JPS61196523A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To attain enlargement, improvement of productivity and mass production of the title deposited films by a method wherein an active compound (A) and another active compound (B) are separately fed to a filming space to be irradiated with photo energy. CONSTITUTION:In the coexistance 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 nitrogen contained filming compound, the deposited films are to be formed by means of irradiating the active compounds (A) and (B) with photoenergy 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 accelerated 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 nitrogen-containing deposited film, particularly a functional film, particularly a nitrogen-sensitive deposited film for semiconductor devices and electrophotography. [Prior art] For example, vacuum evaporation, plasma CVD, CVD, reactive sputtering, ion blasting, photo-CVD, etc. have been tried to form an amorphous silicon film. Generally, the plasma CVD method is 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. Forming an amorphous silicon deposited film using a method requires a large amount of equipment investment for mass production equipment, and the management items for mass production are also complex, the tolerance range for management is narrow, and the adjustment of the equipment is delicate. 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 the characteristics, film formation speed, and reproducibility of the film to be formed, and to make the film uniform in quality. The object of the present invention is to provide a deposited film forming method that can be easily achieved.

The above purpose is to create an active species (A) generated by decomposing a compound containing 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). A deposited film is formed on the substrate by separately introducing active species (B) generated from interacting nitrogen-containing compounds and irradiating them with light energy to cause a chemical reaction. This is achieved by the deposited film forming method of the present invention.

[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 nitrogen-containing compound for film formation are used. In coexistence with the active species (B) generated by the active species (B), by applying light energy to the active species (B), a chemical interaction is caused, or is promoted or amplified by the active species (B), so that a deposit is formed. 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.

Furthermore, excitation energy is applied uniformly or selectively to the raw material that has reached the vicinity of the substrate for film formation, but if optical energy is used, the entire base can be irradiated using an appropriate optical system. The deposited film can be formed by selectively controlling only the desired area, or the deposited film can be formed partially by irradiating only the desired area, or by using a resist etc. to irradiate only the predetermined graphic area. It is advantageously used because it has the convenience of being able to form a deposited film with a high temperature.

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). As a result, it is possible to increase the film formation rate compared to the conventional CVD method, and in addition, it is possible to further lower the substrate temperature during deposited 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 present invention, the active species (A) is a species that chemically interacts with the active species (B) generated from the nitrogen-containing compound to impart energy or cause a chemical reaction. Therefore, the active species (A) may include constituent elements constituting the deposited film to be formed. Alternatively, it may not include such components.

Correspondingly, the nitrogen-containing compound used in the present invention may be a nitrogen-containing compound that can serve as a raw material for forming a deposited film by containing constituent elements constituting the deposited film to be formed; It may be a nitrogen-containing compound that does not contain the constituent elements constituting the deposited film to be formed and can simply be a raw material for film formation, or it can be a nitrogen-containing compound that can be a raw material for forming a deposited film and a film-forming compound. It may also be used in combination with a nitrogen-containing compound that can be a raw material for.

The nitrogen-containing compound used in the present invention is activated space (B)
For example, when using liquid and solid compounds in the standard state, an appropriate vaporization device is added to the compound supply system. can be connected to vaporize the compound and then introduce it into the activation space (B).

Examples of the nitrogen-containing compound include simple nitrogen (N2), and compounds having nitrogen and one or more atoms other than nitrogen as constituent atoms.

Examples of atoms other than nitrogen include hydrogen (H) and halogen (
X=F, CI, Br or ■), sulfur (S), carbon (C
), boron (0), silicon (St), germanium (Ge
), and in addition, most atoms that can be combined with nitrogen among atoms of elements belonging to each group of the periodic table and that can be constituent atoms of a compound that can achieve the purpose of the present invention. atoms can be used.

By the way, for example, as a compound containing N and H.

NH3, NH4N3, NH3, H2NNH2.

Compounds containing N and X, such as primary to tertiary amines, halides of these amines, hydroxylamine, NX
3, N3X, N2X2, N.

