JPS61193426A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To attain enlargement, improvement of productivity and mass produc tion of the title films by a method wherein an active compound cantaining silicon and halogen as well as another active compound produced from a carbon contained filming compound are separately fed to a filming space to form said films by means of supplying them with thermal energy. CONSTITUTION:An active compound A produced by decomposing a silicon and halogen contained compound as well as another active compound B pro duced from a carbon contained filming compound chemical-reacting to the former are separately fed to a filming space to form the title films on a sub strate by means of supplying them with thermal energy for making them chemi cally react to each other. The life of applicable active compound A is recommended to exceed 10 seconds in terms of productivity and easy handling. A gaseous or easily gasified compound such as SiF4 may be recommended for the silicon and halogen contained compound while methane CH7 etc. may be recommended for the carbon contained compound. Finally the preferable weight ratio of active compounds B and A may be 8:2-4:6.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Application of the Invention] The present invention relates to a method suitable for forming an amorphous or crystalline deposited film containing carbon.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using vacuum evaporation method, plasma CVD method, CVD method, reactive Snok method, taring method, ion blating method, and photo-CVD method. The CVD method is 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 parameters for the formation of the deposited film (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, plasma generation method) Such)
Due to the combination of many of these 24 parameters, Zolazma sometimes becomes unstable and often has a significant adverse effect on the deposited film formed. Moreover,
The actual situation is that 74 parameters unique to each device must be selected for each device, and therefore 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 to achieve mass production with high reproducibility through high-speed film formation.
Forming an amorphous silicon deposited film using the plasma CVD method requires a large amount of equipment investment for mass production equipment, and the management items for mass production are also complex, with narrow control tolerances and equipment adjustments. Because it is subtle,
These have been pointed out as problems that should be improved in the future. On the other hand, with the conventional technology using the normal CVD method,
This method requires high temperatures, and a deposited film with practical characteristics 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 the properties of the film to be formed, the film formation speed, the reproducibility, and the uniform quality of the film, while making it suitable for increasing the area of the film, improving productivity of the film, and mass production. 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 a halogen in a film forming space for forming a deposited film on a substrate, and a chemical reaction between the active species (A) and the active species (A). A deposited film is formed on the substrate by separately introducing active species (B) generated from a carbon-containing compound for film formation, which interact with each other, and applying thermal energy to them to cause a chemical reaction. This is achieved by the deposited film forming method of the present invention, which is characterized by forming.

[Embodiment]

In the method of the present invention, instead of generating plasma in a film forming space for forming a deposited film, when a compound containing silicon and halogen is decomposed, active species (A) generated by pressure are generated.
and active species (B) generated from carbon-containing compounds for film formation.
By applying thermal energy to these elements in coexistence with these elements, chemical interactions are caused, promoted, and amplified, so the deposited film that is formed is
It is not affected by etching effects or other adverse effects such as abnormal discharge effects.

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

In the present invention, the thermal energy for exciting and reacting the raw materials for forming the deposited film is applied to at least a portion of the film forming space near the substrate or the entire film forming space, and is particularly limited by the heat source used. Instead, conventionally known heating media such as heating by a heating element such as resistance heating, high frequency heating, etc. can be used. Alternatively, thermal energy converted from light energy can be used. Furthermore, 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 portion, so that the deposited film on the substrate can be irradiated with light energy. It can be used advantageously because it makes it easy to control the formation position and film thickness, and it also has the convenience of being able to form a deposited film by irradiating only a predetermined graphical part using a resist or the like. It will be done.

One of the differences between the method of the present invention and the conventional CVD method is that active species activated in advance in a space different from the film forming space (hereinafter referred to as activation space) are used.

This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and also to further reduce 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.

Incidentally, the active species (A) in the present invention refers to active species (A) generated from a carbon-containing compound that is a compound of a raw material for forming a deposited film.
A substance that has the effect of promoting the formation of a deposited film by chemically interacting with B) and, for example, applying energy or causing a chemical reaction. Therefore, the active species (A) may contain constituent elements constituting the deposited film to be formed, or may not contain such constituent elements.

