JPS61198621A - 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 species B produced out of a nitrogen-containing compound are separately introduced, which are then made to chemically react by the action of discharge energy, thus forming a deposited film. CONSTITUTION:A discharge energy 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 species B produced out of the film-forming oxygen-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 by lower discharge energy than conventional. The formed deposited film very hardly receives adverse effects 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 suitable for forming a deposited film containing oxygen, particularly a functional film, especially a deposited film containing oxygen sensitive for semiconductor devices and electrophotography. Concerning methods.

[Prior art]

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

Deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility.
In terms of mass production, there is room to further improve the overall characteristics.

The reaction process in forming an amorphous silicon deposited film by the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma becomes unstable at 5 o'clock, often having a significant adverse 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.

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 uniformity of S quality, and also 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 equipment investment for mass production equipment, and the management items for mass production are also complex, the tolerance range for management is narrow, and the adjustment of the equipment is delicate. These issues have been pointed out as issues that should be improved in the future. On the other hand.

Conventional techniques using normal CVD methods require high temperatures and have not been able to provide deposited films with practically usable characteristics.

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

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

[Purpose and outline of the invention]

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

The above purpose is to create an active species (A) generated by decomposing a compound containing silicon and halogen in a film forming space for forming a deposited film on a substrate, and to chemically interact with the active species (A). By introducing active species (B) generated from an oxygen-containing compound for film formation to each side and causing a chemical reaction by applying discharge energy to these, a film is deposited 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 such as plasma is used as the energy to excite and react the raw materials of the deposited film forming method, but active species (A ) and the active species (B) generated from the vomerine-containing compound for film formation, by applying discharge energy to them, a chemical interaction is caused by them, or In order to accelerate and amplify the process, film formation is possible with lower discharge energy than conventional methods, and the deposited film that is formed has an etching effect.

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

Further, if desired, in addition to the discharge energy, light energy and/or thermal energy can be used in combination.The light energy can be applied to the entire substrate using an appropriate optical system, or can be applied to a desired portion. Since it is also possible to irradiate selectively and in a controlled manner, it is possible to easily control the formation position, film thickness, etc. of the deposited film on the substrate. 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 rate compared to the conventional CVD method, and in addition, it is possible to further lower the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

In addition, the active species (A) in the present invention is a species that chemically interacts with the active species (B) generated from an oxygen-containing compound to impart energy or cause a chemical reaction. ,
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 oxygen-containing compound used in the present invention may be an oxygen-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 an oxygen-containing compound that does not contain any constituent elements constituting the deposited film to be formed and can only serve as a raw material for film formation, or it may be an oxygen-containing compound that can serve as a raw material for forming these deposited films. An oxygen-containing compound that can be used as a raw material for film formation may be used in combination.

The oxygen-containing compound used in the present invention is activated space (B)
For example, when using a solid compound, it is preferable that the compound is already in a gaseous state before being introduced into the gaseous state, or is introduced in a gaseous state. After vaporizing the activation space (B
) can be introduced. Examples of the oxygen-containing compound include simple oxygen such as oxygen (02) and ozone (03), and compounds having one or more constituent atoms of oxygen and atoms other than oxygen. The atoms other than oxygen include hydrogen (H).

Halogen 7 (X=F, C1, Br or engineering), sulfur (S
), carbon (C), silicon (Si), germanium (Ge
), and almost any other atom of an element belonging to each group of the Periodic Table can be used as long as it can combine with oxygen.

Incidentally, for example, compounds containing 0 and H include H2O, H
As a compound containing 0 and S, such as 2O2, so2.503
Examples of oxides such as 0 and C include C010
Compounds containing 0 and St, such as oxides such as 02, include siloxanes such as disiloxane (H3S its 1H3), ) disiloxane (H3S i OS i H2O5i H3), (CH3)2Si (OCOCH3)2-
CH3S i (OCOCH3) 3 etc. (7) t)
Ltga/7setoxysilane, (CH3)3SiOCH3
.

(CH3)25 i (OCH3)2 , CH3
Furkylalkoxysilane such as S1(OCH3)3.

(CH3)3 S i OH, (CH3)2 (CH3
)5 i OH, organosilanols such as (C2H5)23 i (OH)2, etc. Compounds containing 0 and Ge include Ge oxides, hydroxides, germanium acids,
H3GeOGeH3, H3GeOGeH20-GeH3
Examples include organic germanium compounds such as.

