JPS61194823A - Deposited film forming method - Google Patents

Abstract

PURPOSE:To improve the various characteristics of a film, a high speed film formation, reproducibility and uniformity of film quality by feeding an active seed made of germanium and halogen and an active seed made of a carbon- containing compound, and making thermal energy act to chemically react them. CONSTITUTION:An Al cylinderlike base 211 is hung in a film forming chamber 201. Solid Ge particles 204 are filled in an activating chamber 202, GeF4 is blown through a guide tube 205 while heating to form an active seed GeF2, and then fed through a guide tube 206 to the chamber 201. Mixture gas of CH4, Si2H6, H2 is fed from a guide tube 217-1 to an activating chamber 219, activated by a microwave plasma generator 220, and fed to the chamber 201. The base 211 is heated, rotated, heated by a thermal energy generator 218, evacuated from an exhaust valve 212 to form a photosensitive layer as a drumlike electrophotographic image forming member.

Description

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

[Prior art]

For example, a vacuum evaporation method or a plasma CVD method is used to form a deposited film such as an amorphous silicon film.

CVD methods, reactive sputtering methods, ion blating methods, photo-CVD methods, and the like have been tried, and in general, plasma CVD methods are widely used and commercialized.

The deposited film, which is composed of amorphous silicon from below the surface, has excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility.
In terms of mass production, there is room to further improve the overall characteristics.

The reaction process in forming an amorphous silicon deposited film using the conventionally popular plasma CVD method is considerably more complicated than that of the conventional C'VD method, and there are many aspects of the reaction mechanism that are unclear. Ta. In addition, there are many formation parameters for the deposited film (e.g., substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, plasma generation method, etc.).
Due to the combination of these many parameters, the plasma sometimes becomes unstable, which often has a significant adverse effect on the deposited film formed. Moreover, parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions. On the other hand, in order to develop an amorphous silicon film that fully satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. There is.

Depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniform film thickness, and uniform film quality, and to achieve mass production with high reproducibility through high-speed film formation.
Forming an amorphous silicon deposited film using the plasma CVD method requires a large amount of equipment investment for mass production equipment, and the management items for mass production also become complex, the management tolerance narrows, and equipment adjustments are delicate. Since it is,
These have been pointed out as problems that should be improved in the future. On the other hand, with the conventional technology using the normal CVD method,
This method requires high temperatures, and a deposited film with practically usable properties has not been obtained.

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

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

[Purpose and outline of the invention]

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

The above purpose is to create an active species (A) generated by decomposing a compound containing germanium, mu and halogen in a film forming space for forming a deposited film on a substrate, and the active species (A).
A deposited film is formed on the substrate by separately introducing active species (B) generated from a carbon-containing compound and chemically interacting with the active species (B), and applying thermal energy to them to cause a chemical reaction. This is achieved by the deposited film forming method of the present invention, which is characterized by forming.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film forming space for forming a deposited film, active species (A) generated by decomposing a compound containing germanium and halogen and a carbon-containing material for film forming are used. In coexistence with the active species (B) generated from the compound, by applying thermal energy to the active species (B), chemical interactions between the compounds are caused, or promoted and amplified. --1 The deposited film that is formed is etched during film formation.

In addition, it is not affected by other adverse effects such as abnormal discharge action.

Furthermore, according to the present invention, a more stable CVD method can be achieved by arbitrarily controlling the atmospheric temperature in the film-forming space and the substrate temperature as desired.

In the present invention, the thermal energy that acts on the active species (A) and/or the active species (B) to cause a chemical reaction between them is applied to at least a portion of the film forming space near the substrate or the entire film forming space. There is no particular restriction on the heat source used, and conventionally known heating media such as heating by a heating element such as resistance heating, high frequency heating, etc. can be used. Alternatively, thermal energy converted from light energy can be used. Furthermore, if desired, light energy can be used in combination with thermal energy. Light energy can be applied to the entire substrate using an appropriate optical system, or can be selectively applied to only desired areas, so that the formation position and thickness of the deposited film on the substrate can be controlled. etc. can be easily controlled.

One of the differences between the method of the present invention and the conventional CVD method is that it uses active species activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and also to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

Note that the active species (A) in the present invention is a species that chemically interacts with the active species (B) generated from the carbon-containing compound that is the compound of the deposited film forming raw material to impart energy, for example. The active species (A) refers to substances that have the effect of promoting the formation of a deposited film by causing a chemical reaction or a chemical reaction.Therefore, the active species (A) does not include the constituent elements that constitute the deposited film that is formed. Alternatively, it may not include such components.

