JPS61198618A - 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 species A produced by decomposing a compound containing silicon and halogen and an active seed 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 silicon and halogen and an active seed B produced out of the film-forming nitrogen-containing compound, the chemical interaction by these species 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 effect such as etching or another action, e.g. abnormal discharge.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention is directed to nitrogen-containing deposited films, particularly functional films, particularly semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, imaging devices, etc. The present invention relates to a method suitable for forming a non-single-crystal deposited film containing amorphous or polycrystalline nitrogen.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using a vacuum evaporation method, a plasma CVD method, a CVD method, a reactive snoccuttering method, an ion silating method, a photo-CVD method, etc. Generally, plasma CVD 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 including uniformity and reproducibility.
Despite the problems in terms of mass production, there is still room for further improvement in overall characteristics.

The reaction process in forming an amorphous silicon deposited film using the conventional plasma CVD method is more complex 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 (reaction vessel structure, pumping speed, plasma generation method, etc.), delasma sometimes becomes unstable and often has a significant negative effect on the deposited film formed. Moreover, device-specific parameters must be selected for each device.
Therefore, the reality is that it is difficult to generalize the manufacturing conditions. On the other hand, in order to develop an amorphous silicon film that fully satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. There is.

Depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniform film thickness, and uniform film quality, and also achieve reproducible mass production 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 are also complicated, the management tolerance is narrow, and equipment adjustments are delicate. Since it is,
These have been pointed out as problems that should be improved in the future. On the other hand, in the conventional technology using the normal CVN 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 above-mentioned drawbacks of the plasma CVD method and provides a new deposited film forming method that does not rely on conventional forming methods.

[Purpose and outline of the invention]

The purpose of the present invention is to improve various characteristics of the film to be formed, film formation speed, reproducibility, and uniform film quality, while being suitable for large-area films, improving film productivity, and mass production. 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 create an active species (A) generated by decomposing a compound containing silicon and a single dan in a film forming space for forming a deposited film on a substrate, and a chemical reaction between the active fJII (A) and the The active 21 (B) generated from the nitrogen-containing compound for film formation, which interacts with the film, is introduced separately, and a chemical reaction is caused by applying discharge energy to the deposited film on the substrate. 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 that can form an activated atmosphere such as plasma is used as energy to excite and cause a reaction in the raw materials for forming the deposited film. In the coexistence of the active species (A) produced by the active species (A) and the active species (B) generated from the nitrogen-containing compound used for film formation, by applying discharge energy to them, the chemical interaction between them can be prevented. Because it causes, accelerates, and amplifies the film, it is possible to form a film even with lower discharge energy than before.
The deposited film that is formed is not adversely affected by etching effects or other adverse effects such as abnormal discharge effects during film formation.

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

Further, in the present invention, in addition to discharge energy, light energy and/or thermal energy can be used in combination, if desired. The light energy can be applied to the entire substrate using an appropriate optical system, or it can be applied selectively to a desired part.
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 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 speed 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.

In addition, the active species (A) in the present invention refers to a species that chemically interacts with the active species (B) generated from the nitrogen-containing compound to impart energy or cause 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 contain constituent elements constituting the deposited film to be formed, or may not contain such constituent elements. 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 any constituent elements constituting the deposited film to be formed and can be simply regarded 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 may be used in combination with a nitrogen-containing compound that can be used as a raw material for film formation.

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), halogen (X=F, CI, Br
or ■), sulfur (S), carbon (C), oxygen (0), silicon (ss), yurmanium (Go), etc., and other atoms that combine with nitrogen among the atoms of elements belonging to each group of the periodic table. Most atoms can be used as long as they are constituent atoms of a compound that can achieve the object of the present invention.

Incidentally, for example, as a compound containing N and H, J(N,
, NH4N, , NH,, H2NNH,, primary to tertiary amines, halides of these amines, hydroxylamine, and other compounds containing N and X include NX,.

N, X, N2X2. NOX, No2X,
As a compound containing N and S, such as No, N4, N4S4
．． Compounds containing N and C, such as N255, include N(C
H,)5. HCN and cyanide, HOCN, H
8CN, compounds containing N and O include N20,
NO, No□* N2O5* N2041N205
Examples include rNO.

