JPH0658879B2 - Deposited film forming method and deposited film forming apparatus - Google Patents

Description

The present invention relates to a deposited film, particularly a functional film, particularly a semiconductor device, a photosensitive device for electrophotography, a line sensor for image input, an image pickup device, and a photovoltaic. The present invention relates to a method and an apparatus suitable for forming an amorphous or crystalline deposited film used for an element or the like.

[Prior art]

For example, in order to form an amorphous silicon film, a vacuum vapor deposition method, a plasma CVD method, a CVD method, a reactive sputtering method, an ion plating method, an optical CVD method and the like have been tried, and generally, the plasma CVD method is used. Widely used and commercialized.

In addition, the deposited film made of amorphous silicon has electrical and optical characteristics, fatigue characteristics after repeated use or usage environment characteristics, as well as productivity and mass productivity including uniformity and reproducibility. There is room for further improvement in overall characteristics.

The reaction process for forming an amorphous silicon deposited film by the plasma CVD method, which has been generalized in the past, is considerably complicated as compared with the conventional CVD method, and the reaction mechanism is not unclear. . In addition, there are many formation parameters for the deposited film (eg, substrate temperature, introduced gas flow rate and ratio, formation pressure, high frequency power, electrode structure,
Due to the combination of many of these parameters (the structure of the reaction vessel, the pumping speed, the plasma generation method, etc.), the plasma sometimes became unstable and the deposited film formed was not significantly adversely affected. Besides,
In the actual situation, it was difficult to generalize the manufacturing conditions because the parameters peculiar to the device had to be selected for each device.

On the other hand, in order to develop an amorphous silicon film having electrical and optical characteristics which can sufficiently satisfy each application, it is currently best formed by the plasma CVD method.

However, in the plasma CVD method, as described above, since the formation parameters of the deposited film are complicated, it is difficult to repeatedly produce uniform film forming conditions. Especially, when the deposited film is formed over a large area. However, it was difficult to form the film with good reproducibility by sufficiently satisfying the uniformity of the film thickness and film quality of the formed film. In addition, when mass production is planned, the management items for mass production become complicated,
These have been pointed out as problems to be improved in the future because the management allowance is narrowed and the adjustment of the device is delicate.

On the other hand, in the conventional technique using the ordinary CVD method, a high temperature is required, and a deposited film having practical properties has not been obtained.

As described above, in forming an amorphous silicon film, it has been earnestly desired to develop a forming method which can be mass-produced by a low-cost apparatus while maintaining its practicable characteristics and uniformity.

The same applies to other functional films such as a silicon nitride film, a silicon carbide film, and a silicon oxide film.

[Object of the Invention]

The object of the present invention is to eliminate the above-mentioned drawbacks of the plasma CVD method, and at the same time provide a novel deposition film forming method and an apparatus therefor which do not depend on the conventional forming method.

Another object of the present invention is to deposit a film having a uniform film thickness over a large area with good reproducibility and high efficiency while maintaining the characteristics of the film to be formed and improving the deposition rate. A film forming method and an apparatus therefor are provided.

Still another object of the present invention is to simplify the management of film forming conditions,
It is an object of the present invention to provide a deposited film forming method and an apparatus therefor capable of easily achieving mass production of films.

[Outline of Invention]

The deposited film forming method of the present invention is characterized in that a mesh-shaped activating means made of tungsten is provided in a film forming space for forming a deposited film on a substrate to activate a gas containing hydrogen. .

Further, the deposited film forming apparatus of the present invention is characterized in that a mesh-shaped member made of tungsten for activating a gas containing hydrogen is provided in a film forming chamber for forming a deposited film on a substrate. .

〔Example〕

In the method of the present invention, in the film formation space for forming the deposited film, instead of generating plasma, in the film formation space, one is generated from the source gas for film formation previously activated in the activation space. Gas containing hydrogen is introduced from the other side, and the gas is activated by the catalytic action of the mesh-like activation means made of tungsten (W) provided in the film forming space, Since the deposited film is formed by chemically reacting with the activated species generated from the raw material gas for film formation that has been activated in advance in the activation space, the formed deposited film has an etching action during film formation, or There is no other adverse effect such as abnormal discharge.

Further, according to the present invention, the ambient temperature of the film forming space and the substrate temperature can be arbitrarily controlled as desired.

