JPS61198619A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To facilitate the increase in area of the film, improvement in productivity, and mass productivity, while contriving the improvement in film properties, film-forming speed, and reproducibility, and the uniformity in film quality, by a method wherein an active seed A produced by decomposing a compound containing carbon and halogen and an active species B produced out of a nitrogen-containing compound are separately introduced, which are then made to chemically react by the action of discharge energy, thus forming a deposited film. CONSTITUTION:A discharge energy which can form an activating atmosphere such as plasma is used as the energy to excite and make react the material for forming deposited films. Under the coexistence of an active seed A produced by decomposing the compound containing carbon and halogen and an active species B produced out of the film-forming nitrogen-containing compound, the chemical interaction by these seeds is caused by making discharge energy act on them or promoted and amplified; therefore, film formation is enabled also by lower discharge energy than conventional. The formed deposited film does not receive adverse effects such as etching or another action, e.g. abnormal discharge substantially.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to oxygen-containing membranes, especially functional membranes,
In particular, the present invention relates to a method suitable for forming an amorphous or crystalline oxygen-containing deposited film for use in semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, photography devices, and the like.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using a vacuum evaporation method, a glasma cyo method, a C'VD method, a reactive sputtering method, an ion blasting method, a photo-CVD method, etc., and in general, plasma CVD method is used. Laws are widely used and corporatized.

Deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity and mass production, including uniformity and reproducibility. , there is room for further improvement of comprehensive 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 method, and the reaction structure is also unclear. It wasn't much. 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 many of these (reaction vessel structure, pumping speed, g2zma generation method, etc.), the glasma is sometimes in an unstable state, but there is little chance of it having a significant negative effect on the deposited film. There wasn't.

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 with electrical, optical, photoconductive, or mechanical properties that can sufficiently satisfy various uses, it is currently considered best to form it by plasma CVD. ing.

Depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniform 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. That 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 silicon oxide films.

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

[Purpose and outline of the invention]

The purpose of the present invention is to improve the properties, film formation speed, and reproducibility of the film to be formed, and to make the film uniform in quality. An object of the present invention is to provide a method for forming a deposited film that can easily achieve the following.

The above purpose is to use the activity 81(A) generated by decomposing a compound containing carbon and halogen in the formation chamber for forming a deposited film on a substrate, and the activation-like chamber and chemical reaction. A deposited film is formed on the substrate by separately introducing the interacting rR element gold-containing compound and the generated active species ω) for film formation, and applying discharge 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, discharge energy capable of forming an activation atmosphere such as f-plasma is used as the energy to excite and cause the raw materials for forming the deposited film to react. The activity ff produced by the active substance produced by the oxygen-containing compound for film formation
In coexistence with (B), applying discharge energy to these components will cause, promote, or amplify chemical interactions, so the discharge energy, which is lower than that in the past, will The deposited film thus formed is substantially free from any adverse effects due to etching effects or other adverse effects such as abnormal discharge effects.

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

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

One of the points in which the method of the present invention differs from the conventional C2 method is that active species activated in advance in a space different from the film forming space (hereinafter referred to as activation space) are used. This makes it possible to dramatically increase the film formation speed compared to the conventional CVD method, and also to further reduce the substrate temperature during deposited film formation, thereby improving film quality. Stable deposited films can be provided industrially in large quantities at low cost.

In the present invention, the activation from within the activation space introduced into the film forming space [(A) is
Those having a lifespan of 0.1 seconds or more, preferably 1 second or more, optimally 10 seconds or more are selected and used as desired, and the composition of this activated Br prisoner is 5! The element constitutes a component constituting the deposited film formed in the film forming space.

In addition, the chemical substances for film formation are activated by an activation technique in the activation space (B), and introduced into the film formation space to form a deposited film. It chemically interacts with active-like vessels containing components that are introduced from and become a constituent part of the deposited film that is formed. the result,
A desired deposited film is easily formed on a desired substrate.

