JPS61101022A - Forming method of accumulated film - Google Patents

Abstract

PURPOSE:To form an accumulated film of uniform quality as compared with that by a plasma CVD method by individually introducing active seed and film forming stock gas into a film forming space, and exciting them by heating to react it. CONSTITUTION:A desired base 103 is placed on a base support base 102 provided in an accumulating chamber 101. A compound which contains germanium and halogen supplied from an inlet tube 115 is decomposed by a decomposing space 112, and the active seed produced there is fed through an inlet tube 116 to the space 101. On the other hand, film forming stock gas or inert gas are fed from gas supply sources 106-109 through a pipe 110. The fed active seed and the film forming stock gas are excited and reacted by thermal energy received from heating means 104. Thus, an accumulated film of uniform quality can be formed on the base 103.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method suitable for forming an amorphous or crystalline deposited film containing germanium.

[Prior art]

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

Deposited films made of amorphous silicon have excellent electrical and optical properties, fatigue properties during repeated use, use environment properties, and productivity, including uniformity and reproducibility.
In terms of mass production, there is room for further improvements in comprehensive characteristics.

The reaction process in forming an amorphous silicon deposited film by 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 (for example, substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure,
Due to the combination of these many parameters (reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma becomes unstable, which often has a significant negative effect on the deposited film formed. Moreover, parameters unique to each device must be selected for each device, making it difficult to generalize the manufacturing process. On the other hand, as an amorphous silicon film, it has various electrical, optical, photoconductive, and mechanical properties.
In order to develop a material that satisfies the above requirements, 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, uniform film thickness, and uniform film quality, and to achieve mass production with high reproducibility through high-speed film formation. Forming an amorphous silicon deposited film using the plasma CVD method requires a large amount of equipment investment for premature production equipment, and the management items for mass production are complicated, the management tolerance is narrow, and equipment adjustments are delicate. For some reason,
These have been pointed out as problems that should be improved in the future. On the other hand, with the conventional technology using the normal CVD method,
This method requires high temperatures, and a deposited film with practically usable properties has not been obtained.

As mentioned above, in forming an amorphous silicon film...
There is a strong desire to develop a forming method that can be mass-produced using low-cost equipment while maintaining practical properties and uniformity. The same can be said of other functional films, such as silicon nitride films, silicon carbide films, and silicon oxide films.

The present invention eliminates the drawbacks of the plasma CVD method described above and provides a new deposited film formation method that does not rely on conventional formation methods.

[Purpose and outline of the invention]

The purpose of the present invention is to improve the characteristics, film formation speed, and reproducibility of the film to be formed, and to make the film quality uniform, while also being suitable for increasing the area of the film, improving film productivity, and facilitating mass production. The object of the present invention is to provide a method for forming a deposited film that can achieve the following.

The above purpose is to create a film that chemically interacts with active species generated by decomposing a compound containing germanium and halogen in the film formation space for forming a deposited film on a substrate. The deposition method of the present invention is characterized in that a deposited film is formed on the substrate by separately introducing raw material gases and applying thermal energy to them to excite the film-forming raw material gases and cause them to react. This is achieved by a film formation method.

[Embodiment]

In the method of the present invention, instead of generating plasma in the film forming space for forming the deposited film, thermal energy is used to excite the raw material for forming the deposited film and cause it to react. There are virtually no 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.

In the present invention, the thermal energy for exciting and reacting the film-forming raw materials is applied to at least the part near the substrate or the entire film-forming space in the film-forming space, and there is no particular restriction on the heat source used. Conventionally known heating media such as heating using a heating element, high frequency heating, etc. can be used. Alternatively, thermal energy converted from light energy can be used. Furthermore, if desired, light energy can be used in combination with thermal energy. The light energy can be applied to the entire substrate using an appropriate optical system, or can be selectively and selectively applied to only desired areas, so that the formation position of the deposited film on the substrate and the film can be controlled. Thickness etc. can be easily controlled.

One of the differences between the method of the present invention and the conventional CVD method is that it uses active species that have been activated (E) in a space different from the film-forming space (hereinafter referred to as the decomposition space).

This makes it possible to dramatically increase the film formation rate compared to the conventional CVD method, and in addition, it is possible to further reduce the substrate temperature during deposition film formation, making it possible to deposit films with stable film quality. Membranes can be provided industrially in large quantities at low cost.

In the present invention, the active species from the decomposition space introduced into the film forming space has a lifespan of 5 seconds or more, more preferably 15 seconds or more, and optimally 30 seconds or more from the viewpoint of productivity and ease of handling. One of these active species is selected and used as desired, and the active species constitutes the main component of the deposited film formed in the film forming space. In addition, when the film-forming raw material gas is excited by thermal energy in the film-forming space and forms a deposited film, it is simultaneously introduced from the decomposition space and contains active species containing constituent elements that will become the main constituents of the deposited film to be formed. interact chemically; As a result, a desired deposited film can be easily formed on a desired substrate.

In the present invention, as the compound containing germanium and halogen introduced into the decomposition space, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic germanium hydride compound is replaced with a halogen atom is used. teeth,
For example, Ge.

Y (u is an integer greater than or equal to 1, Y is F, CI, 2u
+2, Br or ■. ), GevY2σV is an integer of 3 or more.

Y has the meaning given above. ) cyclic germanium halogenide, Ge HY (u and Yu
X y has the meaning given above. x+y=2u or 2u+2. ), and the like.

Specifically, for example, GeF4, (GeF2)S, (GeF
2) 6, (GeF2)4, Ge2 F6, Ge3
FB, GeHF3, Get(2F2, GeCl4
(GeC12)S, GeBrco, (GeBr2)5.
Examples include those that are in a gaseous state or can be easily gasified, such as Ge2C16 and Ge2C13F3.

Further, in the present invention, in addition to the active species generated by decomposing the compound containing germanium and halogen, the active species S generated by decomposing the compound containing silicon and halogen and/or the active species generated by decomposing the compound containing silicon and halogen Active species generated by decomposing a compound containing can be used in combination.

As the compound containing silicon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic silane compound is replaced with a halogen atom is used, and specifically,
For example, 5iuY, (u is an integer of 1 or more, Y is F, CI, 2u+2Br or ■), SiY (v is an integer of 3 or more, 2v Y is the meaning described above) The annular halo denoted by ) has the above meaning. x+y=2u or 2u+2.

), and the like.

Specifically, for example, SiF4, (SiF2)S, (S i
F? ) 6, (SiF2)4. Si2 F6, Si
3 FB, SiHF3. SiH2F2. 5iC
14(SiC12)5, 5iBr, , (Si
Br2)5. Examples include those in a gaseous state or those that can be easily gasified, such as 5i2C16 and 5i2C13F3.

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

Further, as a compound containing carbon and halogen, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound is replaced with a halogen atom is used. Specifically, for example, CuY2u+2 (U is 1 or greater, Y is F
, C1, Br or ■. ) Chain halide carbon, CY (v is an integer of 3 or more -L, Y is the above-mentioned meaning v
2v Has a taste. ) cyclic silicon halogenide,
CHY (u and Y have the above meanings)
y do it. >(+y=2u or 2u+2), and the like.

Specifically, for example, CF4, (CF2)S, (CF2)6
・(CF2)4・C2F6・C3F8・C)lF3
, CH2F2 , CC14 (CC12)5, CBr4
, (CB F2) s, C2C16.

Examples include those in a gaseous state or easily gasifiable, such as C2Cl3F3.

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

In order to generate active species, for example, when generating active species of a compound containing germanium and a halogen, in addition to this compound, if necessary, a germanium compound such as germanium alone, hydrogen, or a halogen compound ( For example, F2 gas, C12 gas, gasified Br2.I2, etc.) can be used in combination.

In the present invention, as a method for generating active species in the decomposition space, the discharge energy,
Excitation energies such as thermal energy, light energy, etc. are used.

Active species are generated by adding decomposition energy such as heat, light, and discharge to the above-mentioned materials in a decomposition space.

The film-forming raw material gas used in the method of the present invention includes hydrogen gas and/or a halogen compound (for example, F2 gas, C
12 gas, gasified Br7, I2, etc.) are advantageously used. In addition to these film-forming raw material gases, an inert gas such as argon or neon can also be used.

When using multiple of these raw material gases, they can be mixed in advance and introduced into the film forming space, or these raw material gases can be supplied individually from independent sources and then introduced into the film forming space. It can also be introduced.

In the present invention, the ratio of the amount of the active species to the film-forming raw material gas in the film-forming space is determined as desired depending on the deposition conditions, the type of active species, etc., but is preferably 10:1.
-1:10 (introduction relative ratio) is appropriate, and more preferably 8:2 to 4:6.

It is also possible to dope the deposited film formed by the method of the invention with an inert element. The impurity elements to be used include those from periodic table 1II as p-type impurities.
Group A elements, such as B, AI.

Suitable examples include G a , I' n , T I, etc., and examples of n-type impurities include Group V A of the periodic table.
Suitable elements include N, P, As, Sb, Bi, etc., particularly B, Ga, and P.

sb etc. are optimal. The gutter of impurities to be doped is
It is determined as appropriate depending on the desired electrical and optical characteristics.

As a compound containing such an impurity element as a component, it is preferable to select a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under deposited film forming conditions, and that can be easily vaporized using an appropriate vaporizing device. . Such compounds include PH3, P, H4, PF3. PF5, PCl
3, AsH3, AsF3, AsF5. AsC13,S
bH3, S bFs, S iH3, BF3, BC13
, BBr3 , B2 Hb , B4 Hlo, B5H
9, B5HI3, B6H1o, B6HI2. Examples include AlCl3. The compounds containing impurity elements may be used alone or in combination of two or more.

In order to introduce a compound containing an impurity element into the film forming space, it is necessary to mix it with the film forming raw material gas etc. in advance, or to introduce these raw material gases individually from multiple independent gas supply sources. can be introduced into 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 diagram for explaining an example of the configuration 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 includes an intermediate layer 1 provided as necessary on a support 11 for the photoconductive member.
2 and a photosensitive layer 13.

The support 11 may be electrically conductive or electrically insulating. Examples of the conductive support include NiCr, stainless steel, AI, Cr, Mo, Au, Ir,
Examples include metals such as Nb, Ta, 2, Ti, PL, and Pd, or alloys thereof.

As the electrically insulating support, films or sheets of synthetic resins such as polyester, polyethylene, polycarbonate, cellulose acetate, polypropylene, polyvinyl chloride, polyvinylidene chloride, polystyrene, polyamide, glass, ceramic, paper, etc. are usually used. . Preferably, at least one surface of these electrically insulating supports is subjected to conductive treatment, and another layer is preferably provided on the conductive treated surface side.

For example, if it is glass, its surface is NiCr, A1.
Cr, Mo, Au, Ir, Nb, Ta, V, Ti, P
L, Pd, I n203, S n02, I To (
In the case of conductive treatment by providing a thin film such as I n203 +S n02 ), or a synthetic resin film such as polyester film, NiCr, AI, Ag
, Pb, Zn, Ni, Au, Cr, Mo, Ir, Nb
, Ta, V, Ti, Pt, etc. by vacuum evaporation, electron beam evaporation, sputtering, etc., or by laminating with the metal, and the surface thereof is subjected to conductive treatment. The shape of the support may be any shape such as a cylinder, a belt, or a plate, and the shape is determined depending on the need. For example, the photoconductive member 10 in FIG. If used as a component, in the case of continuous high-speed copying,
It is desirable to have an endless belt shape or a cylindrical shape.

For example, the intermediate layer 12 includes a photosensitive layer 13 from the support 11 side.
This effectively prevents the inflow of carriers into the photosensitive layer 13 and causes the photocarriers generated in the photosensitive layer 13 by irradiation with electromagnetic waves and moves toward the support 11 to move from the side of the photosensitive layer 13 to the side of the support 11. It has a function that allows easy passage to.

This intermediate layer 12 may be made of amorphous germanium (hereinafter, aG e (S i+ H+
X). ), and also contains p-type impurities such as B or P as substances that control electrical conductivity.
Contains p-type impurities such as.

In the present invention, the content of substances governing conductivity, such as B and P, contained in the intermediate layer 12 is preferably 0.
001 to 5X1O' atomic ppm, more preferably 0.5 to IX11X104ato ppm, optimally 1 to 5×103103ato ppm.

When forming the intermediate layer 12, it can be performed continuously up to the formation of the photosensitive layer 13. In that case, the active species generated in the decomposition space, the film-forming raw material gas, and optionally an inert gas and a compound gas containing an impurity element as ingredients are used as raw materials for forming the intermediate layer. The intermediate layer 12 may be formed on the support 11 by introducing them separately into the film forming space where the support 11 is installed and using thermal energy.

A compound containing germanium and halogen, which is introduced into the decomposition space to generate active species when forming the intermediate layer 12, easily generates active species such as GeF2 at high temperatures.

The thickness of the intermediate layer 12 is preferably 30A to 10A, more preferably 40A to 8IL, and optimally 50A to 5P.

The photosensitive layer 13 may contain, for example, hydrogen, halogen,
Amorphous silicon whose constituent atoms are germanium etc.=+
a-3i (H,X,Ge) or optionally hydrogen,
It is composed of amorphous silicon germanium a-3iGe (H, .

The thickness of the photosensitive layer 13 is preferably l-100#.
L, more preferably 1-80#L, optimally 2-50IL
It is desirable that this is done.

The photosensitive layer 13 is made of non-doped a-3i (H.

X, Ge) or a-S iGe (H, Alternatively, if the actual amount contained in the intermediate layer 12 is large, the amount of the substance that controls the conduction characteristics of the same polarity may be much smaller than a few orders of magnitude. It may be included.

Similarly to the case of the intermediate layer 12, the photosensitive layer 13 is formed by introducing, for example, a compound containing silicon and a halogen in addition to a compound containing germanium and a halogen into the decomposition space, and decomposing these at high temperature. Active species are generated and introduced into the film forming space. Separately, if necessary, an inert gas, a compound gas containing an impurity element as a component, etc. are introduced into the film forming space where the support 1 is installed, and heat is applied to the film forming raw material gas. The intermediate layer 12 may be formed on the support 11-1 by using energy.

FIG. 2 shows a-3iGe(H) doped with an impurity element produced by carrying out the method of the present invention.

X) A schematic diagram showing a typical example of a PIN type diode device using a deposited film.

In the figure, 21 is a substrate, 22 and 27 are thin film electrodes, 23 is a semiconductor film, an n-type a-3iGe (H, X) layer 24,
Type i Noa-3t Ge (H.

X) layer 25, p-type c7) a-3iGe (H,X) layer 2
Consisting of 6. 28 is a conducting wire.

As the substrate 21, a semiconductive, preferably electrically insulating material is used. As the semiconductive substrate, for example, Si
, Ge, and other semiconductors. Examples of the thin film electrodes 22.27 include NiCr, Al, Cr, Mo, and Au.
, Ir, Nb, Ta, V, Ti, Pt, Pd, In2O
3,5n02, ITO (In203 +5n02)
It can be obtained by forming a thin film such as the above on a substrate using a process such as vacuum evaporation, electron beam evaporation, or sputtering. The film thickness of the electrode 22.27 is preferably 30 to 5×1
04A, more preferably 100 to 5X103A.

In order to make the film forming the a-3iGe (H, It is formed by doping an impurity or both impurities into the layer while controlling the wrinkles.

n-type, i-type and p-type c7) a-3i Ge (H,X)
In order to form the layer, according to the method of the present invention, compounds containing silicon and halogen in addition to compounds containing germanium and halogen are introduced into the decomposition space, and by decomposing these at high temperature, for example, GeF2 and Active species such as S i F2 are generated and introduced into the film forming space. Separately, a film-forming raw material gas and, if necessary, a compound gas containing an inert gas and an impurity element as components are added to the support body.
The film may be introduced into the film forming space provided in step 1 and formed by using thermal energy. n-type and p-type a-
The thickness of the 3iGe (H,X) layer is preferably 1
A range of 00-104A, more preferably 300-2000A is desirable.

Further, the thickness of the i-type (7)a-S i Ge (H,

Incidentally, the PIN type diode device shown in FIG. 2 has P,
It is not necessarily necessary to produce all the I and N layers by the method of the present invention, and the present invention can be practiced by producing at least one layer of P, I, and N by the method of the present invention.

Specific examples of the present invention are shown below.

Example 1 Using the apparatus shown in Figure 3, i
type, n-type and n-type a-Ge(Si.

H, X) A deposited film was formed.

In FIG. 3, 101 is a deposition chamber, and a desired substrate 103 is placed on a substrate support 102 inside.

Reference numeral 104 denotes a heater for heating the substrate, which is supplied with electricity via a conductive wire 105 and generates heat. Although the substrate temperature is not particularly limited, in carrying out the method of the present invention, preferably 5
The temperature is preferably 0 to 150°C, more preferably 100 to 150°C.

Reference numerals 106 to 109 indicate gas supply sources, which are provided depending on the number of gases of film forming raw materials, inert gases used as necessary, and compounds having impurity elements as components. When using liquid raw material compounds, an appropriate vaporization device is provided.

In the figure, the gas supply sources 106 to 109 are marked with a for branch pipes, b for flowmeters, C for pressure gauges that measure the pressure on the high pressure side of each flowmeter, and d. The symbol ``e'' indicates a valve for adjusting each gas flow. 11
0 is a gas introduction pipe into the film forming space, and Ill is a gas pressure gauge.

In the figure, 112 is a decomposition space, 113 is an electric furnace, 114 is a solid Ge grain, and 115 is an introduction tube for a compound containing gaseous germanium and halogen, which is a raw material for active species.The active species generated in the decomposition space 112 are is introduced into the film forming space 101 via the introduction pipe 116. In addition, in the case of forming a film body containing Si or the like as constituent atoms in addition to Ge, a separate decomposition space (not shown) similar to 112 is provided to separate active species from a compound containing silicon and halogen and, for example, solid Si particles. can be generated and introduced into a film forming space lot.

Reference numeral 117 denotes a thermal energy generating device, and for example, a normal electric furnace, a high frequency heating device, various heating elements, etc. are used.

The heat from the thermal energy generator 117 acts on the raw material gas etc. flowing in the direction of the arrow 119, and excites the film forming raw material gas etc. and causes it to react, thereby producing a-Ge( A deposited film of Si, H, X) is formed. In addition, in the figure, 120 is an exhaust valve, 121
is the exhaust pipe.

First, a polyethylene terephthalate film substrate 103
was placed on the support stand 102, and the inside of the deposition space 101 was evacuated using an exhaust device for 10-6T.

The pressure was reduced to rr. At the substrate temperature shown in Table 1, use the gas supply source 106 to supply 150 SCCM of H2 gas, or this and PH3 gas or B2H6 gas (both io00pp
A gas mixed with 403 CCM (hydrogen gas dilution) was introduced into the deposition space.

In addition, the decomposition space 102 is filled with solid Ge grains 114, heated in the electric furnace 113 to melt the Ge, and GeF4 is blown therein from the cylinder through the GeF introduction pipe 115 to generate active species of GeF2. and introduce tube 1
16, and is introduced into the film forming space 101. Similarly, active species such as S i F24 are introduced into the film forming space 101 as required.

While maintaining the atmospheric pressure in the film forming space lO1 at 0.1 Torr,
The thermal energy generator generates 250
℃ and undoped or doped a-Ge (S i , H, X)/SeC.

Next, the obtained non-doped or p-type a-Ge
(Si, H,
After forming a comb-shaped AI gap electrode (length 250IL, width 5■■) at 0-5T or r, the applied voltage lO
Measure the dark current at V, find the dark conductivity σ, and
(Si,H,X) films were evaluated. The results are shown in Table 1.

Example 2 H2/F2 instead of H2 gas from the gas supply source 106 etc.
The same a-Ge (
A Si, H, X) film was formed. The dark conductivity was measured and the results are shown in Table 1.

From Table 1, it can be seen that according to the present invention, a-Ge (St, ) (,
A film was obtained and a-
Ge (S i , H, X) HfJ is obtained.

Example 5 Using the apparatus shown in Fig. 4, the first
A drum-shaped electrophotographic image forming member having a membrane structure as shown in the figure was prepared.

In FIG. 4, 201 is a film forming space, 202 is a decomposition space, 203 is an electric furnace, 204 is a solid (re particles), 205 is an active species raw material introduction pipe, 206 is an active species introduction pipe, 207
is a motor, 208 is a heating heater, 209 is a blowout pipe, 210 is a blowout pipe, 211 is an AI cylinder, 2
12 indicates an exhaust valve. Also, 213 to 21
6 is a raw material gas supply source similar to 106 to 109 in FIG. 1, and 217 is a gas introduction pipe.

An At cylinder 211 is suspended in the film forming space 201, and a heater 208 is provided inside the cylinder so that it can be rotated by a motor 207. Reference numerals 218, 218, . . . indicate thermal energy generating devices, such as ordinary electric furnaces, high-frequency heating devices, various heating elements, and the like.

In addition, solid Ge particles 204 are packed in the decomposition space 202 and heated in the electric furnace 203 to melt the Ge, and GeF4 is blown into it from a cylinder to generate active species of GeF2', which are then passed through the introduction pipe 206. , is introduced into the film forming space 201. In addition, active species of s t F : are generated from the solid St grains and SiF 4 by a decomposition space (not shown) similar to 202 and introduced into the film forming space 201 .

On the other hand, H2 is introduced into the film forming space 201 from the introduction pipe 217. While maintaining the atmospheric pressure in the film forming space 201 at 1.0 Torr, the inside of the film forming space 201 is heated to 2.
Maintain at 50°C.

The At cylinder 211 is heated and maintained at 280°C by the heater 208 and rotated once, and the exhaust gas is passed through the exhaust valve 21.
Exhaust through 2. In this way, the photosensitive layer 13 is formed.

Further, the intermediate layer 12 is connected to the introduction pipe 21 prior to the photosensitive layer 13.
7, a mixed gas of H2/B2Hb (0.2% B2H6 by volume) was introduced to form a film with a thickness of 2000 Å.

Comparative Example 1 - GeF4 and SiH were produced by a general plasma CVD method.
4, H2 and B2H6 to the film forming space 201 in FIG.
An amorphous silicon deposited film was formed using a 3.56 MHz high frequency device.

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

Example 6 Using the apparatus shown in FIG. 3, a PIN diode shown in FIG. 2 was manufactured.

First, the 1000A (7) ITO III 22 vapor-deposited ethylene naphthalate film 21 was placed on a support stand, the pressure was reduced to 10-6 Torr, and then GeF2' and S I F2cy)
Active species, H2150SCCM and phosphine gas (PH311000pp diluted with hydrogen) are introduced from the introduction pipe 110, and halogen gas 20SCCM is introduced from another system.
0. The n-type a-3iGe(H,X) film 24 doped with P (thickness 70'
0A) was formed.

Next, the n-type a-S except that the introduction of PH3 gas was stopped.
i-type a-5 using the same method as for the iGe(H,X) film.
An iGe(H,X) film 25 (thickness: 5000 A) was formed.

Next, diporane gas (B2H610
00 ppm hydrogen dilution) 403 CCM, plja-3i Ge doped with B under otherwise the same conditions as n-type.
A (H,X) film 26 (III thickness 700A) was formed.

Further, an AI electrode 27 having a thickness of 1000 Å was formed on this p-type film by vacuum evaporation to obtain a PIN-type diode.

I of the diode element thus obtained (area 10 m2)
-V characteristics were measured, and rectification characteristics and photovoltaic effects were evaluated. The results are shown in Figure 3.

In addition, regarding light irradiation characteristics, light is introduced from the substrate side,
At light irradiation intensity AMI (approximately 100 mW/cm2), conversion efficiency is 8.5% or more, open circuit voltage is 0.92 V, and short circuit current is 1.
0.5 mA/cm2 was obtained.

Example 7 A PIN diode was fabricated in the same manner as in Example 6, except that H2/F2i combined gas was used instead of H2 gas from the inlet pipe 11O. Evaluate the rectification characteristics and photovoltaic effect,
The results are shown in Table 3.

Table 3 shows that according to the present invention, the a-3i has good optical and electrical characteristics even at a lower substrate temperature than the conventional one.
A Ge (H,X) deposited film is obtained.

〔Effect of the invention〕

According to the method for forming a deposited film of the present invention, the desired electrical, optical, photoconductive, and mechanical properties of the film to be formed are improved, and high-speed film formation is possible at a low substrate temperature. Also,
It improves the reproducibility in film formation, makes it possible to make the film quality uniform, and is advantageous for increasing the area of the film, improving film productivity and facilitating mass production. can be achieved. Furthermore, since relatively low thermal energy can be used as excitation energy, effects such as being able to form a film even on a substrate with poor heat resistance and shortening the process through low-temperature treatment are exhibited.

[Brief explanation of drawings]

FIG. 1 is a schematic diagram for explaining an example of the structure of an electrophotographic image forming member manufactured using the method of the present invention. FIG. 2 is a schematic diagram for explaining a configuration example of a PIN diode manufactured using the method of the present invention. FIG. 3 and FIG. 4 are schematic diagrams for explaining the configuration of an apparatus for carrying out the method of the present invention used in Examples, respectively. 1O...sha Image forming member for electrophotography, 11... Substrate, 12... Intermediate layer, 13... Photosensitive layer, 21... Substrate, 22, 27... Thin film electrode, 24 1111 II n Type a-Si layer, 25e
11 e i-type a-Si layer, 26 --- p-type a-Si layer, 101.201 ... film formation space, Ill, 202
... Decomposition space, 106.107,108,10
9゜213.214,215,216...Gas supply source, 103.211...War base, 117,218...Thermal energy generation device. Agent Patent Attorney Seki Yamashita Figure 1 Figure 2

Claims (1)

[Claims] In a film forming space for forming a deposited film on a substrate, active species generated by decomposing a compound containing germanium and a halogen, and a film forming raw material gas that chemically interacts with the active species. A method for forming a deposited film, characterized in that a deposited film is formed on the substrate by introducing each separately and applying thermal energy to them to excite the film-forming raw material gas and cause it to react.