Patent Application
20120152339
A. Field of the Invention
This invention relates to a method for manufacturing a thin film silicon solar cell with a substrate structure, and to a thin film solar cell formed by this manufacturing method.
B. Description of the Related Art
Thin film solar cells, which are a representative example of a solar cell (photoelectric conversion device) in which a plurality of photoelectric conversion elements formed on the same substrate are connected in series, are regarded as the future mainstream of solar cells due to their thin shape, light weight, low manufacturing costs, and ease of manufacture in large sheets. In addition to supplying electric power, demand is increasing for both commercial and general household applications, in which solar cells are mounted on building roofs, windows and similar for use.
Thin film solar cells, particularly thin film silicon-system solar cells which employ as the main material amorphous silicon (a-Si), amorphous silicon-germanium (a-SiGe) or microcrystalline silicon, are already in the stage of mass production, and at the same time active development is underway aiming at further cost reductions.
Glass, plastic film, stainless steel foil, or similar is used as the material of the substrate of a thin film silicon solar cell. Among these there are the advantages to using glass or a plastic film, which are insulators, because an integrated series-connected structure can be fabricated on the substrate and arbitrary high voltages can be realized.
A transparent electrode 102, photoelectric conversion layer 103, and metal electrode 104 are formed in this order on a glass substrate 101. After formation of each of the layers, laser light 100 is used in laser patterning for division into rectangular strips, and series connection is completed. Here, the laser most widely used in laser patterning is a YAG (yttrium aluminum garnet) laser; the fundamental wave at 1,064 nm is used for fabrication of the transparent electrode 102, and the second harmonic at 532 nm is used for separation of the photoelectric conversion layer 103 and metal electrode 104.
Separation of the transparent electrode 102 and photoelectric conversion layer 103 may be performed from either the side of the glass substrate 101 or the side of the transparent electrode 102, but fabrication of the metal electrode 104, which is the final process, is performed from the side of the glass substrate 101. Upon irradiation with laser light 100 from the side of the glass substrate 101, light absorption occurs in the photoelectric conversion layer 103 comparatively close to the incidence side, and by blowing away the upper layer portion, removal processing is possible.
Further, the fabrication method of simultaneously blowing away the photoelectric conversion layer and metal electrode is difficult for thick film cells of several microns in size, such as tandem cells with microcrystalline silicon. As a means of addressing this, Japanese Patent Application Laid-open No. 2001-267618 indicates that light in a wavelength band to which microcrystalline silicon is sensitive is used in irradiation from the glass side, and the microcrystalline layer is removed to some degree in advance, after which the second harmonic of the YAG laser is used to remove a-Si. Here, the wavelength of the laser used to remove microcrystalline silicon is 670 to 900 nm; as the laser, a ruby laser, alexandrite laser, GaAlAs laser, or similar may be used.
On the other hand, with respect to realizing flexibility and lightness of weight in order to enhance freedom of installation on roofs and outer walls, plastic film is preferable to glass substrate, and among these, aramid, polyimide and similar sheets with excellent heat resistance are preferable. However, because these materials are opaque, a so-called substrate structure, in which a metal electrode, photoelectric conversion layer, and transparent electrode are stacked in this order on a substrate, is employed. Y. Ichikawa, et al., Conference Record 1994 IEEE 1st World Conference on Photovoltaic Energy Conversion (1994), 441, discloses an example of a thin solar cell employing a substrate-type series-connected structure.
Here, in order to series-connect the metal electrodes 302 and back-face electrodes 305 which have been completely separated and formed on the two faces of the film substrate 301, collector holes 306 and series connection holes 307 are formed (see
For reference, paragraph [0116] of Japanese Patent Application Laid-open No. 2009-177225 states, using the symbols of this reference, that “the back-face electrode division line 29 can for example be formed by using the second harmonic of a YAG laser to scribe the back-face electrode 11 and the first to third photoelectric conversion layers 5, 7, 9”.
Further, paragraph [0038] of Japanese Patent Application Laid-open No. 2009-44184 states, using the symbols of this reference, that “a transparent electrode layer 112 of SnO2, having a micro-relief structure on a planar face, was formed by a thermal CVD method. Next, a YAGIR pulse laser was used in laser scanning parallel to the short edge of the substrate, to form grooves 117 of width 40 μm which divided the SnO2 film 112 into a plurality of strip-shape patterns”.
