JPS6190425A - Deposited film formation method - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to carbon-containing amorphous or crystalline sediment awJ.
It relates to a method suitable for forming.

(Prior Art) For example, vacuum evaporation, plasma CVD, CVD 1 reactive sputtering, ion blasting, photo-CVD, etc. have been attempted to form an amorphous silicon film, and these methods are generally used.

The plasma CVD method is widely used and commercialized.

Deposited films made of amorphous silicon from Amphitheater 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 deposit formed. Moreover,
The actual situation is that parameters unique to each device must be selected for each device, making it difficult to generalize 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.

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.
In the formation of an amorphous silicon deposit film by plasma CVD method.

A large amount of capital investment is required for mass production equipment, and the management items for mass production also become complex, and the tolerance for management becomes narrower.
Since the adjustment of the device is also delicate, 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 produce a deposited film with practically usable characteristics.

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

[Purpose and outline of the invention]

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

The above purpose is to generate a carbon compound by decomposing a carbon compound, which is a raw material for a deposited film forming method, and a compound containing carbon and halogen in a film forming space for forming a deposited film on a substrate. The present invention is characterized in that a deposited film is formed on the substrate by separately introducing active species that chemically interact with each other and applying thermal energy to them 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 a deposited film, thermal energy is used to excite the film-forming raw material gas and make it 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.

In the present invention, the thermal energy for exciting and reacting the raw material for forming the deposited film is applied to at least a portion of the film forming space near the substrate or the entire film forming space,
There is no particular restriction on the heat source used, and conventionally known heating media such as heating by a heating element such as resistance heating, high frequency heating, etc. can be used. Alternatively, thermal energy converted from light energy can be used. Furthermore, if desired, light energy can be used in combination with thermal 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 of the deposited film on the substrate and the formation of the film can be controlled. Thickness etc. can be easily controlled. - One of the differences between the method of the present invention and the conventional CVD method is that the method of the present invention is activated in advance in a space different from the film-forming space (hereinafter referred to as the decomposition space). The method is to use activated species. This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and in addition, it is possible to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

In addition, the active species 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 contain constituent elements constituting the deposited film to be formed, or may not contain such constituent elements.

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 or more from the viewpoint of productivity and ease of handling. 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 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, which have carbon and hydrogen as their main constituent atoms, and one or more of oxygen, nitrogen, halogen, sulfur, etc. as constituent atomic groups. Among organic compounds and silicon 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 tL tough (CHa), z
Tough (C2H6), Propy (C,3H8), n-
Buta 7 (n-C4H1°), pentane (C5H12),
Ethylene hydrocarbons include ethylene (C2H4), propylene (C3H&), butene-1 (CaHa), butene-2
(C4Ha), i') Butylene (C4H8), pentene (C5Hlo), acetylene hydrocarbons include acetylene (C2H2), methylacetylene
IL/7 (C3H4), spot 7 (C4'H&
) etc. 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 a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon are replaced with halogen atoms. , Y is F, C1, Br or! It is. ) Cyclic halogenated carbon represented by Te (V is an integer of 3 or more, Y has the above meaning), Cx+y
=2u or 2u+2. ), and the like.

Specifically, for example, CF4, '(CF2)s, (CF
2) 6, (CF2)4-, C2F&, c, F8. C
HF3. CH2F2゜CC1a (CC12)S, CBra.

(CBr2) 5. Examples include those that are in a gaseous state or can be easily gasified, such as C2C16, C, and Cl3F3.

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, Si
Cyclic silicon halide represented by Y (u is an integer of 1 or more u 2u+2, Y is F, CI, Br or I) (V is an integer of 3 or more, Y has the above meaning), SiHxY, (u and Y have the meanings given above.

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

Specifically, for example, S i F4, (SiF2)s, (S
iF2) 6, (SiF2)4. Size F&,
Sf3 FB, SiHF3. SiH2F2.

