JPS61245519A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To stably form a deposited film excellent in electric, optic and photoconductive characteristics by a method wherein an active seed activated beforehand in an activating space and a compound containing Ge and halogen are supplied to a film-forming chamber and an optical energy is applied thereto to make them react chemically with each other. CONSTITUTION:A compound containing Ge, halogen, etc. are supplied from gas supply sources 106-109 to an activation chamber 123, and an active seed is produced therefrom by the operation of a microwave plasma generating unit 122 and then supplied to a film-forming chamber 101 through an introduction pipe 110. Meanwhile, a compound containing Ge and halogen is supplied from a supply source 112 to the film-forming chamber 101 through an introduction pipe 113. When a light from an optical energy generating unit 117 comprising a mercury-vapor lamp, etc. is applied to the compound containing Ge and halogen and the active seed, the compound containing Ge and halogen and the active seed which are irradiated react with each other, and thus a deposited film is formed on the whole or in a desired part of a substrate 103.

Description

Detailed description of the invention [Technical field to which the invention pertains] The present invention relates to a deposited film containing germanium, particularly a functional film, particularly a semiconductor device, a photosensitive device for electrophotography, a line sensor for image input, and an imaging device. ,
The present invention relates to a method for forming a deposited film containing amorphous or crystalline germanium for use in photovoltaic devices and the like.

[Description of prior art]

Conventionally, several types of amorphous germanium (hereinafter simply referred to as "a-Gθ") have been used as element materials for semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, imaging devices, photovoltaic devices, etc. ) membranes have been proposed, some of which have been put into practical use.

Then, along with the a-Ge film, they are a-σθ-
Several methods have been proposed for forming ``, including vacuum evaporation, ion silating, so-called CVD, plasma CVD, and photo-CVD, among which plasma CVD is considered the most suitable for practical use. and is widely used in general.

By the way, conventional a-Ge films, such as those obtained by plasma CVD, have excellent properties and are considered to be somewhat satisfactory, but even so, there are certain requirements required for the establishment of a reliable product. Satisfies all aspects of electrical, optical, photoconductive properties, fatigue resistance for repeated use, use environment properties, stability over time and durability, and homogeneity; -9= There is still a long way to go to solve the problem.

The reason for this is that the desired a-Ge film cannot be obtained by a simple layer deposition operation, not to mention the materials used, and the particular process operations require skilled ingenuity. However, it is thick.

Incidentally, for example, in the case of the so-called CVD method, after diluting the Ge-based gas material, so-called impurities are mixed, and then 50%
Since thermal decomposition occurs at high temperatures of 0 to 650°C, precise process operations and control are required to form the desired a-Ge film, and the equipment becomes complicated and costs are considerably high. However, in such a situation, it is extremely difficult to regularly obtain a homogeneous a-Gθ film product having the desired characteristics as described above, and therefore it is difficult to employ it on an industrial scale.

However, even with the plasma CVD method, which is widely used as the optimal method, there are still some problems in process operation and 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, by taking the O parameters of the interrelationships among the substrate temperature, the flow rate and flow rate ratio of the introduced gas, the pressure during layer formation, the high frequency power, the electrode structure, the structure of the reaction vessel, the exhaust speed, and the plasma generation method. As you can see, there are already many .-- and .-. ram meters, and in addition to these, there are also .-. ram. And strictly selected. Since it is a Q-laminator, one of its components, especially plasma, becomes unstable and the film formed will be severely adversely affected and cannot be used as a product. becomes. As for the equipment, as mentioned above, strict selection of Q parameters is required, so the structure naturally becomes complicated, and the equipment size and
If the type changes, it must be designed to be compatible with each individually selected Nomura meter. For these reasons, although the plasma CVD method is considered to be the most suitable method at present, as mentioned above, a large amount of equipment investment is required in order to mass produce the desired a-Ge film. However, the process control items required for mass production are many and complex, and the allowable range for process control is narrow.
Furthermore, since the adjustment of the equipment is delicate, there is a problem that the product ends up being expensive to manufacture.

On the other hand, the various devices mentioned above have become diversified, and in other words, element materials 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-Ge film products at low cost, which are large-area products, and it is necessary to develop methods and equipment that meet this demand. There are situations where it is desperately needed.

These also apply to other element members such as germanium nitride films, germanium carbide films, and germanium oxide films.

