JPS61196522A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve the various characteristics, filming sped and reproducibility while stabilizing the film quality by a method wherein an active compound (A) and another active compound (B) are separately fed to a filming space to be supplied with thermal energy. CONSTITUTION:In the coexistence of an active compound (A) produced by decomposing a germanium and halogen contained compound substituting for producing plasma in a filming space for forming the title deposited films as well as another active compound (B) produced from a germanium contained filming compound, the deposited films are to be formed by means of supplying the active compounds (A) and (B) with thermal energy to make them chemical- react to each other or accelerate and amplify the chemical reaction. Through these procedures, the deposited films with stable film quality may be mass-produced industrially at low cost since the filming speed may be accelerate remarkably compared with that by any conventional CVD process as well as the substrate temperature in case of forming the deposited films may be lowered considerably.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention is suitable for forming a deposited film containing germanium, particularly a functional film, particularly a semiconductor device, and a deposited film containing electromorphic germanium. Concerning methods.

[Prior art]

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

Deposited films composed of amorphous silicon have been improved in terms of 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 by the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, which often has a significant negative effect on the deposited film. 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.

According to Hyakunen et al., 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, as well as mass production with high reproducibility through high-speed film formation. In the formation of amorphous silicon deposited films using the method, a large amount of equipment investment is required for mass production equipment, and the management items for mass production are also complicated, the management tolerance is narrow, and the adjustment of the equipment is delicate. Therefore, these issues have been pointed out as issues that should be improved in the future. On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to provide a deposited film with practically usable characteristics.

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

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

[Purpose and outline of the invention]

The purpose of the present invention is to improve various characteristics of the film to be formed, film formation speed, reproducibility, and uniform film quality, while being suitable for large-area films, improving film productivity, and mass production. The object of the present invention is to provide a deposited film forming method that can be easily achieved.

The above purpose is to create an active species (A) generated by decomposing a compound containing germanium and a halogen in a film forming space for forming a deposited film on a substrate, and a chemical reaction between the active species (A) and the active species (A). The active species (B) generated from the germanium-containing compound for film formation that interact with each other are introduced separately,
This is achieved by the deposited film forming method of the present invention, which is characterized in that a deposited film is formed on the substrate by applying thermal energy to these to cause a chemical reaction.

[Embodiment]

In the method of the present invention, instead of generating plasma in a film formation space for forming a deposited film, active species (A) generated by decomposing a compound containing germanium and a halogen and a germanium-containing compound for film formation are used. Deposits formed in coexistence with active species (B) generated by the active species (B) by applying thermal energy to them to cause, promote, or amplify chemical interactions. The membrane is not adversely affected by etching effects or other adverse effects such as abnormal discharge effects.

Further, 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 for exciting and reacting the raw materials for forming the deposited film is applied to at least the part near the substrate or the entire film forming space, and there is no particular restriction on the heat source used. Conventionally known heating media such as heating using 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 addition to 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.

In addition, the active species (A) in the present invention refers to the active species (B) that chemically interacts with the active species (B) generated from the germanium-containing compound that is the compound of the raw material for forming the deposited film 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 by causing a chemical reaction. It may contain such components, or it may not contain such components.

In the present invention, the activated species (A) from the activation space (A) introduced into the film forming space have a lifetime of 0.1 seconds or more, more preferably 1 second, from the viewpoint of productivity and ease of handling. A length of at least 1 second, preferably at least 10 seconds, is selected and used as desired.

In addition, the germanium-containing compound for film formation is in the activation space CB.
) is activated by activation energy to generate active species (B), and when the active species (B) is introduced into the film formation space and forms a deposited film, the activation space is simultaneously (A
) and chemically interacts with the active species (A) introduced from the active species (A). As a result, a desired deposited film can be easily formed on a desired substrate. The active species (B) generated from the germanium-containing compound constitutes the components constituting the deposited film formed in the film forming space, as in the case of the active species (A).

