JPS61190923A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To attain enlargement, improvement of productivity and mass production of the title films by a method wherein an active compound containing silicon and halogen as well as another active compound chemical-reacting to the former are separately fed to a filming space to make them chemical-react to each other by means of irradiating them with photoenergy. CONSTITUTION:Under the coexistance of an active compound A produced by decomposing a silicon and halogen contained compound as well as another active compound B produced from a carbon contained filming compound substituting for producing plasma within a filming space to form the deposited films, said active compounds A and B are made chemical-react to each other by means of supplying them with photoenergy to form the deposited films. The life of applicable active compound A is recommended to exceed 10sec in terms of productivity and easy handling while e.g. SiF4 etc. may be recommended for the silicon and halogen contained compound. Finally the preferable weight ratio of active compounds B and A may be 8:2-4:6.

Description

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

[Prior art]

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

Deposited films composed of amorphous silicon have excellent electrical and optical properties, fatigue properties due to repeated use, and use environment properties, as well as productivity including uniformity and reproducibility, and mass production. , there is room for further improvement of comprehensive characteristics.

The reaction process in forming an amorphous silicon deposited film using 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 (e.g., substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, plasma generation method, etc.).
Due to the combination of these many parameters, the plasma sometimes becomes unstable, which often has a significant adverse 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, the conventional technique using the normal CVD method requires a high temperature, and a deposited film having practically usable characteristics has not been obtained.

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

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

[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 uniform in quality. The object of the present invention is to provide a deposited film forming method that can be easily achieved.

The above purpose is to create an active species (A) generated by decomposing a compound containing silicon and a halogen in a film forming space for forming a deposited film on a substrate, and a chemical reaction between the active species (A) and the active species (A). By separately introducing active species (B) generated from a carbon-containing compound for hydrogenation, which interact with each other, and irradiating them with light energy to cause a chemical reaction, a film is deposited on the substrate. The deposit of the present invention is characterized by forming n
This is achieved by a method of forming a mold.

[Embodiment]

In the method of the present invention, instead of generating plasma in the deposition space for forming the deposited film.

In the coexistence of active species (A) generated by decomposing halogens and compounds containing halogens and active species (B) generated from carbon-containing compounds for film formation, light energy is applied to them. The deposited film that is formed to cause, promote, or amplify chemical interactions due to these factors may be adversely affected by etching effects or other effects such as abnormal discharge effects during film formation. There is virtually no such thing.

Furthermore, activation energy is imparted uniformly or selectively to each active species that reaches the vicinity of the substrate for film formation, but if light energy is used, the entire substrate can be irradiated using an appropriate optical system. can be irradiated to form a deposited film,
Alternatively, it is convenient to be able to selectively control and irradiate only a desired area to form a deposited film, or to form a deposited film by irradiating only a predetermined graphic area using a resist or the like. It is advantageously used because it has

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. Note that the active species (A) in the present invention refers to active species (CB) generated from a carbon-containing compound that is a compound of the raw material for forming a deposited film, and chemically interacts with the active species (CB) 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 (A) may contain constituent elements constituting the deposited film to be formed, or may not contain such constituent elements. The activated species (A) from the activation space (A) introduced into the membrane space are
Those having a lifespan of 0.1 seconds or more, more preferably 1 second or more, optimally 10 seconds or more are selected and used as desired.

It is preferable that 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 (B), or 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 activation space (B).

As the carbon-containing compound used in the present invention, most carbon-containing compounds can be used as long as they can be activated by the action of activation energy such as light, heat, electricity, etc. and efficiently generate active species (B). Among them, so-called carbon compounds, such as compounds containing carbon as a positive component, can be used.

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 whose constituent atoms are one or more of these halogens, sulfur, etc. Among organosilicon compounds having a hydrocarbon group as a constituent and organosilicon compounds having a bond between silicon and carbon, those in a gaseous state or those that can be easily vaporized are preferably used.

Among these, hydrocarbon compounds include 1, for example, 1 to 1 carbon atoms.
Examples of saturated hydrocarbons include methane (CH4), x tough (C2
H8), propane (CeHs), n-butane (n-C4
H1o), pentane (C5H12), ethylene hydrocarbons include ethylene (C2H4), propylene (C3H
6), Butene-1 (C4H8), Butene-2 (C4H
s), imbutylene (C4H8), pente7 (C5Ht
o), acetylene hydrocarbons include acetylene (C
2H2), methylacetylene (C3H4), butyne (C
4H6), etc.

