JPS61110420A - 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 materials for forming the deposited film are excited to react by using a thermal energy in a film-forming space for forming a deposited film. CONSTITUTION:An active seed 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 a thermal energy is made to act 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 supporting board 102, a pressure inside a deposition space 101 is reduced, and O2 is introduced into the deposition space at a substrate temperature of about 280 deg.C. Meanwhile, solid Si particles 114 are packed in a dissolution space 102, and heated to melt down Si, SiF4 is blown thereinto and the active seed thus produced is introduced into the film-forming space 101. Then, an atmospheric pressure being maintained at 0.1Torr and the inside of the film-forming space 101 being kept at 250 deg.C, an oxygen-containing amorphous deposited film is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides oxygen-containing deposited films, particularly functional IQ
In particular, the present invention relates to a method suitable for forming an amorphous or crystalline oxygen-containing deposited film for use in semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, imaging devices, etc.

[Prior art]

For example, in the formation of an amorphous silicon film.

Vacuum deposition method, plasma CVD method. CVD method, reactive sputtering method, ion plating method.

Photo-CVD methods have been tried, and in general.

The plasma CVD method is widely used and commercialized.

Deposited films made of amorphous silicon from Shoji et al. have excellent electrical and optical properties, fatigue properties due to repeated use, use environment properties, and uniformity. Productivity including reproducibility,
in terms of productivity. There is still room for further improvement of the overall characteristics.

The reaction process for forming amorphous silicon deposited films by the conventionally popular plasma CVD method is considerably more complex than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. Also, that pile 1! i
There are many parameters for N formation (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.) and combinations of these many parameters. As a result, 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.

Depending on the application of the deposited film, Shoji et al. must satisfy the requirements of large area, uniform film thickness, and uniform film quality, and mass-produce with high reproducibility through high-speed film formation.
In the formation of an amorphous silicon deposited film by plasma CVD method.

A large amount of capital investment is required for mass production equipment, and the management items for mass production also become complicated, and the allowable management range becomes complicated.
This is because the adjustment of the equipment is delicate.

These have been pointed out as problems that should be improved in the future. On the other hand, in the conventional technology using the normal CVD method,
This method requires a high temperature, and a deposited film having properties suitable for "X" has not been obtained.

As mentioned above, there is a strong desire to develop a method for forming amorphous silicon/films that can be mass-produced using low-cost equipment while maintaining practical characteristics and uniformity. The same can be said of other functional films, such as silicon nitride films, rR silicon 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 deposited film 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 chemically interact with active species generated by decomposing a compound containing silicon and halogen in a film forming space for forming a deposited film on a substrate! ! The deposited film forming method of the present invention is characterized in that a deposited film is formed on the substrate by introducing each of the m-element compounds separately and applying thermal energy to them to excite and cause the m-element compounds to react. achieved by law.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film forming space for forming the deposited film, thermal energy is used to excite the raw material for forming the deposited film and cause it to react. There are virtually no other adverse effects such as abnormal discharge effects.

Further, according to the present invention, the atmospheric temperature of the film forming space.

By arbitrarily controlling the substrate temperature as desired, a more stable CVD method can be achieved.

In the present invention, the thermal energy for exciting and reacting the raw materials for forming a deposited film is applied to at least a portion of the film forming space close to the substrate or the entire film forming space, and there is no particular restriction on the heat source used. .

Conventionally known heating media such as heating by a heating element such as resistance heating, high frequency heating, etc. can be used. Alternatively, thermal energy converted from light energy can be used. Also, as desired.

Light energy can be used in addition to ripe energy. 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.

One of the differences between the method of the present invention and the conventional CVD method is that a space C or lower, which is different from the film forming space, is created in advance.

The method is to use activated species activated in the decomposition space (called decomposition 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 reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

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. Active species that have a stimulating effect may include constituent elements constituting the deposited film that is formed, or even if they do not contain such constituent elements. Also, 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 these deposited films and a combination of It may also be used in combination with an oxygen compound that can be used as 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) and ozone (03)
JII! Compounds that are constituent atoms are mentioned. As for atoms other than oxygen.