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

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

In the present invention, the compound containing silicon and halogen introduced into the activation space (A) is as follows.

For example, a chain or cyclic silane compound in which some or all of the hydrogen atoms are replaced with halogen atoms is used, specifically 1, for example, 5tuY2u+2 (u is an integer of 1 or more, Y is F, CI.

At least one selected from Br and I. ) chain silicon halide, 5ivY2v (
v is an integer of 3 or more, and Y has the meaning described above. ) Cyclic silicon halide, S i uH) (Yy (
u and Y have the meanings given above. x+yz2u or 2u
+2. ), and the like.

Specifically, for example, SiF4゜ (SiFz)5. (SiF2)6゜ (SiF2)a, 5i2Fe, 5i3Fs.

5IHF3. SiH2F2,5iC14゜(SiC12
)5, SiBr4° (SiBr2)5.5i2C1e.

5i2Brs, 5iHCJ13, 5iHBr3.

Examples include those in a gaseous state or those that can be easily gasified, such as 5iHI3.5i2C13F3.

In order to generate the active species (A), in addition to the above-mentioned compound containing silicon and halogen, other silicon-containing compounds such as simple silicon, hydrogen, and halogen-containing compounds (for example, F2 gas) are optionally added.

CJ12 gas, gasified Br2. I2 etc.) can be used in combination.

In the present invention, methods for generating active species in the activation spaces (A) and (B) include microwave and RF, taking into consideration the respective conditions and equipment.

Activation energy such as electrical energy such as low frequency or DC, thermal energy such as heater heating or infrared heating, and light energy is used.

Activated species (A) and (B) are generated by adding activation energy such as heat, light, discharge, etc. to the above-mentioned materials in activation spaces (A) and (B), respectively.

In the present invention, in addition to the oxygen-containing compound, hydrogen gas, Halogen compounds (e.g. F2 gas, C12 gas, gasified Br2.I2, etc.), inert gases such as helium, argon, neon, etc., and silicon-containing compounds, carbon-containing compounds, germanium composites as chemical substances for forming deposited films. It is also possible to introduce a compound or the like into the activation space (B). When using a plurality of these raw material gases, they can be mixed in advance and introduced into the activation space (B), or these chemical substances can be supplied individually from independent sources and activated. They can be introduced into the activation space (B), or they can be introduced into individual activation spaces and activated individually.

As the silicon-containing compound introduced into the activation space (B), silanes and siloxanes in which hydrogen, halogen, hydrocarbon groups, etc. are bonded to silicon can be used. Particularly suitable are chain and cyclic silane compounds, and compounds in which part or all of the hydrogen electrons of the chain wave and cyclic silane compounds are replaced with halogen atoms.

Specifically, for example, SiH4, Si2H6,5i
3HB, S i 4HLO, S i 5HL2.5i6
S i PH2F+2 such as H14 (p is an integer of 1 or more, preferably 1 to 15, and more preferably 1 to 10).

) A linear silane compound represented by

5iH3SiH (SiH3)SiH3゜5iH3SiH
(SiH3)Si3H7゜Si 2HssiH(SiH
3) A chain silane compound having a branch represented by 5ipH2p+2 (p has the above-mentioned meaning) such as Si2H5.

Compounds in which part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with halogen atoms, 5i3He, 5i4H8, 5i5H10, 5isHt
A cyclic silane compound represented by 5iqH2q (q is an integer of 3 or more, preferably 3 to 6) such as 2, etc., in which some or all of the hydrogen atoms of the cyclic silane compound are replaced by other cyclic silanyl groups and/or chains. Examples of compounds substituted with silanyl groups such as SiH3F, 5
iH3C1, 5iH3Br, 5iH3I etc. c7) S i
rHsXt (X is a halogen atom, r is an integer of 1 or more, preferably 1 to 1O1, more preferably 3 to 7, s+
t=2r+2 or 2r. ) are halogen-substituted linear or cyclic silane compounds. These compounds may be used alone or in combination of two or more.

Further, as the carbon-containing compound introduced into the activation space (B), a chain or cyclic saturated or unsaturated hydrocarbon compound,
An organic compound whose main constituent atoms are carbon and hydrogen, and whose constituent atoms are 1M or two or more of silicon, halogen, sulfur, etc.