Examples of compounds containing N and S such as X, N02X, N03X4, etc. include Na54. Compounds containing N and C such as N255 include N (CH3)3HCN, cyanide compounds, HO
As a compound containing CN, H5CN, N and O, N20
, NO, NO2.

Examples include N2O3, N2O4, N2O5, NO3, and the like.

In addition, silazane and organosilicon compounds having a 5t-N bond, such as organosilazane, organosilicon isocyanate, organosilicon inthiocyanate, and the like can also be mentioned. Specifically, silazane includes disilazane and trisilazane.

As organosilazane, triethylsilazane (C2H5)
3 S i NH2 hexamethyldisilazane
((CH3)3Si)2NH hexaethyldisilazane ((C2H5)3Si)2NH organosilicon isocyanate.

Trimethyl silicon isocyanate (CH3)3S
iNCO dimethyl silicone diisocyanate (CH3
)2Si (NCO)2 organosilicon inthiocyanate includes trimethyl silicon inthiocyanate (CH3) 3 Si NCS and the like.

The nitrogen-containing compounds used in the present invention are not limited to these.

Even if one type of these nitrogen-containing compounds is used, the
) from the viewpoint of productivity and ease of handling, the active species (A) is selected as desired, with a lifespan of 0.1 seconds or more, more preferably 1 second or more, optimally 10 seconds. and used.

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 1, for example, a chain germanium halide represented by GeuY2u+2 (u is an integer of 1 or more, Y is at least one element selected from F, C1, Br, and I), G e vY Cyclic germanium halide represented by 2 y (V is an integer of 3 or more, Y has the above-mentioned meaning), GeuHxYy (u and Y have the above-mentioned meaning. X+7=2u or 2u+2) Examples include chain or cyclic compounds.

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

(GeF2)e, (GeF2)4. Ge2Fs.

Ge3FB, GeHF3, GeHBr3.

GeCl4. (GeC12)5. GeBr4゜(GeB
r2)5. Ge2C1s, Ge2Brs.

GeHCl3. GeHBr3. GeHI3. Ge2c1
Examples include those in a gaseous state or easily gasified, such as 3F3.

Furthermore, in the present invention, active species (A
), active species produced by decomposing a compound containing silicon and halogen and/or active species produced by decomposing a compound containing carbon and halogen can be used in combination.

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, 5iuY2u+2 (u is 1 or more). integer, Y
are F, C1, Br and I. ), a cyclic silicon halide represented by 5iyY2v (v is an integer of 3 or more, Y has the above-mentioned meaning), 5iuHXYy (U and Y have the above-mentioned meaning).

x+y=2u or 2u+2. ), and the like.

Specifically, for example, SiF4. (SiF2)5, (Si
F2)s, (SiF2)4,5i2FB, Si3F8.
SiHF3. SiH2F2°5fCI4. (SiCl2
)5. SiBr4゜(SiBr2)5.5i2C16,
5i2Br6.5iHCu3, 5iHBr3, 5iHI
These silicon-containing 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, 1, for example, cuy2u+2(uj* An integer greater than or equal to 1, Y
is F, C1.

Br or I. ) chain halogenated carbon,
Cyclic silicon halide, CuHxYy, represented by CVY2V (V is an integer of 3 or more, Y has the above meaning)
(U and Y have the above-mentioned meanings. X+7=2u or 2u+2.) Chain or cyclic compounds, etc. are mentioned.

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

(CF2)s, (CF2)4. C2F6゜C3FB,C
HF3. CH2F2. CCl4° (CCI2)5. C.B.
r4. (CBr2) 5° C2C16, C2Cl3F3, etc., which are in a gaseous state or can be easily gasified are mentioned.

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

In order to generate an active species, for example, when generating an active species (A) of a compound containing germanium and a halogen, in addition to this compound, if necessary, a germanium compound having the same ability as germanium alone, hydrogen, and a halogen are added. Compounds (e.g. F2 gas, ci2 gas, gasified Br2゜■
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, infrared heating, and light energy is used.

In the present invention, the ratio of the amount of the active species (B) generated from the nitrogen-containing compound introduced into the film forming space and the active species (A) can be determined as appropriate depending on the deposition conditions, the type of the active species, etc. Although it is determined according to
It is desirable to set it to 6.