In the present invention, the active species (A) from the activation space (A) introduced into the film forming space preferably has a lifetime of 0.1 sand amount from the viewpoint of productivity and ease of handling. is 1 second or more, preferably 1 second or more, and is selected and used as desired.

The carbon-containing compound for film formation used in the present invention is already in a gaseous state before being introduced into the activation space (B), or is in a gaseous state.

For example, when using a liquid compound, the compound can be vaporized by connecting a suitable vaporizer to the compound supply system and then introduced into the activation space (B). Carbon-containing compounds include chain or cyclic saturated hydrocarbon compounds, organic compounds whose main constituent atoms are carbon and hydrogen, and one or more constituent atoms such as halogens, sulfur, etc., and hydrocarbon groups. Among organosilicon compounds having a bond of silicon and carbon, those in a gaseous state or those that can be easily vaporized are preferably used.

Among these, as a hydrocarbon compound, for example, carbon number 1
-5 saturated hydrocarbons, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylenic hydrocarbons having 2 to 4 carbon atoms, etc. Specifically, saturated hydrocarbons include methane (CH4), ethane (
C2H6), propane (CsHs), n-buta7 (n-
C4H1o), Penta7 (C5H12), xf
Examples of 1/7 hydrocarbons include ethylene (C2H4), propylene (C3H6), butene-1 (C4H8), butene-2 (C4H8), isobutylene (C4H8), and pentene (CsHlo), and acetylene hydrocarbons include acetylene ( C2H2), methylacetylene (C3H4)
, butyne (compounds in which at least one hydrogen, which is a component of a C4-containing hydrocarbon compound, has been replaced with F, C1, Br, or ■) are particularly effective. Compounds in which hydrogen is substituted with F or C1 are particularly effective. As a substitute for hydrogen, at least one or two rogens may be substituted for hydrogen in one compound.
It may be more than one species. As the organosilicon compound used in the present invention, organosilane, organohalogen milane, etc. can be mentioned. Organosilane and organo/\rogenmilane have the general formula, RIS 1H4-n, RmSiX4-m (however, R:
Alkyl group, aryl group%, X: F, C1, Br, I
, %n=1.2.3.4, hem=1.2.3,), and representative examples include alkylsilanes, arylsilanes, alkylhalogensilanes, and arylhalogensilanes. I can do it.

Specifically, as organochlorosilane, trichloromethylsilane CH35iCu
3dichlorodimethylsilane (CH3)
2sicJ12 chlorotrimethylsilane
(CH3) 2S i Cl trichloroethylsilane C2H55iCJ13 dichlorodiethylsilane (C2H5)25iCJL2
As organochlorofluorosilane, chlordifluoromethylsilane CH35iF2CJL dichlorofluoromethylsilane CH3S i FCI
2-chlorofluorodimethylsilane (CH3)
2S i FCfL Chlorethyldifluorosilane
(C2H5)SiF2C! ;L dichloroethylfluorosilane C2H55iFCJ12 chlordifluoropropylsilane C3H75iF2CJl
Dichlorofluoropropylsilane C3l (7si
FcJlz organosilane is tetramethylsilane (CH3)
4S i Ethyltrimethylsilane (C
H3) 3sic2H5 trimethylpropylsilane
(CH3) 3sic3H7 Triethylmethylsilane CH35i (C2H5)3 Tetraethylsilane (C2H5)4
As Si organohydrogenosilane, methylsilane CH35iH3
Dimethylsilane (CH3)
2S iH2 trimethylsilane
(CH3)3S iH diethylsilane
(C2H5) 2siH2 triethylsilane
(C2H5) 3S iH tripropylsilane (C3H7)3S
iH diphenylsilane (C6H
5) As 2siH2 organofluorosilane.

Trifluoromethylsilane CH35iF3
Difluorodimethylsilane (CH3)
2S t F2 Fluorotrimethylsilane
(CH3)3S i F ethyltrifluorosilane
C2H55iF3 diethyldifluorosilane (C2H5)23iF2 triethylfluorosilane (C2H5)3S i F trifluoropropylsilane (C3H7)
As S i F3 organobromosilane.

