JPH0722131B2 - Deposited film forming equipment - Google Patents

Description

TECHNICAL FIELD The present invention relates to a functional film, particularly a semiconductor device, a photosensitive device for electrophotography, an optical input sensor for an optical image input device, an imaging device, and a photovoltaic device. The present invention relates to an apparatus that is advantageous for forming a functional deposited film that is useful for electronic devices such as power devices.

[Conventional technology]

Conventionally, an amorphous or polycrystalline functional film such as a semiconductor film, an insulating film, a photoconductive film, a magnetic film, or a metal film is individually formed from the viewpoint of desired physical characteristics or intended use. The method has been adopted.

Vacuum deposition method, plasma CVD method, thermal CVD method
Method, photo CVD method, reactive sputtering method, ion plating method and the like have been tried, and in general, plasma CVD method is widely used and commercialized.

However, since the deposited film obtained by these methods for forming a deposited film is required to be applied to electronic devices and optoelectronic devices that require higher functions, electrical and optical characteristics and repeated use There is room for improvement in overall characteristics in terms of fatigue characteristics, use environment characteristics, and productivity and mass productivity including uniformity and reproducibility.

FIG. 3 shows an example of a conventional apparatus for forming a deposited film by the plasma CVD method. In the figure, 301 is a film forming chamber as a film forming space, and an internal substrate support base. 302
A desired substrate 303 is placed on top.

304 is a heater for heating the substrate, which is supplied with power through the conducting wire 305 to generate heat.

306 to 309 is a gas supply source, a silicon-containing compound,
It is provided according to the kind of gas of hydrogen, a halogen compound, an inert gas, and a compound containing an impurity element. When using a liquid form of these raw material compounds in the standard state, an appropriate vaporizer is provided. In the figure, reference numerals of gas supply sources 306 to 309 are a branch pipes, b is a flow meter, c is a pressure gauge for measuring the pressure on the high pressure side of each flow meter, d Alternatively, a valve denoted by e is a valve for adjusting each gas flow rate. The gas of the raw material compound is introduced into the film forming chamber 301 through the introduction pipe 310.

311 is a plasma generator, and the plasma generator 311
Plasma acts on the source gas flowing in the direction of the arrow to excite and decompose the acted compound, and the decomposed compound chemically reacts to form an amorphous deposited film on the substrate 303. is there. Reference numeral 312 is an exhaust valve, and 313 is an exhaust pipe, which is connected to an exhaust device (not shown) for evacuating the film forming space.

When a deposited film of, for example, a-Si: H is formed using such an apparatus, an appropriate substrate 303 is placed on the support 302, and an exhaust device (not shown) is used to form the film through an exhaust pipe. The inside of the film chamber 301 is exhausted and the pressure is reduced.

Then, if necessary, the substrate is heated, and a raw material gas such as SiH ₄ and Si ₂ H ₆ is introduced from the gas supply cylinder into the film formation chamber 301 through the gas introduction pipe 310, and the pressure inside the film formation chamber is set to a predetermined value. While maintaining the pressure, plasma is generated in the film forming chamber 301 by the plasma generator to form an a-Si: H film on the substrate 303.

By the way, conventional deposited films, for example, those obtained by the plasma CVD method are said to be rich in characteristics and satisfactorily tentatively satisfied, but even then, the electrical deposition required for the solid establishment of the product is required. , Optical and photoconductive characteristics, fatigue resistance after repeated use, points of use environment characteristics, points of stability and durability over time, and points of homogeneity as a whole. It is still in a state where there is still a solution.

The cause is not that the target deposited film can be obtained by a simple layer deposition operation, not to mention the materials used, but it requires a great deal of skill and ingenuity in the process operation during the process. .

Incidentally, for example, in the case of the so-called CVD method, so-called impurities are mixed after diluting the gas material, and then pyrolyzed at a high temperature of 500 to 650 ° C. Therefore, it is necessary to perform a precise process operation for forming a desired deposited film. Since control is required, the device becomes complicated and the cost is considerably high.
It is extremely difficult to constantly obtain a deposited film product having the above-mentioned desired properties by homogenizing it in such a place, and therefore, it is difficult to adopt it on an industrial scale.

