JPH01731A - Deposited film forming equipment - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention is applicable to deposited films, particularly functional films, particularly semiconductor devices, photosensitive devices for electrophotography, life sensors for image input, imaging devices, optical -i industrial packaging suitable for continuously forming a large area of amorphous (including microcrystalline), non-single crystalline or single crystalline deposited film such as polycrystalline for use in electromotive confectionery, etc. Regarding.

[Prior art]

For example, attempts have been made to form an amorphous silicon film using Vcij, X-vacuum evaporation, plasma CVD, CVD, reactive sputtering, ion grating, and photo-CVD. It is used and corporatized.

According to Hyakunen et al., the deposited film composed of amorphous silicon has excellent electrical and optical properties, fatigue properties due to repeated use, usage environment properties, and productivity and electrical production including uniformity and reproducibility. There is room for further improvement of comprehensive characteristics in this respect.

The reaction process in forming an amorphous silicon deposited film using plasma CVD, which has been widely used for a long time, is considerably more complicated than that of the conventional CVD method.
Many aspects of the reaction mechanism remain unclear. In addition, there are many formation parameters for the deposited film (e.g. substrate temperature, flow rate and ratio of introduced gas, pressure during formation, high frequency power, electrode structure, reaction vessel structure, pumping speed, glazma generation formula, etc.). Depending on the combination of parameters, the plasma sometimes becomes unstable and often has a significant negative effect on the deposited film. Moreover,
In reality, it is difficult to generalize the manufacturing conditions because it is necessary to trace the factors and parameters specific to each device for each device.

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

In the plasma CVD method, as mentioned above, the parameters for forming the deposited film are complex, so it is difficult to repeatedly create uniform film forming conditions.Especially when forming the entire deposited film over a large area, It has been difficult and difficult to form a film with good reproducibility while fully satisfying the uniformity of the thickness and quality of the film to be formed. In addition, when mass production is attempted, the management items for mass production become complicated.
The width of the managed ffd has become narrower, and equipment adjustments have become more delicate.These have been pointed out as problems that should be improved in the future.

On the other hand, the conventional technique using the normal CVD method requires a high Fi1 temperature, and a deposited film having practically usable characteristics has not been obtained.

As mentioned above, in forming an amorphous silicon film, there is a strong desire to develop a formation method that can be used for JIi production using low-cost equipment while maintaining its practicable characteristics and uniformity.

These are not limited to the amorphous silicon film mentioned above, but also include polycrystalline, non-monocrystalline, monocrystalline, etc.
chemical I &, for example, silicon-germanium alloy film,
The same can be said of silicon nitride films, silicon carbide films, and silicon oxide films.

[Problems to be solved by the invention]

The present invention has been made to eliminate the drawbacks of the plasma CVD method described above, and at the same time to provide a new mass-produced deposited film forming apparatus that does not rely on conventional forming methods.

The present invention also maintains the properties of the formed film and improves the deposition rate, as shown in FIG. This was made to provide W made by membrane formation.

A further object of the present invention is to provide a deposited film forming apparatus that can simplify the management of film forming conditions and easily achieve mass production of films.

The deposition forming apparatus provided by the present invention excites a raw material gas for forming a deposited film to generate a precursor or 1d/1d/ which becomes a raw material for forming a deposited film, and all active species that interact with the precursor. In a deposited film forming apparatus comprising a heating element made of a single transition metal element or an alloy thereof, and a film forming chamber for forming a deposited film on a substrate, the heating element is disposed inside the film forming chamber. The heating element is characterized in that a number of base body holding means are provided around the heating element to rotate or slide the base body.

In the present invention, instead of generating all the plasma in the film forming chamber for forming the deposited film, a raw material gas for forming the deposited film is introduced into the film forming space, and a transition gas is placed in the gas gold film forming space. A deposited film is formed by being activated by the catalytic action of a heating element made of metal to generate precursors and/or active species that are raw materials for forming a deposited film containing halogen or/and hydrogen. The deposited film is not adversely affected by etching effects or other adverse effects such as abnormal discharge effects during film formation.

