JPS61228618A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To make the improvement of film productivity and mass production easy contriving to improve the properties of a film, a film forming speed and reproducibility and the uniformity of film quality by chemical reaction irradiating carbon and a halogen and an active seed made from a compound containing carbon for forming film. CONSTITUTION:A compound containing carbon and a halogen and an active seed made from a carbon containing compound which reacts chemically with the compound and is used for forming a film are each introduced in a film forming space 101 and a deposition film is formed on a substrate 103 by a chemical reaction irradiating light energy. For example, the substrate 103 made of a polyethylene terephtalate film is placed on a susceptor 102, within the film forming chamber 101 is exhausted, then CH4 gas is introduced in an activa tion chamber 123 from a cylinder 106 for gas supply, is activated by a micro wave plasma generation equipment 122 and introduced in the film forming chamber 101. Whereas, CF4 gas is introduced in the film forming chamber 101 from a supply source 112 and an amorphous [a-C(H,X)] deposition film containing carbon is formed by irradiating light 118 from a light energy genera tion equipment 117.

Description

Detailed Description of the Invention [Field of Application of the Invention] The present invention is applicable to carbon-containing deposited films, functional films, especially semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, and photographic devices. The present invention relates to a method suitable for forming an amorphous or crystalline deposited film for use in photovoltaic devices, photovoltaic devices, and the like.

[Prior art]

For example, in the formation of an amorphous silicon film.

Vacuum deposition method, plasma CVD method, CVD method 1 reactive sputtering method, ion blating method.

Photo-CVD methods have been tried, but in general.

The Gutzu-vcvD 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 for forming amorphous silicon deposited films using the conventionally popular plasma CVD method is considerably more complex than that of conventional CVD methods, 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, etc.).

Due to the combination of these many parameters (pressure during formation, high frequency power, structure of electrode structure 1 reaction vessel, pumping speed, plasma generation method, etc.), the plasma is not in an unstable state at one time, and the formed deposited film is This often resulted in significant negative effects.

Moreover, it is necessary to select a pan meter specific to each device, making it difficult to generalize the manufacturing conditions. on the other hand.

Electrical and optical as an amorphous silicon film.

In order to achieve sufficient photoconductive and mechanical properties, it is currently considered best to form the film by plasma CVD.

According to Heigo et al., depending on the application of the deposited film, large area, uniform film thickness, and uniform film quality can be fully satisfied.

Moreover, since it is necessary to achieve mass production with high reproducibility through high-speed film formation, the formation of amorphous silicon films using plasma CVD requires a large amount of capital investment in mass production equipment. Management items are becoming more complex, the tolerance range for management is narrower, and equipment adjustments are delicate.

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 CVD method,
This method requires high temperatures, and a deposited film with practically usable properties has not been obtained.

As mentioned above, in forming an amorphous silicon film, there is a strong desire to develop a method of forming an amorphous silicon film that can be mass-produced using low-cost equipment while maintaining its practical characteristics of S resistance. About these things.

The same can be said of other functional films 1 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.

[Objective of the Invention and Disclosure] The object of the present invention is to improve the characteristics of the film to be formed, the film formation speed, the reproducibility, and to make the film quality uniform, while also providing a film suitable for increasing the area of the film. It is an object of the present invention to provide a method for forming a deposited film that can easily achieve improved film productivity and mass production.

The above purpose is to create active species generated from a compound containing carbon and halogen and a carbon-containing compound for film formation that chemically interacts with the compound in a film formation space for forming a deposited film on a substrate. and by introducing them respectively.

This is achieved by the deposited film forming method of the present invention, which is characterized in that a deposited film is formed on the substrate by irradiating these with light energy and causing a chemical reaction.

[Embodiment]

In the method of the present invention, instead of generating plasma in a film forming space for forming a deposited film, a compound containing carbon and halogen coexists with active species generated from the carbon-containing compound for film forming. By applying light energy to these, chemical interactions are caused or promoted.