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 C1, Br, I can be mentioned,
Particularly effective are compounds in which hydrogen is substituted with F or C1.

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.

Organosilane and organohalogensilane each have the general formula; Rn5iH4-1, RmSiX4-m (however,
R: alkyl group, aryl group, X: F, CfL, Br,
I, n=1,2,3,4, m=1.2.3), and typical examples include alkylsilane, arylsilane, alkylhalogensilane, and arylhalogensilane. .

in particular.

As organochlorosilane, trichloromethylsilane CH35iC!
L3 dichlorodimethylsilane (CH3)
25iCjL2 Chlortrimethylsilane
(CH3.)2SiCi trichloroethylsilane
C2H55iC13 dichlorodiethylsilane (C2H5)2SiCJL2 Organochlorofluorosilane includes chlordifluoromethylsilane CH3SiF2CJl dichlorofluoromethylsilane CH35iF, CfL2 chlorofluorodimethylsilane (CH3) 2siF
cJl Chlorethyldifluorosilane (C2H
5) SiFz (,1 dichloroethylfluorosilane
C2H55iFC dichlorodifluoropropylsilane CC3H75iF2C dichlorofluoropropylsilane (:3H7SiFC12 As organosilane, tetramethylsilane (CH3) 4
Si ethyltrimethylsilane (CH
3) 3SiC2Hs trimethylpropylsilane
(CH3)351c31(ytriethylmethylsilane CH35i (C2H5)3tetraethylsilane (C2H5)as
iAs an organohydrogenosilane.

Methylsilane CH35iH3
Dimethylsilane (CH3)2
SiH2 trimethylsilane (C
H3) 3S iH diethylsilane
(C2H5)2SiH2 triethylsilane
(C2H5) 3 S i H tripropylsilane (C3H7)3S f
H diphenylsilane (CaH2)
As 2SiH2 organofluorosilane, trifluoromethylsilane CH35iF3
Difluorodimethylsilane (CH3)2S
iF2 Fluorotrimethylsilane (CH
3) 3S i F ethyltrifluorosilane
C2H55iF3 diethyldifluorosilane
(C2H5)23iF2Triethylfluorosilane (C2H5)3S i Ftrifluoropropylsilane (C3H7) S i
As F3 organobromosilane, Bromotrimethylsilane (CH3)3
SiBrdibromdimethylsilane (C
H3) 25iBr2 etc. can be mentioned, and other organopolysilanes include.

Hexamethyldisilane ((CH3)3
As Si)2organodisilane.

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 silicon and halogen introduced between one decomposition chamber, 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, 5iuY
2u+2 (u is an integer greater than or equal to 1, Y is F, CI.

Br and is at least one element selected from I. ) chain silicon halide, 5ivY2v
(v is an integer of 3 or more, Y has the above-mentioned meaning.) Cyclic silicon halide, S i uHXYy (
u and Y have the meanings given above. X+7=2u or 2u
+2. ), and the like.

Specifically, 1, for example, SiF4. (SiF2) 5゜(SiF2) e, (SiF2) 4.5i2Fs
, 5i3FB.

5tHF3.　　SiH2F2.　5iC14.

(SiC12)5, SiBr4.

(SiBr2)5.　5i2C1B.

Examples include those that are in a gaseous state or can be easily gasified, such as 5i2C13F3.

In order to generate the active species (A), in addition to the above-mentioned compound containing silicon and halogen, other silicon-containing compounds such as simple silicon, hydrogen, and halogen compounds (for example,
F2 gas, C2 gas, gasified Br2. I2 etc.) etc. can be used in combination.

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

Activated species (A) are generated by adding excitation energy such as heat, light, electricity, etc. to the above-mentioned species in the activation space (A).

In the present invention, the ratio of the amount of active species (mu), which is a raw material for forming the deposited B film introduced into the film forming space, and the active species (kaku) depends on the film forming conditions, the type of active species, etc. It can be determined as desired, but preferably 10:1 to 1:10 (
(introduction flow rate ratio) is appropriate, more preferably 8:2 to 4.
:6 is desirable.

