JPS61220323A - Deposition film forming - Google Patents

Abstract

PURPOSE:To form the deposition layer on a substrate, by introducing the compound containing carbon and halogen, and the active species made from the film-forming chemical compound which react upon said chemical compound with each other, and making them react chemically by irradiating photo energy. CONSTITUTION:The photoconductive material 10 has the layer structure on the supporting body 11. This layer structure is constituted of the intermediate layer 12 which is installed according to necessity and the photo-sensitive layer 13. The intermediate layer 12 has the function, for example, to prevent effectively the carrier from flowing from the side of supporting body 11 into the photo- sensitive layer 13, and to allow easily the photo-carrier to pass from the side of photo-sensitive layer 13 to the side of supporting body 11. The photo-sensitive layer 13 is formed in the same way as the intermediate layer 12, that is, the compound containing carbon and halogen, the compound containing silicon and halogen which is different from the above one, the active species made from the chemical material for film-forming, and, according to necessity, the inactive gas and the gas of material to introduce impurity, etc. are introduced into the film-forming space, and the photo-sensitive layer 13 is formed on the intermediate layer 12 by applying photo energy.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a method suitable for forming an amorphous or crystalline deposited film containing carbon.

[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, etc. Generally, plasma CVD is the most popular method. Widely used and commercialized.

Deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity and mass production including uniformity and reproducibility. , there is room for further improvement of comprehensive 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,
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.

Depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniform film thickness, and uniform film quality, and to achieve mass production with high reproducibility through high-speed film formation.
Forming an amorphous silicon deposited film using the plasma CVD method requires a large amount of equipment investment for mass production equipment, and the management items for mass production are also complex, the management tolerance narrows, and equipment adjustments are difficult. Because it is subtle,
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, 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.

[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 chemically interact with a compound containing carbon and halogen in a film forming space for forming a deposited film on a substrate. The deposition method of the present invention is characterized in that a deposited film is formed on the substrate by introducing active species generated from chemical substances for film formation and irradiating them with light energy to cause a chemical reaction. This is achieved by a film formation method.

[Embodiment]

In the method of the present invention, instead of generating plasma in a film forming space for forming a deposited film, in the coexistence of a compound containing carbon and halogen and active species generated from a chemical substance for film forming, By applying light energy to these components, chemical interactions are caused, promoted, and amplified by these components, so that the deposited film that is formed is not susceptible to etching effects or other abnormal discharge effects, etc. will not be adversely affected by.

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, excitation energy is applied uniformly or selectively to the compounds and active species that have reached the vicinity of the substrate for film formation, but if light energy is used, the excitation energy can be applied to the substrate using an appropriate optical system. It is possible to form a deposited film by irradiating the entire area, or it is possible to selectively and controlly irradiate only a desired part to form a partially deposited film, or by using a resist etc. It is advantageously used because it has the convenience of being able to form a deposited film by irradiating only a graphic part.

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 the present invention, the activated species from the activation space introduced into the film forming space are:
Those having a lifetime of 0.1 seconds or more, more preferably 1 second or more, optimally 10 seconds or more are selected and used as desired, and the constituent elements of this active species form a deposit in the film forming space. It constitutes the components that make up the membrane. Furthermore, when a compound containing carbon and halogen is introduced into the film forming space and excited by the action of light energy to form a deposited film, it is simultaneously introduced from the activation space and becomes a component of the deposited film to be formed. chemically interacts with active species containing constituents.

As a result, a desired deposited film can be easily formed on a desired substrate.

In the present invention, as the compound containing carbon and halogen introduced into the film forming space, for example, a compound in which a part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically, 1 For example, CuY2u÷
2 (U is an integer of 1 or more, Y is at least one element selected from F, CI, Br, and engineering), CvY2V (V is an integer of 3 or more,
Y has the meaning given above. ) Cyclic halogenated carbon.

Examples include chain or cyclic compounds represented by S i uH) (Yy (u and Y have the above-mentioned meanings; x+y=2u or 2u+2).

Specifically, for example, CF4, (CF2)s.

