JPS61193427A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To attain enlargement, improvement of productivity and mass production of the title films by a method wherein an active compound containing carbon and halogen as well as another active compound produced from a nitrogen contained filming compound are separately fed to a filming space to form said films by means of making them chemically react to each other. CONSTITUTION:An active compound A produced by decomposing carbon and halogen contained compound as well as another active compound B produced from a nitrogen contained filming compound chemically reacting to the former are separately fed to a filming space to form said films on a substrate by means of making them chemically 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 e.g. CF4 may be recommended for the carbon and halogen contained compound while a compound comprising nitrogen and one or exceeding two kinds of component atoms other than nitrogen may be recommended for the nitrogen contained compound. Finally the preferable weight ratio of active compounds A and B may be 8:2-4:6.

Description

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

[Prior art]

For example, vacuum evaporation method, plasma CVD method, CVD reactive snow emitting method, ion silating method, photo-CVD method, etc. have been tried to form an amorphous silicon film. The CVD method is widely used and commercialized.

The film has improved VC' comprehensively in terms of electrical and optical properties, fatigue properties due to repeated use, usage environment properties, productivity including uniformity and reproducibility, and mass production. There is room for improvement in these characteristics. □The reaction process in forming a thymorphous silicon deposited film using the plasma CVD method, which has been popular for a long time, is different from that of the conventional CVD method.A:7::::
::,::Nini::″″″:2::su, (e.g., substrate temperature, flow rate and ratio of introduced gas, pressure can high-frequency power during formation, electrode structure, reaction vessel structure, pumping speed, Zorazu - generation method, etc.) Kok et al.

Due to the combination of many i45 meters, sometimes the plug
□Zuma becomes unstable and has □significant negative effects on the deposited film that has been formed. In addition, parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions. On the other hand, as an amorphous silicon film, it has electrical and optical properties.

In order to achieve fully satisfactory photoconductive and mechanical properties, it is currently considered best to form the film by the plasma C2 method.

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 also become complex, the management tolerance narrows, and equipment adjustments are delicate. Since it is,
These have been pointed out as problems that should be improved in the future. On the other hand, with 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, 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 all of the drawbacks of the plasma CVD method described above 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, film formation speed, and reproducibility of the film to be formed, and to make the film quality uniform, making it suitable for large-area films, improving film productivity, and mass production. The object of the present invention is to provide a complete deposited film formation pattern that can be easily achieved.

The above purpose is to create an active species (A) generated by decomposing a compound containing carbon and halodane in a film forming space for forming a deposited film on a substrate, and to chemically interact with the active species (A). A feature of forming a JF6 film on the substrate by introducing active species (B) generated from a nitrogen-containing compound for film formation to each side and causing a chemical reaction. This is achieved by the deposited film forming method of the present invention.

[Embodiment]

In the method of the present invention, since plasma is not generated in the film forming space for forming the entire deposited film, the deposited film formed is not affected by etching effects or other adverse effects such as abnormal discharge effects. 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). be. This makes it possible to dramatically increase the film formation speed compared to the conventional CVD method, and also to further reduce the substrate temperature during deposited film formation, resulting in stable film quality. Deposited films can be provided industrially in large quantities at low cost. In the present invention, the activation space (A) introduced into the film forming space
From the viewpoint of productivity and ease of handling, the activated species (A) are selected as desired, with a lifetime of 0.1 seconds or more, more preferably 1 second or more, optimally 10 seconds or more. The components of this active species (A) constitute all the components constituting the deposited film formed in the film forming space. Further, the chemical substance for film formation is activated by activation energy in the activation space (B), and is introduced into the film formation space, and when forming a deposited film, the chemical substance is activated in the activation space (B). (A) and chemically interacts with the active species (A) containing constituent elements that will become constituents of the deposited film to be formed. As a result, a desired deposited film can be easily formed on a desired substrate.

In the present invention, the compound containing carbon and halodane introduced into the activation space (A) is, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon are replaced with halodane atoms. For example, Cu”
2u+2 (u ill: an integer greater than or equal to 1, Y is F,
CI, Br or ■. ), a chain halogonated carbon represented by CvY2v (v is an integer of 3 or more, Y has the above-mentioned meaning),
S11□HxYy (u and Y have the above-mentioned meanings.

