JPS61185919A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To form a film having a large area, to improve the productivity of the film as well as to contrive accomplishment of mass production by a method wherein an activating seed grown by decomposing a compound containing silicon and halogen and an activating seed grown by a compound containing silicon are introduced into a film forming vacant space, and optical energy is made to work on the above-mentioned activating seeds. CONSTITUTION:Under the state of coexistence of the activating seed A formed by decomposing the compound containing silicon and halogen and the activating seed B formed by a silicon containing compound in a film forming vacant space, the adverse effect generated by the action of etching or the abnormal discharge action and the like, for example, while the film is being formed can be prevented by having optical energy worked on the above-mentioned materials, instead of growing plasma. Also, film-forming speed can be increased remarkably, and the substrate temperature when a deposition film is formed can be lowered by using the activating seed activated in the vacant space different from the film-forming vacant space, thereby enabling to industrially mass produce the deposition film of stabilized film quality at low cost.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention is directed to silicon-containing deposited films, particularly saturable films, particularly semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, and imaging devices. [Prior art] For example, vacuum evaporation is used to form an amorphous silicon film. methods, plasma CVD methods, CVD methods, reactive sputtering methods, ion blating methods, photo-CVD methods, etc. have been tried.

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

Deposited films composed of amorphous silicon have been improved in terms of 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 in forming an amorphous silicon deposited film by the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure 1
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 that fully satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. There is.

According to Hyakunen et al., depending on the application of the deposited film, it is necessary to satisfy the requirements of large area, uniform film thickness, and uniform film quality, and also achieve reproducible mass production through high-speed film formation.
Forming an amorphous silicon deposited film using the plasma CVD method requires a large amount of equipment investment for mass production equipment, and the management items for mass production also become complex, the management tolerance narrows, and equipment adjustments are delicate. Since it is,
These have been pointed out as problems that should be improved in the future. On the other hand, with the conventional technology using the normal CVD method,
This method requires high temperatures, and a deposited film with practically usable properties has not been obtained.

As mentioned above, 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 1 such as silicon nitride films, silicon carbide films, and silicon oxide films.

The present invention eliminates the above-mentioned drawbacks of the plasma CVD method and provides a new deposited film forming method 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 create an active species (A) generated by decomposing a compound containing silicon and a halogen in a film formation space for forming a deposited film on a substrate, and a chemical reaction between the active species (A) and A deposited film is formed on the substrate by separately introducing active species (B) generated from a silicon-containing compound that interacts with each other and causing them to react by applying light energy. This is achieved by the deposited film forming method of the present invention, which is characterized by the following.

[Embodiment]

In the method of the present invention, instead of generating plasma in a film forming space for forming a deposited film, active species (A) are generated by decomposing a compound containing silicon and halogen.
In the coexistence of active species (B) generated from a silicon-containing compound, by applying light energy to these, chemical interactions are caused, or promoted and amplified. The deposited film that is formed is not adversely affected by etching effects or other adverse effects such as abnormal discharge effects during film formation.

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

One of the differences between the method of the present invention and the conventional CVD method is that 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.

In addition, the active species (A) in the present invention is a compound that chemically interacts with the active species (B) generated from the silicon-containing compound that is the compound of the raw material for forming the deposited film to impart energy, for example. Active species (A) are substances that have the effect of promoting the formation of deposited films by
) may include constituent elements constituting the deposited film to be formed, or may not include such constituent elements.

In the present invention, the activated species (A) from the activation space (A) introduced into the film forming space have a lifetime of 0.1 seconds or more, more preferably 1 second, from the viewpoint of productivity and ease of handling. A length of at least 1 second, preferably at least 10 seconds, is selected and used according to the desired condition ψ.

The silicon-containing compound for forming a deposited film used in the present invention is
It is preferably already in a gaseous state before being introduced into the activation space CB), or preferably introduced in a gaseous state. For example, when using a liquid compound, connect an appropriate vaporizer to the compound supply source. The compound can be vaporized and then introduced into the activation space (B).