Because of the amplification, it is not affected by any negative effects such as deposits aFi formed, etching effects, or other abnormal discharge effects.

Also, according to 8AVc from one shot, the atmospheric temperature in the film forming space.

In particular, a more stable CVD method can be achieved by arbitrarily controlling the substrate temperature as desired.

Furthermore, excitation energy is applied uniformly or selectively to each active species that reaches the vicinity of the substrate for film formation;
By using light energy, it is possible to irradiate the entire substrate using an appropriate optical system to form a deposit mt-,
Alternatively, it is possible to selectively control and selectively irradiate only a desired part to form a deposited film tube, or it is convenient to irradiate only a predetermined graphic part using a resist or the like to form a deposited film. It is advantageously used because it has

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

The method is to use active species activated in a FC called an activation chamber. This makes it possible to significantly increase the film formation rate compared to conventional CVD methods, and in addition, it is possible to further reduce the substrate temperature during deposition film formation.
It is possible to industrially provide a deposited film of stable quality in large quantities at low cost.

1. In the present invention, the active species refers to species that chemically interact with a compound containing carbon and halogen introduced into the film forming space to impart energy and cause a chemical reaction. This term refers to substances that have the effect of promoting the formation of deposited films. Therefore, as an active species.

The deposited St to be formed may include components constituting the constituent components, or may not include such components.6 In the present invention, the activation space introduced into the acid film space From the viewpoint of productivity and ease of handling, the active species from
A time period of at least 10 seconds is selected and used as desired.

It is preferable that the carbon-containing compound used as a raw material for forming a deposited film used in the present invention is already in a gaseous state before being introduced into the activation space, or is introduced in a gaseous state. For example, when using a liquid compound, the compound can be vaporized by connecting a suitable vaporizer to the compound supply source and then introduced into the activation space. As a carbon-containing compound.

A chain or broken saturated or unsaturated hydrocarbon compound.

The main constituent atoms are carbon and hydrogen, and other halogens.

Among organic compounds whose constituent atoms are one or two atoms such as sulfur, organosilicon compounds whose constituent elements are hydrocarbon groups, and organosilicon compounds which have a bond between silicon and carbon, are they in a gaseous state? Those that can be easily vaporized are preferably used.

Among these, hydrocarbon compounds include 1, for example, 1 to 1 carbon atoms.
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 (CH, ), ethane (C,
aS ), propane (CaH8).

n-butane (n-C41()6) spenta:/
(C,Hl), 1 Ethylene hydrocarbons include ethylene (C,a, ), propylene (CjH,), butene-1 (C4H), and fluoride.

ten-2 (c, n.), inbutylene (Ca Hs )
-Pentene (C,H,.), acetylene hydrocarbons include acetylene (CtHg) -methylacetylene (
Examples include CaH4)-butyne (04H11).

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

One or more types of Hezonogun for total water volume substitution may be used in one compound.

Compounds used in the present invention as organosilicon compounds include organosilicon, organohalogensilane, and the like.

The organosilane and the organosilane have the general formula; Rn5IH, -n*RmSiX, -m(
However, R: alkyl group, aryl group X: p.

CJeBr*Is n==1e2*3s4mm==1*
Typical examples of the compounds represented by 2e include alkylsilanes, arylsilanes, alkylsilanes, and arylhalogensilanes.

in particular.

As organochlorosilane.

Trichloromethylsilane CH, 5ICJ.

Dichlorodimethylsilane (CHs) 5ICA! m
As chlorotrimethylsilane (CH,), 81 (J trichloroethylsilane C5HsSiCJa dichlorofluorosilane (Cans)*SiCJm organo-tetrafluorosilane.

Chlordifluoromethylsilane CHsS i FsC
ldichlorofluoromethylsilane CHm81 FCI
Rich fluorofluordimethylsilane (CHI), S 1
FCJ Chlorethyldifluorosilane (Cans)
S I F Cl dichloroethylfluorosilane C,
H, S I FCJ.