X+y-2u or 2u+2. ), and the like.

Specifically, for example, CF4. (CF2)5. (CF
2) 6° (OF2)4. C2F6. C3F8. CHF,
, CH, 2F2.0C14° (CCI 2 ) 51 C
Br4, (CBr2)5, c2ct6,
Examples include those in a gaseous state or easily gasifiable, such as c2c 13F5.

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 halodane atom is used, and specifically, for example, 51uz2u+2 (" is 1 or more an integer of 2
is at least one element selected from F, CI, Br and (2). ) Chain silicon halide represented by 5Ivz2v (v is an integer of 3 or more, 2 has the above meaning), cyclic silicon halide, 81 u
Examples include chain or cyclic compounds represented by Hx Z y ('u and 2 have the above-mentioned meanings, x+y=2u or 2u+2).

Specifically, for example, SiF4. (SiF2)5. (Si
F2) 6° (SiF2) 4.812F6. Si3F8,
5IHF,,5IH2F2゜5IC14,(S'1C1
2) 5,5iBr'4. (SiBr2)5,5i2C1
6゜512Br6,5iHC1'3.5IHBr3.5
Examples include those that are in a gaseous state or can be easily gasified, such as iHI5, 5i2C13F3.

In order to generate active species (A)', in addition to the above-mentioned compounds containing carbon and halogen (and silicon), other silicon-containing compounds such as simple silicon, hydrogen , halogen compounds (e.g. F2 gas,
C12 gas, gasified Br2, I2, etc.) can be used in combination.

In the present invention, as a method for generating active species (A) and (B)'e in active chemical spaces (A) and (B), respectively, microwave, RF, low frequency , electrical energy such as DC, thermal energy such as heater heating, infrared heating, and activation energy such as light energy.

The active species (B) used in the present invention, the nitrogen-containing compound that generates Ir, is already in a gaseous state before being introduced into the activation space (B), or can be introduced in a gaseous state. preferable. For example, when using liquid and solid compounds, the compounds can be vaporized by connecting all appropriate vaporizers to the compound supply source and then introduced into the film forming space.

Examples of the nitrogen-containing compound include compounds whose constituent atoms are nitrogen and one or more types of atoms other than nitrogen.

Examples of atoms other than nitrogen include hydrogen (H) and halogen (
X=F, CI, Br or I), sulfur (S), carbon (
C), oxygen (0), phosphorus (P), silicon (st), germanium (G@), boron (B), alkali metals, alkaline earth metals, transition metals, and other groups of the periodic table. Among the atoms of elements belonging to , any atom that can be combined with nitrogen can be used.

Incidentally, for example, compounds containing N and H include NH5,
NH4N, , N2H5N, , T(2NNH2, 1st
Examples of compounds containing N and X, such as tertiary amines, halodated products of these amines, and hydroxylamine, include N3X;

N2X2. NXy, etc., NOX, No□X, N03
Examples of compounds containing N and S such as X4 include N4S4. N2
Examples of compounds containing N and C such as 55 include HCN and cyanide, HO (J and its salt, H8CN and its salt, etc.), and compounds containing N and Oi such as N20, No, N
02. N2O3, N2O4, ・N2O5, NO3, etc., N
Examples of compounds containing P, N5. P2N3. P.N.
In addition to this, triethylsilazane (C2H5)! , S
1NH2*hexamethyldisilazane [(CH3), sf
i] 2NH, hexaethylsisilazane [(C2H5)3
Organosilazane such as Si]2NHI, trimethylsilicon isocyanate (CH3)3SiNCO, dimethylsilicon diisocyanate (CH3)25i (NCO)
(CH3)5SiNC8 and the like, but the nitrogen-containing compounds used in the present invention are suitable for achieving the purpose of the present invention. If so, it is not necessarily limited to these.

These nitrogen-containing compounds may be used alone or in some cases, two or more may be used in combination.

In the present invention, the activated species (B) from the activation space (B) 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. that's all,
Optimally, a length of 10 seconds or more is selected and used as desired.