5iC14 (SiC12)5. SiBr4, (SiBr
z) S, 5i2C16, 5i2C13F3 and the like, which are in a gaseous state or can be easily gasified.

In order to generate active species, in addition to the above-mentioned compounds containing carbon and halogen (and compounds containing silicon and halogen), 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, 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 applying decomposition energy such as heat, light, or electric discharge to the above-described material between one decomposition chamber.

In the present invention, the ratio of the silicon compound serving as a raw material for forming a deposited film in the film forming space to 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 :l-1:10 (introduction flow rate ratio) is appropriate.

More preferably, the ratio is 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, 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 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.

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 halogen atoms.

Specifically, for example, 5tH4, Si2H6°5isH
s, 5isHso, 5isH12, 5i6Hs*, etc.
A linear silane compound represented by t'H (p is an integer of 1 or more p2p+2, preferably 1-15, more preferably 1-1O).

SiH3SiH(SiH3)SiH3,5iH3SfH
(Sins)Si3H7,5i2H5SiH(SiH3
) Chain silane compounds having a branch represented by Sf Hp 2p+2 (p has the above-mentioned meaning) such as Si2 H5, some or all of the hydrogen atoms of these linear or branched chain silane compounds Compound in which is substituted with a halogen atom, 5i3H6,Si4H8,31
A cyclic silane compound represented by SiH (q is an integer of 3 or more, preferably 3 to 2q6) such as 1,H1 Compounds substituted with a cyclic silanyl group and/or a chain silanyl group,
Examples of compounds in which part or all of the hydrogen atoms of the silane compounds exemplified above are replaced with halogen atoms
Hs F, S f H3x (x is a halogen atom,
r is 1 or more, preferably 1 to lO1, more preferably 3 to
An integer of 7, S+t=2r+2 or 2r. ) and halogen-substituted linear or cyclic silane compounds.

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

Also, the compost formed by the method of the present invention! It is possible to dope the l film with impurity elements. The impurity elements to be used are p-type impurities such as those from Periodic Table 1LI
Group A elements, such as B, AI.

Preferred examples include G a , I n , T 1 , etc., and preferred n-type impurities include elements in Group V A of the periodic table, such as N, P, As, Sb, Bi, etc. However, 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.

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゜P 2 Ha , PF 3 ,
P F s, PCl3%AsH3, AsF3, A
sF5, AsC13.

S bH3, S bFs, S iH3, BF3, BC
l3. BBr3. B2H6, B4H10゜B5Hg
, Bs Ht s , B6 Hs
o ・Bf, HI2, AlCl3, etc. can be mentioned. 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 configuration of a typical photoconductive member obtained by the present invention.

The photoconductive member 10 shown in FIG. 1 and the electrophotographic image forming member kL? Application ""1 gain 61 o-r: hol/light guide
1. An intermediate layer 12 is provided as needed on the support 11 for electrical components. and a photosensitive layer 13.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NfCr, Stair L/S, AI, Cr, and Mo.

Examples include metals such as Au, Ir, 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. Ru. Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

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

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

V, Ti, Pt, Pd, In203.5n02.

If it is conductive treated by providing a thin film such as I To (I B203 +S n02 ) or a synthetic resin film such as polyester film, N1cr
, AI, 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, electron beam evaporation, sputtering, etc., or laminated with the metal, so that the surface thereof is 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, the intermediate layer 12 includes the photosensitive layer 1 from the side of the support 1.1.
3, and the photocarriers generated in the photosensitive layer 13 by electromagnetic wave irradiation and moving toward the support 11 from the photosensitive layer 13 side to the support 11 side. It has a function that allows easy passage of.

This intermediate layer 12 is made of amorphous silicon (hereinafter referred to as a-3i(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 governing conductivity, such as B and P, contained in the intermediate layer 12 is preferably 0.
001~5X10" atomic cppm, more preferably 0.5~1X104a'tomic ppm,
The optimum range is preferably 1 to 5 x 103103 at 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 gases of the compounds contained therein into the film forming space where the support 11 is installed and using thermal 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 layer thickness of the intermediate layer 12 is preferably 30A to 10 pL, more preferably 40A to 8 pL, and optimally 50A to 5 pL.