Further, since the active species of the gas containing hydrogen can be generated in the vicinity of the substrate for forming the deposited film by the catalytic action of tungsten, the active species of hydrogen having a relatively short life can be efficiently deposited on the substrate. Therefore, the usage efficiency of the gas containing hydrogen can be significantly improved.

Further, since the means for activating the gas containing hydrogen has a mesh shape, by adjusting the area of this mesh arbitrarily according to the size of the film forming surface of the substrate, a uniform amount on the film forming surface can be obtained. Active species generated from a gas containing hydrogen can be supplied, and a uniform deposited film can be formed over a large area.

In the present invention, the active species generated from the raw material gas for film formation in the activation space have a life of 0.1 seconds or more, more preferably 1 second or more, optimally from the viewpoint of productivity and ease of handling. Those having 10 seconds or more are selected and used as desired.

In the present invention, the raw material gas for film formation introduced into the activation space includes a compound containing silicon and halogen, a compound containing carbon and halogen, a compound containing germanium and halogen, and the like.

These compounds may be used alone, or may be used in combination as required.

As the compound containing silicon and halogen, for example, a compound obtained by substituting a part or all of hydrogen atoms of a chain or cyclic silane compound with a halogen atom is used, and specifically, for example, Si _u Y _{2u + 2} (u Is an integer of 1 or more, Y is at least one element selected from F, Cl, Br and I.) Si _v Y _2v (v is an integer of 3 or more, Y have the abovementioned meaning. annular silicon halide represented _{by), Si u H x Y y} (u and Y are .x + y = 2u or 2u + 2 have the abovementioned meaning.) a linear or cyclic compound represented by the And so on.

Specifically, for example, SiF ₄ , (SiF ₂ ) ₅ , (SiF ₂ ) ₆ , (SiF ₂ ) ₄ , S
i ₂ F ₆ , Si ₃ F ₈ , SiHF ₃ , SiH ₂ F ₂ , SiCl ₄ (SiCl ₂ ) ₅ , SiBr ₄ ,
(SiBr ₂ ) ₅ , Si ₂ Cl ₆ , Si ₂ Br ₆ , S: HCl ₃ , S: HBr ₃ , S: HI ₃ , S
Examples thereof include those in a gas state such as i ₂ Cl ₃ F ₃ or those that can be easily gasified.

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

As the compound containing carbon and halogen, for example compounds part or the whole substituted with a halogen atom of the hydrogen atoms of the chain or cyclic hydrocarbon compound is used, specifically, for example, C _u Y _{2u + 2} (u is an integer of 1 or more, Y is F, C
At least one element selected from l, Br and I. ) A chain carbon halide, C _v Y _2v (v is 3
The above integers and Y have the above-mentioned meanings. Cyclic silicon halide represented _{by), C u H x Y y} (u and Y like a .x + y = 2u or 2u + 2 have the abovementioned meaning.) Chain or cyclic compounds represented by.

Specifically, for example, CF ₄ , (CF ₂ ) ₅ , (CF ₂ ) ₆ , (CF ₂ ) ₄ , C
₂ F ₆ , C ₃ F ₈ , CHF ₃ , CH ₂ F ₂ , CCl ₄ (CCl ₂ ) ₅ , CBr ₄ (CBr ₂ ) ₅ , C
₂ Cl _6, those _{C 2 Br 6, CHCl 3,} CHI 3, C 2 Cl 3 which may or easily gasified gas conditions such as F ₃ and the like.

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

Further, as the compound containing germanium and halogen,
For example, a compound in which a part or all of hydrogen atoms of a chain or cyclic germanium hydride compound is replaced with a halogen atom is used, and specifically, for example, Ge _u Y _{2u + 2} (u is an integer of 1 or more, Y Is at least one element selected from F, Cl, Br and I.) Chain germanium Ge _v Y _2v (v is an integer of 3 or more, and Y has the above-mentioned meaning). A cyclic germanium halide represented by
Ge _u H _x Y _y (u and Y have the above-mentioned meanings. X + y = 2
u or 2u + 2. ) And a chain or cyclic compound.