Further, as described above, even the plasma CVD method, which is generally widely used as the optimum method, has some problems in process operation and also problems in capital investment. Regarding the process operation, the conditions are more complicated than the above-mentioned CVD method, and it is difficult to generalize it. That is, for example, the parameters of the interrelation between the substrate temperature, the flow rate and flow rate of the introduced gas, the pressure at the time of layer formation, the high frequency power, the electrode structure, the structure of the reaction vessel, the exhaust speed, and the plasma generation method are already many. There are other parameters, and there are other parameters as well. Therefore, in order to obtain a desired product, a strict selection of parameters is required, and the parameters are strictly selected. One of the constituent factors of the above, especially if it is a plasma and becomes unstable, the formed film is significantly adversely affected and cannot be realized as a product. As for the device, since the strict selection of parameters is required as described above, the structure naturally becomes complicated, and it is designed so that it can correspond to the individually selected parameters if the device scale and type change. Must.

For these reasons, the plasma CVD method has been regarded as the most suitable method so far, but from the above, if the desired deposited film is mass-produced, a large amount of equipment investment is required for the device. By the way, the process control items for mass production are many and complicated, the process control allowable range is narrow, and the device adjustment is delicate, so that there is a problem that the cost of the product is considerably high in the end. is there.

On the other hand, the above-mentioned various devices have been diversified, and element members therefor, that is, satisfying the requirements such as the above-described various characteristics in general, and corresponding to the application target and application,
And in some cases, it is a large area, and it is a social requirement that a stable deposited film product is constantly supplied at low cost, and a method to meet this requirement,
There are situations in which the development of devices is eagerly awaited.

[Object of the Invention]

The present invention solves the above-mentioned problems and solves the above-mentioned problems in a conventional device for forming a deposited film used in a photovoltaic device, a semiconductor device, a line sensor for image input, an imaging device, a photosensitive device for electrophotography, and the like. The purpose is to satisfy.

That is, the main object of the present invention is that electrical, optical, and photoconductive properties are substantially always stable without depending on almost any use environment, have excellent light fatigue resistance, and can be used repeatedly. Even if there is, it does not cause a deterioration phenomenon and has excellent durability,
It is an object of the present invention to provide a deposited film forming apparatus for forming a uniform and improved deposited film which has moisture resistance and does not cause a problem of residual potential.

Another object of the present invention is to improve the utilization efficiency of the raw material gas used while improving various characteristics of the film to be formed, film forming rate, reproducibility, and homogenization and homogenization of the film quality. It is an object of the present invention to provide a deposited film forming apparatus that is suitable for high efficiency and can easily achieve film productivity improvement and mass production.

[Constitution and effect of the invention]

The present inventor has conducted intensive studies to overcome the above-mentioned problems of the conventional apparatus and achieve the above-mentioned object, and as a result, a raw material that can be turned into a gaseous state for forming a deposited film and an oxidation to the raw material. A gaseous halogen-based oxidant having the property of acting,
Is introduced into the reaction space and brought into contact therewith to chemically generate a precursor in an excited state, and the precursor is used as a supply source of the deposited film constituent to form a desired deposited film on the substrate in the film forming space. We have found a device that can improve the gas utilization efficiency and can form a large area.

That is, the deposited film forming apparatus of the present invention introduces into the reaction space a raw material that can be made into a gaseous state for forming a deposited film and a gaseous halogen-based oxidizer having a property of oxidizing the raw material. To produce a plurality of precursors chemically including excited state precursors, and at least one of the precursors is used as a supply source of the deposited film constituent in the deposition space. In a deposited film forming apparatus for forming a deposited film thereon, an introduction pipe for the gaseous raw material and an introduction pipe for the gaseous halogen-based oxidant are arranged in a multi-concentric structure, and the introduction pipe group is provided. At least one of them is made of a porous tube, and an outer tube having at least one opening is arranged in the direction in which the substrate is arranged.

The introduction tube serving as the porous tube and the outer tube can be made of, for example, a metal material, a ceramic material, a resin material, a composite material, or the like.

〔Example〕

In order to enhance the reaction efficiency and utilization efficiency of gas, the shape of the gas introduction tube is an important factor in addition to the film forming factors such as the flow rate of the raw material and the halogen-based oxidant and the pressure in the reaction space.