Silicon-containing compounds include silicon, hydrogen, halogen,
It is possible to use silanes and halogenated silanes to which silanes such as the like are bonded. Particularly suitable are chain and cyclic silane compounds, and compounds in which part or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with /\logen atoms.

Specifically, 1, for example, 5iHa, 5i2Hs, S i
31 (e, S i 4H10, 5i5H12, 5t6
5ipH2p+2 such as H1a (p is preferably 1 or more, k is 1
~15. More preferably, it is an integer of 1 to 10. ), a linear silane compound represented by 5iH3SiH (SiH3
)SiH3,5iH3SiH(SiH3) 5i3H
7, 5i such as 5i2H5SiH (SiH3) Si2H5
Branched chain silane compounds with pH 2p+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 ,5t3H6,5i4
1 (e, 5i5HIO, S i 6 HI3 etc. (7) S
A cyclic silane compound represented by i (lH2q (q is an integer of 3 or more, preferably 3 to 6), in which some or all of the hydrogen atoms of the cyclic silane compound are replaced by other cyclic silanyl groups and/or chain Examples of compounds substituted with sitenyl groups and compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are substituted with halogen atoms include SiH3F, 5
iH3CI, 5tH3Br, 5iH3I etc. c7) S i
yH3Xt (X is a halogen atom, r is an integer of 1 or more, preferably 1 to 1O1, more preferably 3 to 7, 5+L!
2r+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 activation space (A), 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. For example, 5
tuy2U+Z (U is an integer greater than or equal to 1, Y is F, CI.

Br and! At least one element selected from ) Chain-like silicon halogenide, 5ivY2v
(V is an integer of 3 or more, Y has the above-mentioned meaning.) Cyclic halogenated silicon, S i u) IXY'
Examples include chain or cyclic compounds represented by / (u and Y have the above-mentioned meanings. x+yz2u or 2u+2).

Specifically, for example, 5iFa, (5iF2) 5° (SiF
2) e, (SiF2)4.5i2Fe.

Si'3F+3,5fHF3. SiH2F2゜5iC1
a, (SiC12)5. SiBr4゜(SiBr2)5
．． 5i2C16,5i2Br6SiHC sentence 3,5iH
Examples include those in a gaseous state or those that can be easily gasified, such as Br3,5iHI3°5i2C13F3.

In order to generate the active species (A), in addition to the above-mentioned compound containing silicon and halogen, other silicon compounds such as simple silicon, hydrogen, and halogen compounds (for example, F2
gas, cfL2 gas, gasified Br2. I2 etc.) can be used in combination.

In the present invention, methods for generating active species (A) in the activation space (A) include electric energy such as microwave, RF, low frequency, DC, heater heating, infrared rays, etc., taking into account each condition and device. Activation energy such as thermal energy from heating or light energy is used.

By adding activation energy such as heat, light, electricity, etc. in the activation space (A) to the above, activated species (A)
is generated.

In the present invention, active species (B) generated from a silicon-containing compound that is a raw material for forming a deposited film introduced into a film forming space
The ratio of the amount of active species (A) to the activated species (A) from the activation space (A) is determined as desired depending on the film forming conditions, the type of active species, etc., but is preferably lO:1 to 1:10 (introduction flow rate The ratio) is appropriate, 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.), inert gases such as helium, argon, and neon are used as raw materials for film formation. It is also possible to introduce and use it into the activation space (B). When using a plurality of these raw materials, they are mixed in advance and placed in the activation space (B
), or these raw materials for film formation can be individually supplied from independent sources and introduced into the activation space CB).
It is also possible to introduce them into independent activation spaces and activate them 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 elements used include p-type impurities,
Elements 1 of Group ⅠA of the periodic table, such as B, AI, Ga, In
, T1, etc., and as the n-type impurity, an element 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 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 under activation conditions, and that can be easily vaporized with an appropriate vaporization device. Such compounds include PH3, P2H4, PF3. PF5. PCl3
゜AsH3, AsF3. AsF5. AsCl3゜SbH
3, SbF5. SiH3, BF3. BCl3, BBr
3. B2H6, B4H10, BSH9, B5H11, B
Examples include 6H10, B6H12, AlCl3, and the like. Compounds containing impurity elements may be used IN or in combination of two or more.

