JPH0647726B2 - Deposited film formation method - 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 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 the plasma CVD method is generally used. Widely used and commercialized.

However, the deposited film made of amorphous silicon has further improved 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 improving overall characteristics.

The reaction process in 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 clear. . In addition, there are many formation parameters for the deposited film (eg, substrate temperature, flow rate and ratio of introduced gas, formation pressure, high-frequency power, electrode structure, reaction vessel structure, exhaust rate, plasma generation method, etc.). Due to the combination of the above parameters, the plasma was sometimes in an unstable state and had a significant adverse effect on the formed deposited film.
In addition, 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 that can sufficiently satisfy each application, it is currently best formed by the plasma CVD method.

However, depending on the application of the deposited film, it is necessary to sufficiently satisfy the requirements of large area, uniformity of film thickness, and uniformity of film quality for mass production with reproducibility. In forming a silicon deposited film, a large amount of capital investment is required for mass production equipment,
Further, the management items for the mass production are complicated, the management allowable range is narrowed, and the adjustment of the device is delicate, and these are pointed out as problems to be improved in the future.

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.

As a new deposited film forming method that eliminates such a drawback of the plasma CVD method, in recent years, a raw material for film formation is previously activated in another space (hereinafter, referred to as “activation space”) to be activated. There has been proposed a method of forming a film by introducing only the active species into a film forming space as a seed.

However, in this method, a low order silane compound such as SiF ₄ or SiF ₆ which is commercially available and easily available is used as a means for generating a precursor in the activation space, but these source gases are stable. Therefore, relatively large excitation energy is required among electric energy such as microwave, high frequency, and DC, thermal energy such as resistance heating and high frequency heating, and light energy. Therefore, in these methods, it is difficult to improve the activation efficiency to a certain degree or more, and when considering mass production at low cost, further improvement is made in terms of the amount of energy used and the consumption efficiency of raw material gas. There is room to do it.

[Object of the Invention]

The present invention has been made in view of the above points, and is a deposited film capable of significantly improving the consumption efficiency of a source gas used when a precursor is generated in an activation space and the energy efficiency used. It is intended to provide a forming method.

[Outline of Invention]

The above-mentioned purpose is to use the precursor and the activation space (B) which are the raw material for forming the deposited film generated in the activation space (A) in the film formation space for forming the deposited film on the substrate. In the deposition formation method of forming a deposited film on the substrate by introducing the activated species that are generated and interact with the precursor, when the precursor is generated in the activation space (A). , General formula (SiX ₂ ) _n , (SiHx) _m , SizHxXy (where X is a halogen atom, n ≧ 7, m ≧ 7, z ≧
7, x ≧ 1, y ≧ 2z + 2-x) is applied to the solid-state halogen-containing polymer silane compound in the solid state to activate it to form a deposited film containing silicon atoms on the substrate. It is achieved by the deposited film forming method.

In the method of the present invention, since plasma is not used in the deposition space for forming a desired deposition film, the formation parameters of the deposition film depend on the introduction amount of the precursor and active species to be introduced, the temperature in the substrate and the deposition space, the deposition It becomes the internal pressure in the space, so that the control of the deposited film formation becomes easy, and the deposited film can be formed with reproducibility and mass productivity.

The "precursor" in the present invention means a material that can be a raw material for the deposited film to be formed. The “active species” is a precursor that more efficiently forms a deposited film by chemically interacting with the precursor to give energy to the precursor or chemically react with the precursor. It is the one that carries the role of making it possible. Therefore, the active species may or may not include a component that constitutes the deposited film to be formed.

In the present invention, the precursor from the activation space (A) introduced into the film formation space has a lifetime of preferably 0.1 second or longer, more preferably 1 second or longer, most preferably 10 seconds or longer,
It is selected and used as desired, and the constituents of this precursor constitute the main constituents of the deposited film formed in the deposition space (A). The active species introduced from the activation space (B) has a lifetime of preferably 10 seconds or less, more preferably 5 seconds or less, most preferably 2 seconds or less. This active species is used when forming a deposited film in the film formation space.
At the same time, it is introduced into the deposition space from the activation space (A) and chemically interacts with the precursor containing the constituent elements that are the main constituent components of the deposited film formed. As a result, the desired deposited film is easily formed on the desired substrate.