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. A period of at least 10 seconds, preferably at least 10 seconds, is selected and used as desired, and the constituent elements of this active species (A) constitute the components constituting the deposited film formed in the film forming space. . In addition, the carbon compound for film formation is activated by activation energy 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, it chemically interacts with the active species (A) introduced from the activation space (A) at the same time due to the action of thermal energy. As a result, a desired deposited film can be easily formed on a desired substrate.

The active species (B) generated from the carbon-containing compound constitutes the components constituting the deposited film, which is formed in the film forming space, as in the case of the active species (A).

The carbon-containing compound used as a raw material for forming a deposited film in the present invention is already in a gaseous state before being introduced into the activation space (B), or is in a gaseous state and then introduced into the activation space (n). It is preferable that it is introduced. For example, when using a liquid compound, 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 carbon-containing compounds include chain or cyclic saturated or unsaturated hydrocarbon compounds, organic compounds whose main constituent atoms are carbon and hydrogen, and one or more constituent atoms such as halogen and sulfur; Among organosilicon compounds having a hydrocarbon group as a constituent and organosilicon compounds having a bond between silicon and carbon, those in a gaseous state or those that can be easily vaporized are preferably used.

Among these, as a hydrocarbon compound, for example, carbon number 1
~5 saturated hydrocarbons, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, etc. Specifically, saturated hydrocarbons include methane (CH4), ethane (02H6), etc. , Noo+7 (CBHB), n-butane (n-C4H1o), pentane (C5H12), ethylene hydrocarbons include ethylene (C2H4), propylene (C3H6), butene-1 (C4H8), zothene-2 ( C4H8), imbutylene (C4H8), pentene (c5H1o), acetylene hydrocarbons include acetylene (C2H2), methylacetylene (C3H4),
Examples include butene (C4H6).

As the halogen-substituted hydrocarbon compound, at least one hydrogen which is a constituent of the above-mentioned hydrocarbon compound is F+
Compounds substituted with Ct, Br, I can be mentioned,
Particularly effective are compounds in which hydrogen is substituted with V or Ct.

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

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

Organosilane and organohalogensilane each have the general formula: Rn5ta4-n s-Rmstx4-m
(However, R-nialkyl group, aryl group: X:F.

ct + Br l I: n = i # 213
+ 4 : m = i 12131) Typical examples include alkylsilanes, alkylsilanes, alkylhalogensilanes, and arylhalogensilanes.

in particular, As organochlorosilane, Trichloromethylsilane CH, 5iCt.

Dichlorodimethylsilane (CH3)2slct2chlorotrimethylsilane (cH,), 81Ct trichloroethylsilane c2a5stcz.

DikuOh diethyl silica 7 (C2H5)2ssct
As the 2-organochlorofluorosilane, chlordifluoromethylsilane CH35lF2ctdichlorofluoromethylsilane CI (3SIFCA2chlorofluorodimethylsilane (CH3)25tIpczchloroethyldifluorosilane (C2Hs)SxF2ct
Dichloroethylfluorosilane C2H5sIFct2
Chlordifluoropropylsilane C3H,5iF2C
jDichlorofluoropropylsilane C3H,S 1F
As ct2 organosilane, tetramethylsilane (CH3)4sl ethyltrimethylsilane (CH3)3slc2H5 trimethylpropylsilane (CH3)3SIC3H.

Triethylmethylsilane CH35i(C2H5)3
Tetraethylsilane (C2H5)4sl Organohydrodanosilane includes Methylsilane:,' ca3sta.

Dimethylsilane (CH3)25IH2 Trimethylsilane (C1i,)3stH Noethylsilane (C2H5)2SIH2 Triethylsilane, / (C2H5)38IH Tripropylsilane (C,H,)3SIH Diphenylsilane (C6H5)28IH2 Organofluorosilane is trifluoromethyl Silane CH35iF3difluorodimethylsilane (CH3)2sIF2fluorotrimethylsilane (CH3)381F ethyltrifluorosilane C2H5slF3diethyldifluorosilane (C
2H5) 2slF2 triethylfluorosilane (C2
H5) 3SiF trifluoropropylsilane (C,
Examples of organobromosilane such as H,)S iF3 include bromotrimethylsilane (CH3)3siBrdibromdimethylsilane (CH3)2siBr2, and in addition, examples of organopolysilane include hexamethyldisilane [(CH3)3Si]2organodisilane. As such, hexamethyldisilane [(CH3)3s1]2hexazologyldisilane [(C3H7)3s1]2 and the like can also be used.