The impurity-introducing substance may be introduced into the activation space (A) and/or the activation space CB) together with each substance that generates the active species (A) and the active species (B), and activated. Alternatively, the impurity introducing substance, which may be activated in a third activation space (C) different from the activation space (A) and the activation space (E), is subjected to the activation energy described above. They can be selected and adopted as appropriate. The active species (PN) generated by activating the impurity introducing substance is mixed with the active species and/or the active species (B) in advance, or is introduced into the film forming space independently.

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 configuration 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.

In manufacturing the photoconductive member 1O, a protective layer provided to protect the intermediate layer 12 and/or the photosensitive layer 13 by the method of the present invention, or a lower barrier provided for the purpose of improving electrical withstand pressure. layers and/or top barrier layers, these can also be made by the method of the invention.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include 1fNicr, stainless steel, 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.

Films or sheets of synthetic resins such as 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 NiCr.

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

V, Ti, Pt, Pd, In2O3,5n02゜I
If it is conductive treated by providing a thin film such as TO (In203+5no2) or a synthetic resin film such as polyester film, NiCr, AI, A
g, 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 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, a photosensitive layer 13 is applied to the intermediate layer 12 from the side of the support 11.
This effectively prevents the inflow of carriers into the photosensitive layer 13 and causes the photocarriers to move toward the support 11 from the photosensitive layer 13 side, which is generated during the photosensitive R13 by the irradiation of electromagnetic waves, and moves toward the support 11 side. It has a function that allows easy passage of.

This intermediate layer 12 is made of amorphous silicon (hereinafter referred to as
a-5i (H,X) Written as J. ), and the substance that controls electrical conductivity is 1, for example, boron C.
P-type impurities such as B) or n-type impurities such as phosphorus (P) are contained.

In the present invention, the content of substances governing conductivity, such as B and P, contained in the intermediate layer 12 is preferably 0.
001-5X104 atomic ppm, more preferably 0.5-1X104 atomic ppm,
The optimum range is preferably 1 to 5×10 3 atomic ppm.

When the intermediate layer 12 has similar or the same components as the photosensitive layer 13, the formation of the intermediate layer 12 can be performed continuously from the formation of the intermediate layer 12 to the formation of the photosensitive layer 13. In that case, the active species (A) generated in the activation space (A) and the active species generated from the silicon-containing compound introduced into the activation space (B) are used as raw materials for forming the intermediate layer. (B) and optionally hydrogen, /\rogen compound,
An inert gas and active species generated from a compound gas containing an impurity element as a component are introduced into the film forming space where the support 11 is installed, either separately or mixed as appropriate. , the intermediate layer 12 may be formed on the support 11 by using light energy.

Compounds containing silicon and halogen that are introduced into the activation space (A) to generate active species (A) when forming the intermediate layer 12 include: 1. For example, compounds that easily generate active species such as S i F2*. is preferably selected from the compounds listed above.

The layer thickness of the intermediate layer 12 is preferably 30 to 10, more preferably 40 to 8 IL, and optimally 50 to 5 IL.

The photosensitive layer 13 is composed of, for example, A-3i (H,

The layer thickness of the photosensitive layer 13 is preferably 1 to 100I
L, more preferably 1-8oIL, optimally 2-50IL
I would like it to be considered that way.

The photosensitive layer 13 is, for example, a non-doped A-5L (H, It may contain a controlling substance, or
If the actual amount contained in the intermediate layer 12 is large, the substance that governs the conduction properties of the same polarity may be contained in an amount much smaller than the dose.

