JPS63234513A - Deposition film formation - Google Patents

Abstract

PURPOSE:To contrive improvement in the consumption efficiency of raw gas used when a precursor is grown in an activating space, the efficiency used and the stabilization in quality of the titled deposition film by a method wherein a specific silicon-germanium compound is used as the material for generation of the precursor. CONSTITUTION:When a deposition film is formed on a substrate by introducing the precursor, which becomes the raw material to be used for formation of the deposition film grown in an activating space A of activation, and the active species which is grown in an activating space B of activation and interacts with the precursor into the film-forming space to be used for formation of a deposition film on the substrate, said precursor is grown from the compound as indicated by the formula separately shown. The X<1>-X<6> in the formula are substituents, and two or more of X<1>-X<3> and also two or more of X<4>-X<6> are selected from hydrogen atoms and halogen atoms. Consequently, the lowering of the substrate temperature when the deposition film is formed can be achieved, and the deposition film can be formed in excellent reproducible and mass- productive manner.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to deposited films, particularly functional films, particularly semiconductor devices, photovoltaic elements, line sensors for human power imaging, imaging devices, and photosensitive materials for electrophotography. The present invention relates to a method suitable for forming an amorphous or crystalline silicon germanium deposited film for use in devices and the like.

[Prior art]

For example, attempts have been made to form an amorphous silicon germanium film using a vacuum evaporation method, a plasma CVD method, a CVD method, a reactive sputtering method, an ion blasting method, a photo-CVD method, etc. Generally, the plasma CVD method is used. Widely used and commercialized.

However, deposited films composed of amorphous silicon germanium have poor electrical and optical properties, fatigue properties due to repeated use, use environment properties, and productivity and mass production, including uniformity and reproducibility. There is room to improve overall characteristics.

The reaction process in forming an amorphous silicon germanium deposited film using the conventionally popular plasma CVD method is considerably more complicated than that of the conventional CVD method, and there are many aspects of the reaction mechanism that are unclear. . In addition, there are many formation parameters for the deposited film (e.g., substrate temperature, flow rate and ratio of each introduced gas, pressure during formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, plasma generation method, etc.). Due to the combination of many parameters, the plasma sometimes becomes unstable, which often has a significant negative effect on the deposited film formed. Furthermore, the actual situation is that parameters unique to each device must be selected for each device, making it difficult to generalize manufacturing conditions.

On the other hand, in order to develop an amorphous silicon germanium film with electrical and optical properties that can sufficiently satisfy various uses, it is currently considered best to form the film by plasma CVD.

However, depending on the application of the deposited film, it is necessary to fully satisfy the requirements of large area, uniformity of film thickness, and uniformity of film quality.
Because it is necessary to achieve mass production with reproducibility, the formation of amorphous silicon germanium deposited films using the plasma CVD method requires a large amount of capital investment in mass production equipment, and the management items for mass production are also complicated. The allowable management range has become narrower, and equipment adjustments have become more delicate, so these have been pointed out as problems that need to be improved in the future.

On the other hand, the conventional technique using the normal CVD method requires high temperatures and has not been able to provide a deposited film with practically usable characteristics.

As mentioned above, it is strongly desired to develop a method for forming an amorphous silicon germanium film that can be mass-produced using low-cost equipment while maintaining its practically usable characteristics and uniformity.

In recent years, as a new deposited film formation method that eliminates the drawbacks of the plasma CVD method, the raw materials for film formation are activated in advance in a separate space (hereinafter referred to as "activation space"). A method has been proposed in which a film is formed by introducing only the active species into a film forming space.

However, in this method, SiF4 and Si2F6, which are generally commercially available and easily available, are used as a means for generating the precursor in the activation space.

Silane compounds such as 5jH4, 5j2H6 and GeH4.

Germanium compounds such as GeF4 are used, but since these raw material gases are stable, they are relatively cheap among electric energy such as microwaves, high frequencies, DC, thermal energy such as resistance heating, high frequency heating, and light energy. Large excitation energy is required. Moreover, the silane compound and the germanium compound must be activated and controlled independently. Therefore, with these methods, it is difficult to improve the activation efficiency beyond a certain level, and when considering mass production at low cost, it is necessary to further improve the amount of energy used and the efficiency of consumption of raw material gas. There is room to do so. Furthermore, it is necessary to consider how to simplify the activation control method and mass-produce stable, high-quality silicon germanium films.