The raw material gas for AIL deposition used in the present invention is preferably one containing halogen and/or hydrogen in its molecules. Precursors and/or active species obtained by exciting a raw material gas for forming a deposited film containing halogen or/and hydrogen are generated by a thermal dissociation reaction using a transition metal as a catalyst. F, :5tu
2r:5tp2. : Lanocal such as 5tHp can be assumed to be the main component and the reaction mechanism can be made very simple.

In the present invention, since plasma is not used in the film forming chamber where the entire desired deposited film is formed, the deposited film containing halodane and/or hydrogen introduced into its molecules can be formed using the deposition film formation parameters. The temperature and position of the heating element from the substrate, the temperature of the substrate, and the internal pressure in the deposited film space.
Therefore, the conditions for forming the deposited film can be easily controlled, and the deposited film can be formed with high reproducibility and mass production.

Note that the term "precursor" in the present invention refers to something that can serve as a raw material for the deposited film to be formed. "Active species" cause a chemical interaction with the precursor, for example, give energy to the precursor, or chemically react with the precursor, and can form a deposited film more efficiently than the precursor. Something that has the role of creating a state. Therefore, the active species may contain constituent elements constituting the deposited film to be formed, or may not contain such constituent elements.

Furthermore, the active species containing halodane and/or hydrogen can be generated in the vicinity of the substrate for forming the deposited film due to the catalytic action of the transition metal. This is a problem when generating precursors in an activation space other than the membrane chamber.Transfer loss due to polymerization of precursors or adsorption of precursors to the transfer tube wall can be prevented, and therefore, halodane or / and the usage efficiency of the raw material gas containing hydrogen in its molecules can be significantly improved.

Furthermore, since the means for activating the raw material gas containing halodane and/or hydrogen in its molecules is a heating element made of a non-transferable metal, the precursor or/and Since all active species can be generated, all deposited films having uniform characteristics can be formed on a plurality of substrates installed in the space surrounding the heating element.

In the present invention, there is no particular restriction on the lifespan of the precursors and/or active species generated from the film-forming source gas in the film-forming space, since the heating element made of a transition metal is located near the substrate.

As the transition metal used as the heating element used in the invention, it is desirable to select a transition metal that is difficult to mix into the deposited film due to sublimation, scattering, etc. It is necessary to select activation conditions.

゛Such materials include materials from the 4th or 5th period of the periodic table.
Mention may be made of the metals and alloys in the 6th period, among them IV, V.

Transition money belonging to the ■, ■, ■ family! ! 4'lzr: Can be suitably used.

Specifically, for example, Tl, Nd r Cr + M
o, W *Fe, Ni, Co + Rh
, Pd, Mn, Ag, Zn, Cd
.

Pd-Ag, Ni-Cr, W-Th, W-
Examples include Re, W-Mo, and the like.

In the present invention, the distance from the substrate to the heating element made of a transition metal disposed within the film formation region is determined from the viewpoint of preventing damage to the substrate due to heat or efficient movement of the precursor to the substrate. , preferably 1 to 20 On++++.

The thickness is preferably 2 to 100 mm, most preferably 5 to 50 mm.

Further, in the present invention, the heating temperature of the heating element made of a transition metal disposed in the membrane chamber is preferably 100°C to 3°C.
000°C, more preferably 200°C to 2500°C, optimally 500°C to 2000°C.

The shape of the heating element can be selected from linear, filament, mesh/flat plate, honeycomb, etc., making it possible to change the shape of the precursor or! It is possible to completely change the generation cross-section of I''i/ and active molecules, to control the reaction between the precursor and the active species, and to produce a uniform deposited film according to the shape of the substrate.

In the invention, haloke9 used for film formation or/
and cedar containing hydrogen in its molecules 1. The raw material gases for formation include compounds with silicone as the main skeleton, compounds with secondary gold as the main skeleton, compounds with dalmanium as the main skeleton, water-based, fluorine-based, chlorine, hydrogen fluoride, and fluoride. Examples include chlorine and hydrogen chloride.

These compounds may be used alone or in combination as appropriate.