In the present invention, in addition to the carbon-containing compound, the activation space (
B), a silicon-containing compound as a raw material for forming the active species (B), or hydrogen gas, a halogen compound (for example, F2 gas, C12 gas, gasified Br2, T2, etc.) as a chemical substance for film formation, helium. It is also possible to introduce an inert gas such as argon or neon into the activation space (B). When using multiple of these film-forming chemicals, they can be mixed in advance and introduced into the activation space (B), or each of these film-forming chemicals can be supplied from an independent source. It is possible to supply each of them individually and introduce them into the activation space (B), or it is also possible to introduce them into independent activation spaces and activate each of them individually.

Silicon-containing compounds for forming active species (B) include silicon, hydrogen, oxygen atoms, and halogens.

Alternatively, silanes, siloxanes, etc. to which hydrocarbon groups or the like are bonded can be used. Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms in the chain and cyclic silane compounds are replaced with herogen atoms.

Specifically, for example, 5iHa, Si 2H6°S i
Si PH2F+2 such as 3HB, Si4H10, 5i5H12, 5i6H14 (p is 1 or more, preferably 1 to
15. More preferably, it is an integer of 1 to 10. ), a linear silane compound represented by S te3s iH (S 1
H3) SiH3,5tH3SiH(SiH3)Si3
H7,5i2H5S iH(S i H3)S i 2
5ipH2F+2 CP such as H5 has the above meaning. ), compounds in which part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with halogen atoms, S,
13H6,5i4HB,5i5)(10,S i 6
5iqH2q such as HI3 (q is 3 or more, preferably 3 to
It is an integer of 6. ), a compound in which some or all of the hydrogen atoms of the cyclic silane compound are substituted with other cyclic silanyl groups and/or chain silanyl groups,
As an example of a compound in which some or all of the hydrogen atoms of the silane compounds exemplified above are replaced with halogen atoms, SiH3F
, 5iH3C1, 5tH3Br, 5iH3I etc.+7)S
i rHsXt (X is a halogen atom, r is an integer of 1 or more, preferably 1 to 10, more preferably 3 to 7,
s+t=2r+2 or 2r. ) are halogen-substituted linear or cyclic silane compounds.

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

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. The impurity elements to be used include elements of group A of the periodic table as p-type impurities, such as B, AI, Ga, In, and T.
1 and the like, and examples of n-type impurities include elements of Group V A of the periodic table, such as P and As.

Sb, BE, etc. are mentioned as suitable ones, but especially B
, Ga, P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical properties.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under activation conditions, and that can be easily vaporized with an appropriate vaporization device. Such compounds which are preferably selected include PH3, P2H4, PF3.

PF5. PCl3. AsH3, AsF3゜AsF5. A
sCl3. SbH3, SbF5°SiH3, BF3. B
Cl3. BBr3゜B2H6, B4H10, B5H9,
B5Htt.

B6H10, B6H12, AlCl3, 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 introduction substance, which may be activated in a third activation space (C) different from the activation space (A) and the activation space (B), , active species (A)
A car can be created in which the above-mentioned activation energies listed in "Creating active species (B)" are appropriately selected and employed. The active species (PN) generated by activating the impurity introduction substance is mixed in advance with the active species (A) and/or the active species (B).

Alternatively, it is introduced into the film forming space independently.

Next, the present invention will be explained with reference to a typical example of an electrophotographic image forming member formed by the method of the present invention.

FIG. 1 is a schematic diagram for explaining an example of the structure of 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 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.

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13 can be created by the method of the present invention. Furthermore, the photoconductive member 10 is provided with a protective layer provided to chemically and 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.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support 7 include NiCr, Steer L/S, Al, Cr, and Mo.

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

Examples include metals such as Pd and alloys thereof.

Polyester is used as the electrically insulating support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and glass.

Ceramic, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.For example, if it is glass, the surface is N
iCr.

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

V, Ti, PL, Pd, In2O3,5n02゜■TO
(I n 203 + S n O2), etc., or if it is a synthetic resin film such as polyester film, NiCr, A1. A
g, Pb, Zn, Ni.

