JPS61100924A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve the productivity of films and to facilitate the bulk production thereof, by introducing a germanium compound and an activator generated by decomposing a compound containing carbon and halogen, and applying discharge energy for exciting and reacting the germanium compound. CONSTITUTION:A germanium compound as material for forming a deposited film and an activator which is generated by decomposing a compound containing carbon and halogen and chemically interacts with the germanium compound are introduced separately into a film forming space 101 for forming a deposited film on a substrate 103. Discharge energy is applied to them so that the germa nium compound is excited and reacted to form a deposited film on the substrate 103. For example, GeH4 from a gas supply source 106 is introduced into the film forming space 101, while a decomposing space 112 is filled with solid C particles 114 which are heated by an electric furnace 113, and CF4 is supplied thereinto from an introducing tube 115 so as to generate an activator of CF*2. The activator is fed via an introducing tube 116 to the film forming space 101, where plasma is applied by a discharge unit 117 to form a-Ge.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a deposited film containing germanium, especially a functional film, especially a semiconductor device. The present invention relates to a method suitable for forming a deposited film containing amorphous or crystalline germanium for use in photosensitive devices for W-shaped photography, line sensors for image input, naked image devices, etc.

[Prior art]

For example, in the formation of an amorphous silicon film.

Vacuum deposition method, plasma CVD method. CVD method, reactive sputtering method, ion plating method.

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 for further improvement in overall characteristics.

The reaction process for forming amorphous silicon salt am by the conventional plasma CVD method is considerably more complicated than that of the conventional CVD method, and the reaction mechanism is still 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 time, often having a significant adverse effect on the formed salt 21 film. Moreover, it is necessary to select parameters unique to each device, and therefore it is difficult to generalize manufacturing conditions. On the other hand, in order to develop an amorphous silicon film with electrical, optical, photoconductive, or mechanical properties that can sufficiently satisfy various uses, it is currently considered best to form it by plasma CVD. ing.

However, 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 an amorphous silicon deposited film by plasma CVD method.

A large amount of capital investment is required for mass production equipment, and the management items for mass production also become complex, and the tolerance for management becomes narrower.
This is because the adjustment of the equipment is delicate.

These have been pointed out as problems that should be improved in the future. On the other hand, with the conventional technology using the normal CVD method,
This method requires high temperatures, and a deposited film with practically usable properties has not been obtained.

As mentioned above, in the formation of an amorphous silicon film, its practical properties and uniformity! ! There is a strong desire to develop a forming method that can be mass-produced using low-cost equipment while maintaining the same quality. The same can be said of other functional films, 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 method for forming a deposited film that does not rely on conventional forming methods.

[Purpose and outline of the invention]

The purpose of the present invention is to improve the characteristics, film formation speed, and reproducibility of the film to be formed, and to make the film quality uniform. It is an object of the present invention to provide a method for forming a deposited film that is suitable for increasing the area of * and that can easily achieve improved productivity and mass production of a.

The above purpose is to provide a germanium compound, which is a raw material for forming a deposited film, in a film forming space for forming a deposited film on a substrate;
Active species that are generated by decomposing a compound containing carbon and halogen and that chemically interact with the germanium compound are separately introduced, and discharge energy is applied to these to excite the germanium compound and cause it to react. This can be achieved by the deposited film forming method of the present invention, which is characterized by forming a deposited film on the substrate.

[Embodiment]

In the method of the present invention, discharge energy such as plasma is used as a double energy to excite and react the raw material for forming the deposited film, but since active species are introduced into the film forming space as one of the raw materials, it is different from the conventional method. It is possible to form a film even with a relatively low discharge energy, and the deposited film that is formed is substantially free from being adversely affected by etching effects or other adverse effects such as abnormal discharge effects.

Further, according to the present invention, the atmospheric temperature of the film forming space.

By arbitrarily controlling the substrate temperature as desired, a more stable CVD method can be achieved.

Furthermore, if desired, in addition to discharge energy, light energy and/or thermal energy can be used in combination.