As a compound having a silicon-gold main skeleton, for example, a compound in which part or all of the hydrogen atoms of a chain or current silane compound is replaced with a halodane atom is used, and specifically, for example, S i uY 2 u+ 2 ( u is an integer greater than or equal to 1,
Y is F, CL, Br, and Engineering! l1 is at least one selected element. ) chained silicon halide represented by S l vY 2 v (v is an integer of 3 or more, Y has the above-mentioned meaning), cyclic silicon halide represented by Si u HxXy (u and Y are the above-mentioned It has a meaning. x + y = 2 u or 2u+
It is 2. ) and the like can be mentioned.

Specifically, for example, 5IF4. (stF2)5 r (
SiF2)6.

(SiF2)4.812F6.81. F8. SiHF
3. SiH2F2゜512H2F4.5t2H,F3
．． 5IC14, (SiCl2)5゜SiBr4+ (S
iBr2) 5t 5t2cz6s 5t2Rr6.5t
Hct3゜5iHBr, , 5iHI, , 812
Examples include those in a gaseous state or easily gasified, such as C23F3.

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

Further, as a compound having carbon as the main skeleton, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic hydrocarbon compound is replaced with halogen atoms is used, and specifically, for example, CY (u is an integer greater than or equal to 1u 2u-1-2, Y is F, CL, Br, and engineering!
1 selected at least one glaze element. ) chain halide carbon represented by CvY2v (v is an integer of 3 or more, Y has the above-mentioned meaning), cyclic halide silicon represented by CuHXYy (u and Y have the above-mentioned meaning). x + y = 2u or 2u+2).

Specifically, for example, CF4. (CF2)5. (CF2)
6゜(CF2)41 C2F6 r C5F8+ CH
F3 r CH2F2 + CCZa r (CCl2)
51 CBr4+ (CBr2)5 r C2CL6
, C2Br, s 1CHC13, C) II3. C2C
Examples include those in a gaseous state or easily gasified, such as 13F3.

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

Further, as a compound having r-rumanium as its main skeleton, for example, a compound in which part or all of the hydrogen atoms of a chain or cyclic germanium hydride compound is replaced with rhodane atoms is used, and specifically, for example, Geu”2u+2 (u
is an integer greater than or equal to 1, Y is F, CL e Br.

and (2) at least one element selected from the group consisting of: )
Chained germanium halide, GevY2v, represented by
(v is an integer of 3 or more, Y has the above-mentioned meaning), GeuHxYy (
u and Y have the meanings given above.

x y = 2 u or 2u+2. ), and the like.

Specifically, for example, GIF4. (GeF2)s, (
ceF,,)6r(G6F2)4 1 G112F61
Ge3Fa + (rsHF3 + Geu2”21
Ge2H2F21 Ge2H3F31 aecta,
(Gl!1cZ2)S lG6Br4. (GeB
r2)5. GezCZ6. Ge2Br6. GeH
Ct3+GeHBr, Go) II, Ge2c
Examples include those in a gaseous state or easily gasified, such as tsF3.

The deposited film formed by the method of the present invention can be doped with an impurity element during or during film formation. The impurity elements to be used include, as p-type impurities, periodic table materials < ■ elements of group A, ψ11, e.g. B, kA
, Ga, In, Tt, etc. are mentioned as suitable ones, and as the n-type impurity, elements of Group V A of the periodic table, such as P t As, Sb t Bi, etc. are mentioned as suitable ones. Especially As, P,
Sb etc. are optimal. The amount of impurity doped is
It is determined as appropriate depending on the desired electrical and optical characteristics.

The substance containing such an impurity element as a component (substance for introducing impurities) is a compound that is in a gaseous state at room temperature and normal pressure, or at least in a gaseous state under the conditions for forming a deposited film, and that can be easily vaporized using an appropriate vaporization device. It is preferable to select Such compounds include PH3, P2H4, PF
3. PF5. PCl3゜AsH,, AsF, +
AsF5. AsCl3. SbH3, SbF, .

BF3. BCt, , BBr3. B2H6,B4
Examples include H, o, B,, H7°B)i, Bl(, BH%).

5j+ 610 612 Compounds containing the impurity element gold may be used alone or in combination of two or more. However, a compound containing TJii monomotosaku as a component does not form a husk even if it is re-entered into the film-forming space directly in a gaseous state or mixed with a film-forming raw material and gas.

Next, the present invention will be explained with reference to a typical example of a PIN type diode device using an a-8l'4 stacked film doped with an impurity element formed by the apparatus of the present invention.

FIG. 4 is a schematic diagram for explaining a configuration example of a typical PIN type diode device obtained by the present invention.

In the figure, 401 is the base, 402 and 407 are the thin film poles, and 4
03 is a semiconductor film made of amorphous silicon a-8l (H,
) layer 4, 04, amorphous silicon a-8l containing i-type hydrogen atoms or/and hyalogen atoms i ()i, : Ge(H,
X) layer 405, amorphous silicon a-8t(H,X) layer 406 containing p-type hydrogen atoms or ζ and hihalon atoms
It is composed of Reference numeral 408 denotes a conductive wire that connects to an external electrical circuit.

As the base 401, a conductive material, a semi-conductive material, or an electrically insulating material is used. If the base body 401 is a conductive type, the thin film material 402 may be omitted. Examples of the semiconductive substrate include Si and Ge.

Examples include semiconductors such as GaAs, ZnO*ZnS, and the like. Mt. Mt.',,! 402,407 as u 9
11 For example, NiCr + At*Cr, Mo, A
u, Ir + Nb, Ta, V, TI
, Pt rPd , In2O3, 5n02. I
Thin films such as TO (In2O3+5nO2) are vacuum evaporated,
The substrate 401 is formed by processing such as electron beam evaporation or sputtering.
Obtained by providing on top. Electrode 402.407
The film thickness is preferably 30 to 5 x IOA1, more preferably 100 to 5 x 10.

A-8i (H,
, V. To make it n-type or p-type depending on the layer formation,
It is formed by doping an n-type impurity, a p-type impurity, or both impurities among the impurity elements into the layer to be formed while controlling their benefits.

To form n-type, i-type, and p-type a-8l (H,X) layers or i-type a-8l: Go (H, and a compound containing a halogen, and if necessary, a compound gas containing hydrogen gas and an impurity element as a component, or a compound gas containing an alloy element such as rumanium as a component, and these introduced The raw material gas comes into contact with a heating element made of a transition metal and is activated by a thermal dissociation reaction, thereby forming a deposited film on the substrate 401. The thickness of the n-type and p-type a-8i(H,X) layers is preferably 100 to IO'A s
It is preferably in the range of 300 to 2000X.

Also, i-type a-8i ()f, X) layer or a-8l
: The thickness of the Ge(H,X) layer is preferably 500
~104k, more preferably 1000~10000X1
7) Range is desirable.

Next, FIG. 5 is a schematic diagram for explaining an example of the configuration of a typical photovoltaic member obtained by the present invention.

The photoconductive member 504 shown in FIG. 5 is one that can be applied as an image forming member for electrophotography, and is an intermediate layer provided as necessary on the support 501 for the photoconductive member. It has a layer structure composed of a layer 502 and a photosensitive layer 503.

The support 501 may be electrically conductive or electrically insulating. Examples of the conductive support include Ni-Cr,
Stainless steel, At+Cr, Mo, Au,
Ir.

Nb, Ta, V, Ti, Pt, P
Examples include metals such as d and alloys thereof.

As the electrically insulating support, polyester, polyethylene, polycargonate, cellulose acetate, polynolopyrene, polyvinyl chloride f 17 vinylidene chloride,
Films or sheets of synthetic resins such as polystyrene and polyamide, glass, ceramic, resin, etc. are usually used. Preferably, at least one surface of these frost/gas insulating supports is conductively treated, and another layer is preferably provided on the conductively treated surface side.

For example, if it is made of glass, the front side is Ni-Cr, At
.

Cr, Mo, Au, Ir, Nb,
Ta, V, TI, Pt.

Pb +' In2O3, SnO□, ITO(In2
It is possible to treat the special + by providing a thin film such as O, +5nO2), or by using a synthetic site such as a polyester film (if it is a fat film: N1-Cr, At+ Ag).
+ Pbr Zn, Ni + Au, Cr
rMo, Au, Ir+Nb, Ta,
Vacuum vaporization of metals such as V, Ti r Pt, etc.
'The shape of the support is C, cylindrical. Samurai in any shape, such as shape, belt shape, plate shape, etc.
The shape is determined depending on the need, but for example, if the optical-only member 504 shown in FIG. It is desirable that the

The intermediate layer 502 contains, for example, a material that prevents carriers from flowing from the support 501 into the photosensitive layer 503 and that is generated in the photosensitive IfJ503 by electromagnetic wave irradiation and directed toward the support 501. It has the function of easily measuring the passage of a moving photo carrier from the side of the photosensitive layer 503 to the side of the support 501.

This intermediate layer 502 is composed of a-81(f(, Contains impurities.

In the present invention, the content of substances governing conductivity, such as B and P, contained in the intermediate layer 502 is preferably as follows:
O,'OO1~5 X ] Oatomic ppm
.

Suitably 0.5 to I x 10 atomic
ppm z a suitably 1 to 5 x 10 atoms
It is preferable that the content be c ppm.

If the intermediate layer 502 has similar or the same components as the photosensitive IfJ 503, the formation of the intermediate layer 502 can be successively followed by the formation of the photosensitive layer 503. In that case, the support 50 is prepared by mixing a compound containing silicon and halogen as raw materials for forming the intermediate layer, a compound containing impurities and chemical elements as components, and a gas containing hydrogen depending on the safety.
1 is installed and introduced into a certain film forming space.

The gas containing silicon and halogen introduced into the film forming space causes a thermal dissociation reaction and is activated by contact with a heating element made of a transition metal to form an intermediate layer 502 on the support 501 .

When forming the intermediate layer 502, a precursor and/or active S? - Compounds containing silicon and halogen that can be easily generated include, for example, compounds that easily generate lasocals such as SiF 2 !
The layer thickness of the intermediate layer 502 that is more preferably selected is preferably 30X to 10μ, more preferably 40X to
It is desirable that the thickness be 8μ, most preferably 50X to 5μ.

The photosensitive layer 503 is, for example, a −8i (n, X) or a
-8i: Made of Ge (H, The layer thickness of the O photosensitive layer 503 is preferably 1 to 1.
100μ, more preferably 1-80μ, optimally 2-50
It is preferable that it be μ.

The photosensitive layer 503 is a non-Dog a-8t (LCX) layer or an a-3t: Go ()i, The conduction properties of another pole a (e.g. n-type))) A! Alternatively, if the actual amount of the substance that controls the same polarity conduction characteristics is contained in the intermediate layer 502, it may be contained in a material that is much smaller than the amount. It's okay.

In the case of forming the photosensitive layer 503, if it is formed by the method of the present invention, as in the case of the intermediate layer 502, a compound containing silicon and nitrogen is added to the film forming space, and hydrogen gas is added as necessary. A gas of a compound containing an impurity element as a component, or a gas of a compound containing an alloy element such as r-rumanium as a component '4? The photosensitive layer 503 may be entirely formed on the intermediate layer 502 by introducing these gases into a heating element made of a transition metal and activating them by a thermal dissociation reaction.

FIG. 2 shows a schematic diagram of a specific shape of a heating element made of a single transition metal element or an alloy used in the present invention.

Figure 2 (&) shows a plurality of filament-shaped heating elements 201 installed in a ladder shape using conductive members 202. and the deposition rate. FIG. 2(b) shows a planar heating element 203 with holes 204 in order to improve permeation of source gas and contact efficiency. There are no particular restrictions. FIG. 2(C) shows a mesh heating element 205 supported by a conductive member 206, and there is no particular restriction on the mesh size.

[Implementation f/IJ] Examples of the present invention are shown below.

Example 1 Using the electrical device shown in FIG. 1, a PIN type diode shown in FIG. 4 was manufactured by the following operations.