In the present invention, in addition to nitrogen-containing compounds, hydrogen gas, halogen compounds (for example, F2 gas, C12 gas, gasified Br2.l2W), helium, fluorine, neon, and other non-containing materials are used as raw materials for film formation. Active gas and active space (
In B), a silicon-containing compound, a carbon-containing compound, a germanium-containing compound is used as a raw material for forming a deposited film to generate the active species CB), and an oxygen-containing compound is used as a raw material for forming a deposited film and/or a film-forming raw material. It can also be used by introducing it into the activation space (B). If a plurality of these chemicals are used, they can be premixed and introduced into the activation space CB) in gaseous form, or they can be individually introduced in gaseous form from separate sources. It can also be supplied to the activation space (B) and introduced into the activation space (B).
Alternatively, they can be introduced into independent activation spaces and activated individually.

As the silicon-containing compound for forming the 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, 5L3H
B, S i 4) (to, S i 5) (12,5i
5ipH2p+2 such as 6H14 (p is an integer of 1 or more, preferably 1 to 15, more preferably 1 to 10).
A linear silane compound represented by S 1H3S iH (
S 1H3)S iH3,5iH3SiH(SiH3)
Si3H7,5i2H5SiH(SiH3)Si2H5
etc. 5ipH2F+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
A cyclic silane compound represented by 5i (lH2q (q is an integer of 3 or more, preferably 3 to 6) such as 6,5i4Hs, 5i5H10, Si6HI3, a part of the hydrogen atom of the cyclic silane compound, or Examples of compounds in which all of the silanyl groups are substituted with other cyclic silanyl groups and/or chain 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
S i rH such as H3C1, 5iH3Br, 5iH3I, etc.
sXt (X is a halogen atom, r is an integer of 1 or more, preferably 1 to 10, more preferably 3 to 7, s + t = 2r
+2 or 2r. ) and halogen-substituted linear or cyclic silane compounds. These compounds are 1
You may use a seed or a combination of two or more types.

In addition, carbon-containing compounds for forming a deposited film include chain or cyclic saturated or unsaturated hydrocarbon compounds whose main constituent atoms are carbon and hydrogen, and one or more of silicon, halogen, sulfur, etc. Among organic compounds having constituent atoms, organosilicon compounds having hydrocarbon groups, etc., those in a gaseous state or those that can be easily vaporized are preferably used. Among these, examples of hydrocarbon compounds include, for example, saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, etc. Hydrocarbons include methane (CH3), ethane (C2Hs), and propa7 (C3H8).

n--buta7 (n-C4H10), pentane (C5
H12), ethylene (C2
H4), propylene (C3H6).

Butene-1 (C4H8), Butene-2 (C4H8), Isobutylene (C4H8), Pentene (C5H10), Acetylene (C2H2) as an acetylene hydrocarbon.
, 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 Cu, Br, I can be mentioned,
Particularly effective are compounds in which hydrogen is substituted with F or CM.

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-n, RmSiX4-m (
However, R: alkyl group, aryl group, X: F, C1, B
r, I, n=1,2,3,4, m=1 + 2 + 3
), and representative examples thereof include alkylsilanes, arylsilanes, alkylhalogensilanes, and arylhalogensilanes.