Bromotrimethylsilane (CH3)3
SiBrdibromdimethylsilane (C
H3) 25iBr2 etc. can be mentioned, and in addition,
7 As organoborisilane, hexamethyldisilane ((CH3)
3Si) As the 2-organodisilane, hexamethyldisilane ((CH3)3
Si)2hexapropyldisilane ((C
3H7) 3S i) 2 etc. can also be used.

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

In the present invention, as the compound containing germanium and halogen introduced into the activation space (A), for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic germanium hydride compound is replaced with a halogen atom is used. Specifically, for example, chain germanium halide GevY2v (v is Cyclic germanium halide, GeuH) (an integer of 3 or more, Y has the above meaning) (Yy (u and Y have the above meaning, x+y=2u or 2u+2) Examples include cyclic or cyclic compounds.

Specifically, for example, GeF4. (GeF2)5゜(GeF
2) e, (GeF2)4. Ge2Fs, Ge3FB, G
eHF3. GeHBr3, GeCl4. (GeC12)
5. GeBr4, (GeBr2)5, Ge2C16, G
e 2B r 6, GeHCl3, GeHBr3, Ge
Examples include those in a gaseous state or those that can be easily gasified, such as 2HI3 and Ge2C13F3.

In addition, in the present invention, the active species (A
), in combination with active species (SiX) generated by decomposing compounds containing silicon and halogens and/or active species (CX) generated by decomposing compounds containing carbon and /\ halogens. can do.

As the compound containing silicon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically, 1 is used.
For example, 5inY2u+2 (u is an integer greater than or equal to 1, Y is F, CI.

At least one element selected from Br and I. ) chain silicon halide, 5ivY2v (
V is an integer of 3 or more, and Y has the meaning described above. ) Cyclic halogen silicon, S i uHxYy (u and Y have the above meanings) (+y=2u or 2u+
It is 2. ), and the like.

Specifically, for example, S'i p 4, (S, 1F2) 5
, (SiF2)s, (SI F 2 ) 4. Si
2 F 6 , 9f 3F B , fs+ HF 3
, Fir H2F 2 , S'i Cl 4, (
S1Cl 2) 5, SiB I4, (s”ln r
2) 5, S′i2Cl 6. 5I2B
r 6.5iHC13,S, HB r 3゜5i2H
Examples include those in a gaseous state or those that can be easily gasified, such as I3.5i2C13F3.

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

Further, as the compound containing carbon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound is replaced with a halogen atom is used. Specifically, for example, Cuy2u+2 (u is 1 above integer, Y is at least one element selected from F, CI, Br, and E).

Cyclic silicon halide, CuHXYy, represented by CVY2V (V is an integer of 3 or more, Y has the meaning described above)
(u and Y have the above meanings.x+y=2u or 2
It is u+2. ), and the like.

Specifically, 1 e.g. CF4, (CF2)5, (CF2)
e, (CF2)a, C2F6. C3F9. CHF3
, CH2F2, CCl4, (CC12)5. C
Br 4, (CBr 2) 5, C2C16,
C2Br6, CHCl3, CHBr3
, CHI3, C2G13F3, etc., which are in a gaseous state or can be easily gasified.

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

In order to generate active species (A), when generating active species of a compound containing germanium and a halogen, in addition to this compound, other germanium-containing compounds such as germanium m-form, hydrogen , halogen compounds (e.g. F2 gas, C12 gas, gasified Br2, I
2 etc.) can be used in combination.

In the present invention, methods for generating activated species (A) and (B) in activation spaces (A) and (B) include microwave, RF, low frequency, DC, etc., taking into account the respective conditions and equipment. Activation energy such as electrical energy, thermal energy such as heater heating or infrared heating, and light energy is used.

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

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

In the present invention, in addition to the carbon-containing compound, the activation space (
In B), a silicon-containing compound for forming a deposited film that generates active species (B), or hydrogen gas, a halogen compound (for example, F2 gas, CI2 gas, gasified Br2,
I2 etc.), an inert gas such as helium, argon, neon, etc. can also be introduced into the activation space CB). When using multiple of these chemical substances, they can be mixed in advance and introduced into the activation space (B) in a gaseous state, or they can be introduced into separate activation spaces and supplied individually. , can also be activated.

As a silicon-containing compound for forming a deposited film.

Silanes and halogenated silanes in which hydrogen, halogen, or hydrocarbon groups are bonded to silicon can be used. Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with halogen atoms.

