JPS6190415A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To enable the improvement in the characteristics of films, a film forming velocity and reproductivity, the uniformity of quality of films, the improvement in productivity and the mass production by introducing a carbon compound for forming a deposited film and an active seed into a film forming space separately to cause an action of a discharge energy. CONSTITUTION:A photoconductive member 10 is composed of a base 11, and an interme diate layer 12 and a photosensitive layer 13 which are arranged on said base 11. As the materials, an active seed produced in a decomposition space, a carbon compound in a gas state, silicon compound, and if necessary, hydrogen, a halogen compound, an inert gas and a gas of a compound including impurity elements are introduced separately into a film forming space where the base 11 is arranged and an intermediate layer 12 is formed on the base 11 by use of a discharge energy. The compound includ ing carbon and halogen (and the compound including silicon and halogen) which was introduced into the decomposition space produces an active seed like SiF*<2> for example easily at high temperature. A photosensitive layer 13 is formed similarly to the interme diate layer 12. Consequently, the electrical, optical, photoconductive and mechanical characteristics of films are improved and the improvement in productivity and the mass production can be attained easily.

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, in the formation of amorphous silicon films.

Vacuum deposition method, plasma CVD method, CVD method, reactive sputtering method, ion blating method.

Photo-CVD methods and the like have been tried, and in general, plasma CVD methods are 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, 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,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, which often has a significant negative effect on the deposited film. 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.

However, 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 Ja film using the plasma CVD method requires a large amount of equipment investment for product production equipment, and the management items for mass production are also complex, the management tolerance narrows, and equipment adjustments are required. However, these issues have been identified as issues that need to 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.

As mentioned above, in forming an amorphous silicon film, there is a strong desire to develop a method of forming an amorphous silicon film that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity. The same can be said of other functional films, such as silicon nitride films, silicon carbide films, and silicon oxide films.

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

[Purpose and outline of the invention]

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

The above purpose is to 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. By separately introducing active species that chemically interact with each other and applying discharge energy to these species to excite the carbon compound and cause it to react,
Deposition 1 of the present invention characterized by forming a deposited film on the body
f! This is achieved by the J-forming method.

[Embodiment]

In the method of the present invention, discharge energy such as plasma is used as energy to excite and react the raw materials for forming the deposited film, but since active species are introduced into the film forming space as one of the raw materials, the energy is lower than that of conventional methods. Film formation is also possible with applied energy, and the deposited film that is formed is substantially free from any adverse effects due to etching or other adverse effects such as abnormal discharge effects.

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

Furthermore, if desired, light energy and/or thermal energy can be used in combination with the discharge energy. The light energy can be applied to the entire substrate using an appropriate optical system, or can be applied selectively to a desired portion, so that the formation position and thickness of the deposited film on the substrate can be controlled. etc. can be easily controlled. Further, as the thermal energy, thermal energy converted from light energy can also be used.

One of the differences between the method of the present invention and the conventional CVD method is that 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 in addition, the deposition rate is 1M! i! The substrate temperature during formation can be further reduced, and deposited films with stable film quality can be provided industrially in large quantities at low cost.

In addition, the active species in the present invention is a compound that causes a chemical interaction with the compound of the raw material for forming a deposited film or its excited decomposition product to impart energy or cause a chemical reaction, Refers to substances that have the effect of promoting the formation of deposited films.
Therefore, the active species may include constituent elements constituting the formed deposit 1g, or may not contain such constituent elements.