In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, a compound containing silicon and halogen is introduced into the activation space (A), as in the case of the intermediate layer 12.
Active species (A) are generated by decomposing them at high temperatures or by exciting them with discharge energy or light energy, and the active species (A) are introduced into the film forming space.

FIG. 2 shows A-5i(H) doped with an impurity element prepared by carrying out the method of the present invention.

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

In the figure, 21 is a substrate, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an n-type A-3i (H, X) layer 24, an i-type (7) A-5i (H, X) layer 25 , p-type A-3i (
(H, X) layer 26. 28 is a conductive wire connected to an external electric circuit device.

The base 21 may be conductive, semiconductive, or electrically insulating. When the base 21 is conductive, the thin film electrode 22 may be omitted. Examples of the semiconductive base include semiconductors such as Si 2 and Ge. For example, the thin film electrodes 22.27 are made of NiCr.

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

V, Ti, Pt, Pd, In2O3,5n02゜I
It can be obtained by providing a thin film of TO (In203+5n02) or the like on a substrate using a process such as vacuum evaporation, electron beam evaporation, or sputtering. The film thickness of the electrodes 22.27 is preferably (*30 to 5×10 4 , more preferably 1 eO to 5×10 3 ).

In order to make the film body constituting the semiconductor layer example of a-3i (H, Alternatively, it can be formed by doping both impurities into the layer to be formed while controlling their amounts.

To form the n-type till and pfi no a-s i (H, For example, by exciting and decomposing S
Active species (A) such as i F2)k are generated, and the active species (A) are introduced into the film forming space. Also, apart from this,
The film-forming compound introduced into the activation space (B) and the compound gas containing an inert gas and an impurity element as necessary are excited and decomposed by activation energy, respectively. Generate active species, introduce each separately or appropriately mixed into the film formation space where the support ti is installed, and use the light energy introduced into the film formation space to cause chemical interaction. A deposited film is formed on the support 11 by causing, accelerating, or amplifying. The thickness of the n-type and p-type (7)a-3i(H,X) layers is preferably 100 to 104, more preferably 300 to 20.
A range of 00 people is desirable.

In addition, the film thickness of the i type (7) & -3i (H,X) calendar is preferably 500 to 104 people, more preferably 10
A range of 00 to 10,000 people is desirable.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 3, l
type, pm and n type a-3i (H.

X) A deposited film was formed.

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

104 is a heater for heating the substrate;
4 is used when heat-treating the base 104 before film-forming processing, or when performing 7-neal processing after film-forming to improve the characteristics of the formed film, and is supplied with power via a conductive wire 105. and develops a fever. The substrate heating temperature at this time is not particularly limited, but when carrying out the method of the present invention, it is preferably 50 to 450°C, more preferably 100 to 350°C.
It is desirable that

106 to 109 are gas supply systems, which supply gas for film formation, hydrogen, halogen compounds,
It is provided depending on the type of inert gas or compound gas containing an impurity element as a component. If these gases are liquid in their standard state, an appropriate vaporizer is provided.

In the figure, the gas supply systems 106 to 109 are marked with a for branch pipes, b for flowmeters, C for pressure gauges that measure the pressure on the high pressure side of each flowmeter, and d for gas supply systems 106 to 109. The ones marked with "e" are valves for adjusting the flow rate of each gas. 12
3 is an activation chamber (B) for generating active species CB), and around the activation chamber 123 is a microwave plasma generator that generates activation energy for generating active species (B). 122 is provided. The raw material gas for generating active species (B) supplied from the gas introduction pipe 110 is activated in the activation chamber CB) 123, and the generated active species (B) are activated in the activation chamber CB) 123.
B) is introduced into the film forming chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge.

In the figure, 112 is an activation chamber (A), 113 is an electric furnace, and 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 the active species (A),
The activated species (A) generated in the activation chamber (A) 112 are introduced into the film forming chamber lot via the introduction pipe 116.

