JPS61191017A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To contrive the uniformity of deposited film quality by the chemical reaction in a film forming chamber separately introduced with an active seed formed by the decomposition of a compound containing silicon and a halogen and an active seed formed from a compound containing nitrogen. CONSTITUTION:The pressure in a film forming chamber 101 is reduced using an exhaust equipment (not shown in the drawing) after a substrate 103 is placed on a susceptor 102. Then, N2 gas or a mixed gas of N2 gas and PH3 gas or B2H6 gas is introduced in an activation chamber B123 from a gas supply cylinder 106, activated with a microwave plasma generation equipment 122 and introduced in the film forming chamber 101. Whereas, an activation chamber A112 is filled with Si grain 114, heated by an electric furnace 113, an active seed is formed blowing SiF4 from a pipe 115 and introduced in the film forming chamber 101. This enables forming a uniform amorphous deposited film containing nitrogen on the substrate 103.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to nitrogen-containing deposited films, especially functional films, particularly semiconductor devices, photosensitive devices for electrophotography, and image input lines. Related to a method suitable for forming a non-single crystal deposited film containing amorphous or polycrystalline nitrogen for use in sensors, imaging devices, etc. [Prior art] For example, for forming an amorphous silicon film, , vacuum evaporation method, plasma CVD method, CVD method, reactive sputtering method, ion grating method, optical CVD method, etc. There is.

The nine deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, productivity including uniformity and reproducibility, and mass production. There is still room for further improvement of the overall characteristics.

The reaction process in forming an amorphous silicon deposited film using the plasma CVD method, which has been widely used for a long time, is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. Ta. In addition, there are many formation parameters for the deposited film (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 (such as the structure of the reaction vessel, pumping speed, plasma generation method, etc.), delasma sometimes becomes unstable and often has a significant adverse effect on the deposited film formed. Moreover, a device-specific noclameter 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 Heigo 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, and to achieve mass production with high reproducibility through high-speed film formation. Forming an amorphous silicon deposited film using a method requires a large amount of capital investment in mass production equipment, and the management items for mass production are also complex, with narrow control tolerances and delicate equipment adjustments. 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 the characteristics of the formed film, the film formation speed, the reproducibility, and to make the film uniform. 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 chemically interact with the active species (A) generated by decomposing a compound containing silicon and halogen in the film forming space for forming a deposited film on the substrate. The deposition method of the present invention is characterized in that a deposited film is formed on the substrate by separately introducing active species (B) generated from a nitrogen-containing compound for film formation and causing a chemical reaction. This is achieved by a film formation method.

[Embodiment]

In the method of the present invention, since plasma is not generated in the film forming space for forming the deposited film, the deposited film that is formed is not adversely affected by etching action or other adverse effects such as abnormal discharge action.

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 deposited film formation, resulting in stable film quality. Deposited films can be provided industrially in large quantities at low cost.

Note that the active species (A) in the present invention refers to species that have chemically interacted with the active N (B) generated from the nitrogen-containing compound to impart energy, or species that have caused a chemical reaction. It refers to a substance that has the effect of promoting the formation of a deposited film. 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 also be a nitrogen-containing compound that can serve as a raw material for forming the deposited film by containing constituent elements constituting the deposited film to be formed. Alternatively, it may be a nitrogen-containing compound that does not contain the constituent elements constituting the deposited film to be formed and can be used merely as a raw material for film formation. Alternatively, a nitrogen-containing compound that can be used as a raw material for forming a deposited film and a di-containing compound that can be used as a raw material for film formation may be used in combination.

The nitrogen-containing compound used in the present invention is activated space (B)
It is preferable that the gas be already in a gaseous state before being introduced into the system, or that it be introduced 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 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), Notsuta Ron (X=F% CLs Br
or ■), sulfur (S), carbon (C), oxygen (0), silicon (separately), rlumanicum (G.), etc., and other atoms of elements belonging to each group of the periodic table. Among them, almost any atom can be used as long as it is an atom that can be combined with nitrogen and is a constituent atom of a compound that can achieve the object of the present invention.