The germanium-containing compound introduced into the activation space (B) used in the present invention is already in a gaseous state before being introduced into the activation space (B), or may be introduced in a gaseous state. For example, when using a liquid compound, the compound can be vaporized by connecting an appropriate vaporizer to the compound supply system and then introduced into the activation space (B).

As the germanium-containing compound, an inorganic or organic germanium compound in which hydrogen, halogen, or a hydrocarbon group, etc. are bonded to germanium can be used. For example, G
eaHb (a is an integer greater than or equal to 1, b = 2a + 2 or 2a
It is. ), a polymer of this germanium hydride, a compound in which some or all of the hydrogen atoms of the germanium hydride are replaced with halogen atoms, a hydrogen atom of the germanium hydride shown in Examples include organic germanium compounds such as compounds partially or wholly substituted with organic groups such as alkyl groups and aryl groups, and optionally with halogen atoms, and other germanium compounds.

Specifically, for example GeH4, Ge2H6, Ge3HB.

n-Ge4H10, tert-Ge4H10゜Ge3
) (8, Ge5HtO, GeH3F.

GeH3C1, GeH2F2. HeGeeFs.

Ge (CH3) 4. Ge (C2H5) 4゜Ge
(GeH5) 4. Ge(CH3)2F2.

CH3G e H3, (CH3) 2 G e H2.

(CH3) 2GeH, (C2H5) 2GeH2Ge
F2. GeF4. Examples include GeS.

These germanium 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, ceuy2u+2 (u is an integer of 1 or more, Y is at least one element selected from F, C1, Br, and I. Cyclic germanium halide, GeuH) represented by e y Y 2 y (■ is an integer of 3 or more, Y has the above-mentioned meaning) (Yy (u and Y have the above-mentioned meaning. x+y=2u or 2u+2 Examples include chain or cyclic compounds represented by the following.

Specifically, for example, GeF4. (GeF2)5.

(GeF2)s, (GeF2)4. Ge2Fs.

Ge3FB, GeHF3, GeHBr3, GeC
l4. (GeC12)5. GeBr4. (GeBr
2) 5. Ge 2 C1s, Ge 2 B
rs.

GeHCl3. GeHBr3. GeHI3゜Ge2CI
Examples include those in a gaseous state or easily gasified, such as 3F3.

Furthermore, in the present invention, active species (A
), combined use of active species (SX) generated by decomposing a compound containing silicon and halogen and/or active species (CX) generated by decomposing a compound containing carbon and halogen. I can do it.

As the compound containing silicon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically,
For example, 5i11Y2u+2 (u is an integer greater than or equal to 1, Y is F, CI.

Br and engineering. ), a cyclic silicon halide represented by 3tyY2v (v is an integer of 3 or more, Y has the meaning described above), S i
uHxYy (u and Y have the above meanings.x+
y=2u or 2u+2. ), and the like.

Specifically, for example, SiF4. (SiF2)5゜(SiF
2) s, (SiF2)4,5t2F6゜5i3FB,5
tHF3. SiH2F2゜5iC14(SiC12)5
．． SiBr4゜(SiBr2)5.5i2C16,5i
Examples include those that are in a gaseous state or can be easily gasified, such as 2Br6°5iHC13, 5iHBr3, 5iHI3°5i2CI3F3.

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

Further, as a 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, and specifically, for example, CuY2u+2 (u is 1 or greater, Y is F
, C.I.

It is at least one element selected from Br and Br. ) Chain halide carbon represented by CVY2V (V is an integer of 3 or more, Y has the meaning described above), cyclic silicon halide represented by CuHxYy (u and Y have the meaning described above.x+y= 2u or 2u+2.

), and the like.

Specifically, 1, for example, CF4. (CF2)5.

(CF2)6. (CF2)a , C2F6 , C3FB
.

CHF3, CH2F2, CC14(CCl2)5
, CBr4. (CBr2)5. C2C16゜C2Br6
．． CHCl3, CHBr3, CHI3. C2Cl3
Examples include those in a gaseous state or easily gasified, such as F3.

