JPS61276977A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve the electrical, optical and mechanical characteristics of the resulting film by introducing a compound contg. Si and halogen and active species of a compound contg. O into a film forming space and by applying electric discharge energy to bring them into a reaction. CONSTITUTION:Active species are produced from a compound contg. O for film formation. The compound interacts chemically with a compound contg. Si and halogen such as a compound represented by a formula SiuY2u+2 (where u is an integer of >=1 and Y is F, Cl, Br or I). The active species and the compound contg. Si and halogen are introduced into a film forming space, where they are brought into a chemical reaction by applying electric discharge energy to form a deposited film on a substrate.

Description

Detailed Description of the Invention [Technical Field to which the Invention Pertains] The present invention relates to oxygen-containing deposited films, particularly functional films, particularly semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, and imaging devices. The present invention relates to a method for forming an amorphous or crystalline oxygen-containing deposited film for use in photovoltaic devices and the like.

[Description of prior art]

Conventionally, semiconductor devices, photosensitive devices for electrophotography,
Several types of oxygen-containing amorphous silicon (hereinafter simply referred to as IA-810J) have been proposed as element components for use in image input line sensors, imaging devices, photovoltaic devices, etc. It has been put into practical use. Along with the 1-810 film, several methods have been proposed for forming the A-810 film, including vacuum evaporation, ion blating, the so-called CVN method, plasma CVD, and former CVD. Among them, the plasma CVD method has been put into practical use as the most suitable method and is generally widely used.

By the way, the conventional A-810 film is produced by, for example, plasma CVD.
Although the products obtained by this method are said to be satisfactory for the time being due to their rich characteristics, there are still some electrical, optical, and photoconductive characteristics that are required for the establishment of a solid product. It is still difficult to solve the problem of satisfying all of the following points: fatigue resistance for repeated use, environmental characteristics for convenience, stability over time and durability, and homogeneity. It is in an intermediate state.

The reason for this is that the desired A-810 film, not only the materials used, cannot be obtained by a simple layer deposition operation, but requires special skill and ingenuity in the process operations. The big thing is that

Incidentally, for example, in the case of the so-called CVD method, the system and O
After diluting the system gas material, so-called impurities are mixed in and then thermally decomposed at a high temperature of 500 to 650°C, so precise process operations and control are required to form the desired A-810 film. Therefore, the equipment becomes complicated and the cost is considerably high, but in such a case, the a-810J[
It is difficult to obtain the product on a regular basis, and therefore it is far from being adopted on an industrial scale.

Furthermore, even with the plasma CVD method, which is generally widely used as the optimal method, there are some problems in process operation and problems in equipment investment. Regarding process operations, the conditions are as described above for CVD.
It is more complicated than the conventional method, and it is extremely difficult to make it into a film.

That is, for example, if we consider the interrelationship parameters among the substrate temperature, the flow rate and flow lid ratio of the introduced gas, the pressure during layer formation, the structure of the high-frequency electric collar electrode, the structure of the reaction vessel, the pumping speed, and the plasma generation method. There are already many 79 parameters, and there are other parameters as well.
In order to obtain the desired product, a strict selection of parameters is required, and because the parameters are strictly selected, one of the constituent factors, especially if it is plasma However, if the film becomes indeterminate, the resulting film will be severely adversely affected and cannot be used as a product. As for the equipment, as mentioned above, strict parameter selection is required, so the structure naturally becomes complex, and if the scale and type of equipment changes, the design must be able to accommodate the carefully selected parameters. Must. For these reasons, although the plasma CVD method is considered to be the most suitable method at present, it is difficult to achieve the desired a-8
Mass production of iOj requires a large capital investment in equipment, and the process control items for mass production are many and complex, the process control tolerance is narrow, and equipment adjustments are delicate. As a result, there are problems such as making the product considerably more expensive.

On the other hand, the various devices mentioned above are becoming more diverse, and the element materials for them, that is, the elements that satisfy all the requirements such as the various characteristics mentioned above, and are suitable for the target object and use.
In some cases, there is a social demand for a constant supply of stable A-810 membrane products at low cost, and the development of methods and equipment to meet this demand is necessary. It's a much needed situation.

These also apply to other element members such as silicon nitride films and silicon carbide films.

[Purpose of the invention]

The present invention solves the above-mentioned problems and satisfies the above-mentioned requirements regarding conventional element members used in semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, imaging devices, and methods for manufacturing the same. The purpose is to satisfy the following.

In other words, the main object of the present invention is to have electrical, optical, and photoconductive properties that are substantially always stable regardless of the usage environment, to have excellent light fatigue resistance, and to be able to withstand repeated use. To provide an improved a-8iO film resistor member which is uniform and homogeneous and does not cause deterioration and development even when used, has excellent durability and moisture resistance, and does not cause the problem of residual potential. It is in.

