 film formation chamber, 123.220
---One activation chamber, 106.107,108,109,112゜202.2
13. ．． 214,215,216---Gas supply source, 103.21J,---One substrate. 117.218--One light energy generator.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, a compound containing germanium and a halogen, and a carbon-containing compound for film forming that chemically interacts with the compound are formed. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing active species and irradiating them with light energy to cause a chemical reaction.