JPH0590178A - Method and apparatus for continuously forming functional deposited film - Google Patents

Abstract

(57) [Abstract] [Purpose] By providing a method and a device for uniformly generating a heating region by microwaves over a large area and a large capacity, it is possible to continuously provide high stability, high efficiency, and high photoelectric conversion efficiency. It is an object of the present invention to provide a method and an apparatus for continuously forming a functional deposited film capable of forming a highly crystalline photovoltaic element. [Structure] While continuously moving a strip-shaped member 101 on which a deposited film is formed, a columnar processing space 116 having a side wall of the strip-shaped member is formed in the middle thereof, and microwave applicator means 107, 108 are provided in the processing space. The processing space 11 by radiating microwave energy by
6. A method and apparatus for continuously forming a functional deposited film, including a microwave heating step of performing a heating process on a side wall of a deposited film of 6, wherein the microwave energy is radiated in parallel with a traveling direction of the microwave. The microwave energy is radiated to the processing space by the microwave applicator means.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method and apparatus for continuously forming a functionally deposited film, in which a uniform microwave heating region is generated over a large area, and a solid phase growth reaction caused by the microwave heating region is generated. The present invention relates to a method and apparatus for continuously forming a functional deposited film capable of continuously forming a functional deposited film over a large area by improving the quality of a previously formed deposited film. More specifically, the present invention relates to a method and an apparatus capable of mass-producing large-area thin-film semiconductor devices such as photovoltaic elements at low cost.

[0002]

2. Description of the Related Art In recent years, attention has been paid worldwide to environmental problems. Environmental pollution by fossil fuels, global warming phenomenon,
Due to issues such as safety of nuclear power generation, it is desired to supply clean energy that is kind to the earth, and expectations are placed on wind power, tidal power, geothermal power, and solar power generation using natural energy. Above all, the method of power generation using solar cells using sunlight attracts more attention because it is possible to spread sunlight all over the earth, uneven distribution of energy sources, and no need for complicated large equipment. Has been done. In a solar cell, semiconductor junctions such as so-called pn junctions and pin junctions are formed in a semiconductor layer which is an important constituent element. These semiconductor junctions are formed by sequentially stacking semiconductor layers having different conductivity types, implanting a dopant of a different conductivity type into a semiconductor layer of one conductivity type by an ion implantation method, or diffusing by thermal diffusion. To be achieved.

Looking at this point in a solar cell using a thin film semiconductor such as amorphous silicon, which has been receiving attention as described above, in its fabrication, phosphine (P
H ₃ ), diborane (B ₂ H ₆ ), or the like, is mixed with a raw material gas containing a dopant element such as silane, which is a main raw material gas, and glow discharge decomposition is performed to obtain a semiconductor film having a desired conductivity type. It is known that a semiconductor junction can be easily formed by sequentially stacking these semiconductor films on a desired substrate. From this, in order to manufacture an amorphous silicon solar cell, a method of providing an independent film forming chamber for forming each semiconductor layer and forming each semiconductor layer in the film forming chamber is proposed. ing.

Incidentally, US Pat. No. 4,400,409 discloses a roll-to-roll method.
There is disclosed a continuous plasma CVD apparatus adopting the Oll system. According to this apparatus, a plurality of glow discharge regions are provided, and a sufficiently long flexible substrate having a desired width is arranged along a path through which the substrates sequentially pass through the glow discharge regions. It is said that an element having a semiconductor junction can be continuously formed by continuously transporting the substrate in the longitudinal direction while depositing and forming a conductive type semiconductor layer required in the discharge region.
In this specification, a gas gate is used to prevent the dopant gas used when forming each semiconductor layer from diffusing and mixing into other glow discharge regions. Specifically, a means for separating the glow discharge regions from each other by a slit-shaped separation passage and forming a flow of a scavenging gas such as Ar or H _{2 in the} separation passage is employed. .. From this, it can be said that the roll-to-roll method is suitable for mass production of semiconductor devices.

However, since the above semiconductor layers are formed by the plasma CVD method using RF (radio frequency), the film deposition rate is improved while maintaining the characteristics of continuously formed films. There is naturally a limit to what can be done. For example, even in the case of forming a semiconductor layer having a film thickness of at most 5000 Å, a predetermined plasma is used for a considerable length,
It is necessary to constantly occur over a large area and keep the plasma uniform. However, doing so requires considerable skill, and it is difficult to generalize the various plasma control parameters involved. Further, the decomposition efficiency and utilization efficiency of the film-forming raw material gas used are low, which is one of the factors that raise the production cost.

In addition, Japanese Laid-Open Patent Publication No. 61-288074 discloses a deposited film forming apparatus using an improved roll-to-roll system. In this apparatus, a hollow continuous slack portion is formed on a part of a flexible continuous sheet substrate installed in a reaction vessel, and active species generated in an activation space different from that of the reaction vessel are formed in the hollow portion. If necessary, another source gas is introduced to cause a chemical interaction by thermal energy, and a deposited film is formed on the inner surface of the sheet-like substrate forming the hollow-like slack portion. By depositing on the inner surface of the hollow-like slack portion in this way, the device can be made compact. Furthermore, since the activated species that have been activated in advance are used, the film formation rate can be increased as compared with the conventional deposited film forming apparatus.

However, this apparatus utilizes a deposited film forming reaction by chemical interaction in the presence of thermal energy, and in order to further improve the film forming rate, the amount of active species introduced and It is necessary to increase the supply of heat energy. However, there is a limit to the method of supplying a large amount of heat energy uniformly and the method of generating a large amount of highly reactive active species and introducing them into the reaction space without loss.

On the other hand, a plasma process using microwaves has been attracting attention recently. Since the microwave has a short frequency band, the energy density can be increased as compared with the case of using the conventional RF, and it is suitable for efficiently generating and sustaining plasma.

For example, in US Pat. Nos. 4,517,223 and 4,504,518, thin films are deposited and formed on a small area substrate in a microwave glow discharge plasma under low pressure. A method of causing is disclosed. According to the method, not only a high-quality deposited film can be obtained by preventing the polymerization of active species, which causes the deterioration of film characteristics due to the process under a low pressure, but also a powder of polysilane or the like in plasma can be obtained. It is said that the generation can be suppressed and the deposition rate can be dramatically improved. However, there is no specific disclosure for forming a uniform deposited film over a large area.

On the other hand, US Pat. No. 4,729,341 discloses a photoconductive semiconductor thin film deposited on a large area cylindrical substrate by a high power process using a pair of radiating waveguide applicators. Although a low-pressure microwave plasma CVD method and an apparatus for forming the same are disclosed, the large-area substrate is limited to a cylindrical substrate, that is, a drum as a photoreceptor for electrophotography. It has not been applied to substrates.

Further, the manufacturing process of the deposited film is a batch type, and the amount of the deposited film formed by one charging is limited, and a large amount of the deposited film is continuously formed on a large-area substrate. There is no disclosure on how to do this.

However, since the plasma using microwaves has a short wavelength of microwaves, energy nonuniformity is likely to occur, and various problems remain that must be solved for increasing the area of the substrate. ..