Chlordifluoroprovircin CaHtSiF Snow C
zdiglorfluoroglopyrsilane C5HtSIFC
As for Jt' Organo 72.

Tetramethylsilane (CasLstethyltrimethylsilane (CHm)ms IC*HsCa
Methylpropylsilane (CH,), SiC,H.

Triethylmethylsilane CHsS i (CmH
s) sTetraethylsilane (C,H,)4
As Si organohydrogenosilane.

Methylsilane CH, SiH.

Dimethylsilane (CHm)aS IH*
Trimethylsilane (CHI), SIB diethyl 7 run (CIHs) * S i H
tTriethylsilane (C,H,), SIH tripropylsilane (CmHt)ssiH Sifueni A/
shi, 7 y (C4H6)ms IH1
As organofluorosilane.

Trifluoromethylsilane CHs S I Fm Difluoromethylsilane (CHI) * S I
Fm fluorotrimethylsilane (CB, ), Si
p-ethyltrifluorosin CIH, SiF.

Diethyldifluorosilane (CmHg)ms IF
m-triethylfluorosilane (C modified Hs) msiF
Trifluoroglopyrsilane (CsHw) as SIFm organobromosilane.

Bromotrimethylsilane (CBs) S I
B r Dipro A dimethic V 9 :/ (C
M@)@81 Br1, etc. can be mentioned, and other organopolysilanes include.

Hexamethyldiy 9 y ((CHm)ss
l) *As an organozin.

Hechu samethyldisilane ((CHI)ss1)*
Hexapropyldisilane ((CmHt)a811
You can also use wealth etc.

These carbon-containing compounds Fiim may be used, or 2'MII or more may be used in combination.

In the present invention #J, the compound containing carbon and halogen introduced into the film forming space is 1 with carbon atoms as its main constituent.
For example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon is replaced with a halogen atom is used, and a specific example is s CuYgu+2 (u is an integer of 1 or more,
Y is at least an element selected from F*C1*Br and ), a cyclic halogenated carbon represented by CvYzv (V is an integer of 3, Y has the meaning given above), cuaXyy (u and Y have the meaning given above *
x+y=2u or 2u+2. ) chain or cyclic compounds represented by

Specifically, one example jC, is CF4- (CFm) s
-(CFm)s.

(CFm) * @ CJ's e C5Ps e CH
F5 * CBsF * @CCl4 e (CCl2)
@ * CBr4 * (CBrl) @ e C, cl
,.

CmBr5, CHCla, CHBr5
- CHIa -CCmC15F, etc., or those that can be easily gasified can be mentioned.

Furthermore, in the present invention, in addition to the above-mentioned compound containing carbon and halogen, a compound containing silicon and halogen can be used in combination. As the compound containing silicon and halogen, for example, a compound in which some or all of the hydrogen atoms of a chain or cyclic silane compound are replaced with halogen atoms is used.

For example, chain silicon halide represented by 5iuZ2u+2 (u is an integer of 1 or more, 2 is at least one element selected from F, CI, Br, and I), 5i
Cyclic silicon halide represented by vZ2v (V is an integer of 3 or more, z has the above-mentioned meaning), 5luH
xYy (u and Y have the above meaning m x+y=
2u or 2u+2. ), and the like.

Specifically, for example, S I F4- (81Fm)s -
(SIFri.

(SIF*)* −StmFs −SlsFm −81
HFm, SIHmFt-8IC14e (SIC1
x) s * 5IBri I (81Br) s *8
1gC1@, St, Brs, 5IHC1,,5iHBr
Examples include those in a gaseous state or those that can be easily gasified, such as s-8I Hl m -81mCl sFa.

Furthermore, in addition to the compounds containing carbon and halogen (and compounds containing silicon and halogen), other silicon-containing compounds such as simple silicon, hydrogen, and halogen compounds (
For example, F, gas, Cj! gas.

