JPS6189626A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve the characteristics, the film forming speed and enable the mass- productivity of films while uniformizing the quality thereof and to enable the films to be increased in surface area and to be mass-produced, by introducing a carbon compound to be a material and an activator separately into a film forming space, and applying optical energy so as to deposit the film on a substrate. CONSTITUTION:By utilizing an activator preactivated in a space different from a film forming space (decomposing space), it is enabled to remarkably improve the film forming speed in comparison with a conventional CVD process. In addition, it is also enabled to further decrease the substrate temperature during the deposition of the film. An activator having a life of 5 seconds or more, preferably of 15 seconds or more and most preferably of 30 seconds or more is selected, in view of productivity, handling convenience or the like, and is introduced from the decomposing space into the film forming space. Preferably, a carbon compound to be used as a material of the deposited film has been gasified before introduced into the film forming space or is gasified to be introduced thereinto. The carbon compound may by either a gaseous or readily gasified compound selected from chain or annular, saturated or unsaturated hydrocarbon compounds or the like.

Description

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

[Prior art]

For example, attempts have been made to form an amorphous silicon film using a page evaporation method, a plasma CVD method, a CVD method, a reactive sputtering method, an ion blasting method, a photo-CVD method, etc. Generally, plasma CVD method is used. is widely used and commercialized.

From last year, deposited films composed of amorphous silicon have improved electrical and optical properties, fatigue properties during repeated use, usage 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 with electrical, optical, photoconductive, or mechanical properties that can sufficiently satisfy various uses, it is currently considered best to form it by plasma CVD. ing.

From last year, depending on the application of the deposited film, it is necessary to achieve large area, uniform film thickness, and uniform film quality, and also 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 is narrow, and equipment adjustments are delicate. For these reasons, these have been pointed out as problems 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.

J: As mentioned above, in forming an amorphous silicon film,
It is desired to develop a forming method that maintains its practically usable characteristics and uniformity, and that can be mass-produced using low-cost equipment. These things are related to other functionality 1Q,
For example, the same holds true for silicon nitride films, silicon carbide films, and silicon oxide 11g.

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

[Purpose and outline of the invention]

The purpose of the present invention is to improve the properties, film formation speed, and reproducibility of the film to be formed, and to make the film uniform in quality, while also being suitable for large-area films, improving film productivity, and mass production. An object of the present invention is to provide a method for forming a deposited film that can easily achieve the following.

The above purpose is to generate a carbon compound by decomposing a carbon compound, which is a raw material for forming a deposited film, and a compound containing carbon and halogen in a film forming space for forming a deposited film on a substrate. This book is characterized in that a deposited film is formed on the substrate by separately introducing active species that act as a chemical internal phase W, and irradiating these with light energy to excite the carbon compound and cause it to react. This is achieved by the deposited film forming method of the invention.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film-forming space for forming the deposited film, light energy is used to excite the film-forming raw material gas and cause it to react. There are virtually no other adverse effects such as abnormal discharge effects.

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

Furthermore, excitation energy is applied uniformly or selectively to the raw material that has reached the vicinity of the substrate, but if optical energy is used, the entire substrate is irradiated using an appropriate optical system to form a deposited film. Alternatively, it is possible to selectively and controlly irradiate only a desired portion to form the deposited H'2, or to irradiate and deposit only a predetermined graphic portion using a resist or the like. It has the convenience of being able to form a membrane, so it is used for right-handed people.

One of the differences between the method of the present invention and the conventional CVD method is that active species activated in advance in a space different from the film forming space (hereinafter referred to as the decomposition space) are used. This makes it possible to dramatically increase the deposition rate compared to the conventional CVD method, and also to further reduce the substrate temperature during deposition film formation, resulting in stable film quality. Deposited films can be provided industrially in large quantities at low cost.

In the present invention, the active species refers to a species that chemically interacts with the compound of the raw material for forming the deposited film or its excited decomposition product to impart energy, for example, 4=7, or to cause a chemical reaction. It refers to a substance that has the effect of promoting the formation of a deposited film. Therefore, the active species may or may not include constituent elements that constitute the deposit that is formed.