For example, as an effective means for homogenizing microwave energy, there is a use of a slow wave circuit. In the slow wave circuit, the microwave coupling of plasma is increased as the lateral distance of the microwave applicator increases. It has a unique problem that a sharp drop occurs. Therefore, as a measure for solving this problem, for example, US Pat.
As disclosed in Japanese Patent Nos. 814,983 and 4,521,717, a method of uniformizing the energy density in the vicinity of the surface of a substrate for changing the distance between the object to be processed and the slow wave circuit. Is being attempted. And in the former, it is described that it is necessary to incline the slow wave circuit to a certain angle with respect to the substrate, but the transfer efficiency of microwave energy to plasma is not satisfactory. Further, in the latter, it is disclosed that two slow wave circuits are provided non-parallel to each other in a plane parallel to the substrate.
That is, it is desirable that the planes perpendicular to the center of the microwave applicator intersect with each other in a plane parallel to the substrate to be processed and on a straight line perpendicular to the moving direction of the substrate. To avoid interference between the two applicators, it is disclosed that the applicators are arranged laterally offset by half the length of the waveguide crossbar relative to the direction of movement of the substrate.

By the way, in recent years, a crystal having excellent stability has been studied as a constituent member of a large-area solar cell in place of amorphous silicon. In the sunshine program under the guidance of the Ministry of International Trade and Industry, the amorphous silicon film deposited by the CVD method was doped with PH ₃ and then heated at 550 ° C. to 60 ° C.
Crystallization is attempted by annealing in a heating furnace at a low temperature of 0 ° C. for 10 to 20 hours. As a result, the grain size is 1.
About 5 μm, Hall mobility of electrons is about 200 cm ² / v
・ Although there are expectations for long-wavelength absorption solar cells to obtain s, the problem of increased capital investment due to the larger size of the annealing furnace for larger area, productivity and cost due to increased annealing process time Is a technical issue that must be resolved in the future.

Further, it has been reported that good quality crystallization can be induced by laser annealing in a thin film having a film thickness of 1000Å to 2000Å (S. Usui, Mat).
initial Research Symposium
Procedings, Vol 71 (1986) P
P. 435). However, the problem of application to large area processing due to the small spot diameter of the laser beam,
Since the absorption depth of laser light is shallow, it is relatively thick 1 μm
It is not suitable to heat-treat a 20 μm thin film at one time.

As means for heat-treating the semiconductor thin film, in addition to the above-mentioned heating furnace by infrared irradiation and laser annealing, induction heating mainly suitable for heating a magnetic material and the like can be mentioned. Further, as a heating means by high-frequency irradiation, a heating method by a microwave can be mentioned, particularly for drying wood containing a large amount of water, but it does not have a means for forming a large area and a uniform microwave. The high absorption of microwave energy resulting from the high dielectric constant of the water contained therein was utilized to bring about the efficient evaporation of the water. In order to heat-treat a semiconductor thin film having a low dielectric constant over a large area by microwave radiation, it is necessary to make a positive effort to make the microwave energy large in area and uniform.

Therefore, at present, there is a demand for early provision of a new microwave introduction process which solves various problems of the microwave radiating means described above.

In addition to the above-mentioned applications for solar cells, thin-film semiconductors are used in thin film transistors (TFTs) for driving the pixels of liquid crystal displays, photoelectric conversion elements and switching elements for contact image sensors. It is suitable for thin-film semiconductor devices that need to be large in area or long and has been partially put into practical use as a key component for image input / output devices. It is expected that the provision of such a new deposited film forming method will allow it to become more popular.

[0019]

DISCLOSURE OF THE INVENTION The present invention overcomes the problems in the conventional method and apparatus for forming a thin film semiconductor device as described above, and forms a functionally deposited film uniformly over a large area at high speed. It is an object of the present invention to provide a novel method and device capable of doing the above. That is, by providing a method and a device for uniformly generating a heating region by a microwave over a large area and a large volume, a crystalline photovoltaic element with high stability and high photoelectric conversion efficiency can be obtained. An object of the present invention is to provide a continuous method and apparatus for forming a functionally deposited film that can be formed.

[0020]

Means and Actions for Solving the Problems The inventors of the present invention solved the above-mentioned problems in the conventional thin film semiconductor device forming apparatus, and conducted intensive studies to achieve the object of the present invention. A gap is provided between the support / conveyance rollers through the support / conveyance rollers for forming the curve start end, the support / conveyance ring for forming the curved portion, and the support / conveyance rollers for forming the curve end end. The strip-shaped member is curved to leave a columnar processing space having the strip-shaped member as a side wall, and microwave energy is radiated to both end faces of the processing space in a direction parallel to the traveling direction of the microwave. A pair of microwave applicator means thus arranged are disposed so as to face each other, and microwave energy is radiated from the microwave applicator means substantially parallel to the side wall. To obtain a finding that may occur substantially uniform heating region in the width direction of the belt-shaped member in the processing space.

The present invention has been completed as a result of further studies based on the above findings, and a large-area functional deposition film is continuously formed by a microwave heating method whose main point is as described below. Includes methods and apparatus for forming.

According to the continuous forming method of claim 1, while continuously moving the strip-shaped member on which the deposited film is formed, a columnar processing space having a side wall of the moving strip-shaped member is formed at the same time, and at the same time, the micro-structure is formed. A microwave heating method in which the microwave energy is radiated from the microwave applicator means to heat a deposited film formed on the surface of the continuously moving strip-shaped member, The microwave is emitted from the applicator means in a direction parallel to the traveling direction of the microwave.

According to a second aspect of the present invention, there is provided a curved start end forming means and a curved end end forming means in the middle of the moving strip-shaped member, wherein the curved start end forming means and the curved end end forming means are used. And a gap is left in the longitudinal direction of the strip-shaped member so that the strip-shaped member is curved to form a side wall of the processing space.

According to a third aspect of the present invention, there is provided at least one or more microwave applicator means provided on one side or both sides of both end faces of a columnar processing space formed with the strip-shaped member as a side wall. The microwave energy is radiated into the processing space via the above.

In the method of forming a fourth aspect of the present invention, the microwave applicator means is arranged in a direction perpendicular to the end face so that the microwave energy is emitted in a direction parallel to the side wall.

The formation method of claim 5 is characterized in that the microwave energy is radiated through a microwave transparent member provided at a tip portion of the microwave applicator means.

The formation method of claim 6 is characterized in that the microwave permeable member keeps the microwave applicator means and the processing space airtight.

According to a seventh aspect of the present invention, in the case where the microwave applicator means are arranged to face each other on the both end faces, the microwave energy radiated from one microwave applicator means is the other microwave energy. It is characterized in that it is arranged so as not to be received by the applicator means.

The formation method of claim 8 is characterized in that the microwave energy radiated into the columnar processing space is prevented from leaking out of the processing space.

Also. The continuous forming apparatus according to claim 11 is an apparatus for continuously forming a functional deposition film on a continuously moving strip-shaped member by a microwave heating method, and continuously moving the strip-shaped member in its longitudinal direction. The processing chamber has a columnar processing chamber that is formed with the band-shaped member as a side wall through a bending portion forming means for bending in the middle thereof and that can substantially maintain the inside thereof in vacuum. A microwave applicator means for radiating microwave energy, an exhaust means for exhausting the processing chamber, and a means for introducing a processing gas into the processing chamber. And a deposited film is formed in advance on the surface of the continuously moving strip-shaped member that is exposed to the microwave energy. Characterized in that the traveling direction and parallel direction so as to emit from the applicator means.

According to a twelfth aspect, the bending portion forming means is composed of at least one set of bending start end forming means and bending end end forming means, and the bending start end forming means and the bending end end forming means. And are arranged with a gap left in the longitudinal direction of the strip-shaped member.