[Purpose of the invention]

The present invention has been made in view of the above points, and it is an object of the present invention to significantly improve the consumption efficiency, energy consumption efficiency, and quality stability of the raw material gas used when generating precursors in the activation space. The purpose of the present invention is to provide a method for forming a deposited film.

[Summary of the invention]

The above purpose is to provide a film forming space for forming a deposited film on a substrate, a precursor which is a raw material for forming a deposited film generated in the activation space (A), and a precursor in the activation space (B). In the deposited film forming method of forming a deposited film on the substrate by respectively introducing active species that are generated and interact with the precursor, the precursor has a thickness of 3. x6 is a substituent, and two or more of x1 to x3 and two or more of x4 to x6 are each selected from hydrogen atoms and halogen atoms.) This is achieved by a deposited film forming method characterized in that it is produced.

One of the differences between the method of the present invention and the conventional CVD method is that it uses a precursor that has been activated by applying excitation energy to the raw material compound for forming the deposited film in a space different from the film forming space. That's true. This makes it possible to further reduce the substrate temperature during the formation of the deposited film, and to provide a deposited film of good quality in an industrially stable manner.

That is, according to the method of the present invention, the film formation parameters for forming a desired deposited film are the amount of introduced precursors and active species, the temperature of the substrate and the deposition space, and the internal pressure of the deposition space. Therefore, the formation of the deposited film can be easily controlled, and the deposited film can be formed with reproducibility and mass production.

Note that the "precursor" in the present invention refers to something that can serve as a raw material for the deposited film to be formed. "Active species" are those that chemically interact with the precursor to give energy to the precursor, or chemically react with the precursor to more efficiently form a deposited film. It refers to something that has the role of making things possible. Therefore, the active species may include constituent elements constituting the deposited film to be formed, or may not include such constituent elements.

When forming a deposited film in the film forming space, these active species are simultaneously introduced into the deposition space from the activation space (B) and chemically interact with the precursor containing the constituent elements that will be the main constituents of the deposited film to be formed. interact with. As a result, a desired deposited film can be easily formed on a desired substrate.

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

General formula % formula % used in the present invention (however, ×1 to ×6 are substituents, XI to ×3
Two or more of these and two or more of ×4 to ×6 are each selected from hydrogen atoms and halogen atoms. The halogen atoms contained in the silicon germanium compound represented by ) are preferably F, CI, Br, and I, and most preferably F and CI. When any of XI to X6 is a substituent other than hydrogen or a halogen atom,
This substituent is a monovalent, divalent, or trivalent hydrocarbon group derived from linear or side-chain saturated or unsaturated hydrocarbons, or a saturated or unsaturated monocyclic or polycyclic group. Mention may be made of monovalent, divalent and trivalent hydrocarbon groups derived from hydrocarbons.

When the silicon germanium compound used in the present invention is activated by applying excitation energy, the 5i-Ge bond is first broken depending on the amount of excitation energy applied, and the following compounds are formed: :5iX2, :GeX7, :5iHX
, :GeHX, :SiH,, :GeH
2. Generates radicals (H is a hydrogen atom, X is a halogen atom) such as :5ill(CH3), :GeH(CH3), etc., and becomes a precursor for forming a high quality silicon germanium deposited film.The above radicals Particularly preferred among these are :5iX7, :GeX2, :5iHX, :G
eHX, :5iH7, :GeH2. Also, according to the inventor's experiments, :Si (CH3) 7, :
It has been found that radicals having two hydrocarbon substituents, such as Ge (CH3) 2, are unfavorable in terms of film formation. Therefore, the set of XI I%l X3, and ×4 to ×6
It is necessary that each set of groups does not contain two or more hydrocarbon substituents such as II3.

When the silicon germanium compound used in the present invention is activated by applying excitation energy, depending on the amount of excitation energy applied: SjX'X2. :SiX
'X', :5iX2X', :GeX5
X6.

:GeX5X6. : Generates GeX5X6, etc., and becomes a precursor for forming a high quality silicon germanium deposited film.

In the present invention, the precursor produced in the activation space (A) is produced efficiently with relatively low excitation energy because a silicon germanium compound with high decomposition efficiency is used.

