JPS61193433A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To attain enlargement, improvement of productivity and mass production of the title films by a method wherein an active compound containing carbon and halogen as well as another compound produced from a germanium contained compound are separately fed to a filming space to form the title films by means of irradiating them with photoenergy. CONSTITUTION:An active compound A produced by decomposing a carbon and halogen contained compound as well as another active compound B produced from a germanium contained compound chemically reacting to the former are separately fed to a filming space to form the title films on a substrate by means of irradiating them with photoenergy for making them chemically react to each other. The life of applicable active compound A is recommended to exceed 10 seconds in terms of productivity and easy handling while e.g. CF4 etc. may be recommended for the applicable carbon and halogen contained compound. Likewise, e.g., GeH4 or the like may be recommended for the germanium contained compound. Finally the preferable weight ratio of active compounds B and A maybe 8:2-4:6.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a germanium-containing deposited film, particularly a functional film, particularly a germanium-containing deposited film suitable for semiconductor devices and electrophotography. Regarding the method.

[Prior art]

For example, vacuum evaporation, plasma CVD, CVD, reactive sputtering, ion blasting, photo-CVD, etc. have been attempted to form an amorphous silicon film, and generally speaking.

The plasma CVD method is widely used and commercialized.

The deposited film made of amorphous silicon has excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility1.
In terms of mass production, there is room for further improvement of 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 becomes unstable at one point, which often has a significant adverse effect on the deposited film formed.

Moreover, parameters unique to each device must be selected for each device, making it 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 best to form it by the Pla-Dama CVD method. It is said that it is crowded.

According to Heigo et al., depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniform film thickness, and uniform film quality, and to achieve mass production with high reproducibility through high-speed film formation. In the formation of amorphous silicon deposited films, a large amount of equipment investment is required for mass production equipment, the pipe items for mass production are complicated, the management tolerance is narrow, and equipment adjustments are delicate. For these reasons, these have been pointed out as problems that should be improved in the future. On the other hand, the conventional technique using the ordinary CVD method requires high temperatures and has not been able to produce a deposited film with practically usable characteristics.

As mentioned above, it is strongly desired to develop a method for forming an amorphous silicon film that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity. About these things.

The same applies to other functional films 1, such as silicon nitride films, silicon carbide films, and silicon oxide films.

The present invention eliminates the drawbacks of the plasma CVD method described above and provides a new deposited film forming method that is longer than conventional forming methods.

[Purpose and outline of the invention]

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

The above purpose is to create an active species (A) generated by decomposing a compound containing carbon and halogen in a film formation space for forming a deposited film on a substrate, and a chemical reaction between the active IN (A) and the activated species (A). A deposited film is formed on the substrate by separately introducing h and active m(B) generated from interacting germanium-containing compounds and irradiating them with source energy to cause a chemical reaction. This is achieved by the deposited film forming method of the present invention, which is characterized by the following.

[Embodiment]

In the method of the present invention, active species (A) generated by decomposing a compound containing carbon and halogen are used for film formation instead of generating plasma in a film formation space for forming a deposited film. In coexistence with the active species (B) generated from the germanium-containing compound, chemical interaction is caused by applying binary energy to these.

In order to promote and amplify vH, the deposited film that is formed is often adversely affected by etching effects or other adverse effects such as abnormal discharge effects during film formation.

Further, according to the present invention, the atmospheric temperature in the film forming space and the substrate temperature can be arbitrarily controlled as desired.
A CVD method can be used.

Furthermore, excitation energy is applied uniformly or selectively to each active species that reaches the vicinity of the substrate for film formation;
Using light energy, it is possible to irradiate the entire substrate using an appropriate optical system to form a deposited film, or selectively control and irradiate only desired areas to form a deposited film. It is advantageously used because it has the convenience of being able to form a deposited film by irradiating only a predetermined graphic portion using a resist or the like.

One of the differences between the method of the present invention and the conventional CVD method is that a space (hereinafter referred to as "space") different from the film-forming space is created in advance.

The method is to use active species that have already been activated in the activation space. This allows the film formation speed to be dramatically increased compared to the conventional CVD method.