Specifically, for example, GeF ₄ , (GeF ₂ ) ₅ , (GeF ₂ ) ₆ , (GeF ₂ ) ₄ , G
e ₂ F ₆ , Ge ₃ F ₈ , GeHF ₃ , GeH ₂ F ₂ , GeCl ₄ (GeCl ₂ ) ₅ , GeBr ₄ ,
_{(GeBr 2) 5, Ge 2} Cl 6, Ge 2 Br 6, GeHCl 3, GeHBr 3, GeHI 3, G
Examples thereof include those in a gas state such as e ₂ Cl ₃ F ₃ or those that can be easily gasified.

In the present invention, as a method for generating active species in the activation space, microwave, R
Electric energy such as F, low frequency and DC, heat energy such as heater heating and infrared heating, and activation energy such as light energy are used. When a plurality of raw material gases for film formation are used, they can be mixed in advance and introduced into the activation space, or these raw material gases for film formation can be individually supplied from independent supply sources. However, it can also be introduced into the activation space. Further, as the gas containing hydrogen which is introduced into the film forming space and activated by the catalytic action of the mesh-like activation means made of tungsten (W), hydrogen alone, or hydrogen and a halogen compound (for example, F ₂ gas) is used. , Cl ₂ gas, gasified Br ₂ , I ₂ etc.), and an inert gas such as Ar or He.

The deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation.
Preferable examples of the impurity element to be used include elements of Group A of Group III of the periodic table, such as B, Al, Ga, In and Tl, as p-type impurities, and examples of the n-type impurity include those of the periodic table. V group A elements, for example, P, As, Sb, Bi, and the like are preferable, but B, Ga, P, Sb are particularly preferable.
Etc. are the best. The amount of impurities to be doped is appropriately determined according to desired electrical / optical characteristics.

The substance containing such an impurity element as a component (impurity introducing substance) is a compound that is in a gas state at room temperature and atmospheric pressure, or is a gas at least under the conditions for forming a deposited film, and can be easily vaporized by an appropriate vaporizer. Is preferably selected. Examples of such compounds include PH ₃ , P ₂ H ₄ , PF ₃ , PF ₅ , and P
Cl ₃ , AsH ₃ , AsF ₃ , AsF ₅ , AsCl ₃ , SbH ₃ , SbF ₅ , SiH ₃ , BF
₃ , BCl ₃ , BBr ₃ , B ₂ H ₆ , B ₄ H ₁₀ , B ₅ H ₉ , B ₅ H ₁₁ , B ₆ H ₁₀ , B ₆
H ₁₂ , AlCl _{3 and the} like can be mentioned. The compound containing an impurity element may be used alone or in combination of two or more.

The compound containing an impurity element as a component may be directly introduced into the film formation space in a gas state or mixed with a gas containing hydrogen, or, like the source gas for film formation, in the activation space. It can be activated in advance and then introduced into the film formation space.

The mesh-shaped member made of tungsten used in the present invention may be a mesh-shaped member made of a tungsten wire, or may be a mesh-shaped member made of a thin pipe at least the surface of which is made of tungsten. In this case, a plurality of holes are provided on the side of the pipe facing the substrate, and the active species generated from the raw material gas for film formation are introduced through the pipe, and the holes above the substrate are introduced through the plurality of holes. The structure may be such that it is supplied onto the film formation surface.

The size of the mesh-shaped member is determined by the size of the substrate on which the film is formed. More preferably, the mesh-shaped member has a length equal to or longer than one direction of the substrate. It is desirable to have.

Next, the present invention will be described with reference to a typical example of a photoconductive member as an electrophotographic image forming member formed by the method of the present invention.

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

The photoconductive portion 10 shown in FIG. 1 can be applied as an image forming member for electrophotography, and the intermediate layer 1 is provided on the support 11 for the photoconductive member as required.
2 and the photosensitive layer 13 has a layer structure.

The support 11 may be conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel, Al, Cr, Mo, Au, Ir, Nb, Ta,
Examples include metals such as V, Ti, Pt, and Pd or alloys thereof.

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

For example, in the case of glass, the surface is NiCr, Al, C
r, Mo, Au, Ir, Nb, Ta, V, Ti, Pt,
If a thin film of Pb, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ + SnO ₂ ) or the like is provided, it is subjected to a conductive treatment, or if it is a synthetic resin film such as a polyester film, NiCr, A
l, Ag, Pb, Zn, Ni, Au, Cr, Mo, I
vacuum deposition with metals such as r, Nb, Ta, V, Ti, Pt,
The surface is subjected to a conductive treatment by treatment with electron beam vapor deposition, spattering, or the like, or by laminating treatment with the metal. The shape of the support may be any shape such as a cylindrical shape, a belt shape, a plate shape, and the shape is determined as desired. For example, the photoconductive member 10 shown in FIG. If it is used as an image forming member, it is preferably an endless belt or a cylinder for continuous high speed photography.