However, laser fabrication of a substrate type integrated type solar cell, in which n, i and p layers are deposited in this order on a metal reflective substrate, has been extremely difficult compared with superstrate type solar cells such as that shown in
First, the principles of fabrication of superstrate type solar cells are explained, and then the difficulty when employing a substrate type structure is explained.
Ordinarily, when an a-Si system film 103 is laser-processed, a molten crystallized region 103a occurs at the processing end face. This is thought to be true of superstrate type solar cells as well, but because the light absorption profile indicates exponential attenuation, as shown in
On the other hand, when processing from the transparent electrode side in a substrate type solar cell, the light absorption amount is smaller for the lower layer than for the upper layer, so that blow-away processing cannot be performed. That is, the entirety is caused to absorb light and be removed, so that the entire end face is crystallized, and insulating properties cannot be maintained.
In the case of an SCAF structure solar cell, if the three layers of the cell face are batch separation-processed, crystallization of the entire end face occurs, and simultaneously melting and alloying of the metal electrode also occurs, so that it is difficult to secure insulation at the end face. As a measure to address this problem, a method has been proposed in which, after performing broad-width laser processing of the metal electrode and depositing the photoelectric conversion layer and transparent electrode, narrow-width laser processing is performed; but there are the problems that:
(1) one additional process is required, and
(2) positioning is necessary in the second laser processing.
Particularly in the case of a solar cell using a plastic film substrate, thermal deformation of the film substrate occurs during the heating process, so that the above positioning in (2) is difficult.
The present invention is directed to overcoming or at least reducing the effects of one or more of the problems set forth above.
This invention was devised in consideration of such a situation, and provides a thin film solar cell in which, by laser irradiation from the transparent electrode side, light is caused to be selectively absorbed by the lower layer of the photoelectric conversion layer, so that fabrication can be performed by blowing-away, as well as a method for manufacturing such a device.
Multijunction cells, which combine a-Si cells and a-SiGe cells or microcrystalline cells with the object of raising the efficiency of the thin film solar cell, have been proposed in the prior art. Thin film silicon solar cells with this type of substrate structure are configured such that, compared with the photoelectric conversion layer of the top cell, the band gap of the i layer of the bottom cell is smaller. This invention resolves such problems, and proposes a method and product to utilize the difference in band gaps in the above-described technology of the prior art, and cause light absorption in the bottom cell which is the lower layer.
That is, one aspect of this invention is a method of manufacturing a thin film solar cell, which is a substrate type solar cell that has a photoelectric conversion layer combining, in a thickness direction, two or more n, i, p junctions with non-single crystal silicon as main materials thereof, and that includes a metal electrode, the photoelectric conversion layer, and a transparent electrode stacked in this order on a substrate, wherein a top cell which is the photoelectric conversion layer on the transparent electrode side and a cell of one or more layers on the metal electrode side relative to the top cell, are provided, and the method includes a process of simultaneously removing at least the two or more photoelectric conversion layers and the transparent electrode, using a laser with a wavelength having selective sensitivity with respect to the cell other than the top cell, from the transparent electrode side.
Specifically, the thin film solar cell is formed of a tandem stacked member having a top cell which is the photoelectric conversion layer on the transparent electrode side and a bottom cell on the metal electrode side, and the method includes a process of simultaneously removing the two photoelectric conversion layers and the transparent electrode, using a laser with a wavelength having selective sensitivity with respect to the bottom cell, from the transparent electrode side.
A band gap of an i layer of the bottom cell in the photoelectric conversion layer is smaller than that of an i layer of the top cell. Further, the top cell i layer is made of amorphous silicon, and the i layer of the bottom cell of the photoelectric conversion layer is made of any one of amorphous silicon-germanium, microcrystalline silicon, and microcrystalline silicon-germanium.
Further, the thin film solar cell is formed of a triple stacked member having a top cell which is the photoelectric conversion layer on the transparent electrode side, a bottom cell on the metal electrode side, and an intermediate middle cell, and the method includes a process of simultaneously removing the three photoelectric conversion layers and the transparent electrode, using a laser with a wavelength having selective sensitivity with respect to at least one of the middle cell and the bottom cell, from the transparent electrode side.
The wavelength of the laser is in the range 600 to 900 nm, and preferably in the range 630 to 810 nm.
The laser used is one of an alexandrite laser, ruby laser, titanium sapphire laser, helium neon laser, krypton ion laser, and a semiconductor laser formed of AlGaAs.