According to the method of the present invention, the deposited film formed without generating plasma in the film formation space is substantially not adversely affected by etching action or other action such as abnormal discharge action. Further, according to the present invention, a more stable CVD method can be realized by arbitrarily controlling the atmospheric temperature of the film forming space and the substrate temperature as desired.

One of the points that the method of the present invention is different from the conventional CVD method is that the precursor is activated by applying excitation energy to the halogen-containing polymer silane compound in the solid state in a space different from the film formation space in advance. Is to use. By this,
The deposition rate can be dramatically increased compared to the conventional CVD method, and in addition, the substrate temperature can be further lowered when forming the deposited film, and a deposited film with stable film quality can be industrially produced. It can be provided in large quantities and at low cost.

The halogen-containing polymer silane compound used in the present invention has at least 7 or more silicon atoms, preferably 1 or more.
0 or more as a chain or ring component, and F, C
Examples of the compound include a halogen atom such as l, Br, and I as a substituent, and optionally one or more H atoms.

When the solid-state halogen-containing polymer silane compound of the present invention is activated by applying excitation energy, the silicon-silicon bond energy is silicon-halogen (in particular, F or C).
l) Since it is smaller than the binding energy, it is easy to use: Si
X ₂ ,: SiHX (X: halogen atom) radicals are generated, and these become precursors for forming a high quality amorphous silicon film.

In the present invention, the precursor generated in the activated space (A) is efficiently generated with a low excitation energy because the halogen-containing polymer silane compound having good decomposition efficiency is used.

In the present invention, the excitation energy used to generate the precursor is preferably one having relatively low excitation energy among electricity, light, heat and the like. For example, it is used at a low output for electric energy such as high frequency and DC, at a low light irradiation amount for light energy such as laser, ultraviolet and infrared rays, and at a low temperature for thermal energy such as resistance heating and high frequency heating.

In the present invention, the halogen-containing polymer silane compound used in the present invention is in a solid state at room temperature, atmospheric pressure or reduced pressure, and does not require a high-pressure container like the gas raw material gas generally used for storage, and can be used as a storage space. In addition, the safety can be significantly improved. Furthermore, since the precursor can be directly generated from the solid state, it is possible to increase the amount of precursor generated per unit volume of the raw material by increasing only the amount of excitation energy. There is no need for a gas flow meter such as a mass flow meter for controlling the raw material gas flow rate.

In the present invention, to generate the precursor, electricity, light,
In addition to the excitation energy of heat or the like, by further using the action of a catalyst, the excitation energy can be further lowered. As such a material, a simple substance and / or an alloy of a transition metal or a non-transition metal or an oxide thereof can be preferably used. However,
It is desirable to select a material that does not easily mix the material into the deposited film due to sublimation, scattering, or the like when excitation energy is applied.

Specifically, for example, Ti, Nb, Cr, Mo, W, F
e, Ni, Co, Rh, Pd, Mn, Ag, Zn, C
d, Na, K, Li, Pd-Ag, Ni-Cr, TiO
₂ , NiO, V ₂ O _{5 and the} like.

In the present invention, the raw materials introduced into the activation space (B) to generate active species include H ₂ , SiH ₄ , and SiH.
_{In addition to 3} F, SiH ₃ Cl, SiH ₃ Br, SiH ₃ I and the like, rare gases such as He and Ar can be used.

In the present invention, as a method of generating active species in the activation space (B), electric energy such as microwave, RF, low frequency, DC, etc., heater heating, infrared heating, etc. are taken into consideration in consideration of each condition and device. Activation energy such as heat energy or light energy is 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.

In the present invention, in addition to the activation energy described above,
Furthermore, the action of a catalyst can be used together.

As such a material, a transition metal, a non-transition metal simple substance and / or an alloy, or an oxide thereof can be preferably used.