In addition, silazane and organosilicon compounds having four 81-N bonds, such as organosiladecy, organosilicon isoquanate, or-silicon isothiocyanate, and the like can also be used. Specifically, the silazane is disilazane, trisilade/, and the organosiladene is triethylsiladene (C2H5)3SIN.
H2hexamethyldisiladene ((CH3)581
]2NH hexaethyldisiladene [(C2H5)
, st ]2Na organosilicon incyanate is trimethyl silicon isocyanate) (C)1
3), 5iNCO dimethyl silicone diisocyaner)
Examples of the (CH,)281(NCO)2 organosilicon inthiocyanate include trimethylsilicon isothiocyanate (CH3) and 5INC8.

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

In the present invention, the active species (2) from the activation space (A) introduced into the film forming space are
Those with a lifetime of 0.1 seconds or more, more preferably 1 second or more, optimally 10 seconds or more are selected and used as desired, and the constituent elements of this active species (6) are formed in the film forming space. It constitutes the components constituting the deposited film.

In addition, the nitrogen-containing compound for film formation is activated by an activation technology in the activation space (B), and is activated to form active species (
B) is generated, and the active species (B) is introduced into the film forming space,
When forming a deposited film under the action of discharge energy,
At the same time, it chemically interacts with the active species (A) introduced from the activated space captive. As a result, a desired deposited film can be easily formed on a desired substrate. The active species (B) generated from the nitrogen-containing compound for film formation, as in the case of the active species (A), constitutes the components constituting the deposited film formed in the film formation space. Become.

In the present invention, as the compound containing silicon and halogen to be introduced into the activated space prisoner, for example, a compound in which some or all of the hydrogen atoms of a chain or cyclic sila/compound are replaced with...rodane atoms is used, Specifically, for example, 5i
uY2u+2 (u is an integer greater than or equal to 1, Y is F + CI
, Br and! At least one element selected from ) chain-like logonized silicon, 51vY
2v (v is an integer of 3 or more, Y has the above meaning.)
Cyclic rhodanide silicon, S l uHxY
y (u and Y have the above meanings. x + y =
2u or 2u+2. ), and the like.

Specifically, for example, 81F'4. (SiF2)5. (
SiF2) 6° (81F2) 4.81□F6.81. F
8.5iHF, , SiH2F2゜5iC14 (SI
C12)5.5IBr4, (SiBr4)5.5t
2C16゜512Br6, 5IHC15, 5iHBr
3, 5iHI3.

Examples include those in a gaseous state or those that can be easily gasified, such as S1□C1,F.

In order to generate the active species (A), the silicon and /5
In addition to compounds containing oil, if necessary, other silicon compounds such as simple silicon, hydrogen, compounds such as F2 gas, Cl2t! gas, and gasified Br2゜■2
etc.) can be used together.

In the present invention, methods for generating activated species (A) and (B) in activation spaces (6) and (B), respectively, include microwave, RF, low frequency, D
Activation energy such as electrical energy such as C, thermal energy such as heater heating, infrared heating, and light energy is used.

In the present invention, the ratio of the amount of the active species (B) generated from the nitrogen-containing compound introduced into the film-forming space and the active species (A) can be adjusted as desired depending on the film-forming conditions, the type of active species, etc. It can be determined, but preferably 10:1 to 1:10 (introduction flow rate ratio) is appropriate, more preferably 8:2 to 4
:6 is desirable.

In the present invention, in addition to nitrogen-containing compounds, chemical substances for film formation include hydrogen gas, nitrogen compounds (e.g., F2 gas, Cl2f, gasified Br2*I2, etc.), helium, argon, neon, etc. An inert gas, and in the activation space (B), a silicon-containing compound, a carbon-containing compound, a germanium-containing compound as a raw material for forming a deposited film that generates active species (B), a raw material for forming a deposited film, and/or Or use an oxygen-containing compound as a film-forming raw material in the activation space (B).
K can also be introduced and used. If more than one of these chemicals is used, they can be premixed and introduced into the activation space (B) in a gaseous state, or they can be introduced in a gaseous state from separate sources. They can be supplied individually and introduced into the activation space (B), or they can be introduced into separate activation spaces and activated individually.