On the other hand, a thin film solar cell of this invention, manufactured by this manufacturing method, is a substrate type solar cell that has a photoelectric conversion layer combining, in a thickness direction, two or more n, i, p junctions with non-single crystal silicon as main materials thereof, and that includes a metal electrode, the photoelectric conversion layer, and a transparent electrode stacked in this order on a substrate, wherein a top cell which is the photoelectric conversion layer on the transparent electrode side, and a cell of one or more layers on the metal electrode side relative to the top cell, are provided, and the thin film solar cell is configured such that the two or more photoelectric conversion layers including the top cell and the transparent electrode are simultaneously removed, using a laser generation device which generates laser light at a wavelength having selective sensitivity with respect to the cell other than the top cell, from the transparent electrode side.
Specifically, a configuration is provided in which, in the case of a tandem stacked member having a top cell which is the photoelectric conversion layer on the transparent electrode side and a bottom cell on the metal electrode side, by means of a laser device which generates laser light at a wavelength having selective sensitivity with respect to the bottom cell, when irradiation with laser light is performed from the transparent electrode side, the bottom cell is caused to absorb laser light, and fabrication by laser ablation is performed, the top cell of the upper layer is also blown away and removed, so that the two photoelectric conversion layers of the top cell and the bottom cell as well as the transparent electrode can be simultaneously removed.
A band gap of an i layer of the bottom cell in the photoelectric conversion layer is smaller than that of an i layer of the top cell.
The i layer of the top cell is made of amorphous silicon, and the i layer of the bottom cell of the photoelectric conversion layer is made of any one of amorphous silicon-germanium, microcrystalline silicon, and microcrystalline silicon-germanium.
In addition, a configuration is provided in which, in the case of a triple stacked member having a top cell which is the photoelectric conversion layer on the transparent electrode side, a bottom cell on the metal electrode side, and an intermediate middle cell, by means of a laser device which generates laser light at a wavelength having selective sensitivity with respect to at least one of the middle cell and the bottom cell, by performing irradiation with laser light from the transparent electrode side, the middle cell or bottom cell is caused to absorb laser light, and fabrication by laser ablation is performed, and other cells are also blown away and removed, so that the three photoelectric conversion layers of the top cell, the middle cell and the bottom cell, and also the transparent electrode, can be simultaneously removed.
The laser generation device is configured so as to generate laser light in the laser wavelength range of 600 to 900 nm.
As a two-step separation method, a first step in which the laser power is adjusted and the two layers of the photoelectric conversion layer and the transparent electrode are removed as described above, followed by a second step in which processing is performed to remove the metal electrode, is substantially easier to execute, and requires less processing time, than two-process methods as in the prior art in which the metal electrode is subjected to broad-width laser processing, and after depositing the photoelectric layers and transparent electrode, narrow-width laser processing is performed.
In a two-step separation method of the prior art, there was a heat process for film deposition between the first laser processing and the second laser processing; but in a two-step separation method of this invention, there is no heat process for film deposition between the first step and the second step, and so there is the advantage that there is no thermal deformation of the film substrate. Further, it was necessary to execute non-parallel or nonlinear complex control of the second processing line in the prior art, but there is no thermal deformation in this invention, thereby parallel and linear processing is sufficient.
With the film substrate fixed to one stage, processing can be performed twice, so that film positioning is also unnecessary. For the above reasons, time for film positioning is unnecessary, and processes can be shortened.
Thus, the occurrence of leakage currents arising from transparent electrode processing of a substrate-structure solar cell can be suppressed, and production of an integrated type solar cell by all-laser processes, which had been difficult for substrate structures, becomes possible.
In order to selectively cause light absorption by the bottom cell, use of laser light at a wavelength of 600 to 900 nm, longer than the second harmonic of the YAG laser used for a-Si processing, and desirably at 630 to 810 nm, is effective.
If the wavelength is shorter than 600 nm, absorption of light in the a-Si cell becomes large, and selectivity cannot be maintained. And if the wavelength is longer than 900 nm, the light absorption coefficient of the bottom cell i layer becomes small, and processing is difficult. Further, the longer the wavelength, the larger the element of the heat processing, so that end face crystallization readily occurs.
As explained above, as a problem of substrate type devices, when processing is performed which causes the top cell below the transparent electrode to absorb laser light, the top cell crystallizes and becomes a source of leaks; hence this invention is characterized in that laser light is caused to be absorbed by the bottom cell or a middle cell other than the top cell, to perform processing such that the top cell is also blown away. Hence by means of a thin film solar cell and a method of manufacture thereof of this invention, crystallization of the bottom cell portion, which had arisen from transparent electrode processing in a substrate-structure solar cell, can be suppressed, and the unit-average leakage current can be suppressed. As a result, production of integrated type solar cells by all-laser processes, which previously had been difficult for substrate-structure devices, is made possible.