Hydrogen (H), halogen (X-F, C1, Br or engineering)
, sulfur (S), carbon* (C), silicon (Si), germanium (Ge), phosphorus (P).

Examples include 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.

By the way, for example, as a compound containing 0 and H.

As a compound containing 0 and X, such as H2O, H20□,
HX O, HX O4, etc., or X2O, X2
Oxides such as O, etc., and compounds containing O and S include H2
Acids such as 302, H2304 and so2. Oxides such as so3, compounds containing 0 and C (i H2co3, etc.)
Compounds containing 0 and Si, such as acids and oxides such as Co and CO2.

Examples of compounds containing 0 and Ge include siloxanes such as siloxane (H3S iO5i Hs) and siloxane (H3S iO5iH20SiH3).

Ge oxides, hydroxides, germanic acids, H3
Organic germanium compounds such as Ge0GeH3, H, Ge0GeH20-GeH3, and compounds containing 0 and P are suitable for use with acids such as H3PO3, H3PO4, and P2o3. P2o
Examples of oxides such as s, compounds containing 0 and B include H, B
Oxygen compounds used in the present invention include, but are not limited to, oxides such as O3 and B202kJ.

These oxygen compounds can be used from one company or from two.
You may use more than one species in combination.

In the present invention, the active particles from the decomposition space introduced into the film forming space have 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, the compound containing silicon and halogen introduced into the decomposition space is 1, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound are replaced with halogen atoms, and specifically 1 For example, SiY
(u is an integer of 1 or more LL 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, SiHY (u and Y have the above-mentioned meanings.

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

Specifically, for example, 5iFa, (SiFz)s.

(SiF2)6, (SiF2)4. Si2 F6, Si
3 FB, SiHF3. SiH2F2,
S i C1, (SiC12)1. 5iBra.

(SiBr2)5. Examples include those in a gaseous state or those that can be easily turned into scum, such as 5i2C16 and 5i2C13F3.

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.

Active species are generated by adding decomposition energy such as heat, light, and discharge to the above-mentioned materials in one 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 l
A ratio of 0:1 to 1:10 (4 person flow) 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.), argon, neon, or other inert gases, or 11[silicon compounds, carbon compounds, germanium compounds, etc. can also be introduced into the film-forming space as raw materials for forming a laminated film. When using a plurality 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 supply sources.

It can also be introduced into the film forming space.

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, 1, for example, SiH4, Si2H6゜5i3H
B, Si, Hl. ,5i5H1□.

A linear silane compound represented by 5i, H, and SiH (P is an integer of 1 or more p 2p+2 , preferably 1-15, more preferably 1-10).

SiH3SiH(SiH3)SiH3,5iH3SiH
(SiH3)Si3H7,5t2H5SiH(SiH3
) Si Hp 2P+2 (p has the above-mentioned meaning) such as Si2H5, a chain silane compound having a branch, and a part or all of the hydrogen atoms of these linear or branched chain silane compounds. Compound substituted with halogen atom, 5i3H6, Sja Hl3.5
A cyclic silane compound represented by SiH (q is an integer of 3 or more, preferably 3 to 2q6) such as i5H16, 5t6H12, etc., a part or all of the hydrogen atoms or children of the cyclic silane compound is replaced by another cyclic silane compound. Examples of compounds in which 21-substituted silanyl groups and/or chain silanyl groups, and compounds in which part or all of the hydrogen atoms of the silane compounds exemplified above are replaced with I\logen atoms, include Si
H3F, 5iH3C1, 5iHiBr, 5fH3I, etc. (
7) Si HS X (X is a halogen atom, r is 1 or more, preferably 1
~10. More preferably an integer from 3 to 7, 5+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, the hydrocarbon compounds include, for example, carbonaceous hydrocarbons having an f number of 1 to 5, ethylene hydrocarbons having a carbon number of 2 to 5, carbon, ? ! [2 to 4 acetylenic hydrocarbons, etc., specifically, saturated hydrogens include methane (CHI), eta7 (C2Hb), propa7 CCs Hs), n-buta7 (n-C4H1°),
Pentane (Cs H+ 2 ), ethylene (C2H4)-propylene CC3 as ethylene hydrocarbon
H & ), butene-1 (C, H8), butene-2 (Cm
Hs), inbutylene (C4H8), pentene (C5H+o), acetylene (C2H2), methylacetylene (03H4) as acetylene hydrocarbons.
), butin (clHb), and the like.