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

In the present invention, as the compound containing silicon and halogen to be introduced into the activation space (A), for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used. For example,
5luY2u+2 (u is an integer greater than or equal to 1, Y is F r C
/-r B At least one element selected from r and I. ) chain silicon halide, 51
Cyclic silicon halide represented by vY2v (v is an integer of 3 or more, Y has the above meaning), 51uHxY
Examples include chain-like or concessional compounds represented by y (u and Y have the above-mentioned meanings, xy-2u or 2u+2).

Specifically, for example, S IF4, ('SiF,2)5, (
SiF2)6, (EiiF2)4.512F6, S 1
3F8, SiHF3.5IH2F2, S i Ct4了S I CH2) 5, S i B r 4, (SiB
r4) 5.5s2ct6.81 Br 5iHCtS
iHB? 8iHI3.5i2Ct3F3na2 6
〜3% 5＼In any gas state or easily gasified.

In order to generate the active species (A), in addition to the compound containing silicon and halogen, other silicon-containing compounds such as simple silicon, hydrogen, orodan compounds (for example, F2 gas, C62 gas, gasified Br2, ■2, etc.)
etc. can be used together.

In the present invention, methods for generating active species in the activation space (A) include electrical energy such as microwave, RF, low frequency, DC, heater heating, infrared heating, etc., taking into account each condition and device. Excitation energies such as thermal energy, light energy, etc. are used.

Activated species (A) are generated by adding excitation energy such as heat, light, electricity, etc. to the above-mentioned species in the activation space (A).

In the present invention, an activation space (
The ratio of the amount of the active species (n) generated by the carbon-containing compound for forming a deposited film introduced in B) and the active species (A) from the activation space (A) is determined depending on the film forming conditions. , may be determined as desired depending on the type of active species, etc., but preferably 1
A suitable ratio is 0:1 to 1:10 (introduction flow rate ratio), more preferably 8:2 to 4:6.

In the present invention, in addition to the carbon-containing compound, the activation space (
In B), silicon-containing compounds, hydrogen gas, halogen compounds (e.g. F2 gas, Ct2 gas, gasified Br2, I2, etc.), alnon as chemical substances for film formation that generate active species (B). , an inert gas such as neon can also be introduced into the film forming space. When using a plurality of these film-forming chemicals, they can be mixed in advance and introduced into the activation space (B), or each of these film-forming chemicals can be supplied from independent sources. They can be supplied individually and introduced into the activation space (B), or they can be introduced into independent activation spaces and activated individually.

As the silicon-containing compound for forming the deposited film, silanes and halogenated silanes in which hydrogen, halogen, or hydrocarbon groups are bonded to silicon can be used.

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, Si, H6, S13
st, H2, such as H8, 814H1o, 815H12, 516H14, etc. (p is 1 or more, preferably 1 to 15,
More preferably, it is an integer of 1 to 10. ) Linear silane compound represented by S iH, S IH (8tH,)s
jH,,sIH,5jn(ssa,)sx,a,,s
s 2n5s 5n (s IH,) s t 81pHzp+2 (p has the above-mentioned meaning) such as s 2n5s 5n (s IH,) s t 2H5, etc. Chain silane compounds having branches, hydrogen of these linear or branched chain silane compounds 813H6, a compound in which some or all of the atoms are substituted with halogen atoms
, 514H8, 815H4o.

8 l A cyclic silane compound represented by Si, H2q (q is an integer of 3 or more, preferably 3 to 6) such as 6H12, and a part or all of the hydrogen atoms of the cyclic silane compound are substituted with other cyclic silanyl. Examples of compounds substituted with groups and/or chain silanyl groups, and compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are substituted with halogen atoms include 5iH5F, 5SH5C1, and 5iH3Br.

