JPS62152121A - Deposited film forming device - Google Patents

Abstract

PURPOSE:To contrive accomplishment of high utilizational efficiency of raw gas by a method wherein an introducing pipe of raw material having an aperture and an oxidizing agent introducing pipe are formed in multiconcentrical structure gas is introduced into a reaction space, and at lest one of the introducing pipe group is constituted with a porous pipe. CONSTITUTION:A porous introducing pipe 214 and an introducing pipe 215 having a slit-shaped aperture part are formed into a multiconcentrical structure. A plurality of substrates 213 are arranged in such a manner that the space located around the pipes 214 and 215 is filled up. The raw material, which will be turned to gas for formation of a deposited film, is introduced into the chamber 220 through the pipe 214, and the gaseous oxidizing agent which performs an oxidizing action is introduced into the chamber 220 through the pipe 215. By setting the specific temperature for the substrate 213 in advance, these gases generate chemical action, and an amorphous film is deposited on the base 213. As a result, the utilizational efficiency of the raw gas can be improved, a deposited film of large area can be obtained, and the improvement in productivity can be achieved.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to functional films, particularly semiconductor devices, photosensitive devices for photosensitive photography, optical input sensors for optical image input devices, imaging devices, and photovoltaic devices. The present invention relates to an apparatus advantageous for forming functional deposited films useful for electronic device applications such as power devices.

[Conventional technology]

Conventionally, amorphous or polycrystalline functional films such as semiconductor films, insulating films, photoconductive films, magnetic films, or metal films have been formed by forming films that are individually suited from the viewpoint of desired physical properties and applications. method has been adopted.

Vacuum deposition method, plasma CVD method, thermal CVD method, photonic carbon method, reactive sintering method, ion silating method, etc. have been tried to form the deposited film, and generally, plasma CVD Laws are widely used and corporatized.

As the deposited films obtained by these deposited film formation methods are required to be applied to electronic devices and optoelectronic devices that require higher functionality, it is difficult to improve electrical and optical properties and fatigue due to repeated use. There is room for further improvement in overall characteristics in terms of productivity and mass production, including characteristics, usage environment characteristics, uniform pouring, and reproducibility.

What is shown in FIG. 3 is an example of a conventional plasma CVD method for forming a deposited film.
Reference numeral 1 denotes a film forming chamber as a film forming space, in which a desired substrate 303 is placed on a substrate support stand 302 inside.

Reference numeral 304 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 305 to generate heat.

Reference numerals 306 to 309 are gas supply sources, which are provided depending on the type of gas of a compound containing a silicon-containing compound, hydrogen, a halogen compound, an inert gas, or an impurity element. If one of these raw material compounds is used in a liquid state under standard conditions, an appropriate vaporizer 5 is provided. In the figure, the gas supply sources 306 to 309 are denoted by a, branch pipes are denoted by a, flowmeters are denoted by b, pressure gauges are denoted by C which measure the pressure on the high pressure side of each flowmeter, and d. The letter ``e'' indicates the pulp used to adjust the flow rate of each gas. The gas of the raw material compound is introduced into the inlet pipe 310'? : is introduced into the film forming chamber 301 through the film forming chamber 301.

311 is a plasma generator, and the plasma generator e
The plasma from 31x acts on the raw material gas flowing in the direction of the arrow, excites and decomposes the affected compounds, and the decomposed compounds undergo a chemical reaction, causing the base 3
03 to form an amorphous deposited film. 31
2 is an exhaust pulp, and 313 is an exhaust pipe, which is connected to an exhaust device (not shown) to evacuate the inside of the film forming space.

Using such a device, for example, a-8i :H deposition fj
(When forming a film, place a suitable substrate 303 on the support stand 302.
The inside of the film forming chamber 301 is evacuated through an exhaust pipe using an exhaust device (not shown) to reduce the pressure.

Then, if necessary, completely heat the base and start the gas supply phase. All raw material gases such as SiH4, 512H6 etc. are introduced from the pump 31
0 into the film forming chamber 301, and while maintaining the pressure inside the film forming chamber at a predetermined pressure, the plasma generator
A-8i is generated on the substrate 303.
: Forms H film.