Among organosilicon compounds having a hydrocarbon group as a constituent, those in a gaseous state or those that can be easily vaporized are preferably used.

Among these, examples of hydrocarbon compounds include carbon atoms of 1 to
Examples of saturated hydrocarbons include methane (CH3), ethane (C2
H6).

propy (C3H8), n-buty (n-C4Hro)
), penta7 (C5H12), z-L/7 hydrocarbons include ethylene (C2H4), propylene (03H
6), butene-1 (C4H8).

Butene-2 (CaHa), inbutylene (C4H8),
Pente7 (C5H1o), acetylene (C2H2) as an acetylene hydrocarbon.

Examples include methylacetylene (C3Ha) and butyne (C4He).

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

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

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

As organosilane and organohalogensilane,
Each has a general formula; Rn5iH4-1. RmSiX4-m (however,
R near) I, r* group, 71J-) Iy group, X: F, C
JL, Br, I.

n=1,2,3,4, m=1.2.3) Typical examples include alkylsilanes, arylsilanes, alkylhalogensilanes, and arylhalogensilanes.

in particular.

As organochlorosilane, trichloromethylsilane CH35iCj
13 dichlorodimethylsilane (CH3
)2siciL2chlorotrimethylsilane
(CH3)25icjL trichloroethylsilane
C2H55iC13 dichlorodiethylsilane (C2H5) 2sic12 organochlorofluorosilane.

Chlordifluoromethylsilane CH35iF2
C1 dichlorofluoromethylsilane CH35i
FCjL2 Chlorfluorodimethylsilane (C
H3) 2S i FCJL Chlorethyldifluorosilane (C2H5)SiF2C1 Dichloroethylfluorosilane C2H55iFCjL2 Chlordifluoropropylsilane C3H75iF2Cj
L dichlorofluoropropylsilane C3H75i
As FCIL2 organosilane.

Tetramethylsilane (CH3) 4
s 1X-fk)')) f Luci 57
(CH3)3SiC2H5 trimethylpropylsilane
(CH3) 3sic31ty triethylmethylsilay CH35i (C2H5
)3 Tetraethylsilane (C2H
5) As a 4st organohydrogenosilane.

Methylsilane CH35iH
3dimethylsilane (CH3)
23 i H2 trimethylsilane
(CH3)3SiHdixthirsine
(C2H5)2SiH2 triethylsilane
(C2H5) 3 S i H tripropylsilane (C3H7)3
siH Jifu Engineering My U7 (C6
H5) 2SiH2 Organofluorosilane includes trifluoromethylsilane CH35iF3
Difluorodimethylsilane (CH3)2S
iF2 Fluorotrimethylsilane (CH
3) 3StF ethyltrifluorosilane
C2H55iF3 diethyldifluorosilane
(C2H5)2Si F2 triethylfluorosilane (C2H5) 3 S i F trifluoropropylsilane (C3H7) S i
As F3 organobromosilane, Bromotrimethylsilane (CH3)3
5iBr dibromdimethylsilane (CH
3) 2siBr2, etc., and other organopolysilanes include hexamethyldisilane ((CH3)
3Si) As the diorganodisilane, hexamethyldisilane ((CH3)
3Si) 2hexapropyldisilane
((C3H7)3Si)2 etc. can also be used.

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

Further, as the germanium-containing compound introduced into the activation space (B), an inorganic or organic germanium-containing compound in which hydrogen, halogen, or a hydrocarbon group, etc. are bonded to germanium can be used, such as Ge4Hb (
a is an integer greater than or equal to 1, and b=2a+2 or 2a. )
A chain or cyclic germanium hydride represented by, 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, one of the hydrogen atoms of the germanium hydride Some or all of them may include, for example, organic groups such as alkyl groups and aryl groups, and optional groups.

Specifically, for example GeH4, Ge2H6, Ge3HB.

n-Ge4H10, t art-Ge4H10゜Ge3
H6, Ge5H10, GeH3F.

GeH3C1, GeH2Fz, H6GeeF6゜Ge
(CH3) 4. Ge(C2H5)4.

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

GeF2. GeF4. Examples include GeS.

These germanium-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. The impurity element used is 1 as a p-type impurity.
Elements of Group ⅠA of the periodic table, such as B, At, Ga, In
, T1, etc., and examples of n-type impurities include elements 1 of group V A of the periodic table, such as P and As.

