JPS61191024A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve film property and forming film speed and to uniformalize quality thereof by a method wherein an active genus obtained from compound including germanium and halogen, and the active genus obtained from compound included Si are introduced to forming film space and an optical energy is projected thereto. CONSTITUTION:A substrate 103 is placed on a support 102 inside a forming film chamber 101 and is heated by a heater 104. An Si5H10 gas etc. is introduced to inside activation chamber 123 from a gas cylinder for supplying 106 and active genus B is created by means of activation by microwave plasma generator 122. On the other hand, an active seed A of a GeF*2 seed is created by means that after an activation chamber 112 is filled up with solid Ge grains 114 and is heated by an electric furnace 113 and then is blown into GeF4. These active genuses A, B are introduced to the forming film chamber 101 and are irradiated by light of an optical energy generator 117. As the result, the active genuses A, B are made to perform chemical reaction, then a deposited film is formed on the substrate 103.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention is directed to deposited films containing silicon, particularly functional films, especially for semiconductor devices and electrophotography, containing non-monocrystalline silicon such as polycrystalline silicon. The present invention relates to a method suitable for forming a deposited film.

[Prior art]

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

Deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity including uniformity and reproducibility, as well as mass production. , there is room for further improvement of comprehensive 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 (e.g., 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 parameters, the plasma sometimes becomes unstable, which often has a significant negative effect on the deposited film formed. Moreover, device-specific parameters must be selected for each device.

Therefore, the reality is that it is difficult to generalize the manufacturing conditions. On the other hand, in order to develop an amorphous silicon/film that fully satisfies each of the electrical, optical, photoconductive, and mechanical properties, it is currently considered best to form it by plasma CVD. ing.

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.
Amorphous silicon salt made by plasma CVD method f!
In the formation of ff#, a large amount of capital investment is required for mass production equipment, and the management items for mass production become complex, the management tolerance narrows, and the adjustment of the equipment is delicate. These issues have been pointed out as issues that should be improved in the future. On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to provide a deposited film 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. These numbers are filled with other functional films, such as silicon nitride films.

The same can be said of silicon carbide films and silicon oxide films.

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

[Purpose and outline of the invention]

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

The above purpose is to create an active species (A) generated by decomposing a compound containing germanium and a halogen in a film forming space for forming a deposited film on a substrate, and a chemical reaction between the active species (A) and the active species (A). A deposited film is formed on the substrate by separately introducing active species (B) generated from a silicon-containing compound for film formation that interact with each other, and irradiating them with light energy to cause a chemical reaction. This is achieved by the deposited film forming method of the present invention, which is characterized by the following.

[Embodiment]

In the method of the present invention, instead of generating plasma in a film forming space for forming a deposited film, active species (A) generated by decomposing a compound containing germanium and halogen and silicon for film forming are used. In coexistence with the active species (B) generated from the contained compounds, by applying light energy to these, chemical interactions are caused, promoted, and amplified. The deposited film is not adversely affected by etching effects or other adverse effects such as abnormal discharge effects.

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

Furthermore, excitation energy is applied uniformly or selectively to each active species that reaches the vicinity of the substrate for film formation, but if light energy is used, it can be applied to the entire substrate using an appropriate optical system. A deposited film can be formed by irradiation, or a deposited film can be formed partially by selectively controlling irradiation only to a desired part, or a resist or the like can be used to form a deposited film in a predetermined graphic part. It is advantageously used because it has the convenience of being able to form a deposited film by irradiating only the target area.

One of the differences between the method of the present invention and the conventional CVD method is that it uses active species activated in advance in a space different from the film-forming space (hereinafter referred to as activation space). This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and in addition, it is possible to further lower the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

Incidentally, the active species (A) in the present invention refers to a species that chemically interacts with the deposited film forming chemical substance or its excited decomposition product to impart energy or cause a chemical reaction. Therefore, the active species (A) may include constituent elements that constitute the constituent σ elements constituting the deposited film to be formed.
Alternatively, such a component may not be included.

