JPS61191023A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve the characteristics of a film and the speed of forming a film and to homogenize quality by introducing an active seed obtained from a compound containing carbon and a halogen and an active seed obtained from a compound containing carbon in a film forming space and by irradiating light energy. CONSTITUTION:A substrate 103 is placed on the susceptor 102 in a film forming chamber 101 and heated by a heater 104. CH4 gas, etc. is introduced in an activation chamber B123 from a gas supply cylinder 106, activated by a microwave plasma generation equipment 122 and an active seed B is formed. Whereas, an activation chamber A112 is filled with solid C grain 114, heated in an electric furnace 113 and an active seed A of CF*2 is formed by blowing CF4. These active seeds A, B are introduced in the film forming chamber 101 and light is irradiated from a light energy generation equipment 117. Consequently, the active seeds A, B mutually react chemically and a film is deposited on the substrate 103.

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, plasma CVD, CVD 1 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,
(reaction vessel structure, pumping speed, plasma generation method, etc.)
Due to the combination of these many parameters, the plasma sometimes becomes unstable, which often has a significant adverse effect on the deposited film formed. Moreover, parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions. On the other hand, in order to develop an amorphous silicon film that fully satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. There is.

Heigo et al. Tsui II! Depending on the application of the membrane, larger area,
Formation of amorphous silicon deposited films by plasma CVD requires a large amount of equipment for mass production, as it is necessary to achieve uniform film thickness and uniform film quality, and to achieve mass production with high reproducibility through high-speed film formation. Equipment investment is required, control items for mass production are complicated, control tolerances are narrow, and equipment adjustments are delicate, so these are issues that need to be improved in the future. It has been pointed out. 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 quality uniform, while also being suitable for increasing the area of the film, improving film productivity, and facilitating mass production. The object of the present invention is to provide a method for forming a deposited film that can achieve the following.

The purpose of this is to introduce active species (A) generated by decomposing a compound containing carbon and halogen into a film formation space for forming a deposited film on a substrate; The active species (B) generated from the carbon-containing compound for film formation that chemically interact with each other are separately introduced, and by irradiating them with light energy and causing a chemical reaction, a deposit is formed on the substrate. This is achieved by the deposited film forming method of the present invention, which is characterized by forming n*.

[Embodiment]

In the method of the present invention, composting m l! Instead of generating plasma in the film formation space for forming the active species (A
) and active #(B) produced from carbon-containing compounds for film formation.
), by applying light energy to these components, chemical interactions are caused, promoted, and amplified. For example, there will be no 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.

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 deposited film, or selectively control and irradiate only desired areas to form a deposited film. It is advantageously used because it has the convenience of being able to form a deposited film by irradiating only a predetermined graphic portion using a resist or the like.

One of the differences between the method of the present invention and the conventional CVD method is that it uses active species activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and also to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost. 1. In the present invention, the active species (A) is a compound that chemically interacts with the active species (B) generated from the carbon-containing compound that is the compound of the raw material for forming the deposited film, thereby imparting energy, for example. A substance that has the effect of promoting the formation of a deposited film by 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. The activated species (A) from the activation space (A) introduced into the membrane space are
Those having a lifetime of 021 seconds or more, more preferably 1 second or more, optimally 10 seconds or more are 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 (B), or is introduced in a gaseous state.

For example, when using a liquid compound, the six-carbon compound that can be introduced into the activation space (B) after being vaporized by connecting an appropriate vaporization device to the compound supply source may be a chain or cyclic compound. organic compounds whose main constituent atoms are carbon and hydrogen, and one or more constituent atoms such as halogen and sulfur; organosilicon whose constituent constituents are hydrocarbon groups; Among compounds 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, examples of hydrocarbon compounds include carbon atoms of 1 to
Examples of saturated hydrocarbons include methane (CH4), ethane (C2
H6).

Propane (C8H8), n-buta7 (n-C4H1o)
, pentane (C5H12), ethylene hydrocarbons such as ethylene (C2H4), propylene L/7 (C3H6)
, Butene-I (Ca H8), Butene-2 (C4H
8), A') F + 7 (C4H8), pentene (C5HIQ), and acetylene (C2H2) as an acetylene hydrocarbon.

Examples include methylacetylene (C3H4) 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 substituted with C1, Br, I can be mentioned,
Particularly effective are compounds in which hydrogen is substituted with F or CJI.

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.