Another object 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 and homogeneous while making it suitable for increasing the area of the film. It is an object of the present invention to provide a novel method for manufacturing the above-mentioned improved a-8iO expanded element member, which can easily achieve improved productivity and integration into one product.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a film-forming oxygen-containing compound that chemically interacts with a compound containing silicon and -logon in a film-forming space for forming a deposited film on a substrate. By introducing active species generated from compounds and applying discharge energy to them to cause a chemical reaction,
This is achieved by forming a 8F film on the substrate.

The method of the present invention includes a compound containing silicon and nologen,
In the coexistence with active species generated from oxygen-containing compounds for film formation that chemically interact with the compound, chemical interactions are caused by applying discharge energy to these compounds. The method of the present invention enables film formation with lower discharge energy than conventional methods.
The deposited film formed is extremely unlikely to be adversely affected by etching effects or other abnormal discharge effects.

Moreover, the method of the present invention can be made into a more stable CVN method by arbitrarily controlling the atmospheric temperature of the film forming space and the substrate temperature as desired.

Furthermore, in the method of the present invention, in addition to discharge energy, light energy and/or thermal energy can be used in combination, if desired. Light energy can be irradiated to the entire substrate using an appropriate optical system, or can be irradiated only to desired parts in a selective and controlled manner.
The formation position, film thickness, etc. of the deposited film on the substrate can be easily controlled. Father, thermal energy converted from light energy can also be used as thermal energy.

One of the points that distinguishes the method of the present invention from conventional CVD methods is that it uses activated species that have been 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 the method of the present invention, a sanurium-containing compound, which is a raw material for forming a deposited film, is activated in an activation space to generate active species. Then, the generated active species are introduced from the activation space into the film forming space, and a deposited film is formed in the film forming space.

Therefore, the constituent elements of the active species constitute the components constituting the deposited film formed in the film-forming space. In the method of the present invention, the active species may be appropriately selected and used as desired. From the viewpoint of productivity and ease of handling, a material with a lifespan of 0.1 seconds or more is usually used, more preferably a material with a life of 1 second or more, and optimally a material with a life of 10 seconds or more.

-〇- Also, the compound containing silicon and -logon used in the method of the present invention is introduced into the film forming space, excited by the action of energy, and simultaneously introduced from the activation space to the film forming space as described above. It has the effect of promoting the formation of a deposited film by chemically interacting with the active species and, for example, imparting energy or causing a chemical reaction. Therefore, the constituents of the silicon- and halogen-containing compound may be the same as or different from the constituents of the deposited film that is formed.

It is preferable that the m-containing compound used in the method of the present invention is already in a gaseous state or is in a gaseous state before being introduced into the activation space. 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. Examples of the oxygen-containing compound include simple oxygen such as Ryusei (02) and ozone (03), as well as compounds having one or more constituent atoms of oxygen and atoms other than oxygen. -10- as atoms other than oxygen are hydrogen (H), halogua (X=F, CL, Br
Or sulfur (8), carbon (c), silicon (sl),
Examples include germanium (Ge), and in addition, almost any atom of an element belonging to each group of the Periodic Table can be used as long as it can be combined with oxygen.

Incidentally, for example, as a compound containing #io and H, H20,
Compounds containing 0 and 8 such as H2O2 include SO2, SO
Examples of oxides such as 3 and compounds containing 0 and C include Co,
Compounds containing 0 and 81, such as CO2 fathom oxides, include nosiloxanes such as nosiloxane (H6SiO8iH6), trisiloxane7 (HsSiO3i)120SiH5), (C!H3)2Eli(OCOCH3)2, CJ
Organoaptoxysilane such as Si(OCOCH3)5, (CH3)ssiOcHg, ((Jb)28i(OC
H3) 2, OH5Eli (OCH3) 5-etc. noalkylalkoxysilane, (C!Ex ) g810H, (
C)15)2(C2H5)SiO)1゜(C2H5)
2si (OH) 2-isoorganosilanols, etc., 0 and [
Examples of compounds containing Ge oxides, hydroxides, germanic acids, )13GeOGeHs, H5G
Examples include organic germanium compounds such as eOGeH20GeH5.

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

In the method of the present invention, silicon introduced into the film forming space and -
- As a compound containing rogene, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with -.logen atoms is used, and specifically, for example, 8
1uY2u+2 (u is an integer greater than or equal to 1, Y4F,
It is at least one selected from C1, Br, and Br. ) chain silicon halide, 8iyY
2y (v is an integer of 3 or more, Y has the above-mentioned meaning.

) Cyclic silicon halide, 81uHzYy
(u and Y have the above-mentioned meanings. x+y=Q!u or 2u+2), and the like can be mentioned.

