JPS61228614A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To make the improvement of film productivity and mass production easy while contriving to improve the properties of a film, a film forming speed and reproducibility and the uniformity of film quality by chemical reaction affecting discharge energy, making the coexistence of a compound containing silicon and a halogen and an active species made from a compound containing silicon for forming film. CONSTITUTION:A compound containing silicon and a halogen and an active species made from a silicon compound which is for forming a film and chemically reacts with the compound are each introduced in a film forming space 101 and a deposited film is formed on a substrate 103 by a chemical reaction affecting discharge energy. For example, the substrate 103 made of a polyethylene terephtalate film is placed on a susceptor 102, the film forming chamber 101 is exhausted, then Si5H10 gas is introduced in an activation chamber 123 from a cylinder 106 for gas supply, is activated by a microwave plasma generation equipment 122 and introduced in the film forming chamber 101. Whereas, SiF4 gas is introduced in the film forming chamber 101 from a supply source 112 and an A-Si(H,X) film is formed by affecting plasma from a discharge equipment 117.

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, imaging devices, The present invention relates to a method suitable for forming a non-single-crystal silicon-containing deposited film such as amorphous or polycrystalline for use in photovoltaic 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 blasting, photo-CVD, and the like.

Generally, the plasma CVD method is widely used and commercialized.

In general, the deposited films produced by these deposited film formation methods have excellent electrical and optical properties, fatigue properties due to repeated use, use environment properties, productivity including uniformity and reproducibility, and mass production. In this respect, there is room to further improve the overall characteristics.

Among these, in order to develop a deposited film that satisfactorily satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. Depending on the application of Compilation II, the area can be increased.

While aiming to make the film thickness uniform and improve the uniformity of the film quality, it is also necessary to achieve mass production with high reproducibility through high-speed film formation. This has been pointed out as an issue that should be improved in the future. On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to provide a deposited film with practically usable characteristics.

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

[Object of the invention and summary of disclosure]

The purpose of the present invention is to improve the characteristics, film formation speed, and reproducibility of the film to be formed, and to make the film uniform in quality. The object of the present invention is to provide a deposited film forming method that can be easily achieved.

The above purpose is to prevent active species generated from a compound containing silicon and halogen and a silicon compound for film formation that chemically interacts with the compound into the r&film space for forming a deposited film on a substrate. This is achieved by the deposited film forming method of the present invention, which is characterized in that a deposited film is formed on the substrate by introducing each of these and applying discharge energy to them to cause a chemical reaction.

[Embodiment]

In the method of the present invention, discharge energy such as plasma is used as the energy to excite and react the raw materials for forming the deposited film, but active species generated from the compound containing silicon and halogen and the silicon-containing compound for film formation are By applying discharge energy to these components in coexistence with other components, chemical interactions are caused by these components.

Alternatively, in order to promote and amplify the discharge energy, it is possible to form a film with lower discharge energy than before, and the deposited film that is formed is extremely unlikely to be adversely affected by etching effects or other abnormal discharge effects during film formation. few.

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, light energy and/or thermal energy can be used in addition to discharge energy. The light energy can be applied to the entire substrate using an appropriate optical system, or can be applied selectively to a desired portion, so that the formation position and thickness of the deposited film on the substrate can be controlled. 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 it uses active species activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and also to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

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

In the present invention, the active species from the activation space introduced into the film forming space has a lifetime of 0.1 seconds or more, more preferably 1 second or more, and optimally from the viewpoint of productivity and ease of handling. 1
Those with a length of 0 seconds or more are selected and used as desired.

The silicon-containing compound introduced into the activation space used in the present invention is either already in a gaseous state before being introduced into the activation space, or is preferably introduced in a gaseous state, for example, in a liquid state. When using a compound, the compound can be vaporized by connecting a suitable vaporizer to the compound supply source and then introduced into the activation space. As the silicon-containing compound, silanes and halogenated silanes in which hydrogen, / 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, 1, for example, 5iHa, Si2H6゜5i3H
B, S of Si4H10, 5i5H12, 5i6H14, etc.
i p H2P÷2 (P is 1 or more, preferably 1-15
．． More preferably, it is an integer from 1 to 10. ), a linear silane compound represented by 5iH3SiH(SiH3)Si
H3゜5iH3SiH(SiH3)Si3Hfu.