Gasified Br1e11, etc.) can be used in combination.

In the present invention, the method for generating active species in the activation space takes into account each condition and device! microwave, R
Electrical energy such as F, low frequency, DC, etc.; Heater 1
, activation energy such as thermal energy by infrared heating, light energy, etc. is used.

In the present invention, the ratio of the amount of the compound containing carbon and halogen introduced into the film-forming space and the active species from the activation space is determined according to Pfi- as appropriate depending on the film-forming conditions, the type of active species, etc. Preferably, 10:1-1:10 (introduction flow rate ratio) is appropriate, preferably 8:2 to 4:6.
It is desirable that this is done.

In the present invention, in addition to the carbon-containing compound, in the activation space, a silicon-containing compound for forming a deposited film that generates active species, hydrogen gas, /-% ethane compound (e.g. F, gas * Cf1m gas) , gasification nr,, 1
．． etc.) *Inert gas such as helium, argon, neon, etc. can also be introduced into the activation space. If more than one of these chemicals is used, they can be premixed and introduced into the activation space in gaseous form, or they can be supplied individually in gaseous form from separate sources. However, it can also be introduced into the activation space.

Alternatively, they can be introduced into independent activation spaces and activated separately.

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 norethane atoms.

Specifically, 1, for example, S' H4, S l tHs −
5lsH@-8i4Ht. -S 1sHu-S 16H
5ipH2p+2 (p is 1 or more, preferably 1 to 1, such as I4)
15. More preferably, it is an integer of 1 to 10. ) Linear silane compound represented by -SIHiSIH (SIHa)
SIHm, 5IHISiH (SIH,)811H? .

S1! HIS IH (S IHI) 81*Hs, etc. Chain silane compounds with branches represented by 5lpH2p+2゛ (p has the above-mentioned meaning), hydrogen atoms of these linear or branched chain silane compounds A compound in which part or all of 81. is substituted with a halogen atom, 81. H.

S l 4Hs s S' sH+. -S l sH
A silane compound represented by S l (iHt (1 (q is an integer of 3 or more, preferably 3 to 6)) such as n,
Compounds in which part or all of the hydrogen atoms of an am-type silane compound are replaced with other cyclic silanyl groups and/or chain silanyl groups, compounds in which part or all of the hydrogen atoms of the silane compounds exemplified above are replaced with halogen atoms As an example.

S iHmF -S IHscl, S IHaB
r, SirHgXt such as S IHsI (X is a halogen atom, r is 1 or more.

Preferably 1-10. More preferably an integer of 3 to 7, s
+t=2r+2 or 2r. ) and halogen-substituted linear or cyclic silane compounds. These compounds may be used alone or in combination of two or more.

Further, it is possible to dope the deposited film formed by the method of the present invention with an impurity element during or after film formation. As for the impurity elements used.

As a p-type impurity, 1 an element in group Ⅰ A of the periodic table, 1, for example, B
@ AI I Ca I I n e T 1 etc. are listed as preferred, and as the n-type impurity, elements 1 of group V A of the periodic table, such as 5PsAa, sb, ni, etc. are listed as preferred. However, special KB, Ca.

p, sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical characteristics.

A substance containing such an impurity element as a component (substance for introducing impurities) is in a gaseous state at room temperature and pressure.

It is preferable to select a compound that is gaseous or at least gaseous under the conditions for forming the deposited film and that can be easily vaporized using an appropriate vaporization device. Such compounds include PHm
-PmHi, PFm -PFs -PCl5-AI
Ha@AI Fa e Asp, @AlI CI
s m S bHa *SbFm, 5IHs,
BFs, BCla, BBrm,
B*He-B4H1 (1# BsH@e BI
HH# BsHto-e BjH7* Aicl
.

etc. can be mentioned. Compounds containing impurity elements are
1'fIi may be used or two or more types may be used in combination.