Specifically, as organochlorosilane, trichloromethylsilane CH3S i
C13 dichlorodimethylsilane (CH
3) 2S i CJL2 chlorotrimethylsilane
(CH3) 3S i Cl trichloroethylsilane C2H55iCu3 dichlorodiethylsilane (C2H5)2S 1
As c12 organochlorofluorosilane, chlordifluoromethylsilane CCH3S1F2C dichlorofluoromethylsilane CH35iFCJ
L2 Chlorfluorodimethylsilane (CH3)
2 S i FCI Chlorethyldifluorosilane
(C2H5)SiF2CJ1 Dichloroethylfluorosilane C2H55iFCmi2 Chlordifluoroprobylsilane C3H75iF2C4 Dichlorofluoropropylsilane C3H75iFCu2
As organosilane, tetramethylsilane (CH3)
4S i Ethyltrimethylsilane (C
H3) 3S 1c2Hs trimethylzorobylsilane
(CH3)3SiC3H7 triethylmethylsilane CH35i (C2H5)3tetraethylsilane (C2H5)4S
As organohydrogenosilane, methylsilane CH35iH3
Dimenarsilane (CH3)
2siH2 trimethylsilane (
CH3) 3 S i H diethylsilane
(C2H5)2SiH2triethylsilane (C2H5)3S iH tripropylsilane (C3H7)3Si
H diphenylsilane (CsHs
)2S iH2 Organofluorosilane is trifluoromethylsilane CH35iF3
Difluorodimethylsilane (CH3)2
5iF2 Fluorotrimethylsilane (CH
3) 3S i F ethyltrifluorosilane
C2H55iF3 diethyldifluorosilane
(C2H5) 2 S i F2 triethylfluorosilane (C2H5) 3 S i
F trifluoropropylsilane (C3H
7) As S i F3 organobromosilane, Bromotrimethylsilane (CH3)3
SiBrdibromdimethylsilane (C
H3)25iBr2, etc., and other organopolysilanes include hexamethyldisilane ((CH3)
3Si) As the diorganodisilane, hexamethyldisilane ((CH3)
3Si) 2hexapropyldisilane
((C3H7) 3 S i) 2 etc. can also be used.

In addition, as organosilicon compounds, (CH3) 4S t, CH3S i Cl 3, (
CH3)25iC12, (CH3)3SiC1,C2H
Organocrosillane such as 55iC13, CH35iF
2C1, CH35iFC12, (CH3)25iFC1
, C2H55iF2C1, C2H55i FCl 2,
Organochlorofluorosilane such as C3H75iF2C1, C3H75i FCl2, [(CH3)3S i
l 2 , [(C3H7)3Si] 2i organodisilazane, etc. are preferably used.

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

In addition, germanium-containing compounds for forming deposited films include:
Inorganic or organic germanium compounds in which hydrogen, halogen, or hydrocarbon groups are bonded to germanium can be used, such as Ge1Hb (a is an integer of 1 or more,
b=2a+2 or 2a. ), a polymer of this hydrogenated germanium, a compound in which part or all of the hydrogen atoms of the hydrogenated germanium are replaced with halogen atoms, one of the hydrogen atoms of the hydrogenated germanium Part or all of it can be substituted with a Ja-containing group such as an alkyl group or an aryl group, and optionally a halogen atom.

Specifically, for example, GeH4, Ge2H6.

Ge3HB, n-Ge4H10, tert-G
e4H10, Ge3H6, Ge5H10.

GeH3F, GeH3C1, GeH2F2゜HsGe6
Fe, Ge (CH3)a, Ge (C2H5) 4.
Ge (GeH5)a, Ge (CH3)2F2,
CH3GeH3,' (CH3)2G13H2, (CH
3) 3GeH, (C2H5)2GeH2, GeF2.
GeF4. Examples include GeS. These germanium compounds may be used alone or in combination of two or more.

Further, as oxygen-containing compounds, oxygen (02), ozone (
Examples include compounds consisting of simple oxygen such as 03) and compounds having oxygen and one or more atoms other than oxygen as constituent atoms. The atoms other than oxygen include hydrogen (
H), /\Roge7 (X=F, Cl, Br or I),
Sulfur (S), carbon (C), silicon (Si), germanium (Ge), etc. are atoms of other elements belonging to each group of the periodic table that can be combined with oxygen, and the present invention Most atoms can be used as long as they are atoms constituting a compound that can achieve the purpose.

For example, compounds containing O and H include H2O, H
Compounds containing o and S, such as 2O2, are S02 and S03
As oxides such as, compounds containing 0 and C,
Compounds containing 0 and Si, such as oxides such as co/CO2, and materials are disiloxane (H3SiO3iH
3), Trisiloxane (H3S i OS i H2O
51H3), (CH3) 2si(O
COCH3)2, CH3S i (OCOCH3)3
Organoacetoxysila Otsu (CH3) 3S 1Oc
H3, (CH3)251(OCH3)2. CH35i
Furkylalkoxysilane such as (OCH3)3, (CH
3) 3SiOH, (CH3)2 (C6H5)StOH
.