In the present invention, the compound containing carbon and halogen introduced into the activation space (A) is, for example, a chain or cyclic hydrocarbon in which some or all of the hydrogen atoms are replaced with halo')'7yj
A compound substituted with L is used, specifically, for example, CuY2u+2 (u is an integer of 1 or more, Y is F,
CL, Br or Engineering. ) chain halo,
Gunnized carbon, CvY2v (Ma is an integer of 3 or more, Y is
has the meaning given above. Examples include chain or cyclic compounds represented by cyclic carbon % 5iuH1Yy (u and Y have the above-mentioned meanings. x+y=2u or 2u+2).

Specifically, for example, CF4. (CF2)5. (CF
2) 6゜(CF2)41 C2F61 C3FB ,C
)IF3 T CH2F2 e CC64゜(CC42
)5. CBr, , (CBr2)5. C2
Examples include those that are in a gaseous state or can be easily gasified, such as CL, , C2C1,F, and the like.

Further, in the present invention, in addition to the active species generated by decomposing the compound containing carbon and halo r/, the active species generated by decomposing the compound containing silicon and halogen are used in combination. be able to.

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. Specifically, for example, 5iuZ2u+2 (u is an integer of 1 or more) is used. , 2 is F
, Ct + Br, and I. ) chain silicon halide represented by S[vZ2v (ma is an integer of 3 or more, Z has the above-mentioned meaning)
Hxzy (u and 2 have the above meanings. x + y
= 2u or 2u+2. ), and the like.

Specifically, for example, 5IF4. (SiF2)5. (
SiF2)6°(SiF2)4.5t2F6. Si,
F, , to Sl field, 5IR2F2゜5ICL41
(SiC62)5.5iBra, (siBr2)
5.812C26゜SI Br, 5
iHCz, 5iHBr,
5IHI, Si. C.L., F.

26 S 5
Examples include those that are in a gaseous state or can be easily gasified, such as S.

In order to generate the active species (A), the compound containing carbon and halogen (and the compound containing silicon and halogen)
In addition, other silicon-containing compounds such as simple silicon, hydrogen, halogs/compounds (e.g. F2 gas, Ct2
Gas, gasified Br2.12, etc. can be used in combination.

In the present invention, the method of generating the active-like bodies and (B) in the activation spaces (A) and Φ) is to use electricity such as microwave, RF, low frequency, DC, etc., taking into account the respective conditions and equipment. Activation energy such as energy, thermal energy such as heater heating, infrared heating, and light energy is used.

The oxygen-containing compound that generates the active species (J3) used in the present invention has already been introduced into the activation space (B).
.

It is preferably introduced in a gaseous state or in a gaseous state. For example, when using liquid and solid compounds, the compound can be vaporized by connecting an appropriate vaporizer to the compound supply source and then introduced into the activation space (B).

Examples of the oxygen-containing compound include compounds whose constituent atoms are oxygen and one or more atoms other than oxygen.

Examples of atoms other than oxygen include hydrogen, halogen (X=
F, CL, Br or I)% sulfur (S), carbon (C), silicon (Sl), kelmanium (G@), phosphorus ψ), borosilicate X (B), alkali metal, alkaline earth metal, In addition to transition metals, atoms of other elements belonging to each group of the periodic table that can be combined with hydrogen atoms can be used.

By the way, 1 for example O,! :) (As a compound containing H
Examples of compounds containing 0 and S include so2. so
.

Examples of oxides such as CO, and compounds containing O and C include CO.

Compounds containing O and Sl, such as oxides such as CO2, include:
Siloxanes such as disiloxane (H,5IO8iH,), trisiloxane (H,SLO8lH2O5iH,), diacetoxydimetercyanine (CH,)2Sl(O
COCR,)2, triacetoxymethylbilane CB,5
Organoacetoxysilanes such as 1 (OCOCH, ), methoxytrimethylsilane (CH3).

S i OCH3, nomethoxydimethyl 7rane (CM,
)2S I(QC)I, )2trimethoxymethylsilane CH,5i(OCR,)3, etc., alkylalkoxy7
Ran, trimethylsilanol (CH,), 5iOH,
Zomethylphenylcinol(CH,)2(C,H6)
SIOI(S-/Ethylsilanediol (C2H5)2
Organosilanols such as Sl(OH)2, etc., 0 and G
- Compounds containing Gc oxides, hydroxides, rumanium hydroxides, Hs G@OG s Hs , Hs
Examples include organic glumanicum compounds such as sG@OG e H20G@H3, but 1112 used in the present invention
g-containing compounds are not limited to these.