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

The surface is treated with a metal such as Ti or PL by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal to make the surface conductive. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined depending on the needs. For example, the photoconductive member 10 shown in FIG. If used, 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 support 11 side.
3, and the photocarriers generated in the photosensitive layer 13 by irradiation with electromagnetic waves and moving toward the support 11 from the side of the photosensitive layer 13 to the side of the support 11. It has a function that allows easy passage of.

This intermediate layer 12 is made of amorphous silicon (hereinafter referred to as "amorphous silicon") containing hydrogen atoms (H) and/or halogen atoms (X) and carbon atoms as constituent atoms.

A-3i (denoted as H, X, )), and
For example, boron (B) is a substance that controls electrical conductivity.
P-type impurities such as phosphorus CP) or n-type impurities such as phosphorus CP) are contained.

In the present invention, the content of substances controlling conductivity such as B and P contained in the intermediate layer 12 is preferably O,
OOl ~5X104ato omi Cppm, more preferably 0.5~IX104104ato ppm,
The optimum range is 1 to 5 x 103 atomic ppm.

If the components are similar or the same as those of 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 a gaseous carbon compound are used as raw materials for forming the intermediate layer.

Activated M (B) generated by activating a silicon compound, optionally hydrogen, a halogen compound, an inert gas, a gas of a compound containing impurity elements as components, and the like are separately added to the support 11. The intermediate layer 12 may be formed on the support 11 by introducing the light into a predetermined film forming space and applying thermal energy to the atmosphere in which each introduced active species coexists.

A compound containing silicon and halogen that is introduced into the activation space (A) to generate active species (A) when forming the intermediate layer 12 is a compound containing silicon and halogen that easily generates active species (A) such as SiF2*. The following compounds can be mentioned.

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

The photosensitive layer 13 has, for example, an A-3i (H,

The thickness of the photosensitive layer 13 is preferably as follows.

1 to 100 mackerel, more preferably 1 to 80 mackerel, most preferably 2 to 80 mackerel
It is desirable that it be set at 50 ru.

The photosensitive layer 13 is an i-type A-3i (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, the substance controlling the same polarity conductivity may be contained in an amount much smaller than the amount. You may let them.

In the case of forming the photosensitive layer 13 as well, if it is formed by the method of the present invention, a compound containing silicon and halogen is introduced into the activation space (A), as in the case of the intermediate layer 12.
Active species (A) are generated by decomposing them at high temperatures or by exciting them with discharge energy or light energy, and the active species (A) are 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, and in this case as well.

The film can be formed by the method of the present invention in the same manner as the intermediate layer and photosensitive layer.

FIG. 2 is a schematic diagram showing a typical example of a PIN type diode device using an A-3i deposited film doped with an impurity element, which is manufactured by carrying out the method of the present invention.

In the figure, 21 is a 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. 28 is a conductive wire connected to an external electric circuit device. These semiconductor layers are A-3i (H,X), A-3iC (H
, I can do it.

The base 21 may be conductive, semiconductive, or electrically insulating. If the base 21 is conductive, it may be omitted in the thin film electrode. Examples of the semiconductive base include Si, Ge, GaAS, ZnO, and Zn.
Examples include semiconductors such as S. Examples of the thin film electrodes 22.27 include NtCr, AI, Cr, Mo, and Au.

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

In2O3,5n02. ITO (In203+5na2
) on a substrate by a process such as vacuum evaporation, electron beam evaporation, or sputtering.

The film thickness of the electrode 22.27 is preferably 30 to 5X.
It is desirable to have 104 people, more preferably 100 to 5 x 103 people.

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

When forming n-type, i-type, and p-type semiconductor layers, any one layer or all of the layers can be formed by the method of the present invention, and the film formation is performed by adding silicon and silicon to the activation space (A). A compound containing a halogen is introduced, and by exciting and decomposing it under the action of activation energy, active species (A) such as SiF2* are generated, and the active species (A) enters the film forming space. be introduced. Separately, in the activation space (B), chemical substances for film formation and, if necessary, inert gas and compound gas containing impurity elements as components are excited and decomposed by activation energy, respectively. to generate each active species,
Each of them may be introduced separately or mixed as appropriate into the film forming space where the support 11 is installed, and formed by using light energy.

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

Further, the thickness of the i-type semiconductor layer is preferably 50
A range of 0 to 104 people, more preferably 1000 to 100 people is desirable.