5ip of Si2HssiH(SiH3)S[zHs etc.
Chain silane compounds with branches represented by H2p+2 (p has the above meaning), compounds in which part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with halogen atoms. ,5f3H6,5i4
S i qH of H13゜5isHto, 5iel12 etc.
2q (q is an integer of 3 or more, preferably 3 to 6.)
A cyclic silane compound represented by, a compound in which some or all of the hydrogen atoms of the cyclic silane compound are substituted with other cyclic silanyl groups and/or chain silanyl groups, some or all of the hydrogen atoms of the silane compounds exemplified above. Examples of compounds in which halogen atoms are substituted include SiH3F, 5iH3C1゜5
5irHsXt such as iH3Br, 5iH3I (X is a halogen atom, r is an integer of 1 or more, preferably 1-1o, more preferably 3-7).

s+tw2r+2 or 2r. ) and halogen-substituted linear 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 silicon and halogen introduced into the film forming space, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically, , for example, 5iuY2
u+2 (U is an integer greater than or equal to 1, Y is F, CI, Br, and I
At least one element selected from ) chain silicon halide, 5ivY2V (V is 3
The above integer, Y, has the above-mentioned meaning. ), a linear or cyclic compound represented by S i 11HxYy (u and Y have the above-mentioned meanings; x+y=2u or 2u+2), and the like.

Specifically, for example, SiF4. (SiF2)5゜(Si
F2)e, (SiF2)a, 5i2Fs.

5i3F9. SiHF3. SiH2F2,5iC14,
(SiC12)5. SiBr4. (SiBr2)5,5
i2C16,5i2Br6゜5iHC13,5iHBr
Examples include those in a gaseous state or those that can be easily gasified, such as 3,5iHI3°5i2CI3F3.

Furthermore, in addition to the compounds containing silicon and halogen, other silicon-containing compounds such as simple silicon, hydrogen,
Halogen-containing compounds (e.g. 1! W 41 (”,
OQ +r-LHi &, l-+ Rr Q-!
2 etc.) can be used in combination.

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

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

In the present invention, the ratio of the amount of the silicon- and halogen-containing compound introduced into the film-forming space and the active species generated from the silicon-containing compound serving as the raw material for forming the deposited film is determined by the film-forming conditions,
It can be determined as desired depending on the type of active species, etc.
Preferably, 10:1 to 1:10 (introduction flow rate ratio) is appropriate, and more preferably 8:2 to 4:6.

In the present invention, in addition to silicon-containing compounds, hydrogen gas, halogen compounds (for example, F2 gas,
C12 gas, gasified Br2. I2 etc.), helium,
An inert gas such as argon or neon can also be introduced into the activation space. When using multiple of these chemicals, they can be mixed in advance and introduced into the activation space in a gaseous state, or these raw material gases can be supplied individually from independent sources and activated. They can be introduced into the activation space, or they can be introduced into independent activation spaces and activated individually.

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. The impurity element used is 1 as a p-type impurity.
Elements of group Ⅰ A of the periodic table, such as B, Al, Ga, In
, TI, etc., and examples of n-type impurities include elements 1 of group V A of the periodic table, such as P.

Preferred examples include As, Sb, Bi, etc.
In particular, B, Ga, P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical properties.

The substance containing such an impurity element as a component (substance for introducing impurities) is in a gaseous state at room temperature and normal pressure, or at least under the conditions for forming a deposited film, and can be easily vaporized using an appropriate vaporization device. Preferably, a compound is selected,
Such compounds include PH3, P2H4, PF3
.

PF5. PCl3. AsH3, AsF3゜AsF5. A
sCl3. SbH3,5bFs.