(CF2)s, (CF2)a, C2FG, C3F
s, CHF3, CH2F2, CCl4, (CC
12) s, cBr4. (CBr2)5. C2C18,C
Examples include those in a gaseous state or easily gasifiable, such as 2Cl3F3.

Further, in the present invention, in addition to the above-mentioned compound containing carbon and halogen, a compound containing silicon and halogen can be used in combination. As the compound containing silicon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used. Specifically, for example, 5iuZ2u+2 (U is one or more An integer, Z is at least one element selected from F, CI, Br, and engineering. ), a chain or cyclic compound represented by S i 11HxZy (u and Z have the above-mentioned meanings, x+y=2u or 2u+2), and the like.

Specifically, for example, SiF4. (SiF2)5゜(SiF
2) e, (SiF2) 4.5tzFs.

5i3FB, 5tHF3. SiH2F2゜5iC14,
(SiC12)5.5iBra.

(SiBr2)s, 5i2C1B, 5i2Br6,5i
HC13, SiH2F2.5iHI3, 5i2C13F
Examples include those that are in a gaseous state or can be easily gasified, such as No. 3.

Furthermore, in addition to the compounds containing carbon and halogen (and compounds containing silicon and halogen).

If necessary, other silicon compounds such as simple silicon, hydrogen, halogen compounds (for example, F2 gas, C12 gas, gasified Br2.I2, etc.) can be used in combination.

In the present invention, methods for generating active species in the activation space include microwave, R
Activation energy such as electric energy such as F, low frequency, DC, thermal energy such as heater heating, 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 activation space used in the method of the present invention, the chemical substances for film formation that generate active species include hydrogen gas and/or halogen compounds (for example, F2 gas, CfL
2 gas, gasified Br2. I2 etc.) are advantageously used. Also.

In addition to these film-forming chemicals, for example helium,
Inert gases such as argon and neon can also be used. When using multiple of these chemical substances for film formation,
Alternatively, they can be mixed in advance and introduced into the activation space in a gaseous state.

Alternatively, these chemical substances for film formation can be individually supplied from independent sources and introduced into the activation space, or they can be introduced into separate activation spaces and activated individually. It can also be converted into

In the present invention, the ratio of the amount of the carbon- and halogen-containing compound introduced into the film-forming space and the active species can be determined as desired depending on the film properties, the type of active species, etc., but is preferably The ratio of the amounts introduced is suitably 10:1 to 1:10, more preferably 8:2 to 4:6.

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 of group m A of the periodic table, such as B, AI, 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 a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under the conditions for forming a deposited film, and that can be easily vaporized with an appropriate vaporization device. Such compounds which are preferably selected include PH3, P2H4, PF3
.

PF5, PCI3, AsH3, AsF3, As
F5. AsCl3. SbH3, SbF5, 5i83, B
F3. BCl3. BBr3. B2H6゜B4H10,B
5H9, B5H11, B8H10゜B6H12, AlC
l3 etc. can be mentioned.

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

The substance for introducing impurities may be introduced into the film forming space directly in a gaseous state or mixed with the above-mentioned compound containing carbon and halogen, or it may be activated in advance in the activation space and then used for forming the film. It can also be introduced into the membrane space. In order to activate the impurity-introducing substance, the above-mentioned activation energies listed for generating active species can be appropriately selected and employed. Active species (PN) generated by activating the impurity introduction substance are mixed with the active species in advance,
Alternatively, it 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 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.

It has a layer structure consisting of a support 11 for a photoconductive member, an intermediate layer 12 provided as necessary, 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. Furthermore, the photoconductive member 10 may include a protective layer provided to chemically and physically protect the surface of the photosensitive layer 13, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical withstand pressure. If so, 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 NiCr I 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 calendar 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
(I n203+5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, AI, Ag,
Pb, Zn, Ni.

A u , Cr , M o , I r , N
b, 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 support 11 side.
This effectively prevents the inflow of carriers into the photosensitive layer 13 and causes the photocarriers generated in the photosensitive layer 13 by electromagnetic wave irradiation and moves toward the support 11 from the photosensitive layer 13 side to the support 11 side. It has the function of allowing easy passage.

