JPS6197817A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To contrive the improvement in the characteristics of the formed films, a film forming velocity, and reproductivity and the uniformity of quality of the films by introducing a germanium compound and the active species which is produced by decomposition of a compound including silicon and halogen and carries out a chemically mutual action with the germanium compound into a film forming space separately and exciting the germanium compound to cause a reaction by an action of a light energy. CONSTITUTION:When an intermediate layer 12 is formed, even the formation of a photosensitive layer 13 is effected continuously. In this case, as the materials of the intermediate layer 12, an active seed produced in a decomposition space, a germanium compound in gas state, and if necessary, a silicon compound, hydrogen, a halogen compound, an inert gas, a carbon compound, a gas of a compound including impurity elements as a component and etc. are introduced separately into a film forming space where a base 11 is arranged. Then by using a light energy, the intermediate layer 12 is formed on the base 11. The compound including silicon and halogen which is introduced into a decomposition space and produces an active species when forming the intermediate layer 12 produces an active species such as Si*2 for example, easily at high temperature.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a deposited film containing germanium, especially a functional film, especially a semiconductor device, a photosensitive device for electrophotography, and a line sensor for image input.

The present invention relates to a method suitable for forming a deposited film containing amorphous or crystalline germanium for use in imaging devices and the like.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using vacuum evaporation, plasma CVD, CVD, reactive sputtering, ion plating, photo-CVD, etc. Generally, plasma CVD is the most popular method. 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.

Amorphous silicon deposition using the plasma CVD method, which has been widely used for a long time! The reaction process for the formation of H is considerably more complicated than that of conventional CVD methods, and the reaction mechanism remains largely unknown. In addition, there are many parameters for forming 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, often having a significant adverse effect on the formed deposit 11. 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 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.
Forming an amorphous silicon deposited film using the plasma CVD method requires a large amount of capital investment in production equipment, and the management items for mass production are complex, the management tolerance is narrow, and equipment adjustments are delicate. Therefore, these have been pointed out as problems that need to be improved in the future.6 On the other hand, conventional techniques using the normal CVD method require high temperatures and cannot produce deposited films with practical properties. It wasn't.

As mentioned above, it is strongly desired to develop a method for forming amorphous silicon films that can be mass-produced using low-cost equipment while maintaining its practical properties and uniformity. The same holds true for 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 properties, film formation speed, and reproducibility of the film to be formed, and to make the quality of the film uniform. An object of the present invention is to provide a method for forming a deposited film that can easily achieve the following.

The purpose of the above is to produce a germanium compound, which is a raw material for forming a deposited film, and a compound containing silicon and halogen, in a film formation space for forming a deposit VIII+2 on a substrate, by decomposing the germanium compound. and active species that chemically interact with each other are introduced separately, and thermal energy is applied to these to excite the germanium compound and cause it to react, thereby forming a deposited film on the substrate described in +iii. This is achieved by the deposited film forming method of the present invention.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film forming space for forming the deposited film, thermal energy is used to excite the raw material for forming the deposited film and cause it to react, so the deposited film that is formed has an etching effect.

In addition, there is substantially no adverse effect π caused by other abnormal discharge effects.

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

In the present invention, the thermal energy for exciting and reacting the raw materials for forming a deposited film is applied to at least a portion of the film forming space near the substrate or the entire film forming space, and there are no particular restrictions on the heat source used. Instead, conventionally known heating media such as heating by a heating element such as resistance heating, high frequency heating, etc. can be used. Alternatively, thermal energy converted from light energy can be used. Furthermore, if desired, light energy can be used in combination with thermal energy. Light energy can be applied to the entire substrate using an appropriate optical system, or can be selectively applied to only desired areas, so that the formation position and thickness of the deposited film on the substrate can be controlled. etc. can be easily controlled.

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") that is different from the film forming space in advance is different from the conventional CVD method.

The method is to use activated species activated in the decomposition space (called decomposition space). This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and in addition, it is possible 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 compound that causes a chemical interaction with the compound of the raw material for forming a deposited film or its excited decomposition product to impart energy or cause a chemical reaction, Refers to substances that have the effect of promoting the formation of deposited films.
Therefore, the active species may contain constituent elements constituting the deposited IB 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.

Salt used in the present invention 81 The germanium compound serving as a film forming raw material is already in a gaseous state before being introduced into the film forming space, or it is preferably introduced in a gaseous state 0 For example, a liquid compound When using a compound supply source, an appropriate vaporizer can be connected to the compound supply source to vaporize the compound, and then the compound can be introduced into the film forming space.

