JPS61110423A - Formation of deposited film - Google Patents

Abstract

PURPOSE:To improve electrical, optical, photoconductive and mechanical characteristics of a film and realize high speed formation of film at a low substrate temperature by exciting and reacting deposited film forming materials using thermal energy at a film forming space for forming a deposited film. CONSTITUTION:The active seed produced by decomposing a compound including carbon and halogen and an oxygen compound which chemically reacts with such active seed are separately introduced into a film forming space. Thermal energy is applied to these starting materials in order to excite and react such active seed and oxygen compound. Thereby, a deposited film is formed on a substrate. For example, a polyethylenetelephtalate film substrate 103 is placed on a support base 102, the deposition space 101 is exhausted and O2 is supplied to the deposition space at the substrate temperature of about 280 deg.C. The deposition space 102 is filled with solid C grain 114. It is heated in order to melt C. Here, CF4 is blown and thereby active seed can be produced and it is then supplied to the film forming space 101. While pressure is kept at 0.1Torr and the film forming space 101 is kept at 250 deg.C, non-doped or doped amorphous deposited film including oxygen can be formed.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to oxygen-containing deposited films, especially functional films, especially semiconductor devices, photosensitive devices for electrophotography, line sensors for image input, ti! The present invention relates to a method suitable for forming an amorphous or crystalline oxygen-containing deposited film for use in devices and the like.

[Prior art]

For example, in the formation of amorphous silicon films.

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

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

Deposited films composed of Shoji et al. amorphous silicon have electrical and optical properties, fatigue properties due to 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 conventionally popular 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 formation parameters for the deposited film (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 becomes unstable at one point, often having a significant adverse effect on the deposits and films formed. Moreover, parameters unique to each device must be selected for each device, making it 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.
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 complicated, the tolerance for management is narrow, and the equipment is not well adjusted. Therefore, these issues have been pointed out as issues that should be improved in the future. On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to provide a deposited film with practically usable characteristics.

As mentioned above, it is strongly desired to develop a method for forming an amorphous silicon film that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity. 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 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 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 facilitating mass production. The object of the present invention is to provide a deposited film forming method that can be easily achieved.

The above purpose is to chemically interact with active species generated by decomposing compounds containing carbon and halogen in the film formation space for forming a deposited Mlt film on a substrate. The deposited film forming method of the present invention, characterized in that a deposit is formed on the substrate by separately introducing oxygen compounds and applying thermal energy to them to excite the oxygen compounds and cause them to react. achieved by.

[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 is practically no possibility of any other adverse effects such as abnormal discharge action.

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 using 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, if desired, 3
Light energy can be used in addition to thermal energy. The light energy can be applied to the entire substrate using an appropriate optical system, or it can be applied selectively to only desired parts, so that the formation position of the deposited film on the substrate and the The film thickness etc. can be easily controlled.

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 better than the conventional CVD method! & The film speed can be dramatically increased, and the substrate temperature during deposition film formation can be further lowered, making it possible to industrially produce large quantities of deposited films with stable film quality. Can be provided at low cost.

In addition, the active species in the present invention refers to the active species that chemically interacts with the oxygen compound or its excited decomposition product to impart energy or cause a chemical reaction, thereby forming the salt 8I.
It refers to something that has the effect of promoting the formation of a film. Therefore, the active species may include constituent elements that constitute the deposited film to be formed, or may contain such constituent elements. It is not necessary, and accordingly,
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 and can only 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.

The oxygen compound used in the present invention is preferably 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, Appropriate vaporization for compound source?
This can be done by connecting the cii to vaporize the compound and then introducing it into the film forming space.

Examples of oxygen compounds include simple oxygen such as oxygen (0□) and ozone (03), as well as one or two types of oxygen and atoms other than oxygen.
Compounds having more than one species as constituent atoms can be mentioned. Examples of atoms other than oxygen include hydrogen (H), halogen (X=F
, C1, B r 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.

Compounds containing O and X, such as H2O and H2o2, include H
Oxygen acids such as XO, HXO4, and X20, X2
Oxides such as 0 and compounds containing O and S include H
Acids such as 2SO4, H2SO, and so2. Oxides such as so3, compounds containing O and C include acids such as H2CO3, and oxides such as co and co□, and compounds containing O and St include disiloxane (H3SiO3iH3) and trisiloxane (H35iO3iH20SiH3). ) and other siloxanes, compounds containing 0 and Ge include Ge oxides, hydroxides, germanic acids, H3Ge0
Organic germanium compounds such as GeH3, H3Ge0GeH20-G e H3, and compounds containing 0 and P include:
Acids such as H3P 03 and H3P Oa and P2O3,
Oxides such as P2O5 and compounds containing 0 and B include:
Examples include acids such as H2BO3 and oxides such as B2O2, 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 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 carbon 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 hydrocarbon is replaced with /\ halogen atoms is used, and specifically, For example, Cux2u+2(
u is an integer of 1 or more, and X is F, CI, Br or I.

