JPS61108122A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To obtain a film having excellent characteristics by a method wherein an activating seed which is grown by decomposing a compound containing silicon and halogen and an oxygen compound which chemically interacts with said activating seed are introduced separately into the film forming space where a deposited film is formed on a substrate, and an excitation-reaction is performed on the compound by the irradiation of photo energy. CONSTITUTION:A substrate retaining stand 102 having a built-in heating heater 104 is placed in a deposition chamber 101, a film substrate 103 such as polyethylene terephthalate and the like is placed thereon, the deposition chamber 101 is decompressed, and the substrate 103 is heated up to 100-105 deg.C. Then, mixed gas is fed into the deposition chamber 101 from gas supply sources 106-109 using a gas introducing pipe 110, and at the same time, solid-state Si grains 114 fused by an electric furnace and the activating seed of SiF4 blown into the deposition chamber 101 are fed into the deposition chamber 101 using an introducing pipe 116. Subsequently,s a beam of light emitted from the photo energy generating device 117 such as a mercury lamp is made to irradiate on the substrate 103, and an oxygen-containing amorphous film of I type, P type, N type and the like is deposited on the substrate 103.

Description

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

[Prior art]

For example, attempts have been made to form an amorphous silicon film using vacuum evaporation, plasma CVD, C'VD, reactive sputtering, ion plating, photo-CVD, etc.; generally, plasma CVD is Laws are widely used and corporatized.

The material (deposited material composed of amorphous silicon) is characterized by its electrical and optical properties, fatigue properties due to repeated use and use environment properties, as well as productivity and mass production, including uniformity and reproducibility. There is room for further improvement of the overall characteristics.

The reaction process in forming an amorphous silicon deposited film by the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. In addition, there are many formation parameters for the deposited film (for example, substrate temperature, flow rate of introduced gas, ratio, pressure during formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, plasma generation method, etc.) ) Due to the combination of these many parameters, the plasma sometimes becomes unstable, often having a significant adverse effect on the deposited film formed. Moreover,
The actual situation is that parameters unique to each device must be selected for each device, and therefore it is difficult to generalize 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.

However, 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 are also complex, the management tolerance is narrow, and equipment adjustments are delicate. For these reasons, these have been pointed out as problems 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. The same can be said of other functional films, such as silicon nitride films, silicon carbide films, and silicon liquefied films.

The present invention eliminates the drawbacks of the dual plasma CVD method and provides a new deposited film formation method that does not rely on conventional formation 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 uniform in quality, while also being suitable for large-area films, improving film productivity, and mass production. An object of the present invention is to provide a method for forming a deposited film that can easily achieve the following.

The above purpose is to introduce active species generated by decomposing a compound containing silicon and halogen into the formation space for forming a deposited film on a substrate, and oxygen that chemically interacts with the active species. This is achieved by the deposited film forming method of the present invention, which is characterized in that a deposited film is formed on the substrate by introducing the oxygen compounds separately and irradiating them with light energy to excite the oxygen compounds and cause them to react. be done.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film-forming space for forming a deposited film, light energy is used to excite and react oxygen compounds, so the deposited film that is formed is not affected by etching or other processes such as etching. There is virtually no adverse effect due to abnormal discharge action.

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 the raw material that has reached the vicinity of the substrate, but if optical energy is used, the entire substrate is irradiated using an appropriate optical system to form a deposited film. Alternatively, it is possible to selectively control and irradiate only the desired area to form a partially deposited film, or use a resist etc. to irradiate only a predetermined graphic area to form a deposited film. It is advantageously used because it has the convenience of being able to be formed.

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 rate 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 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. Refers to something that has a stimulating effect. Therefore, the active species may contain constituent elements constituting 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 any constituent elements constituting the deposited film and can simply serve as a raw material for film formation. Alternatively, an oxygen compound that can be a raw material for forming these deposited films and an oxygen compound that can be a raw material for film formation may be used together.

It is preferable that the oxygen compound used in the present invention is already in a gaseous state before being introduced into the film forming space, or is introduced in a gaseous state. For example, when using liquid and solid compounds, the compound can be vaporized by connecting an appropriate vaporizer to the compound supply source and then introduced into the film forming space.

Oxygen compounds include oxygen (02) and ozone (03)
Examples include simple oxygen such as, and compounds having oxygen and one or more atoms other than oxygen as constituent atoms. Examples of atoms other than oxygen include hydrogen (H) and halogen (X=
F, C1, B r or engineering), sulfur (S), carbon (C)
, silicon (Si), germanium (Ge), phosphorus (P)
, boron (B), alkali metals, alkaline earth metals, transition metals, etc. In addition, atoms of elements belonging to each group of the periodic table that can be combined with oxygen can be used.