In addition, the temperature of the substrate during the formation of the deposited film can be further lowered, and deposited films with stable film quality can be provided industrially in large quantities at low cost.

In addition, in the present invention, the active species (Al means chemical interaction with the active species (B) generated from the germanium-containing compound, which is a compound of the raw material for forming the deposited film, for example, to impart energy, It refers to a substance that causes a chemical reaction and has the effect of promoting the formation of a deposited film.Therefore, active species (A)
may include constituent elements constituting the deposited film to be formed, and a certain b may not include such constituent elements.

In the present invention, the activated species (A) from the activation space (A) introduced into the film forming space have a lifetime of 0.1 seconds or more, more preferably 1 second, from the viewpoint of productivity and ease of handling. A period of at least 10 seconds, preferably at least 10 seconds, is selected and used as desired, and the germanium-containing compound for film formation is activated by applying activation energy in the activation space (B). active species (I3)%, and the active species (B
) is introduced into the film forming space and when forming a deposited film, it chemically interacts with the active species (A) simultaneously introduced from the activation space (A) by the action of light energy.

As a result, a desired deposited film can be easily formed on a desired substrate.

Active species (B)i generated from germanium-containing compounds
j, as in the case of the active species (A), its constituent elements constitute several parts of the deposited film formed in the film forming space.

The germanium-containing compound used in the present invention as a raw material for forming a deposited film may be already in a gaseous state before being introduced into the activation space (B), or may be introduced in a gaseous state. I like it.

For example, when using a liquid compound, the compound can be vaporized by connecting an appropriate vaporizer to the compound supply source and then introduced into the activation space (B).

The germanium-containing compound is an inorganic or organic germanium compound in which hydrogen, halogen, or a hydrocarbon group is bonded to germanium, where b=2a+2 is an integer and 2a. ), a polymer of this germanium hydride, a compound in which some or all of the hydrogen atoms of the germanium hydride are replaced with 710 gen atoms, hydrogen atoms of the germanium hydride Organic germanium compounds such as compounds in which part or all of is substituted with an organic group such as an alkyl group or an aryl group, and optionally a p-no-10-gen atom.

and other germanium compounds.

Specifically, 1, for example, G e H4s G e In2
, -G e iHg, n-Ge, H, o, ter
t-G e4H,o , G eBn6 , Ge5
H1o.

GeH, F 11 GeHsCl , Go)1. Fz,
HaGeaFa, Ge(CHa), ,Ge(C,H,)
,,Go (C6H3) 4%Q e (CH@)
, Fz, CHIG e Hs, (CHs) tG
e Hz, ('CH,), GeH, (CaB6)*G
Examples include eHt-aeF', , GeF4, and G13S. These germanium compounds may be used alone or in combination of two or more.

In the present invention, the compound containing carbon and . is used, specifically, for example,
Chain halide carbon represented by CY (u is an integer of 1u 2.u+2 or more, Y is at least one element selected from li', C1, Br, and I), CY (v is 3 or more 2v Y has the meaning given above. x+y=2u or 2u+2. ), and the like.

Specifically, for example, CF (Crt)e, (CFt)9
(CF,)4. C, F'6, C5Fa, CHFm
, C'H3Fz, CC' 14 (CC1*)i,
CB r'i −(CB r *) s, CTCIs
, CBr6, CHCl1 s -CHB"rs, CH
I,,C,C11F.

What is in a gaseous state or can be gasified into a gaseous state?
Can be mentioned.

Furthermore, in the present invention, in addition to the active species generated by decomposing a compound containing carbon and halogen, active species generated by decomposing a compound containing silicon and halogen can be used in combination. . Compounds containing silicon and halogen include, for example, compounds in which part or all of the hydrogen atoms of a chain or cyclic silane compound are replaced with halogen atoms [U is an integer of 1 or more, Y is F, 'C1,
At least one element selected from Br and ■. ) (V is an integer greater than or equal to 3, Y has the above meaning.) (U and Y have the above meaning. x+y=2
u or 2u+2. ) and the like are button-like or hi-like compounds.