As the silicon-containing compound for forming the deposited film, silanes and rhodanized silanes in which silicon is bonded with hydrogen, -rodane, or hydrocarbon groups, etc. 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
Compounds substituted with no atom are suitable.

Specifically, for example, 5if(A, 512H6, 5t3
H81St4H,. *5i5H1□, 5t6H14
St, H2, +2 (p is 1 or more, preferably 1 to 1), etc.
5, more preferably an integer of 1 to 10. ), a linear silane compound represented by SiH, 81H(SIH3)S
iH,,Sin,5iH(SIH,)St,H,,st
St, H2 such as 2u5sta(siH3)si□H5
, +2 (p has the above-mentioned meaning), and some or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with halogen atoms. Compound, 5t3f (61514H6
.

515H,. , 519H29 such as 5L6H12 (q is 3
The above is preferably an integer of 3 to 6. ), a compound in which some or all of the hydrogen atoms of the cyclic silane compound are substituted with other cyclic silanyl groups and/or chain silanyl groups, some of the hydrogen atoms of the silane compounds exemplified above, or An example of a compound in which all halogen atoms are substituted is 5lf (3F, 5IH3C1).

5irf(, Xt(
X is a halogen atom, r is 1 or more, preferably 1 to 10.
More preferably an integer from 3 to 7, s + t = 2
r +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 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 (C2H6), demipane (C,H8), and n-butane (
n -C4H10), intane (C5H12), ethylene hydrocarbons include ethylene (C2H4), propylene (C3H6), butene-1 (C4H8), butene-2
(C4H8), inbutylene (C4H8), pente/(
C5H4°), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4), butyne (C4H6), and the like.

- As the Rodan-substituted hydrocarbon compound, F
Compounds in which hydrogen is substituted with I C1# Br #I can be mentioned, and compounds in which hydrogen is substituted with F or CI are particularly effective. The halogen that replaces hydrogen may be one type or two or more types in one compound. Examples of the organosilicon compounds used in the present invention include organo-silane, organo-silane, and the like. organo 7
Ran and organohalogensilane each have a general formula;
%Formula% (However, R=alkyl group, aryl group; X:F.

It is a compound represented by CI, BrI; n=1+2,3t4; m=1+2°, and representative examples include alkylsilane, arylsilane, alkylhalogensilane, and arylhalogensilane.

Specifically, as organochlorosilane, trichloromethylsilane CH,5IC1
゜Dichlorodimethylsilane (CH,)
2Sil12Chlortrimethylsilane
(CI(,)3SiCltrichloroethylsilane
C2H55iC13 dichlorodiethylsilane
As the (C2H5)2SIC12organochlorofluoro7rane, chlorfluorodithylsilane CH,5iF2Cldichlorofluoromethylsilane CH5iFC12chlorofluorodimethylsilane (CH3)25IFC! Chlorethyldifluorosilane (02H5)SiF2Cldichloroethylfluorosilane 02H5SiFC
1□ChlordifluoroI lopylsilane C5H,5I
F2Cl dichlorofluoroIropyrsilay C3H
75IFC12 Organosil/Toji is Tetramethylsilane (CH3)4
SI ethyltritylsilane (CH3),
5iC3H5 trimethylpropylsilane
(CI(3), SIC, H.

Triethylmethylsilane CH,5i (
C2H5)3tetraethylsilane
(C2H5), Sl organohydrogenosilane includes methylsilane CH35IR3 dimethylsilane (CH,)2SIH2 trimethylsilane (CH,)3SIH noethylsilane (C2H5)2SiH2
Triethylsilane (C2H5), SiH
Tripropylsilane (C,H,)3Si
H nophenylsilane (C6I(5)2
As SiH2 organofluorosila/, trifluoromethyl 7rane Cf (3SiF
3difluorodimethylsilane (CH3)2
SiF2 fluorotrimethylsilane (C
H3) 3SiF ethyltrifluorosilane
C2H55IF3 diether difluor 7ran
(C2I(5)2SiF2Triethylfluorosilane (C2H5)38IF trifluoropropylsilane (C3H,)SiF3As organobromosilane, Bromotritylsilane (CH,)3Si
Brdibromdimethylsilane (CH3)
2stnr2, etc., and in addition to these organopolysilanes, hexamethyldisilane [:(CH3)3
As Si]z organosilane, hexamethyldisilane t: (ca,),
st]2hexaglobildisilane ((C3
H7) 3Si]2 can also be used.