The organosilane and organohalogensilane have the general formula: Rn5iH4-41, RmSiX4-m (where R: full*) Lp group, 7-aryl group, X: F, C1,
Br, I, n=1.2, 3, 4, m= 1, 2, 3
), and representative examples include alkylsilanes, arylsilanes, alkylhalogensilanes, and arylhalogensilanes.

Specifically, as organochlorosilane, trichloromethylsilane CH35iCf
L3 dichlorodimethylsilane (CH3
) 2sicJ12 chlorotrimethylsilane
(CH3) 3 S i C41 trichloroethylsilane C2H55iCJL3 dichlorodiethylsilane (C2H5)2SiC
As J12 organochlorofluorosilane, chlordifluoromethylsilane CH35iF2CJl
Dichlorofluoromethylsilane CH35fFC
fL2 Chlorfluorodimethylsilane (CH3
) 2S i FCJL Chlorethyldifluorosilane (C2H5)Sj F2O,Q Dichloroethylfluorosilane C2H55iFCu2Chlordifluoropropylsilane C3H75iF2CJ
ldichlorofluoropropylsilane C3H75i
As FCfL2 organosilane, tetramethylsilane (CH3)
as iethyltrimethylsilane (C
H3) 3SiC2H5 trimethylpropylsilane
(CH3)3S 1C3H7 triethylmethylsilane CH35i (C2H5)3tetraethylsilane (C2H5)
As 4S i organohydrogenosilane, methylsilane CH3S i
H3 dimethylsilane (C
H3) 2SiH2 trimethylsilane
(CH3)3S iH diethylsilane
(C2H5)2S im2 triethylsilane (C2H5)3S iH tripropylsilane (C3H7)3S
iH diphenylsilane (Ce
Hs) 2 S i H2 organofluorosilane.

Trifluoromethylsilane CH35iF3
Difluorodimethylsilane (CH3) 2
S i F2 fluorotrimethylsilane
(CH3) 3S i F ethyltrifluorosilane C2H55iF3 diethyldifluorosilane (C2H5) 2SiF2 triethylfluorosilane (C2H5)3S i F trifluoropropylsilane (C3H7)
As S i F3 organobromosilane, Bromotrimethylsilane (CH3)3
SiBrdibromdimethylsilane (CH
3) 25iBr2, etc., and other organopolysilanes include hexamethyldisilane ((CH3)
3Si) As the diorganodisilane, hexamethyldisilane ((CH3)
3si) 2hexapropyldisilane ((
C3H7) 3 S t) 2 etc. can also be used.

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

In the present invention, the compound containing carbon and halogen introduced into the activation space (A) has a carbon atom as its main constituent, and is in a position where it can generate cx* (cx is a halogen) when activated. Compound 1 to which X is chemically bonded 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. Specifically, for example, CuY2u+2 (U is an integer of 1 or more) is used. ,
Y is at least one element selected from F, CI, Br, and Br. ) Chain halogenated carbon represented by CVY2V (V is an integer of 3 or more, Y has the above-mentioned meaning), CuHxYy
(U and Y have the above-mentioned meanings. X+y=2u or 2u+2.) Chain or cyclic compounds and the like can be mentioned.

Specifically, for example, CF4, (CF2)5.

(CF2)s, (CF2)4. C2F6.

C3F8. CHF3. CH2F2. CCl4゜(CC1
2)5. C13r4. ((Br 2)5゜C2C1
6, C2Br6. CHCIL3. CHBr3, CHI
3, C2Cl3F3 & etc. (7) Examples include those in a gaseous state or those that can be easily gasified.

Furthermore, in the present invention, in addition to the active species generated by decomposing the compound containing carbon and halogen, active species generated by decomposing the compound containing silicon and halogen can be used in combination. As the compound containing silicon and halogen, 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. Specifically, for example, -5iuZ2
u+2 (u is an integer greater than or equal to 1.

Z is at least one element selected from F, C1, Br, and Br. ) chain silicon halide,
Cyclic silicon halide, Si'uH, represented by 5ivZ2v (v is an integer of 3 or more, Z has the above-mentioned meaning)
xYy (u and Y have the above meanings. x+y=2u
Or 2u+2. ), and the like.

For example, SiF4. (SiF2)5゜(SiF
2) e, (SiF2)4,5i2Fs.

