JPS61102724A - Method of forming deposited film - Google Patents

Abstract

PURPOSE:To form a deposit film by separately introducing an silica compound and an active seed, which decomposes a compound containing germanium and halogen and conducts chemical interaction with the silica compound, into a film formation space and exciting and reacting the silica compound. CONSTITUTION:A silica compound as a raw material for forming a deposit film and an active seed, which is formed by decomposing a compound containing germanium and halogen and conducts chemical interaction with the silica compound, are introduced severally into a film formation space for shaping the deposit film onto a base body, and discharge energy is worked to these silica compound and active seed and the silica compound is excited and reacted,thus shaping the deposit film onto the base body. A film formation rate can be increased remarkably by previously using an active seed activated in a space different from a film formation space, the temperature of a substrate temperature on the formation of the deposit film can also be lowered, and the deposit film having the stable quality of the film can be manufactured industrially at low cost in large quantities. A compound in which one part or the whole of hydrogen atoms in a straight-chain or chain silane compound are replaced with halogen atoms is employed as the silica compound.

Description

Detailed Description of the Invention (Field of Application of the Invention) The present invention is directed to silicon-containing deposited films, particularly functional films, particularly semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, and tI image devices. The present invention relates to a method suitable for forming a deposited film of amorphous silicon or polycrystalline silicon for use in, for example, amorphous silicon or polycrystalline silicon.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using a vacuum evaporation method, a plasma CVD method, a CVD method, an anti-binary sputtering method, an ion blasting method, a photo-CVD method, etc. Generally, plasma C' The VD method is widely used and commercialized.

The deposited film composed of amorphous silicon has excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility.
In terms of mass production, there is room to further improve the overall characteristics.

The reaction process for forming amorphous silicon deposited films using the plasma CVD method, which has become popular since then, is considerably more complex than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. . In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, often having a significant adverse effect on the deposited film formed. Moreover, device-specific parameters must be selected for each device.
Therefore, the reality is that it is difficult to generalize the 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.

Depending on the application of the deposition or 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 by the method requires a large amount of equipment investment for mass production equipment, the management items for mass production are complicated, the management tolerance is narrow, and the adjustment of the equipment is delicate. from.

These have been pointed out as problems that should be improved in the future. On the other hand, in 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, 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. 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, while also being suitable for increasing the area of the film, improving film productivity, and facilitating mass production. The object of the present invention is to provide a method for forming a deposited film that can achieve the following.

The above purpose is to produce a silicon compound by decomposing a silicon compound, which is a raw material for forming a deposited film, and a compound containing germanium and halogen in a film forming space for forming a salt film on a substrate. A salt 81 film is formed on the substrate by introducing active species that chemically interact with the silicon compound into each side, and applying discharge energy to these to excite the silicon compound and cause it to react. This is achieved by the deposited film forming method of the present invention.

[Embodiment]

In the unreleased method, discharge energy such as plasma is used as the 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, a more stable CVD method can be achieved by arbitrarily controlling the atmospheric temperature in the film forming space and the substrate temperature as desired.

Furthermore, 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 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. Also,#! Thermal energy converted from light energy can also be used as energy.

One of the differences between the method of the present invention and the conventional CVD method is that it uses an activation bar that is activated in advance in a space different from the film forming space (hereinafter referred to as the 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. The membrane can be provided industrially in large quantities and at low cost.The active species, which has not yet been invented, is a compound that chemically interacts with the compound of the raw material for membrane formation or its excited decomposition product in the sediment 8. For example, active species refer to substances that have the effect of promoting the formation of a deposited film by imparting energy or causing a chemical reaction.Therefore, active species are the constituent elements that constitute the deposited film that is formed. , or may not include such components.