As the germanium compound, an inorganic or organic germanium compound in which hydrogen, oxygen, halogen, or a hydrocarbon group, etc. are bonded to germanium can be used. 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, #
Organic germanium compounds such as compounds in which some or all of the hydrogen atoms of germanium hydride are replaced with m groups such as alkyl groups and aryl groups, and optionally halogen atoms; other germanium oxides and sulfides; Nitride, hydroxide, imide, etc. can be mentioned.

Specifically, for example, G e H4, G e 2 H6,
Ge3H,3,n-Ge4HH. , tert-Ge4H
10, Ge3H6, Ge5H+o, GeH3F, GeH
3CI, GeH2F2, H6Ge,, F6, Ge
(CH3) 4 ,Ge (C2Hs)a
,Ge(C(,Hs)a.

Ge(CH3)2F2, Ge(OH)2
, Ge(OH) 4. G e 01Ge02 ,G
eF2. GeFa, GeS, Ge3 N4. G
e (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 silicon and halogen introduced between one decomposition chamber, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically, , for example, a linear silicon halide represented by Si Y u 2u+2 (u is an integer of 1 or more, Y is F, C1, Br, or engineering), Si Yv 2v (V is a !l number of 3 or more, Y has the above-mentioned meaning.) SiX+Y=2u or 2u+2. ) chain-like or door-like compounds, etc. are mentioned.

Specifically, for example, SiF4, (SiF2)5, (S i
F2) 6, (SiF2)4. Si2 F6, Si
3 FB, SiHF3. SiH2F2.5iC14(S
iC12)5,5iBr,.

(SiBr4)5. Examples include those in a gaseous state or that can be easily gasified, such as Siz CIG and Siz C13F3.

In order to generate active species, in addition to the above-mentioned compound containing silicon and halogen, other silicon compounds such as simple silicon, hydrogen, halogen compounds (for example, F2 gas,
C12 gas, gasified Br2. I2 etc.) can be used in combination.

In the present invention, as a method for generating active species in the decomposition space, considering each condition and device, electric discharge machine Nerky,
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 and halogen compounds (for example, F2
gas, C12 gas, gasified Br2. I2, etc.), argon, neon, and other inert gases; silicon compounds, carbon compounds, and the like can also 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 done by 4 people.

Silanes, siloxanes, and the like in which hydrogen, halogen, or hydrocarbon groups are bonded to silicon can be used as the silicon compound serving as a raw material for forming the deposited film.

Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with halogen atoms.

Specifically, for example, SiH4, Si2H6, 5i3H
B, S of 5i4H16, 5i5H12, 5i6H14, etc.
iH (P is an integer of 1 or more p2p+2, preferably 1 to 15, more preferably 1 to 10), SiH3S
iH(SiH3)SiH3,5iH3SiH(SiH3
)Si3°H7,5i2Hs S 1H(SiH・)S
Chain silane compounds having a branch represented by 5i, H2, +2 (p has the above-mentioned meaning) such as i, H, etc., and one hydrogen atom of these linear or branched chain silane compounds. Compound partially or entirely substituted with halogen atoms, 5
t3H6, S l 4 HB, S i 5 Hl
. , 5i6H12, etc., cyclic silane compounds represented by SiH (q is 3 or more, preferably q% of 3 to 2Q6), in which some or all of the hydrogen atoms of the cyclic silane compounds are replaced by other cyclic silanyl SiH
3F, S 1H3C1, SiH3Br, SiH3I etc.c
7) SiHS
r+2 or 2r. ) and halogen-substituted linear or cyclic silane compounds.

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

In addition, the carbon compound used as a raw material for forming a deposited film is a chain or cyclic saturated or unsaturated hydrocarbon compound whose main constituent atoms are carbon and hydrogen, and in addition, kerosene, halogen, sulfur, etc. Among organic compounds having one or more constituent atoms, and organosilicon compounds having a hydrocarbon group as a constituent, those in a gaseous state or those that can be easily vaporized are preferably used. 'le 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, C is a saturated hydrocarbon, and C is methane (CH3), ethane (C2H4), carbonate (C3HB), n-butane (n-CaH+1.),
Pentane (C5H12), ethylene sequentially (as arsenic, ethylene (C2H4), probire 1 (C3H6)
, butene-1 (C4He), butene-2 (C4He)
H[] ), inbutylene CC4H8), pentene (
C5HIO), acetylene hydrocarbons include acetylene (C2B2), methylacetylene (C3Ha),
Examples include butyne (C4H6).