Compounds containing O and Ge, such as organosilanols such as (C2H5)2S i (OH)2, include Ge oxides, hydroxides, germanic acids, H3GeOGeH
Examples include organic germanium compounds such as 3, H3GeOGeH20-GeH3.

Even if one of these oxygen-containing compounds is used, it is possible to dope with a certain impurity element. The impurity element used is, as a p-type impurity, an element of group Ⅰ A of the periodic table, such as B.

Preferred examples include Al, Ga, In, TI, etc., and preferred n-type impurities include elements of group V A of the periodic table, such as P, As, Sb, Bi, etc. Especially B, Ga.

p, sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical-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 activation conditions, and that can be easily vaporized with an appropriate vaporization device. Such compounds which are preferably selected include PH3, P2H4, PF3.

PF5. PCl3. A5H3, AsF3. AsF5. A
sCl3. SbH3, SbF5. SiH3, BF3. B
Cl3. BBr3. B2H6゜B4H10, B5H9,
Examples include B5H11, B6H10°B6H12, and AlCl3. 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 M (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 CB), is subjected to the activation energy described above. They can be selected and adopted as appropriate. Impurely mixed,
Alternatively, it is introduced into the film forming space independently.

Next, the present invention will be described with reference to typical examples of electrophotographic image forming members 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 1O 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 manufactured 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 13, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical breakdown voltage. In some cases, these can also be created using 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, Al, Cr, and Mo.

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

Examples include metals such as Pd and alloys thereof.

Polyester is used as the electrically insulating support.

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.

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

V, Ti, Pt, Pd, In2O3, 5n02゜ITO
(I n203+5no2), 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 irradiation, sputtering, etc., or laminated with the metal, so that the surface thereof is conductive. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined depending on the needs.For example, the photoconductive member 10 in FIG. If used as a member, in the case of continuous high-speed copying, 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.
From the side of the photosensitive layer 13 to the side of the support 11, the photo-carriers are generated in the photosensitive layer 13 by the irradiation of electromagnetic waves and move toward the side of the support 11, effectively preventing the inflow of carriers into the photo-carrier. It has a function that allows easy passage of.

This intermediate layer 12 is made of amorphous germanium (under U, A-Ge (H ,
In the present invention, the content of substances controlling conductivity, such as B and P, contained in the intermediate layer 12 is preferably 0.
001 to 5×104 atomic PPm, more preferably 0.5 to 1×11×104 atomic ppm, optimally 1 to 5×1θ3 atomic ppm.

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

Alternatively, if they are the same, the formation of the photosensitive layer 13 can be performed continuously after the formation of the intermediate layer. In that case, the activation space (A) is used as a raw material for forming the intermediate layer.
The activated species (A) generated in the above, a nitrogen-containing compound in a gaseous state, hydrogen, a halogen compound, an inert gas as necessary,
Active species (B) generated from a silicon-containing compound, a carbon-containing compound, a germanium-containing compound, an oxygen-containing compound, and an active species generated by activating a gas of a compound containing an impurity element as a component, respectively. The support 11 is introduced into the film forming space in which the support 11 is installed, either separately or mixed as necessary, and by irradiating the coexistence atmosphere of each introduced active species with light energy.
The intermediate layer 12 may be formed thereon.

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 the above-mentioned compounds.

The thickness of the intermediate layer 12 is preferably 30 mm to 10 mm, more preferably 40 mm to 8 mm, most preferably 50 mm to 5 mm.

The photosensitive layer 13 is made of, for example, A-SiGe (H).

X), and 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 as follows.

1 to 1 OOIL, more preferably 1 to 80-1 optimally 2
It is desirable that the amount be set at ~50 ru.

The photosensitive layer 13 is made of non-doped (7)A-3iGe (H.