Light energy can be applied to the entire substrate using an appropriate optical system, or it can be applied selectively to only desired areas, so the formation position of the deposited film on the substrate and the formation of the film can be controlled. Thickness etc. can be easily controlled. Further, as the thermal energy, thermal 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 active species activated in advance in a space different from the film forming space (hereinafter referred to as the decomposition space) are used. This makes it possible to dramatically increase the film formation speed compared to the conventional Cvrf method, and also to further reduce the substrate temperature during 8i stacked film formation, resulting in stable film quality. Deposits and membranes can be provided industrially in large quantities at low cost.

1. In the present invention, the active species refers to a compound that chemically interacts with the compound of the raw material for forming the deposited film or its excited decomposition product to impart energy or cause a chemical reaction, A substance that has the effect of promoting the formation of a sedimentary film.
Therefore, the active species may contain constituent elements constituting the salt film to be formed, or may not contain such constituent elements.

In the present invention, the active species introduced into the film forming space from the decomposition space has a lifespan of 5 seconds or more, more preferably 15 seconds or more, and optimally 30 seconds or more from the viewpoint of productivity and ease of handling. are selected and used as desired.

The germanium compound used as a raw material for forming a deposited film used in the present invention is either already in a gaseous state before being introduced into the film forming space, or is preferably introduced in a gaseous state.For example, a liquid compound may be used. When used, a suitable vaporizer can be connected to the compound supply source to vaporize the compound before it can be introduced into the film forming space.

As the germanium compound, an inorganic or permissive germanium compound in which water, oxygen, halogen, or a hydrocarbon group is bonded to germanium can be used. For example, Ge, HC& is an integer of 1 or more, b = 2a + 2, or It is 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 halogen atoms, a hydrogen atom of the germanium hydride shown in Some or all of them are, for example, alkyl groups.

Examples include organic groups such as aryl groups, organic germanium compounds such as compounds substituted with halogen atoms if desired, and other germanium oxides, sulfides, nitrides, water oxides, imides, and the like.

Specifically, for example, GeH, Ge2H6.

G C3HB, n-G C4Hs o, tert
-Ge4 Hlo, Ge3 H6, Ge5H16,
GeH3F, GeH3C1, GeH2F2, H6Ge
6 F6 , Ge (CH3), , Ge (C2Hs)
a, Ge(CsHs)4.

Ge(CH3)2F2, Ge(OH)
2, Ge(OH)4, Gem, GeO2,
GeF2, GeF, , GeS, Ge3 H4
, Ge (NH2) 2 and the like. These germanium compounds may be used alone or in combination of two or more.

In the present invention, as the compound containing carbon and halogen introduced into the decomposition space, 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, and specifically, 1 For example, CuY2
Chain halide carbon represented by u+2 (u is an integer of 1 or more, Y is F, C1, Br or I), CY
Cyclic halogenated carbon represented by 2v (V is an integer of 3 or more, Y has the above meaning), CuHx Yy
(u and Y have the meanings given above.

X+7=2u or 2u+2. ), and the like.

Specifically, for example, CF4, (CF2)S, (CF2), (CF2)a, C2F&, Cs Fs.

CHF5, CH2F2, CC1m (CC12)
s, CBra, (CBrz)s, C2C1 &, C2C1
Examples include those in a gaseous state or those that can be easily gasified, such as 3Fs.

Furthermore, in the present invention, in addition to the active species generated by decomposing the compound containing carbon and halogen, active species generated by decomposing the compound containing silicon 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, and specifically, 1, for example, 5iuY2
LI+2 (u is an integer greater than or equal to 1, Y is F, CI.

Br or! It is. ) Chain-like/silicon halogenide, SjY (v is an integer of 3 or more, Y is v
2v has the above meaning. ) is indicated by annular! -Silicon rogenide, Si HY (u and Y have the meanings mentioned above)
x y has a taste *

), and the like.

Specifically, for example, S i F,, (SiFz)s, (S
iF2)b, (SiFz)a, Siz F&, Si3
FB, SiHF3,5iH2Fz.

SiC1m (SiCl2) 5.5iBrs.