The optical layer 13 is made of, for example, A-3i (H,

The layer thickness of the photosensitive layer 13 is preferably 1 to 100-
More preferably, it is 1 to 80 JL, and most preferably 2 to 50 JL.

The photosensitive layer 13 is an i-type a S l (H+ It may contain a controlling substance, or
If the actual amount of the substance that governs the conductivity of the same polarity contained in the intermediate layer 12 is large, it may be contained in an amount much smaller than the actual amount.

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 thermal 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 an example of a PIN type diode device type 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-St layer 24, an i-type a-3i
Layer 25. It is constituted by a p-type 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. Examples of the thin film electrode 22.27 include NiCr, Al, Cr, Mo, Au, I
r, Nb, Ta, V, Ti, PL, Pd, In2O3,
It is obtained by providing a thin film of 5n02, ITO (In203 +5n02), etc. on a substrate by vacuum evaporation, electron beam evaporation, sputtering, or the like. Electrode 2
The film thickness of 2.27 is preferably 30 to 5×104
A, more preferably 100 to 5×103A.

In order to make the film body constituting the a-Si semiconductor layer 23 n-type 24 or p-type 26 as necessary, an n-type impurity, a p-type impurity, or both impurities must be added to the impurity elements during layer formation. It is formed by doping the layer into the formed layer in a controlled amount.

When forming n-type, i-type, and p-type a-5T layers, any one layer or all 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 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, the thickness of the n-type and p-type a-Si layers, which may be formed by using thermal energy, is preferably in the range of 100 to 104 Å, more preferably in the range of 300 to 2000 Å.

Further, the thickness of the i-type a-3t layer is preferably 5
00-104A, more preferably 1000-10000
A range of λ is desirable.

Specific examples of the present invention are 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 through a conductive wire 105 and generates one heat. Although the substrate temperature is not particularly limited, in carrying out the method of the present invention, preferably 5
The temperature is preferably 0 to 150°C, more preferably 100 to 150°C.

106 to 109 are gas supply sources, carbon compounds,
and hydrogen, a halogen compound, an inert gas, and an impurity element, depending on the number of compounds to be used as components. 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 the pressure gauge that measures the pressure on the high pressure side of each flowmeter, d or e
The valves marked with are used to adjust the flow rate of each gas. 110 is a gas introduction pipe to the film forming space, ll is a gas pressure gauge, 112 in the figure is a decomposition space, 113 is an electric furnace, 1
Reference numeral 14 indicates zero solid particles, and reference numeral 115 indicates an introduction pipe for a compound containing gaseous carbon and halogen, which is a raw material for active species. will be introduced in

Reference numeral 117 denotes a thermal energy generating device, for example, an ordinary electric furnace, a high frequency heating device, various heating elements, etc. are used.

The heat from the thermal 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 forming carbon Mq 7a holes in the entire substrate 103 or in a desired part. Form a deposited film.

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

First f, polyethylene terephthalate film substrate 1
03 was placed on the support stand 102, and the inside of the deposition space 101 was evacuated using an exhaust device, and the temperature was 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 11000 ppp
A gas mixed with 403 CCM (hydrogen gas dilution) was introduced into the deposition space.

In addition, the decomposition space 102 is filled with solid 0 grains 114, heated in an electric furnace 113 to melt C, and CF is blown into the decomposition space 102 through a CF4 introduction pipe 115 from a cylinder to generate active species of CF-. 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 maintaining it at ITorr, the inside of the film forming space 01 is heated to 250℃ using a thermal energy generator.
It was an undoped or doped carbon-containing amorphous deposited film/sec.