SiH3, BF3. BCl3. BBr3゜B2H8,B
4H10, B5H9, B5H11゜B6H10, B6H
12, AlCl3, etc. The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity-introducing substance can also be introduced into the film-forming space directly in a gaseous state, or by mixing a compound containing silicon and a halogen, or by activating it in the film-forming space. To activate the impurity-introducing substance, the above-described activation energy can be appropriately selected and employed. Active species (PN) generated by activating the impurity introducing substance are mixed with the active species in advance or are introduced independently into the film forming space.

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

FIG. 1 is a schematic diagram for explaining an example of the structure of a photoconductive member as a typical electrophotographic image forming member obtained by the present invention.

The photoconductive member 1O shown in FIG. 1 can be applied as an electrophotographic imaging member.

An intermediate layer 12 provided as necessary on the support 11 for photoconductive member. and a photosensitive layer 13.

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13 can be created by the method of the present invention. Further, the photoconductive member 10 may include a protective layer provided to chemically and materially protect the surface of the photosensitive layer 13, or a lower barrier layer and/or an upper layer provided for the purpose of increasing electrical withstand pressure. If a barrier layer is included, these can also be created by the method of the present invention.

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

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

Examples include metals such as Pd and alloys thereof.

Polyester is used as the electrically insulating support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

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

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

V, Ti, Pt, Pd, In2O3, 5n02゜ITO
(In203+5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, Al, Ag,
Pb, Zn, Ni.

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

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

The intermediate layer 12 effectively prevents carriers from flowing into the photosensitive layer 13 from the support 11 side.

The photosensitive layer 13 of the photocarrier is generated in the photosensitive layer 13 by irradiation with electromagnetic waves and moves toward the support 11.
It has a function of easily allowing passage from the side to the support body 11 side.

This intermediate layer 12 has silicon atoms as its base material, and hydrogen atoms (
Amorphous silicon containing H) and/or halogen atoms (X) (hereinafter referred to as "A-3i (H,
), and also contains a p-type impurity such as boron (B) or an n-type impurity such as phosphorus (P) as a substance that controls electrical conductivity.

In the present invention, the content of substances governing conductivity such as B and P contained in the intermediate layer 12 is preferably o,
ooi to 5X104 atomic ppm, more preferably 0.5 to IX11X104 atomic ppm, optimally 1 to 5xto:3 atomic ppm.

If the intermediate layer 12 has similar or the same constituent components as the photosensitive layer 13, the formation of the photosensitive layer 13 can be carried out continuously after the formation of the intermediate layer 12. In that case,
As raw materials for forming the intermediate layer, a compound containing silicon and a halogen, an active species generated from the silicon-containing compound introduced into the activation space, and hydrogen, a halogen compound, an inert gas, and an impurity element as necessary are used. The active species generated by activating the gas of the compound contained as a component are separately introduced into the film forming space where the support 11 is installed, and discharge energy is applied to the atmosphere in which the introduced active species coexist. The intermediate layer 12 may be formed on the support 11 by acting on the support 11.

The layer thickness of the intermediate layer 12 is preferably 30 to 10 JL,
More preferably 40 people to 8#L, optimally 50 people to 5#L.

The photosensitive layer 13 is made of silicon atoms, for example, and has both a charge generation function of generating photocarriers by irradiation with hydrogen atoms and/or halogen atoms (x) light, and a charge transport function of transporting the charges. .

The thickness of the photosensitive layer 13 is preferably 1-100 mm, more preferably 1-80 mm, and most preferably 2-50 mm.

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 , the substance that governs the conduction characteristics of the same polarity is added to the intermediate layer 1.
If the actual amount contained in 2 is large, it may be contained in an amount much smaller than the above amount.

In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, as in the case of the intermediate layer 12, a compound containing silicon and halogen is used in the film forming space, and a silicon-containing compound for film forming is used. The generated active species and, if necessary, inert gas, compound gas containing impurity elements as components, etc.
It is introduced into the film forming space where the support 11 is installed.