In the present invention, the active species introduced into the film forming space from the decomposition space has a lifespan of 5 seconds or more, more preferably 15 seconds or more, and optimally 30 seconds from the viewpoint of productivity and ease of handling. Those listed above are selected and used as desired.

The carbon compound used as the raw material for forming the M film in the present invention is
It is preferable that the compound is already in a gaseous state before being introduced into the film forming space, or is introduced in a gaseous state.For example, when using a liquid compound, an appropriate vaporizer is connected to the compound supply source. The compound can be vaporized and then introduced into the film forming space. Carbon compounds include chain or cyclic saturated or unsaturated hydrocarbon compounds, organic compounds whose main constituent atoms are carbon and hydrogen, and one or more constituent atoms such as oxygen, nitrogen, halogen, and sulfur. Among compounds, organosilicon compounds having a hydrocarbon group as a constituent, those in a gaseous state or those that can be easily vaporized are preferably used.

Among these, as a hydrocarbon compound, for example, carbon number 1
-5 saturated hydrocarbons, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylenic hydrocarbons having 2 to 4 carbon atoms, etc. Specifically, saturated hydrocarbons include methane (CH4), ethane (
CZH&), propane (C3H5), n-butane (n-
C4H1゜), pentane (C5Hl 2 ), ethylene hydrocarbons include ethylene (C2H4), propylene (C3Hb), butene-1 (CaHe), butene-2 (C4He), inbutylene (CaHe)
, pentene (C5H1o), acetylene hydrocarbons such as acetylene (C2H2), methylacetylene (C
3I(4), butyne (C4H6), and the like. These hydrocarbons may be used alone or in combination of two or more.

In the present invention, the compound containing carbon and halogen introduced into the decomposition space is, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon are replaced with halogen atoms, and specifically ( 7) q4 number, Y is F, C
1, Br or! It is. ) (V is an integer of 3 or more, Y has the above-mentioned meaning), Cx+y=2u or 2u+2. ), and the like.

Specifically, for example, CF4, (CF2)s, (CF2)
6, (CF2)4. Cz F6゜C3F8, CHF3,
CH2F2, CC'14 (CC1'2 )s, CB"'ra, (
Examples include CBr2)1, C2C16, C2Cl3F3, which are in a gaseous state or can be easily exposed to gas.

Furthermore, in the present invention, in addition to the active species generated by decomposing the compound containing carbon and halogen, active species generated by decomposing the compound containing silicon and halogen can be used in combination. As this compound containing silicon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically, for example, an integer of , Y is F , C1, Br or ■. ) (V is an integer of 3 or more, Y has the above-mentioned meaning), siH, cyclic silicon halide, Yy (u and Y have the above-mentioned meaning).

x+y=2u or 2u+2. ) and the like.

Specifically, for example, SiF4, (S i F2 )'S,
(S i F2 ) b, (SiF2), 5i2FG
, Si3 FB, SiHF3. SiH2F2,S!
C14(S i Cl 2 )s,
S i B r 4 , (SiBr2)5
．． Examples include those that are in a gaseous state or can be easily gasified, such as 5i7C161 and 5i2C13F3.

In order to generate active species, in addition to the above-mentioned compound containing carbon and halogen (and compound containing silicon and /x halogen), other silicon compounds such as simple silicon, if necessary, are added.
Hydrogen, /\rogen compounds (for example, F2 gas, C12 gas, gasified Brz, 1., etc.) can be used in combination.

In the present invention, as a method for generating active species in the decomposition space, the discharge energy,
Excitation energies such as thermal energy, light energy, etc. are used.

Active species are generated by adding decomposition energy such as heat, light, and discharge to the above-mentioned materials in a decomposition space.

In the present invention, the ratio between the silicon compound serving as a raw material for forming a deposited film in the film forming space and the active species from the decomposition space is determined as desired depending on the deposition conditions, the type of active species, etc., but is preferably lO :1~1:10 (introduction flow j
It is desirable that the stop ratio (stop ratio) is appropriate, more preferably 8:2 to 4:6.