Specifically, for example, SiF4, (Sil'i'2)5
, (siF2)6, (SiF2)4.5i2FIS,8
1sFa, SiHF3.8iH2F2.5iC24,
(SiC22)5, SiBr4, (81Br2)5
, E112Ct6.5i2Br6.5iHCt5.81
Examples include those that are in a gaseous state or can be easily gasified, such as HBrs, 5iHI3, and Si2CA5Fg.

Furthermore, in addition to the above-mentioned compound containing silicon and -logen, other silicon-containing compounds such as simple silicon,
Hydrogen, -・logen-containing compounds (e.g. F2 gas, ct2
Gas, gasified Br2, I2, etc.) can also be used in combination.

In the method of the present invention, in order to generate active species in the activation space, electric energy such as microwave, RF, low frequency, DC, thermal energy such as heater heating, infrared heating, etc. is used in consideration of each condition and device. , activation energy such as light energy can be used.

That is, active species can be generated by applying activation energy such as heat, light, or electric discharge to the above-mentioned oxygen-containing compound in an activation space.

In the method of the present invention, the amount ratio between the silicon and -logen-containing compound and the active species generated from the oxygen-containing compound between the film walls depends on the film forming conditions and the type of active species. It is determined as desired, but preferably 10:1 to 10:1.
A ratio of 1:10 (introduction flow rate ratio) is appropriate, and more preferably a ratio of 8:2 to 4:6.

In the method of the present invention, in addition to the oxygen-containing compound, hydrogen gas, -rogen compounds (such as HF2
gas, Ct2 gas, gasified Br2, I2 '4
), an inert gas such as helium, argon, or neon; silicon-containing compounds, carbon-containing compounds, germanium-containing compounds, etc. can also be introduced into the activation space as chemical substances for forming the deposited film. When using these multiple raw material gases, they can be mixed in advance and introduced into the activation space, or these chemical substances can be supplied individually from independent sources and introduced into the activation space. Alternatively, they can be introduced into individual activation spaces and activated individually.

As the silicon-containing compound that can be introduced into the activation space, silanes, siloxanes, etc. in which silicon is bonded with hydrogen%%T2, or hydrocarbon groups, etc. can be used. Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen electrons of the chain and cyclic silane compounds are replaced with -.logene atoms.

Specifically, for example, 81H4, Si2H6, Si, H
8,814H1a, 815Ht2.816B14 etc.
1pH2p+2 (p is an integer of 1 or more, preferably 1 to 15, more preferably 1 to 10) is a chain silane compound, BiJBiH (Sins) 81Es
, 5iBsBiH (SiH3) 8isHz, 812H5
SiH (SiHg) Si2E (5ipH2p+2 such as 5
(p has the above-mentioned meaning), a part or all of the water bulk atoms of these linear or branched chain silane compounds are replaced with -.rogen atoms. Compound, 5L5Hs, 514Ea, 8
1sH1o, 516H12, etc. 5iqH2q (q is 3
Above, preferably it is an integer of 5 to O. ), 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, some of the hydrogen atoms of the silane compounds exemplified above, or Examples of compounds in which all atoms are substituted with -.logen atoms include 8ihsF X81HsCt, 5iH3
51) HsXt such as Br, 5iHsl (X is a halogen atom, r is an integer of 1 or more, preferably 1 to 10, more preferably 6 to 7, s + t = 2r + 2 or 2)
It is r. ) -・logen-substituted linear or cyclic silane compounds, etc. These compounds are 1f! J may be used or two or more types may be used in combination.

The above-mentioned return-containing compounds introduced into the activation space include chain or cyclic saturated or unsaturated hydrocarbon compounds, carbon and hydrogen atoms, and silicon, -rogen,
It is preferable to use a gaseous compound or one that can be easily vaporized among an organic compound having one or more than 211 atomic groups such as sulfur, and an organosilicon compound having a hydrocarbon group as a constituent component.

Among these, examples of hydrocarbon compounds include carbon atoms of 1 to
5 saturated hydrocarbons, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylenic hydrocarbons having 2 to 4 carbon atoms, etc.
Methane (CH4) and ethane (0
2H6), propane (C3H8), n-butane (n-0
4H1o), pentane (05H12)% Ethylene hydrocarbons include ethylene (02H4), nolopyrene (c3H6), butene-1 (C4Ha),! Ten-2 (C4H8), isobutylene (04H8), pentene (CsHlo), acetylene hydrocarbons include acetylene (02H2), methylacetylene (C3
H4) and butin (04H4).

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 CL, Br, and I can be mentioned, and compounds in which hydrogen is substituted with y and ct are particularly effective.

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

Compounds used in the present invention as organosilicon compounds include organosilane, organohalogensilane,
etc. can be mentioned.