The intermediate layer 12 includes, for example, the photosensitive layer 13 from the support 11 side.
The carrier 1 from the side of the photosensitive layer 13 of the photocell that effectively blocks the inflow of carriers into the photosensitive layer 13 by the irradiation of electromagnetic waves and moves toward the side of the support 11.
It has a function to easily allow passage to the 1 side.

The intermediate layer 12 is made of amorphous silicon containing hydrogen atoms (H) and / or halogen atoms (X) (hereinafter referred to as a
-Si (H, X). ), And contains a p-type impurity such as boron (B) or a p-type impurity such as phosphorus (P) as a substance that controls electrical conductivity.

In the present invention, the content content of the substance that controls conductivity such as B and P contained in the intermediate layer 12 is preferably
0.001-5 × 10 ⁴ atomic ppm, more preferably 0.5-1 × 10 ⁴
Atomic ppm, optimally 1 to 5 × 10 ³ atomic ppm is desirable.

When the intermediate layer 12 has the same or similar constituents as the photosensitive layer 13, the formation of the intermediate layer 12 and the formation of the photosensitive layer 13 can be continuously performed. In that case,
As the raw material for forming the intermediate layer, the active species generated from the compound containing silicon and halogen in the activated space, the gas containing hydrogen and the compound gas containing the inert gas and the impurity element as the components as necessary are respectively supported. It is introduced into the film forming space where the body 11 is installed.

The hydrogen-containing gas introduced into the film formation space is activated by the catalytic action of the mesh-shaped member made of tungsten,
The intermediate layer 12 is formed on the support 11 by chemically reacting with the active species introduced from the activation space.

As the compound containing silicon and halogen, which is introduced into the activation space to form the active species when the intermediate layer 12 is formed, for example, a compound which easily produces the active species such as SiF ₂ ^* can be selected from the above compounds. It is more desirable to select.

The layer thickness of the intermediate layer 12 is preferably 30 Å to 10 µ, more preferably 40 Å to 8 µ, and most preferably 50 Å to 5 µ.

The photosensitive layer 13 is composed of, for example, a-Si (H, X),
It has both a charge generating function of generating photocarriers by irradiation of laser light and a charge transporting function of transporting the charges.

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

Although the photosensitive layer 13 is a non-doped a-Si (H, X) layer, it may have a conductivity characteristic of a polarity (for example, n-type) different from the polarity of the substance contained in the intermediate layer 12 that governs the conductivity characteristic, if desired. A substance that controls the conductivity may be contained, or a substance that controls the conduction characteristics of the same polarity may be contained in the intermediate layer 12 in a much smaller amount than the actual amount. You may let me.

Also in the case of forming the photosensitive layer 13, if it is formed by the method of the present invention, as in the case of the intermediate layer 12, the activity generated from the compound containing silicon and halogen in the activation space is formed in the film formation space. By introducing a gas containing a species and hydrogen, and a gas of a compound containing an impurity element as a component as necessary, these gases are activated by the catalytic action of tungsten, and are reacted with the active species to form an intermediate layer. The photosensitive layer 13 may be formed on the surface 12.

FIG. 2 is a schematic diagram showing a typical example of a PIN diode device using an a-Si deposited film doped with an impurity element, which is manufactured by carrying out the method of the present invention.

In the figure, 21 is a substrate, 22 and 27 are thin film electrodes, 23 is a semiconductor film, and an n-type a-Si (H, X) layer 24, an i-type a-Si (H, X) layer 25, p. Type a-Si (H,
X) layer 26. Reference numeral 28 is a lead wire connected to an external electric circuit device.

As the base 21, a conductive, semiconductive, or electrically insulating material is used. If the substrate 21 is conductive, the thin film electrode 22 may be omitted. Examples of the semiconductive substrate include semiconductors such as Si, Ge, GaAs, ZnO and ZnS. The thin film electrodes 22 and 27 are, for example, NiCr, Al, Cr, Mo, Au, Ir, N.
b, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ ,
It can be obtained by providing a thin film of ITO (In ₂ O ₃ + SnO ₂ ) or the like on the substrate 21 by a process such as vacuum deposition, electron beam deposition, or sputtering. The thickness of the electrodes 22 and 27 is preferably 30 to 5 × 10 ⁴ Å, more preferably 10
It is desirable to set it to 0-5 × 10 ³ Å.