Specifically, for example, 5IF4- (SiFz). , (S
iF2)6. (SiF,) si, F,, St,
F8, S 1HFB, S i H2F2. SI
C14(SICl2)H1SiBr4, (SiB
rt) e, Si, CIo, Sl, Br6.5iHC
/,, S I HB r s, S I HI 3 s
Sl! Examples include those in a gaseous state or easily gasifiable, such as CI B F s .

In order to generate active Fn (A), in addition to the above-mentioned compounds containing carbon and halogen (and compounds containing silicon and halogen), carbon-containing compounds such as carbon grasses (and other compounds such as simple silicon) may be added as necessary. silicon-containing compounds), hydrogen, halogen compounds (e.g. F, gas, C1, gas,
Gasified Br, 17, etc.) can be used in combination.

In the present invention, the method for generating active species (A), c, B) f in activation spaces (A) and (B) is as follows:
Microwave considering each condition and equipment.

Electric energy such as RF, low frequency, DC, heater heating,
Thermal energy such as infrared heating and excitation energy such as light energy are used.

By adding excitation energy such as heat, light, electricity, etc. in the activation spaces (A) and (B) to the above, active spaces (A) and (B) are generated.

In the present invention, the amount of active at (B) from the activation space (B) and active species (A) from the activation space (A) generated from the germanium-containing compound introduced into the film forming space. The ratio can be determined as desired depending on the film forming 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 present invention, in addition to germanium-containing compounds, hydrogen gas and/or halogen compounds (for example, F, gas, CI, gas, gasified Br) are used as chemical substances for film formation.
7), an inert gas such as argon or neon, or a silicon-containing compound, a carbon-containing compound, etc. as a raw material for forming a deposited film can also be introduced into the film forming space. When using a number of these chemical substances for film formation, it is possible to mix them in advance and introduce them into the activation space (CB) in a gas state, or alternatively, these chemical substances for film formation can be mixed in advance and introduced into the activation space (CB) in a gas state. They can be individually supplied from independent sources and introduced into the activation space (B), or they can be introduced into independent activation spaces and activated individually.

As the silicon-containing compound introduced into the activation space (B), silanes and halogenated silanes in which silicon is bonded with hydrogen, halogen, a certain b is a hydrocarbon group, etc. can be included. especially linear and cyclic silane compounds,
Compounds in which part or all of the hydrogen atoms of the chain-like and cyclic silane compounds are replaced with halogen atoms are suitable.

Specifically, for example, SiH4,5ilHSi, H,
, (p is 1 or more, preferably 1 to 15, preferably 1
~10 integer. ), a linear silane compound represented by SiH, 5iH(SiHa)SiHs.

S 1Hss iH (S 1Hi) S 1sHt, S
i! HIIS iH (S iHa )S i 2H
A chain silane compound having a branch represented by 5, a compound in which part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with a halogen atom * si
, H6, S'<Has S'++H+om S'eH1
It is an integer of 2. ), a compound in which some or all of the hydrogen atoms of the cyclic silane compound are substituted with other cyclic silanyl groups and/or chain silanyl groups,
Examples of compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are replaced with halogen atoms include S I H
xF s S I 101Bc 1 , 5IHBBr
.

r is l, or more, preferably 1 to 10, more preferably 3
-7 integer m s+t=2r+2 or 2r. )
These include halogen-substituted linear or cyclic silane compounds shown in the following. These compounds may be used alone or in combination of two or more.

In addition, the carbon-containing compounds introduced into the activation space (B) include chain or cyclic saturated or unsaturated hydrocarbon compounds, carbon and hydrogen as the main constituent atoms (7, and silicon, halogen, sulfur, etc.). Among organic compounds having 1 m or more of the constituent atoms, organic silicon purple compounds having a hydrocarbon purple group as constituent atoms, those in a gaseous state or those that can be easily vaporized are preferably used.

Among these, examples of hydrocarbon compounds include:

Saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, etc.
Specifically, the saturated hydrocarbon is methane (CH,)
, ethane (C,H,), propane (c,n,'
), n-butane (n-C4H1o) s-pentane (C
,H1! )% Ethylene hydrocarbon bulk is ethylene (
C,H,)% propylene (C,H,),butene-1
<c4Ha), butene-2 (c, H8), inbutylene (C4H8), pentene (C,H,,), acetylene (02H,) as an acetylenic hydrocarbon,
Methylacetylene (C,H4)', butyne (C4H
6) etc.