[Purpose of the invention]

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

That is, 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. It is an object of the present invention to provide an improved a-Ge film element member which is uniform and homogeneous and does not cause any deterioration phenomenon even under the conditions, has excellent durability and moisture resistance, and does not cause the problem of residual potential.

Another object of the present invention is to improve the properties, film formation speed, and reproducibility of the film formed, and to make the film quality uniform and homogeneous, while also being suitable for large-area films and improving film productivity. The above-mentioned improved a-G which can be easily improved and mass-produced
The object of the present invention is to provide a new method of manufacturing an e-membrane element member.

[Structure of the invention]

The above-mentioned object of the present invention is to provide a germanium-containing film-forming material that chemically interacts with a compound containing germanium and a nitrogenous compound in a film-forming space for forming a deposited film on a substrate. This is achieved by forming a deposited film on the substrate by introducing active species generated from a compound and irradiating them with light energy to cause a chemical reaction.

The method of the present invention enables active species generated from a compound containing germanium and nitrogen and a germanium-containing compound for film formation to chemically interact with the compound to be produced without generating plasma. By applying light energy to these in the coexistence of these, a desired deposited film is formed by causing, or further promoting and amplifying, chemical interactions between them. In the method of the present invention, the deposited film formed is not adversely affected by etching effects or other adverse effects such as abnormal discharge effects.

Furthermore, the method of the present invention allows for a more stable CVD method by arbitrarily controlling the atmospheric temperature in the film forming space and the substrate temperature as desired.

Furthermore, in the method of the present invention, excitation energy is applied uniformly or selectively to each active species that has reached the vicinity of the substrate for film formation, but if light energy is used, an appropriate optical system can be applied. It is possible to form a deposited film by irradiating the entire substrate using the irradiation method, or it is possible to form a deposited film partially by irradiating only the desired area in a selective and controlled manner. It is advantageously used because it has the convenience of being able to form a deposited film by irradiating only a predetermined graphical portion.

One of the points that distinguishes the method of the present invention from 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 the method of the present invention, a germanium-containing compound serving as 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, active species are selected and used as desired, and from the viewpoint of productivity and ease of handling, those with a lifetime of 0.1 seconds or more are usually used, but more are used. Preferably 1 second or more, optimally 1 second
It is desirable to use a time period of 0 seconds or more.

Further, the compound containing germanium and halogen used in the method of the present invention is introduced into the film forming space, excited by irradiation with light energy, and the above-mentioned active species that are simultaneously introduced from the activation space to the film forming space. By causing a chemical interaction with the substance, for example, imparting energy or causing a chemical reaction, it exerts an effect in the system that promotes the formation of a deposited film. Therefore, the constituent elements of the compound containing germanium and...logene may be the same as the constituent elements of the deposited film that is formed, or they may still be different.

It is preferable that the germanium-containing compound for forming a deposited film 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.

As the germanium-containing compound, an inorganic or organic germanium-containing compound in which hydrogen, halogen, or a hydrocarbon group, etc. are bonded to germanium can be used, for example, GeaHl) (a is an integer of 1 or more -, b = 2a +
2 or 2a. ) Chain or cyclic germanium hydride, a polymer of this germanium hydride,
A compound in which some or all of the hydrogen atoms of the germanium hydride are substituted with hydrogen atoms, a compound in which some or all of the hydrogen atoms of the germanium hydride are replaced with, for example, an alkyl group,
Examples include organic groups such as an aryl group r, and organic germanium compounds such as compounds substituted with a halogen atom if desired.

Specifically, for example, GeH4, Ge2H6, Ge3H8, n-Ge, Hlo
, tart-()e4I(10°Ge3H6,Ge5
H10, GeH3F, GeHBr3. GeH2F2
．． H6Ge6F6゜Ge(CH3)4, Ge(C
2H5)4, Ge(C6H5), , Ge(CH
3) 2F2.

CH3GeH3, (CH3)2GeH2, (CH3)3
Examples thereof include GeH, (C3H5)2GeH2, and the like.

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

In the method of the present invention, the germanium and rogen-containing compound introduced into the film forming space is, for example, a compound in which some or all of the hydrogen atoms of a chain or cyclic germanium hydride compound are replaced with rogen atoms. Specifically, for example, G"uY2u+2 (u is an integer of 1 or more, YijF.

Ct, Br and ■. ), a chain germanium halide represented by GeVY2V (V is an integer of 3 or more, Y has the meaning given above), a cyclic kermanium halide represented by GeuHxYy (u and Y have the meaning given above.x- 1-y=2u or 2u+2), and the like.