In addition, as organosilicon compounds, (CH3) 4 S i , CH3S i C13
, (CH3)2Si'C12, (CH3)3SiC
1. Organochlorosilane such as C2H55iC13,
CH3S! F2 Cl, CH3S i FC
l2, (CH3)25iFC1, C2B5 SiF2
C1, C2B55iFC12, C3B7 SiF2 C
1, organochlorofluorosilane such as C3B75iFC12, [(CH3)3si]2, [(C3H7)3S
Organodisilazane such as i]2 and the like are preferably used.

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

It is also possible to dope the deposited film formed by the method of the invention with an impurity element. The impurity elements to be used include P-type impurities such as those from Periodic Table 1TI.
Group A elements such as B, Al.

Preferred examples include Ga, In, T1, etc., and preferred examples of the n-type impurity include elements of Group V A of the periodic table, such as N, P, As, Sb, Bi, etc. However, especially B, Ga, and P.

sb etc. are optimal. The amount of impurity doped is
It is determined as appropriate depending on the 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 PH3, F2 H4, PF3, PFs, P
Cl3, AsH3, AsF3. AsF5. AsC13,
SbH3, SbF5. SiH3, BF3.

BC13, BBr3, B2 H6, B4 Hlo,
B5 Hg,, 135H1 (, B6 Hl.

B6, B12, AICI3, etc. can be mentioned.

The compounds containing impurity elements may be used alone or in combination of two or more.

In order to introduce a compound containing an impurity element as a component into the film forming space, it can be mixed with the germanium compound etc. in advance, or it can be introduced individually from multiple independent gas supply sources. be able to.

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 illustrating an example of the structure of a typical photoconductive member obtained by the present invention.

The photoconductive member 1O 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 NiCr, Steer L/S, A1. Cr, Mo, A 11. I
r, Nb, Ta, V, Ti, Pt
, Pd, etc., or alloys thereof.

Examples of electrically insulating supports include polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride,
Films or sheets of synthetic resins such as 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, A1.
Cr, Mo, Au, Ir, Nb, Ta, ■, Ti, P
t, Pd, In2O3, 5n02, I T'O(I B
203 +S n02 ), or a synthetic resin film such as a polyester film, NiCr, A1. Ag, Pb
, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta
, V, Ti, Pt, etc. by vacuum evaporation, electron beam irradiation, sputtering, etc., or by laminating with the metal, and the surface thereof is subjected to conductive treatment. 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 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, 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.

It has a function of easily allowing the photocarrier moving toward the support 11 to pass from the photosensitive layer 13 side to the support 11 side.

This middle ruI layer 12 may include silicon (Si),
It is composed of amorphous germanium (hereinafter referred to as a-Ge (Si, H, It contains p-type impurities such as or p-type impurities such as P.

In the present invention, the content of substances governing conductivity, such as B and P, contained in the intermediate layer 12 is preferably 0.
001 to 5X104 atomic ppm, more preferably 0.5 to IX11X104 atomic ppm, optimally 1 to 5XIO3 atomic ppm.

When forming the medium M layer 12, it can be performed continuously up to the formation of the photosensitive layer 13. In that case, the active species generated in the decomposition space, a germanium compound in a gaseous state, and optionally a silicon compound, hydrogen, a halogen compound, an inert gas, a carbon compound,
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 thermal energy, the intermediate layer 12 is formed on the support 11. Just let it happen.

A compound containing silicon and halogen that is introduced into the decomposition space to generate active species when forming the intermediate layer 12 easily generates active species such as 5iF2X at high temperatures.

The thickness of the intermediate layer 12 is preferably 30A to 10L, more preferably 40A to 8L, most preferably 50A to 5L.

The photosensitive layer 13 may contain, for example, hydrogen, halogen,
Amorphous silico containing germanium, etc. as constituent atoms
A charge that is composed of a-3i (H, X, Ge) or amorphous silicon germanium a-3i Ge (H, It has both a generation function and a charge transport function to transport the charge.

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

The photosensitive layer 13 is made of /7 doped a-Si(H.

X,Ge) or a-5iGe(H,X)l'
However, if desired, the intermediate layer 12 may contain a substance that controls the conduction characteristics with a polarity different from that of the substance that controls the conduction characteristics (for example, n-type), or the same If the actual amount contained in the intermediate layer 12 is large, the material controlling the polar conduction properties may be contained in a much smaller amount than in the layer.

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. The intermediate layer 12 may be formed on the support 11 by introducing it into a predetermined film forming space and using thermal energy.

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

X) A schematic diagram showing an example of a PIN type diode device type using a deposited film.