In addition, organic silicate compounds [7 are (CH,), St, CH, SiC15w (CHs)
xsicl,,(CH,),5iC1,C2H,8iC
Organochlorosilane, CH,5iFIC1, etc.
CHASiFCl, (CHI) *S I F CI
, CtHsS I F2Ol, C4HaS i
FCl*, CIH, S i F, Cl s CBH
, S i FCl , organochlorofluorosilane, ((CM,) 1Si )2, [(CmHy
) IS 1 ) *Organodisilazane and the like are preferably used.

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

Further, the deposit and film formed by the method of the present invention can be doped with an impurity element during or after film formation. As for the impurity elements used.

Preferred p-type impurities include those from group 111 A of the periodic table, such as B, AI, Ga, In, 'l'1, etc., and n-type impurities include those from group 1 of the periodic table. A
Examples of preferable elements include B, such as PIA81SblBi.

ca, p, Sb, etc. are optimal. The amount of impurities to be doped is determined as appropriate depending on desired electrical and optical characteristics.

Items that contain such impurity elements as ingredients! As the impurity-introducing substance, it is preferable to select a compound that is in a gaseous state at room temperature and normal pressure, or at least under activation conditions, and that can be easily vaporized using an appropriate vaporization device.

Such compounds include PH-P, H-pFs, and PF.
B. PCI.

ASH Hatake's A 8 Fl, A 8 F,,
A 8 Cl 3 s S b Hm 5SbF
,, stn,, BFx, BCI,, B B r m
, B tHa, BaH+o-' BsHo-BnH++
, BeH+o, BaHlt, AlCl a, and the like. The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity-introducing substance may be activated by being introduced into the activation space (A) and/or the activation space (B) together with each substance that generates the active species (A) and the active species (B). Alternatively, it may be activated in the activation space (A), the activation space (B), and a third activation space (C) separate from Tokebetsu. Apply the above-mentioned activation energy to the impurity-introducing substance,
You can choose and adopt them as you see fit. The activity m (PN) generated by activating the impurity introducing substance is an active species or/
and active m(B). Alternatively, it is introduced into the film forming space independently.

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

FIG. 1 is a schematic diagram for explaining an example of the formation of a typical electrophotographic image forming member and photoconductive 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 one-component conductive layer 10 is a protective layer provided to chemically and materially protect the surface of the photosensitive layer 13, or a lower barrier layer provided as a measure to improve electrical withstand pressure. These can also be created by the method of the present invention if the upper barrier layer is to be disrupted.

The support 11 may be electrically conductive or electrically insulating, and may be a conductive support or a conductive support. For example, N i Cr
, Sudenres, AI, Cr, Mo, Au.

Examples include metals such as Ir, Nb, Ta, v, Tj, Pt, and Pd, and alloys thereof.

Examples of the electrically insulating support include films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl vinylidene, polyvinylidene vinylidene, polystyrene, polyamide, glass 5,1 ceramic, and paper. etc. are usually used. Preferably, at least one surface of these electrically insulating supports is subjected to a conductive treatment, and another layer is preferably provided on the conductive treated surface side.

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

A1. Cr, Mo5Au, Ir, Nb, Ta, V.

Tt, Pt, Pd, In, 0. SnO,
, ITO (I nz03 +S n 02 ), etc., is conductive treated with a film such as Ni
Cr5A1%Ag1P b , Z n -N i s
A u s Cr 1M o s I r s
Vacuum evaporation of metals such as Nb, Ta, V, Ti, and Pt.

The surface is conductively treated by depositing by electron beam evaporation, sputtering, etc., or by laminating with the metal. Unusual shapes of supports include cylindrical, belt-shaped, plate-shaped, etc.
It can be of any shape, and its shape is determined as desired, but for example, if the photoconductive member 1O of FIG. 1 is used as an electrophotographic imaging member, it will be For this reason, it is preferable to use an endless belt shape or a cylindrical shape.