This intermediate layer 12 is made of amorphous carbon (hereinafter referred to as a-C(H,X)J) containing carbon atoms, hydrogen atoms (H) and/or halogen atoms (X) as constituent atoms.
It also contains p-type impurities such as boron (B) or phosphorus (P) as a substance that controls electrical conductivity.
Contains n-type impurities such as. Furthermore, silicon atoms may be included for the purpose of improving film quality.

In the present invention, the content of substances governing conductivity such as B and P contained in the intermediate layer 12 is preferably o,
It is desirable that the range is ooi to 5X104 atomic ppm, more preferably 0.5 to IX11X104 atomic ppm, optimally 1 to 5X103 atomic ppm.

The intermediate layer 12 has similar components to the photosensitive layer 13.

Alternatively, if they are the same, the formation of the photosensitive layer 13 can be performed continuously after the formation of the intermediate layer 12. In that case, the raw materials for forming the intermediate layer include a compound containing carbon and halogen, active species generated from film-forming chemicals introduced into the activation space, and optionally an inert gas and impurities. By introducing a gas or active species of a compound containing the element as a component separately or mixing as necessary, into the film forming space where the support 11 is installed, and applying light energy, The intermediate layer 12 may be formed on the support 11.

The layer thickness of the middle layer 1j12 is preferably 30 to 10 layers,
More preferably 40 people to 8 years, most preferably 50 people to 5 years.

The photosensitive layer 13 is made of an amorphous material (hereinafter referred to as rA-3i (H, It has both a charge generation function of generating photocarriers by irradiation with light and a charge transport function of transporting the charges.

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

The photosensitive layer 13 is a non-doped a-3i (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, it may be contained in a much smaller amount than the actual amount of the substance that controls the same polarity conduction characteristics. Good too.

In the 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 carbon and halogen and a compound containing silicon and halogen in the film forming space are used. By introducing a compound, an active species generated from a chemical substance for film formation, an inert gas, a gas of an impurity introduction substance, etc. as necessary into the film formation space, and using light energy, the intermediate layer 12 is formed. A photosensitive layer 13 may be formed thereon.

FIG. 2 is a schematic diagram showing a typical example of a PIN type diode device using an A-3L 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, 23 is a semiconductor film, an n-type semiconductor layer 24, an i-type semiconductor layer 2
5. Consisting of a p-type semiconductor layer 26. The present invention can be applied to the production of any one of the semiconductor layers 24, 25 and 26, but the conversion efficiency can be particularly improved by producing the semiconductor layer 26 by the method of the present invention.
When forming the semiconductor layer 26 by the method of the present invention, the semiconductor layer 26 is made of an amorphous material (rA-SiC (H,X)J). 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, Ge, GaAs, ZnO, and Zn.
Examples include semiconductors such as S. Examples of the thin film electrodes 22.27 include NiCr, AI, Cr, Mo, and Au.

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

In2O3,5n02. ITO (In203+5n02
), etc., on the substrate 21 by a process such as vacuum evaporation, electron beam evaporation, or sputtering. The film thickness of the electrode 22.27 is preferably 30~
It is desirable to have 5 x 104 people, more preferably 100 to 5 x 103 people.

In order to make the film forming the semiconductor layer n-type or p-type as necessary, during layer formation, n-type impurity, p-type impurity, or both impurities are added to the layer to be formed. It is formed by doping while controlling the amount.

When forming n-type, i-type, and p-type semiconductor layers, any one layer or all of the layers can be formed by the method of the present invention. During film formation, a compound containing carbon and halogen and a compound containing silicon and halogen are introduced into the film formation space, and in addition to this, chemical substances for film formation and inert gas and impurity elements are introduced as necessary. are excited by activation energy and decomposed to generate respective active species, and these active species are mixed separately or appropriately to form the support 11 The layer thickness of the n-type and p-type semiconductor layers, which may be introduced into a film-forming space and applied with light energy in the film-forming space, is preferably 100 to 104 cm.
A range of 300 to 2000 people is desirable.

Further, the thickness of the i-type semiconductor layer is preferably 50
A range of 0 to 104 people, more preferably 1000 to 1000 people is desirable.