81rH, Xt (X is a halogen atom,
r is 1 or more, preferably 1 to 10, more preferably 3 to
An integer of 7, a+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.

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 to be used, as a p-type impurity, elements of group Ⅰ A of the periodic table, such as B, At, Ga, l[n
, Tt, etc., and as n-type impurities, elements of Group V A of the periodic table, such as P+As, Sb
, Bi, etc. are mentioned as suitable ones, but especially n, G
a+P+Sb etc. are optimal. The amount of impurity doped is appropriately determined depending on desired electrical and optical characteristics.

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

Such compounds include PH3, P2H4, PF3
, PF5, BCl3, ABH3, A m F 3, A
mF5, AsCt5, SbH3, SbF5,
S IH,, BF,, BCl3, BBr 5'% B
2H4~B4H1o\B5I (9% B5H11-.

B! Examples include I■101' B 6'H12, htct, and the like.

The compounds containing impurity elements may be used alone or in combination of two or more.

The impurity introduction substance may be introduced into the activation space (A) or/and the activation space (B) together with each substance that generates the active species (A) and the active species (B) and 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). To activate the impurity introducing substance, active species (A
) and the above-mentioned activation energies listed for generating activated species (B) can be appropriately selected and employed. Active species (PN) generated by activating impurity introduction substances
is mixed in advance with the active species (4) and/or the active species (B), or is introduced into the film forming space independently.

Next, the present invention will be explained with reference to a typical example of an electrophotographic image forming member formed by the method of the present invention. FIG. 3 is a schematic diagram for explaining a configuration example of a photoconductive member.

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 the manufacture of photoconductive member 10, intermediate layer 12 and/or photosensitive layer 13 may be formed by the method of the present invention. Furthermore, the photoconductive member 10 may include a protective layer provided to chemically or physically preserve the surface of the photosensitive layer 13, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical 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 NiCr, stainless steel, AZsCr%Mo, Au%Ir
1Nb% Metals such as Ta, V, TI, Pt, and Pd, or alloys thereof can be mentioned.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is glass, its surface is NiCr, AL, C.
r,, MO% Auv Ir, Nbv Tax v,
'rt, pt, pd, In2O3,5n02,
If it is conductive treated by providing a thin film such as ITO (In203 + 5n02), or if it is a synthetic resin film such as polyester film, NlCr, A
t, Ag.

Pb, Zns Au-, Cr, MO% Irx
Vacuum evaporation with metals such as Nb, Tas V, Ti, Pt, etc.
The surface is conductively treated by electron beam evaporation, sputtering, etc., or by laminating with the metal. The shape of the support may be any shape such as a cylinder, a belt, a plate, etc., and the shape is determined depending on the need. For example, the photoconductive member 10 of FIG. If used as an 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 is made of amorphous silicon (hereinafter, a-Si (H, X, CI
). ), and also contains a p-type impurity such as boron (B) or an n-type impurity such as phosphorus (P) as a substance that controls electrical conductivity.

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 ppm, more preferably 0.5-I X 10' atomic ppm
m % optimally 1-5 X 10' atomic p
It is desirable to set it as pm.

When the intermediate layer 12 has similar or the same components as the photosensitive layer 13, the formation of the intermediate layer 12 can be performed continuously from the formation of the intermediate layer 12 to the formation of the photosensitive layer 13. In that case, the active species (A) generated in the activation space (A), a gaseous carbon-containing compound, a silicon-containing compound, and optionally hydrogen, a halogen compound, and the like are used as raw materials for forming the intermediate layer. The active species (B) generated by activating an inert gas and a gas of a compound containing an impurity element as a component can be installed separately or mixed as necessary, and the support 11 can be installed. The intermediate layer 12 may be formed on the support 11 by introducing the active species into a certain film forming space and applying thermal energy to the coexistence atmosphere of each introduced active species.

When forming the intermediate layer 12, a compound containing silicon and -.9-9, which is introduced into the activation space (A) and generates an active species (A), can easily form an active species (A) such as 5IF2*.
) is preferably selected from among the above-mentioned compounds.