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

The carbon compound used as a raw material for forming a deposited film in the present invention is
It is preferable that the material is already in a gaseous state before being introduced into the film forming space, or that it is introduced in a gaseous state. For example, when using a liquid compound, the compound can be vaporized by connecting an appropriate vaporizer to the compound supply source and then introduced into the film forming space. Examples of carbon compounds include chain or cyclic saturated or unsaturated hydrocarbon compounds whose main constituent atoms are carbon and hydrogen, and one or more of oxygen, nitrogen, halogen, sulfur, etc. Among organic compounds having the above-mentioned constituent atomic groups and organosilicon compounds having hydrocarbon groups as constituents, 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 (
C2H6), propane (Ce) (e), n-butane (
n-C4H1゜), pentane (Cs H+ 2),
Ethylene hydrocarbons include ethylene (C2H4), propylene (03Hb), butene-1 (04HEI),
), butene-2 (C4H8), isobutylene (C4
Ha ), pentene (Cs H+.), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4), butyne (Ca Hb), 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, For example, CY (
u is an integer of 1 or more LL2u+2, and Y is F, C1, Br, or Ic. ) chain halogenated carbon, CY v 2v (V is an integer of 3 or more, Y has the meaning as stated above)
Cyclic halogenated carbon, CHY (u and Y have the meanings given above).

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

Specifically, for example, CF4, (CF2)s, (CF2
)6, (CF2)a, C2F&, C3F8. CHF
3. C) 12F2, CCla (CC12) 2. CBra, (C'Br
, ) 5. Examples include C2C16, C2CIAF, etc., which are in a gaseous state or can be easily gasified.

Furthermore, in the present invention, in addition to the active species generated by decomposing the compound containing carbon and norogen,
Active species generated by decomposing compounds containing silicon and halogen can be used in combination. As this compound containing silicon and halogen, for example, a compound in which some or all of the basic atoms of a chain or cyclic silane compound are substituted with a halogen atom is used, and specifically, for example, an integer of , Y is F, C1, Br or engineering. ) A linear silicon halide represented by St Yv 2v (V is an integer of 3 or more, Y has the above-mentioned meaning), a cyclic silicon halide, SiHY (u and Y have the above-mentioned meaning).

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

Specifically, for example, SiF, (SiF2)s, (S
i F2 ) b , (SiF2)4 ,
Si2 F6゜Si3 FB, SiHF3.
SiH2F2. 5tC1, (SiC12)s,
5iBra, (SiBr2) 5, S
Examples include those that are in a gaseous state or can be easily gasified, such as i2C16, 5i2C13F3.

In order to generate active species, in addition to the above-mentioned compounds containing carbon and I\halogen (and compounds containing silicon and halogen), other silicon compounds such as simple silicon, hydrogen, and halogen compounds (for example, F2 gas, C12 gas, gasified Br2.I2, etc.) can be used in combination.

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

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

In the present invention, the ratio between the silicon compound serving as a raw material for forming a deposited film in the formation 11g 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 10 :1 to 1:10 (introduction flow rate ratio) is appropriate, more preferably 8:2 to 4:6
It is desirable that this is done.

In the present invention, in addition to carbon compounds, a silicon compound may be used as a raw material for forming a deposited film, or hydrogen gas or a halogen compound (for example, F2) may be used as a raw material for forming a deposited film.
gas, C12 gas, gasified Br2. I2, etc.), argon, neon, or other inert gas can also be introduced into the film forming space. When using a plurality of these raw material gases, they can be mixed in advance and introduced into the film forming space, or they can be supplied individually from independent sources and then introduced into the film forming space. It can also be introduced into

As the silicon compound serving as a raw material for forming the deposited film, silanes, siloxanes, etc., in which hydrogen, oxygen, halogen, or hydrocarbon groups are bonded to silicon, can be used. Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with norogen atoms.

