JP2505732B2 - Deposited film formation method - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to a deposited film containing silicon, particularly a functional film, particularly a semiconductor device, a photosensitive device for electrophotography,
The present invention relates to a method suitable for forming a non-single crystalline silicon-containing deposited film such as an amorphous or polycrystalline material used in a line sensor for image input, an imaging device, and the like.

[Prior art]

For example, vacuum vapor deposition method, plasma CVD method, CVD method, reactive sputtering method, ion plating method, optical CVD method, etc. have been tried for forming an amorphous silicon film. Is widely used,
It has been commercialized.

In addition, the deposited film composed of amorphous silicon has electrical and optical characteristics, fatigue characteristics after repeated use or environment characteristics, and productivity, including uniformity and reproducibility, and mass productivity. There is room to improve the overall characteristics.

The reaction process in the formation of amorphous silicon deposited film by the plasma CVD method, which has been generalized in the past, is considerably more complicated than that of the conventional CVD method, and the reaction mechanism is not clear. . In addition, there are many formation parameters for the deposited film (for example, substrate temperature, introduced gas flow rate and ratio, formation pressure, high-frequency power, electrode structure,
Due to the combination of these many parameters (the structure of the reaction vessel, the exhaust rate, the plasma generation method, etc.), the plasma sometimes becomes unstable and the deposited film formed is significantly adversely affected. Moreover, device-specific parameters must be set for each device,
Therefore, it is difficult to generalize the manufacturing conditions. On the other hand, in order to develop an amorphous silicon film that can sufficiently satisfy each of electrical, optical, photoconductive and mechanical properties, it is currently best formed by the plasma CVD method. ing.

However, depending on the application of the deposited film, it is necessary to achieve a large area, uniform film thickness, uniform film quality, and mass production with reproducibility by high-speed film formation. In the formation of amorphous silicon deposited film by the method, a large amount of capital investment is required for mass production equipment, and the management items for mass production are complicated, the control allowance is narrowed, and the adjustment of equipment is delicate. Therefore, 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 the formation of the amorphous silicon film,
It is earnestly desired to develop a forming method that can be mass-produced by a low-cost device 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.

The present invention eliminates the above-mentioned drawbacks of the plasma CVD method and provides a novel deposited film forming method which does not rely on the conventional forming method.

[Object and Summary of Invention]

The object of the present invention is to obtain various characteristics of a formed film, a film formation rate,
It is an object of the present invention to provide a deposited film forming method capable of easily achieving improvement in productivity and mass production of a film against a large area of the film while improving reproducibility and uniforming film quality. .

An object of the present invention is to provide a first active species (A) generated by decomposing a compound containing silicon and halogen in a film formation space for forming a deposited film on a substrate, and the first active species (A). Includes a second active species (B) produced from H ₂ gas or a mixed gas of H ₂ gas and F ₂ gas that chemically interacts with species (A) and an element of Group III A of the periodic table And a mixed species of the activated impurity-introducing substance gas or a mixed species of the activated species (B) and the activated impurity-introducing substance gas containing an element of Group V group A of the periodic table, respectively. This is achieved by a deposited film forming method of forming a deposited film on the substrate by introducing them separately and irradiating them with light energy.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film formation space for forming a deposited film, active species (A) generated by decomposing a compound containing silicon and halogen and a chemical substance for film formation are used. Active species generated (B)
In the coexistence with, in order to cause, promote, or amplify the chemical interaction of these by applying light energy to them, the deposited film formed has an etching effect or other For example, it is not adversely affected by the 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.

Further, the excitation energy is uniformly or selectively applied to each active species that has reached the vicinity of the substrate for film formation. However, if light energy is used, the entire substrate is prepared by using an appropriate optical system. The deposited film can be formed by irradiation, or the deposited film can be partially formed by selectively and selectively irradiating only a desired portion, and only a predetermined graphic portion can be formed by using a resist or the like. It is advantageously used because it has the convenience of being able to irradiate the surface of the film and form a deposited film.