By the way, conventional deposited films, such as those obtained by the plasma CVD method, have excellent properties and are considered to be somewhat satisfactory. , optical and photoconductive properties, fatigue resistance properties for repeated use, use environment properties, stability over time and durability, and homogeneity. There is still a long way to go to solve the problem.

The reason for this is that the desired deposited film, not only the materials used, cannot be obtained by a simple layer deposition operation, but the process operations in particular require skilled ingenuity. .

Incidentally, for example, in the case of the so-called CVD method, the gas material f+
After diluting it, all the so-called impurities are mixed in, and then 500 ~
Since thermal decomposition occurs at a high temperature of 650°C, precise process operations and control are required to form the desired deposited film, and the equipment required is complicated and costs are considerably high. However, it is extremely difficult to regularly obtain a deposited film product that is homogeneous and has the desired characteristics as described above, and therefore is difficult to be adopted on an industrial scale.

Furthermore, even with the plasma CVD method, which is widely used as the optimal method as described above, there are some problems in process operation and problems in equipment investment. Regarding process operations, the conditions are the CV described above.
It is more complicated than method D, and is extremely difficult to form into a film. That is, for example, if we consider the basic parameters of the interrelationships among substrate temperature, flow rate and flow rate ratio of introduced gas, pressure during layer formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, and plasma generation method. There are already many parameters, and there are also other parameters, and in order to obtain the desired product, it is necessary to have a strict A' lame.
One of the constituent factors, especially the plasma, which forms when the film becomes unstable, is necessary, and because it is a strictly selected membrane meter. will be affected by such a significant adverse effect that it will no longer be viable as a product. As for the equipment, since strict parameter selection is required as mentioned above, the structure naturally becomes complex, and as the scale and type of equipment changes, the design must be able to accommodate the carefully selected parameters. Must.

For these reasons, plasma C justice is considered to be the optimal method at present, but as mentioned above, mass production of the desired deposited film requires a large amount of equipment investment. However, the process control items for mass production are numerous and complex, the process control tolerance is narrow, and equipment adjustments are delicate.
In the end, there are problems such as making the product considerably expensive.

On the other hand, the various devices mentioned above are becoming more diverse, and the element materials for them, that is, the requirements such as the insertion characteristics mentioned above, are being satisfied as a whole, and the devices are being developed in accordance with the applicable target and purpose.
In some cases, there is a social demand for a steady supply of stable deposited film products at a low cost, and the development of methods and equipment that meet this demand is urgently needed. There are situations where

[Purpose of the invention]

The present invention relates to a deposited film used for photovoltaic elements, semiconductor devices, line sensors for image input, imaging devices, photosensitive devices for electrophotography, etc. It is an object of the present invention to solve all of the above-mentioned problems and to satisfy the above-mentioned requirements regarding the conventional device to be manufactured.

In other words, the main object of the present invention is to have electrical, optical, and photoconductive properties that are virtually always stable regardless of the usage environment, to have excellent light fatigue resistance, and to be durable even after repeated use. Excellent durability without causing deterioration even if
It is an object of the present invention to provide a deposited film forming apparatus for forming an improved deposited film that has moisture resistance and is uniform and homogeneous without causing the problem of residual potential.

Another object of the present invention is to improve the properties, film formation speed, and reproducibility of the film formed, and to make the quality of the film uniform and homogeneous, while increasing the utilization efficiency of the raw materials used and increasing the size of the film. It is an object of the present invention to provide a deposited film forming apparatus that is suitable for increasing the area and can easily achieve improved film productivity and mass production.

[Structure and effect of the invention]

As a result of extensive research in order to overcome the aforementioned problems with conventional devices and achieve the above-mentioned objectives, the present inventor has discovered a raw material that can be made into a gaseous state for forming a deposited film, and a material that can be oxidized into the raw material. By introducing a gaseous halogen-based oxidizing agent having the property of acting into the reaction space and bringing it into contact with each other, a precursor of the excited structure is chemically generated, and the precursor is used as a source of the deposited film components. As a result, we have discovered an apparatus that can greatly improve gas utilization efficiency and form a desired deposited film over a large area on a substrate in a film-forming space.