In the forming apparatus according to the thirteenth aspect, the curved portion forming means is formed of at least a pair of supporting / conveying rollers and a supporting / conveying ring, and the pair of supporting / conveying rollers of the belt-shaped member. It is characterized in that they are arranged in parallel with a gap left in the longitudinal direction.

In the apparatus of the present invention according to claim 14, at least one or more microwave applicator means is disposed on one side or both sides of both end surfaces of a columnar processing chamber formed by using the belt-shaped member as a side wall. It is characterized by

The forming apparatus according to a fifteenth aspect is characterized in that the microwave applicator means is disposed in a direction perpendicular to the end surface.

According to a sixteenth aspect of the present invention, in the tip portion of the microwave applicator means, the processing chamber and the microwave applicator means are hermetically separated from each other, and the microwave is emitted from the microwave applicator. A microwave permeable member for transmitting microwave energy into the processing chamber is provided.

The apparatus of the present invention according to claim 17 is characterized in that at least one surface of the belt-shaped member is subjected to a conductive treatment.

The device of the present invention according to claim 18 is characterized in that microwave energy is transmitted to the microwave applicator means through a rectangular and / or elliptical waveguide.

[0038] In the forming apparatus according to claim 19, when the microwave applicator means is arranged to face each other on both end faces of the processing chamber, the rectangular and / or rectangular shape connected to the microwave applicator means is used. The elliptical waveguide is characterized in that planes including long sides, planes including long axes, or planes including long sides and planes including long axes are arranged so as not to be parallel to each other.

The forming apparatus according to claim 20 is characterized in that the square and / or
Alternatively, it is arranged such that an angle formed by a surface including a long side of the elliptic waveguide and / or a surface including a long axis and a surface including a central axis of the pair of supporting and conveying rollers is not perpendicular. And

The experiment conducted by the inventor to complete the invention will be described below. In this experiment, microwave heating conditions for uniformly heat-treating the deposited film on the strip-shaped member were examined using the apparatus of the present invention shown in FIGS.

(Experimental Example 1) In the first experimental example, the microwave heating due to the difference in the mounting angle of the pair of waveguides 111 and 112 of the apparatus shown in FIG. 1 was examined.

FIG. 3 shows a schematic cross-sectional schematic diagram for explaining the mounting angles of the rectangular waveguides 111 and 112.

The rectangular waveguide 111 shown by the solid line and the rectangular waveguide shown by the dotted line are connected to a microwave applicator (not shown) arranged so as to face both end surfaces of the processing chamber 116. For example, the rectangular waveguide 111 is on the front side of the drawing,
The rectangular waveguide 112 is arranged on the back side. O is the center of the curved shape, and A-A 'is the supporting / conveying roller 10.
A plane including the central axes of 2 and 103 is shown, and a plane perpendicular to this is designated as H-H '. The angle formed by the planes BB ′ and HH ′ parallel to the plane including the long side of the rectangular waveguide 111 is θ ₁ and this is the mounting angle of the rectangular waveguide 111. Further, the angle formed by the planes CC ′ and HH ′ parallel to the plane including the long side of the rectangular waveguide 112 is θ _2, and this is the attachment angle of the rectangular waveguide 112. Here, when the mounting angles θ ₁ and θ ₂ of the rectangular waveguides 111 and 112 exceed 180 °, respectively, H when the angle is 180 ° or less
Since the arrangement is symmetric with respect to -H ', the arrangement relation is 18
This is equivalent to the case of 0 ° or less. Of course, even if the angles θ ₁ and θ ₂ are interchanged with each other, they are opposed to each other, so that the arrangement relationship is the same.

Further, the supporting / conveying rollers 102 and 1
The distance L between the curved ends of the strip-shaped member, which is defined by 03, is defined as the gap L.

Under the microwave heating conditions shown in Table 1, Table 2
Experiments and evaluations were carried out on the stability of microwave heating under the conditions in which θ ₁ and θ ₂ of various values shown in Table ₁ were combined.

[0046]

[Table 1] Note that the degree of microwave leakage is determined by the support / transport roller 10
A microwave detector was provided at a position about 5 cm away from the gap portion of 2,103 for evaluation.

The evaluation results are shown in Table 2.

[0048]

[Table 2] From these results, it was found that the in-plane temperature distribution of the band-shaped member due to microwave heating was changed significantly by changing the attachment angle of the rectangular waveguide to the microwave applicator. Specifically, θ ₁ and / or θ ₂ is 0
In the case of °, the amount of microwave leakage is the largest, and the in-plane temperature distribution of the band-shaped member due to microwave heating is also the largest, and the amount of microwave leakage is small at about 15 °, but the a-Si on the band-shaped member is small. The ultimate temperature of the (amorphous silicon) temperature is about 200 ° C to 400 ° C. Also, 3
At 0 ° or more, microwave leakage disappeared and the reached temperature was as high as 600 ° C and was stable. However, when the angle formed by θ ₁ and θ ₂ is 0 ° or 180 °, that is, when the planes including the long sides of the rectangular waveguide are arranged parallel to each other, the oscillation is generated regardless of the microwave leakage amount. Power supply noise due to an abnormality becomes large, and the in-plane temperature distribution of the belt-shaped member becomes maximum.

In this experiment, the belt-shaped member 101
Was carried out and the case was carried out at a carrying speed of 1.2 m / min, but no particular difference was observed in the in-plane temperature distribution of the belt-shaped member between them.

Further, when H _{2 of} 20 sccm was introduced from 113 and the pressure in the processing chamber was set to 4 mTorr and the same experiment was conducted, no particular difference was observed in the in-plane temperature distribution and the reached temperature of the belt-shaped member.

(Experimental Example 2) Next, in a second experimental example, a microwave plasma CVD having the same configuration as in Experimental Example 1 was performed.
An amorphous silicon thin film was deposited on a strip-shaped member manufactured by using the apparatus, and further, an annealing experiment was conducted in the microwave heating apparatus described in Experimental Example 1.

From the gas pipe 113a of the apparatus shown in FIG.
iH ₄ 100 sccm was introduced, and an amorphous silicon thin film was deposited on the strip-shaped member under the microwave plasma conditions shown in Table 3.

First, a vacuum container 301 having a substrate feeding mechanism was thoroughly degreased and washed to obtain SUS430BA.
Band-shaped substrate (width 45 cm x length 200 m x thickness 0.25
mm) wound bobbin 303 is set, and the substrate 101 is attached to the gas gate 401 and the isolation container 300a, 3a, 3a.
00 and -300b, and further through the gas gates 402, 403, and 404 to the vacuum container 302 having the substrate winding mechanism, the tension was adjusted to the extent that there was no slack.

Therefore, after the vacuum vessels 301 and 302 and the isolation vessels 300a, 300 and 300b are roughly evacuated by a rotary pump (not shown), and then a mechanical booster pump (not shown) is activated to evacuate to a pressure of around 10 ^-3 Torr. Further, by using the temperature control mechanism 106a, while maintaining the surface temperature of the belt-shaped member at 280 ° C., an oil diffusion pump (HS-32 manufactured by Varian, not shown) was used for 5 × 10 ⁻⁶ Torr.
It was evacuated to the following.

Manufacturing conditions Table 3 shows conditions such as the shape and the curved shape of the microwave applicator.