Specifically, for example, GeF4. (GeF2)5. (
GeF2)6゜(GeF2),, Ge2F6. Ge
3F8. GeHBr3. GeH2F2. GeCt
,.

(GeC,/,2)5. GeBr, , (GeBr
2)5. Ge2Cz6. Ge2Br6゜Ge2Cz
6. GeHBr3. GeHL3. Ge2C73F
Examples include those in a gaseous state or those that can be easily gasified, such as '3.

Further, in the method of the present invention, in addition to the compound containing germanium and a halogen, a compound containing silicon and a halogen and/or a compound containing carbon and a halogen can be used in combination.

As this compound containing silicon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound are replaced with halogen atoms can be used. Specifically, for example, 51uY2u+2 (u is 1 or more, Y is F, (4°13r and king) chain-like silicon rogenide, 5iyY2y (V is an integer of 3 or more, Y has the above meaning) Cyclic silicon halide, 5iuHzYy (u and Y have the above meanings. x+y=2u or 2u+2)
Examples include chain or cyclic compounds shown in the following.

Specifically, for example, SiF, (SiF2)5. (
Sin2) 6° (Sin2), Si2F6. Si
3F8. SiHF3.5iH3F2.5ict.

(SiCz2)5. EIiBr, , (SiBr2)5.
si, 2cm, 8i2Br6゜EliHCt3.5i
Examples include those that are in a gaseous state or can be easily gasified, such as HBr3, SiH 3.51aC13F, and the like.

These silicon-containing compounds may be used alone or in combination.
You may use more than one species in combination.

However, as compounds containing carbon and halogen, for example, compounds in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound are replaced with halogen atoms can be used,
Specifically, for example, a chain halogenated carbon represented by CuY2u+2 (u is an integer of 1 or more, Y is at least one element selected from F, CL, Br, and ■), CVY2V Cyclic silicon halide represented by (V is an integer of 3 or more, Y has the above-mentioned meaning), C
uHxYy (u and Y have the above meanings. X+y=
2u or 2u+2. ), and the like.

Specifically, for example, CF4. (CF2)5. (CF
2) 6° (CF2), C,, F6. C3F8.
CHF3. CH3F2. CCmu+ (CCti)3
.

CB'4+ (CBr2)51 c, c, /4. C2
Br6. cacz3. CHBr3゜CH 3. C2
Examples include those in a gaseous state or easily gasifiable, such as Ct3F3.

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

In addition to the above-mentioned compound containing germanium and halogen, in the method of the present invention, if necessary, a germanium compound such as germanium alone, hydrogen, a halogen compound (for example, F2 gas, Ct2F2 gasified Br2,
12 etc.) etc. can 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, taking into consideration each condition and device. , light energy, or any other activation energy can be used.

In the method of the present invention, the ratio between the amount of active species generated from the germanium-containing compound, which is a raw material for forming a deposited film, and the amount of the compound containing germanium and halogen, which is introduced into the film-forming space, is It is determined as desired depending on the conditions, the type of active species, etc., but is preferably 10:1 to 1:1.
It is appropriate that the ratio be 0 (introduction flow rate ratio), and more preferably 8:2 to 4:6.

In the method of the present invention, in addition to the germanium-containing compounds described above, silicon-containing compounds, carbon-containing compounds, hydrogen gas, halogen compounds (for example, F2 gas, Ct2F2 gasified Br2゜2, etc.) can be used, and an inert gas such as helium, argon, neon, etc. can also be introduced into the activation space. When using multiple film-forming chemicals, they can be mixed in advance and introduced into the activation space in a gaseous state, or each of these film-forming chemicals can be supplied from independent sources. They can be supplied individually and introduced into the activation space, or they can be introduced into independent activation spaces and activated individually.

As the silicon-containing compound that serves as a raw material for forming a deposited film, silanes and halogenated silanes in which silicon is bonded with hydrogen, halogen, or a hydrocarbon group, etc. can be used. especially linear and cyclic silane compounds,
Compounds in which part or all of the hydrogen atoms of the chain-like and cyclic silane compounds are replaced with halogen atoms are suitable.

Specifically, for example, SiH4, Si2H6, EIi3
HB.

514H10, 515H12, 516H] 4 etc. 81p
A linear silane compound represented by H2p+2 (p is an integer of 1 or more, preferably 1 to 15, more preferably 1 to 10), 5iH3SiH(SiH3)SiH3, 5i
H3SiH(SiH3)Si3H,.