In the present invention, in addition to nitrogen-containing compounds, raw materials for film formation include hydrogen gas, halogen compounds (for example, F2 gas, C12 gas, gasified B r 2, I2, etc.), argon, neon, etc. Activated gas, silicon-containing compounds, carbon-containing compounds, dalmanium-containing compounds, oxygen-containing compounds, etc. are used as raw materials for forming a thin film.
) can also be used. When using a plurality of these raw material gases, they are mixed in advance and placed in the activation space (B).
Alternatively, these source gases can be individually supplied from independent supply sources and introduced into the activation space (B), or they can be introduced into each independent activation space (B). They can also be installed and activated individually.

Silicon-containing compounds that serve as raw materials for forming deposited films include:
A silicon compound in which hydrogen, halogen, etc. 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 in the chain and cyclic silane compounds are replaced with halodane atoms.

Specifically, for example, 5IH4, Si□H6, 513I
(8゜514H1,., 5i5H12, 5i6H14 etc. Si, H2, +2 (p is 1 or more, preferably 1 to 15
A linear silane compound represented by a), preferably an integer of 1 to 10, S 1Hss IH (S IH
3) S IH3, S 1H3s IH (S IH3) S
15H7.

512H5SiH (SI■3) SI2■■5 etc. 81p
A chain silane compound with all branches represented by H2p+□ (p has the above-mentioned meaning), a part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with halogen atoms. Compound, 513H6,814H
8゜515H1o, 519H2 such as 5I6H42, (q
A cyclic silane compound represented by (d3 or more, preferably an integer of 3 to 6), in which some or all of the hydrogen atoms of the cyclic silane compound are substituted with other cyclic silanyl groups and/or chain silanyl groups. Examples of compounds in which some or all of the hydrogen atoms of the silane compounds exemplified above are substituted with halodane atoms include SiH3F and 5iH3C].

5lrHBX such as 5iH3Br, 5iHxI, (X
is a l atom, r is 1 or more, preferably 1 to 10
, more preferably an integer from 3 to 7 r s + t-2r
+2 father is 2r. ), and halodane-substituted linear or cyclic silane compounds. These compounds are 1
One species may be used or two or more species may be used in combination.

In addition, carbon-containing compounds that serve as raw materials for forming deposited films include chain or cyclic saturated or unsaturated hydrocarbon compounds, carbon and hydrogen as the main constituent atoms, and silicon, halogen,
Among organic compounds having one or more constituent atoms such as sulfur, and organosilicon compounds having hydrocarbon groups as a constituent, those in a gaseous state or those that can be easily vaporized are preferably used. Among these, examples of hydrocarbon compounds include, for example, saturated hydrocarbons having 1 to 5 carbon atoms, ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, etc. Methane (CH
3), ethane (C2H6), zoronochen (C3H8),
n-butane (n -C4H10), pentane (C5H1
2), the ethylene hydrocarbon is ethylene (C2H4
), zolopyrene (C3H6), butene-1 (C4HEl
), butene-2 (C4H8), isobutylene (04H
8), pentene (C5H10), acetylene hydrocarbons such as acetylene (02H2), methylacetylene (
Examples include C3l(4), butyne (C4H6), and the like.

In addition, as organosilicon compounds, (CH,)4Sf, CH35icl, , (
CH3)2SfCI□.

(CH5)3SiC1, C2H55ill, organochlorosilane, CH35IF2C1, CH35IFC
12, (CH3)2SiFCI.

C2H55iF2C1, C2H55iFC12, C3H
75iF2CI.

Organochlorofluorosilane such as C3H,5IFC12, C(CH3)3Si ]2 r C(C3H7)g
Organodisilazane such as sl:]2 and the like are preferably used.

These carbon-containing compounds may be used alone or in combination of two (14) or more.

In addition, as a germanium-containing compound that is a raw material for forming a deposited film, an inorganic or organic germanium compound in which hydrogen, halogen, or a hydrocarbon group is bonded to germanium can be used, such as GeaH5 (a is an integer of 1 or more). , b = 2 a + 2 or 2a.)
A chain or cyclic damanium hydride represented by, a polymer of this germanium hydride, a compound in which some or all of the hydrogen atoms of the germanium hydride are replaced with halodane atoms, a hydrogen atom of the germanium hydride Examples thereof include organic dalmanium compounds such as compounds partially or wholly substituted with organic groups such as alkyl groups and aryl groups, and optionally with 10 carbon atoms, as well as germanium sulfides, imides, and the like.

Specifically, for example, GeH4, Ge2H6, Ge3H
6.