[0056]

[Table 3] When the gas is sufficiently degassed, the deposition film forming raw material gas is introduced from the gas introduction pipe 113a, and the opening of the throttle valve attached to the oil diffusion hoop is adjusted to adjust the pressure in the isolation container 300a. Was held at 8 mTorr. Due to the stable pressure, a pair of applicators 1 provided with a microwave power of 2.45 GH _Z specification (not shown) facing the microwave of 0.55 kW × 2 in effective power.
It was made to radiate into the film-forming chamber from 07a, 108a. right away,
The introduced source gas is turned into plasma to form a plasma region, and the plasma region is the supporting / transporting roller 102.
There was no leakage from the gap between a and 103a toward the isolation container. In addition, no microwave leakage was detected.

Therefore, the supporting / conveying rollers 102a,
103a and supporting / transporting rings 104a and 105a
(Neither drive mechanism is shown) is activated
The conveyance speed of No. 1 was controlled to be 1.2 m / min.

The gas gates 401, 402, 40
Gate gas introduction pipes 405, 406, 40 are provided at 3,404.
From 7,408, 500 sc of H ₂ gas as gate gas
cm flow, exhaust from the exhaust holes 409, 410, 411, 412 by an oil diffusion pump (not shown), the gas gate internal pressure is 1 m
It was controlled to be Torr.

Subsequently, in the conditions described in Experimental Example 1, the angles θ ₁ and θ ₂ formed by the applicators 107 and 108 were set to 30 ° and 30 °, respectively, and the other microwave emission conditions were the same as in Table 4. ..

[0060]

[Table 4] The band-shaped member obtained by the above treatment is wound on the winding bobbin 304, the throttle valves 309a, 309 and 309b are fully opened, and the vacuum container 302 is returned to the atmospheric pressure.
The winding bobbin 304 is taken out. Next, the sample is arbitrarily set in the width direction and the length direction of the winding bobbin 304.
When the crystallinity was evaluated by Raman scattering spectroscopy after cutting into mm square, it was found to be polycrystalline silicon having a sharp TO mode scattering peak at 520 cm ^-1 . The full width at half maximum of the peak was calculated to be 6.5 cm ^-1 ,
The variation in the width direction and the longitudinal direction of the belt-shaped member is 6.4 to
It was found to be in the range of 6.6 cm ⁻¹ , and there was little variation. Further, by observation with a transmission electron microscope, it was found that the obtained crystals had a large average particle size of about 2 μm and had a small variation, and were uniform in the width direction and the longitudinal direction of the belt-shaped member. From the results of Experimental Examples 1 and 2 described above, in the method and apparatus of the present invention, in order to reduce the leakage from the processing chamber at the time of introducing the microwave and to efficiently heat the strip-shaped member, the angles of the applicators to each other are increased. However, it was found that even if the processing chamber is in a vacuum state and the introduction of gas such as H ₂ does not affect the in-plane distribution of the strip-shaped member.

In addition, SUS is made by the microwave plasma method.
It was found that by preliminarily depositing an amorphous silicon thin film on a strip-shaped member made of aluminum and radiating microwaves, annealing with less variation in crystallinity in the width direction and the longitudinal direction of the strip-shaped member can be realized.

The method for continuously forming a deposited film according to the present invention will be described in more detail based on the facts found by the above experiment.

In the method of the present invention, in order to uniformly generate microwave heating in the columnar processing space 116, the film forming chamber of the film forming chamber is arranged in a direction parallel to the side wall formed by the strip-shaped member 101. Microwave energy is radiated from one side or both sides of both end surfaces to confine the microwave energy in the processing space.

When the width of the belt-shaped member is relatively narrow,
Even if the microwave energy is radiated from only one side, the uniformity of the microwave heating that occurs in the processing space 116 is maintained, but the width of the band-shaped member 101 exceeds, for example, one wavelength of the microwave. In this case, it is preferable to radiate microwave energy from both sides in order to keep the microwave heating region uniform.

Of course, the uniformity of microwave heating occurring in the processing space requires that microwave energy be sufficiently transmitted in the processing space, and the columnar processing space is similar to a so-called waveguide. It is preferably structured. For that purpose, first, the band-shaped member is preferably made of a conductive material, but at least one surface thereof may be subjected to a conductive treatment.

Further, in the method of the present invention, both ends of the columnar processing space 116 formed by bending the moving strip-shaped member 101 using the bending start end forming means 102 and the bending end end forming means 103. The surface is preferably formed so that the microwave energy radiated in the processing space is almost uniformly transmitted into the processing space, and is similar to a circular shape, an elliptical shape, a rectangular shape, or a polygonal shape. It is desirable that the curved shape be substantially symmetrical and relatively smooth. Of course, the bending start end forming means 102
In the gap portion left in the longitudinal direction of the strip-shaped member between the curved end forming means 103 and the curved end forming means 103, the end surface shape may be discontinuous.

Further, in the method of the present invention, in order to efficiently transmit microwave energy in the processing space and stably generate, maintain and control microwave heating, the microwave applicator is used. Means 20
The microwave transmission mode in 0 is preferably a single mode. Specific examples thereof include TE ₁₀ mode, TE ₁₁ mode, eH ₁ mode, TM ₁₁ mode and TM ₀₁ mode, but TE ₁₀ mode and TE ₁₁ mode are preferable.
Mode, eH ₁ mode is used. These transmission modes may be used alone or in combination.

The waveguide 208 capable of transmitting the above-mentioned transmission mode to the microwave applicator means 200.
Microwave energy is transmitted via. Further, the microwave energy is radiated into the processing space 116 through the airtight microwave permeable member 202 provided at the tip portion of the microwave applicator means.

In the method of the present invention, a gap is left in the processing space between the bending start end forming means and the bending end end forming means, and the processing gas is exhausted from the gap to perform the processing. The space between the spaces is maintained at a predetermined reduced pressure, but the dimension L of the gap provides sufficient exhaust conductance, and at the same time, the microwave energy radiated into the processing space is discharged to the outside of the processing space. Special consideration needs to be taken to prevent leakage.

Specifically, the direction of the electric field of the microwave traveling in the microwave applicator means, the support shaft as the bending start end forming means, the central axis of the carrying roller, and the support shaft as the bending end end forming means. The microwave applicator means is arranged so that the surface including the central axis of the transport roller is not parallel to each other. When the microwave energy is radiated into the processing space through the plurality of microwave applicator means, it is necessary to consider each microwave applicator means as described above.

Further, the maximum dimension L of the opening width in the longitudinal direction of the strip-shaped member in the gap left between the bending start end forming means and the bending end end forming means is preferably 1 / the wavelength of the microwave. It is desirable that the wavelength is 2 wavelengths or less, and more preferably 1/4 wavelength or less.

In the method of the present invention, when a plurality of the microwave applicator means are arranged to face each other, the microwave energy radiated from one microwave applicator means is transferred to the other microwave applicator means. Received by the microwave power source, and the received microwave energy reaches the microwave power source connected to the other microwave applicator means, causing damage to the microwave power source or abnormal microwave oscillation. It is necessary to give special consideration so as not to have an adverse effect such as. Specifically, the microwave applicator is arranged so that the electric field directions of the microwaves traveling in the microwave applicator means are not parallel to each other.

In the method of the present invention, when the microwave energy is radiated from only one side of the both end surfaces of the processing space, it is necessary to prevent the microwave energy from leaking from the other end surface. The end face is sealed with a conductive member, or the hole diameter is preferably 1/2 wavelength or less of the microwave wavelength used, and more preferably 1/4 wavelength.
It is desirable to cover it with a wire mesh of a wavelength or less, a punching board, or the like.