Incidentally, for example, compounds containing 0 and H include F20,
Compounds containing 0 and X, such as H2O2, include HXO, H
X04 etc. (la element acid resistant compounds or x20, X207 etc. oxides, compounds containing 0 and S include H2SO2, H
Examples of acids such as 2SO4 and oxides such as SO2 and SO3, and compounds containing O and C include acids such as H2O03 and CO,
Compounds containing O and St, such as oxides such as CO2, include:
Compounds containing O and Ge, such as siloxanes such as disiloxane (H3S iO3iH3) and trisiloxane (H3S i O3iH70S iH3), include Ge oxides, hydroxides, germanic acids, H3GeOGe
Organic germanium compounds such as H3, H3Ge0GeH20-GeH3, and compounds containing 0 and P include H3PO
3. Acids such as H3PO4 and oxides such as P2O3 and P2O5; compounds containing O and B include acids such as H3PO3 and oxides such as B2O2; however, the oxygen compounds used in the present invention are but not limited to.

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 introduced into the film forming space from the decomposition space has a lifespan 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, SiY
(u is an integer of 1 or more u 2u+2, Y is F, C1, Br or I), Si Y 2v (V is an integer of 3 or more, Y has the above meaning .) Cyclic silicon halide, Stx+y=2u or 2
It is u+2. ), and the like.

Specifically, for example, SiF4, (SiF2)3, (SiF
2)6, (SiF2)4. Si2 F6, Si3 Fe
, SiHF3. SiH2F2.5iC14 (SiC12
)5,5iBr, , (SiBr2)5.5i2C16
, 5i2C13F3 and the like, which are in a gaseous state or can be easily gasified.

In order to generate active species, in addition to the above-mentioned compounds containing silicon and halogen, a silicon compound such as a silicon carrier, hydrogen, or a halogen compound (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 the decomposition space, the discharge energy,
Excitation energies such as thermal energy, light energy, etc. are used.

Active species are generated by adding decomposition energy such as heat, light, and discharge to the above-mentioned materials in a decomposition space.

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, in addition to oxygen compounds, hydrogen gas, halogen compounds (for example, F2 gas, C
12 gas, gasified Br2, I2, etc.), an inert gas such as argon, neon, etc., and silicon compounds, carbon compounds, germanium compounds, etc. can also be introduced into the film forming space as raw materials for forming the deposited film. . 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 the chain and cyclic silane compounds are replaced with halogen atoms.

Specifically, for example, SiH4, S12H6, Si
3 H8, Si4 Hl. , S I5 H+ 2.5i
6H14$ SiH (p is an integer of 1 or more p2p+2, preferably 1 to 15, more preferably 1 to 1O), a linear silane compound, SiH3Si
H(SiH3)SiH3,5iH3SiH(SiH3)
Si3H7,Si2 H5SiH(SiH3)Si2
Si Hp 2p+2 (p has the above-mentioned meaning) such as Hs, a chain silane compound having a branch, and a part or all of the hydrogen atoms of these linear or branched chain silane compounds are replaced with halogen. Compounds substituted with atoms, 5i3H6, Si4 HB, 5i
SiH such as 5H1゜, 5i6H12 (q is 3 or more,
Preferably it is an integer of 3 to 2q6. ), 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,
As an example of a compound in which some or all of the hydrogen atoms of the silane compounds exemplified above are replaced with halogen atoms, SiH3
F, S 1H3C1, SiH3Br, SiH3I, etc. (7
) SiHS X (x is a halogen atom, r is 1 or more, preferably 1
−10, more preferably an integer from 3 to 7, s+t=2r+
2 or 2r. ) and halogen-substituted linear or cyclic silane compounds.

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

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, 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:
I), ethane (C2H6), propa7 (C3H8)
, n-butane (n-C4H1.), pentane (C3H
12), ethylene (C2H
71), propylene (C3H6), butene-1 (C4
H8), butene-2 (C4H8), inbutylene (
Examples of acetylene hydrocarbons include acetylene (C2I(2)), methylacetylene (C3HA), and butyne (C4H6).

