JPS61189627A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To contrive the improvement in characteristics, film-forming speed, and reproducibility of the amorphous or crystalline deposited film containing carbon and the uniformity of film quality, by a method wherein a specific activation seed previously activated in a space different from the film-forming space is used to carry out chemical reaction. CONSTITUTION:In the film-forming space to form a deposited film 10 over a substrate 11, an activation seed produced by decomposing a compound containing carbon and halogen and an activation seed produced out of a compound containing carbon which chemically interacts with it are separately introduced, and the deposited film 10 is formed over the substrate 11 by making the activation seeds to carry out chemical reaction. This process allows the formed film 10 to receive no adverse effects caused by etching action or another action such as abnormal discharge because of no generation of plasma in the film-forming space to form the film 10.

Description

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

[Prior art]

For example, attempts have been made to form an amorphous silicon film using vacuum evaporation, plasma CVD, CVD 1 reactive sputtering, ion blasting, photo-CVD, etc. Generally, plasma CVD is the most popular method. Widely used and commercialized.

Deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility.
In terms of mass production, there is room to further improve the overall characteristics.

The reaction process for forming amorphous silicon deposited films using the conventional plasma CVD method is considerably more complex than that of conventional CVD methods, and there are many aspects of the reaction mechanism of kudzu 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 effect on the deposited film formed. Moreover, 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 that fully satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. There is.

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 film by the method requires a large amount of equipment investment for mass production equipment, and the management items for mass production also become complex, the management tolerance narrows, and the adjustment of the equipment is delicate. Therefore, these issues have been pointed out as issues that should be improved in the future. On the other hand.

Conventional techniques using normal CVD methods require high temperatures and have not been able to provide deposited films 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 above-mentioned drawbacks of the plasma CVD method and provides a new deposited film forming method that does not rely on conventional forming methods.

[Purpose and outline of the invention]

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

The above purpose is to create an active species (A) generated by decomposing a compound containing carbon and halogen in a film forming space for forming a deposited film on a substrate, and to create a chemical reaction between the active species (A) and the active species (A). interact.

This is achieved by the deposited film forming method of the present invention, which is characterized in that a deposited film is formed on the substrate by separately introducing active species CB) generated from a carbon-containing compound and causing a chemical reaction. Ru.

[Embodiment]

In the method of the present invention, since plasma is not generated in the film forming space for forming the deposited film, the deposited film that is formed is not affected by etching effects or other adverse effects such as abnormal discharge effects. Never.

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

One of the differences between the method of the present invention and the conventional CVD method is that it uses active species activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and also to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost. In addition, the active species (A) in the present invention refers to the active species (B) that chemically interacts with the active species (B) generated from the carbon-containing compound that is the compound of the raw material for forming the deposited film to impart energy, for example. A substance that has the effect of promoting the formation of a deposited film by causing a chemical reaction.

Therefore, the active species may include constituent elements constituting the deposited film to be formed, or may not contain such constituent elements. The activated species (A) introduced from the activation space (A) have a lifespan of 0.1 seconds or more, more preferably 1 second or more, and optimally 10 seconds from the viewpoint of productivity and ease of handling. Those listed above are selected and used as desired.

The carbon-containing compound used as a raw material for forming a deposited film used in the present invention is already in a gaseous state before being introduced into the activation space CB), or is introduced into the activation space (B) in a gaseous state. For example, when using a liquid compound, the compound can be vaporized by connecting a suitable vaporizer to the compound supply source and then introduced into the activation space (B). Examples of carbon-containing 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 halogen and sulfur, and carbonized Among organosilicon compounds whose constituent components are hydrogen groups and organosilicon compounds which have a bond between silicon and carbon, are they in a gaseous state?
Those that can be easily vaporized are preferably used.

Among these, examples of hydrocarbon compounds include carbon atoms of 1 to
Examples of saturated hydrocarbons include methane (CH4), ethane (C2
Hs), propane (CsHe), n-Buty (n-C4
HIO), Penta7 (C5H12), x-chi L/
Examples of 7-series hydrocarbons include ethylene (C2H4), propylene (C3H6), butene-1 (C4Hs), and butene-1.
2 (C4H8), inbutylene (C4H8), pentene (C5H1o), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4),
Examples include butyne (C4H6).

As the halogen-substituted hydrocarbon compound, at least one of the hydrogens that are constituents of the hydrocarbon compound described above is F,
Compounds substituted with CJL, Br, and I can be mentioned, and compounds in which hydrogen is substituted with F and C1 are particularly effective.