That is, the deposited film forming apparatus of the present invention introduces into the entire reaction space a raw material that can be made into a gas for forming a deposited film, and a gaseous halogen-based oxidizing agent that has the property of oxidizing the raw material. A plurality of precursors including excited state precursors are chemically generated by contacting the substrate with the substrate in the deposition space, and at least one of these precursors is used as a source of a deposited film component. In the deposited film forming apparatus for forming a deposited film on top, the introduction pipe for the raw material material that can be made into a gas and the introduction pipe for the gaseous halogen-based oxidizing agent are arranged in a multiple concentric structure, and the introduction pipe group The device is characterized in that at least one of the outer tubes is a porous tube and has at least one opening in the direction in which the base body is disposed.

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 increase the reaction efficiency and utilization efficiency of gas, the shape of the gas introduction pipe is an important factor in addition to film-forming factors such as the flow rate of the raw material, the halogen-based oxidizing agent, and the pressure in the reaction space.

For example, the gas introduction tube having the structure shown in FIGS. 1(a) and 1(b) has a structure including a porous tube 101 made of At on the inside, an outer tube 102 made of At on the outside, and an opening 103. For example, the diameter of the inner tube is preferably 0.1 to 50 mm,
More preferably 0.2 to 30 mm, optimally 0.3 to 2
It is desirable to set it to 0m. Similarly, the diameter of the outer tube is preferably 02-60M1, more preferably 0.3-4Q+m
m, preferably 0.4 to 30 .mu.m. The tube opening ratio relative to the surface area of the porous tube is preferably 10% or more, more preferably 20% or more, and optimally 30% or more.

The opening 103 provided in the outer tube is circular, elliptical, polygonal, or slit-shaped, and is open in the direction in which at least one base body is arranged, or the opening 103 is in the shape of a circular, elliptical, polygonal, or slit-shaped opening. The same porous tube may be used. The aperture ratio relative to the surface area of the openings is preferably 10% or more, more preferably 20% or more, and optimally 30% or more.

Although the length of the gas introduction tube used in the present invention is determined by the desired length of the substrate, it can be used without any particular limitation.

FIG. 1(,) is a side view when the gas introduction pipe and the cylindrical base are arranged, and FIG. 1(b) is a top view. Base body 104
can rotate about 1070 degrees around the rotation axis.

Further, it is desirable that the base body 104 be disposed so as to encircle the space around the gas introduction pipes 101 and 102, for example, so that the shape of the rotating shafts 107 connected together forms a polygon, preferably a regular polygon.

In the present invention, when the material of the gas introduction pipe used is metal, stainless steel, At, Cr, Mo, Au,
PL, Nb, Ta, V, Ti, Fe, Pd,
In the case of N1-Cr resin, polyester, polyethylene, I licargenate, cellulose acetate,
For ceramics such as polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, etc., At20□, 5in2, Bed, MgO1Z
rO2, SiC.

TicSzrc, BN% AtN% 513N4
etc.

Preferably, At or stainless steel is used from the viewpoint of workability, corrosion resistance, etc.

In order to improve the efficiency of film formation, a plurality of gas introduction pipes used in the present invention are arranged in the film formation space, and this can also be achieved by arranging a base body to surround these.

Although the multiple concentric arrangement structure used in the present invention is used, when introducing gas into the gas introduction pipe, even if the gas introduced into the inner pipe and the outer pipe are exchanged, it is essentially There is no change in the quality of the deposited film obtained.

Since the apparatus of the present invention has no chance of generating radiation in the film forming space, that is, the reaction chamber, the deposited film formed is free from undesirable effects such as ion damage and other abnormal discharge effects. I never receive it.

According to the deposited film forming apparatus of the present invention, it is possible to achieve energy saving, enlargement of area, uniformity of film thickness, and uniformity of film quality, simplify management and mass production, and achieve IkYL
There is no need for large equipment investments, the management items for mass production become clear, the management tolerance is wide, and the adjustment of the equipment becomes easy.