In the figure, 21 is a substrate, 22 and 27 are thin film electrodes, 23 is a semiconductor film, and an n-type a-5iGe (H,X) layer 24.
i type cy) a-5iGe (H.

X) layer 25 and p-type a-3iGe (H,X) layer 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. Examples of the thin film electrode 22.27 include NiCr, Al, Cr, Mo, Au, I
r, Nb, Ta, V, Ti, Pt, Pd, In203
．． It is obtained by providing a thin film of 5n02, ITO (In203 +5n02), etc. on a substrate by vacuum evaporation, electron beam evaporation, sputtering, or the like. The film thickness of the electrode 22.27 is preferably 30 to 5×10
4A, more preferably 100 to 5×103A.

a-5iGe (H, p
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-3iGe (H, As a result, active species such as S IF2 are generated and introduced into the film forming space.

°・Separately, a gas of a compound containing a silicon compound, a germanium compound in a gaseous state, and an inert gas and an impurity element as necessary is applied to the support 11.
n-type and p-type a-S, which can be formed by introducing the film into the film-forming space where the film is installed and using thermal energy.
The thickness of the iGe (H,X) layer is preferably 1
A range of 00 to 104 people, more preferably 300 to 2000 A is desirable.

The thickness of the i-type c7)a-3iGe (H,X) layer is preferably in the range of 500-104A, more preferably in the range of 1000-100OOA.

Incidentally, the PIN type diode device shown in FIG. 2 has P,
It is not necessarily necessary to fabricate all of the P, I, and N layers by the method of the present invention, and the present invention can be carried out by fabricating 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
type, p-type and n-type a-Ge(Si.

H, X) A deposited film was formed.

:iS3 In the figure, 101 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 via a conductive wire 105 and generates heat. Although the substrate temperature is not particularly limited, in carrying out the method of the present invention, preferably 5
The temperature is preferably 0-150°C, more preferably 100-150°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, an appropriate vaporization device is provided.
The symbol 9 with a is added to the branch pipe, b is added to the flowmeter, C is added to the pressure gauge that measures the pressure on the high pressure side of each flowmeter, and d or e is added to the number. /(lube) for adjusting each gas flow rate. 110 is a gas introduction pipe to the film forming space, 111 is a gas pressure gauge. In the figure, 112 is a decomposition space,
113 is an electric furnace, 114 is a solid Si particle, 115 is an introduction pipe for a compound containing gaseous silicon and halogen, which is a raw material for active species, and the active species generated in the decomposition space 112 are passed through an introduction pipe 116. It is introduced into the film forming space 101.

Reference numeral 117 denotes a thermal energy generating device, and for example, a normal electric furnace, a high frequency heating device, various heating elements, etc. are used.

The heat from the thermal energy generator 117 is irradiated onto the raw material gas flowing in the direction of the arrow 119, and a-Ge is applied to the entire substrate 103 or a desired portion by a bar that excites and reacts the raw material gas. A deposited film of (Si, H, X) is formed. In addition, in the figure, 120 is an exhaust valve, 121
is the exhaust pipe.

First, a polyethylene terephthalate film substrate 103
was placed on the support stand 102, and the inside of the deposition space 101 was evacuated using an exhaust device to 10-6T.

The pressure was reduced to rr. At the substrate temperature shown in Table 1, using the gas supply source 106, GeHa 150SCCM, or this and PH3 gas or B2H, gas (both loop
A gas mixed with pm hydrogen gas dilution) and 40 SCCM was introduced into the deposition space.

In addition, the decomposition space 102 is filled with solid Si particles 114, heated in an electric furnace 113 and kept at 1100°C to melt the Si, and then SiF4 is blown therein from a cylinder through the SiF4 introduction pipe 115. , active species of SiF2 are generated and introduced into the film forming space 101 through the introduction pipe 116.

The atmospheric pressure in the A2 space 101 is set to 0. ITorr4: The inside of the film forming space 101 is heated to 2
The undoped or I-doped a-Ge (S i , H, X) film/se
It was c.

Next, the obtained non-doped or p-type a-Ge
(S i , H,

After forming a double electrode (length: 250 mm, width: 5 am), the dark current is measured with an applied voltage of 10 V, the dark conductivity σ is determined, and a
-Ge (S i , H, X) films were evaluated.

The results are shown in Table 1.

Examples 2-4 Linear Ge4H instead of GeH7+. , branched Ge4
The same a-Ge (S i , H, X) as in Example 1 except that H1o or H6Ge6 F6 was used.
'A film was formed. The dark conductivity was measured and the results are shown in Table 1.

