JPS61110422A - Method of forming deposited film - Google Patents

Abstract

PURPOSE:To improve the electrical, optical, photoconductive and mechanical characteristics of a deposited film and to enable the high-speed formation of the film at a low substrate temperature by a method wherein an oxide is excited to react by applying an electro-discharge energy thereto in a film-forming space for forming the deposited film. CONSTITUTION:An active species produced by dissolving a compound containing silicon and halogen, and an oxide acting chemically with this active seed, are introduced separately into a film-forming space, and an electro-discharge energy is applied on these materials to excite the oxide so as to make it react, whereby a deposited film is formed on a substrate. For instance, a polyethylene terephthalate film substrate 103 is laid on a support 102, a deposition space 101 is evacuated so as to reduce the pressure inside of it, and O2 is introduced into the deposition space at a substrate temperature of about 280 deg.C, by using a gas supply source 106. Meanwhile, solid Si particles 114 are packed in a dissolution space 102 and heated to melt down Si, and SiF4 is blown thereinto. The active seed thus produced is introduced into the film-forming space 101. Then, an atmospheric pressure being maintained at 0.1Torr and plasma being made to act thereon, an oxygen-containing amorphous deposited film is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a deposited film containing oxygen, particularly a functional film, especially an amorphous film used for semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, 1i image devices, etc. The present invention also relates to a method suitable for forming a deposited film containing crystalline oxygen.

[Prior art]

For example, vacuum evaporation, plasma CVD, CVD, reactive sputtering, and ion plating can be used to form an amorphous silicon film.

Photo-CVD methods and the like have been tried, and in general, plasma CVD methods are widely used and commercialized.

The deposited film composed of amorphous silicon has 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 conventional plasma CVD method is considerably more complicated than that of the conventional CVD method, and the reaction mechanism is still unclear. In addition, there are many parameters for forming the MM (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, often having a significant adverse 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 with electrical, optical, photoconductive, or mechanical properties that can sufficiently satisfy various uses, it is currently considered best to form it by plasma CVD. ing.

Depending on the application of the deposited film, plasma CVD is required to achieve large area, uniform film thickness, uniformity of quality, and mass production with high reproducibility through high-speed film formation. Forming an amorphous silicon deposited film by this method requires a large investment in equipment for mass production, and the management items for mass production are also complicated.
The allowable management range has become narrower, and equipment adjustments have become more delicate, so these have been pointed out as problems that need to 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. 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 drawbacks of the plasma CVD method described above and provides a new method for forming a 8tM layer 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 above purpose is to create an active species generated by decomposing a compound containing silicon and halogen, and an oxygen compound that chemically interacts with the active species in the film forming space for forming a deposited film on a substrate. This is achieved by the deposited film forming method of the present invention, which is characterized in that a deposited film is formed on the substrate using a vehicle that introduces each of the oxygen compounds separately and applies discharge energy to them to excite the oxygen compounds and cause them to react. be done.

[Embodiment]

In the method of the present invention, discharge energy such as plasma is used as energy to excite and react raw materials for forming a deposited film, but since active species are introduced into the film-forming space as one of the raw materials, compared to conventional methods, Film formation is possible even with low discharge energy, and the deposited film formed is substantially free from 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, if desired, in addition to discharge energy, light energy and/or thermal energy can be used in combination.

Light energy can be applied to the entire substrate using an appropriate optical system, or can be selectively applied to only desired areas, so that the formation position and thickness of the deposited film on the substrate can be controlled. etc. can be easily controlled. Further, as the thermal energy, thermal energy converted from light energy can also be used.

One of the differences between the method of the present invention and the conventional CVD method is that active species activated in advance in a space different from the film forming space (hereinafter referred to as the decomposition space) are used. This makes it possible to dramatically increase the film formation speed compared to the conventional CVD method, and in addition, it is possible to further lower the substrate temperature during the formation of the salt 81 film, resulting in stable film quality. Deposited films can be provided industrially in large quantities at low cost.