Organosilane and organohalogen silane each have the general formula; Rn5iH4-n, E]I]81X4-
m (however, P: alkyl group, aryol group, X: F.

CL, Br lI, n-1+ 2m 5+ 4, m
-11216'), and representative examples thereof include argylsilane/, arylsilane, alkylno)halogensilane, and arylhalogensilane/.

Specifically, as organochlorosilane, trichloromethylsilane cHs Si C
L5 dichlorodimethylsilane (CHs)2
sict2chlorotrimethylsilane (CHs
)2sicz trichloroethylsilane C2H
58iCtsnochlorodiethylsilane (C2
H5) 2sic2organochlorfluoroschicine is chlordifluoromethylthicine CH35iF
2Ct dichlorofluoromethylsilane, CH3S
, iFC/2 chlorofluoromethylsilane (CH
s) 2si Fct Chlorethylzofluorosilane
02H5SIF2Ct dichloroethylfluorosilane C2H581FC! t2Chlordifluorozolovylsilane C5H7SiF2CtDichlorofluoropropylsilane C3HpSIFC12I engineering as organosilane, Tetramethylsilane (CH3)4si engineeringfk)')l fkV Rough (Gb
)ssi(!2Hs trimethylpropylsilane
(CH!1)s81c3H7 triethylmethylsilane
CH3S1(C2H5)5tetraethylsilane (C2Hs)4siorganohydrogenosicin includes: Methylsilane CH35in3dimethylsilane (CB5)281H2
Trimethylsilane (CH3)3siH
Diethylsilane (02H5) 28
1H2 triethylsilane (02H5)
ssiH tripropylsilane (058
7) ssiE cosyphenylsilane (C
2Hs)2E]iH2organofluorosilane/as trifluoromethylsilane CH38iF5sofluorodimethylsilane (CHa)2siF2fluorotrimethylsilane (CB3)5siF ethyltrifluorosilane 02H581F3 noethylnofluorosilane (02H5)2SIF2
Triethylfluorosilane (02H5)581
F trifluoroglopyrsilane (05H7)SI
F5 organobromosilane is Bromotrimethylsilane (CH3)3siB
rNobromutmethyl7u7 (CH,5)2
Examples of organopolysilanes include SiBr2, and other organopolysilanes include hexamethylsilane
]2hexaprovirsocyanine r(CxH7)
5si]2 etc. can also be used.

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

Further, as the germanium-containing compound introduced into the activation space, an inorganic or organic germanium-containing compound to which germanium dihydrate, halogen, or hydrocarbon group is bonded can be used. For example, GeaHb (a
ltl An integer greater than or equal to 1, b=2a+2 or 2a. ) Chain or cyclic germanium hydride represented by
This germanium hydride polymer, a compound in which some or all of the hydrogen atoms of the germanium hydride are replaced with halogen atoms, a compound in which some or all of the hydrogen atoms of the germanium hydride are substituted with, for example, an alkyl group, an aryl group, etc. Examples include organic germanium compounds such as compounds substituted with an organic group and optionally a rogen atom, and other germanium compounds.

Specifically, for example, GeH4, Ge2H6, Gem)
1B.

n-Ge4H+o, tert-Ge4H+o, Ge5
H6, Ge5H10, GeHsF, GeH3CA
, GeH2F2, H4Ge6F6, Go(CHs)4
, Ge(C2H5)4, Ge(c6Hs)4, Ge(C
B,)+F2, GeF2.

Examples include GeF4 and GeS.

These germanium-containing 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. As the impurity elements used, as n-type impurities,
° elements of group A of the periodic table, for example B, AL, Ga1
Preferred examples include In, '1', etc., and examples of n-type impurities include elements of group A of the periodic table, such as P,
As, Sb.

B1 etc. are mentioned as suitable ones, but especially B1Ga
, P, 8b, 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 deposited film forming conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to select Such compounds include PHs, P2H4, PF
'5, PF5, PCl3, Ashs, A8F5
, AsF5 , kScts , 8bH3, Sk+Fs
, BIHs, BF5, BCl3, BBrs, B
2H6, B4H10\B5H9, B5HH1EllHI
Q% B6H12, AlCl2, etc. can be mentioned.

Compounds containing impurity elements may be used alone or in combination.
You may use more than one species in combination.

The substance for introducing impurities may be introduced into the film forming space directly in a gaseous state, or mixed with the above-mentioned compound containing silicon and nitrogen, or may be activated in the activation space before forming the film. It may also be introduced into the space.

To activate the impurity-introducing substance, the above-mentioned activation energy for generating active species can be appropriately selected and employed. Active species (PN) generated by activating the impurity introducing substance are mixed with the active species in advance or introduced alone into the film forming space.