The halogen that replaces hydrogen may be one type or two or more types in one compound.

Examples of the organosilicon compounds used in the present invention include organosilanes and organohalogensilanes.

Orcassilane and organohalogensilane have general formulas; Rn5iH4-1 and RmSiX4-m (chemical formula 1.
．． R: alkyl group, aryl group, X: F, CM, Br,
I, n = 1.2, 3, 4, m = 1.2.3) 1 Representative examples include alkylsilane, arylsilane, alkylhalogensilane, and arylhalogensilane. .

Specifically, as organochlorosilane, Torikachi Methylsilane CH35iCJ
13 dichlorodimethylsilane (CH3
) 251cJ12 Chlortrimethylsilane
(CH3)25 ici trichloroethylsilane
C2H551c13 dichlorodiethylsilane (C2H5)2S 1C12 organochlorofluorosilane.

Chlordifluoromethylsilane CH35iF2
Cu dichlorofluoromethylsilane CH35i
FC12 Chlorfluorodimethylsilane (CH
3) 25 i FCu chloroethyldifluorosilane
(C2H5)S 1F2cl dichloroethylfluorosilane C2H55iFCJLz chlordifluorobrobylsilane CC3H75iF2C dichlorofluoropropylsilane C3H75iFC1
2 Organosilane is tetramethylsilane (CH3)
4S i Ethyltrimethylsilane (C
H3) 3Sic2H5 trimethylpropylsilane
(CH3)3S 1c3H7 Triethylmethylsilane CH35i (C2H5)3 Tetraethylsilane (C2H5)4
As Si organohydrogenosilane.

Methylsilane CH35iH
3dimethylsilane (CH3)
25 iH2 trimethylsilane
(CH3)3S iH diethylsilane
(C2H5)2S iH2 triethylsilane
(C2H5)3S iH Tripropylsilane (C3H7)3S i
H diphenylsilane (C6H5
) 2 S i H2 organofluorosilane includes trifluoromethylsilane CH35iF3
Difluorodimethylsilane (CH3)2
5 iF2 fluorotrimethylsilane (
CH3) 3 S i F ethyltrifluorosilane
C2H55iF3 Diethyldifluorosilane (C2H5)2Si F2 Triethylfluorosilane (C2H5)3S i F
Trifluoropropylsilane (C3H7)
As SiF3 organobromosilane, Bromotrimethylsilane (CH3)3
SiBrdibromdimethylsilane (CH
3) 25iBr2, etc., and other organopolysilanes include hexamethyldisilane ((CH3)
3 Si) As a 2-organodisilane.

Hexamethyldisilane ((CH3)
3Si) 2hexapropyldisilane
((C3H7)3Si)2 etc. can also be used.

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

In the present invention, as the compound containing carbon and halogen introduced into the activation space (A), for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon is replaced with a halogen atom is used. For example, CuY
Chain halide carbon represented by 2u+2 (u is an integer of 1 or more, Y is F, C1°Br or I), CVY
2V (V is an integer of 3 or more, Y has the above-mentioned meaning.

), CuHXYy (u and Y have the above meanings) (+y=2u or 2u+
It is 2. ), and the like.

Specifically, for example, CF4. C2F6゜(CF2)s
, (CF2)e, (CF2)a.

C2F6. C3F8, CHF3, CH2F2゜CC
l4. (CC12) 5. CBr4, (
CBr2) 5, C2C16, C2Br6. CH
Cl3, CHBr3, CHI3. C2Cl3F
Examples include those that are in a gaseous state or can be easily gasified, such as No. 3.

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 the compound containing silicon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically, for example, S i u
Y2 u+2 (u is an integer greater than or equal to 1, Y is F, CI, B
It is at least one element selected from r and engineering.

) chain silicon halide, 5iyY2v(v
is an integer of 3 or more, and Y has the above meaning. ) Cyclic silicon halide, S i uH) (Zy (u
and Z have the meanings given above. X+V=2u or 2u+
It is 2. ), and the like.

Specifically, for example, SiF4. (SiF2)5゜(SiF
2)s, (SiF2)4.5i2Fs.

Si3F8. SiHF3. SiH2F2゜5iC14,
(SiC12)5. SiBr4゜(SiBr2)5.5
Examples include those that are in a gaseous state or can be easily gasified, such as t2C1s and 5i213F3.

In order to generate the active species (A), the compound containing carbon and halogen (and the compound containing silicon and halogen)
In addition, other silicon-containing compounds such as simple silicon, hydrogen, halogen compounds (e.g. F2 gas, CJ1
2 gas, gasified Br2. I2 etc.) can be used in combination.