Incidentally, for example, compounds containing N and He include HN3,
Compounds containing N and X include NH4N3, NH3, H2NNH2, primary to tertiary amines, halides of these amines, hydroxylamine, etc.
Compounds containing N and S such as x2, NOX1NO2X, N03X4, etc. include N4S4, N255, etc. Compounds containing N and C include N(CH,), , HCN and cyanide, HOCN, H8CN, N and 0. Compounds include N20, N01NO2, N2O3, N2O4,
Examples include N2O5 and No3. Other examples include silazane and organosilicon compounds having an 81-N bond, such as organosilazane, organosilicon isocyanate, organosilicon isothiocyanate, and the like. Specifically, the silazane includes disilazane and trisilazane, and the organosilazane includes tersilazane (C2H5) and 5iNH2.
Hexamethyldisiladene [:(CH3)3ss)
2NH hexaethyldisilazane [(C2H5)3
31:12NH organosilicon isocyanate is trimethyl silicon isocyanate (CH,), 5
INCO dimethyl silicone diisocyanate (CH3
) 25l (NCO) 2 organosilicon isothiocyanate is trimethyl silicon isothiocyaner)
(CH,)3SINC8 etc. can be mentioned.

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

In the present invention, the activity m<A) from the activation space (A) introduced into the film forming space has a lifetime of 0.1 seconds or more, more preferably 1 second or more, 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 the present invention, the compound containing silicon and halo r:,/ to be introduced into the activation space (A) is, for example, a part or all of the hydrogen atoms of a chain or cyclic silane compound.
A compound substituted with an atom is used, specifically, for example, "uY2u+2 (11 is an integer of 1 or more 1Y is F%
At least one element selected from CLz Br and (2). ) chain silicon halide represented by 81.
Y2. (Ma is an integer of 3 or more, and Y has the above meaning.

) Cyclic silicon halide, 5fiuH Yy
(u and Y have the above meanings.x + y±2u
Or 2u+2. ), and the like.

A physical Ktt example 5iF4, (SiF2)5, (Si
F2)6, (SiF2)4, 812F6, S
Amount 3F8, 5IHF3, 5jH2F2.5i
C24 (SiC12)5.5sBr4, (SiBr4)
5.5i2Ct6, SI 2Br6, 5iHC1
,,S I HBr s, 5IHI, ,
Examples include those that are in a gaseous state or can be easily gasified, such as Si 2 C 2 3 F 3 .

In order to generate active species (active species), in addition to the above-mentioned compounds containing silicon and halogeno, silicon compounds such as simple silicon, hydrogen, and halogeno compounds (for example, F2 gas, ct2 gas, gasified B r2, r2, etc.) can be used in combination.

In the present invention, the method for generating active species (A) and (B) t- in activation spaces (A) and (B), respectively, is as follows:
Activation energy such as electrical energy such as microwave, RF', low frequency, DC, thermal energy such as heater heating, infrared heating, and light energy is used in consideration of each condition and apparatus.

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) is determined as desired depending on the deposition conditions, the type of the active species, etc. However, preferably 10:1 to 1:10 (introduction flow rate ratio) is appropriate, more preferably 8:2 to 4:
In the present invention, in addition to nitrogen-containing compounds, hydrogen gas, halogen compounds (for example, F2 gas, ct2 gas, gasified B r 2, 2, etc.) are used as raw materials for film formation. ), an inert gas such as helium, argon, neon, etc. In the activation space (B), a silicon-containing compound, a carbon-containing compound, as a raw material for forming a deposited film that generates active species (B),
Glumanicum-containing compounds, raw materials for deposited film formation, and/or oxygen-containing compounds as film-forming raw materials are added to the activation space (B
) can also be used. When using multiple of these chemicals, mix them in advance and place them in the activation space (B).
Alternatively, these chemicals can be individually supplied in gaseous form from separate sources and introduced into the activation space (B); They can also be introduced into independent activation spaces and activated individually.

Silicon-containing compounds for forming deposited films include silicon-containing compounds with hydrogen, hydrogen, or hydrocarbon groups bonded to silicon.
Runs, /10rn silanes, and the like can be used. Suitable examples include linear and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms in these linear and cyclic silane compounds are replaced with halogen atoms.