Specifically, for example, SiH4, Si2H6゜5i
3HB,5i4HtO,5i5)(12,5i61(i
A linear silane compound represented by S i PH2P+2 such as 4 (p is an integer of 1 or more, preferably 1 to 15, and more preferably 1 to 1O), 5iH3SiH (SiH
3) SiH3,5iH3siH(SiH3)Si3H7
゜5i2H5SiH (SiH, 3) S such as Si2H5
1PH2P+2 (p has the above-mentioned meaning) chain-shaped silane compounds with branches; compounds in which part or all of the hydrogen atoms of these linear or branched chain-shaped silane compounds are replaced with halogen atoms; , S i 3H6
, S i 4HB, 5i5H10, 5i6H12, etc.
A cyclic silane compound represented by fqHq (q is an integer of 3 or more, preferably 3 to 6), a part or all of the hydrogen atoms of the cyclic silane compound are replaced by other cyclic silanyl groups and/or
Examples of compounds substituted with chain silanyl groups, compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are substituted with halogen atoms include SiH3F, 5iH3CI
, 5iH3Br, 5iH3I, etc.
L (x is a halogen atom, r is 1 or more, preferably 1-
10, more preferably 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.

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 element to be used, as a p-type impurity, elements of Group 1II A of the periodic law, such as B, Al, Ga, I
Examples of suitable n-type impurities include elements of group V A of the periodic table, such as P.

Preferred examples include As, Sb, Bi, etc.
In particular, B, Ga, P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical properties.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under activation conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to select
Such compounds include PH3, P2H4, PF3°PF5. PC13, ASH3, AgF2. AsF5. A
3Cl3, SbH3, SbF5. SiH3, BF3.
BCl3, BBr3, B2H6, B a H
1o, B5 Hci, B5 Htt
, B6H10, B6H12, AlCl3, etc. Compounds containing impurity elements may be used alone or in combination.

The impurity-introducing substance may be introduced into the activation space (A) and/or the activation space (B) together with each substance that generates the active species (A) and the active species (B) for activation. Alternatively, the impurity-introducing substance, which may be activated in a third activation space (C) different from the activation space (A) and the activation space (B), is subjected to the activation energy described above. can be selected and adopted as appropriate. The active species (PN) generated by activating the impurity introducing substance is mixed with the active species and/or the active species (B) in advance, or is introduced into the film forming space independently.

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

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

The photoconductive member 10 shown in FIG. 1 can be applied as an electrophotographic image forming member, and includes an intermediate layer 1 provided as necessary on a support 11 for the photoconductive member.
2 and a photosensitive layer 13.

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

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A1. Cr, Mo.

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

Examples include metals such as Pd and alloys thereof.

Polyester is used as the electrically insulating support.

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

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

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

V, Ti, Pt, Pd, In2O3, 5n02゜ITO
(I n203 + 5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, AI, Ag, P
b, Zn, Ni.

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

The surface is treated with a metal such as Ti or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal to make the surface conductive. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, as desired.

For example, if the photoconductive member 10 shown in FIG. 1 is used as an electrophotographic image forming member, it is preferable to use an endless belt or a cylindrical shape for continuous high-speed copying. desirable.

For example, a photosensitive layer 13 is applied to the intermediate layer 12 from the side of the support it.
Effectively prevents the inflow of carriers into the photosensitive layer 11 and causes the photocarriers generated in the photosensitive layer 13 by electromagnetic wave irradiation and moves toward the support 11 from the side of the photosensitive layer 13 to the side of the support 11. It has a function that allows easy passage to.

This intermediate layer 12 is an amol 77 film (hereinafter referred to as a-G
It is composed of eC (denoted as H, X, Si)), and
For example, boron (B) is a substance that controls electrical conductivity.
P-type impurities such as phosphorus CP) or n-type impurities such as phosphorus CP) are contained.

In the present invention, the content of substances governing conductivity, such as B and P, contained in the intermediate layer 12 is preferably 0.
001-5X104 atomic ppm, more preferably 0.5-IX11X104 atomic ppm,
The optimum range is preferably 1 to 5×10 3 atomic ppm.

The intermediate layer 12 has similar components to the photosensitive layer 13.

Or if they are the same, when forming the intermediate layer 12, i
! ! It can be done continuously. In that case, the active species (A) generated in the active activation space (A), a gaseous carbon-containing compound, a silicon-containing compound, and optionally hydrogen and a halogen compound are used as raw materials for forming the intermediate layer. , active species generated by activating inert gas and compound gas containing impurity elements as components, respectively.
/ or appropriately mixed as necessary and introduced into the film forming space where the support 11 is installed, and by applying thermal energy to the coexistence atmosphere of each introduced active species, the support 11L is The intermediate layer 12 may be formed.