Table 1 shows that according to the present invention, an a-Ge (Si, H, G
e (S i , H, X) film 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 Si particle, 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 blowing pipe, 210 is a blowing pipe, 211 is an A1 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.

An At cylinder 211 is suspended in the film forming space 201, and a heater 208 is provided inside the cylinder so that it can be rotated by a motor 207. 218.218...Φ is a thermal energy generating device, and for example, a normal electric furnace, a high frequency heating device, various heating elements, etc. are used.

In addition, solid Si particles 204 are packed in the decomposition space 202, heated in an electric furnace 203, kept at 1100°C to melt Si, and 5iFa is blown into it from a cylinder to generate active species of SiF2'. It is introduced into the film forming space 201 through the introduction pipe 206.

On the other hand, Si2H6 and GeH are introduced from the introduction pipe 217.

and H2 are introduced into the film forming space 201. Film forming space 201
The inside of the film forming space 201 is maintained at 250° C. by a thermal energy generator while maintaining the internal atmospheric pressure at 1.0 Torr.

The Al cylinder 211 is heated and maintained at 280°C by a heater 208 and rotated, and the exhaust gas is discharged through the exhaust valve 21.
Exhaust through 2. In this way, the photosensitive layer 13 is formed.

J, the intermediate layer 12 is filled with Si2 H6, GeH, , H2 and B2H, (8
9 of a mixed gas containing 0.2% BZH et al.
The film was formed to a thickness of 2000A.

Comparative Example 1 SiF4 and Si2
Using H6, GeH4, H2 and B2H5, a 13.56 MHz Takaoka M apparatus ξ was installed in the film forming space 201 of FIG. 11 to form a drum-shaped electrophotographic image forming member having a similar layer structure.

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 GeH as a germanium compound.

First, a polyethylene naphthalate film 21 on which a 100OA ITO film 22 was vapor-deposited was placed on a support stand, and 1o6
After reducing the pressure to Torr, the 4 entry pipes 116 were opened as in Example 1.
active species of SiF2'' from the inlet pipe 110, and S t
3H6150sccM.

G e H450S CCM, phosphine gas (PH
311000pp hydrogen dilution) was introduced, halogen gas 20SCCM was introduced from another system, 0.1 Torr, 25
n-type a-5i doped with P while keeping at 0 °C
A Ge(H,X) film 24 (thickness: 700 A) was formed.

Next, the n-type a-5 except that the introduction of PH3 gas was stopped.
Same method as for iGe ('H,X) film"'Q/7
Doped a-5iGe (H,X) 1li25 (thickness: 5000 Å) was formed.

Next, diporane gas (B2
P doped with B under the same conditions as the n-type except that H61000p pm hydrogen gas dilution) 40SCCM was used.
Type a-S i Ge (H,X) film 26 (film thickness 700
A) was formed. Further, an Al electrode 27 having a thickness of 1000 Å was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

I of the diode element thus obtained (area 1 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,
At light irradiation intensity AMI (approximately 100 mW/Cm2), conversion efficiency 7.0% or more, open circuit voltage 0.88 V, short circuit current 1
1 mA/cm2 was obtained.

Example 7 Instead of GeH4 as a germanium compound, linear G
e4H+o, branched Ge4H, or H6G
A PIN diode identical to that of Example 6 was manufactured except that e6F6 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 germanium-containing a-3iGe (H,

〔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 moreover, high-speed film formation and rif performance are achieved 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 IQ area, improving film productivity and easily achieving mass production. be able to. Furthermore, since relatively low thermal energy can be used as excitation energy, a film can be formed even on a substrate with poor heat resistance. The low-temperature treatment has the effect of shortening the process.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining a configuration example of a PIN diode manufactured using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the method of the present invention used in Examples, respectively. 10... Image forming member for electrophotography. 11... Substrate, 12... Intermediate layer, 13... Photosensitive layer, 21 φ... Substrate, 22, 27 E-type thin film electrode, 24 11 e a n-type a=Si layer, 25 11
a a i type a-Si layer, 26 --- p type a-
3i layer, toi, zot --- film formation space, ill, 202 --- decomposition space, 106.107, 108, 109° 213.214, 215, 216 ... gas supply source, 103, 211 ... and Base, 117.218...- Thermal energy generator.

Claims (1)

[Claims] A germanium compound, which is a raw material for forming a deposited film, is generated by decomposing a compound containing silicon and halogen in a film forming space for forming a deposited film on a substrate, 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 active species and applying thermal energy to them to excite the germanium compound and cause it to react.