One of the differences between the method of the present invention and the conventional CVD method is that the activated species previously activated in a space different from the film formation space (hereinafter referred to as an activation space) are used. As a result, it is possible to dramatically increase the deposition rate compared to the conventional CVD method, and it is also possible to further lower the substrate temperature for forming the deposited film, and to obtain a deposited film with stable film quality. It can be provided industrially in large quantities and at low cost. In the present invention, the active species (A) from the activation space (A) that is introduced into the film formation space is, in terms of productivity and ease of handling,
The lifetime of which is 0.1 second or more, more preferably 1 second or more, optimally 10 seconds or more is selected and used as desired, and the constituents of the active species (A) are formed in the film formation space. It constitutes the constituents of the membrane. or,
The chemical substance for film formation is activated by being activated with activation energy in the activation space (B), introduced into the film formation space, and excited by the action of light energy to form a deposited film. At the same time, it chemically interacts with the active species (A) which is introduced from the activation space (A) at the same time and includes the constituent elements which are constituent components of the deposited film formed. As a result, the desired deposited film is easily formed on the desired substrate.

In the present invention, as the compound containing silicon and halogen introduced into the activation space (A), 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. _Specifically , for example, Si _u Y _{2u + 2} (u is an integer of 1 or more, Y is F, CL, Br and I
It is at least one element selected from the above. ), A chain silicon halide represented by Si _V Y _2V (v is an integer of 3 or more, Y has the above-mentioned meaning), and Si _u HxYy (u and Y have the above-mentioned meanings). And a chain or cyclic compound represented by x + y = 2u or 2u + 2.

Specifically, for example, SiF ₄ , (SiF ₂ ) ₅ , (SiF ₂ ) ₆ , (SiF _{4
F 2) 4, Si 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 , SiHCl ₃ , SiHBr
Examples thereof include those that are in a gas state or can be easily gasified, such as ₃ , SiHi ₃ , and Si ₂ Cl ₃ F ₃ .

In order to generate the active species (A), in addition to the compound containing silicon and halogen, other silicon compounds such as simple substance of silicon, hydrogen and halogen compounds (for example, F ₂
Gas, Cl ₂ gas, gasified Br ₂ , I _2, etc.) can be used together.

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

By adding excitation energy such as heat, light, or electricity in the activation space (A) to the above, the active species (A)
Is generated.

In the activation space (B) used in the method of the present invention, the chemical substances for forming the active species (B) are hydrogen gas or hydrogen gas and halogen gas (for example, F ₂ gas, Cl ₂ gases, gasified Br ₂ , I ₂ etc.) are advantageously used. In addition to these film-forming chemicals,
For example, an inert gas such as helium, argon or neon can be used.

In the present invention, the ratio of the amount of the active species (A) and the amount of the active species (B) introduced into the film forming space depends on the film forming conditions,
It is determined as appropriate depending on the kind of the active species and the like, but it is preferably from 10: 1 to 1:10 (introduction flow ratio), and more preferably from 8: 2 to 4: 6.

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

As the substance containing such an impurity element as a component (impurity introducing substance), a compound that is in a gas state at room temperature and atmospheric pressure or is a gas at least under activation conditions and can be easily vaporized by an appropriate vaporizer is used. It is preferable to select it. 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.

Next, the present invention will be described with reference to typical examples of electrophotographic image forming members formed by the method of the present invention.

FIG. 1 is a schematic view for explaining a structural example of a photoconductive member as a typical electrophotographic image forming member obtained by the present invention.

The photoconductive member 10 shown in FIG. 1 can be applied as an electrophotographic image forming member, and an intermediate layer 12, which is optionally provided on a support 11 for a photoconductive member,
And a photosensitive layer 13.