Next, the content of the method of the present invention will be explained using typical cases of an electrophotographic image forming member and a semiconductor device as specific examples.

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 image forming member, and includes an intermediate layer 12 provided as necessary on a support 11 for removing the photoconductive part, and It has a layered structure composed of a photosensitive layer 16.

In manufacturing the photoconductive member 10, the intermediate layer 12 or/and
and photosensitive layer 16 can be created by the method of the present invention. Furthermore, the photoconductive member 10 may include a protective layer provided to chemically and physically protect the surface of the photosensitive layer 16, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical withstand pressure. If so, these layers 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 include tfNicr, stainless steel, ALlCr, M
o, Au, Ir, Nb, 'ra, v,'r1
, pt.

Examples include metals such as Pd and alloys thereof.

Examples of the electrically insulating support include polyester, polyethylene, polycarbonate, cellulose acetate,
Examples include films or sheets of synthetic resins such as polyzolopyrene, polyvinyl chloride, tetravinylidene chloride, polystyrene, and polyamide, glass, ceramics, and paper. 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 NiCr.

AL % Cr % MO-, Au, Ir % k3
b-,Ta,v,'r1,pt.

pa, In2O3,5n02, ITO(In20s
+8I]02), etc., or if it is a synthetic resin film such as a polyester film, NiCr, At, Ag, Pb, Z
n, Ni, Au, Or, Mo, Ir, Nb, T
The surface is treated with a metal such as a, V, Ti, or Pt by true wall evaporation, electron beam evaporation, S-9 sintering, or the like, or laminated with the metal, and the surface thereof is subjected to conductive treatment. The shape of the support can be any shape, such as a cylinder, a belt, or a plate. Although its shape can be appropriately determined depending on the luminance desired for the intended use, for example, if the light guide IS material 10 shown in FIG. 1 is used as an image forming member for electrophotography, in the case of continuous high-speed copying, It is desirable to have an endless belt shape or a cylindrical shape.

The intermediate layer 12 effectively prevents carriers from flowing into the photosensitive layer 13 from the support 11 side, for example, and prevents the photosensitive layer 13 from being generated in the photosensitive layer 13 by irradiation with electromagnetic waves and moving toward the support 11 side. Support 1 from the side of the photosensitive layer 16 of the carrier
It has the function of easily allowing passage to the 1 side.

This intermediate layer 12, for example, has silicon atoms as its base material,
Amorphous silicon containing hydrogen (LH) and/or -halogen (X) and oxygen (0) as constituent atoms if necessary [hereinafter referred to as la-81(H,X,'O)J. ], and also contains a p-type impurity such as boron (B) or an n-type impurity such as phosphorus (P) as a substance that controls electrical conductivity.

In the method of the present invention, B contained in the intermediate layer 12
, P and other substances that control conductivity are preferably &@,
I X 10-5~5 X 10' atomicpp
m.

More preferably 610.5 to I x 10' atomic
ppm, optimally 1-5 X 103 atomic
It is desirable to set it to ppm.

When the components of the intermediate layer 12 and the components of the photosensitive layer 13 are similar or the same, the formation of the intermediate layer 12 can be successively followed by the formation of the photosensitive layer 16.

In that case, active species generated from a compound containing silicon and halogen as a raw material for forming the intermediate layer and a gaseous T oxygen-containing compound that is a chemical substance for film formation introduced into the activation space. , or optionally a silicon-containing compound,
active species generated from a carbon-containing compound, a germanium-containing compound, hydrogen, a halogen-containing compound, an inert gas, and a gas of a compound containing an impurity element as a component, respectively, or by mixing them as appropriate. It is introduced into the film forming space where the support 11 is installed. An intermediate layer 12 is formed on the support 11 by applying discharge energy to the compound containing silicon and halogen and the active species.

The thickness of the intermediate layer 120 is preferably 3X10-3 to 10μ
, more preferably 4X10-3 to 8μ, optimally 5X10
-'~5μ is desirable.

The photosensitive layer 13 is composed of, for example, a-81 (HrX), and has both a charge generation function of generating photocarriers by laser irradiation and a charge transport function of transporting the charges.

The thickness of the photosensitive layer 130 is preferably 1 to 100 microns, more preferably 1 to 80 microns, and optimally 2 to 50 microns.

The photosensitive layer 13 is composed of non-doped f a-8i (H, (for example, n-type) may be included, or if the actual amount of the substance controlling the conduction properties contained in the intermediate layer 12 is large,
A substance that controls conductivity of the same polarity may be contained in a material that is one step smaller than that of the material.

The photosensitive layer 16 is formed by the method of the invention in the same manner as the intermediate layer 12.