(SiBrz)s, S i2 C16, 5i2C13F
Examples include those that are in a gaseous state or can be easily gasified, such as No. 3.

In order to generate active species, in addition to the above-mentioned compounds containing carbon and halogen (and compounds containing silicon and halogen), other carbon compounds such as simple carbon (and other silicon such as simple silicon) may be added as necessary. Compound?J!I), hydrogen, halogen compounds (e.g. F2 gas, C12 gas, gasified Br
2. I2 etc.) can be used in combination.

In the present invention, as a method for generating active species in the decomposition space, the discharge energy,
Excitation energies such as thermal energy, light energy, etc. are used.

Active species are generated by adding decomposition energy such as heat, light, and discharge to the above-mentioned materials in a decomposition space.

In the present invention, the ratio between the germanium compound serving as a raw material for forming a deposited film in the film forming space and the active species from the decomposition space is determined as desired depending on the deposition 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 to 4:
It is desirable to set it to 6.

In the present invention, in addition to germanium compounds.

Hydrogen gas, halogen compounds (e.g. F2 gas, C12 gas, gasified Brz, Iz:
f) Inert gases such as fulvone and neon, as well as silicon compounds, carbon compounds, etc., can be introduced into the film forming space as raw materials for forming the deposited film. When using multiple of these raw material gases, they can be mixed in advance and introduced into the film forming space, or these raw material gases can be supplied individually from independent sources and then introduced into the film forming space. It can also be introduced.

As the silicon compound serving as a raw material for forming the #XT11 film, silanes, siloxanes, etc. in which hydrogen, oxygen, halogen, or hydrocarbon groups are bonded to silicon can be used. Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with halogen atoms.

Specifically, for example, SiH, Si2H6°Si3
SiH such as HB, Sin Hto, 5isH1z, 5i6Hta (P is 1 or more p 2p+2 preferably 1 to 15゛, more preferably 1 to 10!I)
I regret it. :) e Linear silane compound shown.

S i H3S i H (S i H3) S i H
s, Si H5SiH (SiHs) Si3H, 5i2H5SiH (SiH3) Si2H5, etc.
Hp 2p+2 (p has the above-mentioned meaning) A linear silane compound having a branch, a part or all of the hydrogen atoms of these linear or branched silane compounds are replaced with a halogen atom. compound, 5i3H6,st,H,,5ts
A cyclic silane compound represented by St H (q is 3 or more, preferably a 'M number of 3 to 2q6) such as H, , si, H, □, a part of the hydrogen atoms of the cyclic silane compound SiH
F, 5iHxC1, SiH3Br, SiH3I, etc. (7)
SiHS x (x is a halogen atom, r is 1 or more, preferably t is 1-10. More preferably 3-7 (rJ9! number, S
t=2r+2 or 2r. ) There are 1 halogen-substituted linear or cyclic silane compounds.

These compounds may be used alone or in combination of two or more. Also, as carbon compounds that serve as raw materials for forming deposited films,
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 silicon, halogen, sulfur, etc.
Among organosilicon compounds having a hydrocarbon group as a constituent, those in a gaseous state or those that can be easily vaporized are preferably used.

Among these, one example is a hydrocarbon compound.

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, methane (CHs) is a saturated hydrocarbon.
, ethane (Cz Ha ), propane (CHR),
n-Butane (n-C,H.

. ), hentane (Cs Hs 2 ), ethylene hydrocarbons include ethylene (C2H4), propylene (
C3Hl), buty-1(C4H6), tbuty'-
2 (Cm Hs ), 47 butylene Cca )! 8)
, pentene (CsH+◎), attylene hydrocarbons such as acetylene (C2B2), methylacetylene (
C3H4), butyne (CaHl), and the like.

In addition, as organosilicon compounds, (CHs)asf, CH3SiCl3, (CHs)
2 S i C12, (CHs)ssicl, c2Hs
Organochlorosilane such as sic13, CHs Si
F2 C1, CHs S i FClz, (CH3
)25iFC1,CI B5 S iF2 C1,CI
B55IFC12, C3H? S iF2 Cl ,
Cs H? Si FCI-2, etc. (1)

[(CsHy)iSilz and other organodisilas 4f are preferably used.