These W1 elemental gold-containing compounds may be used in one proportion, or in combination with 281 or more.

In the present invention, from the viewpoint of productivity and ease of handling, the activation space (m) introduced into the film forming space is
Those having a lifetime of 0.1 seconds or more, more preferably 1 or more seconds, optimally 10 seconds or more are selected and used as desired.

In the present invention, in addition to oxygen-containing compounds, raw materials for film formation include water, halogen compounds (e.g., F2 gas, ct2f gas, gasified Br2, 2, etc.), alcohols, neon, and other materials. An active gas or a silicon-containing compound, a carbon-containing compound, a rumanium-containing compound, etc. as a raw material for forming a deposited film can also be introduced into the activation space. When using multiple of these film-forming chemicals, they can be mixed in advance and introduced into the activation space ψ) in a gaseous state, or each of these film-forming chemicals can be used independently. They can be supplied individually from a supply source and introduced into the activation space (B), or they can be introduced into independent activation spaces and activated individually.

Silicon-containing compounds that serve as raw materials for forming deposited films include:
A silicon compound in which hydrogen, halogen, etc. are bonded to silicon can be used. In particular, chain and cyclic silane compounds, some or all of the hydrogen atoms of these chain and cyclic silane compounds are /1c! Compounds substituted with dene atoms are preferred.

For example, S iH4, S l 2) H6,
81,H,,814FI,. ,515H,2,5i6H
ss such as 44, H2, +z (p is 1 or more, preferably 1 to
15, more preferably an integer of 1 to 1O. ) Linear silane compound, SIH, 5IH (SIH, )
SIM,,SiH,81) [(SIH,)815H,,
S1□H5SiH (SiH,) S12N (6 grade sl,
1 (zp + z (p has the above-mentioned meaning)) Chain silane compounds having branches, some or all of the hydrogen atoms of these linear or branched chain silane compounds No. 7 Compounds substituted with atoms, 5I3H6,5t
4H,,515) (,.,316H,2 etc. Sl, H2
11 ((1 is an integer of 3 or more, preferably 3 to 6.

) cyclic silane compounds, compounds in which part or all of the hydrogen atoms of the cyclic silane compounds are substituted with other cyclic silanyl groups and/or extended chain silanyl groups, one of the hydrogen atoms of the silane compounds exemplified above Examples of compounds partially or entirely substituted with halogen atoms include SiH, F, SIR, Ct
, SiH, BrJiH, I etc. Sl, H, Xj (X
is a halo f7 atom, r is 1 or more, preferably 1~! 0,
Preferably an integer from 3 to 7, s −) − t =
2 r + 2 or 2r. ) and the like. These compounds may be used alone or in combination of two or more.

Nine, carbon-containing compounds that serve as raw materials for forming deposited films include chain or cyclic saturated or unsaturated hydrocarbon compounds, p
f, organic compounds whose main constituent atoms are elemental atoms and hydrogen, and one or more constituent atoms such as silicon, halogen, sulfur, etc.; organic compounds whose constituent atoms are hydrocarbon groups; gases; Those in a solid state or those that can be easily vaporized are preferably used. Among these, examples of hydrocarbon compounds include saturated hydrocarbons having 1 to 5 carbon atoms, and saturated hydrocarbons having 2 to 5 carbon atoms.
Ethylene hydrocarbons, acetylene hydrocarbons having 2 to 4 carbon atoms, etc., specifically saturated hydrocarbons and sitehamethane (
CM, ), ethane (CzH6), deronodane (03H
, ), n-buta/ (n-C4H10), (silane (C
5H42), ethylene (C
zH4), propylene (03H6), butene-1 (C
4H8),! ten-2(C4)I,), inbutylene (
C4H8), pentene (C6H4°), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C,H4), butyne (C4H,), and the like.