In order to make the film body constituting the semiconductor layer of a-Si (H, X) n-type or p-type, if necessary, n-type impurities or p-type impurities among impurity elements, or Both impurities are formed by controlling the amounts in the formed layer and doping.

In order to form the n-type, i-type and p-type a-Si (H, X) layers, active species generated from a compound containing silicon and halogen are introduced into the film formation space in the activation space by the method of the present invention. Separately from this, a gas containing hydrogen and, if necessary, a gas of a compound containing an impurity element as a component are introduced into the film forming space, and the introduced gas containing hydrogen is a mesh member made of tungsten. Is activated by the catalytic action of
A chemical reaction with the active species introduced from the activation space forms a deposited film on the substrate 21. n-type and p-type a-S
The layer thickness of the i (H, X) layer is preferably 100 to 10
⁴ Å, more preferably 300 to 2000 Å is desirable.

The layer thickness of the i-type a-Si (H, X) layer is preferably 500 to 10 ⁴ Å, more preferably 1000 to 1
A range of 0000Å is desirable.

Specific examples of the present invention will be shown below.

[Embodiment 1] Using the apparatus shown in FIG.
A -Si (H, X) deposited film was formed.

In FIG. 3, reference numeral 307 denotes a film forming chamber in which a desired substrate 311 is placed on a substrate support 310 inside.
Reference numeral 312 is a shielding plate. Reference numeral 313 is a heater for heating the substrate, which is supplied with power via a conductor 315 and generates heat. The heater 313 heats the base 311 before film formation, performs annealing to further improve the characteristics of the film formed after film formation, and heats the base 311 during film formation as necessary. Used when When the substrate is heated in carrying out the method of the present invention, the substrate heating temperature is preferably 30 to 450 ° C, more preferably 50 to 350 ° C. Reference numeral 14 is a thermocouple for monitoring the temperature. Reference numeral 301 denotes an introduction pipe, and the raw material gas for film formation is introduced into the activation chamber 303 from the gas supply source (not shown) through the introduction pipe 301. The activation chamber 303 is filled with solid particles 304 that react with the raw material gas. 306 is an activation means for activating the raw material gas for film formation,
The source gas is previously activated in the activation chamber 303 to become active species and introduced into the film forming chamber 307. On the other hand, a gas containing hydrogen is introduced into the film formation chamber 307 from the introduction pipe 302. In the film forming chamber 307, a mesh-shaped member 309 made of tungsten is installed, and electric power is supplied through a conductor 315 to heat it to a desired temperature. Introductory pipe 3
The hydrogen-containing gas introduced from 02 is activated by its catalytic action when passing through the mesh-shaped member 309 made of tungsten, and becomes activated hydrogen or the like, which reacts with the above-mentioned active species, whereby the substrate A desired deposited film is formed on top.

In the present invention, excitation energy such as light energy, heat energy, and discharge energy may be supplementarily used in the film forming chamber, if necessary.

First, Corning 7059 glass was used as the base 311, and it was placed on the support table 310, the inside of the film forming chamber 307 was evacuated using an exhaust device (not shown), and the pressure was reduced to 10 ⁻⁶ Torr. The Corning 7059 glass substrate was heated to 200 ° C. by the substrate heating heater 313. The activation chamber 303 is filled with solid Si particles 304, heated by an electric furnace 306 and kept at about 1150 ° C. to bring Si into a red heat state, and 30 SCCM of SiF ₄ is blown into the activation chamber 303 from a cylinder (not shown) through an introduction pipe 301. Accordingly, the SiF ₂ to generate SiF ₂ ^* as active species ^*
Was introduced into the film forming chamber 307. On the other hand, the introduction pipe 302
Then, H ₂ gas was introduced into the 10 SCCM film forming chamber 307. The tungsten mesh 309 in the film forming chamber was heated to about 2000 ° C., and the base 313 and the tungsten mesh 309 were arranged so that the distance between them was about 1 cm.

Film formation was performed in this state, and an amorphous silicon (a-Si (H, X)) film was deposited on the substrate. The thickness of the obtained film was 1.8 μm.