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

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

Such compounds include PH3 and P2H4.

PF3, PFs, PCl3, ASH3.

AsF3. AsF5. AsCl3. SbH3゜SbF5
．． SiH3, BF3. BCl3°BB T3. B2H6
, B4H10, B5H9.

Examples include B5H11, B6H10, B6H12, AlCl3, 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 (A) and/or the activation space (B) together with each substance that generates the active species (A) and the active species (B) for activation. Alternatively, to activate the impurity-introducing substance, which may be activated in a third activation space (C) different from the activation space (A) and the activation space CB), Active species (A)
The above-mentioned activation energies listed in ``and for generating activated species (B)'' can be appropriately selected and employed. The active species (PN) generated by activating the impurity introduction substance are mixed in advance with the active species (A) and/or the active species CB), 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 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 IO is provided with a protective layer provided to chemically and physically protect the surface of the photosensitive layer 13, or t1.
When a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical withstand pressure are provided, it is also possible to create these by the method of the present invention.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, Stair L/S, AI, Cr, and Mo.

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

Examples include metals such as Pd and alloys thereof.

Polyester is used as the electrically insulating support.

Polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride.

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and 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 the punch is made of glass, its surface is NiCr.

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

V, Ti, Pt, Pd, In2O3, 5n02゜ITO
(I n 203 + S n O2), or if it is a synthetic resin film such as polyester film, NiCr, AI, A
g, Pb, Zn, Ni.

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

The surface is treated with a metal such as Ti or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal to make the surface conductive. The shape of the support may be any shape, such as a cylinder, a belt, or a plate, and the shape is determined depending on the need. For example, the photoconductive member 10 in FIG. In the case of continuous high-speed copying, it is preferable to use an endless belt or a cylindrical shape.

For example, the intermediate layer 12 includes the photosensitive layer 1 from the support 11 side.
3, and the photocarriers generated in the photosensitive layer 13 by irradiation with electromagnetic waves and moving toward the support 11 from the side of the photosensitive layer 13 to the side of the support 11. It has a function that allows easy passage of.

This intermediate layer 12 has, for example, silicon atoms as its base material,
Consisting of amorphous silicon (hereinafter referred to as A-5i (H, X, O)) containing hydrogen (H) and/or halogen (X) and oxygen (0) as constituent atoms as necessary. In addition, a p-type impurity such as boron (B) or an n-type impurity such as phosphorus (P) is contained as a substance that controls electrical conductivity.

In the present invention, the content of substances governing conductivity such as B and P contained in the intermediate layer 12 is preferably o,
Desirably, the range is oot to 5X104atomie cppm, more preferably 0.5 to IX104atoppm, optimally 1 to 5XIO3atomie PPm.

When the intermediate layer 12 has similar or the same constituent components as the photosensitive layer 13, the photosensitive layer 13 is formed following the formation of the intermediate layer 12.
The process can be carried out continuously up to the formation of . In that case, the active species (A) generated in the activation space (A) and the chemical substance for film formation introduced into the activation space (B) are used as raw materials for forming the intermediate layer. (Active species CB) generated from the active species (B) and, if necessary, hydrogen, a halogen-containing compound, an inert gas, a silicon-containing compound, a carbon-containing compound, a germanium-containing compound, and a compound gas containing impurity elements as components. and the intermediate layer 12 is formed on the support 11 by introducing the mixture separately or as needed into the space where the support 11 is installed, and using discharge energy. That's fine.

The silicon- and halogen-containing compound that is introduced into the activation space (A) to generate active species when forming the intermediate layer 12 is, for example, a compound that easily generates active species such as SiF2*. It is more desirable to be selective.

The layer thickness of the intermediate layer 12 is preferably 30 to 10 IL,
More preferably, it is 40 people to 8 meridians, and most preferably 50λ to 5IL.

The photosensitive layer 13 has, for example, an A-3i (H,

The layer thickness of the photosensitive layer 13 is preferably 1 to 100I
L, more preferably 1 to 80 wins, optimally 2 to 50 wins.

The photosensitive layer 131t/y is a doped A-5t (H,
2 may contain a substance that controls conduction characteristics of a polarity different from that of the substance that controls conduction characteristics (for example, n-type), or a substance that controls conduction characteristics of the same polarity. If the actual amount contained in the intermediate layer 12 is large, it may be contained in a much smaller amount.