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

In order to generate the active species (A), for example, when generating the active species (A) of a compound containing germanium and a halogen, in addition to this compound, if necessary, a germanium compound such as germanium alone is added. , hydrogen, halogen compounds (for example, F2 gas, C!; L2 gas, gasified Br2.I2, etc.) can be used in combination.

In the present invention, methods for generating activated species (A) and (B) in activation spaces (A) and (B), respectively, include microwave, RF, low frequency, D
Activation energy such as electrical energy such as C, thermal energy such as heater heating, infrared heating, and light energy is used.

In the present invention, the ratio of the amount of active species (A) from the deposited and generated active species (8) and △(A) introduced into the film forming space depends on the film forming conditions, the type of active species, etc. It can be determined as desired, but preferably 10:1 to 1:10 (introduction flow rate ratio), more preferably 8:2 to 4:
It is desirable to set it to 6.

In the present invention, in addition to germanium-containing compounds, hydrogen gas, halogen compounds (for example, F2 gas, CI2 gas, gasified Br2, I2, etc.) are used as raw materials for film formation.
An inert gas such as helium, argon, neon, etc., or a silicon-containing compound, a carbon-containing compound, etc. as a raw material for forming a deposited film can also be introduced into the activation space (B).

When using a plurality of these chemicals, they can be mixed in advance and introduced into the activation space CB) in a gaseous state, or they can be supplied individually from independent sources. , can be introduced into the activation space (B), or can be introduced into independent activation spaces and activated individually.

Silicon-containing compounds that serve as raw materials for forming deposited films include:
Silanes, silokinanes, etc. 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, S i 4H10, S i 5H
5iH3Si
H(SiH3)SiH3,5iH3SiH(SiH3)
Si3H7,5i2H5SiH(SiH3)Si2H5
etc. 5ipH2P+2 (P has the above meaning.)
A linear silane compound having a branch represented by , a compound in which part or all of the hydrogen atoms of these linear or branched silane compounds are replaced with a halogen atom, 5i3H
6,5i4HB, 5t5H1o, S i 6 H12
A cyclic silane compound represented by 5tqH2q (q is an integer of 3 or more, preferably 3 to 6) such as Examples of compounds substituted with silanyl groups and compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are substituted with halogen atoms include SiH3F, 5i
H3C1, 5iH3Br, 5iH3I, etc. (7) S i
rHsXt (X is a halogen atom, r is an integer of 1 or more, preferably 1 to 1O1, more preferably 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.

In addition, carbon-containing compounds that serve as raw materials for forming deposited films include chain or cyclic saturated or unsaturated hydrocarbon compounds, carbon and hydrogen as the main constituent atoms, and one or more of silicon, halogen, sulfur, etc. Among organic compounds having two or more types of constituent atoms, organosilicon compounds having hydrocarbon groups as constituent elements, those in a gaseous state or those that can be easily vaporized are preferably used.

Among these, examples of hydrocarbon compounds include carbon atoms of 1 to
Examples of saturated hydrocarbons include methane (CH3), ethane (C2
He), propane (C3H8), n-butane (n-c4
Hto), pentane (C5H12), ethylene hydrocarbons include ethylene (C2H4), propylene (C3H
6), butene-1 (C4H8), butene-2 (CaHe
), inbutylene (C4I(8), pentene (C51
1o), acetylene hydrocarbons include acetylene (
C2H2), methylacetylene (C3H4), butyne (
C4H6), etc.

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

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

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

Organosilane and organohalogensilane each have the general formula; Rn5iH4-4, RmSiX4-m (however,
R: alkyl group, aryl group, X: F, CfL, Br,
I.

n=1,2,3,4, m=1,2,3) Representative examples include alkylsilanes, arylsilanes, alkylhalogensilanes, and arylhalogensilanes.