In the present invention, as the excitation energy used to generate the precursor, one with relatively low excitation energy among electricity, light, heat, etc. is preferably used. For example, electric energy such as high frequency and DC has a low output, and optical energy such as laser, ultraviolet, and infrared rays has a low light irradiation amount.
Thermal energy such as resistance heating and high frequency heating is used at low temperatures.

In the present invention, electricity, light,
In addition to excitation energy such as heat, it is possible to further reduce the excitation energy by using the action of a catalyst. As such materials, transition metals, non-transition metals, simple substances and/or alloys, or oxides thereof can be suitably used. However, it is desirable to select a material that is unlikely to mix into the deposited film due to sublimation, scattering, etc. when excitation energy is applied.

Specifically, for example, Ti, Nb, Or, Mo,
W, Fe.

Ni, Go, Rh, Pd, Mn, Ag, Z
n, Cd, Na, K, Li.

Pd-Ag, Ni-Cr, TiO2, Nip, V
2O, , W-Mo, W-Rh.

Examples include W-Re.

In the present invention, the raw materials introduced into the activation space (B) to generate active species are:)17. SiH4゜SiH3
F, 5iH3CI, 5iH3Br, 5iH3I
In addition to hydrogen-containing compounds such as, inert gases such as lle and Ar can be used as diluent gases.

In the present invention, methods for generating active species in the activation space (B) include electrical energy such as microwave, RF, low frequency, DC, heater heating, infrared heating, etc., taking into account each condition and device. Activation energy such as thermal energy, light energy, etc. is used.

In the present invention, in addition to the activation energy described above for generating active species, a catalyst that can be used in combination for generating the precursor described above can also be used here.

In addition to resistance heating by directly applying electricity to the catalyst material, the activation conditions include filling a quartz tube or the like with the catalyst and indirectly heating it from the outside using an electric furnace, an infrared furnace, etc.

The cross-sectional area of active species generation can be changed by selecting the shape of the catalyst from among granules, fine metal particles attached to a porous inorganic carrier, filaments, meshes, tubes, and honeycombs. , it is possible to control the reaction between the precursor and the active species and create a uniform deposited film.

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 include, as p-type impurities, elements of group A of the periodic table, such as B, AI,
Suitable examples include Ga, In, TI, etc.
Suitable n-type impurities include elements of Group V A of the periodic table, such as N, P, As, Sb, Bi, etc., with p and sb being particularly preferred.

As is optimal.

As the raw material for introducing such impurities, those that are in a gaseous state at normal temperature and normal pressure, or that can be easily gasified at least under layer-forming conditions, are employed. Specifically, starting materials for introducing such impurities include PH3, P2H4, PF3.
, PF5, PCl3. AsH3°AsF3.
AsF5. AsG13, SbH3,S
bF5. RoiH3, RF3.

BCl3, Br3, B2H6, B4H1
゜, B5H9, RO5Ho+B6H,. ,86H12,
AIGI:+ etc. can be mentioned.

These substances for introducing impurities may be introduced into the activation space (8) and/or the activation space (B) together with each substance that generates the precursor and the active species, and activated. Alternatively, the activation may be performed in a third activation space (C) that is separate from the activation space (A) and the activation space (B).

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, Z, etc.
AI, Or, Mo, Au, Ir, Nb.

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

As the electrically insulating substrate, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, boramid, etc., glass, ceramics, etc. are usually 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 N1Gr or AI.

Cr, Mo, Au, Ir, Nb, Ta, V
, Ti, Pt, Pd.

In2O3, 5n02. ITO (In203 +5n
02), or a synthetic resin film such as a polyester film, NiCr, AI, Ag, Pb, Zn.
, Ni, 8u, Gr, Mo, Ir
.

The surface is conductively treated by processing with a metal such as Nb, Ta, V, Ti, or Pt by vacuum evaporation, electron beam evaporation, sputtering, or the like, or by laminating with the metal. 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. Therefore, select a substrate that has a similar difference in thermal expansion between the two. It is preferable to do so.

In addition, the surface condition of the substrate is directly related to the structure (orientation) of the film and the generation of chain structures, so it is important to treat the surface of the substrate so that it has a film structure and structure that provides the desired characteristics. is desirable.

An example of a method for implementing the present invention will be described in detail below based on the drawings.