In addition, as an organosilicon compound, (CH3) 4S
1, CH, S t ct3, (ca,)2sicz2,
(Ci(3), S I CL, C2H55ICt.

Organochlorosilanes such as CH, 5IF2Ct, C
H,5LFct2, (CH3)25iFC2SC2H5
SIF2Ct, C2H55IFCt2, C, H, 5I
Organochlor 7A/orsilane such as F2CL, C,H,5IFC22, ((aH,),5t)2, ((Cs
Hy)ss')z and the like are preferably used.

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

In addition, as a dallmanium-containing compound that is a raw material for forming a deposited film, an inorganic or organic dallmanium compound in which hydrogen, halo r7, or a hydrocarbon group, etc. are bonded to germanium can be used. is 1
or more, b=2m+2 or 21. ), a polymer of this germanium hydride, a compound in which some or all of the hydrogen atoms of the above damanium hydride are replaced with halogen atoms, the above germanium hydride Examples include organic dalmanium compounds such as compounds in which some or all of the hydrogen atoms of are substituted with organic groups such as alkyl groups and aryl groups, and optionally dihalogen atoms, and other rumanium sulfides, imides, etc. I can do it.

Specifically, for example, G-H4, Go2H6, Go3H
6s n-Ga4 t@rt-Ga4)1. . , Ga
3H6, Gas horse. , GeFt, F SG function H, C
L SG@H2F2, H, Ga, H6, Gs (Q(
, )4, Ga (C2H5)4, Go (C6H5)4,
Examples include Go(CH,)2F2, GaF2, GaF4, Gas, and the like. These cocszz nicum compounds may be used alone or in combination of two or more. In addition to these, gases such as 0□ and 05 may also be used depending on the case.

In the present invention, the active species (A
) and the active species (B) can be determined as desired depending on the deposition conditions, the type of active species, etc., but it is preferably lO:1 to 1:10 (introduction flow rate ratio),
More preferably, the ratio is 8:2 to 4:6.

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. The impurity elements used include p-type impurities,
Elements of group m A of the periodic table, such as B, A1. ,
Suitable examples include Ga, In, Tt, etc., and preferable n-type impurities include elements in the V group of the periodic table, such as P, As, Sb, B1, etc. In particular, B #GalP, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on the desired electrical and optical properties.

The substance containing such an impurity element as a component (substance for impurity introduction) is a compound that is in a gaseous state at room temperature and normal pressure, or at least a compound that is a gas under activation conditions and can be easily vaporized with an appropriate vaporization device. Such compounds which are preferably selected include PH,e P2H4e P
F5 e PF5 z PGA1 e AsH3゜As
F5 l AmFs l input mct5 e
SbH3+ SbF5 e 5IH5eBF3
e BC2s # BBrx -B2H6* B4H
1 (1e B, Kg CH5 to 1.e B6H1゜,
Examples include 86H, □, AI, CL15, etc. Compounds containing impurity elements may be used alone or in combination of 2fi 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 φ) and activated. ,
In order to activate the impurity-introducing substance, which may be activated in a third activation space (C') Ic that is different from the activation space (A) and the activation space (B), The above-mentioned activation energies listed for generating the activation-like organ and the activity m (a) can be appropriately selected and employed. The active species (PN) generated by activating the impurity introduction substance are mixed with the active species (A) and/or the active species (B) in advance, or are introduced into the film forming space independently.

Next, the present invention will be fully 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 the structure fPJ of the light 4 [member] as a typical electrophotographic image forming member obtained by the present invention.

FIG. 1 shows the structure of the light 41 as a typical electrophotographic image forming member obtained by Kinei 1jAK. 15
! It is a schematic diagram for IM.

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

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCre stainless g A-! t # Cr g Mo g AL
I g Ir gNb p Ta e V # Ti
Examples include metals such as *Pt*Pd and alloys thereof.

Examples of the electrically insulating support include films or sheets of composite resins such as polyester, polyethylene, -licarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. Usually used.

Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if the surface is NlCr r At
#Cr t Mer Au, Ir * Nb *
Tm t V F Tl r Pt rPd , In
zC)3r 5n02 e ITO(In2(13+
5n02), etc., or if it is a synthetic resin film such as polyester film, NlCr r^t, Ag e Pb r Z
n e Nt T^U.