In the present invention, the deposited film previously formed on the belt-shaped member may be any of a semiconductor material, a metal material and an insulating material, and may be an inorganic material or an organic material. Further, it does not need to be composed of only a single component, and may be a mixture of these plural components. The structure is applicable to any of amorphous, microcrystal, polycrystal, and single crystal. From the viewpoint of manufacturing method, RF and DC plasma C
VD method, sputtering method and reactive sputtering method, optical CVD method, thermal CVD method, MOCVD method, MBE
Method, HR-VCD method, microwave CVD method, or other deposition film formation method by vapor phase reaction, or liquid phase growth method in which a solid substance is precipitated from a solution-like substance, further heat ray / electron ray, ion ray, radiation, laser beam Solid phase growth method such as the above, or a combination thereof. Further, it may be formed by a deposition method by electrolytic polymerization by an electrochemical reaction.

Further, prior to the microwave heat treatment, an additive may be introduced into the deposited film formed in advance in an appropriate ratio for the purpose of controlling crystal grains by the heat treatment, and the concentration distribution thereof may be added. It is also possible to control the particle size by appropriately adjusting

Further, the microwave heating method of the present invention is effective as a means for activating the impurity atoms for controlling the valence electrons of the semiconductor.

The processing gas in the present invention is intended to promote structuring of the deposited film and passivation of defects when microwave energy is radiatively heated to the deposited film previously formed in the strip portion. It is preferable that the gas is introduced into the deposited film and easily diffuses into the deposited film, and specific examples thereof include inert gases such as He, Ar, Xe, Kr, and Rn, and H ₂ , F _{2 and the like.} it can be suitably selected such as C1 _2, O _2.

Further, the processing gas in the present invention may be introduced into the processing space 16 by the gas introducing means 113 to absorb a part of the microwave energy and be decomposed and excited. The temperature may be increased, or the band-shaped member 101 forming the processing space may be heated by microwaves to absorb the thermal energy and be decomposed and excited, and the gas temperature may be increased.

In the present invention, it is possible to control the depth of annealing in the film thickness direction of the thin film deposited on the band-shaped member by changing the intensity of microwave energy.

The configuration and characteristics of the device of the present invention will be described in more detail below.

According to the apparatus of the present invention, the microwave heating region is confined by the moving band-shaped member, so that the microwave energy efficiently heats the band-shaped member on which the deposited film is formed. be able to.

Furthermore, since the uniform microwave heating region is generated in the processing space 116 by using the microwave applicator means of the present invention, the deposited film formed in the width direction of the strip-shaped member 101 is uniform. Of course, the deposition is formed in the longitudinal direction of the strip-shaped substrate by continuously conveying the strip-shaped member in a direction substantially perpendicular to the longitudinal direction of the microwave applicator means 107, 108. The processing apparatus has excellent film uniformity.

Further, according to the apparatus of the present invention, since the heat treatment can be continuously and stably maintained with good uniformity, a functional deposited film having stable characteristics can be continuously formed on the long strip-shaped member. Therefore, it is possible to manufacture a device having excellent interface characteristics of crystal grain boundaries.

In the apparatus of the present invention, when the strip-shaped member functions as a structural material, the outside of the processing chamber may be atmospheric air, but the functional deposition formed by the inflow of atmospheric air into the processing chamber. If the characteristics of the film are affected, an appropriate air inflow prevention means may be provided. Specifically, a mechanical sealing structure using an O-ring, a gasket, a helicopter, a magnetic fluid, or the like, or a diluting gas atmosphere that has little influence on the characteristics of the deposited film formed by treatment or is effective, Alternatively, it is desirable to dispose an isolation container for forming an appropriate vacuum atmosphere in the periphery. In the case of the mechanical sealing structure, special consideration needs to be given so that the band-shaped member can continuously move while maintaining the sealed state. When the apparatus of the present invention is connected to a plurality of other deposited film forming means to continuously stack the deposited films on the strip-shaped member, it is desirable to connect each apparatus by using a gas gate means or the like.

In the apparatus of the present invention, the pressure outside the processing chamber may be in a depressurized state or a pressurized state, but if the band-shaped member is largely deformed due to the pressure difference between the inside and the processing chamber, an appropriate assistance is provided. The structural material may be arranged in the processing chamber. As the auxiliary structural material, it is preferable that the auxiliary structural material has a shape substantially the same as that of the side wall of the processing chamber and is formed of a wire material, a thin plate, or the like, which is made of metal, ceramic, reinforced resin, or the like having appropriate strength.

The material of the belt-shaped member preferably used in the method and apparatus of the present invention is deformed at the temperature required for forming a functional deposited film by microwave heating,
It is preferable that it has a small amount of strain, has a desired strength, and has electrical conductivity, specifically, stainless steel, aluminum and its alloys, iron and its alloys,
Thin plates of metal such as copper and its alloys and their composites, and metal thin films and / or Si of different materials on their surfaces
An insulating thin film of O ₂ , Si ₃ N ₄ , Al ₂ O ₃ , AlN, etc., which has been subjected to surface coating treatment by a sputtering method, a vapor deposition method, a plating method or the like, or polyimide, polyamide, polyethylene terephthalate, epoxy, etc. A simple metal or alloy, and a transparent conductive oxide (TCO) on the surface of a heat-resistant resin sheet or a composite of these with a glass fiber, carbon fiber, boron fiber, metal fiber, etc.
And the like, which have been subjected to a conductive treatment by a method such as plating, vapor deposition, sputtering, and coating.

Further, the thickness of the belt-shaped member is possible in consideration of cost, storage space, etc. as long as it is within a range in which the curved shape formed during the transportation by the transportation means can be maintained. As thin as possible is desirable. Specifically, the thickness is preferably 0.01 mm to 5 mm, more preferably 0.02 mm to 2 mm, and most preferably 0.05 mm to 1 mm, but it is preferable to use a thin plate of a metal or the like. Even if the thickness is reduced, the desired strength can be easily obtained.

Regarding the width of the strip-shaped member,
When the microwave applicator means is used, it is preferable that the uniformity of the microwave heating region in the longitudinal direction is maintained and the curved shape is maintained, specifically, preferably 5 cm to 100 cm.
It is desirable that the thickness is cm, more preferably 10 cm to 80 cm.

Further, the length of the belt-shaped member is not particularly limited, and may be such a length that it can be wound into a roll, and a long member can be made longer by welding or the like. It may be one that has been made.

In the apparatus of the present invention, as a means for supporting and conveying the belt-shaped member while continuously curving the belt-shaped member, the curved shape of the belt-shaped member does not cause slack, wrinkles, lateral deviation, etc. during the conveyance. It is necessary to keep it constant. For example, at least one pair of supporting / transporting rings having a desired curved shape is provided, and preferably both ends of the strip-shaped member are supported by the supporting / transporting rings, and the strip-shaped member is curved along the shape, The supporting / conveying rollers as at least a pair of the bending start end forming means and the bending end end forming means provided in the longitudinal direction of the member narrows down and bends into a substantially columnar shape, and further the supporting / conveying ring and the supporting / conveying A driving force is applied to at least one of the application rollers to convey the belt-shaped member in its longitudinal direction while maintaining the curved shape.

As a method of supporting / conveying the belt-shaped member by the supporting / conveying ring, simple sliding friction may be used, or a sprocket hole or the like may be formed on the belt-shaped member, or the supporting / conveying ring may be used. As the transport ring, a so-called gear-shaped ring provided with a saw-tooth-shaped projection around the ring may be used.