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

As mentioned above, heat is applied in the activation space (A).

Active species are generated by applying excitation energy such as light or electricity.

In the present invention, an activation space (B
) The ratio of the amount of active species (B) generated from the silicon-containing compound for forming a deposited film introduced into the deposited film and the amount of active species (A) from the activation space (A) is determined depending on the film forming conditions and the active species. It can be determined as desired depending on the type, etc., but preferably 10:l~
A suitable ratio is 1:10 (introduction flow rate ratio), more preferably 8:2 to 4:6.

In the present invention, in addition to the carbon-containing compound, the activation space (
In B), a silicon-containing compound for forming a deposited film that generates active species (B), or hydrogen gas, a halogen compound (for example, F2 gas, C12 gas, gasified Br2, It is also possible to introduce an inert gas such as helium, argon, ne, ion, etc. into the activation space (B). If more than one of these chemicals is used, they can be premixed and introduced into the activation space (B) in a gaseous state, or they can be introduced in a gaseous state from separate sources. They can be supplied individually and introduced into the activation space (B), or they can be introduced into separate activation spaces and activated individually.

As the silicon-containing compound for forming the deposited film, silanes and halogenated silanes in which hydrogen, 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, SiH4, Si2H6, 5i3)
1B, S i 4H10, S i 5H12, 5isH
Linear silane compounds represented by Si PH2F+2 such as 14 (p is an integer of 1 or more, preferably 1 to 15, more preferably 1 to 1O), 5iH3SiH (SiH
3) SiH3゜5iI(35iH(SiH3)Si3H
7,5i2H5SiH (SiH3) 5i such as Si2H5
Chain-like silane compounds with branches represented by pH2F+2 (p has the meaning described above); compounds in which part or all of the hydrogen atoms of these straight-chain or branched-chain silane compounds are replaced with halogen atoms; ,5i3H6,5i
A cyclic silane compound represented by S i qH2q (q is an integer of 3 or more, preferably 3 to 6) such as 4H8, S i 5 H1□, and S i 6H12, and a part of the hydrogen atoms of the cyclic silane compound SiH3F, 5i
H3C1, 5iH3Br, 5iH3I etc. c7) SirH
sXt (X is a halogen atom, r is an integer of 1 or more, preferably 1 to 10, more preferably 3 to 7, S + t = 2
r+2 or 2r. ) 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 element used is, as a p-type impurity, an element of group Ⅰ A of the periodic table, such as B.

Preferred examples include Al, Ga, In, TI, etc. Preferred n-type impurities include elements 1 of group V A of the periodic table, such as P, As, Sb, Bi, etc. , especially B.

Ga, P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical characteristics.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under activation conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to select
Such compounds include PH3, P2H4, PF3P
F5, PCl3, ASH3, AgF2
.

AsF5. AsC13, SbH3, SbF5゜SiH3
, BF3. BCl3. BBr3゜B2H6, B4HIO
, B5H9, B5Hil.

B6HIO, B6H12, AIC13, etc. can be mentioned. The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity-introducing substance may be introduced into the activation space (A) and/or the activation space (B) together with each substance that generates the active species (A) and the active species (B) for activation. Alternatively, to activate the impurity-introducing substance, which may be activated in a third activation space (C) different from the activation space (A) and the activation space CB), Active species (A)
The above-mentioned activation energies listed in ``and for generating activated species (B)'' can be appropriately selected and employed. The active species (PN) generated by activating the impurity introduction substance are mixed with the active species (A) and/or the active species (B) in advance, or are introduced into the film forming space independently.

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

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

The photoconductive member 10 shown in FIG. 1 can be applied as an electrophotographic imaging member.

It has a layer structure consisting of a support 11 for a photoconductive member, an intermediate layer 12 provided as necessary, and a photosensitive layer 13.

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13 can be created by the method of the present invention. Further, the photoconductive member 0 may be a protective layer provided to chemically or materially protect the surface of the photosensitive layer 13, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical withstand pressure. , these can also be created by the method of the present invention.

As the support body 11, 2. It may be electrically conductive or electrically insulating. Examples of the conductive support include NfCr, Stair L/S* A I , Cr, Mo.

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

Examples include metals such as Pd and alloys thereof.

Polyester is used as the electrically insulating support.

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

For example, if it is glass, its surface may be NiCr, AI,
Cr, Mo, Au, Ir, Nb.