The photosensitive layer 13 may be formed on the intermediate layer lz formed on the support 11 by using discharge energy.

FIG. 2 is a schematic diagram showing a typical example of a PIN type diode device using an A-3i deposited film doped with an impurity element, which is manufactured by carrying out the method of the present invention.

In the figure, 21 is a base, 22 and 27 are thin film electrodes, and 23 is a semiconductor film, including an n-type semiconductor layer 24, an i-type semiconductor layer 2
5. It is composed of a p-type semiconductor layer 26. 28 is a conductive wire connected to an external electric circuit device.

The base 21 may be conductive, semiconductive, or electrically insulating. If the substrate 21 is conductive, the thin film electrode 22 may be omitted. Examples of semiconductive substrates include Si, Go, Ga, As, ZnO,
Examples include semiconductors such as ZnS. Examples of the thin film electrodes 22.27 include N[Cr, AI, Cr, and Mo.

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

Pd, I n203.5n02, ITO (I n2
03 +S noz) on the substrate 21 by a process such as vacuum evaporation, electron beam evaporation, or sputtering. The layer thickness of the electrode 22.27 is preferably 30 to 5×104, more preferably 10
It is desirable that the number be 0 to 5 x 103 people.

In order to make the film constituting the semiconductor layer of A-5i (H, It is formed by doping both impurities into the layer to be formed while controlling their amounts.

In order to form n-type, i-type, and p-type A-3t(H,

Alternatively, a silicon-containing compound in a base state,
If necessary, compound gases containing inert gases and impurity elements as components are excited and decomposed by activation energy to generate each active species, and each is supported separately or mixed as appropriate. The substrate 11 is introduced into the film forming space where the substrate 11 is installed, and by using discharge energy, chemical interactions are caused, promoted, or amplified, and a deposited film is formed on the substrate 11. n-type and p-type A-3i (H
,

Further, the thickness of the i-type A-5i layer is preferably 5
00 N104 people, more preferably 1000~tooo
A range of o people is desirable.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 3, i
A-3i (H,X) deposited films of type, p-type and n-type were formed.

In FIG. 3, 101 is a film forming chamber, and a desired substrate 103 is placed on a substrate support stand 102 inside.

104 is a heater for heating the substrate;
4 is used when heat-treating the substrate 104 before film-forming processing, or when performing 7-neal processing to further improve the characteristics of the film formed after film-forming, and is supplied with power via conductor m l 05. and develops a fever. Although the substrate temperature is not particularly limited,
When it is necessary to heat the substrate in carrying out the method of the present invention, the substrate temperature is preferably 30 to 450°C.
, more preferably 50 to 350°C.

Reference numerals 10B to 109 are gas supply sources, which are provided depending on the number of raw materials for film formation and compounds containing hydrogen, a halogen compound, an inert gas, and an impurity element, which are used as necessary.

When using these raw material compounds that are liquid in the standard state, an appropriate vaporization device should be provided. In the figure, the gas supply sources 106 to 109 are indicated by a branch pipe, and b is a branch pipe. Flowmeters are marked with C, pressure gauges are used to measure the pressure on the high pressure side of each flowmeter, and valves with d or e are used to adjust the flow rate of each gas. 123 is an activation chamber for generating active species, and around the activation chamber 123 is provided a microwave plasma generator 122 that generates activation energy for generating active species. Raw material gas for generating active species supplied from the gas introduction pipe 110 is activated in the activation chamber, and the generated active species are introduced into the film forming chamber lot through the introduction pipe 124. 111 is a gas pressure gauge.

In the figure, 112 is a compound supply source containing silicon and halogen, and a've attached to the symbol 112 is from 106 to 1.
The same thing as in the case of 09 is shown. Compounds containing silicon and halogens.

It is introduced into the film forming chamber 101 via the introduction pipe 113.

117 is a discharge energy generating device.