Then, the obtained a-Si (H, X) film sample was placed in a vapor deposition tank to form a comb-type Al gear gap electrode (gear length 250 μ, width 5 mm) at a vacuum degree of 10 ⁻⁵ Torr, and then applied voltage 5
The dark current was measured at 0 V, the dark conductivity σ _d was obtained, and the film characteristics were evaluated.

The dark conductivity obtained was 5 × 10 ^-10 (Ω-cm) ^-1 .
Then, white light of 100 mw / cm ² was irradiated to obtain the bright conductivity σp. The obtained bright conductivity σp is 7 × 10 ^-5 (Ω-cm) ^-1
Thus, a film having good photoconductive characteristics was obtained.

Example 2 An a-Si (H, X) film was formed in the same manner as in Example 1 except that B ₂ H ₆ gas was introduced from the introducing pipe 302 at 5000 ppm with respect to the SiF ₄ gas flow rate in addition to H ₂ gas. Were formed and the characteristics were evaluated. The dark conductivity σd measured by vapor-depositing a comb-shaped Al electrode in the same manner as in Example 1 was 8 × 10 ⁻⁵ (Ω-cm) ⁻¹ . The film obtained was found to be p-type by measurement of thermoelectromotive force.

Example 3 An a-Si ((H, X) film was formed in the same manner as in Example 1 except that PH ₃ gas was introduced into the introduction pipe 302 in addition to H ₂ gas at 1500 ppm with respect to the SiF ₄ gas flow rate. The film was formed and evaluated for characteristics, and the dark conductivity σd measured by vapor deposition of a comb-shaped Al electrode was 7 × 10 ⁻⁴ (Ω-cm) ⁻¹ in the same manner as in Example 1. Further, the thermoelectromotive force was obtained. The obtained film was N type.

Example 4 A drum-shaped electrophotographic image forming member having a layer structure as shown in FIG. 1 was prepared by the following operations using the apparatus shown in FIG.

In FIG. 4, 440 is a film forming chamber, 421 is a compound gas introduction tube containing silicon and halogen, 422 is an activation chamber, 4
Reference numeral 24 is a solid Si particle, 423 is an electric furnace, 426 is an active species introduction tube opening, 431 is a tungsten mesh, 432 is a cylindrical substrate, 433 is an infrared lamp for heating the cylindrical substrate, 434 is a reflecting plate. is there. Also, 427, 42
Reference numeral 8 is an H ₂ gas introduction pipe, and its discharge portions 429 and 430 are shaped so that the diameter thereof widens toward the discharge port. Reference numeral 435 is an exhaust pipe.

An Al cylinder substrate 432 was installed in the film forming chamber 440 and heated to about 300 ° C. by an infrared lamp.

The activation chamber 422 is filled with solid Si particles 424, and the electric furnace 2
3 to maintain the temperature at 1150 ° C. to make the Si a red hot state, and inject SiF ₄ gas through an inlet pipe 421 from a cylinder (not shown) at 300 SCCM to produce SiF ₂ ^* as an active species ^.
Was generated and the SiF ₂ ^* was introduced into the film forming chamber 440. On the other hand, from the inlet pipe 428, 5000 ppm of B ₂
H ₂ gas containing H ₆ was introduced into the 300 SCCM film forming chamber 440.

A tungsten mesh 431 is placed in the film forming chamber 440.
It was installed concentrically with the 1-cylinder base body 432 at a distance of about 1 cm. The tungsten mesh 431 was heated to about 2000 ° C. by energizing it. The internal pressure of the film forming chamber is kept at 1 Torr, the substrate is rotated in this state to form a film, and a film containing B is contained on the Al cylinder substrate.
An i (H, X) layer was formed.

Next, the introduction of B ₂ H ₆ gas was stopped, and SiF ₄ gas was added to 600 SCC.
The non-doped a-Si (H, X) layer was formed by setting the MH ₂ gas to 1200 SCCM.

[Comparative Example 1] By using SiF ₄ , SiH ₄ , H ₂ , and B ₂ H ₆ gases, a general plasma CVD method equipped with a 13.56 MHz high frequency device was used.
A drum-shaped electrophotographic image forming member having the layer structure shown in FIG. 1 was formed.

Table 1 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image-forming members obtained in Example 4 and Comparative Example 1.