These carbon 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, hydrogen, hydrocarbon groups, etc. are bonded to germanium can be used, for example, Ge aHl (a is an integer of 1 or more, b = 2 m + 2 or 2 times). linear or cyclic hydrogenated r/I/manium represented by ), polymers of this germanium hydride, and compounds in which some or all of the hydrogen atoms of the germanium hydride are replaced with -.a gun atoms. , organic dalmanium compounds such as compounds in which some or all of the hydrogen atoms of the germanium hydride are replaced with an organic group such as an alkyl group or an aryl group, and optionally a dihalogen atom, and other rumanium compounds. be able to.

Specifically, for example, GeH41Ge2H6+G-kai5H
B +n-G@Hr t@rt-Go H* Ge3
H41Ge5H10141041G G@H3F, GeH3C1, GeH2F2, H
6Go6F6. Go(CH3)*.

Ge(C2H5)4 r Ge(C6H5)4 s C
115G@H5+ (CH3)2G@H2'(C1(3
)3G@H, (C2H5)2G@H2,0・(CH3)
2F2, GeF2.

Examples include GeF4 and GeS. These dallmanium compounds may be used alone or in combination of two or more.

Further, examples of the oxygen-containing compound include compounds having a simple oxygen component such as oxygen (02) and ozone (C6), and compounds having one or more atoms other than oxygen as constituent atoms. &1 as atoms other than oxygen, hydrogen (H)
, I-H? '7 (X=F, CI FBr or I
), sulfur (S), carbon (C), silicon (81),
Among the atoms of elements belonging to each group of the periodic table, such as germanium (Os), atoms that can be combined with oxygen and that constitute a compound that can achieve the purpose of the present invention may be used. can do.

Incidentally, for example, compounds containing 0 and ■ include H2O,
H2O2, etc., OL! :As a compound containing S, SO□
, 803, etc., and compounds containing O and C include:
Acids such as H2CO, oxides such as co, co□, etc.
Compounds containing O and 81 include disiloxane (f(,
5tostH5), trisiloxane (H, Si 081
Siloxanes such as H2O5i H,), (cH,)2
st(ococa5)2゜0H3SS (OCOCR,
) 3 organoacetoxysilane, (CH, ), 5I
OCH3, (CH,)2St(OCR,)2. CH,
81 (OCH3).

Alkylalkoxysilanes such as (CH3), 5iOH
.

(CHs)2(CtHs)SjOH-(CzHs)2S
Compounds containing 0 and Ge, such as organosilanols such as i(OH)z, include oxides of G, hydroxides, germanic acids, HGe0GeH, HG50Gef(O-
Examples include organic r-diram compounds such as GeH3.

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

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. As the impurity element used, as a p-type impurity, an element of group Ⅰ A of the periodic table, such as B*AI, Ga
* In, TI, etc. are mentioned as suitable ones,
Suitable examples of the n-type impurity include elements of group V A of the periodic table, such as P # As l Sb l B1, and particularly B * Ga m P t Sb.
etc. is 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 PH5r P2H4* PF
5 r PF5 a PCl5 r AlB2.

AsF t AIF * AsC1+ SbH *
SbF5 + 5IH3tBF5 e BCl3,B
Br3 t B2H6, B4H10e BSH9rB,
Examples include H, , B6H1°, B6H12, AlCl, and the like. 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 (1) or/and the activation space (B) together with each substance that generates the active species (A) and the activity 81 (B), and activated. Alternatively, the activated space may be activated in a third active space (Q) different from the activation space prisoner and the activation space (B).The impurity introducing substance may be employed by appropriately selecting the activation energy described above. The active species (PN) generated by activating the impurity introducing substance can be an active species or/and an active species (PN).
It is mixed with B) in advance or 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 typical electrophotographic image forming member photoconductive member obtained by the present invention.