These carbon compounds may be used alone or in combination of 2M or more.

It is also possible to dope the deposited film formed by the method of the invention with an impurity element. The impurity element used is a p-type impurity.

r4M rate table 1st summer ■ Group AlF) elements 0 e.g. B, Al
.

Suitable examples include Ga, In, TI, etc., and examples of n-group impurities include elements of Group V A of the periodic table, such as N
, P, As, Sb, Bi, etc. are mentioned as preferable ones, and especially B, Ga, and P.

Sb:4 is optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical characteristics.

As a compound containing such an impurity element as a component, it is preferable to select 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 using an appropriate vaporizing device. , such compounds include PH,, F2 Ha, PF3, PF5
, PC13.

AsH3, AsF3, AsFt, AsC11.

SbHs, SbF5, S
iH3, BFs-BCl2, BBr3, B
2 HG, B4 Hlo.

11s Hs, B5H1t, BiH14).

Examples include B, H, . . . AlCl3. As for the compound containing an impurity element, 21R4 may be used or two or more kinds thereof may be used in combination.

In order to introduce a compound containing an impurity element into the film forming space, it can be mixed with the germanium compound or the like in advance, or it can be introduced using a plurality of independent gas supplies. Each of these raw material gases can be introduced individually through the IM.

Next, the present invention will be explained with reference to a typical example of 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 structure of a typical 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.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include, for example.

NiCr, stainless steel, AI%Cr, Mo, Au
, Ir, Nb, Ta, V%Ti, Pt, Pd, or alloys thereof.

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

For example, if it is glass, its surface may be NlCr, A1. C
r, Mo, Au, Ir, Nb, Ta.

V, Ti, Pt, Pd, In2O3, 5n02.

If it is conductive treated by providing sM such as ITO (I n203 +5n02 ), or if it is a synthetic resin film such as polyester film, NiCr, A1
．． Ag, Pb, Zn, Ni, Au.

The surface is treated with a metal such as Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. 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.For example, the photoconductive member shown in FIG.
If O is used as an electrophotographic imaging member,
In the case of continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape.

For example, the intermediate layer 12 includes a photosensitive layer 13 from the support 11 side.
It effectively prevents carriers from flowing into the photosensitive layer 13 and is generated in the photosensitive layer 13 by irradiation with electromagnetic waves.

The function of easily allowing the photocarrier moving toward the support 11 to pass from the photosensitive layer 13 side to the support 11 side is achieved.

This intermediate layer 12 may be made of amorphous germanium (hereinafter referred to as a-Ge (SL, H,
), a p-type impurity such as BMP or P is contained as a substance that controls electrical conductivity.

In the present invention, the content of substances controlling conductivity such as B and P contained in the intermediate M112 is as follows.

Preferably, 0.001 to 5XIO' atomic
ppm, more preferably 0.5 to lXl0'atomic
PPI! L, optimally 1-5X103atomic
It is desirable to set it as ppm.

When forming the intermediate layer 12, it can be performed continuously up to the formation of the photosensitive layer 13. In that case, active species generated in one decomposition chamber and a germanium compound in a gaseous state, silicon compounds, hydrogen, halogen compounds, inert gas, carbon compounds as necessary, are used as raw materials for forming the intermediate layer.
and a gas of a compound containing an impurity element as a component are separately introduced into the film forming space where the support 11 is installed, and by using discharge energy, the support 11 is
An intermediate layer 12 may be formed thereon.

A compound containing carbon and I\logen, which is introduced into the decomposition space to generate active species when forming the intermediate layer 12, easily generates active species such as cv,' at high temperatures.

The layer thickness of the intermediate layer 12 is preferably 30λ to log, more preferably 40^ to 8t, and optimally 50A to 5IL.

The photosensitive layer 13 may contain, for example, hydrogen, halogen,
Amorphous silicon a-5i (1(,
It is composed of amorphous silicon germanium a-3iGe (H, has.