A compound containing germanium and halogen, which is introduced into the activation space (A) to generate active species (A) when forming the intermediate layer 12, can easily form an active species (such as GeF2*).
It is desirable to select a compound that produces A) from among the above-mentioned compounds.

The layer thickness of the intermediate layer 12 is preferably 30 to 1oAL,
More preferably 40 people ~ aIL, optimally 50 people ~ 5JL
It is desirable that this is done.

The photosensitive layer 13 is made of amorphous silicon A-5i (H, X, G
e, C) or amorphous germanium A-Ge (H, It has both a charge generation function and a charge transport function to transport the charges.

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

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

X, Ge, C) layer or A-Ge (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, a substance that controls the conduction properties of the same polarity may be contained in an amount much smaller than the dose. It may also be contained.

Also in the case of forming the photosensitive layer 13, compounds containing the method of the present invention are introduced, and by decomposing them at high temperature,
Alternatively, active species (A) are generated by excitation by applying discharge energy or light energy, and the active species (A')
is introduced into the film forming space.

Furthermore, if desired, an amorphous deposited film containing carbon and silicon as constituent atoms can be formed as a surface layer on this photosensitive layer, and in this case as well.

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

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

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

These semiconductor layers are A-5i(H,X), A-3iC(
H, X), A-SiGeC (H.

X) etc., and the method of the present invention can be applied to the production of any layer, but in particular, the method of the present invention can be applied to the production of the semiconductor layer 26
By creating the method of the present invention, the conversion efficiency can be improved.

28 is a conductive wire connected to an external electric circuit.

The base 21 may be electrically conductive, semiconductive, or electrically insulating. If the substrate 21 is conductive, the thin film electrode 22 may be omitted. As a semiconductive substrate, for example, St, Ge, GaAs, ZnO
, ZnS, and other semiconductors. Thin film electrode 22.27
Examples include NiCr, AI, Cr, and Mo.

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

Pd, I n203.5n02, ITO (I n2
It can be obtained by providing a thin film such as 0:1 + S no 2) on the substrate 211- by processing such as vacuum evaporation, electron beam evaporation, or sputtering. The layer thickness of the electrode 22.27 is preferably 30 to 5×10 4 A, more preferably 100 to 5×10 3 A.

゛1'- In order to make the film constituting the conductor layer n-type or p-type as necessary, it is necessary to form an n-type impurity, a p-type impurity, or both impurities among the impurity elements during layer formation. It is formed by doping the layer in a controlled amount.

When forming n-type, i-type, and p-type semiconductor layers, any one layer or all of the layers can be formed by the method of the present invention, and the film formation is performed by adding germanium and germanium to the activation space (A). A compound containing a halogen is introduced, and by exciting and decomposing it under the action of high-temperature activation energy, an active species (A) such as GeF2* is generated, and the active species (A
) is introduced into the film forming space. Separately, gaseous carbon-containing compounds, silicon-containing compounds, and compound gases containing inert gases and impurity elements as necessary are excited by activation energy and decomposed. , each active species (B) is generated and introduced into the film forming space where the support 11 is installed, either separately or mixed as appropriate. By using thermal energy, the active species introduced into the film-forming space are caused, promoted, or amplified by a chemical phase pressure effect, and a deposited film is formed on the support 11h. The layer thickness of the n-type and p-type semiconductor layers is preferably 100 to 104, more preferably 300 to 204.
A range of 0 people is desirable.

Further, the thickness of the i-type semiconductor layer is preferably 50
0 to 104 people, more preferably.

A range of 1,000 to 10,000 people is desirable.

A specific example of the present invention is shown below.

Example 1 Using the apparatus shown in Figure 3, i
Amorphous deposited films containing germanium, p-type, and n-type germanium and carbon were formed.

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

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 105 and generates heat. Although the substrate temperature is not particularly limited, it is preferably 3 when carrying out the method of the present invention.
0-450℃.

More preferably, the temperature is 50 to 350°C.