) chain halogenated carbon, CX (v is 3
or more 2v An integer of A, X has the above-mentioned meaning. ), a chain or cyclic compound represented by CHx (u and Xxy have the above-mentioned meanings, x+y=2u or 2u+2), and the like.

Specifically, for example, CF 4, (CF2)S, (CF2)
6, (CF2) 4, C2F&, C3Fe,
CHF3, CH2F2, CCla (C.

CI, )s, CBr4, (CBr2)s, czC1
6, C2Cl3F3, etc., which are in a gaseous state or can be easily gasified.

Furthermore, in the present invention, in addition to the active species generated by decomposing the compound containing carbon and /\logen, active species generated by decomposing the compound containing silicon and /\rogen are used in combination. can do. As the compound containing silicon and / An integer greater than or equal to 1, Y is F,
u 2u+2 C1, Br or ■. ) chain/alogenated silicon, St Y (v is an integer of 3 or more 2
v number, Y has the meaning given above. ) Cyclic silicon halide, Si HY (u and Y are u x
y TrlM(1) has meaning. x+y=2u or 2u+
It is 2. ), and the like.

Specifically, for example, SiF, (SiF,)s.

(S i F2 ) 6, (SiF2)a, 5t2F6
, Si3Fg, SiHF3. SiH2F2, Si
Cl 4 (S i Cl 2 ) 5. Si
B r 4, (SiBr2) 5.5i2C16°5i2C13F3 and the like 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 compounds containing carbon and halogen (and compounds containing silicon and halogen), other silicon compounds such as elemental silicon (and carbon compounds equivalent to elemental carbon) are added as necessary. , hydrogen, halogen compounds (
For example, F2 gas, C12 gas, gasified Br2. I2
etc.) can be used together.

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 applying decomposition energy such as heat, light, or 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
O:l to 1:10 (introduction flow rate ratio) is suitable.

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, and other inert gases; silicon compounds, carbon compounds, germanium compounds, and the like can also be introduced into the film-forming space as raw materials for forming the salt 8I 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.

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

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

Specifically, for example, SiH, Si2 H6,5i3
S i , H2, +2 (north of p'±1, preferably 1
-15, more preferably an integer of 1-10. ), a linear silane compound represented by SiH3SiH (SiH3
)SiH3,5iH3SiH(SiH3)Si3H7,
Si, F such as 5i2H5SiH (SiH3) Si2H5
2. +2 (p has the above-mentioned meaning) chain-like silane compounds having a branch, and compounds in which part or all of the hydrogen atoms of these straight-chain or branched chain-like silane compounds are replaced with halogen atoms. , Si3H6, Si4
HB, 5i5H1. , 5i6H, 2 etc.
(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 replaced with other cyclic silanyl groups and/or chain silanyl groups. Compounds substituted with
SiH
3F, S1H3C1, SiH3Br, SiH3I, etc. St HS X (X is a halogen atom, r is 1 or more, preferably 1
~lO1, preferably an integer from 3 to 7, S+t = 2
r+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. As a hydrocarbon, methane (CH3
), ethane (C2H & ), propane (C3He),
n-butane (n-C4H1゜), pentane (C5H+
2), ethylene (C
z Ha), propylene (C3H6), butene-
1 (CaHa), butene-2 (C4HIS),
Inbutylene (C,H8), pentene (C5HIO)
-Acetylene hydrocarbons include acetylene (C2H2
), methylacetylene (C3H4), butyne (C4H
etc.).

In addition, as organosilicon compounds, (CH3) 4 S t, CH3S iC
13, (CH3) 2 S t c 17
, (CHs): Organochlorosilane such as 5SiC1, C2H55iC13, CH35iF2 C1, CH
35iFci2, (CH3) 2 S i FC1,C
2H5S iF2 C1, C2H5SiFC12, C3
Organochlorofluorosilane such as H7SiF2 C1, C3H7S iFc 12, [(CH3)5 St
Organodisilazane such as C(C3Hy)sSilz and the like are preferably used.