Next, the obtained non-doped or p-type Keishan tomb
After placing the film sample in a deposition tank and forming a comb-shaped AI gap electrode (length 250 l, width 5 mm) under a vacuum degree of 10-'' Torr, the dark current was measured at an applied voltage of 10 V, and the dark conductivity σ The composite film was evaluated by determining the following.The results are shown in Table 1.

Examples 2-4 Linear c2H6, c2H, or C2H instead of CHa
, was used, but the same carbon-containing amorphous deposited film as in Example 1 was formed. Measure the dark conductivity and record the results in the first
Shown in the table.

Table 1 shows that 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 low substrate temperatures, and a carbon-containing amorphous film that is sufficiently doped 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 At 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 thermal energy generating device, and for example, an ordinary electric furnace, a high frequency heating device, or various heating elements are used.

In addition, by filling the decomposition space 202 with solid 0 grains 204 and heating it in the electric furnace 203 to melt C, and blowing CF4 into it from a cylinder, active species of C wood F2 are generated, and the introduction pipe 206 is After that, it is introduced into the film forming space 201.

On the other hand, CH4, Si2H6, and F2 are introduced into the film forming space 201 through the introduction pipe 217. While maintaining the atmospheric pressure in the film forming space 201 at 1.0 Torr, the pressure inside the film forming space 201 is maintained at 25,000 Torr using a thermal energy generator.

The At cylinder 211 is heated and maintained at 280°C by the heater 208 and rotated, 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 has H2/B 2H&
A mixed gas of (0.2% B2H6 by volume) was introduced to form a film with a thickness of 2000 Å.

Comparative Example 1 CF4 and CH4,S
i2 Hb, F2 and B2H, to film formation space 2 in Figure 4
01 was equipped with a 13.56 MHz high frequency device 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 using 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 100OA ITO film 22 was vapor-deposited was placed on a support stand, and
After reducing the pressure to -6 Torr, active species of CF2 were introduced from the introduction pipe 116 as in Example 1, and St3 H6150SCCM and phosphine gas (P) were introduced from the introduction pipe 110.
H311000pp hydrogen dilution) was introduced, and from another system /
＼Introducing 20SCCM of rogen gas, O, 1 Torr,
P-doped n-type a-
A 5t film 24 (thickness: 700 A) was formed.

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

Then, CH450SCCM, Diporan gas (B2H611000pp hydrogen diluted) 405 with 5i3H6 gas
A p-type carbon-containing a-3i film 26 (thickness: 700 A) doped with B was formed under the same conditions as the n-type except for CCM. Furthermore, on this p-type film, a film thickness of 1
An AI electrode 27 of oooA was formed to obtain a PIN type diode.

I of the diode element thus obtained (area 10 m2)
-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/cm2), conversion efficiency is 8.5% or more, open circuit voltage is 0.92 V, and short circuit current is 1.
0.5 mA/cm2 was obtained.

Example 7 Instead of CH4 as a carbon compound, C2H6, C2H,
Or the same PIN as in Example 6 except that C2H2 was used.
A type diode was fabricated. The rectification characteristics and photovoltaic effect were evaluated and the results are shown in Table 3.

1 from Table 3 According to the present invention, the a-5i 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 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 I& films can be formed at low substrate temperatures. 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. Moreover, since relatively low thermal energy can be used as excitation energy, effects such as being able to form a film even on a substrate with poor heat resistance and shortening the process through low-temperature treatment are exhibited.

[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 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... Image forming member for electrophotography, 11...
Substrate, 12... Intermediate layer, 13... Photosensitive layer, 21... Substrate, 22, 27... Thin film electrode, 24 11 @ II n-type a-5L layer, 25 11
e e i type a-5L layer, 26 z-p type a-5
i layer, 101.201 ... film formation space, 111.202
... Decomposition space, 106.107.108.10
9. 213.214,215,216...Gas supply source, 103.211...Base, 117.218・Φ・Mature energy generator.

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 act on the active species and applying thermal energy to them to excite the carbon compound and cause it to react.