The support 11 may be conductive or electrically insulating. As the conductive support, for example, NiCr, stainless steel,
Examples thereof include metals such as Al, Cr, Mo, Au, Ir, Nb, Ta, 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 desirable 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, its surface NiCr, Al, Cr, Mo, Au, I
r, Nb, Ta, V, Ti, Pt, Pb, In ₂ O ₃ , SnO ₂ ,, ITO (In ₂ O ₃ + SnO ₂ )
Conductive treatment by providing a thin film such as, or synthetic resin film such as polyester film,
NiCr, Al, Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb, Ta, V, Ti, Pt, etc., processed by vacuum evaporation, electron beam evaporation, sputtering, etc. After laminating, the surface is conductively treated. 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.
When used as an electrophotographic image forming member, in the case of continuous high speed copying, an endless belt shape or a cylindrical shape is desirable.

The intermediate layer 12, for example, 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 allowing the photocarrier to easily pass from the photosensitive layer 13 side to the support 11 side.

The intermediate layer 12 includes hydrogen atoms (H) or hydrogen atoms (H).
And an amorphous silicon containing a halogen atom (X) (hereinafter referred to as a-Si (H, X)), and as a substance that controls electric conductivity, for example, p (p) such as boron (B) is used. Type impurities or n-type impurities such as phosphorus (P) are contained.

In the present invention, the content of the substances that control conductivity such as B and P contained in the intermediate layer 12 is preferably 0.00
1-5 × 10 ⁴ atomic ppm, more preferably 0.5-1 × 10 ⁴ atom
ic 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 can be performed continuously from the formation of the intermediate layer 12 to the formation of the photosensitive layer 13. In that case, as the raw material for forming the intermediate layer, the active species (A) generated in the activation space (A) and the active species (B) generated from the chemical substance for film formation were activated. The mixed species with the substance gas for introducing impurities is mixed with and introduced into the film formation space in which the support 11 is installed, and the coexisting atmosphere of each introduced active species is caused to act on the light energy, thereby supporting The intermediate layer 12 may be formed on the body 11.

As the compound containing silicon and halogen which is introduced into the activation space (A) to form the active species (A) when the intermediate layer 12 is formed, an active species (A) such as SiF ₂ ^* can be easily used.
It is desirable to select the compound producing the above from among the compounds described above.

The layer thickness of the intermediate layer 12 is preferably 30Å to 100000Å, more preferably 40Å to 80,000Å, and most preferably 50Å to 50000Å.

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

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

The photosensitive layer 13 is a non-doped a-Si (H, X) layer,
If desired, a substance having a different polarity (for example, n-type) that has a conductivity property from the polarity of the substance that has a conductivity property that is contained in the intermediate layer 12 may be contained, or the same polarity conductivity property may be used. When the actual amount contained in the intermediate layer 12 is large, the controlling substance may be contained in a much smaller amount than that.

Also in the case of forming the photosensitive layer 13, as long as it is formed by the method of the present invention, as in the case of the intermediate layer 12, a compound containing silicon and halogen is introduced into the activation space (A), and it is heated at a high temperature. The active species (A) are generated by decomposing these or by exciting by applying discharge energy or light energy, and the active species (A) is introduced into the film formation space.

FIG. 2 is a schematic view 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, i-type a-Si (H, X)
The layer 25 is composed of a p-type a-Si layer (H, X) 26. 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. As the thin film electrodes 22 and 27, for example, NiCr, Al, Cr,
Mo, Au, Ir, Nb, Ta, V, Ti, Pt, Pd, In ₂ O ₃ , SnO ₂ , ITO (In ₂ O ₃ +
It can be obtained by providing a thin film such as SnO ₂ ) on the substrate 21 by a process such as vacuum vapor deposition, electron beam vapor deposition, and sputtering. The thickness of the electrodes 22 and 27 is preferably 30 to 5 × 1
It is desirable that it is 0 ⁴ Å, more preferably 100 to 5 × 10 ³ Å.