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

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13 can be created by the method of the present invention. Furthermore, the photoconductive member 10 is provided with 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 the electrical layer 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 NlCr, stainless steel, AI, Cr, Mo*Ana
Ir rNb + Ta r V a Ti * P
Examples include metals such as t#Pd and alloys thereof.

As the electrically insulating support, 4-lyester, polyethylene, ? Films or sheets of synthetic toilet fat such as liquorinate, cellulose acetate, polypropylene, polyvinyl chloride, divinylidene chloride, 4-listyrene, and lyamide, glass, ceramics, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is electrically conductive treated, and another layer is preferably provided on the electrically conductive surface.

For example, if it is glass, its surface is NiCr*Al
eCr # Mor Au * Ir p Nb +
Ta #V * Ti t Pt #Pd, I
n2O,,5n02. ITO (In2O, +5n0
2) If it is conductive treated by providing a thin film such as 1. or a synthetic resin film such as a polyester film. NlCr, AI + Ag p Pb *
Zn, Ni, Au.

Cr, MO, Ir l Nb I Ta l V
#TI t Pt The surface is conductively treated by vacuum evaporation, electron beam evaporation, sputtering, etc. with a fine metal, or by laminating with the metal. The shape of the support may be any shape such as cylindrical, belt-like, plate-like, etc., and the shape is determined depending on the need.
For example, if the photoconductive member 10 of FIG. 1 is to be 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 generated in the photosensitive layer 13 by electromagnetic wave irradiation and moves toward the support 11 from the photosensitive layer 13 side to the support 11 side. It has the function of allowing easy passage.

This intermediate layer 12 has, for example, silicon atoms as its base material,
Amorphous silicon (hereinafter referred to as
a, -81N (denoted as H,
) or p-type impurities such as phosphorus e).

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

The content of the substance controlling conductivity such as P is preferably 0.001 to 5 x 10 atomic pp
m, more preferably 0.5 to I x 10 atoms
c ppm, optimally 1-5 X l Oatomi
C ppm is preferable. O If the intermediate layer 12 has similar or the same constituent components as the photosensitive layer 13, the intermediate layer 12 is formed after the formation of the photosensitive layer 13. It can be done continuously up to. In that case, as raw materials for forming the intermediate layer, the active species (A) generated in the activated space captive, a nitrogen-containing compound in a gaseous state, hydrogen, a halo compound, an inert gas, if necessary, Activity generated from silicon-containing compounds, carbon-containing compounds, r-rumanium-containing compounds, and oxygen-containing compounds
(B) and active species generated by activating the gas etc. of a compound containing an impurity element as a component, either side by side or mixed as necessary, to form a support 11.
By introducing the activated species into the deposition space where the activated species is installed and applying discharge energy to the atmosphere in which the introduced active species coexist,
The intermediate layer 12 may be formed on the support 11.

The compound containing silicon and halogen that is introduced into the activation space (A) to generate active species (A) when forming the intermediate layer 12 is, for example, a compound that easily generates active species (A) such as SiF2*. is preferably selected from among the above-mentioned 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-81(H,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 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-doped a-81 (H, (for example, n-type), or a substance that controls conductivity of the same polarity, if the actual amount contained in the intermediate layer 12 is large. In the case of forming the photosensitive layer 13, as well 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 confinement may be reduced. Compounds containing silicon and halogen are introduced into the system, and active species (A
) is generated, and the active Al(A) is introduced into the film forming space.

Furthermore, if desired, an amorphous deposited film containing carbon and silicon as constituent atoms can be formed as a surface layer on this photosensitive layer. can be carried out in the same manner as in the method of the present invention.

FIG. 2 is a schematic diagram showing a typical example of a PIN type diode 9.r-bis using an a-8i deposited film doped with an impurity element and manufactured by carrying out the 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 I-type semiconductor layer 2
5. Consisting of a p-type semiconductor i-layer 26. 28 is a conductive wire connected to an external electric circuit device.