It is equipped with a matching box 117a, a cathode electrode 117b for high frequency introduction, and the like.

The discharge energy from the discharge energy generating device 117 is applied to the silicon- and halogen-containing compound and the active species flowing in the direction of the arrow 119, and causes the acted compound and the active species to undergo a mutual chemical reaction, thereby producing A. -5l
A deposited film of (H,X) is formed. Also, in the figure, 120
121 is an exhaust valve, and 121 is an exhaust pipe.

First, a substrate 10 made of polyethylene terephthalate film
3 was placed on the support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device (not shown) to reduce the pressure to 104 Torr. SisHto150S from gas supply pump 106
CCM, or it and PH3 gas or B2H6 gas (
A gas mixed with 11,000 pp hydrogen gas (diluted with hydrogen gas) and 403 CCM was introduced into the activation chamber 123. The 5isH10 gas and the like introduced into the activation chamber 123 were activated by the microwave plasma generator 122 and turned into silicon hydride active species, etc., and the silicon hydride active species were introduced into the film forming chamber IO1 through the introduction pipe 124. .

On the other hand, SiF4 gas is introduced into the pipe 11 from the supply source 112.
3 and then introduced into the film forming chamber 101.

While maintaining the pressure in the film forming chamber 101 at 0.6 Torr, plasma is applied from the discharge device 117 to form a non-doped or doped A-5i (H,X) film (thickness: 700). did. Film deposition speed is 38 people/
*Next, the obtained non-doped or p-type A-5i (
H,
After forming a comb-shaped AI gap electrode (gap length 250!, width 5 mm), the dark current was measured at an applied voltage of 10 V, and the dark conductivity σd was determined to evaluate the film characteristics of each sample.

The results are shown in Table 1.

Examples 2 to 4 Linear 5i4F10, branched 5i instead of Si5H10
An A-5i film was formed according to the same method and procedure as in Example 1, except that 4H1(1) or H65i6F6 was used. Dark conductivity was measured and the results are shown in Table 1.

From Table 1 1 A-3i with excellent electrical characteristics according to the present invention
It was found that a (H,X) film was obtained and that a sufficiently doped A-3i (H,X) film was obtained.

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

In FIG. 4, 201 is a film forming chamber, 202 is a compound supply source containing silicon and halogen, 206 is an introduction pipe, 207 is a motor, 208 is a heating heater used in the same manner as the heater 104 in FIG. 210 is a blowout pipe, 211 is a cylindrical base such as an At cylinder, and 212 is an exhaust valve. Also, 213 to 216 are the third
It is a raw material gas supply source similar to 106 to 109 in the figure,
217-1 is a gas introduction pipe.

The AI Kushinder base 211 is suspended in the film forming chamber 201,
There is a heater 208 inside it, and a motor 207.
Allows for rotation. Reference numeral 218 denotes a discharge energy generating device, which includes a matching box 218a, a high frequency introduction cando electrode 218b, and the like.

SiF4 is introduced from the supply source 202 into the film forming chamber 201 through the introduction pipe 206.

On the other hand, S i 2H6 and H2 gases were introduced into the activation chamber 219 through the introduction pipe 217-1. 5i introduced
In the activation chamber 219, the 2He and H2 gases are subjected to activation processing such as plasma conversion by the microwave plasma generator 221 to become silicon hydride and active species active hydrogen, which are then introduced into the film forming chamber 201 through the introduction pipe 217-2. was introduced in. At this time, impurity gases such as PH3 and B2H8 were also introduced into the silicon hydride and active species activation chamber 219 to be activated.

Next, while maintaining the internal pressure in the film forming chamber 201 at 1.0 Torr, plasma generated by the discharge device 218 was applied.

The AI Kushinder base 211 is heated to 220°C by the heater 208.
The exhaust pulp 212 is heated, held, and rotated, and the exhaust gas is exhausted by appropriately adjusting the opening of the exhaust pulp 212. In this way, the photosensitive layer 13 was formed.