5i2H5SiH (SiH3)Si, 5ipH such as H5
Chain silane compounds having branches represented by zp+a (p has the above-mentioned meaning), some or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with... rogene atoms. compound, 5i3H6°Si,
81qH2q such as H8, 5i5H1o, 5i6H12, etc.
(q is an integer of 3 or more, preferably 3 to 6.)
A cyclic silane compound represented by, 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 or all of the hydrogen atoms of the silane compounds exemplified above. Examples of compounds in which halogen atoms are substituted include SiH3F, 6tiH3(4
, 5iH3Br, 8irHsXt such as 5in3 engineering (
X is a halogen atom, r is 1 or more, preferably 1 to 10,
More preferably, it is an integer from 3 to '7, S+t-2r+2 or 2r. ) and halogen-substituted linear or cyclic silane compounds. These compounds may be used alone or in combination of two or more.

The carbon-containing compounds used as raw materials for forming the deposited film include chain or cyclic saturated or unsaturated hydrocarbon compounds;
Among organic compounds whose main constituent atoms are carbon and hydrogen and one or more constituent atoms such as silicon, halogen, and sulfur, and organosilicon compounds whose constituent constituents are hydrocarbon groups, gaseous It is preferable to use something that can be easily vaporized.

Among these, examples of hydrocarbon compounds include carbon atoms of 1 to
Examples of saturated hydrocarbons include methane (CH3), ethane (C2
H6), Zolonon (C3H8), n-butane (nC
4H10), Omethane (C5H12), ethylene hydrocarbons include ethylene (C2H4), propylene (C5H12),
3H6), butene-1 (C4Hs), butene-2 (
C4H8), inbutylene (C4H8), pentene (C
3HIO), acetylene hydrocarbons include acetylene (C, H2), methylacetylene (C3H4), butyne (C4H6), and the like.

As the halogen-substituted hydrocarbon compound, at least one of the hydrogens that are constituents of the hydrocarbon compound described above is F,
Compounds in which hydrogen is substituted with CL, Br, or ■ are listed below, and compounds in which hydrogen is substituted with F or CL are particularly effective.

The hydrogen substituted 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 a general formula: % formula % (However, R: alkyl group, aryl group, X: F.

(4, Br, engineering, n = 1.2.3.4, m = 1.2. It is a compound represented by the formula: alkylsilane, silane, alkylhalogensilane, arylhalogensilane. can be mentioned.

Specifically, the organochlorosilane includes trichloromethylsilane CH35iC,
43 dichlorodimethylsilane (CH3)
2SiC42 chlorotrimethylsilane (
CH3)3Si(4trichloroethylsilane
C2H55iC43 dichlorodiethylsilane
(C2H5)2 S i CL2 Organochlorofluorosilane includes Chlordifluoromethylsilane CH35iF2CtDichlorofluoromethylsilane CH35iFCz2Chlorfluorodimethylsilane (CH3)25iFC7 Chlorethyldifluorosilane (C2H5)SiF2C
,/.

Dichloroethylfluorosilane C3H3SiF
Cz2 chlordifluorozolopylsilane C3H7
5IF2Ct dichlorofluoropropylsilane C
3H,7SiFC72 organosilane includes tetramethylsilane (CH3), S
iEthyltrimethylsilane (CH3)3
SiC2H5 trimethylzolopylsilane (
CH3)3SIC3H7 triethylmethylsilane
CH35i(C2H5)r5tetraethylsilane (CaHa)4Si organohydrogenosilane includes methylsilane CH35iH3
Dimethylsilane (CH3)2
S I H2 trimethylsilane (
CH3)3SIH diethylsilane
(C2H5)2 S iH2 triethylsilane
(C2H5)3SIH tripropylsilane (C3H7)3SiH diphenylsilane (C6H5)2SIH2 Organofluorosilane includes trifluoromethylsilane CH35iF3
Difluorodimethylsilane (CH3)2S
iF2 fluorotrimethylsilane (0%)
, stt ethyltrifluorosilane C2H
55iF3 diethyldifluorosilane (C
2H6) 2SiF2 triethylfluorosilane
(C2H5)3SiF trifluoropropylsilane (03N(7)SiF3 organobromosilane is bromotrimethylsilane (CH3)3E
liBrdibromdimethylsilane (CH
3) 25iBr2, etc., and other organopolysilanes include hexamethyldisilane [(CH3)3
B 1] As the 2-organodisilane, hexamethyldisilane C(CH3)3
Si]2hexazolobyldisilane [(C
sH7) ssi:h etc. can also be used.