Ta, V, Ti, Pt, Pd, In2O3゜S n02
, a thin film of ITO (I n203+s n02) etc.
NiCr,
AI, Ag, Pb.

Zn, Ni, Au, Cr, Mo, Ir, Nb.

The surface is treated with a metal such as Ta, 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.

The shape is determined as desired, but for example, the first
If the photoconductive member 10 shown in the figure 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, a photosensitive layer 13 is applied to the intermediate layer 12 from the support 11 side.
From the side of the photosensitive layer 13 to the side of the support weight 1 of the photocarrier that is generated in the photosensitive layer 13 by irradiation of electromagnetic waves and moves toward the side of the support 11, effectively blocking the inflow of carriers into the photocarrier. It has a function that allows easy passage of.

This intermediate layer 12 is composed of amorphous carbon (hereinafter referred to as a-C(H,X)) containing carbon atoms, hydrogen atoms (H), and/or halogen atoms (X) as constituent atoms, and For example, an n-type impurity such as boron (B) or an n-type impurity such as phosphorus (P) is contained as a substance that controls electrical conductivity. or.

Silicon atoms can also be included for the purpose of improving film quality.

In the present invention, the content of substances governing conductivity, such as B and P, contained in the intermediate layer 12 is preferably 0.
001-5X104 atomic ppm, more preferably 0.5-IX11X104 atomic ppm, optimally 1-5X103 atomic ppm.

When the intermediate layer 12 has similar or the same components as the photosensitive layer 13, the formation of the intermediate layer 12 can be performed continuously from the formation of the intermediate layer 12 to the formation of the photosensitive layer 13. In that case, the active species (A) generated in the activation space (A) and the active species (B) generated from the gaseous carbon-containing compound and silicon-containing compound are used as raw materials for forming the intermediate layer. If necessary, hydrogen, a halogen compound, an inert gas, and an active species generated by activating a gas of a compound containing an impurity element as components, respectively, separately or mixed as necessary to form a support. The intermediate layer 12 may be formed on the support 11 by introducing the active species into the film forming space where the active species 11 are installed and creating an atmosphere in which each introduced active species coexists.

Compounds containing carbon and halogen (and compounds containing silicon and halogen) that are introduced into the activation space (A) to generate active species (A) when forming the intermediate layer 12 are easily oxidized, for example, into SiF2*. It is more desirable to select a compound that generates an active species (A) such as SiF2* from among the compounds mentioned above. More preferably, it is selected from the compounds listed above.

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

The photosensitive layer 13 is made of an amorphous material (hereinafter referred to as rA-5i (H, It has both a charge generation function of generating photocarriers by irradiation with light and a charge transport function of transporting the charges.

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

The photosensitive layer 13 is made of non-doped a-Si(H.

X) layer, if desired, it may contain a substance that controls the conduction characteristics of a polarity different from the polarity of the substance that controls the conduction characteristics (for example, n-type) contained in the intermediate layer 12, or , the substance that governs the conduction characteristics of the same polarity is added to the intermediate layer 1.
If the actual amount contained in 2 is large, it may be contained in an amount much smaller than the dose.

In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, as in the case of the intermediate layer 12, a compound containing carbon and /\logen in the activation space (A), and separately from this, Compounds containing silicon and /\rogen are introduced, and active species (
A) is generated, and the active species (A) is introduced into the film forming space.

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 likewise be carried out by the method of the invention.

FIG. 2 is a schematic diagram showing a typical example of a PIN diode device using an a-Si deposited film doped with an impurity element, which is manufactured by carrying out the method of the present invention.

In the figure, 21 is a base, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an n-type semiconductor layer 24, an i-type semiconductor layer 2
5. Consisting of a p-type semiconductor layer 26. Semiconductor layers 24 , 25 .

The present invention can be applied to the production of any one layer of the semiconductor layer 26, but in particular, the conversion efficiency can be increased by producing the semiconductor layer 26 by the method of the present invention. When created, the semiconductor layer 26 is
For example, an amorphous material (hereinafter rA
-SiC(H,X)J). 28 is a conductive wire connected to an external electric circuit device.

The base 21 may be conductive, semiconductive, or electrically insulating. If the base body 21 is conductive, the thin film electrode 22 may be omitted. Examples of the semiconductive substrate include St, Ge, GaAs, ZnO,
Examples include semiconductors such as ZnS. Examples of the S film electrode 22.27 include NiCr, Al, Cr.
, Mo.