FIG. 1 is a schematic diagram of a deposited film forming apparatus for carrying out the forming force method for forming a thin film multilayer structure according to the present invention.

This device includes a heating element 105 made of a single transition metal or an alloy as a means for generating a precursor and/or an active species for forming a deposited film, and two activation chambers (A);
(B) is provided.

101 is a vacuum chamber, in which a heating element 105 made of a single transition metal or an alloy is placed facing a base 117. The heating element 105 is connected to a power supply device (not shown) through a conductive wire 106, and is supplied with electric power and generates heat.

Reference numeral 102 denotes a raw material introduction pipe for forming a deposited film, into which raw material is introduced from a cylinder (not shown) through a valve 104 and a gas supply vibrator 103.

Reference numeral 120 denotes a substrate heating heater that heats the substrate 117 to an appropriate temperature during film formation, preheats the substrate 117 before film formation, and further heats the substrate 117 to anneal the film after film formation. It is.

The heater 120 for heating the substrate is supplied with electric power by a temperature controller 122 via a conductive wire 128 .

121 is a thermocouple for measuring and controlling the temperature of the substrate (Ts), and is connected to the temperature controller 122 by a conductive wire 108.

Further, the distance between the base holder 138 on which the base 117 is installed and the heat generating element 105 can be changed as appropriate using a fixing jig 119.

The vacuum chamber 101 also includes an activation chamber (A) 11.
2 and (B) 107, an excitation energy generation device 114 is connected to the activation chamber (A), and an excitation energy generation device 109 is connected to the activation chamber (B).

The activation chamber (A) 112 is filled with a catalyst or the like as required, and excitation energy is applied by an excitation energy generator 114. The raw material gas for precursor generation introduced from a cylinder (not shown) is supplied to the valve 116 and the gas supply vibrator 1.
The precursor is introduced into the activation chamber (A) 112 via the inlet pipe 15 and activated to produce a precursor for forming a deposited film.

On the other hand, in the activation chamber (B) 107, the raw material gas for active species generation introduced from a cylinder (not shown) through the valve 111 and the gas supply vibrator 110 is converted into the excitation energy supplied from the excitation energy generator 109. Active species are generated under the action, and the active species enter the film forming space 1 from the introduction pipe 127.
It will lead you to 25.

In the case of the present invention, the distance between the substrate 117 and the gas outlet of the inlet pipe 113. It can be determined so that the state will be

Each gas introduction pipe, each gas supply vibe line, and the vacuum chamber 101 are evacuated by a vacuum exhaust device (not shown) via a main vacuum valve 123 and a main exhaust pipe 124, and the pressure inside the vacuum chamber 101 at that time is A total of 126 monitors are used.

In this way, by carrying out the present invention using the above-mentioned apparatus or the like, a deposited film containing silicon atoms and germanium atoms is formed.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to Examples.

Example 1 First, a substrate 117 made of glass (Corning 7059) was placed on the substrate holder 118 of the apparatus shown in FIG.
The pressure inside the vacuum chamber 101 was reduced to approximately 1 O-GTorr via the main vacuum valve 123 and the main exhaust pipe 124 using an exhaust device (not shown).

Next, 200 SCCM of hydrogen gas (10% diluted with Ar) was introduced into the activation chamber (B) 107 via the valve 111 and the gas supply vibe 110 using a cylinder (not shown).

The hydrogen gas etc. introduced into the activation chamber (B) 107,
Microwaves (15
0W), and introduced into the film forming space 125 through the introduction pipe 127.

On the other hand, a silicon germanium compound represented by the structural formula shown in Table 1 was supplied to the valve 11 from a cylinder (not shown).
6, Activation chamber (A) through gas supply pipe month 5 11
Introduced at a flow rate of 30 SCCM into 2 and infrared heating furnace 11
4 to maintain the interior at 300 ''C to generate precursors such as :SiF2.:GeF2, which were introduced into the film forming space 25 through the introduction pipe 113.

While maintaining the pressure in the film forming space 125 at 1.2 Torr, the temperature of the substrate 117 was maintained at 200° C. using the substrate heating heater 120, and a silicon germanium deposited film was formed.

Next, the optical band gap of the sample on which the obtained silicon germanium deposited film was formed was measured. The results are shown in Table 1.