Eight A specific example of the present invention is shown below.

Example 1 Using the apparatus shown in FIG. 3, a carbon-containing amorphous deposited film was formed by the following operations.

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 base 104 before film-forming processing or annealing the film after film-forming in order to further improve the properties of the formed film, and is supplied with power via a conductive wire 105. I get a fever. During film formation, the heater 104 is not driven.

Reference numerals 106 to 109 denote gas supply sources, which are provided depending on the type of film-forming gas, an inert gas used as necessary, and a compound gas containing an impurity element as a component.

When these gases are liquid in standard conditions, the ones marked with a are branch pipes, the ones marked with b are flow meters, and the ones marked with C are flow meters.
Those marked with ``d'' or ``e'' are pressure gauges that measure the pressure on the high-pressure side of each flowmeter, and those marked d or e are valves for adjusting 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. The raw material gas for active species generation supplied from the gas introduction pipe 110 is supplied to the activation chamber 123.
The generated active species are introduced into the film forming chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge.

In the figure, 112 is a compound supply source containing carbon and halogen, and the ae attached to the symbol 112 are 106 to 109.
It shows something similar to the case of . A compound containing silicon and halogen is introduced into the film forming chamber 101 via the introduction pipe 113.

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.

Light 118 is directed from the optical energy generating device 117 to the entire substrate 103 or a desired portion of the substrate 103 using an appropriate optical system, and is irradiated onto compounds and active species containing carbon and halogen flowing in the direction of an arrow 119. , the irradiated compound and active species chemically react with each other to form A-9i (H
, X) 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, and the inside of the film forming chamber 101 was evacuated using an exhaust device (not shown) to reduce the pressure to about 1 O-8 Torr. H2 gas 150S from gas supply pump 106
CCM was introduced into the activation chamber 123 via the gas introduction pipe 110. The H2 gas and the like introduced into the activation chamber 123 were activated by the microwave plasma generator 122 to become activated hydrogen and the like, and the activated hydrogen and the like were introduced into the film forming chamber 101 through the introduction pipe 124.

On the other hand, CF4 gas is supplied to the inlet pipe 11 by the supply source 112.
3, it was introduced into the film forming chamber 101.

In this way, the internal pressure inside the film forming chamber 101 is reduced to 0.3 Torr.
A carbon-containing amorphous film (film thickness: 700 mm) was formed by irradiating the substrate 103 perpendicularly from a 1KWXe lamp while maintaining the temperature at r. The membrane speed was 17 people/sec.

Next, the obtained carbon-containing amorphous film sample was placed in a vapor deposition tank, and a comb-shaped AI gap electrode (gap length 250 mm, width 5 mm) was formed at a vacuum degree of 1 O-5 Torr, and the dark current was measured at an applied voltage of 10 V. Then, the film characteristics of each sample were evaluated by determining the dark conductivity θd. The results are shown in Table 1.

Example 2 H2/F instead of H2 gas from gas supply cylinder 106
A carbon-containing amorphous (A-C(H, The dark conductivity of each sample was measured and the results are shown in Table 1.

Table 1 From Table 1, it was found that according to the present invention, a carbon-containing amorphous film with excellent electrical properties could be obtained.

Example 3 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 a compound supply source containing carbon and halogen, 206 is an introduction pipe, 207 is a motor, 208. is a heater used in the same way as 104 in FIG.

Reference numerals 209 and 210 indicate a blowoff pipe, and 211 indicates an AI cylinder-shaped body 212 indicates an exhaust valve. Also, 213
Reference numerals 216 to 216 are raw material gas supply sources similar to 106 to 109 in FIG. 3, and 217-1 is a gas introduction pipe.

The AI cylinder base 211 is suspended in the film forming chamber 201,
A heating heater 208 is provided inside the motor 207.
Allows for rotation. 218 is a light energy generating device.

Light 219 is irradiated toward a desired portion of AI cylinder 211.

Further, CF4 gas was introduced from the supply source 202 into the film forming chamber 2.01 through the introduction pipe 206.

Further, SiF4 was introduced in the same manner from a supply source (not shown) having the same structure as the supply source 202.