In FIG. 1, reference numeral 101 denotes a film forming chamber, and a heating element 103 made of a tungsten filament having the shape shown in FIG. 2 (a) is disposed approximately in the center thereof. This heating element is fully supplied with electric power from the power source 107 via four wires 117 and generates heat. Two sets of base sliding mechanisms are disposed above and below the heating element 103. Reference numeral 102 denotes a belt-shaped substrate having a stainless steel foil surface, which is sent out from a feeding mechanism 109, and is wound up by a winding mechanism 110 while being supported by a substrate support roller 108. Here, the feeding mechanism 109 and the winding mechanism 110 can be rotated in both left and right directions, and can be used by reversing the grooves 51 for feeding and winding. 104 is a substrate heating table. The heater 105 is supplied with power through four wires 106 to generate heat, and the heater 105 is connected to the thermocouple 118 and the temperature display section 11.
The temperature is monitored by 9. 111 is a vacuum gauge.

112 to 115 are raw material gas supply lines, and raw material gas is supplied via a cylinder and a mass flow controller (not shown). 120 is a raw material gas introduction pipe, and 116 is an opening adjustment device (υF air hole having a diameter of 1.1).

When heating the substrate in carrying out the method of the present invention, the substrate heating temperature is preferably 30 to 450°C, more preferably 50 to 350°C, but heat generation from the heating element 103 during film formation When the amount is large, the output of the heater 105 can be significantly lowered than the output for substrate heat treatment up to the start of film formation, and depending on the conditions, it is also possible to turn off the heater.

When the gas of the compound containing silicon and halogeno is passed over the heating element 103 consisting of a tungsten filament, it is activated by a thermal dissociation reaction to produce a precursor such as 5IF2. When the generated hydrogen gas passes over the heating element 103, which is also made of a tungsten filament, it is activated by the catalytic action of the heating element 103 to become activated hydrogen, etc., and these react with the aforementioned precursors to generate the heating element. Desired deposited films are formed on two sets of substrates disposed above and below 103.

First, a stainless foil substrate having a width of 30 crn, a length of 5 ms, and a thickness of 0.2 sq.
The inside of the film forming chamber 101 was heated to 1lo-'Torr.
The pressure was reduced to

Therefore, 512F6 is supplied to the raw material gas supply line 112 from a cylinder (not shown)! l140 sec, 5lF4jf
PF5-gas f20 diluted to 4000 ppm with
■12 gas 1 from gas supply line 113 with secm
00 sec all of the gas was supplied through the supply line 114 and into the Q chamber 101 through the introduction pipe 120. At the same time as the introduction of the raw material gas starts, the tungsten filament heating element 103 is heated to about 1700°C, and the base heating table 10 is heated.
The temperature setting in step 4 was 150°C, and the sliding speed of the base was 20c.
A film of about 500X n-type a-8t (H, The internal pressure during film formation was adjusted by adjusting the opening degree of the exhaust hole.
It was set to 7 Torr.

Next, stop the supply of PF5 gas diluted with SIF gas,
812F6 gas flow M k 80 sec N 1-
12 Gas flow + i total 180 sec, sliding direction reversed δ, sliding speed 3 cm/sec, heating element 1
03 to about 1800℃ to form n-type a-8t (H,
) Type 1 a-8t (I
i, X) A film 405i was formed. The internal pressure during film formation is Q, 5
Torr.

Next, ff'c of S i 2F6 gas, m k 30
secm % H2 gas flow It total 80 accm
, I3F diluted to 2000 ppm with 5IF4 is re-entered with gas k 15 sec, the sliding direction is reversed again, the sliding speed is set to 25α/See, and the total heating element 103 is approximately 17
A film was formed by heating to 00°C. The internal pressure during film formation was 0.7 To
It was set as rr. As a result, the l-type a-8t()l,X) film 4
Approximately 300X p-type IL-8l (H,X) film 4 on top of 05
06 was formed.

Next, the PIM of the upper and lower 20-rings was created using the above method.
Using a-81(H,X) NA layer film of the type, o −/I
/y-.

- A 20α×30z solar cell module was created using a Roll to Roll continuous modularization device.