The layer thickness of the photosensitive layer 513 is preferably 1 to 1
.

00 islands, more preferably 1-80 islands, optimally 2-50 islands
It is desirable to set it to L.

The photosensitive layer 13 is made of non-doped a-5i (HzX,
G e ) or a-5iGe (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, it may be contained in a much smaller amount than the actual amount of the substance that controls the same polarity conduction characteristics. Good too.

In the formation of the photosensitive layer 13, similarly to the case of the intermediate layer 12, a compound containing silicon and halogen is introduced into the decomposition space, and by decomposing these at high temperature, active species are generated and introduced into the film forming space. be done. Separately, a gas of a compound containing a gaseous silicon compound, a germanium compound, and, if necessary, hydrogen, a halogen compound, an inert gas, a carbon compound, an impurity element, etc., is applied to the support 11. It's installed! & Intermediate on the support 11 by introducing the membrane chamber space and using discharge energy! What is necessary is to form f#12.

FIG. 2 shows a-5iGe (H) doped with an impurity element produced by carrying out the method of the present invention.

X) 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, which is n-type a-5iGe(H,X)
fi24, i-type cy) a-5iGe (H.

X) Calendar 25 and p-type a-5iGe (H,X) Calendar 26. 28 is a conducting wire.

The substrate 21 is semiconductive, preferably electrically insulating. As the semiconductive substrate, for example, Si
, Ge, and other semiconductors. For example, the thin film electrodes 22 and 27 may be used.

NiCr, AI, Cr, Mo, Au, Ir.

Nb, Ta, V, Ti, Pt-1Pd, 1n203.5
It can be obtained by providing a thin film of n02, ITO (In203 +5n02), etc. on a substrate by a process such as vacuum evaporation, electron beam evaporation, or sputtering. Electrode 22
．． The film thickness of 27 is preferably 30 to 5×104A.
, more preferably 100 to 5×103A.

a-5iGe (H,
It is formed by doping a type impurity or both impurities into the layer to be formed while controlling the amount thereof. To form n-type, i-type, and p-type a-5iGe (H, As a result, active species such as CF2 are generated and introduced into the film forming space. Separately, a gas of a compound containing a gaseous silicon compound, a germanium compound, and, if necessary, an inert gas and an impurity element, is introduced into the film forming space where the support 11 is installed. However, the thickness of the n-type and p52 a-5iGe(H,X) layer, which may be formed by using discharge energy, is preferably 100 to io'A, more preferably 300
A range of ~2000A is desirable.

Further, the film thickness of the i-type a-5iGe (H,X) calendar is preferably 500 to 10'A, more preferably 10
I/% is preferably in the range of 0G-1000OA.

Note that the PIN type diode device shown in the t52 diagram is P
, I, and N do not necessarily need to be produced 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.

A specific example of the present invention is shown below.

Example 1 Using the apparatus shown in Figure 3, i
Type, pHi, and n-type a-Ge (Si, H, X) deposited films were formed.

In FIG. 3, lot is a deposition chamber, and a desired substrate 103 is placed on a substrate support 102 inside.

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity through a conductive wire 105 and generates one heat. Although the substrate temperature is not particularly limited, in carrying out the method of the present invention, preferably 5
The temperature is preferably 0 to 150°C, more preferably 100 to 150°C.

106 to 109 are gas supply sources, which are provided depending on the number of germanium compounds and, if necessary, hydrogen, halogen compounds, inert gases, silicon compounds, carbon compounds, compounds containing impurity elements, etc. It will be done. When using a liquid raw material compound, provide an appropriate vaporization of 11 tM.In the figure, the gas supply sources 106 to 109 are marked with a for branch pipes, and b for flowmeters. , C indicates a pressure gauge that measures the pressure on the high pressure side of each flow meter, and d or e indicates a valve for adjusting the flow rate of each gas. 110 is a gas introduction pipe to the film forming space, 111 is a gas pressure gauge, 112 in the figure is a decomposition space, 113 is an electric furnace 2114 with 0 solid particles, and 115 is gaseous carbon and halogen which are the raw materials for active species. The activated species generated in the decomposition space 112 are introduced into the film forming space 101 through the introduction pipe 118.