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

Optical energy generator 117 generates an appropriate optical energy -++
The light 118 directed to a desired part is irradiated onto the active species flowing in the direction of an arrow 119.

The irradiated active species react chemically with each other to form a-3i (H,
A deposited film is formed. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

Substrate 10 made of pre-screened polyethylene terephthalate film
3 was placed on the support stand 102, the inside of the deposition space 101 was evacuated using an exhaust device, and the pressure was reduced to 1 (16 Torr).
M, or a gas mixed with 403 CCM of PH3 gas or B2H6 gas (both diluted with 11000 pp hydrogen gas) is supplied to the activation chamber (33 CCM) through the gas introduction pipe 110.
) 123. The H2 gas etc. introduced into the activation chamber (B) 123 is activated by the microwave plasma generator 122 and turned into activated hydrogen etc.
-Five words゛も Introduced into 101.

On the other hand, the activation chamber (A) 102 is filled with solid Si particles 114, heated in an electric furnace 113 and kept at about 1100°C to bring the Si to a red-hot state, and CF4 By injecting S i F2)tc as the active species (A), the S
iF2* was introduced into the film forming chamber 101 through the introduction tube 116.

IKW while maintaining the atmospheric pressure in the film forming chamber 101 at 0.3 Torr.
Undoped or doped a-3i (H,
(II thickness 700 people) was formed. The film formation rate is 45λ/
It was sec.

The obtained non-doped or p-type a-3i (
Place the sample on which the H,
After forming a comb-shaped Al gap electrode (gap length 250mm, width 5mm) at −5 Torr, an applied voltage of 10
The dark current was measured at V, the dark conductivity σd was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2 to 4 Linear Si4H10, branched 5 instead of Si2H6
a-3i(H) in the same manner as in Example 1 except that iaH10 or H65i6FB was used.

X) A film was formed. Measure the dark conductivity of each sample,
The results are shown in Table 1.

From Table 1, it can be seen that according to the present invention, a-5i has excellent electrical characteristics.
It was found that a (H,X) film was obtained and that a sufficiently doped a-3t(H,X) film was obtained.

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

In FIG. 4, 201 is a film forming chamber, 202 is an activation chamber,
203 is an electric furnace, 204 is a solid Si particle, 205 is an active species (A) raw material introduction pipe, 206 is an active species (A) introduction pipe, 207 is a motor, and 208 is used in the same way as the heater 104 in FIG. 209 and 210 are blowout pipes, and 211 is an AI cylindrical body 212 is an exhaust valve. Further, 213 to 216 are raw material gas supply sources similar to 106 to 109 in FIG.
7 is a gas introduction pipe.

An AI cylindrical substrate 211 is suspended in the film forming chamber 201, a heating heater 208 is provided inside the substrate, and a motor 20 is installed.
7 so that it can be rotated. Reference numeral 218 denotes a light energy generator, which irradiates light 219 toward a desired portion of the AI cylinder base 211.

Further, 51 solid particles 204 were packed in the activation chamber (A) 202 and heated in an electric furnace 203.

Keep the temperature at 1100°C to make Si red-hot, and insert tube 20 into it.
By blowing SiF4 from a cylinder (not shown) through 6, 5tF2* as an active species (A) is generated,
The S i F2)k is passed through the introduction pipe 206 to the membrane chamber 1 & membrane chamber 2.
It was introduced into 01.

Meanwhile, Si2H6 and F2 were introduced into the activation chamber 220 through the introduction pipe 217-1. Introduced Si2H6 gas, F
In the activation chamber (B) 220, the two gases are subjected to activation processing such as plasma conversion by the microwave plasma generator 221 to become activated hydrogen silicate and activated hydrogen, and are introduced into the film forming chamber through the introduction pipe 217-2. It was introduced in 201. At this time, adjust the pH to 3 if necessary.

An impurity gas such as 82H6 is also introduced into the activation chamber (B) 220 and activated. Then, while maintaining the atmospheric pressure in the film forming chamber 201 at 1.0 Torr, the IKWXe lamp 218 is used to inject air around the AI cylinder base 211. Light was irradiated perpendicular to the surface.