These semiconductor layers are a-81(H,X) t a-3
i(N, H.

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

The base 21 may be conductive, semiconductive, or electrically insulating. When the base 21 is conductive, the thin film electrode 22 may be omitted. For example, as a semiconductive substrate, St v GorGaAg, Z
Examples include semiconductors such as nOr ZnS. Thin film electrode 22
．． 27, for example, NiCr, Al, Cr
.

Mo, Au, Ir, Nb + Ta,
V * Tl + Pt t Pd rZn203.5
It can be obtained by providing a thin film of n02 r ITO (In2O3+ 5n02 ) or the like on the substrate 21 through a process such as vacuum evaporation, electron beam evaporation, or sputtering. The electrode 22,270 layer thickness is preferably 30 to 5x1
0'l, more preferably 100 to 5x10x.

In order to make the film body constituting the semiconductor layer described above necessarily a di-type or p-type depending on gK, a layer containing an n-type impurity, a p-type impurity, 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 the layers can be formed by the method of the present invention, and the film formation is performed using activated space confinement. Compounds containing silicon and halogen are introduced into the molecule, and by exciting and decomposing them under the action of activation energy, active species (A) such as 5IF1* are generated, and the active species (A) Introduced into the film forming space. Also, apart from this,
A nitrogen-containing compound in a gaseous state, a silicon-containing compound, a germanium-containing compound, an oxygen-containing compound as necessary, and a compound gas containing an inert gas and an impurity element as necessary are excited by activation energy, respectively. The activated species (B) are then decomposed to produce the respective active species (B), which are introduced into the film forming space where the support 11 is installed, either separately or mixed as appropriate. The active species introduced into the film forming space are caused to undergo chemical interaction, promoted or amplified by using discharge energy, and a deposited film is formed on the substrate 21. The thickness of the semiconductor layer is preferably 100 to 10
A range of 4X, more preferably 300 to 2000X is desirable.

Further, the thickness of the i-type semiconductor layer is preferably 50
0-10Xl, 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 Si, N4 insulator films, partially nitrided 81 films, etc. by the CVD method, which constitute semiconductor devices such as IC%) transistors, diodes, and photoelectric conversion elements. For example, by controlling the timing and amount of nitrogen compound introduced into the film-forming space, S
i-film can be formed. Alternatively, by appropriately combining hydrogen, halogen, silicon-containing compound, germanium-containing compound, carbon-containing compound, oxygen-containing compound, etc. in the nitrogen compound, N and these H9X,
It is also possible to form a film body with desired characteristics using a bond with Si, G., C20, etc. as a constituent unit.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Fig. 3, 1 was carried out by the following operations.
Nitrogen-containing amorphous deposited films of type, p-type, and n-type were formed.

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.

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 105 and generates heat. The substrate temperature is not particularly limited, but if it is necessary to heat the substrate in carrying out the method of the present invention, the substrate temperature is preferably 30 to 450℃.
℃, more preferably 50 to 350℃.

106 to 109 are gas supply systems, nitrogen compounds,
and, if necessary, provided according to the type of gas such as hydrogen, halogen compounds, inert gas, silicon-containing compounds, carbon-containing compounds, germanium-containing compounds, oxygen-containing compounds, compounds containing impurity elements, etc. . When using one of these raw material compounds that is liquid in a standard state, an appropriate vaporization device is provided. In the figure, a is added to the gas supply systems 106 to 109, and b is a branch pipe.
Those marked with a are flow meters, those marked with C are pressure gauges that measure the pressure on the high pressure side of each flow meter, and those marked with d or e are pulps for adjusting the flow rate of each gas. 123 is the active species (
B) in the activation chamber for producing B), and the activation chamber 12
A microwave plasma generator 122 that generates active energy for generating active species (B) is provided on the 30th cycle.