Specific examples of the present invention are shown below.

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

In FIG. 3, 101 is a film forming chamber.

A desired base 103 is placed on the base support 102 inside.

104 is a heater for heating the substrate;
4 is a gas supply system in which the substrate 104 is heat-treated before the film formation process, and is subjected to a 7-neal treatment to further improve the properties of the formed film after the film formation process.106 to 109 are gas supply systems; compound, and optionally hydrogen,
It is provided depending on the type of gas of a compound containing a halogen compound, an inert gas, or an impurity element. If one of these raw material compounds is used that is in a liquid state under standard gas conditions, 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
is a solid Si particle, 115 is an introduction pipe for a compound containing gaseous silicon and halogen, which is a raw material for the active species (A),
The activated species (A) generated in the activation chamber (A) 112 are introduced into the film forming chamber 101 via the introduction pipe 116.

Reference numeral 117 denotes a light energy generating device, for example, a mercury lamp, a xenon lamp, a carbon dioxide laser, an argon ion laser, an excimer laser, or the like.

Light 118 directed from the optical energy generating device 117 to the entire substrate 103 or a desired portion of the substrate 103 using an appropriate optical system is irradiated onto the active species flowing in the direction of the arrow 119, and the irradiated active species mutually interact. A-5iC (
A main stacked film of H, X) is formed.

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

First f, the substrate 103 made of polyethylene terephthalate film was placed on the support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device, and the pressure was reduced to to-e''rorr. Using the gas supply cylinder 106, CH4150SCC
M, or a gas mixed with 403 CCM of PH3 gas or B2H6 gas (both diluted with 11000 pp hydrogen gas) is supplied to the activation chamber (B) 12 through the gas introduction pipe 110.
It was introduced in 3. m Ashita ± child = CH4 introduced into the activation chamber (B) 123
The gas and the like were activated by the microwave plasma generator 122 to become active hydrogen and the like, and the activated hydrogen and the like were introduced into the film forming chamber 101 through the introduction pipe 124 .

On the other hand, solid Si particles 11 are placed in the activation chamber (A) lII・2.
4 and heated in an electric furnace 113 to about 1100°C.
By keeping the Si at a temperature of , and introduced into the film forming chamber 101.

While maintaining the internal pressure in the film forming chamber 101 at 0.3 Torr, the I
A non-doped or doped carbon-containing amorphous deposited film (
A film thickness of 700 layers was formed. Film deposition rate is 27 people/sec
Met.

Next, the obtained non-doped, p-type, or n-type carbon-containing amorphous film sample was placed in a vapor deposition tank, and the vacuum degree was 1O.
After forming a comb-shaped Al gap electrode (gear length zsog, width 5 mm) at −5 Torr, dark current was measured at an applied voltage of 10 V, dark conductivity σd was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2 to 4 Linear c2H,3, C2H4° or C2 instead of CHa
A carbon-containing amorphous deposited film was formed in the same manner as in Example 1 except that H2 was used. 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 a solid Si particle, 205 is an active #(A) raw material introduction tube, 206 is an active species (A)
An inlet pipe, 207 a motor, 208 a heater used in the same manner as 104 in FIG. 3, 209 and 210 blowout pipes, 211 an AI cylinder-shaped base, and 212 an exhaust valve. Further, 213 to 216 are raw material gas supply systems similar to 106 to 109 in FIG.
17 is a gas introduction pipe.

An At cylindrical base 211 is suspended in the film forming chamber 201, and a heater 208 is installed inside the At cylindrical base 211.
7 so that it can be rotated. Reference numeral 218 denotes a light energy generator, which irradiates light 219 toward a desired portion of the AJI cylindrical base 211.

In addition, the activation chamber (A) 202 is filled with solid Si particles 204, heated in an electric furnace 203, and kept at about 1100°C.
By bringing Si into a red-hot state and blowing 5iFa into it from a cylinder (not shown) through the introduction pipe 206, Si F2)k as an active species (A) is generated, and the Si
F2* was introduced into the film forming chamber 201 through the introduction pipe 206.