In addition, as organosilicon compounds, (CH3) 4 S i, CH3S iC13.

(CH3), 25iC12, (CH3)3 StC1,
Organochlorosilane such as C2HlS i C13,
CH3S i F2 Cl, CH3S j FC
l2, (CH3)25iFC1, C2H5SiF2 C
1, C2H5, 5iFC12, C3H? 5fF2C1
, C3H7S i F Cl 2″J?, orcanoglorfluorosilane, [(CHx)
C3H7)3si]z'V organodisilazane and the like are preferably used.

These carbon compounds may be used singly 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). , bx2a+2b or 2a), a chain or cyclic germanium hydride formed by 4<, a combination of this germanium hydride, and a part or all of the hydrogen atoms of the germanium hydride replaced with halogen atoms. Compounds, organic germanium compounds such as compounds in which some or all of the hydrogen atoms of germanium hydride are replaced with organic groups such as alkyl groups and aryl groups, and optionally halogen atoms; other germanium sulfides; Imide # can be mentioned.

Specifically, for example, G e H4, G e 2 H6,
Ge3H6, n-Ge, Hlo, tert-Ge, H
,0,Ge3H6,Ge5H1,,GeH3F,GeH
3C1, GeH2F2. HbGe6 F6 , Ge (
CH3)4, Ge (C2Hs)a, Ge (C&
H5) a.

Ge(CH3)2F2, GeF2, GeFa
.

Examples include GeS. These germanium compounds may be used alone or in combination of 244 or more.

It is also possible to dope the deposited JA film formed by the method of the invention with a pure element.

The impurity elements to be used include, as p-type impurities, elements 1 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 V MA of the periodic table, such as N, P, etc.
, As, Sb, Bi, etc. are mentioned as preferable ones, but B and Ga are particularly preferable.

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°F2 H4, PF3, PF5,
PC13.

AsH3, AsF3, AsF5, AsC1,,S
bH3, S bF5 , S iH3, BFs.

BCl3. BBr3. B2H6, BaHto.

B, H,・BSHII・B&HI O・H6H12,
A IC13:i can be mentioned. The number of compounds containing impurity elements may be 18 or two or more kinds may be used in combination.

In order to introduce a compound containing an impurity element as a component into the film forming space, it can be mixed with the above-mentioned alcoholic compound etc. in advance, or it can be introduced individually from multiple independent gas supply sources. can do.

Next, the present invention will be explained with reference to a typical example of an electrophotographic imaging member formed by an uninvented method.

FIG. 1 is a schematic diagram for explaining an example of the structure 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 either electrically conductive or electrically insulating; for example, one example of the conductive support is 1.

NiCr, steer 1. rs, A1. Cr, Mo.

Examples include metals such as Au, Ir, Nb, Ta, V, Ti, Pt, and Pd, and alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, borinytylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc., lamic 2 paper, etc. are usually used. Ru. Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another calendar 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,
Ti, Pt, Pd, In2O3,5n02.

I To (I nz O3+S noz) t of f
If it is conductive treated by providing 311Qt or a synthetic resin film such as polyester film,
N1cr, AI, Ag, Pb, Zn, Ni, Au.

The surface is treated with a metal such as Cr, Mo, Ir, Nb, Ta, V, Tf, Pt, etc. by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, so that the surface thereof is 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 needs. If used as a forming member, it is desirable to have an endless belt shape or a cylindrical shape in the case of continuous high-speed copying.