In order to form the n-type, i-type and p-type a-Si (H, X) layers, a compound containing silicon and halogen is introduced into the activation space (A) by the method of the present invention, and the activation energy By exciting and decomposing these by action, active species (A) such as SiF ₂ ^* are generated, and the active species (A) are introduced into the film formation space. Separately from this, the chemical substance for film formation and the substance gas for introducing impurities are excited by activation energy and decomposed to generate each active species, and each is separately or appropriately mixed. And is introduced into the film forming space where the support 11 is installed. The active species introduced into the film formation space are subjected to a chemical interaction by using light energy, or are promoted or amplified to form a deposited film on the support 11. The thickness of the n-type and p-type a-Si (H, X) layers is preferably 100 to 10 ⁴ Å, more preferably
The range of 300 to 2000Å is desirable.

Moreover, i-type a-Si (H, X) as the thickness of the layer, preferably 500 to ⁴ Å, more preferably in the range of 1000~10000Å it is desirable.

 Specific examples of the present invention will be shown below.

Example 1 Using the apparatus shown in FIG. 3, i-type, p-type and n-type a-Si (H, X) deposited films were formed by the following operations.

In FIG. 3, 101 is a deposition chamber as a film forming space, on which a desired substrate 103 is placed on a substrate support 102.

104 is a heater for heating the substrate, and the heater 104
Is used when the substrate 104 is heat-treated before the film formation process or after the film formation is annealed to further improve the characteristics of the formed film. To do. The heater 104 is not driven during film formation.

Reference numerals 106 to 109 denote gas supply systems, which are provided in accordance with the gas for film formation and the substance gas for introducing impurities. If these gases are liquid in the standard state, an appropriate vaporizer is provided.

In the figure, reference numerals of the gas supply systems 106 to 109 are denoted by a, 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. 123 is an activation chamber (B) for generating active species (B), and microwave plasma generation that generates activation energy for generating active species (B) is provided around the activation chamber 123. apparatus
122 is provided. The raw material gas for generating the active species (B) supplied from the gas introduction pipe 110 is activated in the activation chamber (B) and the generated active species (B) is introduced through the introduction pipe 124 to form a film formation chamber. Introduced in 101. 111 is a gas pressure gauge.

In the figure, 112 is an activation chamber (A), 113 is an electric furnace, and 114 is solid S.
i grain, 115 is an introduction pipe of a compound containing silicon and halogen in a gaseous state, which is a raw material of the activated species (A), and the activated species (A) generated in the activation chamber (A) 112 flows through the introduction pipe 116. It is introduced into the film forming chamber 101 through the above.

Reference numeral 117 is a light energy generator, and for example, a mercury lamp, a xenon lamp, a carbon dioxide gas laser, an argon ion laser, an excimer laser or the like is used.

Light directed from the light energy generator 117 to the entire substrate 103 or a desired portion of the substrate 103 using an appropriate optical system.
118 is irradiated to the active species flowing in the direction of arrow 119,
The irradiated active species chemically react with each other to form an a-Si (H, X) deposited film on the whole or a desired portion of the substrate 103.

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

First, a base made of polyethylene terephthalate film
103 was placed on the support 102, and the inside of the film forming chamber 101 was evacuated using an exhaust device (not shown) to reduce the pressure to about 10 ⁻⁶ Torr. From the gas supply cylinder 106, H ₂ gas 150 SCCM, and PH ₃ gas (100
A gas mixed with 0 ppm hydrogen gas 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 is activated by the microwave plasma generator 122 into activated hydrogen or the like,
Active hydrogen or the like was introduced into the film forming chamber 101 through the introduction pipe 124.

On the other hand, the activation chamber (A) 102 is filled with solid Si particles 114, heated in an electric furnace 113 and kept at about 1100 ° C. to bring Si into a red heat state, and Si is introduced into the SiF from a cylinder (not shown) through an introduction pipe 115. By blowing in ₄ , as active species (A)
The SiF ₂ ^* is generated, and the SiF ₂ ^* is introduced into the film forming chamber 1 through the introduction pipe 116.
Introduced to 01.