As n-Go H, tert-oxygen-containing compound, 0
2.03, and compounds having oxygen and one or more types of atoms other than oxygen as constituent atoms.

Examples of atoms other than oxygen include hydrogen (H), nitrogen (X=F, CI, Br or H), and sulfur (S).
, carbon (C), silicon (sl), yurmanium (Ge)
, phosphorus (P), boron (B), alkali metals, alkaline earth metals, transition metals, etc. In addition, any atom of an element belonging to each group of the periodic table that can be combined with oxygen may be used. It is possible to do so.・Incidentally, examples of compounds containing O and H include ■20, and examples of compounds containing O and S include S02. Oxides such as S03, compounds containing 0 and CI include oxides such as CO1CO2, 0 and 8
Compounds containing 1k include disiloxane (H3SIO
8IH3), trisiloxane () (3S1081H20
Siloxanes such as SiH5).

Diacetoxydimethylsilane (CH3)2S i (O
COCH,)2.

Triacetoxymethylsilane CH3S I (OCOC
Organoacetoxysilanes such as H5)3, alkyl alkoxysilanes such as methoxytrimethylsilane (CI(,5IOCI(3, dimethoxydimethylsilane (CH3)281(OCH3)2.)rimethoxymethylsilane CH381(OCR,)5 .

Trimethylsilanol (CH3)3SiOH, dimethylphenylsilanol (CH3)2(06H5)SiO
H, diethylsilanediol (C2H5)2Sl(OH
) Compounds containing organosilanols such as 2, 1, 0 and G@wo include G.

oxides, hydroxides, and armanium acids.

I(3CeOGeH3r H3GeOGeH20GeH
The oxygen-containing compound used in the present invention is not limited to these as long as it is compatible with achieving the object of the present invention.

In addition to these, N2 gas may also be used depending on the case.

In the present invention, the active species (A
) and the active species (B) can be determined as desired depending on the deposition conditions, the type of active species, etc., but preferably 10:1 to 1:10 (introduction flow rate ratio) is appropriate. ,
More preferably, the ratio is 8:2 to 4:6.

Further, the deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. The impurity elements used include p-type impurities,
Also, 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, an element of group A of the periodic table, such as B,
A.I.

Suitable examples include Ga, In, 'T1, etc., and examples of n-type impurities include elements of group A of the periodic table,
For example, P h Aa + Sbr Bi etc. are mentioned as suitable ones, but especially B , Ca, P t S
b 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 in a mogas state at room temperature and normal pressure, or at least is a gas under activation conditions, and can be easily vaporized with an appropriate vaporization device. It is preferable to select compounds. Such compounds include PH3, P2H4, PF3lPF5.
PCl31AsH3゜AsF', AsF'5,
AsCl3, 8bH5h SbF5, 5IH5.

BF3, BCl3, BBr3, B2H6,
B4) 11°, 85B5+.

B5H11# B6H'1゜, B6H42, AlCl
3- etc. Compounds containing impurity elements may be used alone or in combination of two or more.

The impurity introduction substance may be introduced and activated together with each substance that generates the activation space (A) and/or the activation space (B) K, the active species (A), and the active species (B). or activation space (A,) and activation space (B)
Even if it is activated in the third activation space (C), which is different from the above, it still bites. To activate the substance for introducing impurities, active species (
A) and active species (B) All of the above-mentioned activation energies listed in ffi generation 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 fully explained with reference to an open mold example of an electrophotographic image forming member formed by the method of the present invention.

FIG. 1 is a schematic diagram for explaining the entire 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 so, they can all be produced 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, Al Cr, Mo I Au l
Ir INb, Ta, V, TI, P
Examples include metals such as Pd, Pd, 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, 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*AI
*Cr r Mo + Au + Ir r Nb
+, Ta +'V * Ti r Pt.

Pb, In2O3, SnO2, ITO(In2O3
+5n02), etc., or if it is a synthetic resin film such as a polyester film, NiCr, AI, Ag, Pb
rZn, Ni.

Au, Cr*Mo+IrlNb, T
The surface is treated with a metal such as a, V, T1 + Pt, etc. by vacuum evaporation, electron beam evaporation, sintering, etc., or laminated with the metal, to make the surface conductive. The shape of the support body may be cylindrical, belt-shaped, plate-shaped, etc.
For example, the photoconductive member 10 of FIG. 1 may be used as an electrophotographic image forming member. If used, in the case of continuous high-speed copying, it is desirable to have an endless belt shape or a cylindrical shape.
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 all the passages easily.