Cr + Mo e Ir # Nb e Ta
r V r Tl r The surface is treated with a metal such as Pt by vacuum evaporation, electron beam evaporation, snoring, 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 need. 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, the intermediate layer 12 includes a photosensitive layer 13 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.

For example, if this intermediate layer 12 is created by the method of the present invention, it may contain silicon atoms, oxygen atoms, carbon atoms, hydrogen (H) and/or halogen (X), and oxygen (0) as necessary. Amorphous material with seven constituent atoms (hereinafter referred to as number-
8+oC (denoted as H, Contains mouth-type impurities.

Furthermore, germanium atoms can be included for the purpose of expanding functionality.

In the present invention, B is contained in the intermediate layer 12.

As for the content of substances that control conductivity, such as P.

Preferably, 0.001 to 5
More preferably 0.5 to I x 10' at ppm1
omic ppm 1 optimally 1-5 x 10 a
Preferably, the amount is tomlc ppm.

If 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 oxygen-containing compound for film formation introduced into the activation space (B) are used as raw materials for forming the intermediate layer. Active species (B) generated from the active species (B) and, if necessary, a hydrocarbon, a halogen compound, an inert gas, a silicon-containing compound, a carbon-containing compound, a germanium-containing compound, and a compound gas containing an impurity element as a component. (B
) are introduced into the film forming space where the support 11 is installed, either separately or mixed as needed, and the intermediate layer 12 is formed on the support 11 using discharge energy. Just let it form.

Middle! Compounds containing carbon and halogen that are introduced into active r and space (A) to generate active species (A) during total formation of 12 are, for example, f-compounds that easily generate active species such as CF3I. is more preferably selected from the compounds listed above.

Similarly, as a compound containing silicon and halogen,
For example, it is more desirable to select from compounds within the entire range of compounds that readily generate active species such as SiF2''.

The layer thickness of the intermediate layer 12 is preferably 30X to 10μ, more preferably 40X to 8μ, and optimally 50X to 5μ.

The photosensitive layer 13 is made of an amorphous material (hereinafter referred to as 1-8t (H,
It has both a charge generation function in which all photocarriers are generated by laser light irradiation and a charge transport function in which the charges are transported.

The thickness of the photosensitive layer 130 is preferably 1 to 100μ
, more preferably from 1 to 80μ, most preferably from 2 to 50μ.

The photosensitive layer 13 is a non-dawg a-8i (H9X) layer, but it has a conductive property of a polarity (for example, n-type) different from the polarity of the substance that governs the conductive property contained in the intermediate layer 12 as desired. Alternatively, if the actual amount contained in the intermediate layer 12 is large, the substance controlling the same polarity conductivity may be contained in a much smaller amount than the amount. You may let them.

In the case of forming the photosensitive layer 13, as well as in the case of the intermediate layer 12, if it is formed by the method of the present invention, a compound containing activated space-occupied carbon and halo r7 is introduced, and the photosensitive layer 13 is formed by the method of the present invention. By decomposing them or by exciting them with discharge energy or light energy, active-like vessels are generated, and the active-like vessels are introduced into the film-forming space.

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

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 l-type semiconductor +W
25, is composed of a p-type semiconductor layer 26. Although the present invention can be applied to the production of only one of the semiconductor layers 24, 25, and 26, f: conversion efficiency can be increased by producing the semiconductor layer 26 by the method of the present invention. . When the semiconductor layer 26 is created by the method of the present invention, the semiconductor layer 26 is made of, for example, an amorphous material containing silicon atoms, carbon atoms, oxygen atoms, and hydrogen atoms and/or halogen atoms as cationic atoms. (hereinafter referred to as rA-stc).

(H,X) written as J). 28
is a conductive wire that is coupled to an external electrical 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.

As the semiconductive substrate, for example, 81#Gev
GaAs.