Specifically, as organochlorosilane, trichloromethylsilane CH35iCJ
13 dichlorodimethylsilane (CH3
)25iC12 chlorotrimethylsilane
(CH3)3SiC1 trichloroethylsilane
C2H55iCJL3 Dichlorodiethylsilane (C2H5)2SiC12 Organochlorofluorosilane includes Chlordifluoromethylsilane CH35iF2CJl Dichlorofluoromethylsilane CH35iFCfL2 Chlorfluorodimethylsilane (CH3) 23 i F
CJI Chlorethyldifluorosilane (C2H
5) SiF2Cl dichloroethylfluorosilane
C2H55iFCJ12 Chlordifluoropropylsilane C3H75iF2Ci Dichlorofluoropropylsilane C3H75iFCIL2 Organosilane includes Tetramethylsilane (CH3)
as iethyltrimethylsilane (C
H3) 3SiC2H5 trimethylpropylsilane
(CH3)3SiC3H7 triethylmethylsilane CH35i (C2H5)3tetraethylsilane (C2H5) 4S
As organohydrogenosilane, methylsilane CH35iH
3dimethylsilane (CH3)
2SiH2 trimethylsilane (
CH3)3SiH diethylsilane
(C2H5) 2siH2 triethylsilane
(C2H5) 3 S i H tripropylsilane (C3H7)3S
iH diphenylsilane (C6H5
)2SiH2 organofluorosilane includes trifluoromethylsilane CH3S i
F3 difluorodimethylsilane (CH3)
2S i F2 fluorotrimethylsilane
(CH3)3S tF ethyltrifluorosilane
C2H55iF3 Diethyldifluorosilane (C2H5)2SiF2 Triethylfluorosilane (C2H5) 3 S i F
Trifluoropropylsilane (C3H7)
As S i F3 organobromosilane, Bromotrimethylsilane (CH3)3
SiBrdibromdimethylsilane (C
H3)25iBr2, etc., and other organopolysilanes include hexamethyldisilane ((CH3)
3 Si) As a 2-organodisilane.

Hexamethyldisilane ((CH3)3
si)2hexapropyldisilane ((C
3H7) 3si)2 etc. can also be used.

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 Ⅰ A of the periodic table, such as B, Al, Ga, In,
Preferred examples include TI, and examples of n-type impurities include elements of Group V A of the periodic table, such as P and As.

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

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

PF5. PCl3. AsH3, AsF3. AsF5. A
sCl3, SbH3, SbF5. SiH3, BF3.
BCl3. BBr3. B2H6゜B4H10, B5H9
, B5H11, B6H10°B6H12, AlCl3, etc.

The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity-introducing substance may be introduced into the activation space (A) and/or the activation space (B) together with each substance that generates the active species (A) and the active species (B) for activation. Alternatively, 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 materials are mixed without tightening or introduced into the film forming space independently.

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

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

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

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

In manufacturing photoconductive member 10, intermediate layer 12 and/or photosensitive layer 13 can be formed using the method of the present invention. In W, a protective layer provided for the photoconductive member 10 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. , 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, Stair L/S, At, Cr, and Mo.

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

Examples include metals such as Pd and alloys thereof.

Polyester is used as the electrically insulating support.

Films or sheets of synthetic resins such as polyethylene, polycarbonate, cell acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramics, paper, etc. are commonly 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 NiCr.

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

V, Ti, PL, Pd, In2O3, 5n02゜ITO
(I n203 + 5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, AI, Ag, Pb
, 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, and the shape is determined depending on the needs.5For example, the photoconductive member 10 in FIG. If used as a continuous high-speed copy.

It is desirable to have an endless belt shape or a cylindrical shape.

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

This intermediate layer 12 has germanium atoms as its base material, and silicon (Si), hydrogen (H), and halogen (X) as necessary.
It is composed of amorphous germanium (hereinafter referred to as A-Ge (Si, H, Alternatively, 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 o,
o o t~5X104ato omi cppm, more preferably 0.5~IX104ato ppm
m, preferably 1 to 5×10 3 atomic ppm.