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

Pd, I n 203 , SnO2, ITO(I
It is obtained by providing a thin film such as n 203+5n02) on the substrate 21 by a process such as vacuum evaporation, electron beam evaporation, or sputtering. The layer thickness of the electrodes 22.27 is preferably 30 to 5×10 4 people, more preferably 100 to 5×10 3 people.

The film body constituting the semiconductor layer 23 may be of n-type or p-type as required.
A type is formed by doping an n-type impurity, a p-type impurity, or both impurities among impurity elements into the layer while controlling the amount thereof during layer formation.

When forming n-type, i-type, and p-type semiconductor layers, any one layer or all of the layers can be formed by the method of the present invention, and the film formation is performed by adding carbon and carbon to the activation space (A). A compound containing a halogen and another compound containing silicon and a halogen are introduced and excited and decomposed under the action of activation energy, resulting in, for example, cp2*.

Active species CA) such as S i F2* are generated, and the active species (A) are introduced into the film forming space. Also, apart from this,
Gaseous carbon-containing compounds, silicon-containing compounds, and compound gases containing inert gas and impurity elements as components are excited and decomposed by activation energy to generate respective active species. However, each of them may be introduced separately or appropriately mixed and introduced into the film forming space where the support 11 is installed, and formed.

The thickness of the n-type and p-type semiconductor layers is preferably in the range of 100-104, more preferably 300-2000.

Further, the thickness of the i-type semiconductor layer is preferably 50
A range of 0-104 people, more preferably 1000-10000 people is desirable.

Specific examples of the present invention are shown below.

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

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

104 is a heater for heating the substrate;
4 is used when heat-treating the base 104 before film-forming processing, or when performing 7-neal processing after film-forming to further improve the characteristics of the formed film, and is supplied with power via a conductive wire 105. , generates a fever. During film formation, the heater 104 is not driven, and the substrate heating temperature is not particularly limited, but when carrying out the method of the present invention, it is preferably 50 to 150
℃, more preferably 100 to 150℃ 6 106 to 109 are gas supply systems, and carbon compounds,
and, if necessary, provided depending on the type of gas of a compound containing hydrogen, a halogen compound, an inert gas, or an impurity element as a component. If these gases are liquid in their standard state, an appropriate vaporizer is provided.

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

In the figure, 112 is an activation chamber (A), 113 is an electric furnace, and 114
115 is an introduction pipe for a compound containing gaseous carbon and halogen, which is the raw material for the activated species (A), and the active species (A) generated in the activation chamber (A) 112 are introduced into the introduction pipe. 1
16 into the film forming chamber 101.

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

First step, base 1 made of polyethylene terephthalate film
03 was placed on the support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device to reduce the pressure to about 10-6 Torr.

CH4150SCCM using gas supply cylinder 106
was introduced into the activation chamber (B) 123 via the gas introduction pipe 110. The CH4 gas etc. introduced into the activation chamber (B) 123 is activated by the microwave plasma generator 1t22 and converted into hydrogenated carbon active species, activated hydrogen, etc. and activated hydrogen, etc., were introduced into the film forming chamber 101.

On the other hand, the activation chamber (A) 102 is filled with solid 0 grains 114, heated in an electric furnace 113, maintained at about 1000°C to bring C to a red-hot state, and CF4 By injecting CF3X
active species were generated, and the CF2) IC was introduced into the film forming chamber 101 through the introduction pipe 116.

In this way, the internal pressure inside the film forming chamber 101 is reduced to 0.3 Torr.
and carbon-containing amorphous [A-C(H,X))
A total of 4,700 people (11%) were formed. Film formation rate is 9.0
It was person/sec.

Next, the sample on which the obtained A-C(H,X) film was formed was placed in a vapor deposition tank, and a comb-shaped At
After forming a gap electrode (gap length 250 JL, width 5 mm), the dark current was measured at an applied voltage of 1Ov, the dark conductivity σd was determined, and the film characteristics of the sample were evaluated. The results are shown in Table 1.

Examples 2-4 Linear C2H6, C2H4, or C2H instead of CH4
, 2 was used, but the same carbon-containing amorphous (A-C(H,X)) film as in Example 1 was formed. The dark conductivity of each sample was measured and the results are shown in Table 1.

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

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

In FIG. 4, 201 is a film forming chamber, and 202 is an activation chamber (
A), 203 is an electric furnace, 204 is 0 solid particles, 205 is an active species (A) raw material introduction pipe, 206 is an active species (A) introduction pipe, 207 is a motor, 208 is the same as 104 in Fig. 3 209 and 210 are blowout pipes, 211 is an AI cylinder-shaped base, and 212 is an exhaust valve. Further, 213 to 216 are raw material gas supply sources similar to 106 to 109 in FIG.
7-1 is a gas introduction pipe.