ITOM side) AMI (100mW/cm”)
When irradiated with light, the conversion efficiency was 15% higher than conventional products.
As described above, it was confirmed that the characteristics were improved by 10 cm or more over the conventional product in terms of open-circuit voltage and by 10 cm or more over the conventional product in short-circuit current.

Moreover, the variation in the characteristics of the solar cell modules obtained from the upper and lower 20-meters was within a factor of 5.

Example 2 +tit of Si F gas is 80 sec % G
e2F6 gas flow ja k 5 secm s H2 gas Hjtk 200 secms Heating element 103 approximately 1
A PIN type a-
8i (f(,X)/a −8i : Ge (H
, X)/a -81(H,X) laminated film was completely formed. Next, in the same manner as in Example 1, a solar module of 20 crn x 30 ports was fabricated.

AM 1 (100mW/cm”
) When irradiated with light, the tear film efficiency was 1% higher than the conventional product.
796 or more, the characteristics were improved by more than 10 factors compared to the conventional product in terms of open circuit voltage and by more than 10 factors compared to the conventional product in terms of short circuit current. Moreover, the variation in the characteristics of the solar-pond modules obtained from the upper and lower 20-meters was within 5%.

Examples 3 to 6 Table 1 shows the mounting conditions and evaluation of solar cell modules manufactured by the same manufacturing method as Example 1. In both cases, improved properties were observed compared to conventional products.

Example 7 In Example 1, the base sliding mechanism for film formation is shown in Figure 3 (
, ) was replaced with the one with the four sliding mechanisms shown in sn type a-3l (H,X) 11 is 5t2F6 gas flow rate 60s
ccmsl-1°gas flow'4150 secm N S
PF5 gas stream diluted to 4000 ppm with iF4 30
The film was deposited at secm, type 1 a-8l (H,X) M
is Si2F6 gas flow ia: 100 sec.

The film was formed at a H2 gas flow rate of 240 sec, and a p-type a-
st(u,x) membrane is 512F6 gas flow'1tr 50
gccm s H2 gas flow it 120 secm
The film was formed using a BF3 gas flow diluted to 20,001) l)m with % SiF4 at a flow rate of 1tE 25 sec. Note that during the film formation, the temperature of the heating element 1'03 was all set to 1700°C.

Next, using the 40-L PIN type a-8i (H, was created.

Then, the ITO film side is deflected AM 1 (100mW/cm
”) After full light irradiation, the conversion efficiency was more than 12 times higher than the conventional product, and the open end pressure was 8≠ more than the conventional product.
A characteristic improvement of more than 5 factors was observed in short-circuit current compared to conventional products.

Further, the variation in the characteristics of the solar cell modules obtained from 40 mm was within 5 mm. In addition, Fig. 3(a)
In the figure, 301 is a heating element made of a tungsten filament shown in FIG.

Example 8 S12F6 gas flow rate 100 seem z GeF4
Gas OIf, iit 158eem N H2 gas flow t
hff 220 sec) Q heating element 103 about 180
A PIN type a-
8i (H,X)/a-8i: Go (H,X)/
A 40-layer a-8i (H,X) laminated film was formed. Then, in the same manner as in Example 1, a 20 cm x 30 cm
The solar cell monoyl was completely fabricated.

And, ITOIIQ side, “9・AMl (100mW
/cm2) When irradiated with light, the conversion efficiency was 15% higher than the conventional product, and the open circuit voltage was 10L4 higher than the conventional product.
As described above, it was confirmed that the short-circuit current was improved by more than 8 inches compared to the conventional product.

Moreover, the variation in the characteristics of the solar cell modules obtained from 40 mm was within 5 mm. The heating element made of W-Mo was used as shown in FIG. 2(C).

Embodiment 9 In FIG. 1, two sets of upper and lower base sliding devices ff'e,
In place of the substrate holding device shown in FIG. 3(b) in which six circular substrates can be installed, a drum-shaped electrophotographic image forming member having a layer structure as shown in FIG. 5 was produced. In FIG. 3(b), 311 is a heating element made of tungsten mesh having the shape shown in FIG. 2(C), 312 is an At cylindrical base, and 313 is a heater for heating the base. Film forming chamber 10
All six At cylindrical substrates were installed in a chamber of 1, and the internal pressure was increased to 10℃ while heating the substrates to approximately 250℃ using a heater for heating the substrates.
The pressure was reduced to Torr.