In the present invention, in addition to carbon compounds, a silicon compound may be used as a raw material for forming a deposited film in the film forming space, or hydrogen gas or a halogen compound (for example, F
2 gas, C12 dregs, dregs Br7. I7, etc.), an inert gas such as argon, neon, etc. can also be introduced into the film forming space. When using multiple of these raw material gases, they can be mixed in advance and introduced into the film forming space, or these raw material gases can be supplied individually from independent sources and then introduced into the film forming space. It can also be introduced.

Silanes, siloxanes, etc. in which hydrogen, fluorine, halogen, or hydrocarbon groups are bonded to silicon can be used as the silicon compound serving as a raw material for forming the deposited film. In particular, chain and cyclic silane compounds, in which part or all of the hydrogen atoms of the chain and cyclic silane compounds are
Compounds substituted with \rogen atoms are suitable.

Specifically, for example, SiH4, Si2 H6, Si3
H+3.5i4 H,. , 5i5I (+7.5i6H
SiH such as 1a (p is north of 1 p 2p+2 preferably 1 to 15, more preferably 4!3 of 1 to 10)
．． It is a number. ) linear silane compound, SiH
3SiH(SiH3)SiH3,5iH3SiH(Si
H3) Si3H7, Si2 H5SiH(SiH3)S
Si Hp 2p+2 (p has the above-mentioned meaning) such as i2Hs, a chain silane compound having a branch, and a part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with halogen. Compounds substituted with atoms, 5i3H6, S I 4 He
, S 15H+. , S r 6 HI is an integer of 26. ), 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, and some of the hydrogen atoms of the silane compounds exemplified in (h) Examples of compounds in which all atoms are substituted with norogen atoms include SiH3F, S1H
3X (X is a halogen atom, r is an integer of 1 or less, preferably 1 to 10, more preferably 3 to 7, S + t = 2r
+2 or 2r. ) /\logen-substituted linear or cyclic silane compounds.

These compounds may be used alone or in combination.

It is also possible to dope the deposited film formed by the method of the invention with an impurity element. The impurity elements to be used include P-type impurities and elements from periodic table 1II.
Group A elements, such as B, AI.

Suitable examples include Ga, In, TI, etc., and examples of n-type impurities include elements of group V A of the periodic table, such as N
, P, As, Sb, Bi, etc. are mentioned as preferable ones, and B, Ga, and P are particularly preferable.

sb etc. are optimal. The amount of impurity doped is
It is determined as appropriate depending on the desired electrical-optical characteristics.

As a compound containing such an impurity element as a component, it is preferable to select a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under deposited film forming conditions, and that can be easily vaporized using an appropriate vaporizing device. , such compounds include PH3, P2 Ha, P F3,
P F5, PCl3, AsH3, AsF3. AsF5
．． AsCl3, SbH3, SbFs, SiHs
, BF3, BC13, BBr3, B2 Hb, B4
Hlo.

Bs B9・Bs Ht 1. B6Ht o・86HI
2. Examples include AlCl3. The compounds containing impurity elements may be used alone or in combination of two or more.

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

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

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

The photoconductive member 1O shown in FIG. 1 can be applied as an electrophotographic image forming member, and includes an intermediate layer 1 provided as necessary on a support 11 for the photoconductive member.
2. and a photosensitive layer 13.

The support 11 may be X-conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A1. Cr, Mo, Au, Ir, Nb, T
Examples include metals such as a, V, Ti, Pt, and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. be done. 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 may be NiCr, Al, etc.
Cr, Mo, Au, Ir, Nb, Ta, V, Ti, Pt
, Pd, I B203 , S n02, I To (I
B203 +s no. Ag
, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb
, Ta, V, Ti, Pt, etc. by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating with the metal, and the surface thereof is subjected to conductive treatment. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined depending on the needs.1 For example, the photoconductive member 10 in FIG. If used as a component, in the case of continuous high-speed copying,
It is desirable to have an endless belt shape or a cylindrical shape.