For example, a film is applied to the intermediate layer 12 from the side of the support 11 to the photosensitive layer 1.
3, and the photocarriers generated in the photosensitive layer 13 by irradiation with electromagnetic waves and moving toward the support 11 from the side of the photosensitive layer 13 to the side of the support 11. It has a function that allows easy passage of.

This intermediate layer 12 is made of amorphous germanium (hereinafter referred to as "amorphous germanium") whose base material is, for example, germanium atoms, and whose constituent atoms are silicon (Si), hydrogen (1f), halogen (X), carbon atoms (C), etc. as necessary.

It is written as A-Ge (St, H, X, C). Alternatively, an amorphous material (hereinafter referred to as p, -8iGe (H, 1 as a substance that controls electrical conductivity.
For example, p-type impurities such as boron (B) or phosphorus CP)
n-type impurities such as

In the present invention, B is contained in the intermediate layer 12.

The content of substances governing conductivity such as P is preferably l
This is 0.001~5 X 10' atomic
ppm.

More preferably u 0.5-1゛X 10' atomic
ppm.

Optimally 1 to 5 X l O” atomtc pp
It is desirable to set it to m.

When the intermediate layer 12 has similar or the same components as the photosensitive layer 13, the formation of the intermediate layer 12 can be performed continuously from the formation of the intermediate layer 12 to the formation of the photosensitive layer 13. In that case, the active species (A) generated in the activation space (A), a germanium-containing compound in a gaseous state, and optionally a silicon-containing compound, hydrogen, a halogen compound, An active species (B) generated by activating an inert gas and a gas of a compound containing an impurity element as a component, respectively, on a support 11
Introduced into the deposition space where the

The intermediate layer 12 may be formed on the support 11 by applying light energy to the atmosphere in which the introduced active species coexist.

When the intermediate layer 12 is completely formed, the compound containing carbon and halogen that is introduced into the activation space (A) and generates the active species (A) is easily converted into a compound such as CF under the action of the activation energy. It is desirable to select the compound that generates the active &f(A) from among the above-mentioned compounds. The layer thickness of the intermediate layer 12 is preferably 308 to 10μ, more preferably ti40A to 8μ, and most preferably 50A to 8μ. The b0 photosensitive layer 13 preferably has a base material of, for example, silicon atoms, and hydrogen, halogen, or germanium as necessary.

Amorphous silicon A-8t whose constituent atoms include carbon, etc.
(H, X, Ge, C) or amorphous silicon germanium A-8iGe (H, X.

C), and has both a charge generation function of generating a 7-electrocarrier by irradiation with laser light and a charge transport function of transporting the charge. The thickness of the photosensitive layer 13 is preferably 1 to 100 μm, more preferably 1 to 8 μm.
It is desirable that it be 0μ, optimally 112 to 50μ.

The photosensitive layer 13 is made of, for example, non-doped A-81 (H).

X, Ge, C) or A-8iG6 (H,
, C) layer, but if desired, the intermediate layer 12 may contain a substance that controls conduction characteristics of a polarity different from that of the substance that controls conduction characteristics (for example, n-type). However, some adversaries argue that if the actual amount of the substance that governs the conduction characteristics of the same polarity contained in the intermediate layer 12 is large, even if it is contained in an amount much smaller than the loading amount, it will be less effective. In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, a compound containing silicon and halogen is introduced into the activation space (A), as in the case of the intermediate layer 12.
By decomposing these under high temperature, the members are excited by applying discharge energy or light energy to generate active species (A), and the active species (A) are introduced into the film forming space. Ru.

FIG. 2 shows an amorphous material (hereinafter A-8iGe (H , X, C)) is a schematic diagram showing a typical example of a PIN type diode device using a deposited film.

In the figure, 21 is a substrate, and 22 and 27 are thin film electrodes.

23 is a semiconductor film, and an n-type semiconductor layer 24. l-type semiconductor layer 25. It is composed of a p-type semiconductor layer 26.

The present invention can be applied to the production of any one of the semiconductor layers 24, 25, and 26 with a difference of h, but in particular, the conversion efficiency can be increased by producing the semiconductor layer 26 by the method of the present invention. When the semiconductor layer 26 is created by the method of the present invention, the semiconductor layer 26 is made of, for example, an amorphous material (hereinafter referred to as rA-8iGeC
(H,X)J).