Si3FB, SiHF3. SiH2F2゜5iC14
, (SiC12)5. SiBr4゜(SiBr2)5,
5i2C1e, 5f2Br6, 5iHC13, 5iHB
Examples include those in a gaseous state or those that can be easily gasified, such as r3,5iHI3.5i2C13F3.

In order to generate the active species (A), the compound containing carbon and halogen (and the compound containing silicon and halogen)
In addition, if necessary, silicon-containing compounds such as simple silicon, hydrogen, and halogen compounds (e.g. F2 gas, C2
gas.

Gasified Br2, I2, etc.) can be used in combination.

In the present invention, the method of generating activated species (A) and (B) in the activation space (A) is determined by using electricity such as microwave, RF, low frequency, DC, etc., taking into account the respective conditions and equipment. Activation energy such as energy, thermal energy such as heater heating, infrared heating, and light energy is used.

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

In the present invention, in addition to the carbon-containing compound, the activation space (
In B), a silicon-containing compound for forming a deposited film that generates active species (B), hydrogen gas, a halogen compound (for example, F2 gas, CI2 gas, gasified Br2.
It is also possible to introduce an inert gas such as helium, argon, neon, etc. into the activation space (B). If more than one of these chemicals is used, they can be premixed and introduced in gaseous form during the activation period (B), or they can be introduced in gaseous form from independent sources. It can be supplied to each province and introduced into the activation chemistry M (B), or it can be introduced into each independent activation space 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.

Particularly suitable are chain and cyclic silane compounds, and compounds in which some or all of the hydrogen atoms of the chain and cyclic silane compounds are replaced with halogen atoms.

Specifically, 1, for example, SiH4,5i2Hs, Si
3HB, S i 4H10, S i 5H12, S i
Linear silane compounds represented by S i PH2F+2 (P is 1 or more, preferably 1 to 15, and more preferably 6 to 1 to io) such as 6H14, SiH3SiH
(SiH3) SfH3, S 1H3S tH(S
1H3) Si 3H, S 12H5S iH (S 1
H3) Branched chain silane compounds represented by 5ipH2p+2 (p has the above-mentioned meaning) such as S i 2H5, some or all of the hydrogen atoms of these linear or branched chain silane compounds Compounds in which is substituted with a halogen atom, S i 3H6, 5i4H8, S i 5
S i qH2q such as Hlo, S i 6H12
(q is an integer of 3 or more, preferably 3 to 6), a part or all of the hydrogen atoms of the cyclic silane compound are replaced with other cyclic silanyl groups and/or chain silanyl groups. Examples of substituted compounds and compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are replaced with halogen atoms include SiH3F, 5iH3C1, 5iH
5irHsXt such as 3Br, 5iH3I (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).

) and halogen-substituted linear or cyclic silane compounds. One of these compounds can be used and doped with an impurity element. The impurity element used is, as a p-type impurity, an element of group Ⅰ A of the periodic table, such as B.

Suitable examples include AI, Ga, In, T1, etc., and examples of n-type impurities include Group V A17) elements of the periodic table;
For example, preferred examples include P, As, Sb, Bi, etc., and B is particularly preferred.

Ga, P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical properties.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under activation conditions, and that can be easily vaporized with an appropriate vaporization device. It is preferable to select
Such compounds include PH3, P2H4・PF3・
PF5, PCl3, A5H3, ASF3.

AsF5. AsCl3. SbH3, SbF5゜SiH3
, BF3. BCl3. BBr3゜B2H6, B4H10
,B5H9,B5H11゜B6H10,B6H12,A
Examples include lCl3 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 introduction substance, which may be activated in a third activation space (C) different from the activation space (A) and the activation space (B), , 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 with the active species (A) and/or the active species (B) in advance, 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 10 may include a protective layer provided to chemically or materially protect the surface of the photosensitive layer 13, or a lower barrier layer and/or an upper barrier layer provided for the purpose of improving electrical withstand pressure. If you have them, you can also create them using this method.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support 11 include NiCr, Stairs, AI, Cr, 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.

Films or sheets of synthetic resins such as 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 subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface may be NiCr, AI, or C.
r, Mo, Au, Ir, Nb.

Ta, V, Ti, Pt, Pd, In2O3゜5n02
, ITO (In203+5n02), etc., or if it is a synthetic resin film such as polyester film, NiCr, AI
, Ag, Pb.

Zn, Ni, Au, Cr, Mo, Ir, Nb.