For example, the intermediate layer 12 includes a photosensitive layer 13 from the support 11 side.
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 14 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 silicon (hereinafter referred to as a-5i (H, X)) containing hydrogen atoms (H) and/or halogen atoms (X) and carbon atoms as constituent atoms.
It also contains, for example, a P-type impurity such as B or a p-type impurity such as 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 0.
001 to 5×10 4 atomic cppm, more preferably 0.5 to ixto 4 atomic PPm, optimally 1 to 5×10 3 103 atomic ppm.

When forming the intermediate layer 12, it can be performed continuously up to the formation of the photosensitive layer 13. In that case, the active species generated in the decomposition space, gaseous carbon compounds, silicon compounds, and optionally hydrogen, halogen compounds, inert gases, and impurity elements are used as raw materials for forming the intermediate layer. The intermediate layer 12 may be formed on the support 11 by separately introducing the gases of the compounds contained therein into the film forming space where the support 11 is installed and using light energy.

Compounds containing carbon and halogen (and compounds containing silicon and halogen) that are introduced into the decomposition space to generate active species when forming the intermediate layer 12 are easily converted to, for example, S at high temperatures.
Generate active species such as iF2'.

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

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

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

The photosensitive layer 13 is an i-type a-5i (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, the substance controlling the same polarity conductivity may be contained in a much smaller amount than that of the layer. It may be included.

In the formation of the photosensitive layer 13, similarly to the case of the intermediate layer 12, a compound containing carbon and halogen is introduced into the decomposition space, and by decomposing these at high temperature, active species are generated and introduced into the film forming space. be done. Separately from this, gaseous carbon compounds, silicon compounds, and, if necessary, gases of compounds containing hydrogen, halogen compounds, inert gases, impurity elements, etc., can be installed on the support 11. By introducing the support into a certain film-forming space and using light energy, the support l
The intermediate layer 12 may be formed on the layer 1.

Furthermore, if desired, an amorphous deposited film containing carbon and silicon as constituent atoms can be formed as a surface layer on this photosensitive layer. This can be carried out in the same manner as in the method of the present invention.

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 substrate, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an n-type a-Si layer 24, an i-type a-Si layer
It is composed of a layer 25 and a p-type (7) a-Si layer 26. 28 is a conducting wire.

The substrate 21 is semiconductive, preferably electrically insulating. As the semiconductive substrate, for example, Si
, Ge, and other semiconductors. The thin film electrodes 22.27 include, for example, NiCr, A1. Cr, Mo, Au, I
r, Nb, Ta, ■, Ti, Pt, Pd, In703
．． 5n02, ITO (In203 +5n02), etc., is formed on the plate by vacuum evaporation, electron beam evaporation, sputtering, etc. The thickness of the electrodes 22.27 is preferably is 30-5
In order to make the film forming the semiconductor layer 23 of 6a-Si preferably having XlO'A, more preferably 100 to 5X103A, to be n-type 24 or p-type 26 as required,
It is formed by doping an n-type impurity, a p-type impurity, or both impurities among impurity elements into the layer while controlling the rate of doping during layer formation.

When forming n-type, i-type, and p-type a-Si layers, any one layer or all of the layers can be formed by the final method, and the film formation is performed in the decomposition space. Compounds containing carbon and halogen are introduced, and by decomposing them at high temperatures, active species such as CF2 are generated and introduced into the film forming space. Separately, a gas of a compound containing a gaseous carbon compound, a silicon compound, and an inert gas and an impurity element as necessary is introduced into the film forming space where the support 11 is installed. However, n-type and p-type a-3i can be formed by using light energy.
The thickness of the layer is preferably in the range of 100 to 104A, more preferably in the range of 300 to 2000A.

Further, the thickness of the i-type a-3i layer is preferably 5
00-104A, more preferably 1000-100OO
A range of A is desirable.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in FIG. 3, i-type, p-type, and n-type carbon-containing amorphous deposited films were formed by the following operations.

In FIG. 3, lOl is the deposition chamber, and the interior (
A desired base 103 is placed on the body support 102.

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 105 and generates heat. Although the substrate temperature is not limited to 50%, it is preferably 5% when carrying out the method of the invention.
It is desirable that the temperature is 0 to 150"C, more preferably 100 to 150"C.