For example, in the gas introduction tube having the structure shown in FIGS. 1 (a) and 1 (b), a structure having an Al porous tube 101 on the inner side, an Al outer tube 102 on the outer side, and an opening 103 may be used. For example, the diameter of the inner tube is preferably 0.1 to 50 mm, more preferably 0.2 to 30 mm.
mm, most preferably 0.3 to 20 mm. Similarly, the diameter of the outer tube is preferably 0.2 to 60 mm, more preferably 0.3 to 40 mm, and optimally 0.4 to 30 mm. The porosity to the surface area of the porous tube is preferably 10%
As described above, it is more preferable that the amount is 20% or more, and most preferably 30% or more.

The opening 103 provided in the outer tube has a circular shape, an elliptical shape, a polygonal shape, a slit shape, or the like, and is open in the direction in which at least one substrate is arranged, or is used for the inner tube. The same porous tube as described above may be used. The opening ratio with respect to the surface area of the opening is preferably 10% or more, more preferably 20% or more, and most preferably 30% or more.

The length of the gas introduction pipe used in the present invention is defined by the desired length of the substrate, but it can be used without any particular limitation.

FIG. 1 (a) is a side view when a gas introduction pipe and a cylindrical substrate are arranged, and FIG. 1 (b) is a top view. The substrate 104 can rotate about a rotation axis 107.

Further, it is desirable that the base 104 is arranged so as to fill the space around the gas introduction pipes 101, 102, for example, so that the shape connecting the rotating shafts 107 is a polygon, preferably a regular polygon.

In the present invention, when the material of the gas introducing pipe used is metal, stainless steel, Al, Cr, Mo, Au, Pt, Nb, Ta,
In the case of V, Ti, Fe, Pd, Ni-Cr resin, polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc., and in the case of ceramics, Al ₂ O ₂ , SiO ₂ , BeO, MgO, ZrO ₂ , SiC,
TiC, ZrC, BN, AlN, Si ₃ N _{4 and the} like can be mentioned. Preferably
Al and stainless steel are used in terms of workability and corrosion resistance.

For the purpose of improving the efficiency of film formation, a plurality of gas introduction tubes used in the present invention are arranged in the film formation space, and it is also achieved by arranging the substrate so as to surround them.

When the gas is introduced into the gas introduction pipe having the multiple concentric circle arrangement structure used in the present invention, even if the gases introduced into the inner pipe and the outer pipe are exchanged and introduced, they are essentially The quality of the obtained deposited film does not change.

Thus, the apparatus of the present invention has no opportunity to cause discharge in the film forming space, that is, the reaction chamber, and thus the deposited film formed is not adversely affected by ion damage or other abnormal discharge action. Never receive.

According to the deposited film forming apparatus of the present invention, energy saving as well as large area, film thickness uniformity, and film quality uniformity can be sufficiently satisfied to simplify management and mass production, and to be used as a mass production apparatus. It does not require a large capital investment, the management items for its mass production are clarified, the management allowance range is wide, and the adjustment of the device is easy.

In the deposited film forming apparatus of the present invention, the gaseous raw material used for forming the deposited film is an substance that undergoes an oxidative action upon contact with a gaseous halogen-based oxidant. It is appropriately selected according to the desired type, characteristics, application and the like. In the present invention, the above-mentioned gaseous raw material and gaseous halogen-based oxidant may be those that are gaseous when introduced and contacted,
In the usual case, it can be gas, liquid or solid.

When the raw material for forming the deposited film or the halogen-based oxidizer is a liquid or a solid, use a carrier gas such as Ar, He, N ₂ or H _{2 and} bubbling while adding heat if necessary. As a result, the raw material for forming the deposited film and the halogen-based oxidizing agent are introduced into the reaction space in a gaseous state.

At this time, the partial pressure and the mixing ratio of the gaseous raw material and the gaseous halogen-based oxidant are adjusted by adjusting the flow rate of the carrier gas or the vapor pressure of the raw material for forming the deposited film and the gaseous halogen-based oxidant. Is set.