While maintaining the pressure in the film forming chamber 101 at 0.4 Torr, the substrate 103 is vertically irradiated from a 1KWXe lamp to form n-type a-Si (H, X) films (film thickness 700Å) doped with phosphorus. did. The film formation rate was 25Å / sec.

Further, the same as the above except that a mixed gas of H ₂ gas 150 SCCM and B ₂ H ₆ gas (1000 ppm hydrogen gas dilution) 40 SCCM is used instead of the mixed gas introduced into the activation chamber (B) 123. A sample having a p-type a-Si (H, X) film doped with boron was prepared by the above method.

In addition, a non-doped a-Si is prepared by the same method as described above except that the use of PH ₃ gas and B ₂ H ₆ gas described above is omitted.
A sample (comparative sample) having a (H, X) film was prepared.

Next, samples obtained by forming a non-doped (comparative non-doped sample), n-type (P-doped sample of the present invention) and p-type (B-doped sample of the present invention) a-Si (H, X) films respectively In a vapor deposition tank, and after forming a comb-shaped Al gear tip electrode (gear length 250μ, width 5mm) at a vacuum degree of 10 ^-5 Torr, the dark current with an applied voltage of 10 V was measured to obtain the dark conductivity σd,
The film characteristics of each sample were evaluated. The results are shown in Table 1.

Example 2 Example 1 was repeated except that an H ₂ / F ₂ mixed gas (mixing ratio H ₂ / F ₂ = 10) was used instead of the H ₂ gas from the gas supply cylinder 106 or the like.
An a-Si (H, X) film was formed according to the same method and procedure as those of the present invention sample and the comparative sample. 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 electric characteristics is obtained.
It can be seen that a (H, X) film can be obtained and an a-Si (H, X) film that is sufficiently doped can be 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 electric furnace, 204 is a solid Si grain, 205 is a raw material introduction pipe of active species (A), and 206 is active species (A). ) Introductory pipe, 2
Reference numeral 07 is a motor, 208 is a heater used in the same manner as 104 in FIG. 3, 209 and 210 are blowing pipes, 211 is an Al cylinder-shaped substrate, and 212 is an exhaust valve. Also, 213 or
216 is a raw material gas supply system similar to 106 to 109 in FIG. 3, and 217-1 is a gas introduction pipe.

An Al cylinder substrate 211 is hung in the film forming chamber 201, a heater 208 is provided inside it, and it can be rotated by a motor 207. 218 is a light energy generator,
l Light 219 toward the desired portion of the film formation surface of the cylinder base 211.
Is irradiated.

Further, the activation chamber (A) 202 is filled with solid Si particles 204, heated by an electric furnace 203 and kept at 1100 ° C. to turn Si into a red heat state, and SiF ₄ is introduced from a cylinder (not shown) through an introduction pipe 206 to the SiF _{4 state.}
Was blown in to generate SiF ₂ ^* as the active species (A), and the SiF ₂ ^* was introduced into the film forming chamber 201 through the introduction pipe 206.

On the other hand, H ₂ gas is introduced from the introduction pipe 217-1 into the activation chamber (B) 220
Introduced in. The introduced H ₂ gas is 220 in the activation chamber (B).
In the inside, the microwave plasma generator 221 receives activation treatment such as plasma conversion into active hydrogen,
It was introduced into the film forming chamber 201 through 217-2. At this time, B ₂
The H ₆ impurity gas was also introduced into the activation chamber (B) 220 and activated.

Next, while maintaining the atmospheric pressure in the film forming chamber 201 at 1.0 Torr,
Light was emitted from the WXw lamp 218 perpendicularly to the peripheral surface of the Al cylinder substrate 211.

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.

For the intermediate layer 12, a mixed gas of H ₂ / B ₂ H ₆ (B ₂ H ₆ gas is 0.2% in volume%) is introduced from the introduction pipe 217-1 to a film thickness of 200.
The film was formed at 0Å.