Specifically, for example, SiH4, S12H6, Si
3H8,5i4H,. , 515H42, S' 6”14
81. etc. H2p+2 (p is 1 or more, preferably 1 to 1
5, more preferably an integer of 1 to 10. ) Linear silane compound represented by SIH,5IR(SiH,)8
1H,,s 1. S IH (S IH3) S s , H
,,S1□H5SiH(SiH3)Si 2H5 etc.O8
'PH2p+2 (p has the above-mentioned meaning) chain-like silane compounds with branches, and some or all of the hydrogen atoms of these straight-chain or branched chain-like silane compounds are replaced with haoyy atoms. compound, Sl, H6, S
i 4H8, 5i5H1゜, S i 6H12, etc. 8
1. A cyclic silane compound represented by H2, (q is an integer of 3 or more, preferably 3 to 6), in which some or all of the hydrogen atoms of the cyclic silane compound are replaced by other cyclic silanyl groups and/or chain silanyl groups. As an example of a compound substituted with a group, a compound in which a part or all of the hydrogen atoms of the silane compound exemplified above are substituted with a rhodane atom, Si'H3F1Si
5irH such as H, C2, 5IH3Br, 5iH3r, etc.
, Xt (X is a halogen atom, r is 1 or more, preferably 1
~10°, preferably an integer from 3 to 7, s+t=2r+
2 or 2r. ) and halogen-substituted linear or cyclic silane compounds. These compounds may be used alone or in combination of two or more.

In addition, carbon-containing compounds for forming a deposited film include chain-like or cyclic saturated or unsaturated hydrocarbon compounds, whose main constituent atoms are carbon and hydrogen, and in addition, one or more of silicon, halogen, sulfur, etc. Among organic compounds having constituent atoms and organosilicon compounds having hydrocarbon groups as constituents, 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 (C2H6), poly(C3H8), n-butane (n-C4H1G), potassium (C5H12),
Ethylene hydrocarbons include ethylene (C2H4), propylene (C3H6), butene-1 (C4H8), butene-2 (04H8), isobutylene (04H8), intene (C5H1°), and acetylene hydrocarbons include acetylene (C2H2). ), methylacetylene (C,H4)
, butyne (C4H6), and the like.

As the halogen-substituted hydrocarbon compound, p'
, C11Br, and r, and particularly effective compounds include compounds in which hydrogen is substituted with VlCt.

The number of halogens substituting hydrogen may be 1 m 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 have general formulas; Rn51H4-n, RnllSIX4-fn, respectively.
(However, R-nialkyl group, aryl group: X:F.

CL, Br; n = 1 F2,3t4
, m=1.2-3. ), typical examples include alkylsilanes, arylsilanes, alkylhalogensilanes, and arylhalogensilanes.

Specifically, the organochlorosilane includes trichloromethylsilane CH,81C23dichlorodimethylsilane (CH3)281C22chlorotrimethylsilane (CH3)3SiCttrichloroethylsilane C2H55iCL3dichlorodiethylsilane (C2H5)28IC22organochlorofluorosilane , chlorofluorodithylsilane CH, 5iF2Ct dichlorofluoromethylsilane CH
5iFCt2Chlorfluorodimethylsilane (CH
3) 25iFCt chloroethyldifluorosilane (
C2H5) SIF2Ct dichloroethylfluorosilane C2H55iFCt.

Chlorfluorodimethylsilane C,H7SiF2Ct
Cyclolfluoroglopyrsilane C,H,5SFC1
2 Organosilanes include: tetramethylsilane (CH3)481 ethyltrimethylsilane (CH,)3SIC2H5 trimethylpropylsilane (CH,)3SIC3H.

Triethylmethylsilane CH35t (C2H5)
3Tetraethylsilane (c2a5)4siorganohydranosilane includes: methylsilane CH3S iH3dimethylsilane (CH,)2SIR2trimethylsilane (CH3), 5l)l diethylsilane
(C2H5)2SIH2triethylsilane (
C2H5), SiH triglobylsilane (C3
H,)3SIH diphenylsilane (C6H5
)2SiH2 Organofluorosilane includes trifluoromethylsilane CM, SiF.

Difluorodimethylsilane (CH3)28IF2Fluorotrimethylsilane (CH3), SIFEthyltrifluorosilane C2I(5SiF3Diethylnofluorosilane (C2H5)2SIF2Triethylfluorosilane (C2H5)3SiFTrifluoroglopyrsilane (c, a) ,)sty.