That is, a compound containing silicon and -.logen, an oxygen-containing compound for film formation, or, if necessary, a silicon-containing compound, a carbon-containing compound, a germanium-containing compound, hydrogen, -
Active species generated from a compound containing a halide, an inert gas, or an impurity element as a component are introduced into the film forming space, and discharge energy is applied to the compound containing silicon and halogen and the active species to support them. A photosensitive layer 13 is formed on the intermediate layer 12 formed on the body 11.

FIG. 2 is a schematic diagram showing a typical example of a PIN type diode device using a deposited film produced by the method of the present invention.

In the figure, 21 is a base, 22 and 27 are thin film electrodes, 23 is a semiconductor layer, 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 24, 25, 26 are a-sBH+x
)+a-81(0,H,X), a-81Ge(0,
H, I can even put it in a tube.

As the base 21, a conductive material, a semiconductive material, or an electrically insulating material is used.

If the base body 21 is conductive, the thin film electrode 22 may be omitted. As a semiconductive substrate, for example, S
Semiconductors such as i, Ge1GaAs, ZnO, and Zn8 can be mentioned. The thin film electrodes 22.27 are, for example, NiCr.
, A1. , Or, Mo, Au, IrXNb,
Ta.

VlTi, Pt, Pa, In2O3,5n02, I
It can be obtained by providing a thin film of T(XIn203 +8n02) or the like on the substrate 21 by a process such as vacuum evaporation, electron beam evaporation, or snowballing. Electrodes 22, 27
The layer thickness is preferably 30 to 5 x 10 4 x, more preferably 10 2 to 5 x 10 6 x.

In order to make the film constituting the semiconductor layer n-type or p-type as necessary, a layer in which n-type impurity, p-type impurity, or both impurities are formed among impurity elements during layer formation. It is formed by controlling and doping the child inside.

When forming n-type, i-type, and p-type semiconductor layers, any one of the hanging layers or the entire layer can be formed by the method of the present invention.

That is, a compound containing silicon and rogen is introduced into the film forming space. Separately, a gas containing an oxygen-containing compound or a silicon-containing compound and/or a germanium-containing compound in a gaseous state, and a compound containing an inert gas and an impurity element as necessary, are activated with respective activation energies. is excited and decomposed to generate each active species, which are introduced separately or mixed as appropriate into the film forming space where the substrate 21 is installed. By applying discharge energy to the surrounding environment where the silicon- and halogen-containing compound and the active species coexist, which have been introduced into the film-forming space,
causing a chemical interaction between the silicon and the active species and the compound containing chlorine introduced into the film-forming space, or
This is accelerated or amplified to form a deposited film on the substrate 21. The layer thickness of the n-type and p-type semiconductor layers is preferably 102 to 1041°, more preferably 5x102 to 2x
A range of 103X is desirable.

Further, the layer thickness of the i-type semiconductor layer is preferably 5×102
~104X, more preferably 103-104X (1)
Range is preferred.

In addition to this example, the method of the present invention can also be applied to 5to2 ie edge films constituting semiconductor devices such as IC1 transistors, diodes, and photom conversion elements, and partially oxidized S1
It is suitable for forming films, etc., and the distribution of the Km element concentration in the layer thickness direction can be controlled by controlling the timing and amount of introduction of active species generated from oxygen-containing compounds into the film-forming space. An S1 film can be formed. Alternatively, in addition to the oxygen-containing compound, a silicon-containing compound, a germanium-containing compound, and a carbon-containing compound are appropriately combined as necessary to form a structure in which the bond between 0 and these Si, Gθ, and C atoms is used as a structural unit. It is also possible to form membrane bodies with specific properties.

“Examples” The present invention will be explained in more detail according to examples below.
The present invention is not limited to these.

Example 1 Using the apparatus shown in Figure 3, 1 was carried out by the following operations.
type, p-type, and n-type oxygen-containing amorphous deposited films were formed.

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

104 C is a heater for heating the substrate, and is supplied with electricity via a conductive wire 105 to generate heat.

The substrate heating temperature is not particularly limited, but when the substrate is heated in the process of the present invention, the substrate heating temperature is preferably 60-450°C, more preferably 50-350°C.
The temperature is preferably 50°C.

106 to 109 are gas supply sources, which are oxygen-containing compounds, hydrogen, halogen compounds, inert gases, silicon-containing compounds, carbon-containing compounds, germanium-containing compounds, and compounds containing impurity elements as components. Provided according to the number. If these gases are liquid in their standard state, an appropriate vaporizer is provided.

σ with a added to the symbols of gas supply sources 106 to 109 in the figure
Fly branch pipes, b marked flow meters, C marked pressure gauges that measure the pressure on the high pressure side of each flow meter, d or e marked valves to adjust the flow rate of each gas. It is. 1
23 is an activation chamber for generating active species, and around the activation chamber 1260 is a microwave plasma generator 122 that generates activation energy for generating active species.
will be established. Raw material gas for generating active species, which is supplied through the gas introduction pipe 110, is activated in the activation chamber, and the generated active species are introduced into the film forming chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge.