Specifically, 1, for example, 5i14, 4. Si2H6,5t
Linear silane compounds represented by SiH (P is an integer of 1 or more, preferably 1 to 15, more preferably 1 to 10) such as 3H8, st, H,, 5i5H12゜5i6H, etc. , SiH3,S
iH(SiH3)SiH3,5iH3SiH(SiH3
)Si3H7,SI2H,,SiH(SiH3)
A chain silane compound having a branch represented by Si Hp 2p+2 (p has the above-mentioned meaning) such as S I2 H5, a part or all of the hydrogen atoms of these linear or branched chain silane compounds Compound in which is substituted with a halogen atom, 5i3H6, Si4 HB, 5i
5H1°, 5i6H12, etc. Cyclic silane compounds represented by S i Examples of compounds substituted with a cyclic silanyl group and/or chain silanyl group, and compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are substituted with halogen atoms include SiH3F, S1H3Xt□ (ljpal: f
f57 atom, ' is 1 or more, preferably 11-< is an integer of 1 to 10, more preferably 3 to 7, S + t = 2r + 2 or 2r
It is. ) and halogen-substituted linear or cyclic silane compounds.

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

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 are p-type impurities such as those found in Section 1II of the periodic table.
Group A elements, such as B, AI.

Suitable examples include Ga, In, and TI. Examples of n-type impurities include elements 1 of group V A of the periodic table, such as N.
, P, As, Sb, Bi, etc. are mentioned as preferable ones, and especially B, Ga, and P.

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

Compounds containing these eight impurity elements as components include:
It is preferable to select a compound that is in a gaseous state at normal temperature and normal pressure, or at least under the conditions for forming the deposited film, and that can be easily vaporized using an appropriate vaporizing device. Such compounds include PH3, P2H4, PF3. PFs, PC
l3, AsH3, AgF2. ASFS, ASC13, S
bH3, SbF5. SiH3, BF3, BCl3
, B B r 3 , B 2 H6, B a Hr
o, B, Hg , B5HH1, B6 Hlo, B6
Examples include H+ 2 and 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 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.

As a support, it can be conductive or electrically insulating.
It's okay to have an i. Examples of the conductive support include:

NiCr, Steer L/S, A1. Cr, Mo, Au, I
Examples include metals such as r, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface may be NiCr, A1. C
r, M, o, Au, I r, Nb, Ta, V, Ti, P
t, Pd, In2O3, 5n02, ITO (I n20
N1cr, A1. Ag, Pb,
Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta,
The surface is treated with a metal such as V, Ti, or Pt by vacuum evaporation, deuteron beam deposition, 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, but for example,
If the photoconductive member 1O of FIG. 1 is used as an electrophotographic imaging member, it is preferably in the form of an endless belt or a cylinder for continuous high-speed copying.

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 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 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 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 controlling conductivity such as B and P contained in the intermediate layer 12 is as follows.

Preferably, 0.001 to 5Xlo' atomic
ppm, more preferably 0.5 to IX11X104ato
ppm, optimally 1-5x103 atomic
It is desirable to set it as 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 introducing a gas containing the compound into the film forming space where the support 11 is installed on each side and using discharge 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 10L, more preferably 40A to 8μ, and optimally 50A to 5L.

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

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 an i-type a-St (H + Alternatively, if the actual amount contained in the intermediate layer 12 is large, the substance controlling the same polarity conduction characteristics may be contained in an amount much smaller than the amount. It's okay.

In forming 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 the compound is introduced into the film forming space. be introduced. 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. The intermediate layer 12 may be formed on the support 11 by introducing it into a certain film forming space and using discharge energy.

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-5i 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 n-thin upper electrodes, and 23
is a semiconductor film, an n-type a-St layer 24, an i-type a-
5i layer 25. It is composed of a p-type c7) a-S i 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. Examples of the thin film electrode 22.27 include NtCr, AI, Cr, Mo, Au,
Ir, Nb, Ta, V, Ti, Pt, Pd, In20
3.5n02, ITO (In203 +5n02)
It can be obtained by forming a thin film such as the above on a substrate using a process such as vacuum evaporation, electron beam evaporation, or sputtering. The film thickness of the electrode 22.27 is preferably 30 to 5×1
04A, more preferably 100 to 5X103A.

In order to make the film constituting the semiconductor layer 23 of a-3i n-type 24 or p-type 26 as necessary, when forming one layer, an n-type impurity, a p-type impurity, or both impurities are added among the impurity elements. It is formed by doping the layer into the layer to be formed while controlling its position.