In the uninvention, the active species from the decomposition space introduced into the film forming 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 silicon compound used as the raw material for forming the deposited film used in the present invention is already in a gaseous state before being introduced into the film forming space, or is preferably introduced in a gaseous state. 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 a silicon compound,
Silanes and siloxanes 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, SiH4, Si2 H6, Si3
HB, 5i4H1°, 5i5H+z, preferably 1-
15, more preferably an integer of 1-10. ) A linear silane compound represented by

SiH3SiH(SiH3)SiH3,5iH3SiH
(SiH3)Si3H7,5i2H1Si (P has the above-mentioned meaning) A linear silane compound having a branch represented by the formula, a part or all of the hydrogen atoms of these linear or branched chain silane compounds can be replaced with a halogen. Compounds substituted with atoms, 5i3H6, 5i4 H[1, S i5
Hl. , 5i6H126 integers. Cyclic silane compounds represented by #), compounds 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, some of the hydrogen atoms of the silane compounds exemplified above, or Examples of compounds completely substituted with halogen atoms include SiH3F, S1H3X (X is a halogen atom, r is an integer of 1 or more, preferably 1-1o, more preferably 3 to 7, and s+t=2r+2 or 2r). ) and halogen WaS-like or cyclic silane compounds.

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

In the present invention, as the compound containing germanium and halogen introduced into the decomposition space, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic germanium hydride compound is replaced with a halogen atom is used. is 1
For example, GeY (u is an integer greater than or equal to 1, Y is F
, C1,2u+2 Br or engineering. ) Chain germanium halide, Ge Y (v is an integer of 3 or more.

2v Y has the meaning given above. ) has the above meaning. x+y=2u or 2u+2. ), and the like.

Specifically, for example, GeF4, (GeF2)s, (G
eFz)6, (GeF2)a, Ge2 F6, Ge3
FB, GeHF3, GeB2 F2, GeC14
(GeC12) 3. GeB r4, (GeB r2
)5, Ge2C16, Ge2C13F3, etc., which are in a gaseous state or can be easily gasified.

Furthermore, in the present invention, in addition to the active species generated by decomposing the compound containing germanium and halogen, active species generated by decomposing the compound containing silicon and halogen and/or carbon and halogen Active species generated by decomposing a compound containing 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,
For example, SiY (u is an integer greater than or equal to 1, Y
is F, CI.

2u+2 Br or I. ) chain halogenated carboxylic acid 5
1. Si Y (v is an integer of 3 or more,
2v Y has the meaning given above. ) cyclic halogenated 'r41g, Si HY (u and Yu
x y has the meaning given above. x+y=2u or 2u+2
It is. ), and the like.

Specifically, for example, SiF, (SiF2)c, (S
i F2 ) b, (SiF2)4. Si2 F6, S
i3 FB, SiHF3. SiH2F2.

5iC14 (SiC12) 5.5iBr, +, (SiB
r2) 5.5i2C16, 5i2C13F3 and the like which are in a gaseous state or can be easily gasified.

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

In addition, as a compound containing carbon and halogen, for example, some or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound can be replaced with halogen atoms! The tested compound is used, specifically, for example, CuY2u+2 (U is an integer of 1 or more, Y is F
, C1, Br or l. ) and cyclic halogenated silicon represented by CY (v is an integer of 3 or more, Y has the meaning described above).

) (+y=2u or 2u+2), and the like.

Specifically, for example, CF4, (CF2)S, (CF2)6
・(CF2)4・C2F,・03FB・CHF3,
CH2F2, CC14 (CC12)3. CBr, (
CBr2)5. c, ct,.

' Examples include those in a gaseous state or easily gasified, such as C2C13F3.

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

In order to generate active species, for example, when generating active species of a compound containing germanium and a halogen, in addition to this compound, if necessary, a germanium compound equivalent to germanium alone, hydrogen, a halogen compound ( 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, 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 of the amount of silicon compound serving as a raw material for forming a deposited film in the film forming space to the active species from the decomposition space can be determined as desired depending on the deposition conditions, the type of active species, etc., but is preferably Suitably, the ratio is 1O:1 to 1:10 (introduction flow rate ratio), more preferably 8:2 to 4:6.

In the present invention, in addition to silicon compounds, hydrogen gas, halogen compounds (e.g. F2 gas,
C12 gas, gasified Br2, 12? ),Argon,
An inert gas such as neon can also be introduced into the film forming space. 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.

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 those from periodic table 1II as p-type impurities.
Group A elements, such as B, AI.

Suitable examples include Ga, In, TI, etc., and examples of n-type 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 etc. are optimal. z and X of impurities to be doped
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°P2H,, PF3. PF5. PCl
3.