The impurity-introducing substance may be introduced into the film forming space directly in a gaseous state or mixed with the compound containing carbon and halogen, or it may be activated in an activation space and then introduced into the film forming space. You can also. To activate the substance for impurity introduction.

The above-mentioned activation energies listed for generating the active species can be appropriately selected and employed.

Active species (PN
) is premixed with said active species, or.

It 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 section 1 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 BAK of the present invention.

A photoconductive member 1o shown in FIG. 1 can be applied as a member for electrophotography, and has an intermediate layer 1 provided on a support 11 for use as a photoconductive member, if necessary.
2. and a photosensitive layer 13.

In manufacturing the photoconductive member 10, the intermediate layer 12 and/or the photosensitive layer 13f can be created by the method of the present invention. The conductive member 10 is a reinforcing layer provided to chemically and materially protect the surface of the photosensitive layer 13, or a lower barrier layer and/or an upper barrier provided for the purpose of improving electrical withstand pressure. If it has layers, these can also be created by the method of the present invention.

The support 1-1 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel*A1. CreMo*Au5Ir, Nb,
Examples include residues of Ta, VeTi*Pt*Pd, etc., and alloys thereof.

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

For example, if it is glass, its surface is NlCr.

Al sCrsMo*Au*Ir, NbeTa, VeT
1 * P t * P d @ I n, 01 @
sno, I ITO(In*Om+ S n Ox
), etc., or if it is a synthetic resin film such as polyester film, N i CT e A 1 e A g * P
b 1zn, Nl*Au*Cr, MoeIr*NbIT
The surface is treated with a metal such as IV or Tlept by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, so that the surface thereof is conductive. The shape of the support may be any shape such as a cylinder, a belt, a plate, etc., and the shape is determined depending on the need, but for example,
#If the photoconductive member 10 shown in Figure I1 is used as an electrophotographic image forming member.

In the case of continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape.

For example, a photosensitive layer 13 is attached to the intermediate layer 12 from the side of the support 11.
This effectively prevents the inflow of carriers into the photosensitive layer 13 by irradiation with electromagnetic waves.

It has a function of easily allowing the photocarrier moving toward the support 11 to pass from the photosensitive layer 13 side to the support 11 side.

This intermediate layer 12 is made of amorphous carbon (hereinafter referred to as A-8IC (H
,X). ), and contains an n-type impurity such as boron CB) (Dp-type impurity or phosphorus CP) as a substance that controls electrical conductivity.

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

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

Preferably s O,001~5 x 1 G'atotn
lc ppm ・More preferably 0.5 to 1×1
0' atomic ppm, optimally 1~sx 1
It is desirable to set the value to 0”atomio I)Pm.

If the intermediate layer 12 is similar or the same in composition 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, as raw materials for forming the intermediate layer, a compound containing carbon and a halogen, a compound containing silicon and a halogen, a carbon-containing compound in a gaseous state, a silicon-containing compound, etc.) and the active species generated and, if necessary, The active species generated by activating hydrogen, a halogen compound, an inert gas, and an impurity element gas, etc. as components are used separately or mixed as necessary to form the support 11. By introducing the film into a film forming space and applying light energy, the support 11 has a μ, more preferably 40 to 8 μ,
#It is desirable that the thickness be suitably 50 or ~5μ.

The photosensitive layer 13 is composed of 1, for example, A-81(H,X),
It has both a charge generation function of generating photocarriers by laser light irradiation and a charge transport function of transporting the charges.

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

The photosensitive layer 13 is a non-doped A-8i (H,
) may contain a substance that controls the conduction characteristics of
Alternatively, if the actual amount contained in the intermediate layer 12 is large, it may be contained in an amount correspondingly smaller than the actual amount of the substance that controls conduction characteristics of the same polarity.

In the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, a compound containing carbon and noethane, a compound containing silicon and halogen, and the active material are added in the film forming space, as in the case of the intermediate layer 12. Seed and Ga.

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. This can be carried out in the same manner as in the method of the present invention.