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

The photosensitive layer 13 is made of, for example, A-8i(H,X),
It has a charge generation function that generates photocarriers by laser irradiation, and a charge transport function that transports 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 13Fi is a non-doped 7°a-8l (H, A substance that controls the conduction properties may be contained, or if the actual amount contained in the intermediate layer 12 is large, the substance that controls the conduction properties of the same polarity may be contained in an amount much smaller than the loading amount. It may also be contained.

In the case of forming the photosensitive layer 13, 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, and the photosensitive layer 13 is formed by the method of the present invention. By decomposing these or by exciting them by applying discharge energy or light energy, active species (A) are generated, and the active species (A) are introduced into the film forming space.

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

FIG. 2 shows a PIN using an a-8i deposited film doped with an impurity element, which is manufactured by carrying out the method of the present invention.
1 is a schematic diagram showing a typical example of a type diode device.

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, a 1-type semiconductor layer 2
5. Consisting of a p-type semiconductor layer 26. Although the present invention can be applied to the production of any one of the semiconductor layers 24, 25, and 26, the conversion efficiency can be particularly improved by producing the semiconductor layer 26 by the method of the present invention.

When creating the semiconductor layer 26 by the method of the present invention, the semiconductor layer 26 is made of an amorphous material (hereinafter referred to as rA-stc(u,x)J). 28 is a conductive wire connected to an external electric circuit device.

The base 21 may be conductive, semiconductive, or electrically insulating. If the base body 21 is conductive, the thin film electrode 22 may be omitted. Examples of the semiconductive substrate include '81, Go, GaAs, Z
Examples include semiconductors such as nO and ZnS. Thin film electrode 22.
Examples of 27 include NiCr, 'At, Cr.

Mo % Aus I r, Nbs 'Tax V, T
i, Pt, Pd, In2O3,5n02, ITO
It can be obtained by providing a thin film of (In205+5n02) or the like on a substrate by a process such as vacuum steaming, electron beam evaporation, or sputtering. The film thickness of the electrode 22.27 is preferably 30 to 5 x 10'l, more preferably 10
It is desirable to set it as 0-5X10'X.

In order to make the film forming the semiconductor layer n-type or p-type as necessary, during layer formation, n-type impurity, p-type impurity, or both impurities are added to the layer to be formed. It is formed by doping while controlling the amount.

When forming n-type, 1-type, and p-type semiconductor layers, any one layer or all the layers can be formed by the method of the present invention, and the film formation is performed in the activation space (A). Compounds containing silicon and halogen are introduced, and they are excited and decomposed by the action of activation energy, resulting in, for example, SiF2"
Active species (A) are generated, and the active species (A) are introduced into the film forming space. Separately, gaseous carbon-containing compounds, silicon-containing compounds, and, if necessary, certain active gases and compound gases containing impurity elements as components are excited by activation energy and decomposed. to generate activated species of husband and husband, each separately or mixed at an appropriate cost,
It may be introduced into the film forming space where the support 11 is installed and formed by using thermal energy. The layer thickness of the n-type and p-type semiconductor layers is preferably 100 to 1
04X, more preferably in the range of 300 to 2000X.

Further, the thickness of the type 1 semiconductor layer is preferably 50
0-10'X, more preferably 1000-10000X
A range of is desirable.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 3, l
Type, p-type, and n-type carbon-containing amorphous deposited films were formed.

In FIG. 3, 101 is 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 the substrate 103 is heat-treated before the film-forming process, and is annealed after the film-forming process to further improve the properties of the formed film, and is supplied with power via the conductive wire 105. I get a fever.

Although the substrate temperature is not particularly limited, when carrying out the method of the present invention, it is preferably 30 to 450°C, more preferably 50 to 350°C.

Reference numerals 106 to 109 denote gas supply systems, which are provided depending on the type of gas of the carbon-containing compound and the compound containing hydrogen, a halogen compound, an inert gas, and an impurity element, which are used as necessary.