28 is a conducting wire.

As the base 21, a conductive material, a semi-conductive material, and preferably an 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:

S 1 s G e s G aA s s Zn O
Examples include semiconductors such as sZn 8 . Thin film electrode 22
．． Examples of 27 include NiCr, Aim C.r, M
o, Au, IrsNbs Ta, V% T is P
ts Pd, In, 0. , Snows I TO(
Thin films such as InlQ, +SnO,).

It can be obtained by providing it on the substrate 21 through a process such as vacuum evaporation, electron beam evaporation, or sputtering.

The film thickness of the electrodes 22 and 27 is preferably 3° to 5°.
X 10', more preferably 100-5 X 10''
It is desirable to be rated A.

The film body constituting the semiconductor layer 23 may be of n-type or p-type as required.
When forming a single layer of a mold, n-type impurity or p-type impurity among impurity elements, some IA is formed by doping both impurities into the layer to be formed while controlling the i-. be done. In order to form n-type, i-type and p-type semiconductor layers, according to the method of the present invention, a compound containing carbon and halogen is introduced into the activation space (A), and these compounds are used downstream to generate activation energy. For example, by decomposing CF
, etc. are generated, and a compound containing silicon and a halogen is introduced into another activation space (C), and by similarly decomposing them under the action of activation energy, Active species such as SiF, etc. are generated and introduced into the film forming space. Separately, silicon-containing compounds and germanium-containing compounds in a gaseous state, as well as inert gases and gases of compounds contained as impurity element (B) f components, etc., are excited and decomposed by activation energy, respectively. Activated species (B) are generated respectively, and the mixture is introduced into the film forming space where the support 11 is installed, either separately or mixed as appropriate. The active species introduced into the film-forming space are chemically interacted with, promoted, or amplified by using light energy, and a deposited film is formed on the support 11 . The layer thicknesses of the n-type and p-type semiconductor layers are as follows:
Preferably, the range is 100.

Further, the thickness of the l-type semiconductor layer is preferably 500 mm.
-10'A, more preferably 1000-10000A is desirable.

Incidentally, the P I Nm diode device shown in FIG.
It is not necessarily necessary to produce all the layers of pl 1 and n by the method of the present invention, and the present invention can be carried out by producing at least one layer of P, I, and N by the method of the present invention.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 3, i
n, p-type and n-type aG e (C+H.

A desired base 103 is placed on a base support 102 .

104 is a heater for heating the substrate.

The heater 104 is used to heat-treat the substrate 104 before film formation, or to perform annealing treatment to further improve the properties of the film formed after film formation. k 10
5 and generates heat.

This is because the heater 104 is not driven during film formation. .

Reference numerals 106 to 109 are gas supply sources, which are gas supply sources for dregs such as germanium-containing compounds and hydrogen, halogen compounds, inert gases, silicon-containing compounds, carbon-containing compounds, and compounds containing impurity elements, which are used as necessary. There are six different types.

If these gases are liquid under normal conditions, an appropriate vaporizer is provided.

In the figure, the gas supply systems 1116 to 109 are denoted by a, branch pipes are denoted by a, flowmeters are denoted by b, and pressure gauges are denoted by C which measure the pressure on the high pressure side of each flowmeter. The valves d or e are for adjusting the flow rate of each gas. 1
23 is an activation chamber (B) for generating active species (H), and around the activation chamber 123 is a microwave plasma generator that generates activation energy for generating active species (B). 122 is provided. The raw material gas for generating active species (B) supplied via the gas introduction pipe 110 is activated in the activation chamber (B) 123, and the generated active species (B) are activated in the activation chamber (B) 123.
) is introduced into the film forming chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge. In the figure, 112 is an activation chamber (
A), 113 is an electric furnace, 114 is 0 solid particles, 115 is an introduction pipe for a compound containing gaseous carbon and halogen, which is the raw material for the activated species (A), and is produced in the activation chamber (A) 112. The active species (A) introduced into the film forming chamber 1 through the td introduction pipe 1]6.
01.