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

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, as p-type impurities, elements of group A of the periodic table, such as B, A, /=, Ga, and
Preferred examples include n, 'rz, etc., and examples of n-type impurities include elements of group A of the periodic table, such as P and As.
, Sb, Bi, etc. are mentioned as suitable ones,
Particularly suitable are B, Ga, P, Sb, etc. 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 deposited film forming conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to choose. Such compounds include PH3, P2H, PF
3. PF5゜P(43,ASH3,AsF3.As
F5. Ascz3. SbH3, SbF5゜SiH3
, B'F3. BCL, BBr3. B2H6,B4
nlO,B5Hg.

B5H□□, BAH□. + B6H12, AA (43, 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 can be introduced into the film forming space directly in a gaseous state, or mixed with the above-mentioned compound containing germanium and]. It can also be introduced into the film forming space later.

In order to activate the impurity-introducing substance, the above-mentioned activation energy for generating the above-mentioned active species can be appropriately selected and employed. The active species (PN) generated by activating the impurity introduction substance may be mixed with the above-mentioned active species in advance, or
Alternatively, it is 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 illustrating an example of the structure of a photoconductive member as a typical electrophotographic image forming member obtained by the present invention.

Photoconductive member 0 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 use as a photoconductive member; It has a layered structure composed of a photosensitive layer 13.

In manufacturing the photoconductive member 10, the intermediate layer 12 or/and
and photosensitive layer 13 can be created by the method of the present invention. Furthermore, the photoconductive member 10 has a protective layer provided to chemically and physically protect the surface of the photosensitive layer 130, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical withstand pressure. In some cases, these layers can also be created using the method of the invention.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel 1AtICr, MO,
Au, Brass, Nb, Ta, V, Ti, Pt,
Examples include metals such as Pa 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 polypropylene, polyvinyl chloride, polyvinylidene 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, NiCr, AI-
.

Cr, Mo, Au, Ir, Nb, Ta, V
, Ti, Pt, Pa.

Engineering n203, 8n02, ■TO (Engineering n203 +
conductive treatment by providing a thin film such as 5nO2),
Or if it is a synthetic resin film such as polyester film, NiCr, At, Ag, Pb, Zn, N
i, Au, Cr, Mo, Engr.

The surface is treated with a metal such as Nb, Ta, V, Ti, Pt, etc. by vacuum evaporation, electron beam evaporation, or snow-driving, 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 purpose and desire, for example, if the photoconductive member 10 of FIG. 1 is used as an electrophotographic image forming member, in the case of continuous high-speed copying, It is preferable 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 side of the support 11, for example, and also prevents photons generated in the photosensitive layer 13 and moving toward the support 11 by irradiation with electromagnetic waves. Support 1 from the photosensitive layer 13 side of the carrier
It has the function of easily allowing passage to the 1 side.

This intermediate layer 12 has germanium atoms as its base material, and optionally contains silicon (Eli), hydrogen (H), nitrogen (
It is composed of amorphous germanium (hereinafter referred to as [a-Ge(Si, H, It contains p-type impurities such as or n-type impurities such as phosphorus (P).

In the method of the present invention, B contained in the intermediate layer 12
, P etc., the amount of the substance controlling the conductivity is preferably ζI
X 10' atomic ppm, optimally 1--
Preferably, the amount is 5 x 10" atomic 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 and the formation of the photosensitive layer 13 can be performed continuously.

In that case, as raw materials for forming the intermediate layer, a compound containing germanium and a halogen, an active species generated from the gaseous germanium-containing compound, and, if necessary, a silicon-containing compound, a carbon-containing compound, hydrogen, and a halogen. A compound, an inert gas, and an active species generated from a compound gas containing an impurity element as a component are introduced into the film forming space where the support 11 is installed, either separately or mixed as necessary. Then, the intermediate layer 12 is formed on the support 11 by applying light energy to the atmosphere in which the introduced germanium- and halogen-containing compound and active species coexist.

The layer thickness of the intermediate layer 12 is preferably 3×10−”~
10μ, more preferably 4-X 10-3~8
μ, optimally 5×1 (1′ to 5μ is desirable).