In the present invention, the activated species (A) from the activation space (A) introduced into the film forming space have a lifetime of 0.1 seconds or more, more preferably 1 second, from the viewpoint of productivity and ease of handling. more than seconds,
Optimally, a time period of 10 seconds or more is selected and used as desired, and the constituent elements of this active species (A) constitute the components constituting the deposited film formed in the film forming space. In addition, the silicon-containing compound for film formation is activated by activation energy in the activation space (B) to generate active species (B), and the active species (B) are transferred to the film formation space. When introduced and forming a deposited film, it chemically interacts with the active species (A) simultaneously introduced from the activation space (A) by the action of light energy. As a result, a desired deposited film can be easily formed on a desired substrate shape.

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

It is preferable that the silicon-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 active space (B), or is introduced in a gaseous state. When using a liquid compound, the compound can be vaporized by connecting an appropriate vaporizer to the compound supply source and then introduced into the activation space (B).

Silicon-containing compounds include silicon and hydrogen.

Silanes and halogenated silanes to which halogen or hydrocarbon groups are bonded 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, Si2H6, Si3
Linear silane compounds represented by 5fpH2p+2 (p is an integer of 1 or more, preferably 1 to 15, more preferably 1 to 1O) such as HB, Si4H10, 5i5H12, 5i6H14, 5iH3SiH(SiH3)SiH3
,5iH3S iH(S 1H3)S i 3H7,5
5ipH2 such as f2HsSiH (SiH3) Si2H5
A chain silane compound having a branch represented by p+2 (P has the above-mentioned meaning), a compound in which part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with a halogen atom. , 5i3H6, 5i4HB,
5t5H10, 5ieH12 etc. 5iqH2q (q is 3
The above is preferably an integer of 3 to 6. ), a compound 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, some of the hydrogen atoms of the silane compounds exemplified above, or Examples of compounds in which all halogen atoms are substituted include SiH3F, 5iH3C1, 5iH3Br
, 5irH5Xt such as 5iH3I (X is a halogen atom, r is 1 or more, preferably 1 to 10, more preferably 3
An integer of ~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.

In the present invention, as the compound containing germanium and halogen introduced into the activation space (A), for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic germanium hydride compound is replaced with a halogen atom is used. , Specifically, for example, GetlY2u+2 (u is greater than or equal to l)
The integer Y is at least one element selected from F, CI, Br and I. ), GevY2v (V is an integer above 31!, Y
has the meaning given above. Examples include cyclic germanium halides represented by ), linear or cyclic compounds represented by GeuHxYy (u and Y have the above-mentioned meanings) (+y=2u or 2u+2), and the like.

Specifically, 1, for example, GeF4. (GeF2)5.

(GeF2)s, (GeF2)4
, Ge2Fe.

Ge3FB, GeHF3. GeHBr3, Ge
C14, (GeC12)5, GeBra, (GeB
r2)5. G) 62c1B, GeHBr3゜GeHCl
3, GeHBr3. Examples include those that are in a gaseous state or can be easily gasified, such as GeHI3°Ge2C13F3.

Furthermore, in the present invention, active species (A
), combined use of active species (SX) generated by decomposing a compound containing silicon and halogen and/or active species (CX) generated by decomposing a compound containing carbon and halogen. I can do it.

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, and specifically, 1
For example, 5iuY2u+2 (u is an integer greater than or equal to 1, Y is F, CI.

At least one element selected from Br and I. ) chain silicon halide, 5ivY2
Cyclic l\silicon halogenide, S i uHxYy, represented by v (v is an integer of 3 or more, Y has the above-mentioned meaning)
(U and Y have the above-mentioned meanings. x+y=2u or 2u+2.) Chain or cyclic compounds and the like can be mentioned.

For example, SiF4. (SiF2)5゜(SiF
2)6. (SiF2)4,5i2FB.

5i3FB, SiHF3. SiH2F2゜5iCI4.
(SiCl2)5.5iBra.

(SiBr2)5,5i2C16,5i2Brs.

S 1HcH3, S 1HBr3. S 1HI3゜5i
Examples include those that are in a gaseous state or can be easily gasified, such as 2CI3F3.

These silicon compounds may be used alone or in combination of two or more.

Further, as the compound containing carbon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound is replaced with a halogen atom is used. Specifically, for example, CuY2u+2 (u is 1 An integer greater than or equal to Y, F, CI.

It is one or more elements selected from Br and I. ), CVY2V (V
is an integer of 3 or more, and Y has the above meaning. ), chain or cyclic compounds represented by CuH) (Yy (u and Y have the above-mentioned meanings, x+y=2u or 2u+'2), etc.).