In the deposited film forming apparatus of the present invention, the deposit VIj used is
Raw materials that can be made into a gaseous form for modeling are oxidized by contact with a gaseous halogen-based oxidizing agent,
It is selected as desired depending on the type, characteristics, application, etc. of the intended deposited film. In the present invention, the above-mentioned raw materials and gaseous halogen-based oxidizing agents that can be made into a gaseous state may be ones that are made into a gaseous state when they are introduced and brought into contact. It does not matter if it is liquid or solid.

When the raw material for forming the deposited film or the halogen-based oxidizing agent is liquid or solid, Ar, He, N2, H
Using a carrier gas such as No. 2 or the like, bubbling is performed while adding heat if necessary, and the raw material for forming the deposited film and the halogen-based oxidizing agent are introduced in gaseous form into the reaction space.

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

As the raw material for forming the deposited film used in the present invention, for example, if a tetrahedral deposition model such as a semiconducting or electrically insulating silicon deposited film or a rumanium deposit can be obtained, it can be directly used. Effective examples include chain and branched chain silane compounds, cyclic silane compounds, and chain r-rumanium compounds.

Specifically, as a linear silane compound, 5InH2n
+2 (n=1,213,4,5,6.7,8), branched graded silane compounds include SiH, 5iH (SiH3
)S I H2S I Hs, l"f as a cyclic silane compound, S i nH2n (n = 3.4, 5.6),
As a linear gluman compound, GernH2m+2 (
m=1s2s3s4s5), etc.

In addition, for example, if a deposited film of tin is to be created, Sn
All effective raw materials include tin hydride such as Ha.

Of course, these raw materials can be used not only alone, but also as a mixture of two or more.

The rocket-based oxidizing agent used in the present invention is in a gaseous state when introduced into the reaction space, and is simultaneously introduced into the reaction space to form a gaseous raw material for forming a deposited film. It has the property of effectively oxidizing just by contact, and F
Effective examples include C1r gases such as 2, C22, B r 2, and 2, as well as nascent fluorine, chlorine, and bromine.

These halogen-based oxidants are in gaseous form, and are introduced into the reaction space together with the gaseous raw material for forming the deposited film at a desired flow rate and supply pressure, and mixed and collided with the raw material. The raw material is oxidized to efficiently generate a plurality of types of precursors including excited state precursors. The excited state precursors and other precursors that are generated serve as a source of components for the deposited film in which at least one of them is formed.

The precursors produced can be decomposed or reacted to form a precursor in another excited state or a building block before being in another excited state, or can be formed in that form, though releasing energy if necessary. By touching the surface of the substrate disposed in the membrane space, a deposited film having a three-dimensional network structure is created when the substrate surface temperature is relatively low, and a crystalline deposited film is created when the substrate surface temperature is high.

In the present invention, the type and type of raw material and halogen-based oxidizing agent are selected as film-forming factors so that the deposited film forming process can proceed smoothly and a film with high quality and desired physical properties can be formed. The combination, their mixing ratio, the pressure during mixing, the flow rate, the internal pressure of the film forming space, the flow rate of gas, and the film forming temperature (substrate temperature and ambient temperature) are appropriately selected as desired. These film-forming factors are organically related and are not determined independently, but are determined depending on each other in relation to each other. In the present invention, the ratio of the amounts of the gaseous raw material for forming a deposited film and the gaseous halogen-based oxidizing agent introduced into the reaction space is determined based on the relationship between the film-forming factors and the intermediate speed of the above-mentioned film-forming factors. The introduction flow rate ratio can be determined as desired, but preferably,
1/20 to 1o0/1 is appropriate, more preferably 1
A ratio of 15 to 50/1 is desirable.

The pressure at the time of mixing when introduced into the reaction space is preferably higher in order to increase the probability of contact between the gaseous raw material and the gaseous halogen-based oxidizing agent, but taking into account reactivity. It is preferable to 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 each introduction is preferably 1×1.
0 atm to 5 atm, more preferably 1 x 10 A to 2 atm
It is preferable to use atmospheric pressure.