On the other hand, CH4, Si2H6 and H2 are introduced from the introduction pipe 217-1.
Each gas was introduced into the activation chamber (B) 220. The introduced H2 gas undergoes activation processing such as plasma conversion by the microwave plasma generator 221 in the activation chamber (B) 220, becomes active hydrogen, and is introduced into the film forming chamber 201 through the introduction pipe 217-2. It was done. At this time, impurity gases such as PH3 and B2H6 are also added to the activation chamber (B) 22 as necessary.
0 introduced into the film forming chamber 201 and activated.
While maintaining the internal pressure at 1.0 Torr, light was irradiated perpendicularly to the circumferential surface of the An cylindrical substrate 211 from a 1KWXe lamp 218.

The At cylindrical base 211 was rotated, and the exhaust gas was exhausted through the exhaust valve 212.

In this way, the photosensitive layer 13 was formed.

Furthermore, prior to the creation of the photosensitive layer 13, the intermediate layer 12 is supplied with an inlet pipe 217-1 in addition to the gas used when creating the photosensitive layer 13.
From H2/82H6 (B2H6 gas is 0.2% by volume%)
) was introduced to form a film with a thickness of 2,000 yen.

Comparative Example 1 SiF2 and CHa, S i 2He , H2 and B2
A film forming chamber with the same configuration as the film forming chamber 201 was prepared using H6 gases, and equipped with a 13.56 MHz high frequency device, and the layer structure shown in FIG. 1 was formed by a general plasma CVD method. An electrophotographic imaging member was formed.

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 The PIN type diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3 using CH4 as a carbon compound.

First, a polyethylene naphthalate film 21 on which 1000 ITO films 22 were deposited was placed on a support stand, and
After reducing the pressure to 8 Torr.

As in Example 1, the active species of SiF2* is introduced into the film forming chamber 101 from the introduction pipe 116, and the SiF2* active species is introduced from the introduction pipe 110 into the film forming chamber 101.
3H6150SCCM, PH3 gas (1000p p
m hydrogen gas diluted) was introduced into the activation chamber (B) 123 and activated.Then, this activated gas was introduced into the inlet pipe 116.
It was introduced into the film forming chamber 101 through the. The pressure in the film forming chamber lot is set to 0. IKWE while keeping IT o r r
n-type A-S doped with P by light irradiation with an e-lamp
A t-film 24 (thickness: 700 layers) was formed.

Next, instead of PH3 gas, B2H6 gas (300pp
n-type A-S i C except that hydrogen gas dilution) was introduced.
i-type A-S i in the same way as for the (H,X) film
A C(H,X) film 25 (500 mm thick) was formed.

Then, C with S i 3H6 gas instead of PH3 gas
H450SCCM, B2Hs (1000ppm hydrogen gas dilution), 403CCM were used, and the rest were n-type A.
-5iC(H,X) film 24 doped with B under the same conditions as the p-type carbon-containing A-3i(H,X) film 26 (thickness 7
00 people) was formed. Furthermore, 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.

- The IV characteristics of the thus obtained diode element (area: 1 cm2) 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 8.5% or more, the open circuit voltage is 0.92 V, and the short circuit current is 10.5. mA/cm2 was obtained.

Examples 7 to 9 C2Hs, C instead of CH4 as carbon-containing compounds
A PIN diode similar to Example 6 was manufactured except that 2H4 or 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 a-5iC (H,

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible without maintaining the substrate at a high temperature. becomes. In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. be able to. Furthermore, since light energy is used as excitation energy, the film can be formed even on a substrate with poor heat resistance, and the process can be shortened by low-temperature treatment.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. It is a diagram. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the invention method used in the examples, respectively. 10--1 electrophotographic imaging member, 11--1 substrate, 12--1 intermediate layer, 13--1 photosensitive layer, 2.l-1-1 substrate, 22.27-- - Thin film electrode. 24---n type semiconductor layer, 25---i type semiconductor layer, 26---p type semiconductor layer. 101.201---Configuration chamber, 214.215,216---Gas supply system, 103
, 211---monosubstrate. 117,218---One light energy generator.

Claims (1)

[Claims] Chemically interacts with active species (A) generated by decomposing a compound containing silicon and halogen in a film forming space for forming a deposited film on a substrate. , active species generated from carbon-containing compounds for film formation (
A deposited film forming method characterized in that a deposited film is formed on the substrate by separately introducing B) and irradiating them with light energy to cause a chemical reaction.