In the case of forming the photosensitive layer 13 as well, if it is formed by the method of the present invention, a compound containing silicon and halogen is introduced into the activation space (A), as in the case of the intermediate layer 12.
Active species (A) are generated by decomposing these at high temperatures or by exciting and decomposing them by applying discharge energy or light energy, and the active species (A) are introduced into the film forming space. .

FIG. 2 is a schematic diagram showing a typical example of a PIN type diode device using a deposited film produced by carrying out the method of the present invention.

In the figure, 21 is a base, 22 and 27 are thin film electrodes, and 23 is a semiconductor film, including an n-type semiconductor layer 24, an i-type semiconductor layer 2
5. It is composed of a p-type semiconductor fi26. 28 is a conductive wire connected to an external electric circuit device.

These semiconductor layers are A-5i (H,X).

A-3t (0, H, X), A-3LGe (0°H,
X), etc., and the method of the present invention can be applied to the production of any layer, but is particularly applicable to the production of the semiconductor layer 26.
The substrate 21, which can be fabricated by the method of the present invention to improve conversion efficiency, may be conductive, semiconductive, or electrically insulating. If the base 21 is conductive, the thin film electrode 22 may be omitted. Examples of semiconductive substrates include Si, Ge, G, etc.
Examples include semiconductors such as aAs, ZnO, and ZnS. For example, the thin film electrodes 22.27 include NiCr, AI, C
r, Mo.

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

Pd, I n203.5n02, ITO (I n2
03+5nO2) or the like on the substrate 21 by vacuum evaporation, electron beam evaporation, sputtering, or the like. The layer thickness of the electrode 22.27 is preferably 30 to 5 x 104, more preferably 100 to 5.
It is desirable that the number be 5 x 103 people.

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

When forming n-type, i-type, and p-type semiconductor layers by the method of the present invention, any one layer or all of the layers can be formed by the method of the present invention. )
A compound containing silicon and a halogen is introduced into the cell, and by exciting and decomposing them under the action of activation energy, an active species (A) such as SiF2* is generated, and the active species (A) is introduced into the membrane space. Also, apart from this,
Oxygen-containing compounds, silicon-containing compounds, germanium-containing compounds in a gaseous state, and gases of compounds containing inert gases and impurity elements as necessary, are excited and decomposed by activation energy, and their respective activities are activated. Seed CB
) and separately or appropriately mixed to form support 1.
By introducing the active species into the film forming space, which is the installation in step 1, and applying discharge energy, the active species introduced into the film forming space are
A deposited film is formed on the substrate 11 by causing, promoting or amplifying the chemical interaction.

The layer thickness of the nM and pHl semiconductor layer is preferably 100-104, more preferably 300-2000.
A range of people is preferable.

Further, the layer thickness of the first base semiconductor layer is preferably 50
A range of 0 to 104 people, more preferably 1000 to 10000 people is desirable.

In addition to this example, the method of the present invention can also be applied to IC.

It is suitable for forming a partially oxidized Si film, etc., which constitutes semiconductor devices such as transistors, diodes, and photoelectric conversion elements. By controlling the introduction timing, introduction amount, etc. of the activated species (B), it is possible to form an SIH having an oxygen concentration distribution in the layer thickness direction.

Alternatively, in addition to oxygen-containing compounds, silicon-containing compounds and germanium-containing compounds.

By appropriately combining carbon-containing compounds and the like as necessary, it is also possible to form a film body with desired characteristics in which the bond between 0 and these Si, Ge, C, etc. is used as a constituent unit.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 1, i
Carbon-containing amorphous deposited films of type, p-type, and n-type were formed.

In FIG. 3, 101 is film formation, ltl.

A desired base 103 is placed on the base support 102 inside.

Reference numeral 104 is a heater for heating the substrate, and is preferably a conductor.

106 to 109 are gas supply sources.

They are provided depending on the number of oxygen-containing compounds, substances used as necessary, and compounds containing impurity elements as components. If these gases are liquid in their standard state, an appropriate vaporizer is provided.