Further, the intermediate layer 12 is inserted into the introduction tube 217-- prior to the photosensitive layer.
1 to 5i2es, H2/ and B2H6 (B2 in volume %
A mixed gas containing 0.2% H6 gas was introduced, and the film thickness was 200%.
The film was deposited by 0 people.

Comparative Example 1 Using SiF4, Si2H6, H2, and B2H6 gases, the film forming chamber 201 was equipped with a 13.56 MHz high-frequency device, and an electrophotograph of the layer structure shown in FIG. 1 was produced by a general plasma CVD method. An imaging member was formed.

The manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 5 and Comparative Example 1 were evaluated in Example 6 using the apparatus shown in FIG. 3 using 5i3He as the silicon-containing compound. A PIN type diode shown in Figure 2 was manufactured.

First, a polyethylene naphthalate film 21 on which 1000 ITO films 22 were vapor-deposited was placed on a support stand, and 104
After reducing the pressure to Torr, the introduction pipe 113 is opened as in Example 1.
Then, SiF4 was introduced into the film forming chamber 101.

In addition, S E 3He150SCCM, PH3 gas (1
000ppm diluted hydrogen gas) was introduced into the activation chamber and activated.Then, the activated gas was introduced into the introduction pipe 1
24 into the film forming chamber 101. Film forming chamber 101
The internal pressure is 0, l T o r r, and the temperature of the substrate is 2.
Plasma is applied from the discharge device 117 while maintaining the temperature at 00°C, and the n-type A-5i(H,X)1 doped with P is
1124 (Ill thickness 700 people) were formed.

Next, the n-type A-5 except that the introduction of PH3 gas was stopped.
Tenon-doped (7
)A-3i (H,X) 1lI25 (film thickness 5000
people).

Next, 32H6 gas (1000ppm
The p-type A-3i (H,X) film 26 (H,
A film thickness of 700 layers was formed. Furthermore, on this p-type film, an AI electrode 27 with a thickness of 1000 people is formed by vacuum evaporation,
A PIN type diode was obtained.

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

In addition, regarding the light irradiation characteristics, light is introduced from the substrate side, and the light irradiation intensity is AMI (approximately 100 mW/cm2), the conversion efficiency is 8.1% or more, the open circuit voltage is 0.91 V, and the short circuit current is 10.2 mA/cm2 was obtained.

"r- Examples 7 to 9 Instead of 5i3H6 as a silicon-containing compound, linear 5
i4Hxo, branched 5i4HIO, or)163i
The PIN was entered in the same manner as in Example 6 except that 6FB was used.
A type diode was fabricated.

The rectification characteristics and photovoltaic effect of this material were evaluated, and the results are shown in Table 3.

From Table 3, it was found that according to the present invention, an A-3i (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 high-speed film formation is possible. In addition, the reproducibility in film formation is improved, which makes it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, and improves the productivity of S and facilitates mass production. be able to. Furthermore, since it is possible to form a film with low discharge energy as excitation energy, it has the effect of, for example, being able to form a film even on a substrate with poor heat resistance, and shortening the process through low-temperature processing.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining an example of the configuration of a PIN diode manufactured using the method of the present invention. FIGS. 3 and 4 are configurations of an apparatus for carrying out the method of the present invention used in Examples, respectively. FIG. 2 is a schematic diagram for explaining. 10--An electrophotographic imaging member; 11--A substrate. 12---One intermediate layer, 13---One photosensitive layer, 21---One substrate, 22.27---Thin film electrode, 24---N type semiconductor layer, 25--- N type semiconductor layer. 26---p-type semiconductor layer. 101, 201---Single point pupil chamber. 214.215,216---Gas supply source, 103
, 211---one base, 117.218---one discharge energy generation device.

Claims (1)

[Claims] A compound containing silicon and halogen and an active species generated from the silicon-containing compound for film formation that chemically interacts with the compound are placed in a film formation space for forming a deposited film on a substrate. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by applying discharge energy to the substrate and causing a chemical reaction.