Specifically, for example, Ti, Nb, Cr, Mo, W, F
e, Ni, Co, Rh, Pd, Mn, Ag, Zn, C
d, Na, K, Li, Pd-Ag, Ni-Cr, TiO
₂ , NiO, V ₂ O _{5 and the} like.

Further, as the activation condition, in addition to resistance heating by directly energizing the catalyst material, a method of packing these catalysts in a quartz tube or the like and indirectly heating it from the outside in an electric furnace, an infrared furnace or the like is adopted.

As the shape of the catalyst, the active cross-section of the active species can be changed by selecting any of granular, porous inorganic carrier with metal fine particles attached, filament, mesh, tube, or honeycomb. By controlling the reaction of the precursor with the active species, it is possible to form a uniform deposited film.

Next, the present invention will be described with reference to typical examples of electrophotographic image forming members formed by the deposited film manufacturing method of the present invention. FIG. 1 is a diagram for explaining a configuration example of a typical photoconductive member obtained by the present invention.

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

The support 11 may be conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, Al, Cr, Mo, Au, Ir, Nb, Ta,
Examples include metals such as V, Ti, Pt, and Pb 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, or polyamide, glass, ceramic, paper or the like is 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 of Ni, Cr, A
l, Cr, Mo, Au, Ir, Nb, Ta, V, Ti,
Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O
₃ + SnO ₂ ) or the like is provided with a conductive film, or if it is a synthetic resin film such as a polyester film, NiCr, Al, Ag, Pb, Zn, N
i, Au, Cr, Mo, Ir, Nb, Ta, V, Ti,
A metal such as Pt is processed by vacuum deposition, electron beam deposition, sputtering, or the like, or is laminated by the metal, and the surface thereof is conductively processed. The shape of the support can be any shape, such as a cylindrical shape, a belt shape, a plate shape,
If desired, its shape is determined, for example, the first
If the photoconductive member 10 shown in the figure is used only as an image forming member for electrophotography, in the case of continuous high-speed copying, it is desirable to have an endless belt or a cylinder.

The intermediate layer 12 effectively blocks the inflow of carriers from the support 11 side into the photosensitive layer 13 and is generated in the photosensitive layer 13 by the irradiation of electromagnetic waves, and moves toward the support 11 side. It has a function of easily allowing passage from the photosensitive layer 13 side to the support 11 side.

The intermediate layer 12 is made of amorphous silicon containing hydrogen atoms (H) and / or halogen atoms (X).
It describes as A-Si (H, X). ), And as a substance that controls electric conductivity, for example, a p-type impurity such as boron (B) or an n-type impurity such as phosphorus (P) is contained.

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

When the intermediate layer 12 is formed, the formation of the photosensitive layer 13 can be continuously performed. In that case, as a raw material for forming the intermediate layer, a precursor produced from the halogen-containing polymer silane compound in the activation space (A), a gas containing hydrogen, and if necessary, an inert gas and an impurity element are used. The compound contained as a component is introduced into the activation space (B) to generate active species, and these are introduced into the film formation space for vacuum deposition in which the support 11 is installed. The intermediate layer 12 may be formed on the support 11 by applying energy for film formation.

Effective starting materials that generate the active species that are introduced into the activation space (B) to form the intermediate layer 12 are SiH ₄ , SiH ₃ Cl, and SiH having H ₂ , Si, and H as constituent atoms.
Halogenated silanes rich in hydrogen such as ₃ F and SiH ₃ Br,
N as a constituent atom or N and H as constituent atoms, for example, nitrogen (N ₂ ), ammonia (NH ₃ ), hydrazine (H ₂ NNH ₂ ), hydrogen azide (HN ₃ ), ammonium azide ( Gaseous or gasifiable nitrogen, such as NH ₄ N ₃ ), nitrogen compounds such as nitrides and azides, C and H
A saturated hydrocarbon having 1 to 5 carbon atoms as a constituent atom,
Ethylene hydrocarbons having 2 to 5 carbon atoms, acetylene hydrocarbons having 2 to 4 carbon atoms, such as methane (CH ₄ ), ethane (C ₂ H ₅ ), propane (C ₃ H ₈ ), n-butane (n-C ₄ H ₁₀ ), pentane (C ₅ H ₁₂ ), ethylene-based hydrocarbons include ethylene (C ₂ H ₄ ), propylene (C ₃ H ₆ ), butene- 1
(C ₄ H ₈ ), butene-2 (C ₄ H ₈ ), isobutylene (C ₄ H ₅ ), pentene (C ₅ H ₁₀ ), acetylene-based hydrocarbons include acetylene (C ₂ H ₂ ), methylacetylene. (C ₃ H ₄ ), butyne (C ₄ H ₆ ), etc., and in addition to these, for example, oxygen (O ₂ ), ozone (O ₃ ), carbon monoxide (CO), carbon dioxide (CO ₂ ). , Carbon monoxide (NO), nitrogen dioxide (NO ₂ ), nitric oxide (N
₂ O) and the like.