The photosensitive layer 13 is made of amorphous silicon (hereinafter referred to as I a-f31 (H, X,
Ge ) It is written as l. ) or amorphous silicon germanium (hereinafter referred to as [a
It is written as -8iGe (H,X) 1. ) consists of
It has both a charge generation function of generating photocarriers by laser light irradiation and a charge transport function of transporting the charges.

The thickness of the photosensitive layer 13 is preferably 1 to 102 microns, more preferably 1 to 80 microns, and most preferably 2 to 50 microns because of the weight of the vehicle.

The photosensitive layer 13 is made of, for example, non-doped a-8i (H,
Ge) or a-8iGe (H, Alternatively, if the actual amount of the substance that controls the conductivity contained in the intermediate layer 12 is large, the amount may be much smaller than the amount that controls the conductivity of the same polarity. It may also contain a substance that does.

When forming the photosensitive layer J3 by the method of the present invention,
This is carried out in the same manner as in the case of forming the intermediate layer 12. That is, a compound containing germanium and nitrogen, a compound containing silicon and nitrogen, an active species generated from a germanium-containing compound for film formation, or an active species generated from a silicon-containing compound, as necessary. An intermediate layer is formed on the support by introducing an inert gas, a gas of a compound containing an impurity element as a component, etc. into the film forming space where the support 11 is installed, and applying discharge energy. A photosensitive layer 13 is formed on 12.

FIG. 2 shows a typical example of a PIN diode, Deinoguis, fabricated by the method of the present invention, using an a-8j, ()e (H,X) deposited film doped with an impurity element. It is a schematic diagram.

In the figure, 21 is a base, 22 and 27 are thin film electrodes, and 24 is a semiconductor film, including an n-type semiconductor layer 24, a 1-type semiconductor layer 5,
It is composed of a p-type semiconductor layer. A conductor is a conductive wire that is coupled to an external electrical circuit device.

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.

Examples of the semiconductive substrate include S], I Ge, G
Examples include semiconductors such as aAs, ZnO, and ZnS. The thin film electrodes 22.27 are made of, for example, Nj, Cr.

Al, Cr, Mo, Au, Tr, Nb, T
a, V, Ti, Pt, Pd.

InzOz r 5n02+ ITO (InzOa +
It can be obtained by forming a thin film such as 5nO2) on a substrate by a process such as vacuum evaporation, electron beam evaporation, or SQ tuttering.

The layer thickness of the electrode 22.27 is preferably 30-5×1
0's, more preferably 102 to 5 x 1.
03X is desirable.

In order to make the film forming the semiconductor layer composed of a-8iGe (H,X) n-type or p-type as necessary,
During layer formation, an n-type impurity, an n-type impurity, or both impurities among impurity elements are formed by 1-ping while controlling the amount in the layer to be formed.

Any one layer or all of the layers composed of n-type, 1-type, and p-type a-3iGe (H+X) can be formed by the method of the present invention. That is, a compound containing germanium and halogen or a compound containing silicon and halogen is introduced into the film forming space. Separately, a gaseous germanium-containing compound or a silicon-containing compound, which is a film-forming compound introduced into the activation space, and a compound containing an inert gas and an impurity element as necessary. Excite each gas etc. with activation energy and decompose it to generate each active species,
Each of them is introduced separately or mixed as appropriate into the film forming space where the base 21 is installed. By using light energy on the compound containing halogen and germanium and the active species introduced into the film forming space, causing a chemical interaction between the compound containing germanium and halogen and the active species, or further This is accelerated or amplified to form a deposited film on the substrate 21. The thickness of the n-type and p-type semiconductor layers is preferably in the range of 102 to ro'X, more preferably in the range of 3X102 to 2x+o3X.

Further, the layer thickness of the l-type semiconductor layer is preferably 5×102
It is desirable to set it in the range of ~10'X, more preferably to3~to'X.

The circular N-type diode device shown in FIG.
Not only can all the layers of pl 1 and n be formed by the method of the present invention, but also the object of the present invention can be achieved by forming at least one layer of pl 1 and n by the method of the present invention. can.

〔Example〕

EXAMPLES The present invention will be explained in more detail below according to Examples, but the present invention is not limited thereto.

Example 1 Using the apparatus shown in Fig. 3, 1 was carried out by the following operations.
type, p-type, and n-type a-Ge(H,X) 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 is a heater for heating the substrate;
4 is used when heat treating the base 103 before film formation, or annealing after film formation in order to further improve the properties of the formed film;
It supplies electricity through the wire and generates heat. During film formation, the heater 1
04 is not driven.