Specifically, 1, for example, CFa, (CF2)s.

(CF2)6. (CF2) 4.02FB, C3FB
.

CHF3, CH2F2, CC14(CCl2)5
, CBr4. (CBr2)5. C2C1B.

C2Br6. CHCl3. CHBr3. CHI3. C2
Examples include those in a gaseous state or easily gasified, such as Cl3F3.

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

To generate active species (A) 1 For example, when generating active species of a compound containing germanium and a halogen, in addition to this compound, if necessary, a germanium compound such as germanium alone, hydrogen, A halogen compound (for example, F2 gas, C12 gas, gasified Br2゜2, etc.) can be used in combination.

In the present invention, methods for generating activated species (A) and (B) in activation spaces (A) and (B), respectively, include microwave, RF, low frequency, D
Activation energy such as electrical energy such as C, thermal energy such as heater heating, infrared heating, and light energy is used.

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

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

In the present invention, in addition to silicon-containing compounds, hydrogen gas, halogen compounds (for example, F2 gas, C12 gas, gasified Br2, I2, etc.), inert gases such as helium, argon, and neon are used as chemical substances for film formation. It is also possible to introduce and use the like into the film forming space. When using multiple of these chemical substances for film formation, they must be mixed in advance and placed in the activation space (B
), or these film-forming chemicals can be supplied individually from independent sources and introduced into the activation space (B), or .

They can also be introduced into independent activation spaces and activated individually.

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 to be used include elements of group m of the periodic table A as p-type impurities, such as B, AI, Ga, In,
Preferred examples include TI, and examples of n-type impurities include elements of Group V A of the periodic table, such as P and As.

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

A substance containing such an impurity element as a component (hereinafter referred to as an impurity-introducing substance) is in a gaseous state at room temperature and normal pressure, or at least under activation conditions, and can be easily vaporized with an appropriate vaporization device. It is preferable to select the compounds obtained as such compounds such as PH3, P2
H4, PF3. PF5. PCl3. AsH3゜AsF3
．． AsF5. AsCl3. SbH3°SbF5. SiH
3, BF3. BCl2. BBr3. B2H6, B4H1
0, B5H9, B5H11, B6H10, B8H12,
Examples include AlCl3. 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 CB), The above-mentioned activation energies listed for generating the species (A) and the activated species (B) can be appropriately selected and employed. The active species (PN) generated by activating the impurity introduction substance is mixed with the active species (A) or/and the active species (B) in advance,
Alternatively, 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 member 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 imaging member.

It has a layer structure consisting of a support 11 for a photoconductive member, an intermediate layer 12 provided as necessary, 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, these can also be created by the method of the present invention.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, and Mo.

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

Examples include metals such as Pd and alloys thereof.

Polyester is used as the electrically insulating support.

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

Films or sheets of synthetic resins such as polyvinylidene chloride, polystyrene, polyamide, etc., and glass.

Ceramic, paper, etc. are commonly used. Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

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

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

V, Ti, Pt, Pd, In2O3, 5n02゜IT
If it is conductive treated by providing a thin film such as O(In203+5n02) or a synthetic resin film such as polyester film, NiCr, Al, Ag
, Pb, Zn, Ni.

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

The surface is treated with a metal such as Ti or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal to make the surface conductive. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined depending on the need. For example, the photoconductive member 10 in FIG. If used as a 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 and causes the photocarriers generated in the photosensitive layer 13 by irradiation with electromagnetic waves and moves toward the support 1'1 from the side of the photosensitive layer 13 to the side of the support 11. It has a function that allows easy passage to.

This intermediate layer 12 is made of amorphous silicon (rA-S i Ge
(H,
type impurities or n-type impurities such as phosphorus CP).

In the present invention, the content of substances governing conductivity such as B and P contained in the intermediate layer 12 is preferably 0.
．． 001-5X104 atomic ppm, more preferably 0.5-1X10' atomic ppm, optimally 1-5X103 atomic ppm.