"a+ V, Ti, P, etc. are treated with metals such as vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metals, and the surface is conductive treated.The shape of the support is as follows: The photoconductive member 10 shown in FIG. 1 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 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 carbon (hereinafter referred to as A-C(H,X)) containing carbon atoms (C), hydrogen atoms (H), and/or halogen atoms (X) as constituent atoms.
In addition, p-type impurities such as boron (B) or phosphorus CP are used as substances that control electrical conductivity.
) and other n-type impurities are contained. Furthermore, silicon atoms can be included for the purpose of improving film quality.

In the present invention, the content of substances governing conductivity such as B and P contained in the intermediate Wj12 is preferably o
, oot~5X104 atomic PPm, more preferably 0.5~IX11X104ato ppm, optimally 1~5X103 atomic ppm.

The intermediate layer 12 has similar components to the photosensitive layer 13.

Alternatively, if they are the same, the formation of the intermediate layer 12 can be performed continuously until the formation of the photosensitive layer 13 following the formation of the intermediate layer 12. In that case, the activated species (A) generated in the activation space (A) are used as raw materials for forming the intermediate layer;
Generated by activating active species (B) generated from gaseous carbon-containing compounds and silicon-containing compounds, and optionally hydrogen, halogen compounds, inert gases, and compound gases containing impurity elements as components. The active species to be added to the support 11 are mixed side by side or as needed.
The intermediate layer 12 may be formed on the support 11 by introducing the active species into a film forming space where the active species are installed and creating an atmosphere in which each introduced active species coexists.

A compound containing carbon and halogen that is introduced into the activation space (A) to generate active species (A) when forming the intermediate layer 12 easily generates active species (A) such as CF2)k. It is more preferable to select the compound from among the above-mentioned compounds, and similarly, the compound containing silicon and halogen is selected from 1
For example, it is more desirable to select from the above compounds compounds that readily generate active species such as 5tF2)k.

The layer thickness of the intermediate layer 12 is preferably 30 to 101L,
More preferably 40 people to 8JL, optimally 50 people to 5JL.

Photosensitive layer 134i, side light JfA -S i (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 as follows.

It is desirable that the amount is 1 to 100 g, more preferably 1 to 80 Ii, and optimally 2 to 50 g.

The photosensitive layer 13 is made of non-doped A-5i(H.

X) layer, if desired, it may contain a substance that controls the conduction characteristics of a polarity different from the polarity of the substance that controls the conduction characteristics (for example, n-type) contained in the intermediate layer 12, or , the substance that governs the conduction characteristics of the same polarity is added to the intermediate layer 1.
If the actual amount contained in 2 is large, it may be contained in an amount much smaller than the dose.

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

Furthermore, if desired, 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 a typical example of a PIN diode device using a semiconductor film doped with an impurity element, which is manufactured by implementing 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, which is composed of an n-type semiconductor layer 24, a non-doped semiconductor layer 25, and a p-type semiconductor layer 26.

The present invention can be applied to the creation of any one of the semiconductor layers 24, 25, and 26. In particular, by forming the semiconductor layer 26 by the method of the present invention, the conversion efficiency can be increased. When the semiconductor layer 26 is formed by the method of the present invention, the semiconductor layer 26 is composed of, for example, silicon atoms and carbon atoms. It can be composed of an amorphous material (hereinafter referred to as rA-5iC(H,X)J) having hydrogen atoms and/or halogen 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. When the substrate 21 is conductive, the thin film electrode 22 may be omitted. As a semiconductive substrate, for example, Si, Ge, GaAs, ZnO
, ZnS, and other semiconductors. Thin film electrode 22.27
Examples include NiCr, Al, Cr, and Mo.

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

Pd, I n203.5n02, ITO (I n2
o 3 + s n O2) or the like on the substrate 21 by a process such as vacuum evaporation, electron beam evaporation, or sputtering. The layer thickness of the electrodes 22.27 is preferably 30 to 5×10 4 people, more preferably 100 to 5×10 3 people.

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 thereof during layer formation.

When forming n-type, i-type, and p-type semiconductor layers, any one layer or all of the layers can be formed by the method of the present invention, and the film formation is performed by adding carbon and carbon to the activation space (A). Compounds containing halogens are introduced and are excited and decomposed under the action of activation energy, resulting in, for example, CF3X.

5iF2) Active species (A) such as IC are generated, and the active species (A) are introduced into the film forming space. Also, apart from this,
Gaseous carbon-containing compounds, silicon-containing compounds, and gases of compounds containing inert gas and impurity elements as necessary are excited by activation energy, respectively.