When the intermediate layer 12 has similar or the same components as the photosensitive layer 13, the formation of the intermediate layer 12 can be performed continuously from the formation of the intermediate layer 12 to the formation of the photosensitive layer 13. In that case, the active species (A) generated in the activation space (A) and the active species (A) generated from the germanium-containing compound introduced into the activation space (B) are used as raw materials for forming the intermediate layer. B) and, if necessary, active species generated from a silicon-containing compound, hydrogen, a halogen compound, an inert gas, a carbon-containing compound, and a gas of a compound containing an impurity element, respectively, separately or as appropriate. The intermediate layer 1 is formed on the support 11 by mixing as necessary and introducing the mixture into the film forming space in which the support 11 is installed, and applying treatment energy to the coexistence atmosphere of each introduced active species.
2 may be formed.

The compound containing germanium and halogen that is introduced into the activation space (A) to generate the active species (A) when forming the intermediate M12 is as follows.

For example, a compound that easily generates an active species such as GeF2* is selected from among the above-mentioned compounds. The photosensitive layer 13 is made of amorphous silicon A-3i (H, ) or amorphous silicon germanium A consisting of silicon atoms, germanium atoms, and optionally hydrogen, halogen, etc.
-3iGe (H,
It has both the charge transport function of transporting the charge.

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

The photosensitive layer 13 is made of, for example, non-doped A-Si (H,
Ge) or A-3iGe (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, it may be contained in an amount that is much smaller than the dose. .

In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, a compound containing germanium and halogen is introduced into the activation space (A), as in the case of the intermediate layer 12, and the photosensitive layer 13 is formed by the method of the present invention. By decomposing these or by exciting them with discharge energy or light energy, active species (A) are generated, and the active species (A) enter the film forming chamber.
introduced in between.

FIG. 2 shows A-Ge (Si) doped with an impurity element produced by carrying out the method of the present invention.

H, X) A schematic diagram showing a typical example of a PIN type diode device using a deposited film.

In the figure, 21 is a base, 22 and 27 are thin film electrodes, and 23 is a semiconductor film, including 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.

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

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

Pd, I n203.5n02, ITO (I n2
03 +s n02) on a substrate by a process such as vacuum evaporation, electron beam evaporation, or sputtering. The layer thickness of the electrode 22゜27 is preferably 30~5x104, more preferably 10~
It is desirable to have 5 x 103 people.

A-Ge (Si, H, X) (1) To make the film forming the semiconductor layer 23 n-type or p-type as necessary,
During layer formation, the layer is doped with an n-type impurity, a p-type impurity, or both impurities among impurity elements while controlling the amount thereof.

n-type, i-type and p-type (7) A-Ge (S i , H
.

To form the layer X), the activated space (A
), a compound containing germanium and halogen was introduced,
By exciting and decomposing these under the action of activation energy, active species (A) such as GeF2* are generated,
The active species (A) is introduced into the film forming space. Separately, the film-forming compound introduced into the activation space (B) and, if necessary, a compound gas containing an inert gas and an impurity element as components, are each excited by activation energy. 1 decompose to generate each active species, introduce each separately or suitably mix them into the film forming space where the support 11 is installed, and form by applying thermal energy. n-type and p-type c7) A-G e
The thickness of the (S i , H, X) layer is preferably in the range of 100 to 104, more preferably 300 to 2000.

Further, the thickness of the i-type A-Ge (S i , H,

Incidentally, the PIN type diode-F device shown in FIG. 2 has p,
It is not necessarily necessary to produce all of the i and n layers by the method of the present invention, and the present invention can be carried out by producing at least one of the p, i, and n layers by the method of the present invention.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 3, i
type, p-type and n-type A-Ge(H.

X) A deposited film was formed.

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

104 is a heater for heating the substrate;
4 is used when the substrate 103 is heat-treated during film formation or before film-forming processing, or when subjected to 7-neal treatment after film formation to further improve the characteristics of the formed film.
5, preferably 30 to 250°C, more preferably 50°C
It is desirable that the temperature is ~200°C.