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 method of the present invention, and the film formation is performed by introducing carbon and halogen into the decomposition space. By introducing compounds containing these substances and decomposing them at high temperatures,
For example, active species such as CF and ' 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-S can be formed by using discharge energy.
The thickness of the i-layer is preferably in the range of lOO to 10'A, more preferably in the range of 300 to 2000A.

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

A specific example of the present invention is shown below.

Example 1 Using the apparatus shown in Figure 3, i
Type, p-type, and n-type carbon-containing amorphous deposited films were formed.

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

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 105 and generates heat. - Although the substrate temperature is not particularly limited, when carrying out the method of the present invention, it is preferably 50 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 the symbol a for branch pipes, and by symbol b for the gas supply sources 106 to 109. Flowmeters marked with C are pressure gauges for measuring the pressure on the high pressure side of each flowmeter, and those marked with d or e are valves for adjusting the flow rate of each gas. 110 is a gas introduction pipe into the film forming space, and 111 is a gas pressure gauge.

In the figure, 112 is a decomposition space, 113 is an electric furnace, 114 is 0 solid particles, and 115 is an introduction pipe for a compound containing gaseous carbon and halogen, which is a raw material for active species. is introduced into the film forming space 10 through the introduction pipe 116.
1.

117 is a discharge energy generating device.

It is equipped with a matching box 17a, a cathode electrode 117b for introducing high frequency waves, and the like.

The discharge energy from the discharge energy generator 117 is applied to the raw material gas flowing in the direction of the arrow 119, and excites the film-forming raw material gas and causes it to react, thereby producing a carbon-containing amorphous material on the entire substrate 103 or a desired portion. Form a deposited film.

Further, in the figure, 120 is an exhaust pulp, and 121 is an exhaust pipe.

First f, polyethylene terephthalate film substrate 10
3 was placed on the support stand 102, and the inside of the deposition space 101 was evacuated using an exhaust device to 10-6T.

The pressure was reduced to rr. At the substrate temperature shown in Table 1, using the gas supply source 106, CH4150sccM, or this and PH3 gas or B2H6 gas (both io00ppm)
A gas mixed with 403 CCM (hydrogen gas dilution) was introduced into the deposition space.

Further, one decomposition space 102 is filled with solid 0 grains 114, heated in an electric furnace 113 to melt C, and CF4 is blown therein from a cylinder through a CF4 inlet pipe 115 to generate active species of CF2. , and is introduced into the film forming space 10L through the introduction pipe 116.

While maintaining the atmospheric pressure in the film forming space 101 at 0.1 Torr, plasma was applied from the discharge device 117 to form a non-doped or doped carbon-containing amorphous deposited film (thickness: 700 A). The deposition rate is 35 A/
It was sec. .

Then, the obtained non-doped or plJl a-
Place the 3i film sample in a deposition tank and set the vacuum to 10-5 Torr.
Comb-shaped AI gap electrode (length 250W, width 5a)
After forming m), measure the dark current with an applied voltage of 10V,
The a-3t film was evaluated by determining the dark conductivity σ. The results are shown in Table 1.

Examples 2-4 Linear C2H6, C2H4, or C2H instead of CH4
The same carbon-containing amorphous deposited film as in Example 1 was formed, except that Example 2 was used. Measure the dark conductivity and record the results in the first
Shown in the table.

From Table 1, according to the present invention, the electrical properties were excellent even at low substrate temperatures. That is, a carbon-containing amorphous film having a high σ value and a sufficiently doped carbon-containing amorphous film 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 a solid Si particle, 205 is an active species raw material introduction tube, 206 is an active species introduction tube, 207 is a motor, and 208 is an active species introduction tube. heating heater, 209 is a blowout pipe, 210 is a blowout pipe, 211 is an At cylinder, 21
2 indicates an exhaust valve. Further, 213 to 21 are raw material gas supply sources similar to 106 to 109 in FIG. 1, and 217 is a gas introduction pipe.