The pressure in the film-forming space, that is, the pressure in the space on which the substrate on which the film is to be formed is disposed, is the pressure of the excited-state Yu precursor produced in the reaction space and, if necessary, the precursor. The precursor (D) derived from the precursor (D) is appropriately set as desired so as to contribute effectively to film formation.

When the film forming space is open and continuous with the reaction space, the internal pressure of the film forming space is the pressure introduced into the reaction space between the substrate-like raw material for forming the deposited film and the gaseous halogen oxidant. In relation to the flow rate, adjustment can be made by using, for example, differential exhaust or a large exhaust device.

Alternatively, if the conductance of the connection between the reaction space and the film-forming space is small, the pressure in the film-forming space can be reduced by installing an appropriate aeration device in the film-forming space and controlling the exhaust volume of the device.
It is possible to adjust L%.

In addition, if the reaction space and film-forming space are integrated and the reaction position and film-forming position are only spatially different, use differential pumping as described above or use a large-scale pump with sufficient exhaust capacity. It is best to install an exhaust system.

As described above, the pressure in the film forming space is determined based on the relationship between the gaseous raw material introduced into the reaction space and the introduction pressure of the gaseous Rodan oxidizing agent, and is preferably 0.0
01 Torr to 100 Torr, more preferably 0.01 Torr to 30 Torr, and most preferably 0.05 to 10 Torr.

The substrate temperature (T8) during film formation is set individually as desired depending on the gas used and the number and required characteristics of the deposited film to be formed. When obtaining , it is desirable that the temperature is preferably from room temperature to 450°C, more preferably from 50 to 400°C. In particular, when forming a crystalline deposited film with good properties such as semiconductivity and photoconductivity, the substrate temperature (T) should be 300 to 700°C.
It is desirable that this is done.

The atmospheric temperature (T, t) of the film forming space is set so that the precursor [previous]) and the precursor (①) produced do not change into chemical species unsuitable for film formation, and the precursor is efficiently (E) is appropriately determined as desired in relation to the substrate temperature (T, ).

The substrate used in the present invention may be electrically conductive or electrically insulating, as long as it is appropriately selected depending on the intended use of the deposited film to be formed. Examples of the conductive substrate include NiCr, stainless steel, At, and C.
r, Mo, Au, Ir, Nb, Ta.

Examples include metals such as V, TI, Pt, and Pd, and alloys thereof.

Examples of electrically insulating substrates include polyester, polyethylene, polycargenate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, etc. Films or sheets of synthetic resins such as listyrene, polyamide, glass, ceramics, etc. are commonly used. Preferably, at least one surface of these electrically insulating substrates is subjected to a conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface is NiCr, A4C
r, Mo, Au, Ir, Nb, Ta, V,
Ti, Pt, Pd.

In2O3, SnO2, ITO (In2O3+SnO□
), or if it is a synthetic resin film such as polyester film, N
lCr.

At, Ag, Pb, Zn, Ni, Au, C
r, Mo, Ir, Nb.

The surface is treated with a metal such as Ta, v, 'ri, pt, etc. by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal, and the surface thereof is made conductive.

The shape of the support may be any shape, such as a cylinder, a belt, or a plate, 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 membrane. Furthermore, if the difference in thermal expansion between the two is large, a large amount of distortion will occur in the film, and a high-quality film may not be obtained, so select and use a substrate with a close difference in thermal expansion between the two. is preferable.

Furthermore, since the surface condition of the substrate is directly related to the orientation (orientation) of the membrane and the generation of cone-shaped structures, the surface of the substrate is treated to create a membrane structure and structure that provides the desired properties. is desirable. The substrate is used in order to increase the uniformity of film quality and film thickness, etc.
In addition to using the gas introduction tube according to the present invention, movements such as rotation and vibration can also be applied within the film forming space.

Hereinafter, the deposited film forming apparatus of the present invention will be explained with reference to the embodiments shown in the drawings.
Although explained in more detail, the deposited film forming apparatus of the present invention is not limited thereto.

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.

The apparatus main body is provided with a reaction space and a film forming space.