If the constituent components are similar or the same as those of the photosensitive layer 13, the formation of the photosensitive layer 13 can be performed continuously after the formation of the intermediate layer 12. In that case, the raw materials for forming the intermediate layer include the active species (A) generated in the activation space (A), a gaseous silicon-containing compound, and optionally hydrogen, a halogen compound, an inert gas and Active species CB) generated by activating a gas of a compound containing an impurity element as a component are placed on each side of the support 1.
The intermediate layer 12 may be formed on the support 11 by introducing the active species into the film forming space where the active species 1 is installed and applying light energy to the coexistence atmosphere of each introduced active species.

Compounds containing germanium and halogen that are introduced into the activation space (A) to generate active species (A) when forming the intermediate layer 12 include, for example, the above-mentioned compounds that easily generate active species such as GeF2*. can be mentioned.

The layer thickness of the intermediate layer 12 is preferably 30 to 10 JL.
, more preferably 40 people to 8JL, optimally 50 people to 5JL
It is desirable that this is done.

The photosensitive layer 13 is made of, for example, silicon as a base material, and as necessary, amorphous silicon A-5i (H, X, Ge) or germanium as constituent atoms of hydrogen, halogen, germanium, etc. Amorphous germanium A-Ge whose constituent atoms are hydrogen, halogen, etc.
H,

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

The photosensitive layer 13 is non-doped +7) A-3i (H,
.

Ge) or A-Ge (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, it may be contained in an amount that is much smaller than the dose. .

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

Figure 2 shows a PI using an A-3iGe stack doped with an impurity element, which is produced by carrying out the method of the present invention.
FIG. 1 is a schematic diagram showing a typical example of an N-type diode device.

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, an i-type semiconductor layer 25, and a p-type semiconductor layer 26. 28
is a conductive wire that is coupled to an external electrical circuit device.

If S is conductive, the thin film electrode 22 may be omitted.
Examples include semiconductors such as i, Ge, GaAs, ZnO, and ZnS. For example, the thin film electrodes 22 and 27 are made of NiC.
r, At, Cr, Mo.

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

Pd, I n203.5n02, ITO (I n2
03+5n02) on a substrate by a process such as vacuum evaporation, electron beam evaporation, or sputtering. The layer thickness of the electrode 22°27 is preferably 30 to 5×104, more preferably 100 to 5×
It is desirable that the number be 103 people.

In order to make the film constituting the semiconductor layer of A-3t n-type or p-type as necessary, it is necessary to form an n-type impurity, a p-type impurity, or both impurities among the impurity elements during layer formation. It is formed by doping the layer in a controlled amount.

n-type, i-type and p-type c7) A-3f G e (H,
') To form the layer, according to the method of the present invention, in addition to compounds containing germanium and halogen, compounds containing silicon and halogen are introduced into the activation space (A), and these are excited at high temperature. By decomposing, for example, G e F2*
Active species such as and SiF2* are generated and introduced during film formation. In addition, apart from this, a silicon-containing compound in a gaseous state introduced into the activation space CB) and a compound gas containing an inert gas and an impurity element as components as necessary,
Each active species is excited and decomposed by activation energy to generate each active species, and each is introduced separately or mixed as appropriate into the film forming space where the support 11 is installed. The layer thickness of n-type and p-type (7) A-5i Ge (H, X) is preferably 100 to 104, more preferably 30
A range of 0 to 2000 people is desirable.

Further, the layer thickness of the i-type c7) SiGe(H,X) layer is preferably 500 to 104, more preferably 100
A range of 0 to 10,000 people is desirable.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 3, i
A-GeSj (H,X) deposited films of type, p-type, and n-type were formed.

In FIG. 3, 101 is a film forming chamber, and a desired substrate 103 is placed on a substrate support stand 102 inside.

104 is a heater for heating the substrate;
4 is used when heat-treating the base 104 before film-forming processing or annealing the film after film-forming in order to further improve the properties of the formed film, and is supplied with power via a conductive wire 105. I get a fever. The heater 104 is not driven during film formation. The substrate heating temperature is not particularly limited, but when carrying out the method of the present invention, it is preferably 50 to 150°C.
1, more preferably 100 to 150°C.

Reference numerals 106 to 109 denote gas supply systems, which are provided depending on the type of gas of the silicon-containing compound and the compound containing hydrogen, a halogen compound, an inert gas, and an impurity element, which are used as necessary. If these gases are liquid in their standard state, an appropriate vaporizer is provided.