In the figure, 112 is a source of a compound containing silicon and halogen, and a to θ attached to the reference numeral 112 are the aforementioned 10
The same items as those given with reference numerals 6 to 109 are shown.

A compound containing silicon and halogen is introduced into the film forming chamber 101 via an introduction pipe 113.

Reference numeral 117 denotes a discharge energy generating device, including a matching dPx 117as cathode electrode 1 for high frequency introduction;
17b etc.

The discharge energy from the discharge energy generating device 117 acts on the active species and compounds containing silicon and halogen flowing in the directions of arrows 116 and 119, and the silicon and...
A chemical reaction between the halogen-containing compound and the active species causes an oxygen-containing amonophore deposited film to be formed on the entire substrate 1D3 or on a desired portion.

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

First, polyethylene terephthalate film substrate 106
was placed on the support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device (not shown) to reduce the pressure to about 10-6 Torr. At the substrate temperature shown in Table 1, using the gas supply source 106, 02 gas (diluted to 10 vol with He) 150S
CCM, or this and PE glaze gas or 82 days 6 gas (both 1000 ppm *diluted with raw gas) 40 SCCM
A mixed gas was introduced into the activation chamber 126 via the gas introduction pipe 110. 02 introduced into the active room 123
A gas etc. is activated by a microwave plasma generator @ 122 to become activated oxygen etc., and then passed through an inlet pipe 124.
Activated oxygen and the like were introduced into the film forming chamber 101.

On the other hand, 5ift'4 gas was introduced into the film forming chamber 101 from the supply source 112 through the introduction pipe 113.

While maintaining the pressure in the film forming chamber ioiF)3 at 0.4 Tarr, plasma was applied from the discharge device 117 to form a non-doped or doped oxygen-containing amorphous deposited film (film thickness 700X).

The film formation rate was 12×/880.

Next, each sample obtained was placed in a vapor deposition tank and the vacuum degree was 10-
Comb-shaped At gigantic electrode (gap length 2) at 5 Torr
After fc, the dark current was measured at a voltage of 10 V, the dark conductivity σd was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.71c.

Examples 2 to 4 As raw material gas for active species generation, 02 gas (10
diluted in vol tlk) and each h 812F6 gas, G
Oxygen-containing amorphous deposition was carried out in the same manner as in Example 1, except that e2H4 gas and C2) (6 gas) were introduced into the activation chamber to generate active species, and then introduced into the film forming chamber 101. A film was formed.The dark conductivity was measured and the results are shown in Table 1.

From Table 1, it was found that according to the method of the present invention, an oxygen-containing amorphous deposited film with excellent electrical properties and sufficient doping could be obtained.

Examples 5 to 8 Taniya H3810SIH5 gas, Hs instead of 02 gas
An oxygen-containing amorphous deposited film was formed in the same manner as in Example 1 except that GeOGeHs gas, CO2 gas, or OF2 gas was used.

The oxygen-containing amorphous deposited film thus obtained had excellent electrical properties and was sufficiently doped.

Example 9 Using the device shown in Figure 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, 202 is a compound supply source containing silicon and hydrogen, 206 is an introduction pipe, and 207
7-ter, 208 heater, 209, 210
&! A blowout pipe, 211 indicates a troublesome cylinder, and 212 indicates an exhaust pulp. Further, 216 to 216 are raw material gas supply sources similar to 106 to 109 in FIG.
7-1 is a gas introduction pipe.

An M cylinder-shaped substrate 211 is suspended in the film forming chamber 201,
A heating heater 208 is provided inside the motor 207.
It can be rotated by I'll do it like that. Reference numeral 21B denotes a discharge energy generator, which includes a matching box 21aa and a cathode electrode 218b for introducing N high frequency.

First, 81F4 gas was introduced from the supply source 202 into the film forming chamber 201 through the introduction pipe 206.

On the other hand, 81F4 gas, 02 gas, and B2 gas were introduced into the film forming space 219 through the introduction pipe 217-1. The introduced 81F4 gas, 02 gas, and B2 gas are subjected to an activation process such as plasma conversion by a microwave plasma generator 220 in an activation chamber 219 to form fluoride active species, oxygen active species, and activated water volume. and introduced into the film forming chamber 201 through the introduction pipe 217-2.

At this time, pH5, B2H? A first class impurity gas was also introduced into the activation chamber 219 for activation. Film forming chamber 2
Plasma was applied from the discharge device 21B while maintaining the atmospheric pressure inside the chamber at 1.0 Torr K.