Examples 2 to 16 Silicon germanium deposited films were formed in the same manner as in Example 1, except that various silicon germanium compounds shown in Table 1 were used and the flow rate and temperature in the activation chamber were varied. Table 1 shows the optical band gap of each deposited film obtained.

Table 1 Table 1 (continued) 3 Examples 17 to 22 Example 1 except that the infrared heating furnace used in Example 1 was replaced with a microwave generator and the conditions shown in Table 2 were used.
A silicon germanium deposited film was formed in the same manner as above, and the evaluation results are shown in Table 2.

Table 2 Example 23 A solar cell having the structure shown in FIG. 2 was manufactured using the deposited film forming apparatus shown in FIG. 1 in the following manner.

This solar cell includes a transparent electrode (not shown) on a glass substrate 200, a p-type amorphous silicon layer 201 (first layer, thickness 250
), i-type amorphous silicon germanium layer 202 (second
The second layer is formed by the method of the present invention. It is.

First, the glass substrate 200 on which a transparent electrode was deposited was placed on the substrate holder 118 in the vacuum chamber 101, and the vacuum chamber 101 was evacuated from the main exhaust pipe 124 to set the pressure in the vacuum chamber 101 to about 10 Torr. Substrate heating heater 1
20 was heated by a temperature controller 122, and the substrate temperature was maintained at 220°C.

Next, in depositing the p-type amorphous silicon layer 201, hydrogen gas is supplied from a cylinder (not shown) at a flow rate of 15S [;M
, 5i2F also has a gas flow rate of 35 SCC, M, O, /
H2 gas (BF3 concentration 5000 ppm) flow rate 105
The main vacuum valve 1 is introduced into the vacuum chamber 101 from the gas introduction pipe 102 via the CCM Teharub 104 and the gas supply pipe 103, and the internal pressure is 1.0 Torr.
The p-type amorphous silicon layer 201 was formed by heating the tungsten filament 105 to about 1800° C. while adjusting the opening degree of the tungsten filament 23 . However, the distance between the filament 105 and the base 117 was 20 mm. After forming the first layer, the heating of the filament 105 is stopped, and the supply of all gases is also stopped, so that the internal pressure in the vacuum chamber 101 is reduced to 1.
The exhaust was pumped to □ where 0= Torr.

Subsequently, the i-type amorphous silicon germanium layer 202 and the n-type amorphous silicon layer 203 are formed using a precursor for forming a deposited film and an active species that interacts with this precursor separately in the vacuum chamber 101. It was deposited by introducing it into a mixture and reacting with it. That is, in the i-type amorphous silicon germanium layer 202, F3SiGeF is heated from a cylinder (not shown).
Three gases were introduced into the activation chamber (A) 112 via a valve 116 and a gas supply pipe 115 at a flow rate of 30 SCCM. At this time, the activation chamber (A) is heated to 450° C. by an infrared heating furnace 114. Next, hydrogen gas (10% diluted with Ar) was supplied from a cylinder (not shown) at a flow rate of 200 S.
:M via valve III and gas supply vibrator 110,
It was introduced into the activation chamber (B) +07. Microwave generator immediately] From 09 to activation chamber (B) 1 in 107
50W of microwave power was supplied. The precursors and activated species generated in the activation chambers (8) 112 and (11) 107 by these operations are introduced into the vacuum chamber 101 through the introduction pipes 113 and 127, and the internal pressure is reduced to 0.9 T.
The second layer 202 of i-type amorphous silicon germanium is adjusted while adjusting the opening degree of the main vacuum valve 123 so that the
was formed.

After forming the second layer, the supply of microwave power from the microwave generator 109 is stopped, and the supply of all gases is also stopped, so that the internal pressure of the vacuum chamber 101 reaches 10=Tor.
It was evacuated until r.

A third layer 203 of phosphorus-doped amorphous silicon is formed by the same operating procedure as for forming the second layer 202, but with SiF instead of F3SiGeF3 gas.
4 gases were introduced into the activation chamber (A) at a flow rate of 305 CCM,
Also, hydrogen gas (10% diluted with Ar) flow rate 20 SCCM
and PF5 gas (OOppm diluted with H2) flow rate 15
S(:CM) is introduced into the activation chamber <B) 107 via the valve 111 and the gas supply vibrator 110.