201 to 205 are each filled with a gas that is used once during film formation. 201a to 205a are gas supply pipes, respectively, and 201b to 205b are mass flow controllers/trollers 120 for adjusting the flow rate of gas from each pump.
1C~205C are gas pressure gauges, 201d~20
5d and 201e to 205e are 4 rubles and 201f, respectively.
-205f are corresponding pressure gauges that indicate the pressure inside the sugonpe.

220 is a vacuum chamber, and a pipe for introducing gas is provided at the bottom. A first gas introduction pipe 210 into which gas from the pumps 101 and 102 is introduced, and a gas pump 20
A second gas introduction pipe 2 into which gases from 3 to 205 are introduced.
11, and is connected to a porous tube 214 made of AA with an opening ratio of 50% and an outer tube 215 having a slit-shaped opening.

The gas supply from the pipe to each s entry pipe is gas supply/#
Eveline 222, 223.

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

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

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

In the case of the present invention, the distance between the substrate and the gas outlet of the gas inlet pipe is determined to be an appropriate distance, taking into consideration the type of deposited film to be formed, its desired characteristics, gas flow rate, internal pressure of the vacuum chamber, etc. However, preferably several 1 to 20 pieces,
More preferably, it is about 5 to 15 degrees.

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

Power is supplied to the base heater 212 via a conductive wire 218 .

219 is a thermocouple for measuring the entire temperature of the substrate (T,).

The present invention will be specifically described below with reference to Examples. Example 1 A deposited film was produced by the method of the present invention in the following manner using the film forming apparatus shown in FIG.

The S iHa filled in Genpe 201 has a flow rate of 1
50 SCCM is connected to the porous tube 2 through the gas introduction tube 210.
14, the F2 filled in the filter 203 flows through the gas at a flow rate of 100 SCCM, and the He filled in the Z pump 204 flows through the gas introduction pipe 21 at a flow rate of 200 SCCM.
1 into the vacuum chamber 220 through an outer tube 215 having a slit-shaped opening.

At this time, the opening/closing degree of the full vacuum pulp 221 in the vacuum chamber 220 was adjusted to 0.9 Torr. Silica glass cracked cylinder (φ80 w x 250 m
) Eight k-bodies were used, and the distance between the gas outlet 215 and the base was set to 3 tyn. Strong blue-white light emission was observed in the mixed region of SiH4 and F2. The substrate temperature (Tg) is 2
The temperature was set at 50°C. When gas was allowed to flow in this state for 3 hours, a Si:H:F film having a thickness as shown in Table 1 was deposited on the substrate.

Furthermore, the unevenness in film thickness distribution for all eight films was within 5% in both the vertical and horizontal directions. The characteristics were also almost uniform over the entire surface. The formed Si:H:F film was confirmed to be amorphous by electron beam diffraction.

On these amorphous Si:H:F films, At comb-shaped electrodes (
A gap length of 200 μm) was deposited to prepare a sample for conductivity measurement. Each sample was placed in a vacuum cryostat, a voltage of 100Ve was applied, and a microcurrent meter (YHP4140B
), and the dark conductivity (σ, ) was determined. 60 again
Irradiated with light of 0 nm and 0.3 mW/cy/, and determined the photoconductivity (σ,). Furthermore, the optical band gap (Eg.pt)', r was determined from the absorption of light. These 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 IJ configuration shown in FIG. 4 was fabricated on an At cylinder base under the conditions shown in Table 2.

Example 1 201t"Si2H6* to O8iH4ytP7
I replaced yKK. Eight Aj cylinder bases with a diameter of 80m+ were installed in the vacuum chamber 220, the inside of the vacuum chamber was evacuated to 10 Torr, and the substrate heating heater 21 was installed.
In step 2, the At Schilling-substrate temperature is set to 2800.

After that, 5IHzype 201 to 512H6 Kasuwo 30
0 SCCM and B HI (He with 1000 pp
m) 202 to B2Hb/He mixture W, x, 23
00 SCCM is introduced into the vacuum chamber 220 from the porous tube 214 via the gas introduction tube 210, and F2yW
F2 from Empe 203 is S13oosccM and He M
7 He 204 to He W 1000 SCCM
and into the vacuum chamber 220 via the gas introduction pipe 211.
introduced within. At that time, the vacuum valve 221 was adjusted so that the internal pressure of the vacuum chamber 220 was 0.8 Torr.