These starting materials for forming the intermediate layer 12 are appropriately selected and used at the time of layer formation so that predetermined atoms are contained in the formed intermediate layer 12 as constituent atoms.

The layer thickness of the intermediate layer 12 is preferably 30 to 100.
It is desirable that it is 0Å, more preferably 50 to 600Å.

The photosensitive layer 13 contains a silicon atom as a base material, contains a halogen (X), and contains hydrogen (X) if necessary so as to have a photoconductive property capable of sufficiently exerting a function as an electrophotographic image forming member. A) containing amorphous silicon A-
It is composed of Si (H, X).

In the formation of the photosensitive layer 13, as in the case of the intermediate layer 12, a precursor is generated by exciting and decomposing the halogen-containing polymer silane compound in the activated space (A). The precursor is introduced into the film formation space. On the other hand, H ₂ , SiH ₄ , S is present in the activation space (B).
Raw material gas such as iH ₃ F is introduced to generate active species. The active species are introduced into the film formation space, and the activation space (A)
To chemically react with the pre-driving member introduced into the film-forming space, and as a result, the desired photosensitive layer 13 is deposited. The layer thickness of the photosensitive layer 13 is appropriately determined in accordance with the purpose according to the purpose of application.

The layer thickness of the photosensitive layer 3 shown in FIG.
The function of the intermediate layer 12 and the function of the intermediate layer 12 are appropriately determined in accordance with the desired relation in the layer thickness relationship with the intermediate layer 12, and in the normal case, with respect to the layer thickness of the intermediate layer 12. It is preferable that the layer thickness is several hundred to several thousand times or more.

A specific value is preferably 1 to 100 μ, and more preferably 2 to 50 μ.

The amount of H or X contained in the photoconductive layer of the photoconductive member shown in FIG. 1 is (halogen atom such as X = F) preferably 1
-40 atom%, more preferably 5-30 atom
ic% is desirable.

The photoconductive member shown in FIG. 1 may further have a surface layer provided on the photosensitive layer 13, if necessary. The surface layer provided is
In the case of a silicon carbide film, for example, SiH ₄ , CH ₄ , H ₂ or SiH ₄ , S in the activation space (B).
A raw material gas such as iH ₂ (CH ₃ ) ₂ is introduced, and excitation energy is further used if necessary, so that each of the precursor and the active species is generated in each space and they are separately supplied to the film formation space. A surface layer is deposited by introducing. Further, the surface layer is preferably a deposited film having a wide band cap such as a silicon nitride film or a silicon oxide film, and the film composition can be continuously changed from the photosensitive layer 13 to the surface layer.
When the surface layer is provided, the layer thickness is preferably 0.
The range of 01 μ-5 μ, and more preferably 0.05 μ-1 μ is desirable.

The deposited film formed by the method of the present invention can be doped with an impurity element during or after film formation. The impurities to be doped are p-type impurities, for example, elements of Group III A of the periodic table, such as B, Al and G.
Preferred examples thereof include a, In, Tl, and the like, and as the n-type impurities, an element of Group V group A of the periodic table, for example, N,
P, As, Sb, Bi and the like are mentioned as suitable ones, but P, Sb and As are particularly suitable.