In the present invention, the active species refers to a species that chemically interacts with the oxygen compound or its excited decomposition product to impart energy or cause a chemical reaction to form a deposited film. Therefore, the active species may contain constituent elements that constitute the deposited film to be formed, or may not contain such constituent elements. Correspondingly, the oxygen compound used in the invention may be an oxygen compound that can serve as a raw material for forming a deposited film by containing constituent elements constituting the deposited film to be formed; It may be an oxygen compound that does not contain the constituent elements constituting the deposited film and can only serve as a raw material for film formation, or it may be an oxygen compound that can be a raw material for forming a deposited film and an oxygen compound that can be used as a raw material for film formation. It may be used in combination with an oxygen compound that can be a raw material.

The oxygen compound used in the present invention is preferably already in a gaseous state before being introduced into the film forming space, or is preferably introduced in a gaseous state. For example, when using liquid and solid compounds, A suitable vaporizer can be connected to the compound supply source to vaporize the compound, and then the compound can be introduced into the film forming space.

Oxygen compounds include oxygen (02), oxy/(03
), and compounds having oxygen and one or more types of atoms other than oxygen as constituent atoms. The atoms other than oxygen include hydrogen (H), halogen (X
=F, CiBr or I), sulfur (S), carbon (C
), silicon (Si), germanium (Ge), phosphorus (P
), boron (B), alkali metals, alkaline earth metals,
In addition to transition metals, atoms of elements belonging to each group of the periodic table that can be combined with oxygen can be used.

Incidentally, examples of compounds containing 1, for example 0 and H include F20.
Compounds containing O and X such as H2O2 include HXO, H
m-base acids such as XO, oxides such as X20, x207, compounds containing 0 and S, H2S 02,
Acids such as H2S04 and oxides such as S02 and S03; compounds containing O and C include acids such as H2CO; and oxides such as Co and co2; compounds containing O and Si include; Disiloxane (83S i OS i H
3), Trisiloxane (H3S iO3iH20S 1
Compounds containing 0 and Ge, such as siloxanes such as H3), include Ge oxides, hydroxides, germanic acids, H3GeOGeH3, H3Ge0GeH20-GeH
Compounds containing germanium compounds such as 1, 0 and P, ugliness such as H3PO3, H3POa, and P2O3,
Oxides such as P2o5 and compounds containing O and B include:
Examples include acids such as H2BO3 and oxides such as B20□, but the oxygen compound used in the present invention is not limited to these.

These oxygen compounds may be used alone or in combination.
You may use more than one species in combination.

In the present invention, the active species from the decomposition space introduced into the r&membrane space has a lifetime of 5 seconds or more, more preferably 15 seconds or more, and optimally 30 seconds or more from the viewpoint of productivity and ease of handling. are selected and used as desired.

In the present invention, as the compound containing silicon and halogen introduced into the decomposition space, 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, For example, Si Y
(u is an integer of 1 or more u2u+2, Y is F, C1, Br or I.) Chain silicon halide, 5ivY2v (V is an integer of 3 or more, Y has the above meaning.) Cyclic silicon halide, 5iuHY (u and Y have the meanings given above).

y x+y=2u or 2u+2. ), and the like.

Specifically, for example, SiF4. (SiF2)s, (SiF
z) b, (SiF2),, Si2 F6゜Si3 FB
, SiHF3. SiH2F2, S i Cl 4 (
S i Cl 2 ) c, , S i B r a
.

(SiBr2)s, 5i2C1b, Si, Cl3F3, etc., which are in a gaseous state or can be easily gasified can be mentioned.

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

In the present invention, as a method for generating active species in one decomposition space, the discharge energy,
Excitation energies such as thermal energy, light energy, etc. are used.

k: Activated species are generated by adding decomposition energy such as heat, light, or electric discharge in a decomposition space to the above.

In the present invention, the ratio of the amount of oxygen compounds in the film formation space to the active species from the decomposition space is determined as desired depending on the deposition conditions, the type of active species, etc., but is preferably 1.
A ratio of 0:1 to 1:10 (introduction flow rate ratio) is appropriate.