FIG. 2 is a schematic diagram showing an example of a PIN type diode device using a semiconductor film doped with an impurity element exploded by implementing the method of the present invention.

In the figure, 21 is a substrate, and 22 and 27 are thin film electrodes.

23 is a semiconductor film, and is an n-type semiconductor layer 24. Non-doped semiconductor layer 25. It is composed of a p-type semiconductor layer 26. The present invention can be applied to any one of the semiconductor layers 24, 25, and 26, but especially to the semiconductor layer 26.
When the semiconductor layer 26t- is created by the method of the present invention, the semiconductor layer 26 is composed of 1, for example, silicon atoms, carbon atoms, and hydrogen atoms. It can be composed of an amorphous material (hereinafter referred to as rA-8IC (H, X month)) having or/and ethane atoms as constituent elements. 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. An example of a semiconductive substrate is Si.

Examples include semiconductors such as Q e , GaAs, ZnO, and ZnS. For example, the thin film electrodes 22 and 27 may be used.

NiCr, Al, Cr*Mo*Au, Ir, Nb.

T a , V , T i , P
t + Pld411n, G, ``; 5fiO,,
Ding 1. Thin films such as TJQ (In, 0.+ SnO,),
It can be obtained by providing it on the substrate 21 by processing such as vacuum evaporation, electron beam evaporation, or sputtering. The layer thickness of the electrodes 22°27 is preferably 30 to 5×10′ or
More preferably, it is 100 to 5X10'X.

The film body constituting the semiconductor layer 23 may be of n-type or p-type as required.
A type is formed by doping an n-type impurity, a p-type impurity, or both impurities among impurity elements into the layer while controlling the amount when forming one layer.

When forming n-type, i-type and p-type semiconductor layers.

Any one layer or all layers can be formed by the method of the present invention. That is, a compound containing carbon and halogen is introduced into the film forming space.

Separately, a carbon-containing compound, a silicon-containing compound in a gaseous state, and a compound gas containing an inert gas and an impurity element if necessary are excited and decomposed by activation energy.

Each active species is generated, and the active strains are introduced into the film forming space where the support 11 is installed, either separately or mixed as appropriate, and chemically interacted with each other by using light energy. the effect is caused, or promoted or amplified,
A deposited film is formed on the support. n-type and p-type A
-8l (C,H.

The thickness of the layer X) is preferably 100-10'^,
More preferably, the range is 300 to 2000X.

In addition, the thickness of the l-type a-81 layer is preferably 5
00-10'A, more preferably 1000-100
A range of OA is desirable.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure FAA, an amorphous carbon deposited film was formed using the following operation buttons.

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 after the film-forming process is annealed to further improve the properties of the formed film, and is supplied with power through the conductor Mj105t-. I get a fever.

During film formation, the heater 104 is not driven.

106 to 109 are gas supply sources, carbon compounds,
and, if necessary, provided depending on the type of gas of a compound containing hydrogen, a halogen compound, an inert gas, or an impurity element as a component. When using liquid gases among these gases.

Equip with appropriate vaporization equipment.

In the figure, the gas supply sources 106 to 109 are denoted by ``al'' and ``al'' are branch pipes, ``It'' and ``9'' are flowmeters, and ``C'' is denoted by pressure gauges that measure the pressure on the high pressure side of each flowmeter. d or・
The ones marked with are pulps for adjusting the flow rate of each gas. Reference numeral 123 is an activation chamber for generating active species, and in the activation chamber 1230 there is a microwave plasma generator 12 that generates activation energy for generating active species.
2 is provided. The raw material gas for activated species growth supplied from the gas introduction pipe 110 is activated in the activation chamber 123, and the generated active species are introduced into the film forming chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge.

In the figure, 112 is a compound supply source containing carbon and halogen, which is introduced into the film forming chamber 101 through an introduction pipe 113''1.

Reference numeral 117 denotes a light energy generating device, for example, a mercury lamp, a xenon lamp, a carbon dioxide laser, an argon ion laser, an excimer laser, or the like.