106 to 109 are gas supply systems, which supply gases such as germanium-containing compounds and hydrogen, halogen compounds, inert gases, silicon-containing compounds, carbon-containing compounds, compounds containing impurity elements, etc., which are used as necessary. Established according to type. When using liquid raw materials, an appropriate vaporization device is provided.

In the figure, the symbol a for the gas supply systems 106 to 109 indicates a branch pipe, and the symbol b indicates a flow meter.

C indicates a pressure gauge that measures the pressure on the high pressure side of each flow meter, and d or e indicates a valve for adjusting the flow rate of each gas. 123 is an activation chamber (B) for generating active species (B), and around the activation chamber 123 is a microwave plasma generator that generates activation energy for generating active species CB). 122 is provided.

The raw material gas for generating active species (B) supplied from the gas introduction pipe 110 is activated in the activation chamber (B) 123, and the generated active species (B) is 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 11
4 is a solid Ge particle, 115 is an introduction pipe for a compound containing gaseous germanium and halogen, which is a raw material for active species, and the active species generated in the activation chamber 112 are transferred to the film forming chamber lot through an introduction pipe 116. be introduced within.

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

The heat from the thermal energy generator 117 is irradiated to the active species flowing in the direction of the arrow 119, and the irradiated active species chemically react with each other to form A-Ge( A deposited film of H, X) is formed. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

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 10-8 Torr. Gas supply cylinder 106J: GGeH4150SCC,
Alternatively, a gas mixed with 403 CCM of PH3 gas or 82H6 gas (both diluted with 11000 pp hydrogen gas) is supplied to the activation chamber (B) 12 through the gas introduction pipe 110.
It was introduced in 3. G introduced into the activation chamber (B) 123
The eH4 gas and the like were activated by the microwave plasma generator 122 to become 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, solid Ge particles 114 are packed in the activation chamber 1 and 2, heated in an electric furnace 113 to bring the Ge to a red-hot state, and GeF4
By injecting GeF2 as an active species (A)
was generated, and the GeF2* was introduced into the film forming chamber 101 through the introduction pipe 116.

The pressure inside the film forming chamber 101 is maintained at 0.4 Torr or the doped A-Ge (H,
0 people) were formed. The film formation rate was 12 seconds/sec.

Next, the obtained non-doped or p-type A-Ge
Place the (H,X) film sample in a vapor deposition tank and
rr with a comb-shaped AI gap electrode (gap length 250.
, width 5 mm), the dark current was measured at an applied voltage of 10 V, the dark conductivity σd was determined, and A-Ge(H,
X) The membrane was evaluated. The results are shown in Table 1.

Examples 2-4 Instead of GeH4, linear Ge4HH), branched Ge4H
Example 1 except that to, or H6Ge6Fs was used.
An A-Ge(H,X) film was formed according to the same method and procedure. Measure the dark conductivity of each sample and share the results with the
Shown in the table.

From Table 1, it is clear that according to the present invention, A-Ge has excellent electrical properties.
It was found that a (H,X) film was obtained and that a sufficiently doped A-Ge(H,X) film was 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 an activation chamber, and 20
3 is an electric furnace, 204 is solid Ge particles, 205 is an active species (A
), 206 is an active species (A) introduction pipe, 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 an At cylindrical base, and 212 is an exhaust valve. Also, 213 to 216 are 10 in Figure 1.
It is a raw material gas supply system similar to 6 to 109, and 217-
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.

Further, the activation chamber (A) 202 is filled with solid Ge particles 204 and heated in an electric furnace 203.

By bringing Ge into a red-hot state and blowing GeF4 into it from a cylinder (not shown) through the introduction pipe 206, GeF2* as an active species (A) is generated.
After that, it was introduced into the GeF2)k film forming chamber 201.

On the other hand, from the introduction pipe 217-1, Si2H6 and GeH4,H
The two gases undergo activation processing such as plasma conversion by the microwave plasma generator 221 in the activation chamber (B) No. 2, and become silicon hydride active species, germanium hydride active species, activated hydrogen, etc. It was introduced into the film forming chamber 201 through 217-2. At this time, the film forming chamber 20
The inside of the film forming chamber 201 was maintained at 205° C. by a thermal energy generator while maintaining the atmospheric pressure inside the film forming chamber 201 at 1.0 Torr.