Regarding the shape of the supporting / transporting ring, it is desirable that it is circular when forming a curved shape, but even if it is elliptical, rectangular, or polygonal, it is continuously constant. There is no particular problem as long as it has a mechanism for maintaining its shape. Maintaining a constant transport speed is an important point in transporting without causing slack, wrinkles, lateral deviation, etc. in the curved shape. Therefore, it is desirable that the support / conveyance mechanism be provided with a mechanism for detecting the conveyance speed of the belt-shaped member and a conveyance speed adjusting mechanism that is fed back by the mechanism. Further, these mechanisms also bring about a great effect on the film thickness control in manufacturing a semiconductor device.

[0093]

EXAMPLES Specific examples of the present invention will be shown below, but the present invention is not limited to these examples.

Example 1 Using the continuous microwave heating device shown in Experimental Examples 1 and 2, a photovoltaic element made of crystalline silicon was produced. FIG. 5 shows a schematic diagram of the configuration of the photovoltaic element.
It shows in (A). The photovoltaic device comprises an n-type semiconductor layer 502, a P-type semiconductor layer 503, and a transparent electrode 504 on a substrate 501.
And a collector electrode 505 in this order to form a photovoltaic element 500. In this photovoltaic element, the transparent electrode 5
It is premised that light is incident from 04.

First, a vacuum container 301 having a substrate delivery mechanism was thoroughly degreased and washed to obtain SUS430BA.
Band-shaped substrate (width 45 cm x length 200 m x thickness 0.25
mm) wound bobbin 303 is set, and the substrate 101 is attached to the gas gate 401 and the isolation containers 303a, 3a, 3a.
00 and 300b, and further through the gas gates 402, 403 and 404 to the vacuum container 302 having the substrate winding mechanism, tension adjustment was performed to the extent that there was no slack.

Therefore, after the vacuum vessels 301 and 302 and the isolation vessels 300a, 300 and 300b are roughly evacuated by a rotary pump (not shown) and then a mechanical booster pump (not shown) is activated to evacuate to a pressure of around 10 ^-3 Torr. While using the temperature control mechanisms 106a and 106b to maintain the surface temperature of the belt-shaped member at 280 ° C., an oil diffusion pump (HS-32 manufactured by Varian, not shown) was used for 5 × 1.
A vacuum was drawn to 0 ^-6 Torr or less.

[0097] Incidentally, the manufacturing conditions, the shape of the microwave applicator, and conditions of the curved shape or the like, except that a mixed gas of SiH ₄ / PH ₃ in place of the SiH ₄ were the same as in Table 3.

When the degassing is sufficiently performed, the raw material gas SiH ₄ 100 for forming a deposited film is introduced through the gas introduction pipe 113a.
introducing sccm (PH ₃ / 100ppm), and the pressure in the oil diffusion pump and adjust the opening degree of the throttle valve attached to and isolation container 300a held in 8 mTorr. When the pressure is stable, 2.45GH not shown
0.85k in execution power from the z-specification microwave power supply
A microwave of W × 2 was radiated into the film forming chamber from a pair of applicators 107a and 108a provided facing each other.
Immediately, the introduced source gas was turned into plasma to form a plasma region, and the plasma region did not leak to the isolation container side through the gap between the supporting / transporting rollers 102a and 103a. In addition, no microwave leakage was detected.

The gas gates 401, 402, 40
Gate gas introduction pipes 405, 406, 40 are provided at 3,404.
From 7,408, 500 sc of H ₂ gas as gate gas
cm flow, exhaust from the exhaust holes 409, 410, 411, 412 by an oil diffusion pump (not shown), the gas gate internal pressure is 1 m
It was controlled to be Torr.

Subsequently, under the conditions described in Experiments 1 and 2, the angles θ ₁ and θ ₂ formed by the applicators 107 and 108 in the isolation chamber 300 are set to 30 ° and 30 °, respectively, and other microwave heating conditions are shown in Table 4. I did the same.

From the gas introducing pipe 113b arranged in the isolation container 300b, the deposited film forming source gas SiH ₄ 1sc
cm (BF ₃ 200 ppm) was introduced and the opening of a throttle valve 309b attached to an oil diffusion pump (not shown) was adjusted to maintain the pressure of the isolation container 300b at 8 mTorr. 2.45G not shown due to stable pressure
Than H _Z specification microwave power source, 0.55K run power
A microwave of W × 2 was radiated into the film forming chamber from a pair of applicators 107b and 108b provided facing each other.
Immediately, the introduced source gas was turned into plasma to form a plasma region, and the plasma region did not leak to the isolation container side through the gap between the supporting / transporting rollers 102b and 103b. In addition, no microwave leakage was detected.

Then, 102b and 103b and supporting / transporting rings 104b and 105b (neither drive mechanism is shown) are activated, and the substrate 101 is transported at a speed of 1.2.
The n and p type semiconductor layers were continuously stacked by being conveyed from the left side to the right side in the drawing at m / min. The conditions such as the shape and the curved shape of the microwave applicator of the isolation container 300b for manufacturing the P layer are the same as those in Table 3.

After the semiconductor layers were laminated and formed over the entire length of the belt-shaped member 101, they were cooled and taken out, and further, a solar cell module of 35 cm × 70 cm was continuously produced by a continuous modularizing device.

Regarding the manufactured solar cell module, A
When the characteristics were evaluated under M1.5 (100 mW / cm ² ) light irradiation, a photoelectric conversion efficiency of 7.2% or more was obtained,
Furthermore, the variation in characteristics between modules was within 5%.

AM1.5 (100 mW / cm ² )
When the rate of change of the photoelectric conversion efficiency with respect to the initial value after continuous irradiation with light for 500 hours was measured, it was within 1%.

It was possible to fabricate a 5 kW power supply system by connecting these modules.

(Example 2) In this example, a crystalline silicon germanium photo-activated power element was produced for the purpose of improving long-wavelength sensitivity with respect to the crystalline silicon photovoltaic element produced in Example 1. From the gas introduction pipe 113a, a deposition film forming source gas SiH ₄ 80 sccm, GeH ₄ 20 sccm
m, PH ₃ 100 ppm was introduced. Further, the microwave power to the processing chamber is changed from 1 kW × 2 of Example 1 to 0.9 k
Reduced to W x 2. Other manufacturing conditions were the same as in Example 1 to form each semiconductor layer.

After the semiconductor layers were laminated and formed over the entire length of the belt-shaped member 101, they were cooled and taken out, and further, a solar cell module having a size of 35 cm × 70 cm was continuously produced by a continuous modularizing device.

Regarding the manufactured solar cell module, A
When the characteristics were evaluated under irradiation with M1.5 (100 mW / cm ² ) light, the photoelectric conversion efficiency was 7.0% or more, and the variation in characteristics between modules was within 5%.

AM1.5 (100 mW / cm ² )
When the rate of change of the photoelectric conversion efficiency with respect to the initial value after continuous irradiation with light for 500 hours was measured, it was within 1%.

A power supply system of 5 kW could be produced by connecting these modules.

(Example 3) In order to obtain higher photoelectric conversion efficiency and stability of the crystalline silicon photovoltaic element manufactured in Example 1, a ZnO film formed on a belt-shaped substrate was used.

First, the same SUS430BA band-shaped substrate as used in Examples 1 and 2 was set in a continuous sputtering apparatus, and an Ag (99.99%) electrode was used as a target to form an Ag thin film of 1000 liters. ZnO continuously
(99.999%) Using the electrode as a target
A 2 μm ZnO thin film is sputter-deposited to form a lower electrode 50.
1'is formed. (See FIG. 5B) Subsequently, the strip-shaped substrate on which the lower electrode 501 'was formed was set in the continuous deposited film forming apparatus shown in FIG. 4 in the same manner as in Example 1.

A deposition film forming source gas SiH ₄ 100 sccm PH ₃ 100 ppm was introduced through the gas introduction pipe 113a. Other semiconductor layers were formed under the same manufacturing conditions as in Example 1.

Regarding the manufactured solar cell module, A
When the characteristics were evaluated under M1.5 (100 mW / cm ² ) light irradiation, a photoelectric conversion efficiency of 7.8% or more was obtained, and the variation in characteristics between modules was within 5%.

AM1.5 (100 mW / cm ² )
The rate of change of the photoelectric conversion efficiency with respect to the initial value after continuous irradiation with light for 500 hours was measured and found to be within 0.9%.

A power supply system of 5 kW could be produced by connecting these modules.

(Embodiment 4) In this embodiment, an n-type amorphous silicon layer is successively deposited by a plasma CVD method using RE, and then P-type amorphous SiC is deposited by the same method.
By suppressing the microwave power to a low level by the microwave heating method of the present invention, only the SiC layer on the surface was microcrystallized, and a photovoltaic element having a large area was formed by continuous film formation.

FIG. 6 is a schematic sectional view of a manufacturing apparatus used in this example. The isolation containers 601 and 602 are RF plasma CVD furnaces. The other transport system and the microwave heating device have the same configuration as in FIG. Isolation container 601
In the isolation container 602, the p ⁺ amorphous SiC layer is 200 Å (conveyance speed 15 cm / mi).
n) Deposit.

First, a vacuum container 301 having a substrate feeding mechanism was thoroughly degreased and washed to obtain SUS430BA.
Belt-shaped substrate (width 45 cm x length 200 m, thickness 0.25 m
m) wound bobbin 303 is set and the substrate 101 is attached to the gas gate 401 and the isolation containers 601 and 60.
The tension was adjusted to such an extent that there was no slack in the vacuum container 302 having a substrate winding mechanism through the transport mechanisms in Nos. 2 and 300 and further through the gas gates 402, 403, and 404.

Therefore, after the vacuum vessels 301 and 302 and the isolation vessels 601, 602 and 300 are roughly evacuated by a rotary pump (not shown), and then a mechanical booster pump (not shown) is activated to evacuate to a pressure of about 10 ^-3 Torr. Further, by using halogen lamps 607 and 608, the surface temperature of the belt-shaped member was maintained at 280 ° C., and an oil diffusion pump (HS-32 manufactured by Varian, not shown) was used for 5 × 10 ⁻⁴ To
A vacuum was drawn to rr or less.

From the gas introduction pipes 605 and 606, SiH ₄
50 sccm, H ₂ 350 sccm and CH _{4 1} scc
m, SiH _{4 2} sccm, and B ₂ H ₆ 300 ppm were introduced. The pressure in the film forming chamber was adjusted to 0.95 Torr by adjusting an exhaust throttle valve (not shown). The RF power was 100 W and 3 W, respectively.

The isolation container 300, which is a processing chamber for microwave heating, has the angles θ ₁ and θ ₂ formed by the applicators 107 and 108 mainly under the conditions described in Experiment 1 and Experiment _2.
To 30 ° and 30 ° respectively, and set the microwave power to 200
W.

The gas gates 401, 402, 40
Gate gas introduction pipes 405, 406, 40 are provided at 3,404.
From 7,408, 500 sc of H ₂ gas as gate gas
cm flow exhaust holes 409, 410, 411, 412 are exhausted by an oil diffusion pump (not shown), and the gas gate internal pressure is 1 mT.
It was controlled to be orr.

First, RF plasma is generated in each film forming chamber, and when the discharge or the like is stabilized, the belt-shaped member 101 is conveyed at a conveying speed of 15 cm / min from the left side to the right side in the drawing, and n ⁻ , A p ⁺ type semiconductor layer was deposited and formed.

[0126] After laminating a semiconductor layer over the entire length of the belt-shaped member 101, taken out after cooling, reflection high observation of the electron beam diffraction image, p ⁺ SiC layer in a mixed pattern of halo and ring Micro I found that it was crystallized. Obviously, in the observation of the same structure without the microwave heat treatment, that is, the observation of the laminated film of n ⁻ amorphous silicon p ⁺ amorphous SiC, a halo pattern and a clear difference was observed.

Further, HF, HNO ₃ , CH ₃ COOH, H
Wet etching was performed with a mixed solution of ₂ O, the surface of the microcrystal p ⁺ SiC was etched, and the reflection high-energy electron diffraction image was observed each time. The microcrystal p ⁺ SiC layer 200 Å had a mixture of halo and ring. It was confirmed that the amorphous silicon n ⁻ layer below the pattern had a halo pattern.

In the present invention, it is also possible to control the distribution of the microcrystallized film in the film thickness direction by appropriately selecting the microwave power.

Amorphous Sin ⁻ layer / microcrystal SiCp ⁺ on the belt-like member 101 thus obtained
After the layers were formed by stacking semiconductor layers over the entire length of the belt-shaped member 101, the layers were cooled and taken out, and further, a solar cell module of 35 cm × 70 cm was continuously manufactured by a continuous modularizing device.

Regarding the manufactured solar cell module, A
When the characteristics were evaluated under irradiation with M1.5 (100 mW / cm ² ) light, the photoelectric conversion efficiency was 7.2% or more, and the variation in characteristics between modules was within 5%.

AM1.5 (100 mW / cm ² )
The rate of change of the photoelectric conversion efficiency with respect to the initial value after continuous irradiation with light for 500 hours was measured and found to be within 9.5%.

It was possible to fabricate a 5 kW power supply system by connecting these modules.

[0133]

EFFECTS OF THE INVENTION By devising a large area and uniform microwave heating means according to the present invention, the annealing time of a thin film semiconductor is greatly shortened. Specifically, the amorphous silicon was annealed for about 10 hours to be crystallized to produce a crystalline silicon solar cell. However, according to the present invention, microwave irradiation for about 1 minute produces a similar annealing effect. Is obtained.

Furthermore, the area capable of being heat-treated at one time can be dramatically expanded as compared with the laser annealing conventionally devised by a large area and uniform heating means.
It enables mass production of low-cost large-area photovoltaic elements.

Further, according to the present invention, the depth of annealing in the film thickness direction can be controlled by appropriately adjusting the microwave power.

From the above, it is possible to provide a method and apparatus for continuously forming a functional deposited film capable of continuously forming a crystalline photovoltaic element having high efficiency and high photoelectric conversion efficiency with good stability. Become.

[Brief description of drawings]

FIG. 1 is a perspective view of a microwave heating device of the present invention.

FIG. 2 is a schematic diagram of a microwave applicator means of the present invention.

FIG. 3 is a schematic cross-sectional view for explaining an attachment angle of the waveguide of the present invention.

FIG. 4 is an overall schematic diagram showing one example of a continuous functional deposition film forming apparatus of the present invention.

5A and 5B are schematic cross-sectional views of a photovoltaic device manufactured in the present invention.