Light 118 is directed from the optical energy generating device 117 to the entire substrate 103 or a desired portion of the substrate 103 using an appropriate optical system, and is irradiated onto compounds containing carbon and halogen and active species flowing in the direction of an arrow 119. , the substrate 103 is formed by chemically reacting the compound and the active species with each other.
A deposited film is formed on the entire surface or a desired portion. In the 9th map,
120 is an exhaust valve, and 121 is an exhaust pipe.

First, a substrate 1 made of polyethylene terephthalate film
03 was placed on the support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device to reduce the pressure to about 1 low 6 TOrr 17C. CH, gas l from gas supply cylinder 106 5
0 SCCM was introduced into the activation chamber 123 via the gas introduction pipe 110. CH introduced into the activation chamber 123
, gas, etc. were activated by a microwave plasma generator 122 to become activated carbon, etc., and introduced into the entire film forming chamber 101 through an introduction pipe 124.

On the other hand, CVA gas is introduced into the pipe 11 from the supply source 112.
3, and then introduced into the film forming chamber 101.

In this way, the internal pressure inside the film forming chamber 101 is reduced to 0.3'for
t K, carbon-containing amorphous (a-C(H,
X)) A deposited film (film thickness 700X) was formed.

The film formation rate was 15X/sea.

Next, the sample on which the a-C(H,

After forming a film with a width of 51111), the dark current was measured at an applied voltage of 10 V, the dark conductivity σd was determined, and the film characteristics were evaluated.

The results are shown in Table 1.

Examples 2 to 4 Substitution of CH4 j) K linear C! H@, C! H4, or C,
H.

A carbon-containing amorphous deposited film was formed according to the same method and method as in Example 1 except that 7111 was used.

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 amorphous carbon film with excellent electrical properties could be obtained.

Example 5 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 FIG. 4, 201 is a film forming chamber, 202 is a compound supply source containing carbon and halogen, 206 is an introduction pipe, 207 is a motor, 208 is a heating heater used in the same manner as 104 in FIG. 3, and 209 and 210 are Blowout pipe, 211 is A
J cylinder, 212 indicates exhaust pulp. or,
213 to 216 are raw material gas supply sources similar to 106 to 109 in FIG. I), 217-1 is a gas introduction pipe.

Suspend the AY cylinder base 211 into the film forming chamber 201,
A heating heater 208 is provided inside it.

It can be rotated by a motor 207.

Reference numeral 218 denotes a light energy generating device, which irradiates light 219 toward a desired portion of the AI Xinder 211.

In addition, CF is introduced from the supply source 202 through the introduction pipe 206,
It was introduced into the film forming chamber 201.

Part of the introduction pipe 21? From -1, CH, 8i, and Hl gases were introduced into the activation chamber 22G. Introduced CH4-81! H@, H@ gas is in the activation chamber 220
In the microwave goods generator 221 & C, it undergoes activation treatment such as plasma formation and becomes hydrocarbon active species, silicon hydride active species, and activated hydrogen.

It was introduced into the film formation 3201 through the introduction pipe 217-2. At this time, PHa-B! Impurity gas such as Ha was also introduced into the activation chamber 220 and activated.

While maintaining the internal pressure in the film forming chamber 201 at t-0.8 Torr K.

IKWXe lamp 218 to A! Light is irradiated perpendicularly to the circumferential surface of the cylinder 211.

The AI Kushinder base 211 is rotated, and the exhaust gas is exhausted through the exhaust valve 212. In this way, the photosensitive layer 13 was formed.

In addition, the intermediate layer 12 has H/B from the introduction pipe 217-1.
A mixed gas of He (B*Hs gas is 0.2 h in terms of capacity) was introduced to form a film with a thickness of 20,001 mm.