Examples of organobromosilane include bromotrimethylsilane (CH3), 5tnr nobromodimethylsilane (cH,)2stnr2, etc. In addition, examples of organopolysilane include hexamethyldisilane ((CH4)3S')z
As organodisilane, hexamethyldisilane C(CH3)35i)2
Hexapropyldisilane C(C,H,)3Si)
2nd class can also be used.

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

In addition, as a dalmanium-containing compound for forming a deposited film,
Inorganic or organic dallmanium compounds in which hydrogen, halogeno, or hydrocarbon groups are bonded to germanium can be used, such as Ga8 (a is an integer of 1 or more, b =
2 fields + 2 or 2a. ), 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 Some or all of them are, for example, alkyl groups,
Examples include organic groups such as aryl groups, organic germanium compounds such as compounds substituted with halogen atoms if desired, and sulfides and imides of rumanium.

Specifically, for example, GeH4, Ge2)16, Go
3H8, n-G14H11% tl! rj-G14H
11) %Ga3H6,G @5H10%GaH,
F, GaH3Ct, GeH2F2, H6G56F
6, Ge(cH3)4, c e (C2HS)4,
Ga(c 6H5) 4, Ga(CH,)2F2, CH
, GaH, , (CH3)2G@H2, (CH3)3Ge
H, (C2H5)2G@H2, Ga F2, GaF2
, Gas, etc. These germanium compounds may be used alone or in combination of two or more.

Furthermore, examples of oxygen-containing compounds include compounds of oxygen as a single component such as oxygen (0□) and ozone (03), and compounds containing oxygen and one or more atoms other than oxygen as gold constituent atoms. It will be done. The atoms other than oxygen include hydrogen (
H), halogen (X=F.

Cl, Br or r), sulfur (S), carbon (C), silicon (Sl), ff rumanium (Ge), etc., and other atoms that can be combined with oxygen among the atoms of elements belonging to each group of the periodic table. Almost any atom can be used as long as it is an atom constituting a compound that can achieve the purpose of the present invention. For example, compounds containing 0 and H include H2O,
Compounds containing 0 and S, such as H2O2, include S02, S
Oxides such as O3, compounds containing 0 and C include H2
Acids such as CO3 and oxides such as CO1CO□, 0 and Si
Compounds containing disiloxane (H3SIO8i
H3), trisiloxane (H3S tos tH2os
Siloxanes (CH3) such as IH3)251 (OC
Organoacetoxysilane such as OCH3)2, CH3S I (OCOCH3), (CH3) 3s+oca
3, (CH3)25 amount (OCH3)2, C
Alkylalkoxysilanes such as H3Si(OCH3) 3, (CH,)3SiOH.

(CH3)2(C6Hs)S10H1(C2H5)2S
Compounds containing 0 and Go, such as organosilanols such as '(OH)2, include G6 oxides, hydroxides, darmanic acids, H5Gs OGs Hs, H, G@OG
Examples include organic r-rumanium compounds such as @H20-GeH4.

These oxygen-containing compounds are type 1 t? They may be used or two or more types may be used in combination.

It is also possible to dope the deposited film formed by the method of the invention with an impurity element. The impurity element to be used is, as a 2m impurity, an element of group Ⅰ A of the periodic table, such as BXkl and Qa.

Preferred examples include Tn, T1, etc., and examples of n-type impurities include elements of group V A of the periodic table, such as PSAs,
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. Preferably.

Such compounds include PH3, P2H4, PF3,
PF5, BCl3, AmHs, AsF AaF
AsCl3, SbH3, SbF5, SiH3, BF3
, BCl3, B B r s, B2H6, B4H9°, B5H7, B5H11% B6H10s B6H12
-, kLct5, etc. The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity-introducing substance is introduced into the activation space (A) and/or the activation space (B) together with each substance that generates the active species (transfer) and the active m(B), and is activated. Alternatively, it may be activated in a third activation space (C) that is separate from the activation space (A) and the activation space (B).

The impurity-introducing substance can be employed by appropriately selecting the activation energy described above. The active species (PtJ) generated by fully activating the impurity introduction material JK is active or/
and the active species (B), or are 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 10 shown in FIG. 1 can be applied as an electrophotographic image forming member, and includes an intermediate layer 12 provided as necessary on a support 11 for use as a photoconductive member; and a photosensitive layer 13.