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

Light 118 directed from the source energy generator 117 to the entire substrate 103 or a desired portion of the substrate 103 using an appropriate optical system is irradiated onto active species flowing in the direction of an arrow 119, and the irradiated active species are By mutual chemical reaction, a deposited film of a-G e (0,71* Also, in Figure 1, t' 120 is an exhaust valve, 121 is υ
This is the trachea.

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 reduce the pressure to about 10-6 Torr.

Gas supply pump 106L GeH, l 50 SC
CM, or this and PH, gas or B, )l, gas (
1000 ppm water accumulation gas) 40 S
A gas mixed with CCM was introduced into the activation chamber (B) 123 via the gas introduction pipe 110.

Active Ihi wealth + (lfj□l 2.3 G has been introduced into the inner garden,
e” Hi Po Xi! , @ is microwave plasma generator 1
22 to form a water-volume germanium active species, etc., and the germanium hydride active species etc. were introduced into the film forming chamber 101 through an introduction pipe 124.

In addition, the activation chamber (A) 102 is filled with solid 0 grains 114, heated in an electric furnace 113, and kept at about 11100°C.
C is brought to a red-hot state, and CF4 is injected into it from a cylinder (not shown) through the introduction pipe 115 to remove the active species (
A) CF, was generated, and the OF, was introduced into the film forming chamber 101 through the introduction pipe 116.

While maintaining the internal pressure in the film forming chamber 101 at 0.4 Torr, the substrate 103 is irradiated perpendicularly from an IKWXe lamp.
H, X) films (thickness 700X) were respectively formed. The film formation rate was 25A/8e (!).

Next, the obtained non-doped p-type A-8i
Place the G'e (H,
After forming a comb-shaped Al gap electrode (gap length 250 μ, rl] 5 tnm) at −1 ITOrr.

Measure the dark current with an applied voltage of 10V, find the dark conduction,
The membrane properties of each sample were evaluated. The results are shown in Table 1.

Examples 2-4 Linear GeaH1os branched Go4H instead of GeH4
A-Ge (C, H, X
) formed glands. The dark conductivity of each section f4i was measured and the results are shown in Table 1.

From Table 1 1 According to the present invention, A-G with excellent electrical characteristics
An e (C, H, X) film is obtained, and a sufficiently doped a-Ge (C1H+X) film is obtained.

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

In FIG. 4, 201 is a film forming chamber, 202i1 is an activation chamber (A), 203 is an electric furnace, 204 is a solid Si particle, 20
5 is a raw material introduction tube for active species (A), and 206 is an active species (A) raw material introduction pipe;
A) Introductory pipe, 207 is a motor.

Reference numeral 208 is a heater used in the same manner as 104 in FIG. 3, reference numerals 209 and 210 are blowout pipes, and reference numeral 211 is an AI cylindrical body 212 is an exhaust valve. Further, 213 to 216 are raw material gas supply sources similar to 106 to 109 in FIG.

217-1 is a gas introduction pipe.

An AI cylinder 211 is suspended in the film forming chamber 201, and a heater 208 is provided inside the cylinder so that it can be rotated by a motor 207. Reference numeral 218 denotes a light energy key generator, which irradiates light 219 toward a desired portion of the film-forming surface of the Al cylindrical substrate 211.

In addition, the activation chamber (A) 202 is filled with solid particles 2C) 4, heated in an electric furnace 203, and kept at about 1100°C.
CF into a red-hot state through the inlet pipe 2116.
, CF as the active species (A),
The CF was generated and introduced into the film forming chamber 201 through the introduction pipe 206.

On the other hand, 5izna, GeH4 and H are introduced from the introduction pipe 217-1.
2 is introduced into the film forming chamber 201.

In the activation chamber (B) 220, the introduced 5- it The germanium oxide activation building becomes activated hydrogen, and is transferred to the film forming chamber 2 through the introduction pipe 217-2.
It was introduced in 01. On this occasion.

Impurity gases such as PH1B, H, etc. were also introduced into the activation chamber (B) 220 for activation as required.