In addition, as organosilicon compounds, (CH3)4S i, CH3S ic 13, (CH
3) 2 SiCl 2, (CH3): +SiCl
, organochlorosilane such as C2H5S i C13, CH3S i F2 Cl, CH3S i F
Cl2, (CH3) 2 S iFC1, C2H5S
1F2C1, C2H55iFC12, C3H75iF2
Organochlorofluorosilane such as C1, C3H7S i FC12, [(CH3):+Si]2, [(C3
Organodisilazane such as H7)3S'i]2 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, etc. are bonded to germanium can be used, such as 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, GeH4, Ge2H6, Ge3H
B, n G C4Hlo, ter't-Ge
,, H,O,Ge3 H6,Ges H,o,Ge
H3F, GeH3C1, GeH2F2, H6Ge6
F6, Ge (CH3)4, Ge
(C2H!,) 4, Ge (CF, Hs)
4, G, e (CH3)2 F2, G
Examples include eF2, GeF4, GeS, and the like.

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

It is also possible to dope the deposited film formed by the method of the invention with an impurity element.

As the impurity element to be used, as a p-type impurity, an element of Group 1II A of the periodic table, such as B, AI, Ga,
Preferred examples include In, T1, 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 characteristics.

As a compound containing such an impurity element as a component, it is preferable to select a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under deposited film forming conditions, and that can be easily vaporized using an appropriate vaporizing device. . Such compounds include PH3, P, H4, PF3, PF5, PCl
3, AsH3, AsF3. AsFc, AsCl3,S
bH3, S bF5 , S iH3, BF3, BC1
3, B]3r3. B2 H6, B4H, o, B5H9・
B5H,,・B6 I(1o・B6H12, AlCl3
etc. can be mentioned. Compounds containing impurity elements are
One type may be used or two or more types may be used in combination.

In order to introduce a compound containing an impurity element as a component into the film forming space, it is necessary to mix it with the above-mentioned butyric compound etc. in advance, or introduce these raw material gases individually from multiple independent gas supply sources. can do.

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. 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.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, steer L/S, Al, Cr, Mo, Au, Ir, Nb, T
Examples include metals such as a, V, Ti, Pt, and 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 subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface may be NiCr, AI, or C.
r, Mo, Au, I r, Nb, Ta, V, Ti, Pt
, Pd, In703.5n07, I To (I n2
03 +S n02 ), or a synthetic resin film such as a polyester film, N1cr, A1. Ag, Pb,
Zn, Ni, Au, Cr, MOI r, Nb, Ta,
Vacuum evaporation, electron beam evaporation, etc. of metals such as V, Ti, and Pt.
The surface is made conductive by sputtering or by laminating with the metal. 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, 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, for example, amorphous silicon (hereinafter a-5i (H
, X, O). ), and contains, for example, a p-type impurity such as B or a p-type impurity such as P as a substance that controls electrical conductivity.

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 5X104ato omi cppm, more preferably 0.5 to IX11X104ato ppm, optimally 1 to 5*103103ato 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 gas of a compound containing an impurity element as a component are introduced into a film forming space in which a support 11 is installed on each side, and by using light energy, an intermediate layer 12 is formed on the support 11. All you have to do is form it.

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 5iF- at high temperatures.

The layer thickness of the intermediate layer 12 is preferably 30A to 10IL,
More preferably, it is 40A to 8, and most preferably 50A to 5#.

The photosensitive layer 13 has, for example, an a-3i (H,

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

The photosensitive layer 13 is made of non-doped a-3i (H.

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

In the formation of the photosensitive layer 13, similarly to the case of the intermediate layer 12, 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. be done. 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 light energy.

In addition to this example, the method of the present invention can also be used to form a 5i02 insulator film 1 partially oxidized Si film, etc. by the CVD method that constitutes semiconductor devices such as ICs, transistors, diodes, and photoelectric conversion elements. For example, by controlling the timing and amount of introduction of oxygen compounds into the film-forming space, Si can be formed with an oxygen concentration distribution in the layer thickness direction.
A film can be formed. Alternatively, in addition to the oxygen compound, silicon compounds, germanium compounds, carbon compounds, etc. may be appropriately combined as necessary.

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
0 to 150'C1, preferably 100 to 150'C
! It is desirable that

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, an appropriate vaporization device is provided. Gas supply source 1 in the diagram
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. 110 is a gas introduction pipe into the film forming space, and 111 is a gas pressure gauge. In the figure, 112 is a decomposition space, 113 is an electric furnace, 114 is a solid Si particle, and 11
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 101 via the introduction pipe 116.

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

Light 118 is directed from a light energy generating device 117 onto the entire substrate or a desired portion of the substrate using a suitable optical system.
is irradiated with a raw material gas flowing in the direction of arrow 119 to excite the film forming raw material gas and cause it to react, thereby forming an oxygen-containing amorphous deposited film on the entire substrate 103 or on a desired portion. Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

First step, polyethylene terephthalate film substrate 103
was placed on the support table 102, and the inside of the deposition space 101 was evacuated using an exhaust device for 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.
1503CCM or this and PH3 gas or B2H
Mogas (all diluted with 11000pp hydrogen gas) 403C
A gas mixed with CM was introduced into the deposition space.