The active species are decomposed to produce respective active species, which are introduced separately or mixed as appropriate into the film forming space where the support 11 is installed. The active species introduced into the film forming space is by using light energy.

Chemical interactions are caused, promoted or amplified to form a deposited film on the support.

The layer thickness of n-type and p-type A-3t (C, H, X) calendar is preferably 100-104 people, more preferably 30
A range of 0 to 2000 people is desirable.

Further, the thickness of the i-type a-5t layer is preferably 5
The range is preferably 00 to 104 people, more preferably 1000 to 1000 people.

A specific example of the present invention is shown below.

Example 1 Using the apparatus shown in FIG. 3, an amorphous carbon deposited film was formed by the following operations.

In FIG. 3, 10.1 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 heat-treating the base 103 before film-forming processing, or when performing 7-neal processing after film-forming to further improve the characteristics of the formed film, and is supplied with power via a conductive wire 105. 1 fever. During film formation, the heater 104 is not driven, and the substrate heating temperature is not particularly limited, but when carrying out the method of the present invention, it is preferably 50-150
℃, more preferably 100 to 150℃.

106 to 109 are gas supply systems, which contain 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, 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, and C for pressure gauges that measure the pressure on the high pressure side of each flowmeter. , d or e are valves for adjusting the flow rate of each gas.1
23 is an activation chamber (B) for generating active species (B), and around the activation chamber 123 is a microwave plasma generator that generates activation energy for generating active species (B). A device 122 is provided. Gas introduction pipe 110
The raw material gas for generating active species (B) supplied from the above is activated in the activation chamber (B) 123, and the generated active species (B) is introduced into the film forming chamber 101 through the introduction pipe 124. be done. 111 is a gas pressure gauge.

In the figure, 112 is an activation chamber (A), 113 is an electric furnace, and 114
115 is an introduction pipe for a compound containing gaseous carbon and halogen, which is the raw material for the active species (A), and the active species generated in the activation chamber (A) 112 are introduced through the introduction pipe 116. and introduced into the film forming chamber 101.

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

Light l18 directed from the light energy generator 117 to the entire substrate 103 or a desired portion of the substrate 103 using an appropriate optical system is irradiated onto the active species flowing in the direction of the arrow 119, causing the active species to undergo a chemical reaction with each other. By doing so, a deposited film is formed on the entire base 103 or on a desired portion. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

Ahead f, ,t! A substrate 103 made of polyethylene terephthalate film was placed on a support stand 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device to reduce the pressure to about 104 Torr. CH4 gas 150sc from gas supply pump 106
cm into the activation chamber (B) 123 via the gas introduction pipe 110
It was introduced in CH introduced into the activation chamber (B) 123
The four gases are activated by a microwave plasma generator 122 to become activated carbon, etc., filled with activated carbon, etc. 114 through an introduction pipe 124, heated in an electric furnace 113, and kept at about 1100°C. C is brought to a red-hot state and CF4 is blown into it from a cylinder (not shown) through the introduction pipe 115 to generate active species of CF3X, and the CF2)
k is introduced into the film forming chamber lot through the introduction pipe 116.

In this way, the internal pressure in the film forming chamber lot was reduced to 0.3 Torr.
and carbon-containing amorphous [a-C(H,X))
Deposition Il! (film thickness 700 years) layer was formed. The deposition rate is 1
There were 8 people/sec.

Next, the sample on which the obtained a-C(H,X) film was formed was placed in a vapor deposition tank, and a comb-shaped AI
After forming a gap electrode (gear length zsog, width 5 mm), the dark current was measured with an applied voltage of lOv, and the dark conductivity σ
The film characteristics were evaluated by determining d. The results are shown in Table 1.

Examples 2-4 CH4(7) Replaces linear C2H6, C2H4, or C
A carbon-containing amorphous deposited film was formed according to the same method and procedure as in Example 1 except that 2H2 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, and 202 is an activation chamber (
A), 203 is an electric furnace, 204 is 0 solid particles, 205 is an active species (A) raw material introduction pipe, 206 is an active species (A) introduction pipe, 207 is a motor, 208 is the same as 104 in Fig. 3 209 and 210 are blowout pipes, 211 is an AI cylinder, and 212 is an exhaust valve. 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 211 is suspended in the film forming chamber 201,
A heating heater 208 is provided inside the motor 207.
Allows for rotation.