In the figure, the gas supply systems 106 to 109 are marked with a for branch pipes, b for flowmeters, C for pressure gauges that measure the pressure on the high pressure side of each flowmeter, and d for gas supply systems 106 to 109. The ones marked with "e" are valves for adjusting the flow rate of each gas. 12
3 is an activation chamber CB) for generating active species (B), and around the activation chamber 123 is a microwave plasma generator 122 that generates activation energy for generating active species CB). is provided. The raw material gas for generating active species (B) supplied from the gas introduction pipe 110 is activated in the activation chamber CB), and the generated active species (B) is introduced into the film forming chamber 101 through the introduction pipe 124. will be introduced in 1
11 is a gas pressure gauge.

In the figure, 112 is an activation chamber (A), 113 is an electric furnace, and 114
is a solid Si particle, 115 is an introduction pipe for a compound containing gaseous silicon and halogen, which is a raw material for the active species (A),
The activated species generated in the activation chamber (A) 112 are transferred to the introduction pipe 11.
6 into the film forming chamber 101.

117 is a discharge energy generator, which includes a matching box 117a and a cathode electrode 117b for introducing high frequency.
Equipped with etc.

The discharge energy from the discharge energy generator 117 acts on the active species flowing in the direction of the arrow 119, causing a chemical reaction to form an oxygen-containing amorphous deposited film on the entire substrate 103 or on a desired portion.

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

First, a polyethylene terephthalate film base 103
was placed on the support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device (not shown) to reduce the pressure to about 1 O-GTorr. 02 (diluted to 1 Ovo 1% with He) for 150 sec using the gas supply source 106 at the substrate temperature shown in Table 1.
M, or a gas mixed with 403 CCM of PH3 gas or B2H6 gas (both diluted with 11000 pp hydrogen gas) is supplied to the activation chamber (B) 12 through the gas introduction pipe 110.
It was introduced in 3. 0 introduced into the activation chamber CB) 123
2 gas etc. are activated by the microwave plasma generator 122 and turned into activated oxygen etc., and the activated oxygen etc. are introduced into the film forming chamber lO1 through the introduction pipe 124, packed with 114, and heated in the electric furnace 113. , kept at 1100℃, S
5tF2* as the active species (A) is generated by heating the i to red heat and blowing SiF4 from a cylinder (not shown) through the introduction pipe 115, and the SiF2)Ic is passed through the introduction pipe 116 to form a film. It was introduced into room 101.

While maintaining the pressure in the film forming chamber 101 at 0.4 Torr, plasma was applied from the discharge device 117 to form a non-doped or doped oxygen-containing amorphous deposited film (thickness: 700 Torr). Film formation speed is 14λ/s
It was e.c.

Next, each sample obtained was placed in a vapor deposition tank and the vacuum degree was 1O-
Comb-shaped Al gap electrode (gap length 2) at 5 Torr
After forming a film (50 IL, width 5 mm), the dark current was measured at an applied voltage of 10 V, the dark conductivity σd was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2-4 02 (diluted to 1Ovo1% with He) and Si2F6. G
Example 1 was carried out in the same manner as in Example 1, except that e2H6 and C2H6 (7) were each used and introduced into the activation chamber (B) to generate active species CB), which were then introduced into the film forming chamber 101. An oxygen-containing amorphous deposited film was formed. The dark conductivity was measured and the results are shown in Table 1.

From Table 1, it was found that according to the present invention, an oxygen-containing amorphous deposited film with excellent electrical properties and sufficient doping could be obtained.

Examples 5-8 02c7) Instead, H3S iO3iH3, H3GeO
An oxygen-containing amorphous deposited film was formed in the same manner as in Example 1 except that GeH3, CO2 or OF2 was used.

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

Example 9 Using the apparatus shown in Figure 1, the first
A drum-shaped electrophotographic image forming member having a layer structure as shown in the figure was prepared.

In the figure, 201 is a film forming chamber, 202 is an activation chamber (
A), 203 is an electric furnace, 204 is a solid Si particle, 205 is a raw material introduction tube for active species (A), and 206 is an active species (A)
Introductory pipe, 207 is a motor, 208 is a heating heater, 2
09゜210 is the blowing pipe, 211 is the AI cylinder,
212 indicates an exhaust valve. or.

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

An AI cylinder base body 211 is suspended in the film forming chamber 201, and a heating heater 20B is provided inside the base body, and a motor 20
7 so that it can be rotated. Reference numeral 218 denotes a discharge energy generating device, which includes a matching box 218a and a cathode electrode 218b for introducing high frequency.