In the present invention, hydrogen gas, halogen compounds (e.g. F2 gas, C
12 gas, gasified Br2, I2, etc.), inert gas such as argon, neon, etc., and silicon compounds, carbon compounds, germanium compounds, etc. as raw materials for forming the deposited film.
T? , it can also be used by introducing it into the membrane space. When using multiple of these raw material gases, they can be mixed in advance and introduced into the film forming space, or these raw material gases can be supplied individually from independent sources and then introduced into the film forming space. It can also be introduced.

Silanes, siloxanes, and the like in which hydrogen, halogen, or hydrocarbon groups are bonded to silicon can be used as the silicon compound serving as a raw material for forming the deposited film.

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

Specifically, for example, SiH4,5i2H6, Si3
HB, Sta Hlo, 5i5H1□, 5i6H, etc. (p is an integer of 1 or more, preferably 1-15, more preferably 1-10)
A linear silane compound represented by 5jH3SiH(Si
H3) SiH3,5iH3SiH(SiH3)Si3H
7, S such as Si2 H55iH (SiH3) Si2H5
t Hp 2p+2 (P has the above-mentioned meaning) A linear silane compound having a branch, a part or all of the hydrogen atoms of these linear or branched silane compounds are replaced with a halogen atom. compound, 5i3H6,5t4H6,Si,
Hl. , 5i6H1□, etc., where q is an integer of 3 or more, preferably 3 to 2Q6), a part or all of the hydrogen atoms of the cyclic silane compound are substituted with other cyclic silanyl groups. and/or a compound substituted with a chain silanyl group,
As an example of a compound in which part or all of the hydrogen atoms of the silane compound exemplified in Item 1 are replaced with halogen atoms, SiH3F
, S 1H3C1, SiH3Br, SiH3I etc.c7)
SiHS
r+2 or 2r. ) and halogen-substituted linear or cyclic silane compounds.

These compounds may be used alone or in combination of 2M or more.

In addition, carbon compounds that serve as raw materials for forming deposited films include:
Chain or cyclic saturated or unsaturated hydrocarbon compounds, organic compounds whose main constituent atoms are carbon and hydrogen, and one or more constituent atoms such as silicon, halogen, sulfur, etc.
Among organosilicon compounds having a hydrocarbon group as a constituent, those in a gaseous state or those that can be easily vaporized are preferably used. Among these, 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. As a hydrocarbon, methane (CH3
), ethane (C2H&), propa7 (C3H6), n
-Buta 7 (n-CaHf0), Pentane (Cs Hf
z), and the ethylene hydrocarbon is ethylene (C
2H4), propylene (C3Hb), butene-1
(CaHa), butene-2 (C4Hll),
Inbutylene (C,H8), pentene (C5H+o)
, Acetylene (C2H2
), methylacetylene (C3H4), butyne (C4H
6) etc.

In addition, as organosilicon compounds, (CH3)4Si, CH3SiCl3, (CH3)2
S i C12, (CH3)3”iCl, C2H2S
Organochlorosilane such as iCl2, CH35iF2C
1, CH35iFC1,, (CH3)25iFC1,C
2H5S iF2 C1, C2H3SiFC12, C3
Organochlorofluorosilane such as H7SiF2 C1, C3H7S i FC12, [(CH3)3 SiF
Organodisilazane such as 2°[(C3H])3Si12 and the like are preferably used.

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

In addition, as a germanium 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.For example, GeH (a is an integer of 1 or more) , b=2a+2b or 2a), a polymer of this germanium hydride, a compound in which some or all of the hydrogen atoms of the germanium hydride are replaced with halogen atoms. , organic germanium compounds such as compounds in which some or all of the hydrogen atoms of the germanium hydride are replaced with organic groups such as alkyl groups and aryl groups, and optionally halogen atoms; other germanium sulfides, imides, etc. can be mentioned.

Specifically, for example, GeH, Ge2H6.

Ge3H6, n G ea H16, ter t
-Gea Hl 6 , Ge3 H6,
Ge5Hf6, GeH3F, Ge
H3C1, GeH2F2, H6Ge6 F,
, Ge (C:H3) 4 , Ge (C2
Hs)a, Ge(C6H5)a.