As such a raw material for introducing impurities, those which are in a gas state at room temperature and normal pressure or which can be easily gasified under at least the layer forming conditions are adopted. Specific examples of such a starting material for introducing impurities include PH ₃ , P ₂ H ₄ , and P.
_{F 3, PF 5, PCl 3} , AsH 3, AsF 3, AsF
₅ , AsCl ₃ , SbH ₃ , SbF ₅ , BiH 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.

These impurities-introducing substances may be introduced into the activation space (A) or / and the activation space (B) together with the substances that generate the precursor and the active species, respectively, to be activated,
Alternatively, it may be activated in a third activation space (C) different from the activation space (A) and the activation space (B).

Example 1 Using the apparatus shown in FIG.
Type, p-type and n-type A-Si (H, X) deposited films were formed.

In FIG. 3, reference numeral 101 denotes a film forming chamber, on which a desired substrate 103 is placed on a substrate supporting base 102.

104 is a heater for heating the substrate,
Is used when the substrate 103 is heat-treated before the film formation process, or when the substrate 103 is annealed after the film formation so as to further improve the characteristics of the formed film. To do.

Reference numerals 106 to 109 denote gas supply sources, which are provided depending on the types of gas containing hydrogen, an inert gas used as necessary, and a gas of a compound containing an impurity element as a component.
If these gases are liquid in the standard state, an appropriate vaporizer is provided.

In the figure, the gas supply sources 106 to 109 are designated by a, a is a branch pipe, 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. 12
3 is an activation chamber (B) for generating active species. 12
Reference numeral 5 is a microwave generator. Gas introduction pipe 110
The source gas for active species generation supplied from the film is activated in the activation chamber (B) under the action of the microwave, and the generated active species is introduced through the introduction pipe 124 to the film forming chamber 10.
Introduced in 1. 111 is a gas pressure type.

In the figure, 112 is an activation chamber (A) for generating a precursor, 1
Reference numeral 13 is an electric furnace, 114 is a solid-state halogen-containing high-molecular-weight silane compound, 115 is an introduction tube of an inert gas as a carrier gas, which is used as necessary, and is a precursor generated in the activation chamber (A) 112. The body is introduced into the film forming chamber 101 via the introduction pipe 116.

Further, in the figure, 120 is an exhaust valve, and 121 is an exhaust pipe.

First, a substrate 1 made of polyethylene terephthalate film
03 was placed on the support 102, the inside of the film forming chamber 101 was evacuated by using an exhaust device, and the pressure was reduced to about 10 ⁻⁶ Torr. Next, H ₂ gas 50SCC is supplied from the gas supply cylinder 106.
M, PH ₃ gas or B ₂ H ₆ gas (100 for each)
A gas mixed with 0 ppm hydrogen gas (diluted with hydrogen gas of 40 SCCM) was introduced into the activation chamber (B) 123 through the gas introduction pipe 110. The H ₂ gas or the like introduced into the activation chamber (B) 123 was activated by the microwave generated by the microwave generator 125 into activated hydrogen or the like, and was introduced into the film forming chamber 101 through the introduction pipe 124.

On the other hand, (SiF ₂ ) _{16 to 18} 114 as a halogen-containing polymer silane compound are loaded in the activation chamber (A) 102, heated in an electric furnace 113 and kept at about 300 ° C., and SiF ₂ as a precursor is stored. ^* Was generated, and the SiF ₂ ^* was introduced into the film forming chamber 101 through the introduction pipe 116.

While maintaining the pressure in the film forming chamber 101 at 0.4 Torr, the temperature of the substrate 103 is set to 20 by the heater 104 for heating the substrate.
Undoped or doped A- kept at 0 ℃
A Si (H, X) film (film thickness 700Å) was formed. The film formation rate was 28Å / sec.

Then, the obtained non-doped or p-type A-Si
The sample with the (H, X) film formed is put in the vapor deposition layer, and the degree of vacuum is 1
After forming a comb type Al gear electrode (gear length 250 μ, width 5 mm) at 0 ⁻⁵ Torr, dark current with an applied voltage of 10 V was measured, dark conductivity σd was determined, and the film characteristics of each sample were evaluated. . The results are shown in Table 1.