51 introduced into the vacuum chamber 220 in this way.
Chemically react 2H6, F2, and B2H6 to form the first layer 3,
It was formed on a 0 μm A1 cylinder substrate.

After forming the first layer, the supply of the B2H67He mixed gas to the vacuum chamber 220 is stopped, and the vacuum pulp 2
21 to set the internal pressure of the vacuum chamber 220 to 0.8.
I set it to Torr. Then, a second layer with a thickness of 20.0 μm was formed. Stop all gas supplies, then clean the gas lines.
Next, replace B2H6M 202 with C2H4 & 202. After that, 5t2H6, C2H4, F2, and Ha were added at 50% each in the same manner as in the first layer formation.
SCCM, 300SCCM, 200SCCM, 1
100OSCC is introduced into the vacuum chamber 220 and the third
A layer of 0.5 μm was formed.

An electrophotographic image forming member was formed in the manner described above. When the electrophotographic properties of this electrophotographic image forming member were measured, it was found that the performance was improved by 10% and the number of single-plane image defects was reduced by 30% compared to conventional image forming members.

〔effect〕

According to the above detailed explanation and each example, the deposited film forming method of the present invention can significantly improve the utilization efficiency of raw material gas, save energy, and easily manage film quality. A deposited film with uniform physical properties over a large area can be obtained. In addition, it has excellent productivity and mass production, and is of high quality and electrical.
A film with excellent physical properties such as optical and semiconductor properties can be easily obtained.

[Brief explanation of drawings]

1(a), (b), FIG. 2, and FIG. 3 are schematic diagrams of a film forming apparatus used in an example of the present invention. FIG. 4 is a schematic illustration of an electrophotographic image forming member manufactured in an example of the present invention. 101... Porous tube, 102... Outer tube, 103...
・Outer tube opening, lO4...Base, 105.106...
・Gas flow, 107...Rotating shaft, 201-205・
... is sudampe, 201 a - 205 a - gas introduction pipe, 201b - 205 b ... mass 70 - meter, 2
01c~205C... is the pressure gauge, 201d~205
d, 2Q1@~205C...pvp, 201f~
205f - Pressure gauge, 210, 211 Gas introduction tube, 212 Substrate heating heater, 213 Substrate, 214 Porous tube, 215 Outer tube, 216
... Drive device, 217 ... Rotating shaft, 218 ... Lead wire, 219 ... Thermocouple, 220 ... Vacuum chamber, 221 ... Exhaust pulp, 222, 223 ... Gas supply gloss 301... Film forming chamber, 302... Substrate support, 3o3... Substrate, 304... Heater for heating the substrate, 305... Conductive wire, 306 to 309... are gas supply sources, a. ... Branch pipe, b... Flow meter, C... Pressure gauge, d, e... Pulp, 310... Raw material introduction pipe, 311... Plasma generator, 312... Exhaust Pulp, 313... Exhaust pipe, 400... Conductive substrate, 401... First layer (charge injection prevention 1-), 402...
...Second layer (photosensitive layer), 403...Third layer (surface protection layer). Agent Patent Attorney Ms. Yamashita Engraving of Heiin Men (no changes to the content) Figure 1 (0) Te Itoda d → 113 ] 3 2 =; (Hogen April 24, 1986)

Claims (1)

[Claims] A precursor in an excited state is produced by introducing a raw material that can be made into a gas for forming a deposited film into a reaction space and bringing them into contact with a gaseous halogen-based oxidizing agent that has the property of oxidizing the raw material. A deposited film forming apparatus that chemically generates a plurality of precursors including a plurality of precursors, and forms a deposited film on a substrate in a film forming space using at least one of these precursors as a source of a deposited film component. wherein the introduction tube for the raw material that can be made into a gas and the introduction tube for the gaseous halogen-based oxidizing agent are arranged in a multiple concentric structure, and at least one of the introduction tube group is composed of a porous tube. Moreover, the deposited film forming apparatus is characterized in that an outer tube having at least one opening is disposed in the direction in which the substrate is disposed.