For example, if this intermediate layer 12 is created by the method of the present invention, it is composed of silicon atoms, nitrogen atoms, carbon atoms, and if necessary, oxygen atoms, hydrogen atoms (H), and/or halodane atoms (X). Amorphous material containing as atoms (hereinafter referred to as a
It is written as -5INC(0,H,X). ) is composed of −
In some cases, as a substance that controls electrical conductivity,
For example, p-type impurities such as boron (B) or phosphorus (P)
Contains p-type impurities such as. Further, for the purpose of expanding the functionality of the film, germanium atoms can be entirely contained.

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

The content of the substance controlling conductivity such as P is preferably O, OO1-5 X 10' atomic pp
m, preferably 0.5 to I x 10 at'om
1a ppm, optimally 1-5 X 10 atoms
It is desirable to set it to ic ppm.

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) and the nitrogen-containing compound for film formation introduced into the activation space (B) are used as raw materials for forming the intermediate layer. Active species (B) generated from compound gas, etc. containing inert gas and impurity elements as components are supported side by side or mixed as appropriate as necessary. The intermediate layer 12 may be formed on the support 11 by introducing it into the film forming space where the support 11 is installed and causing a chemical reaction.

Examples of compounds containing carbon and halogen that are introduced into the activation space (A) to generate active species (A) when forming the intermediate layer 12 include compounds that easily generate all active species, such as CF2*. is preferably selected from the compounds listed above. Similarly, as the compound containing silicon and halogen, it is more desirable to select it from all the above-mentioned compounds that easily generate active species such as SiF2*.

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

The photosensitive layer 13 is made of, for example, an amorphous material (hereinafter referred to as rA-8t(H, It has both a charge generation function of generating photocarriers by irradiation with light 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-8l (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, the substance controlling the same polarity conductivity may be contained in an amount much smaller than the loading amount. You may let them.

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

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

In the figure, 21 is a base, 22 and 27 are thin film electrodes, 23 is a semiconductor layer, an n-type semiconductor layer 24, a 1-type semiconductor layer 2
5. Consisting of a p-type semiconductor layer 26VC. 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, for example, an amorphous material (rA-5iNC(H,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 and shrinks, the thin film electrode 22 may be omitted.

As the semiconductive substrate, for example, Si*Ger
Examples include semiconductors such as GaAs+2nO and ZnS. As the thin film electrode 22.27, for example, NiC'r +"A
l l cr-;'Mo * Au: Ir r N
b + Ta + V, Ti r Pt IPd
+In2()5.5n02s ITO(In2O5+
5n02) etc., by vacuum evaporation, electron beam evaporation,
It is obtained by forming a layer on the substrate 21 by a process such as sputtering. The film thickness of the l electrode 22; 22 is as follows:
It is preferably 30''□~5X10''l, more preferably 10゛0~5'xs6B'' (26)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 rut.

When forming n-type, n-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 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, such as CF2'',
Active species (A) such as 5IF2* are generated, and the active species (A)
) is introduced into the film forming space.

Separately, the chemical substance for film formation introduced into the activation space (B) and, if necessary, a gas of a compound containing an inert gas and an impurity element as components, are respectively supplied with activation energy. Excite and decompose, each active fII
It is only necessary to generate all the components f, separately or appropriately mix them, and introduce them into the film forming space where the support 11 is installed to form the film. The layer thickness of the n-type and p-type semiconductor layers is preferably 100 to 104X, more preferably 300 to 204X.
A range of 0X is desirable.

Further, the thickness of the n-type semiconductor layer is preferably 50
0-104X, more preferably 1000-1000
A range of 0X is preferable.Specific examples of the present invention are shown below.

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

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 heat-treating the base 104 before the film-forming process, or annealing the film after film-forming to improve the properties of the formed film, and is supplied with power through the conductor 105 to generate heat. do. At that time, the substrate heating temperature is not particularly limited, but when carrying out the method of the present invention, it is preferably 3.
The temperature is preferably 0 to 450°C, more preferably 100 to 250°C.

Reference numerals 106 to 109 denote gas supply sources, which are provided depending on the type of film forming raw material gas, an inert gas used as necessary, and a compound gas containing an impurity element as a component. If these gases are liquid in their standard state, all appropriate vaporization equipment should be provided.

In the figure, the gas supply systems 106 to 109 are indicated by a branch pipe, a flowmeter by b, a pressure gauge for measuring the pressure on the high pressure side of each flowmeter, d or The valve labeled F1a1 is for adjusting the flow rate of each gas. 1
23 is an activation chamber (B) for generating active species (B)'
A microwave plasma generator 122 is provided around the activation chamber 123 to generate activation energy for generating active species (B). The raw material gas for producing active species (B) supplied through the gas introduction pipe 110 is activated in the activation chamber (B) 123, and the generated active species (B) passes through the introduction pipe 124 to form a film. It is introduced into the chamber 101. 111 is a gas pressure gauge.

In the figure, 112 is an activation chamber (A), and 113 is an electric furnace.

114 is a fixed 0 grain, 115 is an introduction pipe for a compound containing gaseous carbon and halo r7, which is a raw material for active species (A), and active species (A) generated in activation chamber (A) 112.
Fi is introduced into the film forming chamber 101 via the Fi introduction pipe 116.

In the figure, 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 system to reduce the pressure to about 10-6 Torr.

Gas supply layer? The gasified triethylsilazane was introduced into the activation chamber (B) 123 through the gas introduction pipe 110 using the entire gas chamber 106. Triethylsilazane and the like introduced into the activation chamber (B) 123 are activated by the microwave plasma generator '122 to become activated triethylsilazane, and are then introduced into the activated triethylsilazane gold film forming chamber 101 through the introduction pipe 124. Introduced.

On the other hand, the activation chamber (A) 102 is filled with solid 0 grains 114, heated in an electric furnace 113, kept at about 1000°C to bring C to a red-hot state, and then heated through an inlet pipe 115 from a cylinder (not shown). By injecting CF41, CF2
All of the active species * were generated, and the cF2* was introduced into the film forming chamber 101 through the entire introduction pipe 116.

In this way, the internal force f O, 3 Torr inside the film forming chamber 101
IfC holding, A-5iNc (H,x) film (i thickness 7
ooX) was formed. The deposition rate was 11×/s@e.

Next, the sample with the entire A-5iNC (H,
than), the dark current was measured at an applied voltage of 12 V, the dark conductivity σd was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.

Example 2 Gas retention was performed using (C2H5)3SINH2/H2/F2 mixed gas (mixture ratio (C2H5) ssINH2/H2/F2 instead of triethylsilazane gas from pump 106 etc.)
= 8: 8: l) A-8iNC(H,
The entire membrane was formed. The dark conductivity of each sample was measured and the results are shown in Table 1.

□ Table 1 From Table 1, it was found that according to the present invention, an amorphous film with excellent electrical properties could be obtained.

Example 3 Using the apparatus shown in Fig. 4, the first
A P-ram-shaped electrophotographic imaging member having a layer structure as shown in the figure was prepared.

In FIG. 4, 201 is a film forming chamber, 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-shaped base, and 212 is an exhaust gas valve. Further, 213 to 216 are raw material gas supply sources similar to 106 to 109 in FIG.
17-1 is a gas introduction pipe.

Suspend the A1 cylinder base 211 in the film forming chamber 201,
A heating heater 208 is provided inside the motor 207.
Allows for more rotations. □Also, activation room (A)
The solid material 204 was packed in the 202 and heated in the electric furnace 203 to about 100 ml.

℃ to make C a red-hot state, and by spraying cF4 from a cylinder (not shown) through the introduction pipe 206, cF2* as an active species (A) is generated, and the CF2
was introduced into the film forming chamber 201* through the introduction pipe 206. In addition, an activation chamber (C) (not shown) having a structure similar to that of the activation chamber (A) 202 is similarly constructed.
5IF2 * (1) 4x active fM (c); 72 A'i217-1 j F)
) IJ xfys)>-y The gasified product was introduced into the activation chamber (B) 220. The introduced triethyldisilazane is subjected to an activation process such as plasma conversion by a microwave plasma generator 221 in an activation chamber (B) 220, and becomes activated triethyldisilazane.
It was introduced into the film forming chamber 201 through the introduction pipe 217-2. At this time, impurity gases such as PH3 and B2H6 were also introduced into the activation chamber (B) 220 for activation, if necessary.