Example 2 Instead of (SiF ₂ ) _{16 to 18} as the halogen-containing polymer silane compound in the activation chamber (A) 102, Si ₁₀ H ₄ F _{18 was used.}
Was heated in an electric furnace 113 and kept at about 400 ° C. according to the same method and procedure as in Example 1.
An i (H, X) film was formed. The dark conductivity of each sample was measured, and the results are shown in Table 1.

From Table 1, according to the present invention, A-Si having excellent electrical characteristics
It was found that a (H, X) film was obtained, and an A-Si (H, X) film that was sufficiently doped was obtained.

Example 3 Using the apparatus shown in FIG. 4, a drum-shaped electrophotographic image forming member having a layer structure as shown in FIG. 1 was prepared by the following operations.

In FIG. 4, 201 is a film forming chamber, 202 is an activation chamber (A), 203 is an infrared heating furnace, and 204 is (SiF ₂ ) _{12 to 14} , 205 as a halogen-containing polymer silane compound.
Is a carrier gas inlet pipe used as necessary, 20
6 is a precursor introduction tube, 207 is a motor, 208 is a heater used in the same manner as 104 in FIG. 3, 209, 2
10 is a blowing pipe, 211 is an Al cylinder-shaped substrate,
Reference numeral 212 denotes an exhaust valve. Also, 213 to 21
6 is a source gas supply source similar to 106 to 109 in FIG. 3, and 217-1 is a gas introduction pipe.

Hanging the Al cylinder substrate 211 in the film forming chamber 201,
A heater 208 is provided on the inside to increase the substrate temperature to 200.
The motor 207 is allowed to rotate while maintaining the temperature at ℃.

Further, the activation chamber (A) 202 to as the halogen-containing polymer silane compound packed _{(SiF 2) 12 ~ 14 204} , heated by an infrared heating furnace 203, maintained at about 280 ° C., through the introduction pipe 205 thereto He as a carrier gas was blown from a cylinder (not shown) to introduce SiF ₂ ^* generated as a precursor together with the He carrier gas into an inlet pipe 206.
After that, it was introduced into the film-forming mold 201.

On the other hand, power is supplied to the honeycomb-shaped tungsten 222 as a catalyst placed in the activation chamber (B) through the conductive wire 221, so that the catalyst is in a red hot state. Therefore, H _{2 is} introduced from the introduction pipe 217-1.
The gas was introduced into the activation chamber (B) 220. The introduced H ₂ gas became active hydrogen in the activation chamber (B) 220 under the action of the catalyst, and was introduced into the film forming chamber 201 through the introduction pipe 217-2. At this time, if necessary, PH ₃ ,
Impurity gas such as B ₂ H ₆ was also introduced into the activation chamber (B) 220 and activated.

The Al cylinder substrate 211 was rotated, and the exhaust gas was exhausted by appropriately adjusting the opening of the exhaust valve 212. Thus, the photosensitive layer 13 was formed.

Further, the intermediate layer 12 is H ₂ / B ₂ from the introduction pipe 217-1.
A mixed gas of H ₆ (0.2% of B ₂ H ₆ gas in volume%) was introduced to form a film with a film thickness of 2000 Å.

Comparative Example 1 A film forming chamber having the same structure as the film forming chamber 201 was prepared by using SiF ₄ and H ₂ and B ₂ H ₆ gases, and 13.56 MH was prepared.
An image forming member for electrophotography having a layer structure shown in FIG. 1 was formed by a general plasma CVD method provided with a high frequency generator of z.

Table 2 shows the manufacturing conditions and performance of the drum-shaped electrophotographic image-forming members obtained in Example 3 and Comparative Example 1.

Example 4 The PIN diode shown in FIG. 2 was produced using the apparatus shown in FIG.