AsH2, AsF3, AsFl, AsCl3, S bH
3, S bFs , S iH3, BF3, BCl3. B
Br3. B2H6,13aI (lo, B5H9・BSH
II.B6 HI OlB, H,2, AlCl3, 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 into the film forming space, it can be mixed with the silicon 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 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 NiCr, stainless steel, A1. Cr, Mo, Au, Ir, Nb, T
Examples include metals such as a, V, Ti, Pt, and Pd, and 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 layer is preferably provided on the conductive treated surface side.

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

Al, Cr, Mo, Au, Ir, Nb, Ta, V, T
i, Pt, Pd, In203,5nOz.

If it is conductive treated by providing a thin film such as ITO (In203 +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, Tt, PL, 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 cylindrical, belt-like, plate-like, etc., and the shape is determined as desired.
If 0 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 is exposed to Je1 from the support 11 side.
3, and the photocarriers generated in the photosensitive layer 13 by electromagnetic wave irradiation and moving toward the support 11 from the photosensitive layer 13 side to the support 11 side. It has the function of easily allowing passage to.

This intermediate layer 12 is made of amorphous silicon (hereinafter referred to as
a-3i (denoted as (H,
type impurities 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 lz is preferably 0.
001 to 5XIO4 atomic cppm, more preferably 0.5 to 1XIO' atomic ppm, optimally 1 to 5XIO3 atomic ppm.

When forming the intermediate ff 112, 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 gaseous silicon compound, and optionally a compound containing hydrogen, a halogen compound, an inert gas, and an impurity element are used as raw materials for forming the intermediate layer. The intermediate layer 12 may be formed on the support 111 by separately introducing gas and the like into the r&membrane chamber space where the support 11 is installed and using discharge energy.

A compound containing germanium and /\logen that is introduced into the decomposition space to generate active species when forming the intermediate layer 12 easily generates active species such as G e F 2 at high temperatures.

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

The photosensitive layer 13 has, for example, an A-S i (H,

The layer thickness of the photosensitive layer 13 is preferably 1 to 100I
L, more preferably 1 to 80 JL, most preferably 2 to 50 pots.

The photosensitive layer 13 is made of non-doped a-5i (H.

x) layer, if desired, it may contain a substance that controls the conduction characteristics of a polarity different from the polarity of the substance that controls the conduction characteristics (for example, n-type) contained in the intermediate layer 12, or In other words, the substance that governs the conduction characteristics of the same polarity is the intermediate R1.
If the actual amount contained in 2 is large, it may be contained in an amount much smaller than the dose.

In the formation of the photosensitive layer 13, similarly to the case of the intermediate layer 12, a compound containing germanium and halogen is introduced into the decomposition space, and active species are generated by decomposing these at high temperature.
Introduced into the film forming space. Also, apart from this, silicon compounds in a gaseous state.

If necessary, a gas of a compound containing hydrogen, a halogen compound, an inert gas, an impurity element, etc. as a component is added to the support 1.
The intermediate layer 12 may be formed on the support 11-A by introducing it into the film-forming space where the support 11-A is installed and using discharge energy. 1 is a schematic diagram showing a typical example of a PIN diode device using an a-St deposited film doped with an impurity element.

In the figure, 21 is a substrate, 22 and 27 are thin FII? ti pole.

23 is a semiconductor film, n-type c7)a-5i! :j24
, i-type c7) a-5i calendar 25, and p-type a-3i 526. 28 is a conducting wire.

The substrate 21 is semiconductive, preferably electrically insulating. As the semiconductive substrate, for example, Si
, Ge, and other semiconductors. The thin film electrodes 22.27 include, for example, NiCr, A1. Cr, Mo, Au, I
r, Nb, Ta, V, Ti, Pt, Pd, In703.
11? by providing a thin film of 5n02, ITO (In703 +5n07), etc. on a substrate by vacuum evaporation, electron beam evaporation, sputtering, etc. It will be done. The film thickness of the electric M422.27 is preferably 30 to 5X.
104A, more preferably 100 to 5×103A.

In order to make the film constituting the semiconductor layer 23 of a-5i n-type 24 or p-type 26 as necessary, when forming the layer, an n-type impurity, a p-type impurity, or both impurities are added among the impurity elements. It is formed by doping into the formed layer while controlling its rate.