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 to move from the side of the photosensitive layer 13 to the side λ of the support 11. It has the function of allowing easy passage.

This intermediate layer 12 contains hydrogen (H) and/or halogen (X) and oxygen (0) as required.
Amorphous silicon (hereinafter referred to as a-5i (
It is composed of (denoted as H,

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

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

As for the content of substances that control conductivity, such as P.

Preferably, 0.001 to 5xlO' at mt c
ppm, more preferably o,s~txto'atomi
c PPm, optimally L~5X103atomic
It is desirable to set it as ppm.

Middle! When forming the photosensitive layer 12, the process can be continued until the photosensitive layer 13 is formed. In that case, active species generated between one decomposition chamber and a gaseous oxygen compound, hydrogen, a halogen compound, an inert gas, a silicon compound, an rR elementary compound, as necessary, are used as raw materials for forming the intermediate layer. germanium compound.

and a gas of a compound containing an impurity element as a component are separately introduced into the film forming space where the support 11 is installed, and by using thermal energy, the intermediate layer 12 is formed on the support 11. Just let it happen.

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 SiF2' at high temperatures.

The layer thickness of the intermediate layer weight 2 is preferably 30A to 10mm, more preferably 40A to 8mm, most preferably 50A to 5mm.

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

The layer thickness of photosensitive R13 is preferably 1 to 100 g.
, more preferably 1 to 80 JL, more preferably 2 to 50 JL.

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

X) FF, but if desired, it may have a polarity different from the polarity of the substance controlling the conduction characteristics contained in the intermediate layer 12 (for example, n
It is also possible to contain a substance that controls the conduction properties of
Alternatively, if the amount actually contained in the intermediate layer 12 is large, the substance controlling the conduction characteristics of the same polarity may be contained in a much smaller 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 thermal energy.

In addition to this example, the '& invention method can be applied to ICs, transistors, diodes, photoelectric transformers 41! ! It is suitable for forming a partially oxidized 5i02 insulating film 1 by CVD for forming a semiconductor device such as an element, and it is also suitable for controlling, for example, the timing and amount of introduction of an oxygen compound into the film-forming space. By controlling this, it is possible to form a Si film having an oxygen concentration distribution in the layer thickness direction. Alternatively, in addition to oxygen compounds, a silicon compound-germanium compound, a carbon compound, etc. may be appropriately combined as necessary to form a body with desired properties whose constituent units are bonds between 0 and these Si, Ge, C, etc. It is also possible.

Specific examples of the present invention are shown below.

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

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

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, it is preferably 5 when carrying out the method of the present invention.
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 a liquid raw material compound, use an appropriate vaporization device. In the figure, the gas supply sources 106 to 109 with an a attached are branch pipes, b
Flow meters are marked with .C are pressure gauges that measure the pressure on the high pressure side of each flow meter.D or e are marked with valves for adjusting the flow rate of each gas. 110 is a gas introduction pipe to the film forming space, and 111 is a gas pressure gauge.
2 is a decomposition space, 113 is an electric furnace, 114 is a solid Si particle,
Reference numeral 115 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 thermal energy generating device, for example, an ordinary electric furnace, a Takaoka wave heating device, various heating bodies, etc. are used.

The heat from the thermal energy generator 117 acts on the raw material gas etc. flowing in the direction of the arrow 119, and excites the film forming raw material gas etc. and causes it to react, thereby depositing oxygen-containing amorphous on the entire substrate 103 or a desired portion. Forms a film. Further, in FIG. 1, 120 is an exhaust valve, and 121 is an exhaust pipe.

First f, polyethylene terephthalate film substrate 103
was placed on the support stand 102 for tL, and the inside of the deposition space 101 was evacuated using an exhaust device, and then 10-'T.

The pressure was reduced to rr. 5@1 At the substrate temperature shown in the table, using the gas supply source 106,
%), or a mixture of this and 403 CCM of PH3 gas or B2H gas (all diluted with looOppm hydrogen gas) was introduced into the deposition space.