Reference numerals 106 to 109 denote gas supply systems, which are provided depending on the type of gas of the carbon-containing compound and the compound containing hydrogen, a halogen compound, an inert gas, and an impurity element, which are used as necessary. If these raw material compounds are liquid in their standard state, an appropriate vaporization device is provided for the gas supply system 106 to 10 in Figure 0.
The symbol 9 with a is added to the branch pipe, b is added to the flowmeter, C is added to the pressure gauge that measures the pressure on the high pressure side of each flowmeter, and d or e is added to the number. This is a valve for adjusting the flow rate of each gas. 123 is an activation chamber (B) for generating activated species (B), and around the activation chamber 123,
A microwave plasma generator 2t122 that generates activation energy for generating active species (B) is provided. The raw material gas for generating active species (B) supplied from the gas introduction pipe 110 is activated in the activation chamber (B) 123, and the generated active species (B) is transferred to the film forming chamber through the introduction pipe 124. 101. 111 is a gas pressure gauge.

In the figure, 112 is an activation chamber (A), 113 is an electric furnace, and 114
115 is a solid Ge grain, and 115 is an introduction tube for a compound containing gaseous germanium and halogen, which is a raw material for active species (A).
is introduced into the film forming chamber 101 via the introduction pipe 116.

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

The heat from the thermal energy generator 117 is applied to the active species flowing in the direction of the arrow 119, and germanium and germanium are applied to the entire substrate 103 or a desired portion of the substrate 103 by a wheel that causes each of the acted active species to undergo a chemical reaction in a phase V manner. Forming a carbon-containing amorphous deposited film. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

Substrate 10 made of pre-screened polyethylene terephthalate film
3 on the support stand 102! ! Then, the inside of the film forming chamber 101 was evacuated using an exhaust device to reduce the pressure to about 10-6 Torr.

At the substrate temperature shown in Table 1, CH4 gas, or this and PH3 gas or B2H gas is supplied from the gas supply pump 106.
6 gas (both LOOOpprn* elemental gas dilution) and warm gas dilution gas are passed through the gas introduction pipe 110 to the activation chamber (B).
It was introduced in 123. The CH4 gas etc. introduced into the activation chamber (B) 123 is activated by the microwave plasma generator 122 and converted into hydrogenated carbon active species, active hydrogen, etc. Hydrogen or the like was introduced into the film forming chamber 101.

On the other hand, the activation chamber (A) 112 is filled with solid Ge grains 114, heated in an electric furnace 113 to bring the Ge to a red-hot state, and Ge F4 is blown therein through an inlet pipe 115 with a cylinder (not shown). , GaF2 zero as active species (A) is generated, and the GeF2t is introduced into the introduction tube 11.
6, and then introduced into the film forming chamber 101.

In addition, the growth rate was 28 seconds/sec.

Next, the obtained non-doped or P-type and n-type germanium and carbon-containing amorphous deposited film sample was placed in a vapor deposition tank, and a comb-shaped AI gap electrode (gap length 250 g, width 5 mm) was formed at a vacuum degree of 10-5 Torr. After that, the dark current was measured with an applied voltage of 10 V, and the dark conductivity σd
The film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2-4 Linear C2H6, C2H4, or C2H instead of CH4
An amorphous deposited film containing germanium and carbon was formed in the same manner as in Example 1, except that Example 2 was used. The dark conductivity was measured and the results are shown in Table 1.

Table 1 shows that according to the present invention, germanium and carbon-containing amorphous films with excellent electrical properties can be obtained, and germanium and carbon-containing amorphous films that are sufficiently doped can be obtained.

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

In FIG. 4, 201 is a film forming chamber, and 202 is an activation chamber (
A), 203 is an electric furnace, 204 is a solid Ge particle, 205 is a raw material introduction tube for active species (A), and 206 is an active species (A)
207 is a motor, 208 is a heating heater used in the same manner as 104 in FIG. 3, 209 and 210 are blowout pipes, and 211 is A! 212 represents an exhaust valve. Further, 213 to 216 are raw material gas supply systems similar to 106 to 109 in FIG.
17-1 is a gas introduction pipe.

An AI cylinder base 211 is suspended in the film forming chamber 201, a heater 208 is provided inside the base, and a motor 20 is installed.
7 so that it can be rotated. 218 is a thermal energy generating device, and for example, a normal electric furnace, a high frequency heating device, various heating elements, etc. are used.

In addition, the activation chamber (A) 202 is filled with solid Ge grains 204 and heated in the electric furnace 203 to bring the Ge into a red-hot state,
There, GeF is introduced from a cylinder (not shown) through an introduction pipe 206.
δmF as an active species (A) by injecting 4
2t was generated, and the Gj F 2 zero was introduced into the film forming chamber 201 through the introduction pipe 206.