X) layer, which optionally contains nitrogen atoms or a substance that controls conduction characteristics of a polarity different from the polarity of the substance that controls conduction characteristics contained in the intermediate layer 12 (for example, n-type). Alternatively, if the actual amount contained in the intermediate layer 12 is large, the substance controlling the conduction properties of the same polarity may be contained in an amount 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 these are heated at high temperature. or introduced between discharge channels.

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. This can be carried out in the same manner as in the method of the present invention.

FIG. 2 is a schematic diagram showing an example of a PIN type diode device using an A-GeN (H, .

In the figure, 21 is a base, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an n-type semiconductor layer 24, an i-type semiconductor layer 2
5. Consisting of a p-type semiconductor layer 26. 28 is a conductive wire connected to an external electric circuit device.

These semiconductor layers are composed of A-GeN (H, The conversion efficiency can be increased by creating the following method.

The base 21 may be conductive, semiconductive, or electrically insulating. If the substrate 21 is conductive, the thin film electrode 22 may be omitted. Examples of semiconductive substrates include Si, Ge, GaAs, and ZnO.
, ZnS, and other semiconductors. Thin film electrode 22.27
Examples include NiCr, Al, Cr, and Mo.

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

Pd, I n203. SnO2, ITO(I n2o
It can be obtained by providing a thin film such as 3+5n02) on the substrate 21 by a process such as vacuum deposition, electron beam deposition, or sputtering. The layer thickness of the electrode 22.27 is preferably 30 to 5 x 104, more preferably 100 to 5
It is desirable that the number be 503 people.

In order to make the film constituting the semiconductor layer n-type or p-type as necessary, a layer containing n-type impurities, p-type impurities, or both impurities among impurity elements is added during layer formation. It is formed by doping in a controlled amount.

When forming n-type, i-type, and p-type semiconductor layers by the method of the present invention, any one layer or all of the layers can be formed by the method of the present invention, and the film formation is performed in an activated space. (
A compound containing germanium and halogen is introduced into A), and by exciting and decomposing them under the action of activation energy, an active species (A) such as SiF2* is generated, and the active species (A) is ) is introduced into the film forming space. Apart from this, gaseous nitrogen-containing compounds, silicon-containing compounds, germanium-containing compounds, oxygen-containing compounds as necessary, and compound gases containing inert gases and impurity elements as necessary, etc. are excited and decomposed by their respective activation energies, and the respective iodine JfJ: 瀘
11) are mixed individually or suitably and introduced into the film forming space where the support 11 is installed. The active species introduced into the film forming space are chemically interacted with, promoted or amplified, and a deposited film is formed on the support 11 . The layer thickness of the n-type and p-type semiconductor layers is preferably 100-104, more preferably 300-20
A range of 00 people is desirable.

Further, the layer thickness of the i-type semiconductor layer is 1, preferably 5.
00-104 people, more preferably 1000-toooo
A range of people is preferable.

Or, in addition to nitrogen-containing compounds, hydrogen.

By appropriately combining halogens, silicon-containing compounds, germanium-containing compounds, carbon-containing compounds, oxygen-containing compounds, etc., N and these HlX, Si,
It is also possible to form a film body with desired characteristics using a bond with Ge, C10, etc. as a constituent unit.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Fig. 2, i
Type, pf! and the substrate support 10 of the n-type nitrogen-containing part.
A desired substrate 103 is placed on the substrate 2 .

104 is a heater for heating the substrate;
4 is used when heat-treating the base 103 before film formation, or performing a 7-neal treatment after film formation to further improve the properties of the formed film, and is supplied with power through a conductor 105. I get a fever. During film formation, the heater 104 is not driven.

106 to 109 are gas supply sources, which supply nitrogen-containing compounds, hydrogen, halogen compounds, inert gases, silicon-containing compounds, carbon-containing compounds, germanium-containing compounds, oxygen-containing compounds, and impurity elements. It is provided depending on the type of gas such as the compound as a component.

When using liquid materials in standard conditions among these raw material compounds, an appropriate vaporization device is provided.