Comparative Example 1 A film forming chamber having the same structure as the film forming chamber 201 was prepared by using SiF ₄ and each gas of H ₂ and B ₂ H ₆ and equipped with a 13.56 MHz high frequency device, and a general plasma CVD method was used. Thus, an electrophotographic image forming member having the layer structure shown in FIG. 1 was formed.

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, a polyethylene naphthalate film 21 having a 1000 Å ITO film 22 deposited thereon was placed on a support and depressurized to 10 ^-6 Torr, and then SiF ₂ ^* active species, and SiF ₂ ^* active species were introduced from the introduction pipe 116 in the same manner as in Example 1. Each of H ₂ gas and PH ₃ gas (diluted with 1000 ppm hydrogen gas) was introduced into the activation chamber (B) 123 from the introduction pipe 110 and activated. Next, this activated gas was introduced into the film forming chamber 101 through the introducing pipe 116. The pressure inside the film forming chamber 101 is 0.1T
Irradiation with a 1 KW Xe lamp while maintaining orr was performed to form a P-doped n-type a-Si (H, X) film 24 (film thickness 700Å).

Then, except for stop PH ₃ gas introducing n-type a-Si (H,
X-film, i-type a-Si (H, X) film 25
(Film thickness 5000Å) was formed. Then, p-type a-Si (H, X) film 2 doped with B under the same conditions as n-type except diborane gas (diluted with hydrogen of B ₂ H ₆ 1000 ppm) together with H ₂ gas 2
6 (film thickness 700Å) was formed. Further, an Al electrode 27 having a film thickness of 1000 Å was formed on this p-type film by vacuum vapor deposition to obtain a PIN type diode.

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, light is introduced from the side of the substrate, light irradiation intensity AMI (about 100 mW / cm ² ), conversion efficiency of 8.5% or more,
An open end voltage of 1.1 V and a short circuit current of 10.3 mA / cm ² were obtained.

Example 5 Instead of the H ₂ gas from the introduction pipe 110, an H ₂ / F ₂ mixed gas (H ₂
A PIN diode similar to that manufactured in Example 4 was manufactured in the same manner as in Example 4 except that / F ₂ = 10) was used. 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 the conventional one can be obtained.

〔The invention's effect〕

According to the deposited film forming method of the present invention, 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. Becomes 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. Further, since light energy is used as excitation energy, it is possible to form a film even on a substrate having poor heat resistance, and it is possible to shorten the process by low temperature treatment.

[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 configuration of the apparatus for carrying out the inventive method 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 a-Si layer, 25 ... i-type a-Si layer, 26 ... p-type a
-Si layer, 101,201 ... Deposition chamber, 111,202 ... Activation chamber (A), 123,220 ... Activation chamber (B), 106,107,108,10
9,213,214,215,216 …… Gas supply source, 103,211 …… Base body, 1
17,218 …… Light energy generator.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication location H01L 31/08 H01L 31/08 (72) Inventor Masahiro Kanai 3-30-2 Shimomaruko, Ota-ku, Tokyo No. Canon Inc. (72) Inventor Shunri Oda 8-11-14-503 Fukasawa, Setagaya-ku, Tokyo (72) Inventor Isamu Shimizu 2-41-21-21 Fujigaoka, Midori-ku, Yokohama (56) References 60-41047 (JP, A) JP-A-61-179869 (JP, A)

Claims (1)

(57) [Claims] 1. A first active species (A) produced by decomposing a compound containing silicon and halogen in a film forming space for forming a deposited film on a substrate, and the first active species. H ₂ gas or H ₂ gas that chemically interacts with (A) and
A mixed species of a second active species (B) generated from a mixed gas composed of F ₂ gas and an activated impurity-introducing substance gas containing an element of Group III A of the periodic table, or the active species ( B) and a mixed species of the activated impurity-introducing substance gas containing an element of group V A of the periodic table are separately introduced, respectively, and these are irradiated with light energy. A method for forming a deposited film, which comprises forming a deposited film on a substrate.