The AI cylinder base 211 was rotated, and exhaust gas was exhausted through the exhaust valve 212.

In this way, the photosensitive layer 13 was formed.

Furthermore, prior to the creation of the photosensitive layer 13, the intermediate layer 12 is supplied with an inlet pipe 217-1 in addition to the gas used when creating the photosensitive layer 13.
From F2/B2H6 (B2H6 gas is 0.2% by volume%)
) was introduced to form a film with a thickness of 2000λ.

Comparative Example 1 A film forming chamber having the same configuration as the film forming chamber 201 was prepared using SiF4, 5i2Hs, F2 and B2H6 gases.
An electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by a general plasma CVD method equipped with a 3.56 MHz high frequency device.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 5 and Comparative Example 1.

Example 6 A PIN type diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3 using 5tzH as a silicon-containing compound.

First, a polyethylene naphthalate film 21 on which a 100-year-old ITO film 22 has been deposited is placed on a support stand, and a 10-
After reducing the pressure to 6 Torr, the inlet pipe 11 was opened in the same manner as in Example 1.
6 to introduce active species of SiF2* into the film forming chamber 101,
In addition, from the introduction pipe 110, S i 2H6150SCCM
.

PH3 gas (io00 ppm hydrogen gas dilution) was introduced into the activation chamber (B) 123 for activation.

Next, this activated gas was introduced into the film forming chamber IO1 via the introduction pipe 116. The pressure inside the film forming chamber 101 is set to 0.
P-doped n-type a-3i (H,
) Film 24 (film thickness: 700 layers) was formed.

Next, B2H6 gas (300p) was added instead of P)13 gas.
N-type A-5i (
H,X) It! The same method as in the case of Tei-5a-S
An i (H,X) film 25 (5000 s thick) was formed.

Next, B21 (
6 gas (lo00ppm diluted with hydrogen gas), otherwise n-type A-3i (H, X) 8124 Tol'f
Doping sale with B under t1C condition;/:pffia-s
i (H, X) [5126 (1! I! Thick 700 people)
was formed. Furthermore, an AI electrode 27 having a thickness of 1000 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 the light irradiation characteristics, light is introduced from the substrate side, and at the light irradiation intensity AMI (approximately 100 mW/cm2), the conversion efficiency is 8.5% or more, the open circuit voltage is 0.92 V, and the short circuit current is 10.
．． 5 mA/cm2 was obtained.

Examples 7-9 Instead of 5i3H6 as a silicon-containing compound, linear 5
i4HtO, branched Si4H10° or H6S i 6
A PIN type diode similar to Example 6 was manufactured except that F6 was used. The rectification characteristics and photovoltaic effect were evaluated and the results are shown in Table 3.

From Table 3, it was found that according to the present invention, an a-5i (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 without maintaining the substrate at a high temperature. becomes. In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. be able to. Furthermore, since light energy is 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 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 structure of a PIN type daiode manufactured using the method of the present invention. FIGS. FIG. 2 is a schematic diagram for explaining the configuration. 10--An electrophotographic imaging member; 11--A substrate. 12---One intermediate layer, 13---One photosensitive layer. 21--m-substrate. 22.27---Thin film electrode. 24---n-type a-Si(H,X), 25---i
) J a -S i (H,X), 2B---p-type a-5i (H,X). 101, 201-----film formation chamber, 111, 202-----activation chamber (A), 106.1
0,7,108,109,213゜214-915-9
1R---Iss abrasive chain work 103, 211---One base. 117.218-1--Optical energy generator.

Claims (1)

[Claims] Chemically interacts with active species (A) generated by decomposing a compound containing silicon and halogen in a film forming space for forming a deposited film on a substrate. Deposition characterized in that a deposited film is formed on the substrate by separately introducing active species (B) generated from a silicon-containing compound and reacting them with light energy. Film formation method.