An AI 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. 218.218 is a discharge energy generating device, which includes a matching box 218a,
It is equipped with a cando electrode 218b for introducing high frequency waves and the like.

In addition, the decomposition space 202 is filled with 0 solid particles 204, heated in the electric furnace 203 to melt C, and CF4 is blown there from a cylinder to generate active species of CF2', which are passed through the introduction pipe 206. It is introduced into the film forming space 201.

On the other hand, CHa, 5t2H6, and H2 are introduced into the film forming space 201 through the introduction pipe 217. Plasma is applied from a discharge device while maintaining the atmospheric pressure in the film forming space 201 at 1.0 Torr.

The A1 cylinder 211 is heated and maintained at 280°C by the heater 208 and rotated once, and the exhaust gas is passed through the exhaust valve 21.
Exhaust through 2. In this way, the photosensitive layer 13 is formed.

In addition, the intermediate layer is supplied with H2/B2 from the introduction pipe 217.
A mixed gas of 'Hb (0.2% B2H6 by volume) was introduced to form a film with a thickness of 2000 Å.

Comparative Example 1 CF4, CH4, and S
A 13.56 MHz high frequency device was installed in the film forming space 201 of FIG. 4 from i2 H6, H2, and B2 H6 to form an amorphous silicon deposited film.

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 Using CH4 as a carbon compound and the apparatus shown in Fig. 3,
A PIN type diode shown in FIG. 2 was manufactured.

First, a polyethylene naphthalate film 21 on which a 1000A ITO film 22 was vapor-deposited was placed on a support stand, and
After reducing the pressure to Torr, the introduction pipe 116 is opened as in Example 1.
from the active species of CF2, and from the introduction tube 110 S i 3
H6150S CCM, phosphine gas (PH31
1000pp hydrogen diluted) was introduced, 20SCCM of halogen gas was introduced from another system, and the n-type a-5i film 24 (film thickness 700A) doped with P was irradiated with light using an IKWXe lamp while maintaining the temperature at O,1 Torr. Formed.

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

Then CH450SCCM, Diporan gas (B2H61QOOppm hydrogen diluted) 40S with 5i3H6 gas
CCM, P-type carbon-containing a-St11226 doped with B under the same conditions as n-type (film thickness 700A)
was formed. Further, an A1 electrode 27 having a thickness of 1000 Å 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 Figure 3.

In addition, regarding the light irradiation characteristics, when light is introduced from the substrate side and the light irradiation intensity is 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. cm2 was obtained.

Example 7 Instead of CH4 as a carbon compound, C2H6°C2H4
Or outside the field using C2H2, use the same PIN as in Example 6.
A type diode was fabricated. The rectification characteristics and photovoltaic effect were evaluated and the results are shown in Table 3.

From Table 3, according to the present invention, a-St has good optical and electrical characteristics even at a lower substrate temperature than before.
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.
It is possible to easily achieve improvement in film productivity and mass production, and it is also possible to form a film 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 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...φ Electrophotographic image forming member, 11...
Substrate, 12...ψ Intermediate layer, 13...@ Photosensitive layer, 21...φ Substrate, 22.27 -@Fist Thin film electrode, 24 @・11 N-type a-5i layer, 25 m a * I-type a- 5i layer, 26...ψ
P-type a-3i layer, 101.201 - Film formation space, 111.202 Nose... Decomposition space, 106.107
, 108, 109° 213.214, 215, 216 ... gas supply source, 103.211 --- substrate. 117.218 ... Discharge energy generation device.

Claims (1)

[Scope of Claims] In a film forming space for forming a deposited film on a substrate, the carbon A deposited film is formed on the substrate by separately introducing active species that chemically interact with the compound, and applying discharge energy to them to excite the carbon compound and cause it to react. Deposited film formation method.