In the figure, the gas supply systems 106 to 109 are marked with a for branch pipes, b for flowmeters, C for pressure gauges that measure the pressure on the high pressure side of each flowmeter, and d for gas supply systems 106 to 109. The ones marked with "e" are valves for adjusting the flow rate of each gas. 12
3 is an activation chamber CB) for generating active species CB), and around the activation chamber 123 is a microwave plasma generator 122 that generates activation energy for generating active species (B). is provided. The raw material gas for generating active species (B) supplied from the gas introduction pipe 110 is activated in the activation chamber (B) 123, and the generated active species C
B) is introduced into the film forming chamber 101 through the introduction pipe 124. 111 is a gas pressure gauge.

In the figure, 112 is an activation chamber (A), 113 is an electric furnace, and 11
4 is a solid Ge grain 9115 is an introduction tube for a compound containing gaseous germanium and halogen, which is a raw material for active species (A), and is used to introduce active species (A) generated in the activation chamber (A) 1.12.
A) is introduced into the film forming chamber lot via the introduction pipe 116.

In addition, when forming a film body whose constituent atoms are Si or the like in addition to Ge, an activation chamber (C) (not shown) similar to 112 is used.
It is possible to separately provide an active species (SiX*) from a compound containing silicon and halogen and, for example, a solid 5ifi, and introduce it 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, a dixima laser, or the like.

Light 118 directed from the optical 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, and the irradiated active species are A-3 is applied to the entire substrate 1.03 or a desired part by mutual chemical reaction.
A deposited film of i is formed. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

Substrate 10 made of pre-screened polyethylene terephthalate film
3 is placed on the support stand 102.

The inside of the film forming space 101 is evacuated using an exhaust device.

The pressure was reduced to 10-6 Torr. Gas supply cylinder 106
using si5HtoL50sccM, or this and PH3 gas or B2H6 gas (both 11000pp
A gas mixed with 40 SCCM (hydrogen gas dilution) was introduced into the activation chamber (B) 123 via the gas introduction pipe 110.

The 5i5H10 gas etc. introduced into the activation chamber (B) 123 is activated by the microwave plasma generator 122 to become activated hydrogen, silicon etc.
Activated hydrogen and the like were introduced into the film forming chamber 101 through.

On the other hand, solid Ge particles 114 are placed in the activation chamber (A) 1112.
The GeF2* is heated in an electric furnace 113 to bring it into a red-hot state, and GeF4 is blown into it from a cylinder (not shown) through an introduction pipe 115 to generate active species of GeF2*. After that, it was introduced into the film forming chamber 101. In addition, in the same manner as above, active species such as SiF2* were introduced into the film forming chamber 101 as needed.

In this way, the internal pressure inside the film forming chamber 101 is reduced to 0.3 Torr.
and undoped or doped A-Ge.
A (Si,H,X) film (thickness: 700 mm) was formed.

The film formation rate was 23 people/sec.

Next, the obtained non-doped or p-type A-Ge
Place the Si (H,
After forming the At gap electrode (gap length 250IL, width 5mm) of the -5TOrr-t' taxi, an applied voltage of 1
The dark current was measured at 0 V, the dark conductivity σd was determined, and the film characteristics of each sample were evaluated. The results are shown in Table 1.

Examples 2 to 4 Linear Si4H10, branched Si instead of st5H1O
A-3iGe(H,
X) A film was formed.

The dark conductivity was measured and the results are shown in Table 1.

From Table 1, it is clear that according to the present invention, a-Ge has excellent electrical properties.
A Si (H,X) film is obtained and also.

Sufficiently doped A-GeSi(H,X)
It was found that a membrane was 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 the film forming chamber, and 202 is the activation chamber (A).
, 203 is an electric furnace, 204 is a solid Ge particle, 205 is an active species (A) raw material introduction pipe, 206 is an active species (A) introduction pipe, 207 is a motor, and 20B is used in the same manner as 104 in FIG. 209 and 210 are blow-off pipes, and 211 is an AI cylindrical body 212 is an exhaust valve. Also, 213 to 216 are 10 in FIG.
It is a raw material gas supply source similar to 6 to 109, 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 20.
7 so that it can be rotated. Reference numeral 218 denotes a light energy generating device, which irradiates light 219 toward a desired portion of the Al cylindrical substrate 211.