As the raw material for forming the deposited film used in the present invention, for example, a linear chain deposited film such as a semiconductor or electrically insulating silicon deposited film or a germanium deposited film may be used in order to obtain a linear film. A chain-like or branched chain-like silane compound, a cyclic silane compound, a chain-like germanium compound and the like can be mentioned as effective ones.

Specifically, as a linear silane compound, SinH ₂ n ₊₂ (n
= 1,2,3,4,5,6,7,8), SiH ₃ SiH (SiH ₃ ) SiH ₂ SiH ₃ as the branched chain silane compound, and SinH ₂ n (n = Examples of the chain germane compound include GemH ₂ m ₊₂ (m = 1,2,3,4,5) and the like. In addition, tin hydride such as SnH ₄ can be cited as an effective raw material if, for example, a deposited film of tin is formed.

Of course, these raw material substances may be used alone or in combination of two or more.

The halogen-based oxidant used in the present invention is gasified when introduced into the reaction space, and is effective only by contact with a gaseous raw material for forming a deposited film which is simultaneously introduced into the reaction space. Has the property of oxidative action, such as F ₂ , Cl
Halogen gas such as ₂ , Br ₂ and I ₂ and nascent fluorine, chlorine, bromine and the like can be cited as effective ones.

These halogen-based oxidants are gaseous, and are introduced into the reaction space at a desired flow rate and supply pressure together with the gas of the raw material for forming the deposited film, and are mixed and collided with the raw material. By oxidizing the raw material, a plurality of precursors including excited precursors are efficiently generated. The excited state precursors and other precursors that are produced serve as a source of constituents of the deposited film, at least one of which is formed.

The generated precursor decomposes or reacts to become a precursor in another excited state or a precursor in another excited state, or releases energy as necessary but forms a film as it is. By touching the surface of the substrate arranged in the space, a deposited film having a three-dimensional network structure is formed when the substrate surface temperature is relatively low, and a crystalline deposited film is formed when the substrate surface temperature is high.

In the present invention, the deposited film forming process proceeds smoothly, and a film having high quality and desired physical properties can be formed. A combination, a mixing ratio of these, a pressure at the time of mixing, a flow rate, a film forming space internal pressure, a gas flow pattern, and a film forming temperature (base temperature and atmosphere temperature) are appropriately selected as desired. These film forming factors are organically related, and are not determined individually but are determined according to each other under mutual relation. In the present invention, the ratio of the amounts of the gaseous raw material substance for forming a deposited film and the gaseous halogen-based oxidant introduced into the reaction space is related to the film forming factors related to the above film forming factors. It is appropriately determined in accordance with the desired flow rate, but the introduction flow rate ratio is preferably 1/20 to 100/1, more preferably 1/5 to 50.
It is preferable to be set to / 1.

The pressure at the time of mixing when introduced into the reaction space is preferably higher in order to stochastically enhance the contact between the gaseous raw material and the gaseous halogen-based oxidant, but the reactivity is taken into consideration. Then, it is preferable to appropriately determine the optimum value as desired. The pressure at the time of mixing is determined as described above, but the pressure at the time of introducing each is preferably 1 × 10 6.
^-7 atm to 5 atm, more preferably 1 x 10 ^-6 atm to 2 atm.

The pressure in the film-forming space, that is, the pressure in the space where the substrate on which the film is to be formed is disposed, is the precursor (E) in the excited state generated in the reaction space and the precursor in some cases. The precursor (D) derived from the body (E) is appropriately set as desired so as to effectively contribute to film formation.

The internal pressure of the film formation space is the pressure introduced into the reaction space between the base material for forming a deposited film and the gaseous halogen-based oxidant when the film formation space is open and continuous with the reaction space. In relation to the flow rate and the flow rate, it is possible to make adjustments by adding, for example, differential exhaust or using a large exhaust device.

Alternatively, when the conductance of the connecting portion between the reaction space and the film formation space is small, an appropriate exhaust device is provided in the film formation space,
The pressure in the film forming space can be adjusted by controlling the exhaust amount of the apparatus.

Further, when the reaction space and the film formation space are integrated and the reaction position and the film formation position are spatially different from each other, differential evacuation as described above or a large size with sufficient evacuation capacity is performed. It suffices if an exhaust device is provided.