[Embodiment 5] Using the apparatus shown in FIG. 3 and the following operation,
The PIN diode shown in FIG. 2 was produced.

First, the Corning 7059 glass substrate 21 on which the 1000 Å ITO film 22 was vapor deposited was placed on a support, the pressure was reduced to 10 ⁻⁶ Torr, and the glass substrate 21 was heated to 200 ° C. by the heater 313. Activation chamber 303 as in the first embodiment
Solid Si particles 304 are filled in and heated in an electric furnace 306 to maintain the temperature at about 1150 ° C. to bring Si into a red heat state, and SiF ₄ is added to the SiF ₄ from a cylinder (not shown) through an introduction pipe 301.
By blowing in SCCM, SiF ₂ ^* was generated as an active species, and the SiF ₂ ^* was introduced into the film forming chamber 307. On the other hand, B ₂ H ₆ gas diluted to 15000 ppm with H ₂ gas was introduced into the 10 SCCM film forming chamber 307 through the introduction pipe 302.
The tungsten mesh 309 in the film forming chamber is heated to about 2000 ° C.
Film formation was performed in a state of being heated to a temperature of about 200 Å to form a p-type a-Si (H, X) film 23 on the ITO film 22.

Next, pure H ₂ gas instead of B ₂ H ₆ gas diluted with H ₂ gas 1
0 SCCM was introduced into the film forming chamber 307 through the introduction pipe 302.

The tungsten mesh 309 was formed into a film while being heated to about 2000 ° C. As a result, about 5000 Å I-type a-Si (H, X) film 2 is formed on the p-type a-Si (H, X) film 23.
4 was deposited.

Next, instead of pure H ₂ gas, PH ₃ gas diluted to 4500 ppm with H ₂ gas was introduced into the film forming chamber 307 through the 10SCCM inlet pipe 302.

As in the case of forming the P layer and the i layer, the tungsten mesh 30
9 was heated to about 2000 ° C. to form a film. As a result, about 500 Å N was deposited on the I-type a-Si (H, X) film 24.
A type amorphous silicon film 25 was formed.

Then, the PIN type a-Si (H,
X) film sample is put in a vacuum evaporation tank, and 1000 Å of Ag electrode having a diameter of 11.8 mm is formed on the N-type a-Si (H, X) film 25 by electron beam heating at a vacuum degree of 1 × 10 ^-6 Torr and PIN
A type diode was obtained. Light intensity of 100 mW / c from the ITO film side to the diode element (area: 1 cm ² ) thus obtained.
When irradiated with m ² of white light, a conversion efficiency of 6.9% or more, an open-end voltage of 0.72 V, and a short-circuit current of 15 mA / cm ² were obtained.

〔The invention's effect〕

According to the deposited film forming method and the apparatus thereof of the present invention, desired electrical, optical, photoconductive and mechanical properties of the formed film are improved, and further, the substrate is not kept at a high temperature,
High-speed film formation becomes possible. Further, particularly when the deposited film is formed over a large area, the deposited film can be formed with high reproducibility and high efficiency, and the management of the film forming conditions can be simplified and the mass production of the film can be easily achieved. .

[Brief description of drawings]

FIG. 1 is a schematic view for explaining a constitutional example of an electrophotographic image forming member manufactured by using the method of the present invention. FIG. 2 is a schematic diagram for explaining a configuration example of a PIN type diode manufactured by using the present invention. 3 and 4 are configuration diagrams of the deposited film forming apparatus of the present invention. 10 ... Electrophotographic image forming member, 11 ... Substrate, 12 ... Intermediate layer, 13 ... Photosensitive layer, 21 ... Substrate, 22, 27 ... Thin film electrode, 24 ... N-type semiconductor layer, 25 ... ... i-type semiconductor layer, 26 ... p-type semiconductor layer, 307, 440 ... film forming chamber, 303, 422 ... activation chamber, 311, 432 ... substrate, 309, 431 ... tungsten mesh.

Claims (2)

[Claims] 1. A method of forming a deposited film, characterized in that a mesh-shaped activation means made of tungsten is provided in a film forming space for forming a deposited film on a substrate to activate a gas containing hydrogen. 2. A film forming chamber for forming a deposited film on a substrate, and a mesh member made of tungsten for activating a gas containing hydrogen is provided in the film forming chamber. Deposited film forming apparatus.