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

Maintain the temperature at 1100°C, make St red hot, and introduce the inlet tube 206 into it.
By blowing SiF4 from a cylinder (not shown) through a cylinder, SiF2 water is generated as an active species (A), and the S
iF2)k was introduced into the film forming chamber 201 through the introduction pipe 206.

After being subjected to activation processing such as plasma formation by the apparatus 221, the hooked silicon active species, oxygen active species, and oxygen active hydrogen were introduced into the film forming chamber 201 through the introduction pipe 217-2. At this time, it is necessary to reduce the atmospheric pressure inside the film forming chamber 201 to 1.0.
While maintaining the temperature at Torr, plasma is applied from the discharge device 218, heated and held by the heater 208, and rotated.
The exhaust gas was exhausted by appropriately adjusting the opening of the exhaust valve 212. In this way, the photosensitive layer 13 was formed.

Further, the intermediate layer 12 is inserted into the introduction pipe 217-1 prior to the photosensitive layer.
From SiF4,02 (SiF4:02=l :1O-5
), He and B2H6 (0.2% B2H6 in volume %)
A mixed gas of 200 nm was introduced, and a film was formed with a thickness of 2,000 mm.

Comparative Example 1 SiF4,02. A drum-shaped electrophotographic image forming member having the layer structure shown in FIG. 1 was produced by a general plasma Cvp method using He and B2H6 gases and equipped with a 13.56 MHz high frequency device in the film forming chamber 201. 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 1O A PIN type diode shown in FIG. 2 was manufactured using o2 as an oxygen compound and the apparatus shown in FIG. 3.

First, a polyethylene naphthalate film 21 on which 1000 ITO films 22 were deposited was placed on a support stand, and
After reducing the pressure to 6 Torr, the active species SiF2* produced in the same manner as in Example 1 was introduced into the film forming chamber 101. Also,
5i3H6 gas and PH3 gas each in an activation chamber (B
) 123 to activate the activated gas. Next, this activated gas is introduced into the film forming chamber discharge device 117 via the introduction pipe 116.
n-type A doped with P by applying plasma from
-5i (H,X) l! 24 (film thickness: 700 layers) was formed.

Next, the n-type A-5i except that the introduction of PH3 gas was stopped.
/7 doped A − in the same way as for the (H,X) film.
S f (H, X) llI25 (g! Film thickness 5000
formed a person.

Then, along with 5i3H6 gas, 02 gas, B2H6 gas (1000 ppm hydrogen gas dilution), and p-type oxygen-containing A-5i doped with B under the same conditions as n-type except for
H,X) film 26 (H4,700 people) was formed. Furthermore, an Al electrode 27 having a thickness of 1000 wafers was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

I- of the diode element thus obtained (area 1 cm2)
The V characteristics were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, light is introduced from the substrate side, and the light irradiation intensity is AMI (approximately 100 mW/cm2).
A conversion efficiency of 8.5% or more, an open circuit voltage of 0.9 V, and a short circuit current of 11.0 mA/cm2 were obtained.

Example 11^1:3 Instead of 02 as a strict compound, H3SiO5iH3,
A PIN diode similar to that in Example 6 was manufactured in the same manner as in Example 6 except that H3GeOGeH3, CO2, or OF2 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-Si (H, X, O) has better optical and electrical properties than the conventional one.
PI Nflf4t - I found out that I can get a lot of money.

〔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. Also.

It improves reproducibility in film formation, makes it possible to improve film quality and make the film uniform, and is advantageous for increasing the area of the film.
Improved membrane productivity and mass production can be easily achieved. Furthermore, film can be formed even on substrates with poor thermal properties.
The low-temperature treatment has the effect of shortening the process.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. Second (
! 1il11. Figure 4 is a schematic diagram for explaining the configuration of an apparatus for carrying out the method of the invention used in the examples. 10--An electrophotographic imaging member, Ll--A substrate, 12--An intermediate layer, 13--A photosensitive layer. 101.201-----film formation chamber, 214.215, 216----gas supply source. 103, 211---monosubstrate. 117.218-1--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
) are introduced separately, and a deposited film is formed on the substrate by applying discharge energy to them to cause a chemical reaction.