Ge (CH3) 2 F2 , GeF2 , Ge
Examples include F, , GeS, and the like. You can use one type of these germanium compounds or two! i or more may be used together.

It is also possible to dope the aM formed by the method of the invention with impurity elements.

The impurity elements to be used include, as P-type impurities, elements in Group 1II A of the periodic table, such as B, AI, Ga,
Preferred examples include In, TI, etc., and examples of n-type impurities include elements of group V A of the periodic table, such as N, P,
Preferred examples include As, Sb, Bi, etc.
Especially B, Ga.

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

As a compound containing such an impurity element as a component, select a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under the conditions for forming a deposited film, and that can be easily vaporized using an appropriate vaporizing device. Preferred examples of such compounds include PH3°P2H4, PF3, PF6. PC
l3゜AsH3, AgF2. AsF5°, AsC13,
SbH3,5bF=,,5IH3,BF3,BC13,
BBr3, B2 Hb, Ba Hf o, BSHI
, BSHI l , B&HIO.

B6H12, AlCl3, etc. can be mentioned. The compounds containing impurity elements may be used alone or in combination of two or more.

In order to introduce a compound containing an impurity element into the film forming space, it can be mixed with the oxygen compound etc. in advance, or it can be introduced individually from multiple independent gas supply sources. be able to.

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 configuration of a typical photoconductive member obtained by the present invention.

The photoconductive member 10 shown in FIG.
2 and a photosensitive layer 13.

The support if may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, A1. Cr, Mo, Au, Ir, Nb, Ta
, V, Ti, Pt, Pd, or alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, celipropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. Ru. 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.

A1, Cr, Mo, Au, Ir, Nb, Ta, V, T
i, Pt, Pd, I n203 , S n 02 .

If it is conductive treated by providing a thin film such as ITO (In203 +5n02), or if it is a synthetic resin film such as polyester film, NiCr, At
, Ag, Pb, Zn, Ni, Au.

The surface is treated with a metal such as Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc. by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, to make the surface conductive. The shape of the support body is cylindrical,
It can be of any shape, such as a belt or a plate, depending on your needs.
The shape is determined, but for example, if the photoconductive member 1Ot in FIG. desirable.

For example, the intermediate layer 12 includes a photosensitive layer 13 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 1, for example, hydrogen (H) as required.
and/or amorphous silicon (hereinafter referred to as a-S i
It is composed of (H,X,O) and Et, and is a substance that controls electrical conductivity.

For example, a p-type impurity such as B or a p-type impurity such as P is contained.

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 to 5X10' atomic cppm, more preferably 0.5 to 1X10' atomic ppm, optimally 1 to 5X103 atomic PPm.

When forming the intermediate layer 12, it can be performed continuously up to the formation of the photosensitive layer 13. In that case, active species generated in the decomposition space, gaseous oxygen compounds, hydrogen, halogen compounds, inert gases, silicon compounds, carbon compounds, germanium compounds as necessary are used as raw materials for forming the intermediate layer. , and a compound gas containing an impurity element as a component are separately introduced into the film forming space where the support 11 is installed, and by using discharge energy, the intermediate layer 12 is formed on the support 11. Just let it form.

A compound containing silicon and halogen that is introduced into the decomposition space to generate active species when forming the intermediate layer 12 easily generates active species such as S L F2 at high temperatures.

The thickness of the intermediate layer 12 is preferably 30A to top, more preferably 40A to 8, and most preferably 50A to 5#L.

The photosensitive i13 has, for example, an a-5i (H,

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

Photosensitive, e13 is non-doped a-3t (H.

X) However, if desired, the intermediate layer 12 may contain a substance that controls conduction characteristics of a polarity different from the polarity of the substance that controls conduction characteristics (for example, n-type), Alternatively, a substance that controls conduction characteristics of the same polarity may be 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 formation of the photosensitive layer 13, as in the case of the intermediate N12, a compound containing silicon and halogen is introduced into the decomposition space, and by decomposing these at high temperature, active species are generated and introduced into the film forming space. Ru. Separately, a gas of a gaseous silicon compound and, if necessary, a compound containing hydrogen, a halogen compound, an inert gas, a carbon compound, a germanium compound, an impurity element, etc., is applied to the support 11. The intermediate layer 12 may be formed on the support 11 by introducing it into a predetermined film forming space and using discharge energy.