Load the Al cylinder base 211 into the film forming chamber 201,
A heating heater 208 is provided inside the motor 207.
Allows for rotation.

In addition, the activation chamber (A) 202 is filled with solid 0 grains 204, heated in an electric furnace 203, kept at about 1000°C, and
The activated species (A
), and the cF2* is introduced into the inlet tube 2.
06, it was introduced into the film forming chamber 201.

On the other hand, CH4, Si2H6 and H2 from the introduction pipe 217-1
Each gas was introduced into the activation chamber (B) 220. The CH4, Si2H6, and H2 gases introduced are activated in the activation chamber (B) 2.
In step 20, hydrogenated carbon activated species are subjected to activation treatment such as plasma generation by a microwave plasma generator 221.
It becomes silicon hydride active species and activated hydrogen.Introduction pipe 21
7-2 into the film forming chamber 201. On this occasion,
If necessary, an impurity gas such as PH3°B2H6 was also introduced into the activation chamber (B) 220 for activation.

The Al cylinder base 211 was rotated, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust pulp 212. In this way, the photosensitive layer 13 is formed.
In the case of 12 layers, the intermediate layer 12 was formed through the introduction pipe 217-1.

Comparative Example 1 A film forming chamber with the same configuration as the film forming chamber 201 was prepared using CF4, CH4, Si2H6, H2 and B2H6 gases, and equipped with a 13.56 MHz high frequency device, and a general plasma An electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by a CVD method.

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

Using the apparatus, a PIN type diode shown in FIG. 2 was manufactured.

First, the polyethylene naphthalate film 21 on which the 1000 TTO film 22 was deposited was placed on a support stand, and the 10-
After reducing the pressure to GTorr, the inlet pipe 11 is opened as in Example 1.
Each of the activated species CF2 dilutions from 6) to the activation chamber CB) 12
3 and activated it. Next, this activated gas was introduced into the film forming chamber 101 via the introduction pipe 116.

The pressure inside the film forming chamber 101 is set to 0. Keep it at ITorrP
n-type a-3iC (H,X) film 24 (
A film thickness of 700 people was formed.

Next, the introduction of PH3 gas was stopped, and SiF2*/
n-type a-3iC (except that the value of CF 2 * was tripled)
H,X) II! A non-doped a-SiC (H,

Next, along with Si2H6 gas, CHa, B2H6 gas (1
A p-type a-5iC (H, Further, an AI electrode 27 having a thickness of 1000 wafers was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

Diode element thus obtained (surface 1M 1cm2)
The I-V characteristics were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, light is introduced from the substrate side, and at the light irradiation intensity AMI (approximately 100 mW/cm2), the conversion efficiency is 7.6% or more, the open circuit voltage is 0.95 V, and the short circuit current is 10.2. mA/cm2 was obtained.

Examples 7 to 9 C2H6°C2H4 instead of CH4 as a carbon compound
Alternatively, a PIN type guide similar to that in Example 6 was manufactured in the same manner as in Example 6 except that C2H2 was used. This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

From Table 3, it was found that according to the present invention, an amorphous semiconductor PIN type diode having better optical and electrical characteristics than the conventional one could be obtained.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible without maintaining the substrate at a high temperature. becomes. In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. be able to. Furthermore, since no excitation energy is used in the film-forming space, films can be formed, for example, on substrates with poor heat resistance or on substrates that are easily susceptible to plasma etching.
The low-temperature treatment has the effect of shortening the process.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using an uninvented method. FIG. 2 is a schematic diagram for explaining an example of the configuration of a PIN type daiode manufactured using an uninvented method. It is a schematic diagram for explanation. 10--An electrophotographic imaging member, 11--One substrate, 12--One intermediate layer, 13--One photosensitive layer, 21--One substrate. 22.27---Thin film electrode, 24---1-N type semiconductor layer, 25----I type semiconductor layer, 26----P type semiconductor layer, 101.201----1 film formation chamber , 111 , 202 --- Activation chamber (A), 106.1
07,108,109,213゜214.215,21
6----Gas supply system, 103, 211---One substrate.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, active species (A) generated by decomposing a compound containing carbon and halogen; Active species produced by carbon-containing compounds that chemically interact (
A deposited film forming method characterized in that a deposited film is formed on the substrate by introducing each of B) separately and causing a chemical reaction.