The pressure in the film formation space as described above is determined in relation to the introduction pressure of the gaseous raw material substance and gaseous halogen oxidizing agent introduced into the reaction space, preferably 0.001 Tor
r to 100 Torr, more preferably 0.01 Torr to 30 Torr, most preferably 0.05 to 10 Torr.

The substrate temperature (Ts) during film formation depends on the type of gas used and the number of types of deposited film to be formed and the required characteristics.
Although it is individually set as desired, it is preferably room temperature to 450 ° C., more preferably 5 to obtain an amorphous film.
The temperature is preferably 0 to 400 ° C. In particular, when forming a crystalline deposited film having better semiconductor properties and photoconductivity, the substrate temperature (Ts) is preferably 300 to 700 ° C.

As the ambient temperature (Tat) of the film forming space, the generated precursor (E) and the precursor (D) do not change into chemical species unsuitable for film formation, and the precursor (E) is efficiently generated. ) Is appropriately determined as desired in relation to the substrate temperature (Ts).

The substrate used in the present invention may be either conductive or electrically insulating as long as it is appropriately selected according to the intended use of the deposited film to be formed. As the conductive substrate, for example, NiCr, stainless steel, Al, Cr, Mo, A
Examples include metals such as u, Ir, Nb, Ta, V, Ti, Pt, and Pd, or alloys thereof.

As the electrically insulating substrate, a film or sheet of synthetic resin such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene or polyamide, glass, ceramic or the like is usually used. It is preferable that at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and another layer is provided on the surface subjected to the conductive treatment.

For example, if it is glass, its surface is NiCr, Al, Cr, Mo,
Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO
NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, in the case of a synthetic resin film such as a polyester film, which is conductively treated by providing a thin film such as (In ₂ O ₃ + SnO ₂ ),
A metal such as Ir, Nb, Ta, V, Ti, or Pt is treated by vacuum vapor deposition, electron beam vapor deposition, sputtering, or the like, or is laminated with the metal, and the surface thereof is subjected to a conductive treatment. The shape of the support may be any shape such as a cylindrical shape, a belt shape and a plate shape, and the shape is determined as desired.

The substrate is preferably selected from the above in consideration of the adhesion and reactivity between the substrate and the film. Furthermore, if the difference in thermal expansion between the two is large, a large amount of strain may occur in the film, and a good quality film may not be obtained. Therefore, select and use a substrate with a close difference in thermal expansion between the two. Is preferred.

Further, since the surface condition of the substrate is directly related to the structure (orientation) of the film and the generation of the conical structure, it is necessary to treat the surface of the substrate so that the film structure and the film structure can obtain desired characteristics. Is desirable. In order to increase the uniformity of film quality and film thickness, the substrate is
In addition to the use of the gas introduction pipe according to the present invention, movement such as rotation and vibration can be added in the film forming space.

Hereinafter, the deposition film forming apparatus of the present invention, according to the embodiment of the drawings,
As will be described in more detail, the deposited film forming apparatus of the present invention is not limited to this.

The deposited film forming apparatus shown in FIG. 2 is roughly divided into three parts: an apparatus main body, an exhaust system and a gas supply system.

A reaction space and a film formation space are provided in the apparatus body.

201 to 205 are cylinders filled with a gas used for film formation, 201a to 205a are gas supply pipes, respectively.
1b to 205b are mass flow controllers for adjusting the flow rate of gas from each cylinder, 201c to 205c are gas pressure gauges, 201d to 205d and 201e to 205e are valves, and 201f to 20b.
Reference numerals 5f are pressure gauges showing the pressure inside the corresponding gas cylinders.

Reference numeral 220 denotes a vacuum chamber, which is provided with a pipe for introducing gas at the bottom thereof, and which has a first gas introducing pipe 210 into which gas from the gas cylinders 101 and 102 is introduced and a second gas introducing pipe from gas cylinders 203 to 205. It has a gas introduction pipe 211 and is connected to an Al-made porous pipe 214 having an opening ratio of 50% and an outer pipe 215 having a slit-shaped opening.

The gas supply from the cylinder to each introduction pipe is performed by gas supply pipelines 222 and 223.