117 is a discharge energy generator, which includes a matching box 117a and a high frequency introduction cathode electrode 1t7b.
Equipped with etc.

The discharge energy from the discharge energy generator W117 is applied to the raw material gas etc. flowing in the direction of the arrow 119, and is applied to the entire base 103 or a desired portion by a vehicle that excites the raw material etc. for deposited film formation and causes a reaction. Ge (S
i, H, X) (F) Form a deposited film. Further, in FIG. 1, 120 is an exhaust valve, and 121 is an exhaust pipe.

First, polyethylene terephthalate film substrate 103
is placed on the support table 102, and the inside of the deposition space 101 is evacuated using an exhaust device, and the inside of the deposition space 101 is evacuated.

The pressure was reduced to rr. At the substrate temperature shown in Table 1, using gas supply [106, GeHa150SCCM, or this and PH3 gas or B2H, gas (both lo00pp
A gas mixed with m hydrogen gas (dilute IR) and 40 SCCM was introduced into the deposition space.

In addition, the decomposition space 102 is filled with 0 solid particles 114, heated in an electric furnace 113 to melt C, and % CF4 is blown into the decomposition space 102 through a CF4 introduction pipe 115 from a cylinder to generate active species of CF2. It is introduced into the film forming space 101 through the introduction pipe 116.

While maintaining the atmospheric pressure in the film forming space lot at 0.1 Torr,
Discharge? Using plasma from c31117, undoped or doped a-Ge (S i
, H,X) II CIIIJ1700 large) was formed. The deposition rate was 35 A/Sec.

Then, the obtained non-doped or py! 1 a-
A Ge (Si,) I, Measure the dark current at a voltage of 10V, find the dark conductivity σ, and find a
-Ge (S i , H, X)lli was evaluated.

The results are shown in Table 1.

Examples 2 to 4 Linear Ge4H instead of GeH. Monobranched Ge, H
, O, or H6Ge6 F6 was used.
The same (7)&-Ge (Si, H, X) film was formed. The dark conductivity was measured and the results are shown in Table 1.

From Table 1, according to the present invention, the Tt temperature characteristics were excellent even at low substrate temperatures. That is, a-Ge films with high σ values (St, If,
X) was obtained, and a was sufficiently doped.
-Ge (St,H,X)II is obtained.

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

In FIG. 4, 201 is a film forming space, 202 is a decomposition space, 203 is an electric furnace, 204 is a solid St grain, 205 is an active species raw material introduction tube, 206 is an active species introduction tube, 207 is a motor, and 208 is an active species introduction tube. Heating heater, 209 is a blowout pipe, 210 is a blowout pipe, 211 is an AI cylinder, 21
2 indicates an exhaust valve. Also, 213 to 216
1 is a raw material gas supply source similar to 106 to 109 in FIG. 1, and 217 is a gas introduction pipe.

Film formation room rl! ! An At cylinder 211 is suspended from the At cylinder 201, a heating heater 208 is installed inside the cylinder, and the motor 2
07 to allow rotation. Reference numeral 218 denotes a discharge energy generating device, which includes a matching box 218a, a cathode electrode 218b for introducing high frequency, and the like.

In addition, by filling the decomposition space 202 with solid 0 grains 204 and heating it in the electric furnace 203 to melt C, and blowing CF into it from a cylinder, active species of C and F2 are generated, and the inlet pipe 206 After.

am space 201.

On the other hand, from the introduction pipe 217, 5i2B, G e Ha and H
2 is introduced into the film forming space 201. While maintaining the atmospheric pressure in the film forming space 201 at 1.0 Torr, the discharge device is installed! ! Plasma is applied from 21B.

The At cylinder 211 is heated and maintained at 280°C by the heater 20B and rotated once, and the exhaust gas is passed through the exhaust valve 21.
Exhaust through 2. In this way, the photosensitive layer 13 is formed.