The AI cylinder base 211 was held and rotated, and the exhaust gas was exhausted through the exhaust valve 212. In this way, the photosensitive layer 13 was formed.

Further, the intermediate layer 12 is connected to the introduction tube 21 before the photosensitive layer 13.
From 7-1, Si2H6, GeH4゜H2 and B2H6 (
A mixed gas containing B2H6 gas (0.2% by volume) was introduced, and a film was formed to a film thickness of 2000.

Comparative Example 1 GeF4 and S f 2H6, GeHa, H2 and B2
A film forming chamber with the same configuration as the film forming chamber 201 is prepared using H13 gases, equipped with a 13.56 MHz high frequency device, and the layer structure shown in FIG. 1 is formed by a general plasma CVD method. A drum-shaped electrophotographic imaging member was formed.

The manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 5 and Comparative Example 1 are as shown in FIG. The PIN type diode shown was fabricated. First, the polyethylene naphthalate film 21 on which the 1000 ITO film 22 was deposited was placed on a support stand, and the IO''
After reducing the pressure to 8 Torr, the introduction pipe 11 was opened in the same manner as in Example 1.
Introducing active species of GeF2* from 6 into the film forming chamber 101,
Also, from the introduction pipe 110, Si2Hs150SCCM, GG
eH450SCC, PH3 gas (diluted with 1000 ppm hydrogen gas) was introduced into the activation chamber (B) 123 and activated.Next, this activated gas was introduced through the introduction pipe 116 to reduce the pressure in the film forming chamber 101. 0. I T o r r
, while keeping the film forming chamber temperature at 240°C, an n-type A-S iGe (H,X) film 24 doped with P (thickness 70
0 people) were formed.

Next, instead of PH3 gas, B2H6 gas (300pp
n-type A-5iGe except that hydrogen gas dilution) was introduced.
(H,X)II! Type i A-5iG in the same manner as in case of
e (H,X) film 25 (thickness: 5000) was formed.

Next, B2H6 gas (looOpp
The p-type A-3iGe(H,X) film 26 (H,
A film thickness of 700 layers was formed. Furthermore, on this p-type film, an AI electrode 27 with a film thickness of 1000 layers is formed by vacuum evaporation.
An IN type diode was obtained.

Diode element thus obtained (area 1cm2)
The r-v characteristics were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, light is introduced from the substrate side, and at the light irradiation intensity AMI (approximately 100 mW/cm2), the conversion efficiency is 6.8% or more, the open circuit voltage is 0687V, and the short circuit current is 11.5mA/cm2. Obtained.

Examples 7 to 9 PIN type diodes were produced in the same manner as in Example 6, except that linear Ge4H10 and branched G+94HIQ were used instead of GeH4 as the germanium-containing compound. The rectification characteristics and photovoltaic effect of this sample were evaluated, and the results are shown in Table 3.According to the present invention, A-StG has better optical and electrical characteristics than the conventional one.
It was found that an e(H,X) PIN type diode can be obtained.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible. In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. be able to. Furthermore,
Because relatively low thermal energy is used as excitation energy during film formation, films can be formed even on substrates 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. It is a diagram. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the invention method used in the examples, respectively. 10--An 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. 101, 201----1 film formation chamber, 106.107, 108, 109, 213°214.2
15.216---Gas supply system, 103, 211-
--One base. 117.218--Thermal energy generating device.

Claims (1)

[Claims] Chemically interacts with active species (A) generated by decomposing a compound containing germanium and halogen in a film formation space for forming a deposited film on a substrate. , active species (B) generated from a germanium-containing compound for film formation are separately introduced, and thermal energy is applied to these to cause a chemical reaction, thereby forming a deposited film on the substrate. Characteristic deposited film formation method.