In the figure, the gas supply sources 106 to 109 with the symbol a are branch pipes, and the symbol b is the 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 activated species (B)
A microwave plasma generator 122 that generates activation energy for generating active species (B) is provided around the activation chamber 123. Gas introduction%l
The raw material gas for generating active species (B) supplied from 11O is activated in the activation chamber (B) 123, and the generated active species (B) passes through the introduction pipe 124. Activation chamber (A), 113 is an electric furnace, 114 is solid Ge particles,
Reference numeral 115 is an introduction pipe for a compound containing gaseous germanium and halogen, which is a raw material for active species (A), and active species (A) generated in activation chamber (A) 112 are introduced into introduction pipe 116.
The film is introduced into the film forming chamber 101 through the film forming chamber 101 .

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

The light 11B directed from the optical energy generator 117 to the entire substrate 103 or a desired portion of the substrate 103 using an appropriate optical system is irradiated onto the active species flowing in the direction of the arrow 119, and the irradiated active species are A mutual chemical reaction forms a nitrogen-containing amorphous deposited film on the entire substrate 103 or on a desired portion.

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

Base made of polyethylene terephthalate film 103
is placed on the support stand 102.

Evacuate the inside of the film forming chamber 101 using an exhaust device (not shown),
The pressure was reduced to approximately 10-8 Torr. Gas supply pump 10
From 6, NN2150SCC, or a gas mixed with 40SCCM of PH3 gas or B2H6 gas (all diluted with 11000pp hydrogen gas) was introduced into the gas introduction pipe 110.
was introduced into the activation chamber (B) 123 via the. Activation chamber (
B) The N2 gas etc. introduced into the chamber 123 is activated by the microwave plasma generator 122 and becomes viscous nitrogen etc., and the activated nitrogen etc. is introduced into the film forming chamber l through the introduction pipe 124.
It was introduced into ot.

On the other hand, the activation chamber (A) l deaf 2 is filled with solid Ge grains 114, heated in an electric furnace 113 and kept at about 1100°C to bring the Ge to a red-hot state. By blowing GeF4 from a pump, active species of GeF2)jc are generated, and while the GeF2* is introduced into the film forming chamber 101 through the introduction pipe 116, the IK
A non-doped or doped nitrogen-containing amorphous deposited film (
A film thickness of 700 layers was formed. Film deposition speed is 30 people/s
It was e.c.

Next, each of the obtained non-doped, p-type, or n-type samples was placed in a vapor deposition tank, and a comb-shaped Al gap electrode (gap length 250 g, width 5
mm), the dark current was measured at an applied voltage of lOv, the dark conductivity σd was determined, and the film characteristics of each sample were evaluated.

The results are shown in Table 1.

Examples 2-4 Along with H2, S i 2H6, Ge2H6, or C2H
A nitrogen-containing amorphous deposited film was formed in the same manner as in Example 1, except that No. 6 was used.

The dark conductivity of each sample was measured and the results are shown in Table 1.

Table 1 shows that according to the present invention, a nitrogen-containing amorphous deposited film with excellent electrical properties can be obtained, and a nitrogen-containing amorphous film that is sufficiently doped can be obtained.

Examples 5-8 N217) Alternatively, NH3, NOF, NO2 or N2
A nitrogen-containing amorphous deposited film was formed in the same manner as in Example 1 except that 0 was used.

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

Example 9 Using the apparatus shown in Fig. 3, the first
A drum-shaped electrophotographic image forming member having a layer structure as shown in the figure was prepared.

In FIG. 3, 201 is a film forming chamber, 202 is an activation chamber (
A), 203 is an electric furnace, 204 is a solid Si particle, 205
206 is the active species (A) raw material introduction pipe; 206 is the active species (A)
) Introductory pipe, 207 is the motor, 208 is 104 in Fig. 2
209 and 210 are blowout q, ztt is an AI cylinder-shaped base, and 212 is an exhaust valve. or.

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 At cylinder 211 is suspended in the film forming chamber 201, and a heater 208 is provided inside the cylinder so that it can be rotated by a motor 207.

Reference numeral 218 denotes a light energy generating device, which irradiated light 219 toward a desired portion of the An cylindrical substrate 211.