Further, the intermediate layer 12 is connected to the introduction tube 21 before the photosensitive layer 13.
7 from 5i2)16. A mixed gas of CeH, Hl, and BzHs (0.2% by volume of B, H&) was introduced to form a film with a thickness of 2000 Å.

Comparative Example 1 CF a and Si
z H& , GeH4, H2 and B,)i, a drum-shaped electrophotographic image forming member having a similar layer structure was formed by equipping the film forming space 201 in FIG. 4 with a 13.56 MHz high frequency device.

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 The PINfi diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3 using GeH as a germanium compound.

First, a polyethylene naphthalate film 21 on which 100OA of ITO@22 was vapor-deposited was placed on a support stand, and
-@T o r After reducing the pressure to r, the active species of CF2 is introduced from the introduction pipe 116 and S L3Hs 150SCCM% GeHa 50scc is introduced from the introduction pipe 110 as in Example G41.
M, phosphine gas (PH31000ppm hydrogen dilute I
R) was introduced, 20SCCM of halogen gas was introduced from another system, and the temperature was 0.1T.

n-type a-5iGe'(H,X)1 doped with P by applying plasma from a discharge device while maintaining the
124 (M thickness 700A).

Next, except for stopping the introduction of PH and gas, the n-type a-5
The same method as in the case of iGe(H,X) film "l'/7 doped a-S i Ge (H,
(film thickness 5000A) was formed.

Next, diborane gas (B
2 H61000P pm hydrogen gas dilution) 405CCM
P-type a-5iGe (H,X)826 (JR thickness 700A) doped with B under the same conditions as the n-type except that
) was formed. Furthermore, an AI electrode 27 having a thickness of 1000 Å was formed on this p-type film by vacuum evaporation to obtain a PINI diode.

I of the diode element thus obtained (surface a1 cm2)
-V characteristics were measured, and rectification characteristics and photovoltaic effects were evaluated. The results are shown in Table 3.

In addition, regarding light irradiation characteristics, light is introduced from the substrate side,
Light irradiation intensity AMI C approximately 100 mW/cm”), conversion efficiency 7.0% or more, open circuit voltage o, aav,!!111
11 current of 11 mA/cm2 was obtained.

Example 7 Instead of Gem4 as a germanium compound.

Linear Ge41(Ha, branched Qe4H1o, or H6
Same PIN as Example 6 except for using G'e and F6
A type diode was fabricated. ! The first flow characteristics and photovoltaic effect were evaluated and the results are shown in Table 3.

From Table 3, it can be seen that the present invention has good optical and electrical characteristics even at lower substrate temperatures than conventional ones! JL-5
An iGe (H,X) salt film is obtained.

〔Effect of the invention〕

The composition of the present invention! According to the No. 4 formation method, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible at a low substrate temperature. 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 H, improving film productivity and easily achieving mass production. be able to. Furthermore, the film can be formed even on a substrate with poor heat resistance, and the process can be shortened by low-temperature treatment.

[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. The second factor is a schematic diagram for explaining a configuration example of a PIN diode manufactured using the method of the present invention. FIGS. 3 and 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the uninvented method used in the examples, respectively. 10... Image forming member for electrophotography. 11... Base, 12... Intermediate layer. 13... Photosensitive layer. 21... Board. 22.27 --- @at pole. 24 e a 11! Type l a -S i Fj
-25---i type a-3i calendar. 26... P type a-3i calendar. lot, 201 ・φ・ Film formation space. ill, 202... decomposition space. 106.107.108,109゜213.214,215,216...Φ gas supply source. 103.211 ... Base. 117.218 ... Discharge energy generation device. My agent, patent attorney, Seki Yamashita, is the first one! Figure 2

Claims (1)

[Claims] In a film formation space for forming a deposited film on a substrate, a germanium compound, which is a raw material for forming a deposited film, is generated by decomposing a compound containing carbon and halogen, and chemical interaction with the germanium compound is generated. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by separately introducing active species that act on the germanium compound and applying discharge energy to them to excite the germanium compound and cause it to react.