The At cylindrical base 211 is heated to 200°C by the heater 20.
8, heated, held, and rotated. The exhaust gas was exhausted by MIIing the opening of the exhaust valve 212 as appropriate.

Although the photosensitive layer 13 was formed in this manner, in order to form the intermediate M12, the intermediate layer 12 is formed prior to the formation of the photosensitive layer. That is, from the introduction pipe 217-1, Sil? 4 gas,
02 gas (81F4:02=1:1O-5), He
gas and B2H6 gas (in volume ikgII, B2H6 is a2
An intermediate layer having a thickness of 2000X was formed in the same manner as photosensitive layer 1'5h except that a mixed gas of 2000X was introduced.

Comparative Example 1 Using each gas of 81F4 gas, 02 gas, He gas, and B2H6 gas, the film forming chamber 201 is equipped with a 1356 MHz high frequency device, and the first film is formed by a general plasma CVD method.
A drum-shaped electrophotographic image forming member having the layer structure shown in the figure was formed.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 9 and Comparative Example 1.

Example 10 A PIN type diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 6 using O2 gas as the oxygen-containing compound.

First, a polyethylene naphthalate film 21 on which a 1000X ITO film 22 was vapor-deposited was placed on a support stand, and a 10-
After reducing the pressure to 6 Torr, as in Example 1,
SiF4 gas was introduced into the film forming chamber 101 from 13. Further, each of Eii3H6 gas and PHs gas was introduced into the activation chamber 126 for activation.

Next, this activated gas was introduced into the film forming chamber 101 via the introduction pipe 124. The pressure inside the film forming chamber is 5
Torr and while maintaining the substrate temperature at 210° C., a nolasma was applied from the discharge device 117 to form an n-type a-8i (H,X) film 24 (film thickness 700×) doped with P.

Next, except for stopping the introduction of PH3 gas, the n-type a-81
Non-doped a-8 was prepared using the same method as the (H,X) film.
An i(H,X) film 25 (thickness: 5000×) was formed.

Next, n except that 02 gas and B2H6 gas (100 [IT] pm hydrogen gas dilution) were used together with 815H6 gas.
p-type oxygen-containing a- doped with B in the same way as the type
An 8i (H,X) film 26 (thickness: 700X) was formed. Further, on this p-type layer, a film of 1000× thickness is deposited by vacuum evaporation.
An L electrode 27 was formed to obtain a PIN diode.

The IV characteristics of the diode collector thus obtained (area: 1 cIIL2) 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 a strong light irradiation Ji AMI (approximately 100 mW/cIn2), the conversion efficiency is >5%, the open circuit voltage is 0.92V, and the short circuit current is 1a4II]A/cIn2. Obtained.

Examples 11 to 16 H3S10S was used as the acid compound instead of 02 gas.
A PIN type diode similar to that in Example 6 was manufactured in the same manner as in Example 6 except that eH5 gas, CO2 gas, or OF2 gas (iH3 gas, H4Ge0C) was used. This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 6.

=44= From Table 3, the method of the present invention shows that a-81(H,X,O) has better optical and electrical properties than the conventional one.
It has been found that a PIN type diode can be obtained.

[Summary of effects 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, the film quality is improved and the film quality is made more uniform, and it is advantageous for making the film into a large four-layer structure, improving the physiological properties of the film and increasing the production of 'jit'. can be easily achieved. Furthermore, the film can be formed even on a substrate with poor heat resistance. The low-temperature treatment has the effect of shortening the process.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. Second
The figure is a schematic diagram for explaining a configuration example of a PIN diode manufactured using the method of the present invention. FIG. 5 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. DESCRIPTION OF SYMBOLS 10... Electrophotographic image forming member, 11... Support, 12... Intermediate layer, 16... Photosensitive layer, 21... Substrate, 22.27... Thin film electrode, 24...・N-type semiconductor layer, 25...1-type semiconductor layer, 26...p-type semiconductor layer, 2B...conducting wire, 101.201...film formation chamber, 112.202...silicon and halogen Compound source containing, 123.219...activation chamber, 106.107, 108, 109, 213, 214, 2
15゜216...Gas supply source, 103.211...Substrate, 11, 7, 218...Discharge energy generation device, 1
02...Substrate support stand, 104, 208...Heater for heating the substrate, 105.
・Conductor, 110.113,124,206.217-1,217
-2...Introduction pipe, 111...Pressure needle, 120.212...Exhaust pulp, 121...Exhaust pipe, 122.220...Activation energy generator, 20
5', 210...Blowout pipe, 207...Motor.

Claims (1)

[Claims] A compound containing silicon and halogen and an active species generated from an oxygen-containing compound for film formation that chemically interacts with the compound are introduced into a film formation space for forming a deposited film on a substrate. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by applying discharge energy to these materials to cause a chemical reaction.