In addition, the decomposition space 102 is filled with solid S i rLl 14, heated by an electric furnace 113 and kept at 1100°C,
By melting Si and blowing SiF into it from a cylinder through the SiF 4 introduction pipe 115, 5 tons of SiF is melted.
Active species of F2' are generated and introduced into the film forming space 101 through the introduction pipe 116.

The atmospheric pressure in the film forming space lot is set to 0. While keeping it at ITorr,
The inside of the film forming space 101 is heated to 250 degrees by a thermal energy generator.
℃ to form a non-doped or doped oxygen-containing amorphous deposited film (thickness: 700 Å). The deposition rate was 35 A/Sec.

Next, each of the obtained non-doped or P-type samples was steamed with J4e! , and the degree of vacuum is 10-'T o r r
Texi-type AI gap electrode (length 250JL, width 5
After forming I), the dark current was measured with an applied voltage of 10 V,
Each sample was evaluated by determining the dark conductivity σ.

The results are shown in Table 1.

Examples 2-4 0, (diluted to 1Ovo1% with He) and Si2H6,G
Use ratio of e2 H6 and c2H, respectively, 1:9
The same oxygen-containing amorphous salt aH as in Example 1 was formed except that it was introduced into the film forming space. The dark conductivity was measured and the results are shown in Table 1.

From Table 1: According to the present invention, an amorphous deposited film containing fluorine and having excellent electrical properties and sufficient doping can be obtained even at a low substrate temperature.

Examples 5 to 8 Instead of 02, H35iO5iHx, H3Ge0GeH
3. The same oxygen-containing amorphous deposited film as in Example 1 was formed except that CO2 or OF 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 blow-off pipe, 210 is a blow-off pipe, 211 is an A1 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 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, . . . are thermal energy generating devices, for example, a normal electric furnace, a high frequency heating device, various heating bodies, etc. are used.

Further, solid Si particles 204 are packed in one decomposition chamber 202, heated in an electric furnace 203, kept at 1100°C to melt Si, and SiF is poured therein from a cylinder.

By blowing in, active species of SiF2' are generated and introduced into the film forming space 201 through the introduction pipe 206.

On the other hand, 5i2H, 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 l,
The inside of the film forming space 101 is maintained at 250° C. by a thermal energy generator while maintaining the temperature at OTor r.

The Al cylinder 211 is heated and maintained at 280°C by the heater 208 and rotated once, and the exhaust gas is passed through the exhaust valve 21.
Exhaust through 2. In this way, the photosensitive layer 13 is formed.

In addition, the intermediate layer 12, prior to the photosensitive layer, also receives 5i2H from the inlet pipe 217, and receives Oz (Si2H6:02=l:l
O″″’), He and B2H4 (capacity %TeB2H& is 0
．． A mixed gas of 2%) was introduced to form a film with a thickness of 2000 Å.

Comparative Example 1 5iFa and Si2
From H6, 02, He and B2H, film formation space 2 in Figure 4
01 was equipped with a 13.56 MHz high frequency device to form a drum-shaped electrophotographic image forming member having the same layer structure.

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 stacked MM 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. Also,
The reproducibility in film formation is improved, making it possible to improve WA quality and make the film uniform. It is also advantageous for increasing the area of the film, and easily achieves improvements in film productivity, rB, and aging. can do. Furthermore, since relatively low thermal energy can be used as excitation energy, effects such as being able to form a film even on a substrate with poor heat resistance and shortening the process through low-temperature treatment are exhibited.

[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... Image forming member for electrophotography, 11...
Base. 12... Intermediate layer, 13... Photosensitive layer. 101.201-- Film formation space. ILI, 202...decomposition space. 106.107, 108, 109° 213.214, 215, 216°... Gas supply source, 103.211... Substrate, 117.218... Thermal 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. By introducing the oxygen compounds into the oxygen compounds and applying thermal energy to them to excite the oxygen compounds and cause them to react,
A deposited film forming method characterized by forming a deposited film on the substrate.