106 to 109 are the number of gas supply sources, germanium-containing compounds, and optionally used silicon-containing compounds, carbon-containing compounds, hydrogen, halogen compounds, inert gases, compounds containing impurity elements, etc. Established accordingly. When using liquid raw material compounds, an appropriate vaporization device is provided.

In the figure, the gas supply sources 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. The symbol suffixed with e is a nomil valve for adjusting the flow rate of each gas. 123 is an activation chamber for generating active species, and around the activation chamber 1230 is provided a microwave plasma generator 122 that generates activation energy for generating active species. Gas introduction pipe 1
The raw material gas for generating active species supplied from 10 is activated in the activation chamber 123, 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 germanium and halogen, and a to e attached to the reference numeral 112 indicate the same as in the case of 106 to 109 described above.

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

Reference numeral 117 is a light energy generating device, and for example, a mercury lamp, a xenon lamp, a carbon dioxide laser, an argon ion laser, an excimer laser, etc. can be used.

Light 118 directed from the light energy generating device 117 to the entire substrate 103 or a desired portion of the substrate 103 using an appropriate optical system is directed to the germanium- and halogen-containing compound and active species flowing in the directions of arrows 116 and 119. a-Ge(
A deposited film of H2χ) is formed. Also, in the figure, 120
121 is an exhaust pipe.

First, a substrate 10 made of polyethylene terephthalate film
3 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 Torr. Gas supply cylinder 106 I) GeH4 gas 150 SC
CML or this and PH3 gas or B2H6 gas (
Both 1000 ppm hydrogen gas dilution) 40SCC
A gas mixed with M was introduced into the activation chamber 123 via the gas introduction pipe 110. Ge introduced into the activation chamber 123
H4 gas and the like were activated by the microwave plasma generator 122 to form germanium hydride active species, and the germanium hydride active species were introduced into the film forming chamber 101 through the introduction pipe 124.

On the other hand, GeH4 gas is introduced into the pipe 11 from the supply source 112.
3, it was introduced into the film forming chamber 101.

I while maintaining the pressure inside the film forming chamber 101 at 0.4 Torr.
A non-doped or doped a-Ge (H, Film formation speed is 19 seconds/se
It was e.

Next, the obtained non-doped or p-type a-Ge
(H,
A comb-shaped Al gap electrode (gap length 25
0μ, width 5ryvn), the applied voltage 1.
Measure the dark current at 0 V, find the dark conductivity σd, and calculate a-
Ge(H,X) film properties were evaluated. The results are shown in Table 1.

Examples 2 to 4 A-GlB (H, X) A film was formed. The dark conductivity of each sample was measured and the results are shown in Table 1.

=38= From Table 1, when an a-Ge(H,X) film is formed by the method of the present invention, an a-Ge(H, conducted a-G
It was found that an e(H,X) film 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, 202 is a compound supply source containing germanium and halogen, 206 is a gas introduction pipe, and 2
07 is a motor, 208 is a heating heater used in the same manner as the heater 104 in FIG. 3, 209 and 210 are blowout pipes, 211 is a hl 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. 1, and 217-1 is a gas introduction pipe.

An Al cylindrical substrate 211 is suspended in the film forming chamber 201, a heating heater 208 is provided inside the substrate, and a motor 20 is installed.
7 so that it can be rotated. Reference numeral 218 denotes a light energy generating device, which irradiates light 219 toward a desired portion of the HLL cylinder 211.

First, GeF and gas were introduced from the supply source 202 into the film forming chamber 201 through the introduction pipe 206.

On the other hand, from the introduction pipe 217-1, sl, H6, GeH, and H
2 gases were introduced into the activation chamber 220. introduced S
The iH6, GeH, and H2 gases are subjected to an activation process such as plasma conversion using a microwave plasma generator 221 in an activation chamber 220 to form silicon hydride active species, germanium hydride active species, and active hydrogen, which are then introduced into an inlet pipe 217. ,2
The film was introduced into the film forming chamber 201 through the film. At this time, if necessary, impurity gas such as PI (3, B2H6, etc.) may also be added to the activation chamber 22.
0 and activated.

While maintaining the atmospheric pressure in the film forming chamber 201 at 1.0 TOrr, the I
Al cylindrical base 21 from KWXe lamp 218
Light is irradiated perpendicularly to the circumferential surface of 1.