106 to 109 are gas supply sources, carbon compounds,
and, depending on the number of compounds containing hydrogen, a halogen compound, an inert gas, and an impurity element, which are used as necessary. If a liquid raw material compound is used, an appropriate vaporization device should be provided. In the figure, the gas supply sources 106 to 109 are indicated by a branch pipe, and b is a flow meter. , C indicates a pressure gauge that measures the pressure on the high pressure side of each flow meter, and d or e indicates a valve for adjusting the flow rate of each gas. 110 is a gas introduction pipe to the film forming space, and 111 is a gas pressure gauge.
is the decomposition space - 113 is an electric furnace, 114 is 0 solid particles, 11
Reference numeral 5 denotes an introduction pipe for a compound containing gaseous carbon and halogen, which is a raw material for active species, and the active species generated in the decomposition space 112 are introduced into the decomposition space 11 through the introduction pipe 116. Ru.

↑17 is a light energy generator, for example.

For example, a mercury lamp, a xenon lamp, a carbon dioxide gas laser, an argon ion laser, an excimer laser, etc. are used.

Light 118 is directed from a light energy generating device 117 onto the entire substrate or a desired portion of the substrate using a suitable optical system.
is irradiated with the raw material gas flowing in the direction of the arrow 119 to excite the film forming raw material gas and cause it to react, thereby forming a deposited film of a-3i on the entire substrate 103 or on a desired portion. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

First step, polyethylene terephthalate film substrate 103
was placed on the holding table 102, and the inside of the deposition space 101 was evacuated using an exhaust device for 10-6T.

The pressure was reduced to rr. At the substrate temperature shown in the fJS1 table, use the gas supply source 106 to supply CH4150SCCM, or this and PH3 gas or B2H, gas (both 11000
A gas mixed with pp hydrogen gas diluted ff) 403 CCM was introduced into the deposition space.

In addition, the decomposition space 102 is filled with solid 0 grains 114 and heated in the electric furnace 113 to melt C, and by blowing C゛F4 into it from the cylinder through the CF4 introduction pipe 115, active species of CF2 are generated. It is generated and introduced into the film forming space 101 through the introduction pipe 116.

The atmospheric pressure in the film forming space 101 is set to 0. While keeping it at ITorr
A KWXe lamp was irradiated perpendicularly to the substrate to form an undoped or doped carbon-containing amorphous deposited film (film thickness 700 Å). Filming speed is 35X/s
It was ec.

Then, the obtained non-doped or p-type a-3i
The film sample was placed in a deposition tank, and a comb-shaped AI gap electrode (length 250 l, rtl 5
After forming am), the dark 'lit current was determined by the applied voltage lov, the dark conductivity σ was determined, and the a-3id film was given an i;f value. The results are shown in Table 1.

Examples 2 to 4 The same carbon-containing amorphous deposited films as in Example 1 were formed, except that linear C2Hb, C2Ha, or C2H2 was used instead of CH4. The dark conductivity was measured and the results are shown in Table 11.

According to the present invention, a carbon-containing amorphous film with excellent electrical properties, that is, a high σ value, can be obtained even at a low substrate temperature, and a carbon-containing amorphous film with sufficient doping can be obtained.

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

In FIG. 4, 201 is a film forming space, 202 is a decomposition space, 203 is an electric furnace, 204 is 0 solid particles, 205 is an active species raw material introduction pipe, 206 is an active species introduction pipe, 207 is a motor, and 208 is a Heater, 209 is a blowout pipe,
210 is a blowout pipe, 211 is an At cylinder, 212
indicates an exhaust valve. Further, 213 to 216 are raw material gas supply sources similar to 106 to 109 in FIG. 1, and 217 is a gas introduction pipe.

An Al cylinder 211 is suspended in the film forming space 201, and a heater 208 is provided inside the cylinder so that it can be rotated by a motor 207. Reference numerals 218, 218, .

In addition, 0 solid particles 204 are packed in one decomposition chamber space 202, heated in an electric furnace 203 to melt C, and CF4 is blown therein from a cylinder to generate active species of CF2'. After that, it is introduced into the film forming space 201.