In order to form n-type, i-type and p-type a-Si layers, a compound containing germanium and halogen is introduced into one decomposition space by the method of the present invention, and by decomposing the cap at high temperature, for example, GeF7* Active species such as these are generated and introduced into the film forming space. Separately, a gaseous silicon compound and, if necessary, a gas of a compound containing an inert gas and an impurity element as components are introduced into the film forming space where the support 11 is installed, and the discharge is carried out. The thickness of the n-type and p-type a-5i layers, which can be formed by using energy, is preferably 100-10'.

Further, the thickness of the i-type a-5i layer is preferably 5
00-104A, more preferably 1000-10000
A range of λ is desirable.

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-5i deposited films were formed.

In FIG. 3, 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 to 150°C, more preferably 100 to 150°C.

Reference numerals 106 to 109 denote gas supply sources, which are provided according to the number of silicon compounds and, if necessary, compounds containing hydrogen, /\rogen compounds, inert gases, and impurity elements. If a liquid raw material compound is used, an appropriate vaporization device should be provided. In the figure, the gas supply sources 106 to 109 with an a attached are branch pipes,
Those marked with b are flow meters, those marked with C are pressure gauges that measure the pressure on the high pressure side of each flow meter, and those marked with d or e are valves for adjusting the flow rate of each gas. 110 is a gas introduction pipe to the film forming space, and ill is a gas pressure gauge.
12 is a decomposition space, 113 is an electric furnace, 114 is solid Ge particles, 115 is an introduction pipe for a compound containing gaseous germanium and halogen, which is a raw material for active species;
The active species generated in step 2 are introduced into the film forming space 101 via the introduction pipe 116.

117 is a discharge energy generator, which includes a matching box 117a and a cathode electrode 117b for introducing high frequency.
Equipped with etc.

The discharge energy from the discharge energy generator tt7 is applied to the raw material gas etc. flowing in the direction of the arrow 119, and is applied to the entire substrate 103 or a desired portion by a bar that excites the gas etc. of the film forming source 1 and causes a reaction. 1 of -3i ([forms the implantation. In the figure, 120 is an exhaust valve;
1 is an exhaust pipe.

First, a polyethylene terephthalate film substrate 103
II! on the support stand 102! , the inside of the deposition space 101 was evacuated using an exhaust device, and the temperature was 10-'T.

The pressure was reduced to rr. At the substrate temperature shown in Table 1, using the gas supply source 106, 5i5H1°150scCM, or this and PH3 gas or B2H, gas (both 1100scCM)
A gas mixed with 405 CCM (0 pp hydrogen gas dilution) was introduced into the deposition space.

In addition, solid Ge grains 114 are packed in one decomposition space 102, heated in an electric furnace 113 to melt the Ge, and GeF4 is blown therein from a cylinder through a GeF4 inlet pipe 115 to generate active species of GeF2. , introduction tube 1
16, and is introduced into the r&film formation chamber 101.

The atmospheric pressure in the film forming space lot is set to 0. While keeping it at ITorr,
Non-doped or doped a-S i FJ (film thickness 700 mm) is produced by applying plasma from a discharge device.
A) was formed. The film formation rate was 35 A/sec.

Next, the obtained non-doped or p-type a-Si
l? Put the 2nd try fitting 1 into the trying fitting 1 and set the vacuum level to 10-5 Tor.
After forming a comb-shaped A1 gap electrode (length 250μ, width 5mm) with r, dark current was measured with an applied voltage of 10V,
The a-Si film was evaluated by determining the dark conductivity σ. The results are shown in Table 1.

Examples 2 to 4 Linear 5i4H16, branched S instead of Si5H10
i4H,. , or except using H6S i6 F6,
The same a-5i film as in Example 1 was formed. The dark conductivity was measured and the results are shown in Table 1.

From Table H1, according to the present invention, an a-3t film with excellent electrical properties, that is, a high σ value, can be obtained even at low substrate temperatures, and
A fully doped a-5i resin 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 Ge particle, and 205 is an active species r! X material introduction tube, 206 is active species 4 person tube, 20
7 is a motor, 208 is a heating heater, 209 is a blowing pipe, 210 is a blowing pipe, 211 is an Al cylinder,
212 indicates an exhaust valve. Also, 213 to 2
16 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. Reference numeral 218 denotes a discharge energy generating device, which includes a matching pole 218a, a cathode electrode 218b for introducing high frequency, and the like.