Examples include semiconductors such as ZnOr ZnS. Thin film pole 2
2゜27 is N5Cr p kl-, Cr
+Mo#Au+Ir*Nb+Ta,
V r Ti r Pt * Pd + In2O5
It is obtained by forming a thin film such as JSnOe ITO (In20x+5nOz) on the substrate 21 by a process such as vacuum evaporation, electron beam evaporation, or sputtering. The film thickness of the electrodes 22°27 is preferably 30 to 5×10
More preferably, it is 100 to 5X10'X.

In order to make the film body constituting the semiconductor layer n-type or p-type as necessary, an impurity element such as 5th M1 impurity or p-type impurity, or both impurities is added to the layer to be formed. It is formed by doping while controlling the amount.

When forming n-type, 1-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 using an activated space (AtK carbon and halogen). r
Compounds containing y are introduced, and by exciting and decomposing them under the action of activation energy, e.g. CF2''
, 5IF2'' etc. are generated, and the active species (A) are introduced into the film forming space.
Activation space (B) K-introduced chemical substance for film formation,
If necessary, compound gases containing inert gases and impurity elements as components are excited and decomposed by activation energy to generate each active species, and each is supported separately or mixed appropriately. The film forming space where the body 11 is installed is introduced.

The active species introduced into the film-forming space are caused to undergo chemical interaction, promoted or amplified by using discharge energy, and Km transshipment is formed on the substrate 21. The thickness of the n-type and p-type semiconductor layers is preferably 10
The range of 300 to 2000X is more preferable than 0 to 10X.

Further, the thickness of the l-type semiconductor layer is preferably SO
O~10'Xs more preferably 1000~10000
A range of 1 is desirable.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in FIG. 3, an amorphous deposited film was formed by the following operations.

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

°104 is a heater for heating the substrate, and a conductor 105
Power is supplied through the device and generates heat. The substrate temperature is not particularly limited, but if it is necessary to completely heat the substrate in carrying out the method of the present invention, the substrate temperature is preferably 30°C.
It is desirable that the temperature is ~450°C, more preferably 50-300°C.

Reference numerals 106 to 109 are gas supply systems, which contain gases for film forming raw materials, hydrogen, non-rhodan compound inert gas, silicon compounds, carbon compounds, germanium compounds, and compounds containing impurity elements, which are used as necessary. etc., depending on the type of gas. If these gases are in liquid form under standard conditions, an appropriate vaporization device should be provided. 1. In Figure 1, the gas supply systems 106 to 109 are marked with an asterisk (&), and b is marked with a branch pipe. The one with C is the pressure gauge that measures the pressure on the high pressure side of each flowmeter, and the one with d or @ is the flow rate of each gas. 111i pulp.

123 is an activation chamber (B) for generating active species (B), and K around the activation chamber 1230 is a microwave glazma generator 122 that generates activation energy for generating active species (B). is provided. Gas introduction pipe 110
The raw material gas for producing activated fi (B) supplied from is activated in the activation chamber (B) 123, and the generated active species (B) are introduced into the film forming chamber 101 through the introduction pipe 124'i. be done. 111 is a gas pressure gauge. In the figure, 112 is an activation space (A), 113 is an electric furnace, 114 is 0 solid particles, and 115 is gaseous carbon and halo r, which are the raw materials for active species.
This is an inlet tube for the compound containing 7, and the activated species (1) generated in the activation space prisoner 112 are introduced into the film forming chamber 10 through the inlet tube 116.
1.

Reference numeral 117 denotes a discharge energy generator, which includes a matching terminal 117 m and a cathode electrode 117 for high-frequency heating.
b, etc.

The discharge energy from the discharge energy generator 117 acts on the active species flowing in the direction of the arrow 119, and each of the acted active species undergoes a mutual chemical reaction to form an amorphous material on the entire substrate 103 or a desired portion. Form a deposited film. Also, in the mouth, 120 is exhaust pulp, 121
comes from the exhaust pipe.

First step, base 1 made of polyethylene terephthalate film
03 on the support stand 102! c Place and exhaust device (not shown)
The inside of the film forming chamber 101 is evacuated using a
Ic pressure was reduced. At the substrate temperature shown in Table 1, the gas supply gas is diluted to 10 mm from 106 (H@).
150SCCM, including this and PH3 gas or B2
H6 gas (all diluted with 1000 ppm hydrogen) 40
Gas mixed with 8 CCM was introduced into the activation chamber (B) 123 via the gas introduction '1io.