On the other hand, CH, 5t2H6, and H2 are introduced into the film forming space 201 from the introduction pipe 217. The atmospheric pressure inside the film forming space 201 was maintained at 1.0 Torr, and the IKWXe lamp 218.
218 ------- irradiates light perpendicularly to the circumferential surface of the Al cylinder 211 .

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

In addition, the intermediate layer has H2/B 2H&
Introducing a mixed gas (B, H, 0.2% by volume),
The film was formed with a film thickness of 2000A.

Comparative Example 1 CF4, CH4, and S
A 13.56 MHz high frequency device is installed in the film forming space 201 in FIG. 4 from i2 H6, H2 and B2H...6.
An amorphous silicon vK film was formed.

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

Example 6 Using CH4 as a silicon compound and using the apparatus shown in FIG. 3, a PIN type diode shown in FIG. 2 was manufactured.

First, two polyethylene naphthalate films 21 placed on two 100OA ITO films are placed on a support stand, and the IO'
After reducing the pressure to Torr, the introduction pipe 116 is opened as in Example 1.
CF2' (D active species, and S1 from the inlet tube 110
3Hb 150SCCM, phosphine gas (PH31
1000 pp hydrogen diluted) was introduced, 20 SCCM of halogen gas was introduced from another system, and while maintaining the temperature at □0.1 Torr, light was irradiated with an IKWXe lamp to form a P-doped n-type a-St film zacH'2 thickness 700 A). Formed.

Next, the n-type a-
I-type a-3i film zs (1
1! J thickness 5000A) was formed.

Next, CH450SCCM, Shiboten gas (B2H211000pp hydrogen diluted) 403 with 5i3H6 gas
A P-type carbon-containing a-3t film 26 (film thickness 70·OA) doped with B was formed under the same conditions as the n-type except for CCM. Furthermore, a film thickness of 1000 mm was formed on this P-type film by vacuum evaporation.
An Al electrode 27 of A was 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 Figure 3.

In addition, regarding light irradiation characteristics, light is introduced from the substrate side,
At light irradiation intensity AMI (approximately 100 mW/am2), conversion efficiency 8.5% or more, open circuit voltage 0.92 V, short circuit current 1
0.5 mA/cm2 was obtained.

Example 7 Instead of CH4 as a carbon compound, C2H et al.C2H,
Or the same PI as in Example 6 except that C2H2.
An N-type diode was manufactured. The wave rectification characteristics and photovoltaic effect were evaluated, and the results are shown in Table 3.

From Table 3, according to the present invention, a-5j has good optical and electrical properties even at a lower substrate temperature than conventional ones.
A deposited film is obtained.

〔Effect of the invention〕

According to the method for forming a deposited film of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the film to be formed are improved, and high-speed film formation is possible at a low substrate temperature. Also,
It improves reproducibility in film formation, makes it possible to improve film quality and make the film uniform, and is advantageous for increasing the area of the film.
Improved membrane productivity and mass production can be easily achieved. Furthermore, since light energy is used as excitation energy, the film can be formed even on a substrate with poor heat resistance, and the process can be shortened by low-temperature treatment.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining a configuration example of a PIN diode manufactured using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the method of the present invention used in Examples, respectively. 10... Image forming member for electrophotography, 11 ・Dispute・
Base. 12. Ordinance, middle layer, 13. Musical instrument, photosensitive layer. 21...Substrate, 22, 27 11 Thin film electrode, 24
m number meeting (type 1 a, -Si
Layer, 25 e a a i type a-5f layer, 2
6... P-type a-5f layer, 101.201... Film formation space, 111.202
Fun C・Decomposition space, 106.107,108,10
9゜213.214,215,216 ・e・Gas supply source, 103.211 ・・Base body, 117.218 ・・Fist Light energy generation device.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, a carbon compound that is a raw material for forming a deposited film and a compound containing carbon and halogen are decomposed, and a chemical interaction with the carbon compound is generated. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by separately introducing active species that perform the following actions, and irradiating them with light energy to excite the carbon compound and cause it to react.