Reference numeral 218 denotes a light energy generator, which irradiates light 219 toward a desired portion of the An cylinder 211.

In addition, the activation chamber (A) 202 is filled with solid 0 grains 204, heated in an electric furnace 203, kept at about 1100°C, and
was brought into a red-hot state, and CF4 was blown into it from a cylinder (not shown) through the introduction pipe 206 to generate active species of CF3X, and the CF2* was introduced into the film forming chamber 201 through the introduction pipe 206.

On the other hand, CH4, Si2H6 and H2 are introduced from the introduction pipe 217-1.
Each gas was introduced into the activation chamber (B) 220. The introduced CH4, Si2H6,1 (2 gases are in the activation chamber (B)
In step 220, activated hydrocarbon species are subjected to activation treatment such as plasma generation by a microwave plasma generator 221
It becomes silicon hydride active species and activated hydrogen, and the inlet pipe 21
7-2 into the film forming chamber 201. On this occasion,
If necessary, impurity gases such as PH3 and B2H6 were also introduced into the activation chamber (B) 220 for activation.

While maintaining the atmospheric pressure in the film forming space 201 at 1.0 Torr,
Light is irradiated from the IKWXe lamp 218 perpendicularly to the circumferential surface of the An cylinder 211.

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

Further, the intermediate layer 12 is supplied with H2/B2 from the introduction pipe 217-1.
A mixed gas of H6 (B2H6 gas is 0.2% by volume) was introduced to form a film with a thickness of 2000.

Comparative Example 1 A film forming chamber with the same configuration as the film forming chamber 201 was prepared using CF4, CH4, Si2H6, H2, and B2H6 gases, equipped with a 3.56 MHz high frequency device, and equipped with a typical An electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by a plasma CVD method.

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 A PIN type diode shown in FIG. 2 was fabricated using CH4 as the carbon compound and the mounting 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 8 Torr, introduce v11 as in Example 1.
6, active species CF2* and active species 5iF2)k were introduced into the film forming chamber 101. In addition, each of S i 2H6 gas and PH3 gas (looOppm hydrogen gas dilution) was introduced into the activation chamber (
B) The activated gas was introduced into the film forming chamber 101 through the introduction pipe 116. The pressure inside the film forming chamber 101 is set to 0. IT or
n-type a-3iC doped with P while keeping r
(H,X) (film thickness: 700 layers) was formed.

Next, the introduction of PH3 gas was stopped, and SiF2*/CF
n-type a-5i C(H,X
) non-doped a-SiC (H,
X) Film 25 (film thickness: 5000 layers) was formed.

Next, an a-SiC (H, did. Furthermore, an A1 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)
-V characteristics were measured, and rectification characteristics and photovoltaic effects were evaluated. The results are shown in Table 3. .

In addition, regarding the light irradiation characteristics, light is introduced from the substrate side, and at the light irradiation intensity AMI (approximately 100 mW/cm2), the conversion efficiency is 7.6% or more, the open circuit voltage is 0.95 V, and the short circuit current is 10.2. mA/cm2 was obtained.

Starting examples 7-9 c2H6 instead of CH4 as the carbon compound.

A PIN type diode similar to that in Example 6 was manufactured in the same manner as in Example 6 except that C2H4 or C2H2 was used. 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, an amorphous semiconductor PIN type 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, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. It's a monkey. Furthermore, since light energy is used as excitation energy, for example, substrates with poor heat resistance,
Films can also be deposited on substrates that are susceptible to plasma etching. 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. It is a diagram. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the method of the present invention used in Examples, respectively. 10--An electrophotographic imaging member. 11---One substrate, 12---One intermediate layer, 13---One photosensitive layer. 21---One substrate, 22.27---Thin film electrode, 24---N-type semiconductor layer. 25---i type semiconductor layer, 26---p type semiconductor layer. 101, 201-----film formation chamber, 112.202-----activation chamber (A). 123.220---1 activation chamber (B), 106, 1
07,108,109,213゜214.215,21
6--Gas supply system, 103.211--1 base, 117.218--11 optical energy generator.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, active species (A) generated by decomposing a compound containing carbon and halogen; A film is deposited on the substrate by separately introducing active species (B) generated from a carbon-containing compound for film formation that chemically interacts with each other, and irradiating them with light energy to cause a chemical reaction. A deposited film forming method characterized by forming.