The 0□ gas etc. introduced into the activation chamber (B) 123 is activated by the microwave glazma generator 122 to become activated oxygen etc., and the activated oxygen etc. are introduced into the entire film forming chamber 101 through the introduction v124. .・On the other hand, activation chamber prisoner 1
02Vc 114 tons of solid C grains were packed, heated in an electric furnace 113, kept at about 1000°C to bring the C to a red-hot state, and then %C was introduced from Hegenbe through the CF introduction pipe 1151C.
By injecting F4, CF2 activity a (B)
is generated, and the active species (B) is introduced into the film forming chamber 101 through the introduction pipe 116.

A-8IOC (H,
) film (!A thickness 700X) was formed. Acquisition rate is 35X
/s-c.

Next, sample 1 formed on the obtained 1-5 iOC(H,
After forming the film, the dark xi was completely measured at an applied voltage of 15 V, the dark conductivity wL ratio σd was determined, and the film characteristics of each sample were evaluated.

The results are shown in Table 1.

Example 2 H3S iO8II3/H2/F2 is mixed instead of disiloxane gas from the gas supply member 106 etc. (Mixing ratio 1 (3SIO8iH3/H2/F2=10:10)
: 3) was formed on the A-8IOC (H,X) film according to the same method and procedure as in Example 1. The dark conductivity of each sample was measured and the results are shown in Table 1.

From Table 1 aE1, it was found that according to Kinei Akiyoshi, an Asor 7As film with excellent electrical properties could be obtained.

Real jlI! Example I 3 Using the apparatus t shown in FIG. 4, a drum-shaped electrophotographic image forming member having the layer structure shown in FIG. 1 was prepared by the following operations.

In FIG. 4, 201 is a film forming chamber, 202 is an activity ratio chamber, 203 is an electric furnace, 204 is 0 solid particles, 205 is an active species (A) raw material introduction pipe, 206 is an activation type vessel introduction pipe, 2
07 is a motor, 208 is a heating heater used similarly to 104 in Fig. 3, 209.210 is a blowing pipe, 2
11 is an At cylindrical base, and 212 is an exhaust pulse f.

Further, 213 to 216 are raw material gas supply sources similar to 106 to 109 in FIG. 3, and 217-1 is a gas introduction pipe.

An At cylinder base 211 is suspended in the film forming chamber 201,
A heating heater 208 is provided inside the motor 207.
It is now possible to rotate. Reference numeral 218 denotes a discharge energy generating device, which is equipped with a cathode electrode 218b for introducing a high frequency of matching shield 218.

In addition, 0 solid grains 204 are packed in the active chamber (A) 202, heated in an electric furnace 203, and kept at about 1000°C.
C1: Bring to a red-hot state, and inject CF4 from a cylinder (not shown) through the introduction pipe 206 to generate CF2'') as an active cell, and the CF? total introduction pipe 20
6, it was introduced into the film forming chamber 201. In addition, the activation chamber (A
) 202 (not shown), solid S1 grains and active species (C) of 5IF2* from SIF'4 were all introduced in the same manner.

On the other hand, gasified disiloxane was introduced into the activation chamber (a) 220 through the introduction pipe 217-1.

The introduced disiloxane gas becomes an active "hi chamber (B) 22
At 0, it undergoes activation processing such as plasma generation from the microwave glazma generator 221￥C to become activated disiloxane, and is introduced into the film forming chamber 20 through the introduction pipe 217-2t-.
It was introduced within 1. At this time, if necessary, PH, 82
Impurity gas such as H6 was also introduced into the activation chamber (B) 220 and activated.

Aj cylinder base 211 is heated to 220°C by heater 208
It was heated and maintained by Vc and rotated, and the exhaust gas was exhausted by appropriately adjusting the ICpl of the opening of the exhaust valve 212. In this way, the intermediate layer 12 was formed to a thickness of 2,000 mm.