The raw material for producing active species (B) supplied through the gas introduction pipe 110 is activated in the activation chamber (B), and the generated active species (B) is introduced into the film forming chamber 101 through the introduction pipe 124. will be introduced in 111 is a gas pressure gauge. 112 in the diagram
is the activation chamber (A), 113 is the electric furnace, 114 is the solid state 83
The particle 115 is an introduction tube for a compound containing gaseous silicon and halogen, which is a raw material for the activated species (A), and is used to introduce a compound containing gaseous silicon and halogen into the activation chamber (
A) The active species generated in 112 are introduced into the film forming chamber 101 via the introduction pipe 116.

Reference numeral 117 denotes a discharge energy generator, which includes a matching gear 117 & a cathode electrode 117b for introducing high frequency.
Equipped with etc.

The discharge energy from the discharge energy generating device 117 acts on active species etc. flowing in the direction of the arrow 119,
A nitrogen-containing amorphous deposited film is formed on the entire substrate 103 or a desired portion by a chemical reaction. Further, in the figure, 120 is an exhaust pulp, and 121 is an exhaust pipe.

Ahead f1. A substrate 103 made of a polyethylene tele-7 tallate film is placed on a support stand 102, and the inside of the film forming chamber 101 is evacuated using an exhaust device (not shown) to a temperature of about 10”f To
The pressure was reduced to rr. N215 from gas supply container 106
0 SCCM or this and PR, gas or B2H
6ffs (all diluted with 1000 ppm hydrogen gas) 40
Gas mixed with SCCM was introduced into the activation chamber (B) 123 via the gas introduction pipe 110. Activation room (B)
The N2 gas and the like introduced into the chamber 123 were activated by the microwave plasma generator 122 to become activated nitrogen, etc., and the activated nitrogen and the like were introduced into the film forming chamber 101 through the introduction pipe 124.

On the other hand, the activation chamber (A) 102 is filled with solid S1 grains 114, heated in an electric furnace 113, kept at about 1100°C, and heated to a red-hot state KL, where it is passed through an inlet pipe 115 to a generator (not shown). By blowing in 5IF4, active species (A) sip2'' is generated, and the SiF2'' is introduced into the film forming chamber 101 through the introduction pipe 116.

In this way, the pressure in the film forming space 101 is f: 0.4To
A non-doped or doped nitrogen-containing amorphous deposited film (700 mm thick) was formed by applying plasma from the discharge device 117 while maintaining the temperature at rr. The film formation rate was 51 i/s·C.

Next, each of the obtained non-doped or p-type samples was placed in a vapor deposition tank, and a comb-shaped AI was placed at a vacuum level of 10 Torr.
After forming a gap electrode (gap length 250μ, width 5), the dark current was measured with an applied voltage of 10V, and the dark conductivity σ,
The film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2 to 4 Nitrogen-containing amorphous deposited films were formed according to the same method and procedure as in Example 1, except that 812H6, G.2H6, or C2H6 was used together with N2. 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 deposited film with sufficient doping can be obtained.

Examples 5-8 Instead of N2, NH,, NOF, NO□ 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 sufficiently doped.

Example 9 Using the apparatus shown in Fig. 4, the first
A drum-shaped electrophotographic image forming member having a layer structure as shown in the figure was prepared.

In Figure 3, 201 is a film forming chamber, 202 is an activation chamber, 203 is an electric furnace, 204 is 81 solid particles, 205 is an active species (A) raw material introduction tube, and 206 is an active species (A) introduction tube. tube, 207 is a motor, 208 is a heater, 209
, 210 is a blowing pipe, 211 is an Al cylinder-shaped substrate, and 212 is an exhaust pulp. 9, 213 to 216 are raw material gas supply systems similar to 106 to 109 in FIG. 4, and 217-1 is a gas introduction pipe.

The AI cylinder base 211 is suspended in the film forming chamber 201,
A heating heater 208 is provided inside the motor 207.
Allows for rotation. Reference numeral 218 denotes a discharge energy generating device, which includes a matching box 218m, a cathode electrode 218b for introducing high frequency, and the like.

In addition, 81 solid particles 204 are packed in the activation chamber (A) 202, heated in an electric furnace 203, and kept at about 1100°C.
5IF2'' as an active species (A) is generated by bringing the Sl into a red-hot state and blowing SiF4 into it from an unillustrated source through the introduction pipe 206, and the 5ir2* is passed through the introduction pipe 206 to form a film. It is introduced into the room 201.