After forming the first to third layers on the substrate 200 in this way,
After cooling, the third layer 2 is removed from the vacuum chamber 101.
An AI electrode 204 was deposited on 03.

The solar cell thus formed is exposed to light (AM-1 is
The light irradiation intensity of 100 mw/cm 2 used as a standard for solar cell evaluation is shown. ) was irradiated and the energy conversion efficiency was measured, and the energy conversion efficiency was improved by 15% or more compared to the case where all layers were formed only by plasma CVD method.

Example 24 An electrophotographic image forming member having the structure shown in FIG. 3 was manufactured using the deposited film forming apparatus shown in FIG. 1 in the following manner.

This electrophotographic image forming member has a light antireflection layer 301 (first layer, an amorphous silicon germanium layer whose forbidden band width is controlled by Ge, and has a thickness of 0.2
5 μIn), charge injection prevention layer 302 (second layer, B-doped amorphous silicon layer, thickness 0.3 μL)
l1), photosensitive layer 303 (third layer, amorphous silicon layer, thickness: 18 μIn), surface protection layer and light absorption increasing layer 304 (fourth layer, amorphous silicon layer whose forbidden band width is controlled by C), The first layer is a silicon carbide layer having a thickness of 0.5 μm, and the first layer is formed by the method of the present invention.

The above-mentioned electrophotographic image forming member was manufactured in the same manner as in Example 23 except that the conditions shown in Table 3 were used. However, "tungsten mesh (1800° C.)" in the deposition method in Table 3 indicates a method using a mesh-like heating element instead of the filament 105 in Example 1.

As a result, the charging characteristics were improved by more than 20% compared to the case where all layers were formed using only the plasma CVD method, and the number of image defects was also reduced by 10%.
The sensitivity was improved by more than 20%.

〔Effect of the invention〕

According to the deposited film forming method of the present invention (where x1 to x6 are substituents, two or more of x1 to x3 and two or more of x4 to x6 are hydrogen atoms, respectively) Since the silicon germanium compound represented by (selected from halogen atoms) is used as the raw material for precursor generation, it can be activated with low excitation energy, saving labor and improving activation efficiency. can. Furthermore, since low-temperature processing is possible, the process can be shortened.

Additionally, the desired electrical, optical, photoconductive, and mechanical properties of the resulting film are improved, and high quality deposited films can be formed without maintaining the substrate at elevated temperatures. In addition, the reproducibility in film formation is improved, making it possible to improve film quality and make the film uniform. It is also advantageous for increasing the area of the film, improving film productivity and easily achieving mass production. be able to.

[Brief explanation of the drawing]

FIG. 1 is a schematic configuration diagram of a deposited film forming apparatus, and FIG. 2 is a
FIG. 3 is a schematic diagram of a solar cell manufactured according to Example 23 of the present invention. FIG. 3 is a schematic diagram of an image forming member for electrophotography manufactured according to Example 24 of the present invention. 101: Vacuum chamber 102: Gas introduction pipe 103, 110.115: Gas supply pipe 104,
III, 116: Valve 105: Heating element 106, 108. 128: Conductor 107: Activation chamber (B) 109, 114: Excitation energy generator 112: Activation chamber (8) 113, 127: Introductory pipe 117: Substrate 118 : Substrate holder 119: Fixing jig 120: Substrate heating heater 121: Thermocouple 122: Temperature controller 123: Main vacuum valve 124: Main exhaust pipe 125: Film forming space 126: Pressure gauge 200 Glass substrate 201: First layer ( p-type amorphous silicon layer) 202: second
Layer (i-type amorphous silicon germanium layer) 203: Third layer (n-type amorphous silicon layer) 204:
Al electrode 300: Al base 301: First layer (amorphous silicon germanium layer)

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, a precursor that is a raw material for forming a deposited film generated in the activation space (A) and the activation space (B) By respectively introducing active species that are generated in and interact with the precursor,
In the deposited film forming method of forming a deposited film on the substrate,
The precursor has a general formula, ▲mathematical formula, chemical formula, table, etc.▼ (However, X^1 to X^6 are substituents, and X^1 to X
Two or more of ^3 and two or more of X^4 to X^6 are each selected from hydrogen atoms and halogen atoms. ) A method for forming a deposited film, characterized in that it is produced from a compound represented by: