JPH01275761A - Deposit film-forming equipment - Google Patents

Abstract

PURPOSE:To form a deposit film having uniform thickness and quality over a large area by introducing a precursor and an active species as deposit film-forming materials into a space in a cylindrical deposition chamber and forming a deposit film on a substrate rotating through the deposition space. CONSTITUTION:A substrate 103 for deposit film formation is rotatably held by means of a supporting plate 102 in a film formation space A in a cylindrical deposition chamber 101. On the other hand, gaseous raw materials for forming active species are supplied from gas-feed sources 105, 106 into a decomposition space C in a cylindri cal member 117 provided in the deposition chamber 101 and microwave energy is introduced from the upper and the lower microwave electric power source 108, by which an active species is formed and uniformly injected through injection holes 118 into the deposition space A. Further, a gaseous raw material for forming a precursor fed through an inlet tube 111 is formed into a precursor for forming deposition film by means of heat energy from an electric furnace 112 in a decomposition space B and injected through injection holes 111'' of a transport tube 111' into the deposition space A. By the above constitution, the substrate 103 is rotated round the cylindrical member 117 by means of a motor 115 and heated by means of a heater 104, by which a deposit film can be formed on the substrate 103.

Description

Detailed Description of the Invention C. Technical Field to Which the Invention Pertains The present invention relates to an apparatus for forming a functional film, particularly a deposited film useful for applications such as semiconductor devices or photosensitive devices for electrophotography, particularly over a large area. The present invention relates to an apparatus for forming a deposited film.

[Description of conventional technology]

For example, attempts have been made to form an amorphous silicon film using vacuum evaporation, plasma CVD, CVD, reactive sputtering, ion blasting, photo-CVD, etc.; is widely used and commercialized.

However, deposited films made of amorphous silicon have poor electrical and optical properties, fatigue properties during repeated use, use environment properties, and even productivity including uniformity and reproducibility. There is room to improve overall characteristics.

Is the reaction process for forming amorphous silicon deposited films using the conventionally popular plasma CVD method considerably different from that of the conventional CVD method? jI is messy,
Many aspects of the reaction mechanism remain 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,
Due to the combination of many parameters (electrode structure, reaction vessel structure, pumping speed, plasma generation method, etc.), the plasma sometimes becomes unstable, which often has a significant negative effect on the deposited film formed. Ta. Furthermore, the actual conditions are that it is difficult to generalize the manufacturing conditions because the parameters of the equipment must be selected for each equipment.

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

However, depending on the application of the deposited film, plasma C
Forming an amorphous silicon deposited film using the VD method requires a large amount of equipment investment for mass production equipment, and the management items for mass production also become complex, the management tolerance narrows, and equipment adjustments are delicate. For these reasons, these were pointed out as problems that should be improved.

As a method to eliminate these drawbacks of the conventional plasma CVD method, a deposition space (A) for forming a deposited film on a substrate is used.
The precursor that is generated in the decomposition space (B) and serves as a raw material for forming a deposited film, and the active species that are generated in the decomposition space (C) and interact with the precursor are separated, respectively. A method of forming a deposited film on the substrate by introducing the method has been proposed in Japanese Patent Laid-Open No. 60-41047 and others.

FIG. 6 schematically shows a typical example of a suitable apparatus for implementing the deposited film forming method. In FIG. 6, 601 is a deposition chamber as a film forming space, and a deposited film forming substrate 603 is placed on a substrate support plate 602 inside. 604 is a heater for heating the substrate;
05 to 606 and 610 are raw material gas supply sources. In the figure, the symbol a added to the raw material gas supply sources 605 to 606 and 610 is the raw material gas pressure regulator, b and C.
What is marked with is a valve for flowing each gas, and what is marked with d is a mass flow controller that adjusts the fiffi of each gas. 607 and 611 are gas introduction pipes for each of these raw material gases. 608 is a microwave power source for converting the raw material gas that has passed through 607 into active species in the decomposition space (C), and 609 is a waveguide. Also, 612 is 61
This is an electric furnace for converting the raw material gas passed through 1 into a precursor in the decomposition space (B). Furthermore, 613 is an exhaust valve, and 614 is an exhaust pipe. The precursors generated in the decomposition space (B) and the active species generated in the decomposition space (C) are deposited to form a deposited film. A deposited film is formed on the substrate 603 by being separately introduced into the space (A) and interacting within the deposition space (A).

However, with the above-mentioned conventional equipment, it is possible to achieve mass production with reproducibility by fully satisfying the requirements of increasing the area of the deposited film, uniformity of film thickness, and uniformity of film quality. Depending on the application, the deposited film must have a uniform thickness and quality over a larger area. It was difficult to make the film quality uniform.

Therefore, in view of the various applications of the deposited film, improvements are needed in order to obtain an apparatus that can form a deposited film having uniform thickness and quality over a wider area.

[Purpose of the invention]

An object of the present invention is to provide a deposited film forming apparatus that is further improved over the conventional deposited film forming apparatus described above.

That is, the main object of the present invention is to provide an apparatus most suitable for obtaining a deposited film having a uniform thickness and quality over a larger area than the conventional apparatus.

Another object of the present invention is to provide a deposition space (A) for forming a deposited film.
It is an object of the present invention to provide an apparatus that can improve the deposition rate while maintaining the properties of the film formed in the process, simplify the film forming conditions, and easily achieve mass production of the film.

[Structure of the invention]

The present invention was completed as a result of intensive research aimed at improving the conventional deposited film forming apparatus, and the gist of the invention is that a deposited film is formed on at least one deposited film forming substrate installed inside the device. Deposition space (A) for forming a deposited film
), a decomposition space (B) for producing a precursor that is a raw material for forming a deposited film, another decomposition space (C) for producing an active species that interacts with the precursor, and a decomposition space (C) for producing an active species that interacts with the precursor. space(
It consists of means for separately introducing the precursor produced in step B) and the active species produced in the decomposition space (C) into the deposition space (A), and means for exhausting the inside of the deposition space (A). In the deposited film forming apparatus, the decomposition space (C) is formed in the deposition space (A) by a cylindrical member installed concentrically with the deposition space (A), and the decomposition space (C) is formed by a cylindrical member installed concentrically with the deposition space (A), and the decomposition space (C) is formed by a cylindrical member installed concentrically with the deposition space (A), and A large number of active species ejection holes are provided, and means for generating the active species by introducing microwave energy from the top and bottom surfaces of the cylindrical member is provided, and the deposited film forming substrate is placed in the deposition space (A ) The deposited film forming apparatus is provided with means for rotating coaxially with the cylindrical member on the outside of the cylindrical member.

Furthermore, in the apparatus of the present invention, the precursor is deposited in the deposition space (
Preferably, the means for introducing gas into A) is a plurality of transport pipes having a large number of gas ejection holes installed in the deposition space (A).

In the apparatus of the present invention having the above configuration, when forming a deposited film, active species that interact with the precursor that is the raw material for forming the deposited film are generated in the decomposition space (C). Since the space (C) is cylindrical and has a large number of ejection holes over the entire area of its side surface, the active species are transferred from the ejection holes to the deposition space (C) provided around the outer circumference of the cylindrical decomposition space (C). It is possible to blow out uniformly and over a wide area toward A).

In addition, since microwave energy for generating active species is introduced from the top and bottom surfaces of the cylindrical decomposition space (C), the volume of the decomposition space (C) in which active species are generated can be increased. Furthermore, since more active species are generated, the area of the substrate used can be made larger than in the past.

Furthermore, by arranging the substrates around the outer periphery of the cylindrical decomposition space (C), a plurality of substrates with a large area can be installed, so that further mass production of membranes can be achieved. By rotating the substrate coaxially with the cylindrical decomposition space (C), it becomes possible to make the deposited film uniform.

Furthermore, in the apparatus of the present invention, it is possible to install a plurality of transport pipes for introducing the precursor into the deposition space (A),
The distribution of the precursor introduced into the deposition space (A) becomes more uniform regardless of location within the deposition space (A).

Furthermore, in the apparatus of the present invention, it is possible to use glow discharge as energy to excite and cause the raw material for forming the deposited film to react, and it is possible to use glow discharge in the coexistence of the precursor for forming the deposited film and the active species. By applying glow discharge to these components, chemical interactions are caused, promoted, and amplified by these components, making it possible to form a film with lower discharge energy than in the past, and the deposits formed. It is extremely unlikely that the membrane will be adversely affected by sowing effects or other adverse effects such as abnormal discharge effects.

In the present invention, it is desirable that the diameters of the ejection holes provided over the entire side surface of the cylinder constituting the decomposition space (C) are the same, but the thickness and quality of the deposited film on the substrate The pore sizes may be non-uniform for control purposes.

Further, although it is desirable that the spacing between the ejection holes be uniform over the entire cylindrical side surface, the spacing between the ejection holes may be non-uniform in order to control the thickness and quality of the deposited film on the substrate.

In the present invention, the materials of the cylinder constituting the decomposition space (C) and the transport pipe for introducing the precursor into the deposition space (A) are those whose frequency is 500 MHz for the microwave used.
Based on the above, microwave transparent members such as quartz glass, alumina ceramics, Teflon, polystyrene, beryllia, and steatite can be cited.

In the present invention, the decomposition space (B) is introduced into the deposition space (A).
The precursor (B) from ) preferably has a lifetime of 0.0
1 second or more, more preferably 0.1 seconds or more, optimally 1 second or more is selected and used as desired, and the constituent elements of this precursor constitute the deposited film formed in the deposition space (A). It constitutes the main component of In addition, the active species (C) introduced from the decomposition space (C) are transferred to the deposition space (A).
), when forming a deposited film, it is simultaneously introduced from the decomposition space (B) into the deposition space (A) and chemically interacts with the precursor (B) containing constituent elements that will be the main constituents of the deposited film to be formed. interact. As a result, a desired deposited film can be easily formed on a desired substrate.

The active species introduced from the decomposition space (C) has a lifetime of
Preferably it is 10 seconds or less, more preferably 8 seconds or less, and optimally 5 seconds or less. According to the invention, the deposition space (
By arbitrarily controlling the ambient temperature and substrate temperature in A) as desired, a more stable CVD method can be achieved.

One of the differences between the deposited film forming method using the apparatus of the present invention and the conventional CVD method is that active species activated in a space different from the preliminary deposition space (A) are used.

As a result, the deposition rate can be dramatically increased compared to the conventional CVD method, and in addition, it is possible to further reduce the substrate temperature during the formation of the deposited film, which improves the film quality. Stable deposited films can be provided industrially in large quantities at low cost.

In the present invention, the precursor produced in the decomposition space (B) is not only excited by energy such as electric discharge, light, or heat, or by a combination of these, but also by contact with or addition of a catalyst, etc. You can.

In the present invention, the raw material introduced into the decomposition space (B) is one in which a carbon atom, silicon atom, or germanium atom is bonded to an atom or atomic group with high electron-withdrawing property, or a polar group. Ru. For example, YllXt-4tcn=1.2.3-,
=F, Cl, Br, r.

Y=C, Si, Ge).

(Y X RiII (n≧3.X=F, CI, Br, I
.

Y=C, Si, Ge).

Y, 1HXzll++(n”1+2+3-, X=F
, C1, Br, LY=C, Si, Ge).

Y, 1HzXz, t(n = L2,3 ・=, X
= F, Cj! , Br, I.

Y=C, Si, Ge).

Examples include.

Specifically, for example, CFa, C2F6.5iFa.

(SiFx)s, (SiFz)a, (Si
Fz) 4゜5izF6, 5itHzFs, 5iHFt
, 5iHzFz.

5ICj! a , (SiCj!t)s , SiB
r.

(SiB rz) s , GeFa , Ge, F=, and the like, which are in a gaseous state or can be easily gasified, may be mentioned.

Further, 5iHz (CiHs)z, 5iHz (CN)z, etc. may also be used depending on the purpose of use of the deposited film to be formed.

These gases may be diluted with a gas such as He or Ar.

The precursor (B) is generated by adding decomposition energy such as heat, light, or discharge to the above-mentioned material in the decomposition space (B). This precursor (B) is introduced into the deposition space (A). At this time, the lifetime of the precursor (B) is preferably 0.01
It is necessary for the deposition space (A) to be in the decomposition space (C) to promote the increase in deposition efficiency and deposition rate.
In order to increase the efficiency of the activation reaction with the active species (C) introduced from the deposition space (A) or on the substrate, heat or
Formation of a desired deposited film is achieved by applying energy such as light.

In the present invention, active species (
The raw material for producing C) is Hz.

In addition to S i Ha, S it Ha, etc., SiH3
Examples include halosilane gases in which the number of hydrogen atoms is greater than the number of halogen atoms, such as F, 5iH3C1°5iH3Br, and SiH,1. These gases may be diluted with a gas such as He or Ar.

In the present invention, the decomposition space (B) in the deposition space (A)
The ratio of the amount of precursor (B) introduced from the decomposition space (C) to the amount of active species (C) introduced from the decomposition space (C) can be determined as desired depending on the deposition conditions, the type of active species, etc., but is preferably A suitable ratio is 10:1 to 1:10 (amount ratio of 2 JiL introduced), more preferably 8:2 to 4:6.

In the present invention, the precursor (B) generated in the decomposition space (B) and the active species (C) generated in the decomposition space (C) are not limited to vehicle types, but may be of multiple types, and in particular, multiple types may be used. And,
The object of the present invention is effectively achieved when they are produced from separate source gases.

Further, 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 elements of group A of the periodic table, such as B, Aj+,
Ga, In, Tj! Examples of n-type impurities include elements of group V A of the periodic table, such as N, P, and As.

Sb, Bi, etc. are mentioned as suitable ones, but especially,
B, Ga, P, Sb, etc. are optimal. The amount of impurities to be doped is appropriately determined depending on desired electrical and optical properties.

The starting material for introducing such impurities is one that is in a gaseous state at room temperature and normal pressure, or one that can be easily gasified under film forming conditions. Specifically, PH3, PzHa, P
Fs, PFs, PClx.

AsH:+, AgF2, AsF5
, AsCj! s + 5bHz + 5bFs
, BiHz, BFs, BCI
s r BBrs.

BzHb, BaH+. , BSH9, BsH+
+, BaH+. .

B, H, □, A7! (J, etc. can be mentioned.

The compounds containing the above impurity elements may be used alone or in combination of two or more.

The impurity introducing substance is introduced into the deposition space (A) directly in a gaseous state or mixed with the compound containing silicon and halogen.
Alternatively, it can be introduced into the decomposition space (C)
It is also possible to activate it with , and then introduce it into the deposition space (A). To activate the impurity-introducing substance, the aforementioned microwave energy can be selected. The active species generated by activating the impurity introduction substance are mixed with the active species in advance or are introduced into the deposition space (A) independently.

The substrate for forming a deposited film may be electrically conductive or electrically insulating. Examples of the electrically conductive substrate include NiCr, stainless steel, and Aj! , Cr, Mo, Au.

Examples include metals such as Ir, Nb, Ta, V, Ti, PL, 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, 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 N i Cr +A
l, Cr, Mo, Au, Tr, Nb, Ta, V.

Ti, Pt, Pd, InzOs, Snug,
If it is conductive treated by providing a thin film such as ITO (Into3+Snug) or a synthetic resin film such as polyester film, NiCr, Am! .

Ag, Pb, Zn, Ni, Au, Cr, Mo, Ir+
The surface is treated with a metal such as Nb, Ta, V, Ti, or Pt by vacuum evaporation, electron beam evaporation, sputtering, etc., or laminated with the metal to make the surface conductive.

The present invention will be explained in detail below with reference to the drawings.
The present invention is not limited to this in any way.

FIG. 1 is a schematic diagram showing a typical example of the deposited film forming apparatus of the present invention.

In the figure, 101 is a deposition chamber as a film forming space (A),
On the substrate support plate 102 installed inside the deposition chamber 101,
A deposited film forming substrate 103 is placed. 104 is a heater for heating the substrate.

Reference numerals 105 to 106 and 110 are source gas supply sources, which are provided depending on the type of gas such as a source gas for film formation, an inert gas, a compound containing an impurity element, etc., used as necessary. When these gases are liquid in the standard state, an appropriate vaporization device is provided.In the figure, gas supply sources 105 to 106 and 11
The symbol 0 with a is the pressure regulator for the raw material gas, the ones with b and C are the valves for flowing each gas, and the one with d is the mass flow controller that adjusts the flow rate of the raw gas. . (C) is a decomposition space for generating active species, and 117 constituting (C) is a cylindrical member, from the top and bottom of which microwaves are transmitted via waveguide 109 to generate active species. Energy is introduced into the decomposition space (C). 10B is a microwave power source, and the raw material gas for active species formation supplied from the gas introduction pipe 107 is activated in the decomposition space (C), and the generated active species spreads over the entire side surface of the cylindrical member 117. Active species ejection hole 11 provided in
It is uniformly blown out from B into the deposition space (A).

On the other hand, 112 is an electric furnace, and the raw material gas for precursor generation supplied from the gas introduction pipe 111 is converted into a precursor by the thermal energy supplied from the electric furnace 112 in the decomposition space (B), and the precursor gas is produced. The precursor is introduced into the deposition space (A) through the gas injection hole 111# provided in the transport pipe 111', and a deposited film is formed on the base vi 103 by chemically interacting with the active species. be done.

Further, in the figure, 113 is an exhaust pulp, 114 is an exhaust pipe, and 115 is a motor for rotating the substrate 103 coaxially with the cylindrical member 117.
3 revolves around a cylindrical member 117 at a uniform speed by a rotating plate 116.

In the present invention, the rotation speed of the substrate is determined to a desired value so as not to impair the properties of the deposited film, but is usually 1 to 10 rpm.
pts.

Further, FIG. 2 is a schematic diagram schematically showing another example of a deposited film forming apparatus suitable for carrying out the present invention. In FIG. 2, the precursor for forming a deposited film generated in the decomposition space (B) is introduced into the deposition space (A) through gas injection holes 111' and 201' provided in a plurality of transport pipes 111' and 201. be done. Since there are a plurality of transport pipes, the concentration distribution of the precursor in the deposition space (A) becomes more uniform than when there is only one transport pipe as shown in FIG. In addition, in FIG. 2, the same members as in FIG. 1 are indicated by the same symbols.

Furthermore, FIG. 3 is a schematic diagram schematically showing another example of a deposited film forming apparatus suitable for carrying out the present invention. This apparatus differs from FIG. 2 in that the top plate 302 of the deposition chamber 101 is lifted from the ground by an insulator 301, and furthermore, a high frequency power source 303 applies high frequency power to the deposition chamber 101.

Reference numerals 304 to 305 are raw gas supply sources for doping the deposited film, and the meanings of the symbols 304 to 305 are the same as described above. Note that the doping source gas supply sources 304 to 305 are not only necessary for the deposited film forming apparatus shown in FIG.
It goes without saying that the deposited film forming apparatus shown in the figure may also be installed to obtain a desired deposited film.

In order to make an amorphous (including microcrystalline) or polycrystalline 5t (H, It is formed by doping a p-type impurity or both impurities into the layer while controlling the amount thereof.

In order to form n-type and p-type polycrystalline 5i(H, Chemical substances for film formation introduced into the space (C) and compound gases containing inert gas and impurity elements as necessary are excited and decomposed by microwave energy in the decomposition space (C). , each active species is generated, mixed appropriately in the decomposition space (C''), and introduced into the deposition space (A) where the substrate is installed, and the active species and a precursor containing silicon and halogen are mixed. A deposited film is formed on the substrate through chemical interaction with the body.

Moreover, FIG. 5 shows a pn using a polycrystalline Si deposited film doped with an impurity element, which is produced using the apparatus of the present invention.
1 is a schematic diagram illustrating a typical example of a type diode device; FIG.

In the figure, 501 is a substrate, 502 and 503 are thin film electrodes,
A semiconductor layer 504 is composed of an n-type semiconductor layer 505 and a p-type semiconductor layer 506. 507 is a conductive wire connected to an external electric circuit device.

For example, the thin film electrodes 502 and 503 are made of NiCr.

A1. Cr, Mo, Au, Ir, Nb, Ta, V.

Ti, Pt, Pd, InxOs, Snow, T
It can be obtained by providing a thin film of TO (InxOs + Snug) or the like on the substrate 501 and the semiconductor layer 504 through a process such as vacuum evaporation, electron beam evaporation, or sputtering. The film thickness of the electrodes 502 and 503 is preferably 30 to 5X10', more preferably 10 to 5X1
It is desirable to be considered a 0” person.

1) Using the deposited film forming apparatus shown in FIG. 1, a non-doped a-3t (H,X) deposited film was formed by the following operations.

First, #7, which is 300m long, 100 fins wide, and 0.8fi thick.
059 glass substrate 103 to the substrate support plate 102 by 180"
Two pieces in total, one on each side facing each other (patient 1 and 1lh2
), and the inside of the deposition chamber 101 was evacuated to 10-'torr via the exhaust pipe 114 using a rotary pump, a mechanical booster pump, and a turbo molecular pump.

Next, the substrate temperature is increased to 30°C using the substrate heating heater 104.
The decomposition space of the transport pipe (
The surface temperature in B) was maintained at 700°C.

Then, drive the motor 115 to rotate the board 1 rp.
It was rotated at a speed of m.

While the substrate temperature and the surface temperature in the decomposition space (B) of the transport pipe are kept constant, H2 gas is supplied from the gas supply source 105 for 50 sec, and Ar gas is supplied from the gas supply source 106 for 15 sec.
The pressure inside the deposition chamber was maintained at 0.1 torr by adjusting the opening degree of the exhaust valve 113, and microwaves with an effective power of 200 W were generated from the microwave power source 108. In this way, H radicals as active species generated in the decomposition space (C) were introduced into the deposition space (A).

On the other hand, 5i is inserted into the gas introduction pipe 111 from the gas supply source 110.
zFa gas was introduced for 30 seconds, and SiF2 radicals as a precursor generated in the decomposition space (B) were introduced into the deposition space (A) through the hole 111'' provided in the transport pipe 111'.

In this way, the deposited film was deposited on the glass substrate at a deposition rate of 5 people/see for 40 minutes. (Sample Capture 11.2) The glass substrate 103 was removed from the substrate support plate 102, and the film thickness and photosensitivity ratio (electrical conductivity and dark conductivity).

The results are shown in Table 1.

Using the apparatus shown in Table 1 and Figure 6, using the same gas flow rate, microwave power internal pressure, substrate size, substrate temperature, and electric furnace temperature as in Production Example 1, a deposition rate of 5 people/sec was applied to the substrate. The deposited film was allowed to accumulate for 1 minute. (Only one substrate was used) The deposited film thus obtained was evaluated and measured in the same manner as in Production Example 1. The results are shown in Table 2.

As is clear from Table 2, in the conventional deposited film forming apparatus,
It has been found that when a large-area substrate is used, some variation in film thickness and unevenness in characteristics occur.

A non-doped polycrystalline sty film was formed using the deposited film forming apparatus shown in Table 2 and FIG.

First, 100 scct of H2 gas is supplied from the gas supply source 105.
Ar gas was introduced for 150 seconds from the ls gas supply source 106, the pressure inside the deposition chamber was maintained at Q, l torr by adjusting the opening degree of the exhaust valve 113, and the microwave power source 10
8, microwave power with an effective power of 400 W was input into the decomposition space (C), and H radicals as active species generated in the decomposition space (C) were introduced into the deposition space (A).

On the other hand, 5i is inserted into the gas introduction pipe 111 from the gas supply source 110.
Flow 3 Q 5 ccva of xF* gas into the decomposition space (B
) The S i F t radicals as precursors generated in ) were introduced into the deposition space (A) by four people.

By increasing the flow rate of the H gas used in this way,
Five persons/year were deposited on a glass substrate under the same conditions as for depositing the non-doped a-3S:H:F film in Production Example 1, except that the microwave power input into the decomposition space (C) was increased.
A deposited film was formed for 30 minutes at a deposition rate of sec. (Samples 3 and 4) The above deposited films were measured in the same manner as in Production Example 1.
We conducted an evaluation. The results are shown in Table 3.

In addition, when we evaluated the crystallinity at each point using electron beam diffraction (RHEED), we found that the plane orientation (
A spot-like diffraction pattern of 110) was obtained, with an average crystal grain size of 1 μm (30 points per thin film sample, 30 points x 2
sample = average value of 60 points).

A pn type diode shown in FIG. 5 was manufactured using the deposited film forming apparatus shown in FIG. 3.

First, only one glass substrate 501 (300 m long, 100 m wide, 0.8 inch thick) on which a 500 ITO film 502 has been deposited is installed on the substrate support plate 102, and the gas supply source 30
From 4, 1Q of PH3 diluted to 300 ppm with Ar
Production Example 2 until the introduction of sccs+ and then the introduction of 5iF1 radicals as a precursor into the deposition space (A).
In addition, from the high frequency power supply 303, 50W
RF power of 10 people/sec is introduced into the deposition chamber 101.
1000 people formed an n-type polycrystalline Si thin film 505 on the ITO film 502 at a deposition rate of .

Next, the introduction of PH, is stopped, and A is supplied from the gas supply source 305.
1105 cc of BF diluted to 300 ppm with r
P was formed on the n-type polycrystalline Si thin film 505 in the same manner as the above-described n-type polycrystalline Si thin film except that r was introduced.
A total of 1000 people formed a type polycrystalline Si thin film 506. Furthermore,
On this p-type polycrystalline Si thin film, an A1 electrode 503 having a thickness of 500 wafers was formed by vacuum evaporation using another device (not shown) to obtain a pn-type diode.

The pn-type diode thus obtained was cut into pieces with an area of 1- to form a total of 300 pn-type diode elements, and the IV characteristics of each were measured to evaluate the rectification characteristics. As a result, the rectification ratio of the diode at a voltage of 1V is 2X
It shows a good value of 10' to 5X103, and the n value is 1.2
It was 5-1.3.

(All values indicate the numerical value range measured for 300 diode elements.) [Summary of the effects of the invention] As described above, according to the deposited film forming apparatus of the present invention, the film thickness can be increased over a larger area than before. A deposited film with more uniform properties and properties can be obtained. Moreover, the obtained film is excellent electrically, optically, and photoconductively, and furthermore, a good crystalline thin film with large grain size can be easily obtained over a larger area.

Therefore, the mass production and area of the deposited film can be further increased, and the manufacturing cost of photosensitive devices such as photoelectric conversion elements can be further reduced.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram showing a typical example of the deposited film forming apparatus of the present invention, and FIGS. 2 and 3 are schematic diagrams showing other examples of the deposited film forming apparatus of the present invention. Fig. 4 is a schematic diagram showing the positions of measurement and evaluation of the deposited films obtained in Examples 1 and 2, and Fig. 5 is a schematic diagram showing the positions of measurement and evaluation of the deposited films obtained in Examples 1 and 2. A schematic diagram of a diode, FIG. 6 is a schematic diagram showing a typical example of a conventional deposited film forming apparatus. In the figure, 101,601...deposition chamber, 102°6
02...Substrate support plate, 103,603,501...
Substrate, 104, 604... Heater for heating the substrate, 10
5.106,304,305,605,606゜610
．． 110... Gas supply source, 107,111°607.
611...Gas introduction pipe, 108,608...Microwave power supply, 109,609...Waveguide, 112゜61
2...Electric furnace, 113,613...Exhaust pulp, 1
14.614...Exhaust pipe, 115...Motor, 1
16... Rotating disk, 117... Cylindrical member, 118.
...Active species vent, 111', 201...Transport pipe, 1
11', 20! '...Gas outlet, 301...Insulator, 302...Top plate, 303...High frequency power supply, 5
02.503... Thin film electrode, 504... Semiconductor layer,
505... N-type polycrystalline Si thin film, 506... P-type polycrystalline St thin film, 507... Conducting wire.

Claims (3)

[Claims] (1) A deposition space (A) for forming a deposited film on at least one deposited film forming substrate installed therein, and a decomposition space (A) for producing a precursor that will be a raw material for forming the deposited film. B), another decomposition space (C) for producing an active species that interacts with the precursor, and a precursor produced in the decomposition space (B) and an activity produced in the decomposition space (C). A deposited film forming apparatus comprising means for separately introducing seeds into the deposition space (A), and means for exhausting the inside of the deposition space (A), the decomposition space (C) being separated from the deposition space ( A) is formed by a cylindrical member installed concentrically with the deposition space (A), a large number of active species ejection holes are provided over the entire side wall surface of the cylindrical member, and from the top and bottom surfaces of the cylindrical member. Providing means for generating the active species by introducing microwave energy, and further means for rotating the deposited film forming substrate outside the cylindrical member in the deposition space (A) coaxially with the cylindrical member. A deposited film forming apparatus characterized by comprising: (2) the means for introducing the precursor into the deposition space (A),
The deposited film forming apparatus according to claim 1, which is a plurality of transport pipes having a large number of gas ejection holes installed in the deposition space (A). (3) The deposited film forming apparatus according to claim (1) or (2), further comprising means for exposing the deposition space (A) to glow discharge.