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13 can be created by the method of the present invention. Further, a protective layer provided on the surface of the photosensitive layer 13 to chemically and physically protect the photoconductive member 10, 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 NlCr5 stainless steel, At, Cr, Mo1Au, TrlNb
Examples include metals such as lTa, V, TI, Pt, and Pd, and alloys thereof.

As electrically insulating supports, polyester, polyethylene, polycargenate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, etc. Films or sheets of synthetic resin such as Lyamide, glass, ceramic, 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 NiCr5At1C
1% Mos Ao, Ir, Nb, Ta, V, T11P
t.

Pd% rn203, S nO2, ITO (r n
NiCr, ALs Ag
s PblZTI% NS% Au.

The surface is treated with a metal such as Cr, Mo, rrSNb, Ta1V, TI, 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 need.
If 0 is used as an electrophotographic image forming member, it is preferably in the form of an endless belt or a cylinder for continuous high-speed copying.

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 to move from the side of the photosensitive layer 13 to the side of the support 11, which is generated in the photosensitive #13 by the irradiation of electromagnetic waves and moves toward the side of the support 11. It has a function that allows easy passage.

This intermediate layer 12 has, for example, silicon atoms as its base material,
Nitrogen (N) and optionally hydrogen (H) and/or halogen (X), amorphous silicon (
Hereinafter, it is composed of a-8iN (hereinafter referred to as I(,
Contains impurities.

In the present invention, the content of the substance controlling conductivity, such as BlP, contained in the intermediate layer 12 is preferably 0.
001-5 X 10 atomic ppm5, more preferably 0.5-I X 10' atomic ppm
pm, optimally 1-5 X 10 mtornlc
ppm is preferably 1°. If the intermediate layer 12 has similar or the same components as the photosensitive layer 13, the formation of the intermediate layer 12 is continuous from the formation of the intermediate layer to the formation of the photosensitive layer 13. It can be done. In that case, as raw materials for forming the intermediate layer, the active species (A) generated in the activation space (A), a gaseous nitrogen-containing compound, hydrogen, a halogen compound, an inert gas, if necessary, Active a generated from silicon-containing compounds, carbon-containing compounds, dalmanium-containing compounds, and oxygen-containing compounds
1 [(B) and active species generated by activating a gas of a compound containing an impurity element as a component, either side by side or mixed as appropriate as necessary to form a support 11
The intermediate layer 12 may be formed on the support 11 by introducing the active species into a film forming space where the active species are installed and creating an atmosphere in which each introduced active species coexists.

A compound containing silicon and halocy that is introduced into the activation space (A) to generate active species when forming the intermediate layer 12 can easily be used as a compound that generates active species (A) such as SIF. It is desirable to select it from among the compounds.

The thickness of the intermediate layer 120 is preferably 30X to 10μ, more preferably 401 to 8μ, and optimally 50X to 5μ.

The photosensitive layer 13 is made of, for example, a-ss (a*x),
It has both a charge generation function of generating photocarriers by irradiation with radar light and a charge transport function of transporting the charges.

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

The photosensitive layer 13 is a non-doped a-st (a, For example, a substance governing conductivity of the n-type may be contained, or a substance governing conductivity of the same polarity may be contained (if the actual amount contained in the intermediate layer 12 is large). In the case of forming the photosensitive layer 13, as in the case of the intermediate layer 12, if the photosensitive layer 13 is formed by the method of the present invention, the activation space ( A) A compound containing silicon and halogen is introduced,
Active species (A) are generated by decomposing them at high temperatures or by exciting them with discharge energy or light energy, and the active species (A) are introduced into the film forming space.

Furthermore, if desired, a surface layer is provided on this photosensitive layer.

As a result, an amorphous deposited film containing carbon and silicon as constituent atoms can be formed, and in this case as well, the film can be formed by the method of the present invention in the same manner as the intermediate layer and photosensitive layer. .

FIG. 2 is a schematic diagram showing an example of a PTN type diode device using an a-81 deposited film doped with an impurity element, which is manufactured by carrying out the method of the present invention.

In the figure, 21 is a substrate, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an NFI semiconductor layer 24, an L-type semiconductor layer 24, an L-type semiconductor layer 24,
1ii25, pm semiconductor layer 26.

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

These semiconductor layers are 凰-5t (ayX), Hatake-betsu (N
, H, Efficiency can be increased.

The base 21 may be conductive, semiconductive, or electrically insulating. If the base 21 is conductive, the thin film 1 pole 22 may be omitted. Examples of semiconductive substrates include Si2, GaAs, Zn, etc.
Examples include semiconductors such as O and ZnS. Thin film electrode 22.2
Examples of 7 include NlCr and AL.

Cr, Mo1Au11r1Nb, Ta, V, TI, P
t.

Pd, In2O,, S no 2, rTo (I
It is obtained by providing a thin film of n2O, +St+02) or the like on the substrate 21 by a process such as vacuum evaporation, electron beam evaporation, or sintering. The layer thickness of the electrodes 22.27 is preferably 30 to 5 x 10'X, more preferably 100 to 5 x 10'.

In order to make the film constituting the semiconductor layer n-type or p-type as necessary, nW of the impurity elements is added during layer formation.
It is formed by doping an impurity, a p-type impurity, or both impurities into the layer to be formed while controlling the amount thereof.

When forming one layer of nm, i-type, and pW semiconductors by the method of the present invention, is it possible to form only one layer or all of the layers? A layer can be formed by the method of the present invention, and the film formation is performed in an activated space (
A compound containing silicon and halogen is introduced into A), and by exciting and decomposing them under the action of activation energy, active species (A) such as SiF2* are generated, and the active species (A) ) is introduced into the film forming space. Apart from this, gases of compounds containing nitrogen-containing compounds in a gaseous state, silicon-containing compounds, r-lumanicum-containing compounds, oxygen-containing compounds, and inert gases and impurity elements as necessary, etc. are each excited and decomposed by activation energy to generate each active f'ff1(B)', and each is introduced separately or mixed as appropriate 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 thickness of the n-type and pfjl semiconductor layers is preferably 100
~10'X%, more preferably 300~2ooo1.

Further, the thickness of the IN semiconductor layer is preferably 50
0-10'l, more preferably 1000-10000X
A range of is desirable.

In addition to this example, the method of the present invention can also be used to form 513N4 insulator films by CVD, partially nitrided Si films, etc. that constitute semiconductor devices such as ICs, transistors, diodes, and photoelectric conversion elements. S is suitable, and also has a nitrogen concentration distribution in the layer thickness direction, for example, by controlling the introduction time, amount, etc. of the nitrogen compound into the film forming space.
When an i-film is formed, it is formed. Alternatively, in addition to the nitrogen compound, t'r and these H,

It is also possible to form a film body with desired characteristics using bonds with C, O, etc. as constituent units.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 2, 1 was carried out by the following operations.
In FIG. 2, reference numeral 101 denotes a deposition chamber, and a desired substrate 103 is placed on a substrate support 102 inside.

104 is a heater for heating the substrate;
4 is used when heat-treating the base 104 before film-forming processing or annealing the film after film-forming in order to further improve the properties of the formed film, and is supplied with electricity via a conductive wire 105 to generate heat. do. The heater is not driven during film formation.

106 to 109 are a gas supply system, a nitrogen-containing compound, and optionally hydrogen, a halogen compound, an inert gas, a silicon-containing compound, a carbon-containing compound, a dalmanium-containing compound, an oxygen-containing compound, and an impurity. It is provided depending on the type of gas of the compound containing the element as a component. If one of these raw material compounds is liquid in the standard state, an appropriate vaporizer i should be provided.In the figure, the gas supply sources 106 to 109 with a numeral 1 are branch pipes, and b is a branch pipe. Flowmeters are marked with C, pressure gauges are used to measure the pressure on the high pressure side of each flowmeter, and valves with d or e are used to adjust 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 (B). A device 122 is provided. The raw material gas for generating activated m (B) supplied from the gas introduction pipe 110 is activated in the activation chamber (B) 123, and the generated activated species (
B) is introduced into the film forming chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge. In the figure, 112 is an activation chamber (A), 113 is an electric furnace, 114 is 81 solid particles, 115
is an introduction pipe for a compound containing gaseous silicon and /% logon, which is the raw material for the activated species (A), and the activation chamber (A) 11
The activity m(A) generated in step 2 is introduced into the film forming chamber 101 through the introduction pipe 116t. In the figure, 120 is an exhaust pulp and 121 is an exhaust pipe.