FIG. 6 is another one of the continuous deposition apparatus for functionally deposited film of the present invention.
It is the whole schematic diagram showing an example.

[Explanation of symbols]

101 band-shaped members 102, 103 transport rollers 104, 104a, 104b, 105, 105a, 10
5b Transport ring 106, 106a, 106b Temperature control mechanism 107, 107a, 107b, 108, 108a, 10
8b Microwave applicator 109,110 Microwave permeable member 111,112 Rectangular waveguide 113,113a, 113b Gas introduction pipe 114 Exhaust pipe 115 Isolation passage 116 Processing chamber 200 Microwave applicator 201,202 Microwave permeable member 203a, 203b Microwave matching disc 204 Inner cylinder 205 Outer cylinder 206 Fixing ring 207 Choke flange 208 Rectangular waveguide 209 Cooling medium 210 O-ring 211 Groove 211 Metal seal 213,214 Cooling air inlet / outlet hole 300, 300a, 300b Isolation container 301, 302, 501, 502 Vacuum container 303 Sending bobbin 304 Winding bobbin 305, 306 Conveying roller 307, 308, 309, 309a, 309b Throttle valve 31 0,311,409,410,411,412 Exhaust hole 312,313 Temperature control mechanism 314,315 Pressure gauge 320,320a, 320b Exhaust pipe 405,406,407,408 Gate gas inlet pipe 401,402,403,404 Gas gate 409 , 410, 411, 412 Gate gas exhaust pipe 500 Photovoltaic device 501 Support 501 'Lower electrode 502 n-type semiconductor layer 503 P-type semiconductor layer 504 Transparent conductive film 505 Upper electrode 601,602 Isolation container 603,604 Cathode electrode 605 606 Gas introduction pipe 607,608 Halogen lamp 609,610 Anode electrode 611,612 Exhaust pipe.

 ─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Goto Yoshino 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc. (72) Inventor Shotaro Okabe 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon (72) Inventor Naoshi Yoshiri 3-30-2 Shimomaruko, Ota-ku, Tokyo Canon Inc.

Claims (20)

[Claims] 1. A columnar processing space having a side wall of the belt-shaped member is formed while the belt-shaped member on which the deposited film is formed is continuously moved, and a microwave is applied to the processing space by a microwave applicator means. A method for continuously forming a functional deposited film, comprising a microwave heating step of performing a heating process on a sidewall of the processing space where the deposited film is formed by radiating energy, wherein the microwave energy is applied in a traveling direction of the microwave. A method for continuously forming a functionally deposited film, characterized in that the microwave energy is radiated in parallel to the processing space by radiating the microwave energy to the processing space. 2. In the middle of the moving belt-shaped member,
Using the bending start end forming means and the bending end end forming means,
The function according to claim 1, wherein the band-shaped member is curved by leaving a gap in the longitudinal direction of the band-shaped member between the curving start end forming means and the curving end forming means to form a side wall of the processing space. Method for continuous formation of porous deposited film. 3. The microwave through at least one or more microwave applicator means provided on one side or both sides of both end surfaces of a columnar processing space formed with the strip-shaped member as a side wall. The method for continuously forming a functional deposited film according to claim 1, wherein energy is radiated into the processing space. 4. The method for continuously forming a functional deposited film according to claim 3, wherein the microwave applicator means is arranged in a direction perpendicular to the end surface, and the microwave energy is emitted in a direction parallel to the side wall. 5. The microwave energy is radiated through a microwave transparent member provided at a tip portion of the microwave applicator means.
5. A method for continuously forming a functional deposited film according to any one of items 1 to 4. 6. The microwave applicator means,
The method for continuously forming a functional deposited film according to claim 5, wherein airtightness with the processing space is maintained by the microwave transparent member. 7. The microwave applicator means,
7. The microwave energy emitted from one microwave applicator means is arranged so as not to be received by the other microwave applicator means when the both end surfaces are arranged to face each other. 2. The method for continuously forming a functional deposited film according to item 1. 8. The continuous formation of the functional deposition film according to claim 1, wherein microwave energy radiated in the columnar processing space is prevented from leaking to the outside of the processing space. Method. 9. A processing gas is introduced into the processing space, and the processing gas is introduced from a gap left in the longitudinal direction of the strip-shaped member between the bending start end forming means and the bending end end forming means. 9. Evacuation is performed according to any one of claims 1 to 8.
The method for continuously forming a functionally deposited film according to item. 10. The method for continuously forming a functional deposited film according to claim 1, wherein at least one surface of the belt-shaped member is subjected to a conductive treatment. 11. A continuous deposition film forming apparatus, characterized in that a microwave is radiated onto a strip-shaped member that continuously moves in the longitudinal direction, wherein the strip-shaped member is continuously moved in the longitudinal direction. Means and a curved portion forming means for forming a columnar processing chamber capable of bending the belt-shaped member and using the belt-shaped member as a side wall to substantially maintain the inside in a vacuum; A microwave applicator for radiating microwave energy in a direction to generate a microwave heating region in the processing chamber, an exhaust means for exhausting the processing chamber, and a processing gas for introducing the processing gas into the processing chamber. And a gas introducing means for the continuous deposition of a functionally deposited film. 12. The bending portion forming means includes at least one set of bending start end forming means and bending end end forming means, and the bending start end forming means and the bending end end forming means are provided. The continuous deposition apparatus for functionally deposited film according to claim 11, wherein a gap is left in the longitudinal direction of the strip-shaped member. 13. The curved portion forming means includes at least a pair of supporting / conveying rollers and a supporting / conveying ring, and the pair of supporting / conveying rollers leave a gap in the longitudinal direction of the belt-shaped member. 13. The apparatus for continuously forming a functional deposited film according to claim 11, wherein the apparatus is continuously disposed in parallel with each other. 14. The at least one microwave applicator means is disposed on one or both sides of both end surfaces of a columnar processing chamber formed with the strip-shaped member as a side wall. The continuous deposition device for functionally deposited film as described in item 1. 15. The microwave applicator means is disposed vertically to the end surface of the processing chamber.
4. The continuous deposition apparatus for functionally deposited film as described in 4. 16. A microwave energy radiated from the microwave applicator is introduced into the processing chamber at an end portion of the microwave applicator means for airtightly separating the processing chamber and the microwave applicator means. 16. The apparatus for continuously forming a functional deposited film according to claim 11, further comprising a microwave permeable member for transmitting the microwave. 17. The conductive treatment is applied to at least one surface of the belt-shaped member.
The continuous deposition apparatus for functionally deposited film as described in the item. 18. The continuous formation of a functional deposited film as claimed in claim 11, wherein microwave energy is transmitted to the microwave applicator means via a rectangular and / or elliptical waveguide. apparatus. 19. The long side of the rectangular and / or elliptical waveguide connected to the microwave applicator means when the microwave applicator means are arranged to face each other on both end surfaces of the processing chamber. 19. The surfaces including the surfaces, the surfaces including the long axis, or the surfaces including the long side and the surfaces including the long axis are arranged so as not to be parallel to each other.
An apparatus for continuously forming a functional deposited film as described in [1]. 20. An angle between a surface including a long side and / or a surface including a long axis of the rectangular and / or elliptical waveguide and a surface including a central axis of the pair of supporting and conveying rollers is perpendicular. 20. The apparatus for continuously forming a functionally deposited film according to claim 18, wherein the continuous deposition apparatus is arranged so as not to become.