When using liquid gases in standard conditions, 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 letter ``e'' indicates the pulp 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). 1
22 are provided. The raw material gas for generating active species (B) supplied from the gas introduction pipe 110 is supplied to the activation chamber CB) 12.
The activated species (B) that are generated are introduced into the film forming chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge. In the figure, 112 is the activation chamber (A), 11
3 is an electric furnace, 114 is a solid Si grain, 115 is an active species (A
) is an introduction pipe for a compound containing gaseous silicon and halogen, which is the raw material for the activation chamber (A) 112 , and active species (A) generated in the activation chamber (A) 112 are introduced into the film forming chamber 101 through an introduction pipe 116 . be done.

Reference numeral 117 denotes a thermal energy generating device, and for example, an ordinary electric furnace, a high-frequency heating device, various heating bodies, etc. are used.

The heat from the thermal energy generator 117 acts on the active species flowing in the direction of the arrow 119, and causes the acted active species to chemically react with each other, so that the entire substrate 103 or a desired portion contains carbon. Forming an amorphous deposited film. Further, in the figure, 120 is an exhaust nozzle, and 121 is an exhaust pipe.

First, polyethylene terephthalate film substrate 103
is placed on the support stand 102, and the film forming chamber 1 is opened using an exhaust system.
The inside of the 01 was evacuated and the pressure was reduced to about 10-' Torr. At the substrate temperature shown in Table 1, the gas supply system 106 and υCH4
150SCCM or this and PH5 gas or B2
H6 gas (all diluted with 1000 ppm hydrogen gas) 4
A gas mixed with 08CCM was introduced into the activation chamber (B) 123 via the gas introduction pipe 110.

The CH4 gas etc. introduced into the activation chamber (B) 123 are activated by the microwave plasma generator 122 and converted into hydrogenated carbon active species, active hydrogen, etc.
Hydrogenated carbon active species, active hydrogen, etc. are introduced into the film forming chamber 10 through
It was introduced in 1.

In addition, 81 solid particles 114 are packed in the activation chamber (A) '102, heated in an electric furnace 113, and kept at 1100°C.
By bringing Sl into a red-hot state and blowing SiF4 into it from a cylinder (not shown) through the SIF4 introduction pipe 115, active species of SIF2'' as active species (A) are generated, and the 5IF2 * is introduced into the film forming chamber 101 through the introduction pipe 116.

A non-doped or doped carbon-containing amorphous deposited film (film thickness 700X) is formed by keeping the internal pressure inside the film-forming chamber 101 at Q, 4 Torr and at 250° C. using a thermal energy generator. Formed.

The film formation rate was 33×/sec.

Next, the obtained sample with a non-doped or p-type deposited film was placed in a vapor deposition tank, and the vacuum level was 10-' Tor.
A comb-shaped At gap electrode (gap length 250μ,
After forming a film with a width of 50), 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 to 4 Linear C2H6, C2H4, or C2H in place of CH4
A carbon-containing amorphous deposited film was formed according to the same method and procedure as in Example 1, except that Example 2 was used. The dark conductivity was measured and the results are shown in Table 1.

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

Example 5 Using the device shown in No. 4-, the first
A drum-shaped electrophotographic image forming member having a layer structure as shown in the figure was prepared.

In FIG. 4, 201 is a film forming chamber, and 202 is an activation chamber (
A), 203 is an electric furnace, 204 is 81 solid particles, 205 is an active species (A) raw material introduction tube, 206 is an active species (A)
An inlet pipe, 207 a motor, 208 a heater used in the same manner as 104 in FIG. 3, 209 and 210 an outlet pipe, 211 an At cylindrical base, and 212 an exhaust knob.

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

An At cylinder base 21'1 is lowered into the film forming chamber 201, a heating heater 208 is installed inside it, and a motor 2 is installed.
Make it possible to rotate more than 07. Reference numeral 218 denotes a thermal energy generating device, for example, an ordinary electric furnace, a high frequency heating device, various heating bodies, etc. are used.

In addition, 31 solid particles 204 are packed in the activation chamber (A) 202, heated in an electric furnace 203, and maintained at 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 a cylinder (not shown) through the inlet pipe 206, and the 8iF2
* was introduced into the film forming chamber 20...1 through the introduction pipe 206.