The base 103 made of ethylene terephthalate film is placed on the support stand 102, and an exhaust device (not shown) is placed on the base 103 made of ethylene terephthalate film.
was used to evacuate the film forming chamber 101 to approximately 10-' Torr.
The pressure was reduced to r. NN2 from Dempe 106 for gas supply
150SCC or this and PH3 gas or B2H6
Gas (all diluted with 11000pp hydrogen gas) 40 S
A gas mixed with CCM was introduced into the activation chamber (B) 123 via the gas introduction pipe 110.

The N2 gas etc. introduced into the activation chamber (B) 123 is activated by the microwave plasma generator 122 to become activated nitrogen etc., and the activated nitrogen etc. is introduced into the entire film forming chamber 101 through the introduction pipe 124. .

On the other hand, 31 solid particles 114 are packed in the activation chamber (A) 102, heated in an electric furnace 113, kept at about 1100°C, brought to a red-hot state at 5 it, and then a gas (not shown) is inserted into the activation chamber (A) 102 through an inlet pipe 115. By injecting SiF4, active species of 5IF2 are generated, and the 5IF2''
was introduced into the film forming chamber 101 through the introduction pipe 116t.

In this way, the internal pressure inside the film forming chamber 101 is reduced to 0.4 Torr.
A non-doped or doped nitrogen-containing amorphous deposited film (thickness: 700×) was formed. The deposition rate was 12X/s@e.

Next, each of the obtained non-dog, p-type, or n-type samples was placed in a vapor deposition tank, and a comb-shaped At gap electrode (gap length 250 μ, width 5
cm ) was formed, the dark current was measured at an applied voltage of 10 V, the dark conductivity σ was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2-4 With N2, Si2H6, Ge2H6 or C2H6'
A nitrogen-containing amorphous deposited film was formed in the same manner as in Example 1, except that a nitrogen-containing amorphous deposited film was used. Measure the dark conductivity of each sample,
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 with sufficient doping can be obtained.

Examples 5-8 Instead of N2, NH,, NOF % N02 or N20
A nitrogen-containing amorphous deposited film was formed in the same manner as in Example 1 except that the nitrogen-containing amorphous deposited film thus obtained had excellent electrical properties and was a well-doped deposited film.・Example 9 Using the device shown in Figure 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 S1 grain, 205 is an active m (A) raw material introduction pipe, 206 is an active species (A)
An inlet pipe, 207 a motor, 208 a heater used in the same manner as 104 in FIG. 2, 209 and 210 a blowout pipe, 211 an At syringe-shaped base, and 212 an exhaust valve.

Further, 213 to 216 are raw material gas supply systems similar to 106 to 109 in FIG. 1, and 9.217-1 is a gas introduction pipe.

The film forming chamber 201 has an At cylindrical base 211 suspended therein, is equipped with a heater 208 inside, and has a motor 20.
7 so that it can be rotated.

In addition, 81 solid particles 204 are packed in one activation chamber (A) 202, heated in an electric furnace 203, and kept at about 1100°C.
SiF4'i is brought into a red-hot state, and SiF4'i is injected into it from a container (not shown) through the introduction pipe 206 to generate active species of SiF2* as the active species (A). was introduced into the membrane space 201.

On the other hand, Si2H6 and N2 gases were introduced into the activation chamber (B) 220 through the introduction pipe 217-1. In the activation chamber (B) 220, the introduced Si2H6 and N2 gases are subjected to activation treatment such as plasma generation by a microwave plasma generator 221, and are converted into silicon hydride active species and activated nitrogen through the introduction pipe 217-. 2, the film forming chamber 201
introduced within. At this time, PH3, B2H as necessary.
An impurity gas such as No. 6 was also introduced into the activation chamber (B) 220 and activated. The internal pressure in the film forming chamber 201 was set to 1.9 T.
I kept it at orr.

The At cylindrical base body 211 is rotated, and the exhaust gas is exhausted through the exhaust pulp 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 the gas used in the production of the photosensitive layer 13 through the introduction pipe 217.
-1, #) Si2H6, N2, N2 and B2H6 (capacity j
Introducing a mixed gas of 0.2% B2H6 gas at t%,
The film was formed with a film thickness of 2000X.