Further, the decomposition space 102 is filled with solid Si particles 114, heated in an electric furnace 113, kept at 1100'C to melt the Si, and then SiF4 is blown therein from a cylinder through the SiF4 introduction pipe 115. Accordingly, SiF2'
active species are generated, and are passed through the introduction pipe 116 to the film forming space 1.
Introduced to 01.

While maintaining the atmospheric pressure in the film forming space 101 at 0 and ITorr, the substrate was irradiated perpendicularly from a 1KWXe lamp to form a non-doped or doped oxygen-containing amorphous deposited film (film thickness 7001). The film formation speed is 3
It was 5 A/'sec.

Next, each of the obtained non-doped or p-type samples was placed in a vapor deposition tank and a comb-shaped AI gap electrode (length 250K, width 5mm) was formed at a vacuum degree of 105 Torr.
Each sample was evaluated by measuring the dark current at an applied voltage of 10 V and determining the dark conductivity σ.

The results are shown in Table 1.

Examples 2 to 4 02 (diluted to 10vol% with He) and 5i2H (
The same oxygen-containing amorphous deposited film as in Example 1 was formed, except that Ge7 H6 and C2Hr were introduced into the film forming space at a ratio of 1:9. The dark conductivity was measured and the results are shown in Table 1.

Table 1 shows that according to the present invention, a phosphorus-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, B35iO3iH3, B3 GeoGe
The same oxygen-containing amorphous deposited film as in Example 1 was formed except that H3, CO2, or OF2 was used.

The oxygen-containing amorphous deposited film thus obtained had excellent electrical properties and was sufficiently doped.

Example 9 Using the apparatus shown in Fig. 3, the first
A drum-shaped electrophotographic image forming member having a membrane structure as shown in the figure 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 blowout pipe, 210 is a blowout pipe, 211 is an AI cylinder, 21
2 indicates an exhaust valve. Also, 213 to 216
1 is a raw material gas supply source similar to 106 to 109 in FIG. 1, and 217 is a gas introduction pipe.

An AI 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.sha. is a light energy generating device, and light 219 is irradiated toward a desired portion of the AI cylinder 211.

In addition, the decomposition space 202 is filled with solid Si particles 204, heated in an electric furnace 203, kept at 1100°C to melt the Si, and by blowing four SiF into it from a cylinder, active species of SiF2 are generated. It is generated and introduced into the film forming space 201 through the introduction pipe 206.

On the other hand, Si2H6 and B2 are introduced into the film forming space 2 through the introduction pipe 217.
01 will be introduced. The atmospheric pressure in the film forming space 201 is set to 1.0T.
Keeping it at orr, I K W X e 77'218
．． 218...E is irradiated with light perpendicularly to the circumferential surface of the Al cylinder 211.

AI cylinder 211 is 280' (! Heater 20
8, the exhaust gas is heated, held, and rotated, and exhaust gas is exhausted through the exhaust valve 212. In this way, the photosensitive layer 1
3 is formed.

Further, the intermediate layer 12 is injected with Si2 H6,02 (Si2 H6:02=1:1) from the introduction pipe 217 prior to the photosensitive layer.
0'), B2 and B2H6 (B2H6 in volume % is 0.2
%) of mixed gas was introduced, and a film was formed to a film thickness of 2,000 yen.

Comparative Example 1 S i F4 and S
i7 H6,02, He and B2 H6 $4 A 13.58 MHz high frequency device was installed in the film forming space 201 shown in the figure, 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 method for forming a deposited film of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the film to be formed are improved, and high-speed film formation is possible at a low substrate temperature. Also,
Improves reproducibility in film formation, enables improved quality and uniform film quality, and is advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. I can do it. Furthermore, since light energy is used as excitation energy, 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 the configuration of an apparatus for carrying out a schematic illustration method for explaining an example of the configuration of an electrophotographic image forming member manufactured using the method of the present invention. 10 ・ψ・ Image forming member for electrophotography, 11 ...
Substrate, 12... Intermediate layer, 13... Photosensitive layer, 101.201---Film forming space, 111.202...0 between decomposition chambers, 106.107, 108, 109° 213.214, 215, 216°...Gas supply source, 103.211---Substrate, 117.218... Light energy generator.

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 the oxygen compound into the substrate and irradiating the oxygen compound with light energy to excite the oxygen compound and cause it to react.