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

Further, 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, such as GaH (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, 1, for example, GeH, Ge2 H6, Ge3H
t3. n Ge3Ht3. tert-Ge, H,...
Ge3H6, Ge5H1゜, GeH3F, GeH3C1
,GeH2F2,H6Ge6F6,Ge(CH
3)a,Ge(C2Hs)a,Ge(C6Hs
) a, Ge (CH3)2 F2 , GeF2 , GeFq,
Examples include GeS. 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.

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,
Examples of suitable n-type impurities include In, "jl, etc., and examples of n-type impurities include elements of group A of periodic table 1v, such as N,
Preferred examples include P, As, Sb, Bi, etc., especially B and Ga.

p, sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical characteristics.

Compounds containing such impurity elements as components must be in a gaseous state at room temperature and pressure, or at least in a sedimentary state.
Preferably, compounds are selected that are gaseous under the formation conditions and can be easily vaporized in a suitable vaporization device; such compounds include PH3, P2H, PF3. PF3. Pc
t, AsH3, AsF3, AsF5. AsC13,
SbH3, SbF5. SiH3, BF3, BCl3. B
Br3. B2Hb, E14HIO1B 5 H9・
BSHII・B 6 H5 0
, B 6 Hl 2 , A I C13, and the like. Even if one type of compound containing impurity elements is used, two
More than one species may be used in combination.

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.

Figure @1 is a schematic diagram for explaining a configuration example of a typical photoconductive member obtained by the present invention.

A photoconductive member 10 shown in FIG. 1 can be applied as an electrophotographic image forming member, and an intermediate fi
12. And photosensitive! It has a layer structure composed of J13.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include, for example.

NiCr, Steer L/S, A1. Cr, Mo, Au,
Ir, Nb, Ta, V, Ti,
Examples include metals such as 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, A1. C
r, Mo, Au, I r, Nb, Ta, V, Ti, Pt
, Pd, In2O3,5n02, ITO(I n7 o
3+5n02), etc., or if it is a synthetic resin film such as polyester film, N1cr, AI, Ag, Pb, Zn,
Ni, Au, Cr, Mo, Ir, Nb, Ta, ■, T
The surface is treated with a metal such as i, PL 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 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, middle! 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,
, 0) as a material that is composed of layers and 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, intermediate! B contained in fj l Z,
The content of the substance controlling conductivity such as P is preferably 0.001 to 5X10' atom cPPm
, more preferably 0.5 to lXl0'atomic p
pm, optimally 1-5X103 atomic ppm
It is desirable that this is done.

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 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 form.

Compounds containing carbon and halogen that are introduced into the decomposition space to generate active species when forming intermediate N12 easily generate active species such as CF2 at high temperatures.

The layer thickness of the intermediate layer 12 is preferably 30A to 1ouL,
The photosensitive layer 13 is more preferably 40A-8, most preferably 50A-5.
It has both a charge generation function of generating photocarriers by laser light irradiation and a charge transport function of transporting the charges.

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

Photosensitive @13 is non-doped a-3i (H.

X) If desired, a polarity other than the polarity of the substance that governs the conduction properties contained in the intermediate NIL2 (for example, n
It is also possible to contain a substance that controls the conduction properties of
Alternatively, the material that governs the conduction properties of the same polarity can be replaced with an intermediate N
If the actual amount contained in 12 is large, it may be contained in an amount much smaller than the dose.

In the formation of the photosensitive layer 13, similarly to the case of the intermediate layer 12, compounds containing carbon and halogen are introduced into the decomposition space, and active species are generated by decomposing these at high temperatures, which then enters the film formation space. be introduced. 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 method of the present invention can also be used to form 5i02 insulator films, partially oxidized Si films, etc. by the CVD method that constitute 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, by appropriately combining silicon compounds, germanium compounds, carbon compounds, etc. in addition to oxygen compounds, 0 and these Si
It is also possible to form a deposited film with desired characteristics in which the bond with , Ge, C, etc. is in the middle of the composition.

Specific examples of the present invention are shown below.

Example 1 As shown in Figure 2? I-type, p-type, and n-type oxygen-containing amorphous deposited films were formed using a carbon oxide film and the following operations.

In FIG. 2, lot 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, it is preferably 5 when carrying out the method of the present invention.
The temperature is preferably 0-150°C, more preferably 100-150°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, an appropriate vaporization device must be provided. Gas supply source 1 in Figure 0
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, 111 is a gas pressure gauge, 112 is a decomposition space, 113 is an electric furnace, 114 is 0 solid particles, 115
is an introduction pipe for a compound containing gaseous carbon 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 through the introduction pipe 116.

Reference numeral 117 denotes a thermal energy generating device, for example, an ordinary electric furnace, a high frequency heating device, various heating elements, etc. are used.