The arrangement of the gas introducing pipe and the cylindrical base 213 is the same as that shown in FIG. 1 (b).

The base 213 is rotated by a driving device 216 via a rotation shaft 217.

Each gas introduction pipe, each gas supply pipeline, and the vacuum chamber 220 are evacuated through a main vacuum valve 221 by a vacuum exhaust device (not shown).

In the case of the present invention, the distance between the substrate and the gas outlet of the gas inlet pipe depends on the type of deposited film formed and its desired properties,
The gas flow rate, the internal pressure of the vacuum chamber, etc. are taken into consideration to determine an appropriate state, but preferably several mm to 20 cm,
More preferably, it is desirable that the length is about 5 mm to 15 cm.

Reference numeral 212 denotes a heater for heating the substrate, which heats the substrate 213 to an appropriate temperature during film formation, preheats the substrate 213 before film formation, and further heats the film after film formation to anneal the film. Is.

Electric power is supplied to the substrate heater 212 via the lead wire 218.

Reference numeral 219 is a thermocouple for measuring the temperature of the substrate temperature (Ts).

Hereinafter, the present invention will be specifically described with reference to Examples.

Example 1 Using the film forming apparatus shown in FIG. 2, a deposited film was prepared by the method of the present invention as follows.

SiH ₄ gas filled in the cylinder 201 at a flow rate of 150 SCCM from the porous tube 214 through the gas introduction pipe 210, F ₂ gas filled in the cylinder 203 at a flow rate of 100 SCCM, He gas filled in the cylinder 204 The flow rate of 200 SCCM through the gas introduction pipe 211 through the outer tube 215 having a slit-shaped opening to the vacuum chamber 2
Introduced within 20.

At this time, the pressure inside the vacuum chamber 220 is controlled by the vacuum valve 221.
The opening and closing degree of was adjusted to 0.9 Torr. Eight quartz glass (φ80 mm × 250 mm) substrates were used, and the distance between the gas outlet 215 and the substrate was set to 3 cm. Pale white emission was strongly observed in the mixed region of SiH ₄ gas and F ₂ gas. Base temperature (Ts) is 250
It was set to ° C. When gas was flowed for 3 hours in this state, a Si: H: F film having a film thickness as shown in Table 1 was deposited on the substrate.

In addition, the unevenness of the film thickness of all eight films was within ± 5% in both the vertical and horizontal directions. The characteristics were almost uniform on the entire surface. It was confirmed by electron beam diffraction that the formed Si: H: F film was amorphous.

Al comb electrodes (gap length 200 μm) were vapor-deposited on these amorphous Si: H: F films to prepare samples for conductivity measurement. A voltage of 100 V was applied to each sample in a vacuum cryostat, the current was measured with a micro ammeter (YHP4140B), and the dark conductivity (σd) was obtained. Further, light having a wavelength of 600 nm and 0.3 mW / cm ² was irradiated to determine the photoconductivity (σp). Furthermore, the optical band gap (Egopt) was obtained from the absorption of light. The results are shown in Table 1.

The gas utilization efficiency was approximately 70%.

Example 2 Using the film forming apparatus shown in FIG. 2, an electrophotographic image forming member having the layer structure shown in FIG. 4 was produced on an Al cylinder substrate under the conditions shown in Table 2.

The SiH ₄ cylinder 201 of Example 1 was replaced with a Si ₂ H ₆ cylinder. diameter
Eight 80 mm Al cylinder substrates were installed in the vacuum chamber 220, the vacuum chamber was evacuated to 10 ⁻⁶ Torr, and the substrate 212 was heated to 280 ° C. by the heater 212 for heating the substrate.

Thereafter, a 300SCCM the Si ₂ H ₆ gas from the Si ₂ H ₆ gas cylinder 201, B ₂
From the H ₆ cylinder (diluted to 1000 ppm with He) 202, the B ₂ H ₆ / He mixed gas of 300 SCCM is introduced into the vacuum chamber 220 from the porous pipe 214 through the gas introduction pipe 210, and the F ₂ cylinder 203 to F _Two gases of 300 SCCM and He gas from the He cylinder 204 of 1000 SCCM were introduced into the vacuum chamber 220 through the gas introduction pipe 211. At that time, the vacuum valve 221 was adjusted so that the internal pressure of the vacuum chamber 220 was 0.8 Torr.