In addition, the decomposition space 202 is filled with solid Ge grains 204, heated in the electric furnace 203 to melt the Ge, and G e F is blown there from a cylinder to generate active species of GeF2, and the inlet pipe 208 After that, the film forming space 201
to be introduced.

On the other hand, 5i2H(, and H2 are introduced into the film forming space 201 from the introduction pipe 217. The atmospheric pressure in the film forming space 201 is set to 1,
Plasma is applied by the discharge device 218 while maintaining the OTo r r.

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

In addition, the intermediate layer is supplied with H2/B2Hb from the introduction pipe 217.
Introducing a mixed gas (B2H, 0.2% by volume),
111 with a thickness of 2000A.

Comparative Example 1 SiF4 and Si2
Film formation space 201 in FIG. 4 from H6, H7 and B2H6
was equipped with a 13.56 MHz high frequency device to form amorphous silicon salt U.

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 PINI diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3 using 5r3H6 as a silicon compound.

First, place a polyethylene naphthalate film 21 on which a 1000λ ITO film 22 has been deposited on a support stand, and
After reducing the pressure to O=T o r r, active species of GeF2 are introduced from the introduction pipe 116 and from the introduction pipe 110 as in Example 1.
150 SCCM of S i3 Hb and 7 Osphincus (PH311000pp diluted with hydrogen) were introduced, 20 SCCM of halogen gas was introduced from another system, and the temperature was 0.1 Tor.
While maintaining the temperature r, plasma is applied by a radiation TL device to form an n-type a-S in! doped with P. i! 2
4 (Il'2 thickness 700A) was formed.

Next, the n-type a-5 except that the introduction of PH3 gas was stopped.
An i-type a-3l film 25 (thickness: 5000 Å) was formed using the same method as for the i film.

Next, along with the H2 dregs, diporane gas (B2H6100
A p-type a-Si film 26 (film J770OA) doped with B was formed under the same conditions as the n-type film except for the following conditions: Furthermore, an AII pole 27 with a film thickness of 1000 A is formed on this P-type film by vacuum evaporation, and the P-type film is
I got an INI diode.

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

In addition, regarding light irradiation characteristics, light is introduced from the substrate side,
At light irradiation intensity AMI (approximately I Q OmW/Cm2),
Conversion dynamic': 48.5% or more, open end voltage 0, 92V,
A short circuit current of 10.5 mA/cm' was obtained.

Example 7 Instead of 5i3H6 as a silicon compound, linear S j
4 HIo, branched 5i4H+o, or H65i6F
The same PINI diode as in Example 6 was manufactured except that PINI diode No. 6 was used. ! Evaluate I current characteristics and photovoltaic effect,
The results are shown in Table 3.

From Table 3, it is clear that according to the present invention, a-Si has good optical and electrical properties even at a lower substrate temperature than before.
A deposited film is obtained.

〔Effect of the invention〕

According to the deposit 81 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 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 Ill, and it facilitates the improvement of film productivity and mass production. Moreover, 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 wSz diagram 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 calligraphy and electrophotography. 11 - Substrate, 12 - @ middle layer, 13 - photosensitive layer, 21 - substrate, 22, 27 - - - thin film 1■ as pole, 24 II @ e (type 1 a-5t layer, 25
see iy! 1ia-5t layer, 26 ・
・Fist p type a-5i7 collage, 101.20
1 --- Film formation space, 111.202 ---
Decomposition space. 106.107,108,109°213.214,215,216... Gas supply source, 103.211... Substrate, 117.218 --- Discharge energy generating device. Attorney: Patent Attorney Johei Yamashita Procedural Amendment (Sealed) November 20, 1985 Director General of the Patent Office Michibu Uga (1985) Patent Application No. 223853 Name of Invention: Deposited Film Formation Method Amendment Relationship with the patent applicant case

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, a silicon compound, which is a raw material for forming a deposited film, and a compound containing germanium and halogen are decomposed, and a chemical interaction with the silicon 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 discharge energy to them to excite the silicon compound and cause it to react.