In addition to this example, the method of the present invention is also suitable for forming 5i02 insulator films by CVD, partially oxidized 5illIll, etc. that constitute semiconductor devices such as ICs, transistors, diodes, and photoelectric conversion elements. Furthermore, by controlling the timing, amount, etc. of introducing an oxygen compound into the film-forming space, it is possible to form a Si film having an oxygen concentration distribution in the layer thickness direction. Alternatively, by appropriately combining silicon compounds, germanium compounds, carbon compounds, etc. in addition to oxygen compounds as necessary, a body with desired characteristics whose constitutional unit is a bond between 0 and these St, Ge, C, etc. is formed. It is also possible.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Fig. 2, i
type, p-type, and n-type oxygen-containing amorphous deposited films were formed.

In FIG. 2, 101 is a deposition chamber, and a desired substrate 103 is placed on a substrate support 102 inside.

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 105 and generates heat. Although the substrate temperature is not particularly limited, in carrying out the method of the present invention, preferably 5
The temperature is preferably 0 to 150°C, more preferably 100 to 150°C.

106 to 109 are gas supply sources, oxygen compounds,
and hydrogen, a halogen compound, an inert gas, a silicon compound, a carbon compound, a germanium compound, a compound containing an impurity element, etc., which are used as necessary. When using liquid raw material compounds, use an appropriate vaporizer! Gas supply source 1 in figure 0 to be provided
06 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 or e for The valves are for adjusting the flow rate of each gas. 11O is a gas introduction pipe to the film forming space, and ill is a gas pressure gauge. In the figure, 112 is a decomposition space, 113 is an electric furnace, 114 is a solid Si particle,
Reference numeral 5 denotes an introduction pipe for a compound containing gaseous silicon and halogen, which serves as a raw material for active species, and the active species generated in the decomposition space 112 are introduced into the film forming space lot via the introduction pipe 116.

Reference numeral 117 denotes a discharge energy generating device, which includes a matching point, a box 117a, and a cathode electrode 1178 for introducing high frequency.
It is equipped with b.

The discharge energy from the discharge energy generator 117 is applied to the raw material gas etc. flowing in the direction of the arrow 119, and excites the f & film raw material gas etc. and causes them to react, thereby producing an oxygen-containing amorphous material on the entire substrate 103 or a desired portion. Form a deposited film.

Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

First, a polyethylene terephthalate film substrate 103
on the support stand 102! IL, evacuate the inside of the deposition space 101 using an exhaust device, and 10-'T.

The pressure was reduced to rr. 02 (diluted to 10vO1% with He) using the gas supply source 106 at the substrate temperature shown in Table 1.
150secM, or this and PH3 gas or B2H
, gas (all diluted with 11000pp hydrogen gas) 405C
A gas mixed with CM was introduced into the deposition space.

Further, the decomposition space 102 is filled with solid 5ial 14, heated in an electric furnace 113 and kept at 1100°C to melt Si, and by blowing SiFa into it from a cylinder through the SiF4 introduction pipe 115, 5sF2 is heated. Active species are generated and passed through the introduction pipe 116 to the as space i o
Introduction to i.

While maintaining the atmospheric pressure in the film forming space lot at 0.1 Torr,
Discharge equipment! Plasma was applied from 1117 to form a non-doped or doped oxygen-containing amorphous deposit s (film thickness 700A). Film formation speed is 35 A
/sec.

Next, each of the obtained non-doped or p-type samples was placed in a vapor deposition tank, and a comb-shaped A1 gap electrode (length 250 l, width 5 cm) was formed at a vacuum degree of 10-5 Torr, and then a voltage was applied. Each sample was evaluated by measuring the dark current at a voltage of lO■ and determining the dark conductivity σ.