Si ₂ H ₆ thus introduced into the vacuum chamber 220,
A first layer was formed on a 3.0 μm Al cylinder substrate by chemically reacting F ₂ and B ₂ H ₆ .

After forming the first layer, the supply of the B ₂ H ₆ / He mixed gas to the vacuum chamber 220 was stopped, and the vacuum valve 221 was adjusted to set the internal pressure of the vacuum chamber 220 to 0.8 Torr. Then, a second layer having a thickness of 20.0 μm was formed. Shut off all gas and then purge the gas line well to remove B ₂ H ₆ cylinder 202
Was replaced with C ₂ H ₄ cylinder 202. After that, Si ₂ H ₆ , C ₂ H ₄ , F ₂ , and He gas were each added to 50 SCC in the same manner as the first layer formation.
M, 300SCCM, 200SCCM, 1000SCCM were introduced into the vacuum chamber 220 to form a third layer of 0.5 μm.

An electrophotographic image forming member was formed as described above. When the electrophotographic characteristics of this electrophotographic image forming member were measured, the charging ability was improved by 10% and the image defects were decreased by 30% as compared with the conventional image forming member.

[Effect] From the above detailed description and each example, according to the deposited film forming method of the present invention, it is possible to significantly improve the utilization efficiency of the raw material gas, save energy, and control the film quality. It is easy to obtain a deposited film having uniform physical properties over a large area. In addition, it has excellent productivity and mass productivity, high quality and electrical,
A film having excellent physical properties such as optical properties and semiconductor properties can be easily obtained.

[Brief description of drawings]

1 (a), (b), FIG. 2 and FIG. 3 are schematic schematic views of the film forming apparatus used in the examples of the present invention. FIG. 4 is a schematic explanatory view of an electrophotographic image forming member produced in an example of the present invention. 101 ... Porous tube, 102 ... Outer tube, 103 ... Outer tube opening, 1
04 …… substrate, 105, 106 …… gas flow, 107 …… rotating shaft,
201-205 ... Gas cylinder, 201a-205a ... Gas inlet pipe, 201b-205b ... Mass flow meter, 201c-205c ...
… Gas pressure gauge, 201d-205d, 201e-205e …… valve, 20
1f to 205f …… pressure gauge, 210, 211 …… gas inlet pipe, 212 ……
Substrate heating heater, 213 ... Substrate, 214 ... Porous tube,
215 ... Outer tube, 216 ... Driving device, 217 ... Rotating shaft, 218 ...
… Lead wire, 219 …… Thermocouple, 220 …… Vacuum chamber, 221
...... Exhaust valve, 222,223 …… Gas supply pipe, 301 ……
Deposition chamber, 302 ... Substrate support, 303 ... Substrate, 304 ... Substrate heating heater, 305 ... Conductor, 306 to 309 ... Gas supply source, a ... Branch pipe, b ... Flowmeter, c ... pressure gauge, d,
e ... Valve, 310 ... Raw material gas introduction pipe, 311 ... Plasma generator, 312 ... Exhaust valve, 313 ... Exhaust pipe, 400
...... Conductive substrate, 401 ...... First layer (charge injection blocking layer), 4
02: second layer (photosensitive layer), 403: third layer (surface protective layer).

Claims (1)

[Claims] 1. Excitation by introducing a raw material substance for forming a deposited film, which can be turned into a gaseous state, and a gaseous halogen-based oxidizing agent having a property of oxidizing the raw material substance into a reaction space and bringing them into contact with each other. Of a plurality of precursors including a precursor in a state, and at least one of these precursors is used as a source of a deposited film component to form a deposited film on a substrate in a deposition space. In the deposited film forming apparatus, the introduction pipe of the gaseous raw material and the introduction pipe of the gaseous halogen-based oxidant are arranged in a multi-concentric structure,
Further, at least one of the introduction tube groups is composed of a porous tube, and an outer tube having at least one opening is arranged in a direction in which the substrate is arranged, the deposited film forming apparatus.