In addition, the activation chamber (A) 202 is filled with solid Ge particles 204, heated in an electric furnace 203, and kept at about 1100°C.
By bringing Ge into a red-hot state and blowing GeF4 into it from a cylinder (not shown) through the introduction pipe 206, active species (A) and Te (1) G e F 2 * are generated,
The GeF2* was introduced into the film forming chamber 201 through the introduction pipe 20B.

Meanwhile, Si2H6 and N2 gases were introduced into the activation chamber (B) 220 through the introduction pipe 217-1. Introduced Si
The 2H6 and N2 gases undergo activation processing such as plasma conversion by the microwave plasma generator 221 in the activation chamber (B) 220 to become activated silicon hydride and activated hydrogen, which are then formed through the introduction pipe 217-2. Introduced into the membrane chamber 201. At this time, impurity gases such as PH3 and B2H6 were also introduced into the activation chamber (B) 220 for activation, if necessary.

While maintaining the atmospheric pressure in the film forming chamber 201 at 1.0 Torr, the I
Light was irradiated from the KWXe lamp 218 perpendicularly to the circumferential surface of the A-vertical cylinder 211.

The Al cylindrical base 211 is rotated, and the exhaust gas is exhausted through the exhaust valve 212.

In this way, the photosensitive layer 13 is formed.

Furthermore, prior to the formation of the photosensitive layer 13, the intermediate layer 12 is supplied with an inlet pipe 217- in addition to the gas used when forming the photosensitive layer 13.
A mixed gas of Si2H6, N2, N2 and B2H6 (B2H6 gas is O32% in volume %) was introduced from 1, and the film thickness was 2.
It was successful with 9,000 people.

Comparative Example 1 GeF4 and S i 2H6, N2, N2 and B2H6
A film forming chamber with the same configuration as the film forming chamber 201 was prepared using each of the following gases, and equipped with a 13.56 MHz high frequency device. Electrophotography of the layer structure shown in FIG. 1 was performed using a general plasma CVD method. An imaging member was formed.

The manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 9 and Comparative Example 1 are shown in FIG. 2 using N2 as the nitrogen compound and the apparatus shown in FIG. The PIN type diode shown was manufactured.

First, a polyethylene naphthalate film 21 on which 1000 ITO films 22 were vapor-deposited was placed on a support stand, and 104
After reducing the pressure to Torr, the active species GeF2)k produced in the same manner as in Example 1 was introduced into the film forming chamber 101. Also, 5
Each of i3H6 gas and PH3 gas (diluted with 1000 ppm hydrogen gas) is introduced into the activation chamber CB) 123, and the activated gases are then introduced into the film forming chamber 101 through the introduction pipe 116. , the pressure inside the deposition chamber was set to 0.4T.
A p-doped n-type A-SiGeN (H,

Next, the n-type A-5 except that the introduction of PH3 gas was stopped.
Non-doped A-SiGeN(H.

X) Film 25 (film thickness: 5000 layers) was formed.

Next, Si 2H6 gas and N2 gas.

B2H6 gas (1000 ppm hydrogen gas dilution) P-type nitrogen-containing A-SiGeN (H,
was formed. Further, an AI electrode 27 having a H film thickness of 1000 mm was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

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 8.4% or more, the open circuit voltage is 0.9 V, and the short circuit current is 10.
2 mA/cm2 was obtained.

Examples 11-13 Instead of N2 as a nitrogen compound, No, N20, N2
Example 1 was carried out in the same manner as in Example 1O except that O4 was used.
A PIN type diode similar to that made in 0 was fabricated. This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible without maintaining the substrate at a high temperature. It becomes 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, since light energy is used as excitation energy in the film forming space, the film can be formed even on a substrate with poor heat resistance, and the process can be shortened by low-temperature processing.

[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. FIGS. 2 and 3 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, 101, 201---One film forming chamber, 11↓, 202---One activation chamber (A), 123 .22
0---1 activation chamber CB) 106.107,108. L
O9,213°214.215,216---Gas supply source, 103,211---One substrate. 117.218---One light energy generator.

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 generated from nitrogen-containing compounds (B)
A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing each of these separately and irradiating them with light energy to cause a chemical reaction.