On the other hand, 812H6 and N2 gas are introduced into the activation chamber (B) 220 from the introduction pipe 217-1. The introduced s'2Hb e N2 scum is in the activation chamber (B) 220
, the silicon hydride active species undergoes an activation process such as plasma generation by the microwave plasma i generator 221 to become active hydrogen, and is introduced into the film forming chamber 20 through the introduction pipe 217-2.
It was introduced within 1. At this time, PH, B2H as necessary.
Impurity gas such as 6 is also activated in silicon hydride active species activation chamber (B)
220 and was activated.

Next, plasma is applied from the discharge device 218 while maintaining the atmospheric pressure in the film forming chamber 201 at 1.0 Torr.

The AI cylinder base 211 is heated to 280°C by the heater 208.
The exhaust pulp 212 is heated, held, and rotated, and the exhaust gas is exhausted by appropriately adjusting the opening of 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 an inlet pipe 217 in addition to the gas used when forming the photosensitive layer 13.
-1 from 812H6t N2. Introducing a mixed gas of N2 and B2H6 (B2H6 gas is 0.2% by volume),
The film was formed with a film thickness of 2000X.

Comparative Example I 5IF4 and 512H6y Using each gas of N2, N2 and B2H6, the film forming chamber 201 was equipped with a 13.56 MHz high frequency device, and an electrophotograph of the layer structure shown in FIG. 1 was taken by a general plasma CVD method. An imaging member was formed.

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 the apparatus shown in FIG. 3 using N2 as an oxygen compound.

First, a 1000X ITO film 22 was deposited. Place the diethylene naphthalate film 21 on a support stand and
After reducing the orrK pressure, the active species SiF2'' produced in the same manner as in Example 1 was introduced into the film forming chamber 101.
H6 gas, PH3 gas (1000ppm hydrogen gas dilution)
were introduced into the activation chamber (B) 123 and activated.

Next, this activated gas is introduced into the film forming chamber 101 through the introduction pipe 116, and the pressure inside the film forming chamber is reduced to 0.4 Torr.
The n-type a-8l (H,X) film 24 is doped with p by applying plasma from the discharge device 117 while maintaining the
(film thickness 700X) was formed.

Next, type 9 a-g except that the introduction of PH and gas was stopped.
Non-doped a-
A 81(H,X) film 25 (thickness: 5000K) was formed.

Then, 81. H67! /S and N2 are S, B2H6
, gas (1000 ppm hydrogen gas dilution), otherwise n
p-type nitrogen-containing a- doped with B under the same conditions as type
An 8IN(H,X) film 26 (film thickness 700X) was formed.

Furthermore, an AI electrode 27 having a thickness of 1000 mm was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

I-V of the diode element thus obtained (with an area of 1)
The characteristics 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,
At light irradiation intensity AMI (approximately 100 mW/cm ), conversion efficiency is 8.4- or higher, open circuit voltage is 0.9 V, and short circuit current is 1.
0.2 mA/cIn was obtained.

Example 11 No, N20 instead of N2 as a carbon compound.

A PIN type diode similar to that in Example 10 was manufactured in the same manner as in Example 1O except that N2O4 was used. This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

From Table 3, according to the present invention, a PIN diode using a-8IN(H,X) having good optical and electrical characteristics can be obtained.

〔Effect of the invention〕

According to the deposited film forming method of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the formed film are improved, and high-speed film formation is possible.

In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. be able to. Furthermore, the film can be formed even on a substrate with poor heat resistance, and the process can be shortened by low-temperature treatment.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining an example of the configuration of a PIN 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 electrode, 24... N-type semiconductor, 2
5... I type semiconductor, 26... P type semiconductor, 101.
201... Film forming space, 111, 202... Activation chamber (A), 123° 219... Activation chamber (B), 10
6,107,108°109.213,214,215
, 216・rW gas supply system, 103, 211...substrate,
117,218...Discharge energy generating device.

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) generated from nitrogen-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.