A flow rate of 60 sec from the 812F6 raw material gas supply line 112 from the d-amp (not shown) is 3 at SIF'4f.
BF3 gas diluted to 000 ppm was flowed for t 25 s.
At CCm, connect the gas supply line 113 and supply H2 gas at a flow rate of 1.
The gas was supplied through the gas supply line 114 at a rate of 50 sec, and introduced into the film forming chamber 101 through the introduction g120. At the same time as the introduction of raw material gas starts, the tungsten heating element 103 is heated to approximately 1600°C, the temperature of the heater for heating the substrate is set to 150°C, and the body is heated without rotating.
A P+ type a-8l (i(, .

Next, the total supply of BF3 gas diluted with 5IF4 gas, the flow of 812F6 gas M p 120 secm N
j (2 gas flow i k 250 sec, heating element 103 heated to about 1800°C, P+ type a-8t (H
,X) About 18 μm of non-doped a on g 502
-8l(H,X)jQ 503k film was formed. In addition,
The internal pressure during film formation was 0.5 Torr.

Comparative Example I S1□F6. 13.For each gasket of H2, B2H6.
A drum-shaped electrophotographic forming member having the layer structure shown in FIG. 1 was formed by an electronic plasma CVD method using a 56 MHz high-frequency device.

Manufacturing conditions and performance of drum-shaped electrophotographic image forming members obtained in Example 9 and Comparative Example 1? , shown in Table 2.

〔Effect of the invention〕

According to the film forming apparatus of the present invention, the desired electrical, optical, photoconductive and mechanical properties of the formed film are improved, making it possible to produce thi. In addition, especially by installing the substrate holding means all around the heating element, it becomes easy to form a deposited film over the dog surface, and the deposited film can be deposited with good reproducibility and high efficiency. It is possible to form one film continuously, simplify the management of film formation conditions, and easily achieve M'fM of the film.

[Brief explanation of the drawing]

FIG. 1 is a schematic diagram of one example of the structure of a film forming apparatus according to the present invention. FIG. 2 is a schematic diagram of a heating element used in the present invention. FIG. 3 is a schematic configuration diagram of a substrate installed in the deposited film forming apparatus of the present invention. FIG. 4 is a schematic diagram for explaining a configuration example of a PIN diode manufactured using the apparatus of the present invention. FIG. 5 is a schematic diagram for fully explaining an example of the structure of an electrophotographic image forming member manufactured using the present invention. 101... Film forming chamber, 102, 302... Belt-shaped substrate, 103... Heating element, 104.303... Substrate heating table, 105... Heater, 106.117... Conductive wire, 107 ...Power source, 108...Substrate support roller, 109...Feeding mechanism, 110... Winding mechanism, 111...Vacuum gauge, 112-115... Raw material gas supply line, 116... Exhaust hole, 118...Thermocouple, 119...Temperature display section, 120...Introduction pipe, 2
01,203,205°301.311...Heating element,
202.206...Guiding member, 204...Hole, 3
12... Cylindrical substrate, 313... Base/J11 thermal heater-1401... Base, 402... Thin film electrode, 404... N-type semi-diamond layer (p-type semiconductor l threat), 40
5...n-type semiconductor layer, 406...p-type semiconducting layer (n
type semiconductor layer), 504... electrophotographic image forming member, 5
01...Substrate, 502...Intermediate layer, 503...Photosensitive layer. Applicant Canon Co., Ltd.

Claims (1)

[Claims] A heating element made of a single transition metal element or an alloy for exciting a raw material gas for forming a deposited film to generate a precursor that becomes a raw material for forming a deposited film and/or an active species that interacts with the precursor. and a film forming chamber for forming a deposited film on a substrate, the heating element is disposed inside the film forming chamber, and the substrate is rotated or rotated around the heating element. A deposited film forming apparatus characterized in that a plurality of slidable substrate holding means are arranged.