Comparative Example I CF, CH4, si, H., H2 and B*Hs
A bottom film chamber with the same configuration as the film forming chamber 201 was prepared using each gas 1a, equipped with a 56 MHz high frequency device,
An electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by a general plasma CVD method.

The manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 5 and Comparative Example 1 are shown in Table f:fa2.

Example 6 The PIN diode shown in FIG. 2 was manufactured using the apparatus shown in FIG. 3 using CH4 as a carbon compound.

First, a polyethylene naphthalate film 21 on which 1oooX of ITO11122 was vapor-deposited was placed on a support stand.
After reducing the pressure to 0 TOrr, the inlet pipe 11 is opened as in Example 1.
3, CF 4 gas, SIF, and gas were introduced into the film forming chamber 101. Also, Si, H, gas, PH.

A gas (diluted with 1000 ppm hydrogen gas) was introduced into the activation chamber 123 for activation. Next, this activated gas was introduced into the film forming chamber 101 via the introduction pipe 124. While maintaining the pressure in the film forming chamber 101 at 0.3 TorrK, P-doped n-type a-8iC(H,X) (film thickness: 700 mm) was formed.

Next, the introduction of Pfll gas was stopped, and the SiF4/CF
Non-doped a-8iC (H,X) was prepared using the same method as for the n-type a-840 (H,
A film 25 (film thickness 5000^) was formed.

Next, St, Ha gas and K CH4-BAH gas (
1000 ppm hydrogen gas dilution), and otherwise doped with B under the same conditions as the n-type to form a 9a-810(H,X) film 26 (film thickness: 700 ppm).

Further, vacuum evaporated ICJ on this p-type film: J) Ik thickness 1
An Al electrode 27 of 000^ was formed to obtain a PIN type diode.

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

Also, regarding the light irradiation characteristics, light is introduced from the substrate side, and the light irradiation intensity is AMIC (approximately 100 mW/cIi).

A conversion efficiency of 7.6 cm or more, a y14 discharge voltage of 0.95 V, and a short circuit current of 10.2 mA/ffl were obtained.

Examples 7 to 9 -C*He -CHH in place of cn as a carbon compound
.

Or in the same manner as in Example 6 except that C*Hmk was used,
A PIN type diode similar to that produced in Example 6 was produced. The rectification characteristics and photovoltaic effect of this sample were evaluated, and the results are shown in Table 3.

From Table 3, it was found that according to the present invention, an amorphous semiconductor PIN pear diode having better optical and electrical characteristics than the conventional one 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 high-speed film formation is possible without maintaining the substrate at a high temperature. becomes. In addition, reproducibility in film formation is improved, film quality can be improved and film quality can be made uniform, and it is advantageous for increasing the area of the film.

Improved membrane productivity and mass production can be easily accomplished. Furthermore, since light energy is used as excitation energy, it is possible to form a film on, for example, a substrate with poor heat resistance or a substrate that is easily susceptible to plasma etching action. The low-temperature treatment has the effect of shortening the process.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram illustrating 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 illustrating an example of the structure of a PIN diode manufactured using the method of the present invention. FIG. j[Figures 3 and 4 are schematic diagrams for explaining the configuration of the apparatus for carrying out the method of the present invention used in the examples, respectively. lO... Image forming member for electrophotography. 1.1...Base. 12...Middle class. Rattan 3...River edge light layer. 21...Base. 22.27... Thin film single pole. 24 =011. n-type semiconductor layer, 25...l-type semiconductor layer. 26...p-type semiconductor layer. 101.201... Film forming chamber. 123.220...Activation room (B). 106.107, 108.109.112゜202.2
13,214,215.216... Gas supply source. 10 (, 211... Base body. 117, 218... Light energy generating device.

Claims (1)

[Claims] A compound containing carbon and halogen and an active species generated from the carbon-containing compound for film formation that chemically interacts with the compound are introduced into a film formation space for forming a deposited film on a substrate. A deposited film forming method characterized in that a deposited film is formed on the substrate by irradiating these with light energy and causing a chemical reaction.