The heat from the thermal energy generator 117 is.

Acted on raw material gas etc. flowing in the direction of arrow 119,
The substrate 1 is formed by exciting and reacting gases, etc., which are the raw materials for film formation.
A film is formed on the oxygen-containing amorphous salt 1 over the entirety or a desired portion of 03. In addition, in the figure, 120 is an exhaust valve;
121 is an exhaust pipe. First, the polyethylene terephthalate film substrate 103 is placed on the support stand 102,
The inside of the deposition space 101 is evacuated using an exhaust device, and 10-"
The pressure was reduced to Torr. At the substrate temperatures shown in Table 1, the gas supply source 106 was used to generate 1Ov of Oy (He).

A mixture of 1503 CCM (diluted to 1%) or 40 SCCM of PH3 gas or B2H gas (all diluted to 11000 pp hydrogen gas) was introduced into the deposition space.

In addition, the decomposition space 102 is filled with solid zero particles 114, heated in the electric furnace 113 to melt C, and CF4 is blown therein from the cylinder through the CF introduction pipe 115, thereby generating active species of CF2. and introduced into the film forming space 101 through the introduction pipe 116.

r! While maintaining the atmospheric pressure in the tIIN space 101 at 0.1 Torr, the temperature inside the film forming space 101 is maintained at 250° C. by a thermal energy generator, and a non-dosed or doped oxygen-containing amorphous deposited film (18! 700 mm thick) is deposited.
A) was formed. The film formation rate was 35λ/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 cm, width 5 cm) was formed at a vacuum degree of 10'' Torr. , the dark current was measured at an applied voltage of 10 V, and the dark conduction σ
Each sample was evaluated by determining the

The results are shown in Table 1.

Examples 2-4 02 (diluted to 1Ovo1% with He) and Si2H6
, Ge2H6, and C2H& (7) were introduced into the film forming space at a ratio of 1:9, but the same oxygen-containing amorphous deposited film as in Example 1 was formed. The dark conductivity was measured and the results are shown in Table 1.

From Table 1IJ1, 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 5-8 Instead of o2, H3S iO5iH3, H3Ge0Ge
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 WIJ31N, a drum-shaped electrophotographic image forming member having a membrane structure as shown in FIG. 1 was prepared by the following operations.

In FIG. 3, 201 is a film forming space, 202 is a decomposition space, 203 is an electric furnace, 204 is solid Ca, 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 At cylinder, 212
indicates an exhaust valve. Further, 213 to 216 are raw material gas supply sources similar to 108 to 109 in FIG. 1, and 217 is a gas introduction pipe.

An At 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, ordinary electric furnaces, high frequency heating devices, various heating elements, etc. are used.

In addition, the decomposition space 202 is filled with solid 0 grains 204, heated in the electric furnace 203 to melt C, and CF is blown there from a cylinder to generate active species of C wood F2, and the introduction pipe 206 is Through.

It is introduced into the film forming space 201.

On the other hand, Si2H6 and H2 are introduced into the film forming space 2 through the introduction pipe 217.
01 will be introduced. ! The atmospheric pressure inside the membrane chamber 201 is 1.0T.
The inside of the film forming space 201 is maintained at 250° C. by a thermal energy generator while maintaining the temperature at 250° C.

A l Shi IJ 7der 211 is 280℃ Ni heater 2
08 to heat, hold and rotate the exhaust gas through the exhaust valve 212. In this way, the photosensitive layer 13 is formed.

Further, the intermediate layer 12 is supplied with S 12H6,02 (Si2Hb :02=1
: 10-5), He and B2H6 (capacity %i'B
A mixed gas containing 2H & 0.2%) was introduced, and the film thickness was 2000.
Comparative Example 1 CF, 5i2H &
, 02, He and B2H, to the film forming space 20 in FIG.
Example 1 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 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,
fIi? , H reproducibility is improved, it is possible to improve film quality and uniform S purchase, and it is advantageous for increasing the area of the film, improving the productivity of the film and making it easier to increase production. can be achieved. 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 carrying out a method for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 10... Image forming member for electrophotography, 11... Substrate, L2 - Intermediate layer, 13 First photosensitive layer, 101.201@... Film formation space, 111.202-... Decomposition space, 106.107,108,109°213.214,215,216. φ...Gas supply source, 103.211...Base 2 117.218.O.Thermal energy generator.

Claims (1)

[Claims] In a film formation space for forming a deposited film on a substrate, active species generated by decomposing a compound containing carbon 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 oxygen compound and applying thermal energy thereto to excite the oxygen compound and cause it to react.