On the other hand, CH4 and 512H6 gases and H2 were introduced into the activation chamber (B) 220 201 through the introduction pipe 217-1.

The introduced CH4, 812H6, and H2 gases enter the activation chamber (
B) At 220, microwave plasma generator 2
After being subjected to activation treatment such as p-plasma conversion by 21, the hydrogenated carbon active species, silicon hydride active species, and active hydrogen were introduced into the film forming chamber 201 through the introduction pipe 217-2.

At this time, impurity gases such as PH, B2H6, etc. were also introduced into the activation chamber (B) 220 for activation, if necessary.

While maintaining the internal pressure inside the film forming chamber 201 at 1.0 Torr, the inside of the film forming chamber 201 is maintained at 250° C. by a thermal energy generator.

The At cylinder base 211 is heated to 280°C by the heater 208.
The v1 gas is heated, held, and rotated by the valve 212, and the v1 gas is 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 tube 217-- prior to the photosensitive layer.
From 1, H2/B 2H6 (B2H6 gas is 0.
A mixed gas of 2%) was introduced to form a film with a thickness of 2000×.

Comparative Example 1 The layer structure shown in FIG. 1 was formed from 5IF4, CH4, 512H6, H2 and B2H6 using a general plasma CVD method using a 13.56 B/IHzO high frequency device in the film forming chamber 201 shown in FIG. An electrophotographic imaging member was formed.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 5 and Comparative Example 1.

Example 6 Using CH4 as a carbon compound and using the apparatus shown in FIG.
The PIN Paris diode shown in the figure was manufactured.

First, a polyethylene naphthalate film 21 on which a 100OA ITO film 22 was vapor-deposited was placed on a support stand, and the ITO
' After reducing the pressure to Torr, as in Example 1,
16 to 5 IF2* active species, cut introduction tube 110 to 8
13H6150SCCM, PH3 gas (PH310
00 ppm diluted hydrogen gas) were introduced into the activation chamber 123, and then the activated gases were introduced into the film forming chamber 101 via the introduction pipe 116.

The pressure inside the deposition chamber was 0.4 Torr, and the temperature of the substrate was 2
P-doped n-type a −
A 81(H,X) film 24 (film thickness 700X) was formed.

Next, except for stopping the introduction of PH and gas, the n-type a-8
A non-doped a-8l film 25 (thickness: 5000×) was formed using the same method as in the case of the 1(H,X)-film.

Next, along with 812H6 gas, CH4, B2H6 gas (
n except that B2H61000ppm hydrogen dilution) was introduced.
p-type carbon-containing a- doped with B under the same conditions as type
A 81(H,X) film 26 (film thickness 700X) was formed.

Furthermore, an At1lt electrode 27 having a film thickness of 1000× 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 儂 2)
The V 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”),
A conversion efficiency of 7.5 cm or higher, an open circuit voltage of 0.98 V, and a short circuit current of 10.1 mA/cWL were obtained.

Example 7 Instead of CH4 as a carbon compound, C2H6, C2H4
Or in the same manner as in Example 6 except that C2H2 was used,
A PIN type diode similar to that produced in Example 6 was produced. This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

From Table 3, it was found that according to the present invention, a PIN diode having good optical and electrical characteristics could 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 moreover, high-speed deposition 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, and it is easy to improve the productivity and limit the film. be able to. Furthermore, since it is possible to use relatively low thermal energy as excitation energy, it is possible to form a film even on a substrate with poor heat resistance or a substrate that is susceptible to the effects of plasma etching. The result is that it can be shortened.

[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 used in Examples to carry out the tC method of the present invention, 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゜108.109,213,214,21
5,216...Gas supply system, 103.211...Base, 117°218...Thermal energy generation device. Agent Patent Attorney Seki Yamashita Figure 1

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 generated from carbon-containing compounds for film formation (
A deposited film forming method characterized in that a deposited film is formed on the substrate by separately introducing B) and applying thermal energy to them to cause a chemical reaction.