First, place the polyethylene terephthalate film 21 having the 1000 Å ITO film 22 vapor-deposited on the support base, and
After the pressure was reduced to ^-6 Torr, the introduction pipe 11 was used as in Example 1.
6 to the precursor of SiF ₂ ^* , and the introduction tube 110 to H ₂
Gas and PH ₃ gas (diluted with 1000 ppm hydrogen gas) were introduced into the activation chamber (B) 123, and activated under the action of the microwave. Next, the activated gas was introduced into the film forming chamber 101 through the introduction pipe 124. The n-type A-Si (H, X) film 24 (film thickness 7) doped with P while maintaining the pressure in the film forming chamber 101 at 0.4 Torr.
00Å) was formed.

Next, instead of PH ₃ gas, B ₂ H ₆ gas (1000 p
i-type A-Si film 25 (film thickness 50) by the same method as in the case of the n-type A-Si film except that pm hydrogen gas dilution was introduced.
00Å) was formed.

Then, diborane gas with _{H 2} gas _{(B 2} H 6 100
A p-type A-Si (H, X) film 26 (film thickness 700 Å) doped with B was formed under the same conditions as n-type except for 0 ppm hydrogen dilution). Further, an Al electrode 27 having a film thickness of 1000 Å is formed on this p-type film by vacuum evaporation, and the PIN is formed.
A type diode was obtained.

I of the diode element (area: 1 cm ² ) thus obtained
The -V characteristic was measured, and the rectification characteristic and the photovoltaic effect were evaluated. The results are shown in Table 3.

Also in terms of light irradiation characteristics, when light is introduced from the substrate side and the light irradiation intensity is AMI (about 100 mW / cm ² ), conversion efficiency is 8.5% or more, open end voltage is 0.92 V, short-circuit current is 10 m.
A / cm ² was obtained.

Example 5 Instead of (SiF ₂ ) _{16 to 18} as a halogen-containing polymer silane compound in the activation chamber (A) 102, (SiHF) _{15 was used.
~ 19} packed, heated by electric furnace 113, about 500 ℃
A PIN diode similar to the one manufactured in Example 4 was manufactured in the same manner as in Example 4 except that the above was maintained. This sample was evaluated for rectification characteristics and photovoltaic effect, and the results are shown in Table 3.

From Table 3, it was found that according to the present invention, an A-Si (H, X) PIN type diode having better optical and electrical characteristics than before can be obtained.

〔The invention's effect〕

According to the deposited film forming method of the present invention, since the halogen-containing high-molecular weight silane compound in the solid state is used as the raw material for the precursor generation, it is possible to activate with a low excitation energy, which saves labor and activation efficiency. Can be improved.
In addition, the storage space and safety of raw material compounds can be significantly improved. Further, since low-temperature treatment is possible, the effect that the process can be shortened is also exhibited.

Furthermore, the desired electrical, optical, photoconductive and mechanical properties of the formed film are improved, and high-speed film formation is possible without keeping the substrate at a high temperature. In addition, the reproducibility in film formation is improved, the film quality can be improved and the film chamber can be made uniform, and it is advantageous for increasing the area of the film, making it easy to improve film productivity and mass production. can do.

[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 diode manufactured by using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams for explaining the constitution of the apparatus for carrying out the method of the present invention used in the examples. 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, 101, 201 ... film forming chamber, 112, 123, 202, 220 ... activation chamber, 203 ... infrared heating furnace, 125 ... microwave Generator, 222 ... Honeycomb-shaped tungsten, 221 ... Conductive wire, 106, 107, 108, 109, 213, 214, 2
15,216 ... Gas supply source, 103, 211 ... Base body.

Claims (1)

[Claims] 1. A precursor as a raw material for forming a deposited film, which is generated in an activation space (A) in a film formation space for forming a deposited film on a substrate, and an activation space (B). In the deposition film forming method of forming a deposition film on the substrate by introducing active species that are generated by the above process and interact with the precursor, the precursor is generated in the activation space (A). At this time, the general formula (SiX ₂ ) _n , (SiHx) _m , SizHxXy (where X is a halogen atom, n ≧ 7, m ≧ 7, z ≧
7, x ≧ 1, y ≧ 2z + 2-x) is applied to the solid-state halogen-containing polymer silane compound in the solid state to activate it to form a deposited film containing silicon atoms on the substrate. Deposited film forming method.