In addition, the photosensitive layer 13 does not use CF4 in the gas used to form the intermediate layer 12, and H2 is used instead of disiloxane.
The intermediate layer 12 was formed in the same manner as in the case of the intermediate layer 12, except that a gas mixture was used and a mixed gas of H2/B2H (8.2% by volume i%, H6 gas 0.2%) was introduced from the introduction pipe 217-1. filmed.

Comparative Example 1 CF4 e 5iHi r disiloxane, H2 and B2
Each gas of H6? A film forming chamber with the same configuration as the film forming chamber 201 was prepared using a 13.56 MHz high frequency equipment fi1m.
An electrophotographic imaging member having the layer structure shown in FIG. 1 was formed.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 3 and Comparative Example 1.

23rd! i! Table 2 (Continued) Example 4 Using the apparatus t shown in FIG. 3, the PIN type diode shown in FIG. Place it on the support stand and hold it for 10 minutes.
-' Torr Ic depressurized. After that, active species 5ir2"i produced in the same manner as in Example 3 were introduced into the film forming chamber 101. Additionally, H2 gas and PH3 gas (1000 ppm hydrogen gas dilution) were each introduced into the activation chamber (B) 123. 0, then this activated gas all inlet pipe 1
16 into the film forming chamber 101. Film forming chamber 101
Reduce the internal pressure to 0. Discharge device 1 while maintaining I Torr
n doped with P by applying glazma from 17
A type a-81(H,X) film 24 (film thickness 700X) was formed.

Then, the introduction of PH gas was stopped, and 5IF2"/CF2"
A non-Dogue Todoroki-5I (H,

Then, instead of H2/'PHs gas, K Hs S +
8 with O8I Hs/112 gas (mixing ratio 1:10)
Full use of 2H6 gas (1000ppm hydrogen),
Other than that, p-type a-SiO(H,X) film 26 doped with 8 under the same conditions as n-type (film thickness 700X)
was formed. Furthermore, an At electrode 27 having a thickness of 1000^ was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

l- of the thus obtained diode element (area lα1)
The V characteristics were measured, and the M light characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, the light sound is introduced from the substrate side, and at the light irradiation intensity AJi4I (approximately 100 mW/cm2), the conversion efficiency is 8.0% or more, and the open end voltage is 0.82V short circuit 1! Flow i.

mA/cps was obtained.

Example 5 Instead of H3SiO8IH3/H2 gas from the inlet pipe 110, Hs SIQ SI H5/J (2/F2 is (H,s tos IH, H2/F2= 1 : 15
A PIN type diode similar to that produced in Example 4 was manufactured in the same manner as in Example 4, except that ':2) f: was used. This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

Third! ! : Skewer 1 N value (Quality Factor) in the ratio of forward wL current and reverse current at a voltage of 1 V [Effects of the Invention] According to the deposited film forming method of the present invention, the desired value of the formed film is Electrical, optical, photoconductive, and mechanical properties are improved, and high-speed film formation is possible.

In addition, the reproducibility of the film deposition process is improved, making it possible to improve the film quality and make the film uniform. Furthermore, since no excitation energy is involved in film formation, it is possible to form a film, for example, on substrates with poor heat resistance or on substrates that are easily susceptible to plasma etching.The process can be shortened by low-temperature treatment. The effect of this is that it is possible to achieve the following.

[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 a configuration example of a PIN diode manufactured using the method of the present invention. 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... Electrophotographic image forming member, 11... Substrate, 1
2... Intermediate layer, 13... Photosensitive layer, 21... Substrate,
22°27... thin film electrode, 24... n-type semiconductor layer,
25... Stand-type semiconductor layer, 26... P-type semiconductor layer, 1
01,201... Film forming chamber, 111,202... Activation chamber prisoner, 106, 107. 108.109,213,214,215,216...
・Gas supply 'Thread, 103, 211...Base, 1
17,218...Discharge energy generation device.

Claims (1)

[Claims] Chemically interacts with active species (A) generated by decomposing a compound containing carbon and halogen in a film formation space for forming a deposited film on a substrate. , active species (B) generated from oxygen-containing compounds for film formation
A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing these separately and applying discharge energy to them to cause a chemical reaction.