The Al cylindrical base 211 was rotated, and the exhaust gas was exhausted through the exhaust/9-lube 212.

The photosensitive layer 13 is formed in this manner, but in order to form the intermediate layer 12, prior to forming the photosensitive layer 13, the introduction tube 21 is
5i2n6 from 7-1. GeH,, H3 and B, H6
A mixed gas of (0.2% B2H6 gas in terms of capacity width) is introduced, and otherwise the film is formed in the same manner as in the case of forming the photosensitive layer 13 to a film thickness of 2xlO''H.

Comparative Example 1 A film forming chamber having the same configuration as the film forming chamber 201 was prepared using GeF4 gas, Si2H6 gas, GeH4 gas, H2 gas, and B2H6 gas, and equipped with a 13.56 MHz high frequency device. A drum-shaped electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by a general plasma 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.

A2-Table 2 Example 6 The PIN type diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3 using GeH4 gas as the kermanium-containing compound.

First, the IJ ethylene naphthalate film 21 on which the 100OX TO film 22 was vapor-deposited was placed on a support stand, and the IF
After reducing the pressure to 6 TOrr, GeF and gas were introduced into the film forming chamber 101 from the introduction pipe 113 as in Example 1, and 513H6 gas 150 SCCM was introduced from the introduction pipe 110.
.

GeI (4 gas 5nSCCM, PH3 gas (1100
0pp diluted hydrogen gas) was introduced into the activation chamber 123 for activation.

Next, this activated gas is introduced through the introduction pipe 124.
The n-type a-5iGe (H,X) film 24 (film thickness: 700 mm
X) was formed.

Next item, PH, instead of gas, B2H6 gas (300pp
n-type a-81Ge (
Type 1 a-5iGe(
A film 25 (film thickness: 5000×) was formed.

Next, B2H6 gas ()000pp was substituted for PH3 gas.
p-type a-5i()e (H,X) doped with B under the same conditions as n-type except that m hydrogen gas dilution)
A film 26 (thickness: 700 N) was formed. Furthermore, this p
An AΔ electrode 27 with a film thickness of 1000X is formed on the mold film by vacuum evaporation.
was formed 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 the light irradiation intensity is AMI (approximately 100 mW/Cm"), the conversion efficiency is 7 inches or more, the open circuit voltage is 0.89 V, and the short circuit current is 11.
, 2 mA 7 cm" were obtained.

Examples 7 to 9 G8H was used as the kermanium-containing compound, and instead of gas, linear Ge and H□ were used. A PIN diode was fabricated in the same manner as in Example 6, except that gas, branched G"4H] and O gas were used. The rectification characteristics and photovoltaic effect of this sample were evaluated, and the results were reported in the following. It is shown in Table 3.

From Table 3, it can be seen that according to the method of the present invention, a-8 has better surface optical and electrical properties than those using the conventional method.
It was found that a Ge(H,X) P-type N-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. It becomes possible. However, it improves the reproducibility of film formation, makes it possible to improve film quality and make film quality uniform, and is advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. can do. Furthermore, since light energy is used as excitation energy, it is possible to form a film even on a substrate with poor heat resistance or easily susceptible to plasma etching, 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. FIG. 2 is a schematic diagram illustrating an example of the configuration of a PIN diode manufactured using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams each illustrating the configuration of an apparatus for carrying out the method of the present invention used in the examples. 10... Electrophotographic image forming member 11... Substrate 12... Intermediate layer 13... Photosensitive layer 21... Substrate 22.27... Thin film electrode 24... N-type semiconductor layer 5. ...1 type semiconductor layer 26...P type semiconductor layer 4...Conducting wires 101, 201...Film forming chamber 1.12.202...Compound supply source 123, 220 containing kermanium and halogen oxide ...Activation chamber 106, 107.108.109.213.214.2
15.216...Gas supply source 103, 211...Base 117, 218...Light energy generator 102...
・Substrate support stand 104, 208...Heater 105 for heating the substrate...
Conductor 110, 113.124.206.217-1.217
-2...Gas introduction pipe 111...Pressure gauge 120, 212...Exhaust valve 121...Exhaust pipe 122, 221...Activation energy generator 209
, 210...Blowout pipe 207...Motor Fig. 1

Claims (1)

[Claims] A compound containing germanium and a halogen and an active species generated from the germanium-containing compound for film formation that chemically interacts with the compound are mixed in 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 introducing a substrate and irradiating the substrate with light energy to cause a chemical reaction.