The results are shown in Table 1.

Examples 2 to 4 02 (diluted to 1Ovo1% with He) and Si2H6.
The usage ratio of each of Ge2 H6 and C2H6 is l:
The same oxygen-containing amorphous deposited film as in Example 1 was formed except that the oxygen-containing amorphous deposited film was introduced into the film forming space in step 9. Measure the dark conductivity,
The results are shown in Table 1.

Table 1 shows that according to the present invention, an oxygen-containing amorphous deposited film with excellent electrical properties and sufficient doping can be obtained even at low substrate temperatures.

Examples 5 to 8 Instead of 02, H3S iO5iH3, H3Ge0Ge
H3: The same oxygen-containing amorphous deposited film as in Example 1 was formed except that CO2 or OF2 was used.

The oxygen-containing amorphous deposited film thus obtained is 1! The deposited film had excellent chemical properties and was sufficiently doped.

Example 9 Using the device shown in Figure 3, H1 was obtained by the following operations.
As shown in the figure! A drum-shaped electrophotographic image forming member having an I-film configuration was prepared.

In FIG. 3, 201 is a film forming space, 202 is a decomposition space, 203 is an electric furnace, 204 is a solid Si particle, 205 is an active species raw material introduction pipe, 206 is an active species introduction pipe, 207 is a motor, and 208 is a Heating heater, 209 is a blowing pipe, 210 is a blowing pipe, 211 is an Al cylinder, 21
2 indicates an exhaust valve. Also, 213 to 216
1 is a raw material gas supply source similar to lO6 to 109 in FIG. 1, and 217 is a gas introduction pipe.

An Al cylinder 211 is suspended in the film forming space 201, and a heater 208 is provided inside the cylinder so that it can be rotated by a motor 207. 218.218@... is a discharge energy generator, and the matching box 21
8a, a cathode electrode 218b for high frequency introduction, and the like.

In addition, solid S4 grains 204 are packed in one decomposition chamber 202, heated in an electric furnace 203, kept at 100°C, melted Si, and injected SiF4 from a cylinder into it to generate active species of 5IF2. Through the introduction pipe 206,
It is introduced into the film forming space 201.

On the other hand, 5j2H6 and H2 are introduced into the film forming space 2 from the introduction pipe 217.
01 will be introduced. The atmospheric pressure in the film forming space 201 is 1,
Plasma is applied from the discharge device 21B while maintaining OTorr.

The At cylinder 211 is heated and maintained at 280°C by the heater 208 and rotated, and the exhaust gas is passed through the exhaust valve 2.
Exhaust through 12. In this way, the photosensitive layer 13 is formed.

Further, in the intermediate [12], prior to the photosensitive layer, S i2 H6,02 (Si2 H6:O□=l:1
O-), He and B2H6 (volume %-C'B2H& is 0
．． A mixed gas of 2%) was introduced to form a film with a thickness of 2000 Å.

Comparative Example 1 SiF and Si2
Film formation space 2 in Figure 4 from H6, 02, He and B2H6
01 was equipped with a 13.56 MHz high frequency device, and a drum-shaped electrophotographic image forming member having the same layer structure was formed.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image forming members obtained in Example 9 and Comparative Example 1.

〔Effect of the invention〕

According to the Al 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 at a low substrate temperature. 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 post-production. can do. Furthermore, the film can be formed even on a substrate with poor heat resistance, 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 and Fig. 2 are schematic diagrams for explaining the configuration of an apparatus for carrying out the method of the present invention used in Examples. 10... Image forming member for electrophotography, 11...
- Substrate, 12... intermediate layer. 13...Fist photosensitive layer, iol, 201Φas film formation space, Ill, 202.9.decomposition space, 106.107,108,109°213. 214, 215, 216. ...Gas supply source, 103.21L---Substrate, 117.218...Discharge energy generating device.

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, active species generated by decomposing a compound containing silicon and halogen and an oxygen compound that chemically interacts with the active species are separated. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing an oxygen compound into the substrate and applying discharge energy to the oxygen compound to excite the oxygen compound and cause it to react.