On the other hand, H2 gas is introduced into the activation chamber 220 from the introduction pipe 217-1.
introduced within. In the activation chamber 220, the introduced H2 gas undergoes activation processing such as plasma generation by the microwave plasma generator 221, becomes activated hydrogen, and is introduced into the film forming chamber 201 through the introduction pipe 217-2. . At this time, impurity gases such as PH3 and 82H6 were also introduced into the activation chamber 220 for activation, as required. Film forming chamber 20
While the internal pressure in the cylinder 1 was maintained at 1.0 Torr, light was irradiated perpendicularly to the circumferential surface of the AI cylinder base 211 from the IKWXe lamp 218.

The AI cylinder base 211 was rotated, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust valve 212. In this way, the intermediate layer 13 was formed.

In addition, the photosensitive layer 13 does not use CF4, and the introduction tube 217
-1, SiH4 gas and H2/B2He (B2 in volume %)
A mixed gas containing 0.2% H6 gas was introduced, and the film thickness was 20I.
The film was formed using L.

Comparative Example 1 A film forming chamber with the same configuration as the film forming chamber 201 was prepared using CF4, SiF4, H2, and B2H6 gases, and 13.5
Equipped with a 6 MHz high frequency device and a general plasma C
An electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by the VD method.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 3 and Comparative Example 1.

Example 4 Using the apparatus shown in FIG. 3, a PIN diode shown in FIG. 2 was manufactured.

First, two polyethylene naphthalate films 21 placed on two 1000 ITO films were placed on a support stand, and 10-
After reducing the pressure to 6 Torr.

As in Example 3, each of CF4 gas and SiF4 gas was introduced into the film forming chamber 101.

In addition, H2 gas and PH3 gas (100
0 ppm hydrogen gas diluted) was introduced into the activation chamber 123 and activated.Then, this activated gas was introduced into the film forming chamber 101 via the introduction pipe 124. Film forming chamber lo
The pressure within t is 0. IK while keeping IT Or r
N-type A doped with P by irradiation with a WXe lamp
-3iC(H,X) film 24 (thickness: 700) was formed.

Next, the introduction of PH3 gas was stopped and S i F2'/C
n-type A-3iC (H,
) film using the same method as for the non-doped A-3i C (
H, X) film 25 (thickness: 5000) was formed.

Next, along with H2 gas, B2H6 gas (1000pp
m hydrogen gas dilution).

A p-type A-5i C(H, Furthermore, a film with a thickness of 10
00 AI electrodes 27 were formed 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 the light irradiation intensity is AMI (approximately 100 mW/cm2), the conversion efficiency is 8.0% or more, the open circuit voltage is 0, 97 V, and the short circuit current is 9.
．． 9 mA/cm2 was obtained.

Example 5 Example 4 except that H2/F2 mixed gas (H2/F2=15) was used instead of H2 gas from the inlet pipe 110.
A PIN type diode similar to that produced in Example 4 was produced in the same manner as described above.

This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

3rd Table 1 Kitamoto 2p- of forward current and reverse current at voltage IV
From Table 3 of the n value (Quality Factor) in the n-junction current equation J=J s (exp +) −1), it is clear that the present invention has better optical-electrical characteristics than the conventional one. It has been found that an amorphous semiconductor PIN type diode can be obtained.

〔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 the drawing]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining an example of the configuration of a PIN diode manufactured using the method of the present invention, and a schematic diagram for explaining the configuration of an apparatus for implementing the method of the present invention. 10--one electrophotographic imaging member, 11--one substrate, 12--one intermediate layer, 13--one photosensitive layer, 21--one substrate, 22.27--thin film electrode, 24--1-n type semiconductor layer, 25-- i type semiconductor layer. 26---p-type semiconductor layer, 101.201----1 film formation chamber, 123.220--11 activation chamber, 106.107,108,109,112°・202
, 213, 214, 215, 216---Gas supply source, 103.211---One substrate. 117.218---One light energy generator.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, an active substance generated from a compound containing carbon and halogen and a film forming chemical that chemically interacts with the compound. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing seeds and irradiating them with light energy to cause a chemical reaction.