I let him in.

They were subjected to activation processing such as plasma formation by the plasma generator 221 to become hydrogenated carbon active species, silicon hydride active species, and activated hydrogen, which were introduced into the growth chamber 201 through the introduction pipe 217-2.

Blunt debris was also introduced into the activation chamber (B) and activated. The internal pressure in the film forming chamber 201 is l.

The A1 cylinder base 211 is heated to 220°C by the heater 208.
heated, held and rotated.

The exhaust gas is exhausted by appropriately adjusting the opening of the exhaust valve 212. In this way, the photosensitive layer 13 is formed.

Further, the intermediate layer 12 is connected to the introduction tube 21 prior to the photosensitive layer 13.
From 7-1, H2/B2H6 (B2H6 gas is 0 in volume %)
．． 2%) mixed gas was introduced.

The film was formed with a film thickness of 2000.

Comparative Example l GeF4 and CH4, S i 2H6, H2 and B2H6
A film forming chamber having the same configuration as the film forming chamber 201 is prepared using each gas, and equipped with a 13.56 MHz high frequency device,
An 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.

Male Side 6 Using CH4 as the carbon compound, the PIN type diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3.

First, a polyethylene naphthalate film 21 on which 1000 ITO films 22 were deposited was placed on a support stand, and 10-
[After reducing the pressure to 1 Torr, the active species GeF2))C produced in the same manner as in Example 1 was introduced into the film forming chamber 101. or.

Each of S i 3H6 gas PH3 (1000 ppm hydrogen gas dilution) was introduced into the activation chamber (B) 123 and activated.

Next, this activated gas is introduced into the film forming chamber 101 through the introduction pipe 116, and the pressure inside the film forming chamber is reduced to 0.3 Torr.
r, n-type a doped with P while kept at 200°C
-StGe(H.

X) Film 24 (film thickness: 700 layers) was formed.

Next, the n-type A-5 except that the introduction of PH3 gas was stopped.
A non-doped A-3t film 25 (thickness: 5000) was formed using the same method as the iGe(H,X) film.

Next, CHa and B2H6 gas (1000 ppm hydrogen gas dilution) were introduced together with the 5i3H6 gas, and the p-type carbon-containing A-SiGe (H, Thickness: 700 A) Fully formed. Furthermore, a film thickness of 1 was formed on this p-type film by vacuum evaporation.
A PIN type diode was obtained by forming an At electrode 27 of 000A.

I of the diode element thus obtained (area 1 cm2)
-V characteristics were measured, and rectification characteristics and photovoltaic effects 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 C approximately 100 mW/cm2), the conversion efficiency is 8.2% or more, the open circuit voltage is 0.93 V, and the short circuit current is 9.
．． 8 mA/cm2 was obtained.

Examples 7 to 9 C2H6, C2H4 instead of CH4 as a carbon compound
Alternatively, a PIN diode similar to that in Example 6 was manufactured in the same manner as in Example 6 except that C2H2 was used. This test vehicle 4 was evaluated for its A-wave characteristics and photovoltaic effect, and the results are shown in Table 3.

From Table 3 1 According to the present invention, carbon-containing A-3iGe (H,
X) It was found that PIN type diodes can be used.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible. In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform.

It is advantageous for increasing the area of the membrane, and it is possible to easily achieve improvement in membrane productivity and mass production.

Furthermore, since relatively low thermal energy can be used as excitation energy, for example, substrates with poor heat resistance,
Films can also be formed on substrates that are susceptible to plasma etching. 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. FIG. 2 is a schematic diagram for explaining an example of the configuration of a PIN type daiode manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining. 10---One electrophotographic imaging member, 11---One substrate, 12---One intermediate layer, 13---One photosensitive layer, 21---One substrate, 22.27---Thin film. electrode. 24---n-type semiconductor layer, 25----i-type semiconductor layer, 26----p-type semiconductor layer, 123, Luyu 4----Activation chamber (B). 106.107,108,109,21"3. 214.215,216---Gas supply system.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, an active species (A) generated by decomposing a compound containing germanium and a halogen; The active species (B) generated from the carbon-containing compound for film formation, which chemically interact with each other, are introduced separately, and thermal energy is applied to them to cause a chemical reaction, thereby depositing them on the substrate. A deposited film forming method characterized by forming a film.