Next, the internal pressure in the film forming chamber 201 was reduced to 1. While maintaining O'pOrr, light was irradiated perpendicularly to the circumferential surface of the Al cylindrical substrate 211 from the IKWXe lamp 218.

The Al cylindrical substrate 211 was rotated, and the exhaust gas was exhausted by appropriately adjusting the closing of the exhaust valve 212. In this way, the photosensitive layer 13 was formed.

The middle part to 12 is the inlet pipe 217- before the photosensitive layer.
81 from 1! A mixed gas of H61G 13 H4,Hl and nzna (B2H in capacity, gas 0.2 in) was introduced to form a film with a thickness of 2000 Å.

Comparative Example 1 +1 cF, and Si, H6, GeH,, H, and B, H,
A film forming chamber having the same configuration as the film forming chamber 201 was prepared using each gas, and equipped with a 13.56 MHz high frequency device.
A drum-shaped electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by a general 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 G e H4 as a germanium-containing compound.

First, a polyethylene naphthalate film 21 on which a 100OA ITO film 22 has been deposited is placed on the support Pi stand 1c*
After reducing the pressure to 10 Torr, active 84 CF * active species SIF * produced in the same manner as in Example 1 was introduced into the film forming chamber 101, and 516 Ha gas and G f
Each of lH gas, PH gas, and 1000 ppm hydrogen gas diluted was introduced into the activation chamber (B) 123 for activation. Next, p-doped n-type A-8iGe (H) was introduced through the activated gas introduction pipe 116 and irradiated with light using an IKWXe lamp while maintaining the pressure inside the film forming chamber at 0.4 Torr.

X) Formation of film 24 (film thickness 700A) [7.

Then B*Ha gas ao instead of pHs gas
I/'in type A- except that OPP stone hydrogen gas dilution was introduced.
The l-type A-
An 8iGe (H,,X) film 25 (thickness: 5000 Å) was formed.

Next, instead of PH and gas, B and H6 gas (11000
p-type A-8iGe (H.

X) A film 26 (film thickness 700A) was formed. Furthermore, this p
AI electrode 27 with a film thickness of 1000H is formed by vacuum evaporation on the mold film.
was formed to obtain a PIN type diode.

The IV characteristics of the diode collector (area: 1 cI/l) thus obtained were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

In addition, even if the light irradiation characteristics are poor, light is introduced from the substrate side, the light irradiation intensity is AMI (approximately 100 mW/CI), the conversion efficiency is 7.0 cm, and the open circuit voltage is 0.89 V.

A short circuit current of 10 mA/i was obtained.
Examples 7 to 9 In place of G 13 H4 as germanium-containing compound
This is a straight gem. A PIN type diode similar to that in Example 6 was manufactured in the same manner as in Example 6 except that monobranched G e 4f (, or HaG eeF'a was used. The rectification characteristics and photovoltaic effect were evaluated and the results are shown in Table 3.

From Table 3, according to the present invention, A-8iGeC(H,X) has better optical and electrical properties than conventional ones.
It has been 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.

In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and facilitating mass production. can be achieved. Furthermore, an effect can be obtained if the process can be shortened by low-temperature treatment during film formation.

[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. 3. FIGS. 1 and 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... Image forming member for electrophotography,
11 ・・・・・・・・・ Base. 12 ・・・・・・・・・ Middle! . 13...... Photosensitive layer, 21...... Substrate, 22, 27... Thin film electrode. 24...... n-type semiconductor layer, 25...
...... L-type semiconductor layer. 26 ...... p-type semiconductor layer, In1.2
01 ・・・・・・ Film formation chamber, 112.202
+! ...Activation room (A). 123, 220 ・・・・・・・・・Activation chamber (
B). 106.107.108.109. 213.214,215,216 ...... Gas supply system. 1 (13,211... Base body. 117.218... Original energy generator.

Claims (1)

[Claims] Chemical interaction between the active species (A) and the active species (A) generated by decomposing a compound containing carbon and halogen in the film formation space for forming a deposited film on the substrate. Active species generated from germanium-containing compounds (
A deposited film forming method characterized in that a deposited film is formed on the substrate by separately introducing B) and irradiating them with light energy to cause a chemical reaction.