In addition, the activation chamber (A) 202 is filled with solid Ge grains 204 and heated in the electric furnace 203 to bring the Ge into a red-hot state,
There, Ge is introduced from a cylinder (not shown) through the introduction pipe 206.
By injecting F4, Ge as active species (A)
F2)C was generated, and the GeF2* was introduced into the film forming chamber 201 through the introduction pipe 206.

On the other hand, S i 2H6 and H2 gas were introduced into the activation chamber (B) 220 through the introduction pipe 217-1. 5i introduced
The zH6 and H2 gases undergo activation processing such as plasma formation by the microwave plasma generator 221 in the activation chamber (B) 220 and become activated hydrogen, which is then introduced into the inlet pipe 217-2.
was introduced into the film forming chamber 201 through the film. On this occasion.

If necessary, impurity gases such as PH3 and B2H6 are also introduced into the activation chamber (B) 220 to maintain activation while -IK
Light was irradiated perpendicularly to the circumferential surface of the Al cylinder base 211 from a WXe lamp 218 .

The Al cylindrical substrate 211 was rotated, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust valve 212. In this way, the photosensitive layer 13 was formed.

Further, the intermediate layer 12 is supplied with H2/B2 from the introduction pipe 217-1.
A mixed gas of H6 (B2H8 gas is 0.2% by volume) was introduced to form a film with a thickness of 2000.

Comparative Example I A film forming chamber having the same configuration as the film forming chamber 201 was prepared using each gas of S i 2H6, H2 and B2H6, and 13.5
6M1 (equipped with Z high frequency device, general plasma CV
A drum-shaped electrophotographic image forming member having the layer structure shown in FIG. 1 was formed by method D.

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 manufactured using the apparatus shown in FIG. 3 using 5i3H6 as a silicon-containing compound.

First, a polyethylene naphthalate film 21t on which 1000 TTO films 22 were deposited was placed on a support stand, and 1000
After reducing the pressure to −6 Torr.

Active species of active species GeF2* generated in the same manner as in Example 1 were introduced into the film forming chamber 101. Also.

Si2H6 gas, H2 gas, PH3 gas (1000pp
m hydrogen gas dilution) were introduced into the activation chamber (B) 123 and activated.

Next, this activated gas was introduced into the film forming chamber 101 through the introduction pipe 116. The internal pressure in the film forming chamber 101 is set to 0.
N-type A-SiGe (H,
was formed.

Next, the n-type A-3 except that the introduction of PH3 gas was stopped.
A non-doped A-3iGe (H,
was formed.

Next, 82H6 gas (1000pp
m hydrogen gas dilution), p-type carbon-containing A-3iGe (H,X) doped with B under otherwise the same conditions as n-type.
A film of 26 (film thickness: 700 layers) was formed. Furthermore, an AI electrode 27 having a thickness of 1000 was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

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

In terms of light irradiation characteristics, light is introduced from the substrate side, and at a light irradiation intensity of AMI (approximately 100 mW/cm2), the conversion efficiency is 7.8% or more, the open circuit voltage is 0.91 V, and the short circuit current is 10.
．． 2 mA/cm2 was obtained.

Examples 7-9 Instead of S i 3H6 as a silicon compound, linear S
i4H10, branched 5t4)1to, or H65i6F
A PIN type diode similar to that in Example 6 was manufactured in the same manner as in Example 6 except that B was used. This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

From Table 3, according to the present invention, A-3iG e (H,
It has been found that a PIN type diode can 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. be able to. Furthermore, since light energy is used as excitation energy, it is possible to form a film even on a substrate that has poor heat resistance and is susceptible to plasma etching, for example. 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 each illustrating the configuration of an apparatus for carrying out the method of the invention used in the examples. 10--An electrophotographic imaging member, 11--A substrate, 12--Interlayer. 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---m-film formation chamber, 112.202---one activation chamber (A), 123.22
0---1 activation chamber (B), 106, 107, 108,
109,213°214.215.216---Gas supply system, 103.211---One base.

Claims (1)

[Claims] Chemically interacts with active species (A) generated by decomposing a compound containing germanium and halogen in a film formation space for forming a deposited film on a substrate. , active species (B) generated from a silicon-containing compound for film formation are introduced separately, and a deposited film is formed on the substrate by irradiating them with light energy and causing a chemical reaction. Characteristic deposited film formation method.