A, 1 cylinder - The base body 211 was rotated, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust valve 212. In this way, the intermediate layer 12 has a film thickness of 2000. formed in j.

In the photosensitive layer 13, CF4 was not used among the gases used to form the intermediate layer 12, H2 gas was used instead of triethyldisilazane, and H2/
A film was formed in the same manner as in the case of the intermediate layer 12, except that a mixed gas of B2H (0.2 cm of B2×6 gas in volume) was introduced.

Comparative Example I CF, SiH, ) ethyldisilazane, H2 and B2H
A high-speed film forming chamber similar to the film forming chamber 201 was prepared using each of the gases described in No. 6 and equipped with a 13.56 MHz high frequency device, and an electrophotographic image forming member having the layer structure shown in FIG. 1 was prepared. was formed.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 3 and Comparative Example 1.

Example 4 Using the apparatus shown in FIG. 3, a PIN diode shown in FIG. 2 was manufactured.

First, a polyethylene terephthalate film 21 on which a 100OX ITO film 22 was vapor-deposited was placed on a support stand, and
After reducing the pressure to Torr, active species 5IF2 generated in the same manner as in Example 3 were introduced into the film forming chamber 101.

Further, H2 gas and PH3 gas (diluted with 1000 ppm hydrogen gas) were each introduced into the activation chamber (B) 123 for activation. Next, this activated gas was introduced into the film forming chamber 101 via the introduction pipe 116. While maintaining the pressure inside the film forming chamber 101 at 0.1 Torr, the P-doped n
A type A-81(H,X) film 24 (thickness: 700×) was formed.

Next, the introduction of PH3 gas was stopped and the non-doped A-8t(H,X) film 25 (film A thickness of 5000×) was formed.

Then, instead of H2/PH3 gas, (C2H5)3SI
P-type a-5 doped with B using B2H6 gas (1000 ppm hydrogen gas dilution) with NH2/H2 gas (mixing ratio 1:10), but otherwise under the same conditions as n-type.
An iNC(H,X) film 26 (film thickness 700X) was formed.

Further, on this p-type film, a 1000X thick electrode 27 was formed by vacuum deposition to obtain a PIN-type diode.

Diode element thus obtained (area 1cIrL2)
The I-V characteristics were measured, and the rectification characteristics and photovoltaic effect were evaluated. The results are shown in Table 3.

In addition, regarding the light irradiation characteristics, light is introduced from the substrate side, and at a light irradiation intensity of AMI (approximately 100 mW/cm"), the conversion efficiency is 9.04 or more, the open circuit voltage is 0.92 V, and the short circuit current is 1.
0 mA/cm" was obtained.

Example 5 In place of (C2H5)581N'H2/H2 gas, (C2H5)3SINH2/H2/F2 gas [(C2H5)3SINH2/H2/F2-1=15=
A PIN type diode similar to that in Example 4 was manufactured in the same manner as in Example 4 except that 2] was used. This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

Table 3 *1 Ratio of forward current to reverse current at voltage 1V V *2 Current formula of p-n junction J -Js (exp(, □
)-1) n value (Quality Factor
) [Effects 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, the substrate can be maintained at a high temperature. High-speed film formation is possible. In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. be able to. Furthermore, since excitation energy is not used for film formation, it is possible to form a film even on substrates with poor heat resistance or easily susceptible to plasma etching, and the process can be shortened by low-temperature treatment. .

[Brief explanation of the drawing]

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 a configuration example of a PIN diode manufactured using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams each illustrating the configuration of an apparatus for carrying out the method of the invention used in the examples. 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...1 type semiconductor layer, 26...p type semiconductor layer, 1
01', 201... film forming chamber, 111. ．． 202...
Activation room (A), 106.107.108.109.2
13,214°215.216...Gas supply system, 10
3,211...Base. Agent Patent Attorney Dan Taira Yamashita Figure 1

Claims (1)

[Claims] Chemically interacts with active species (A) generated by decomposing a compound containing carbon and halogen in a film formation space for forming a deposited film on a substrate. , active species (B
) are separately introduced and chemically reacted to form a deposited film on the substrate.