Comparative Example 1 A film forming chamber with the same configuration as the film forming chamber 201 was prepared using SiF4, Si □ H6, N2, N2 and B2H6, and equipped with a high frequency device of 13.56 MH3. An electrophotographic imaging member having the layer structure shown in FIG. 1 was formed by a general plasma CVN method.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 9 and Comparative Example 1.

Example 10 A PIN type diode shown in FIG. 2 was manufactured using N2 as an oxygen compound and the apparatus shown in FIG. 3.

First, a polyethylene naphthalate film 21 on which a 1000X ITO film 22 was vapor-deposited was placed on a support stand, and a 10-
After reducing the pressure to 6 Torr, active species 5iF2f produced in the same manner as in Example 1 were introduced into the film forming chamber 101. Also 5
Each of i3H6 gas, PH, and gas (diluted with 1000 ppm hydrogen gas) was introduced into the activation chamber (B) 123 and activated. Then, this activated gas was introduced into the film forming chamber 101 via the introduction pipe 116. Then, the pressure inside the deposition chamber is Q, 4
I-type a-8i doped with p kept at Torr
A (H,X) film 24 (film thickness 700X) was formed.

Next, except for stopping the introduction of PH3 gas, the n-type a-s
+ (npx) film using the same method as the non-doped 8-
A 81(H,X) film 25 (film thickness: 5000×) was formed.

Next, along with S i 3H6 gas, N2 gas, B2H6
Gas (1000ppm hydrogen gas dilution), otherwise nf
p-dispersed nitrogen-containing a doped with B under the same conditions as i
-SIN (H,X) film 26 (film thickness 700X) was formed. Furthermore, a film thickness of 100 mm was formed on this PM film by vacuum evaporation.
A 0X ktt pole 27 was formed to obtain a PINfi diode.

The IV characteristics of the diode element thus obtained (area: 1 cIN2) were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

In addition, regarding light irradiation characteristics, light is introduced from the substrate side,
For light irradiation intensity (approximately 100 mW/wound 2), conversion efficiency is 8.41 or more, open circuit voltage is 0.9 V s, short circuit current is 10
-2 mA/crR2 was obtained.

Example 11 N01N20, N20 in place of N2 as carbon compounds
Example 1 was carried out in the same manner as in Example 10 except that 4ft 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. becomes. In addition, the reproducibility in film formation is improved, which makes it possible to improve film quality and make the film quality uniform. It is also advantageous for increasing the area of the film, improving film productivity and facilitating mass production (
can be achieved. Furthermore, since no excitation energy is used between the film forming chambers, the film can be formed even on substrates with poor heat resistance. The low-temperature treatment has the effect of shortening the process.

[Brief explanation of the drawing]

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 method of the present invention used in 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, 2
5... i-type semiconductor layer, 26... p-type semiconductor layer, 10
1.201... Film formation chamber, 111,202... Activation chamber (A), 123, 220... Activation chamber (13),
106,107,108,109,213゜21412
15.216...Gas supply system, 103,211...
Base. Agent Patent attorney Johei Yamashita Procedural amendment (method) June 14, 1985 Commissioner of the Patent Office Manabu Shiga Indication of the case 1985 Patent Application No. 31869 2 Name of the invention Deposited film forming method 3 Amendment Relationship to this case Name of patent applicant (100) Canon Co., Ltd. 4 Agent
105 Address 40 Toranomon 5-13-1 Toranomon, Minato-ku, Tokyo
Mori Building 6 Correction Target 4, Brief Explanation of Drawings 7 Contents of Correction 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. 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 method of the present invention used in 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...i-type semiconductor layer, 26...p-type semiconductor layer, 1
01,201... Film formation chamber, 111°202... Activation chamber (A), 123,220... Activation chamber (B), 1
06,107,108. 109.213,214,215,216...Gas supply system, 103,211...Substrate, 117.218...
・Thermal energy generator.

Claims (1)

[Claims] Chemically interacts with active species (A) generated by decomposing a compound containing silicon and halogen in a film forming space for forming a deposited film on a substrate. Active species (B
) are separately introduced and chemically reacted to form a deposited film on the substrate.