The foregoing advantages and features of the invention will become apparent upon reference to the following detailed description and the accompanying drawings, of which:
Below, thin film solar cells and methods of manufacture thereof of the invention are explained in detail, based on embodiments and referring to the drawings.
Specifically, in the substrate type solar cell of the first embodiment of the invention, as shown in
Current flowing into the transparent electrodes 7 passes through collector holes 5 and is collected at the back-face electrodes 8, and series connection of unit cells is performed by means of series connection holes 2.
A stepping roll apparatus comprising a CVD chamber and a sputtering chamber is used as an apparatus to manufacture the thin film solar cell of the first embodiment of the invention. The electrode size in the CVD chamber is 12,000 cm2, and six 1,720 cm2 thin film solar cells can be manufactured per film deposition area on a film substrate 1 m in width.
Each chamber can be completely sealed while sandwiching the film substrate 1, and cells can be manufactured by a stepping roll film deposition method in which film deposition and transport are repeated in alternation.
Below, a method for manufacturing solar cells using an apparatus for manufacture of substrate type thin film solar cells is explained, referring to
Formation of First Electrode
First, as shown in
Stepping Roll Film Deposition
Film substrate 1, onto and in which have been formed a metal electrode 3, first back-face electrode 4, series connection holes 2, and collector holes 5, is mounted, in roll form, on a stepping roll apparatus, and film deposition is performed. First, as shown in
The structure of a device trial-manufactured in this way is an a-Si/a-SiGe tandem cell. The bottom i layer and top i layer have film thicknesses of 120 nm and 200 nm respectively, and the respectively optical gaps are 1.5 eV and 1.8 eV. The Ge content in the a-SiGe layer is approximately 30%.
Next, as shown in
Laser Processing
Next, the processed film substrate 1, wound into roll form, is mounted on a laser processing device, and the cell face-side processing line 9 and back face-side processing line 10 shown in
Comparative Example 1 is a method of batch processing to divide the three layers of the photoelectric conversion layer 6, transparent electrode 7, and metal electrode 3; Example and Comparative Example 2 are methods which perform division in two steps.
In Example and Comparative Example 2, which are two-step division processing methods, the laser power is adjusted, the two layers of the photoelectric conversion layer 6 and transparent electrode 7 in
From Table 1, in Example the laser in the first step was an alexandrite laser (wavelength 755 nm), and the laser in the second step was the second harmonic of a YAG laser (wavelength 532 nm).
In Example, after depositing in order the metal electrode 3, bottom cell and top cell of the photoelectric conversion layer 6, and transparent electrode 7, irradiation with laser light from the transparent electrode 7 was performed as the first step, in a laser ablation process realized by causing the bottom cell to absorb laser light, and the top cell and transparent electrode 7 were also blown away and removed; immediately thereafter, laser processing of the metal electrode 3 was performed in the second step.
In Comparative Example 2, after depositing the metal electrode 3, broad-width laser processing of the metal electrode in the first step is performed, and then, after depositing the photoelectric conversion layer 6 and transparent electrode 7, laser processing of the photoelectric conversion layer 6 and transparent electrode 7 using a narrow-width laser is performed in the second step.
The two-step division processing method of Example entails increased tasks compared with the batch division processing of Comparative Example 1, but crystallization of the end faces of the top cell is suppressed, and insulation of the transparent electrode 7 and metal electrode 3 is secured, so that thin film solar cells with little leakage and high efficiency are obtained. Further, comparing Example and Comparative Example 2, which are both two-step division processing methods, processing is substantially easier, and processing time is shorter, compared with broad-width laser processing of the metal electrode and depositing the photoelectric conversion layer rand transparent electrode, and then performing narrow-width laser processing to perform processing twice, as in Comparative Example 2 of the prior art.
One reason for this is that, when processing is performed twice, between the first laser processing and the second laser processing, there was a heat process for film deposition, but in the two-step division method of this invention, there is no heat process for film deposition between the first step and the second step, so that there is no thermal deformation of the film substrate 1. Further, it was necessary to execute complex non-parallel or nonlinear control of the second-time processing line in the prior art, but there is no thermal deformation in this invention, thereby parallel and linear processing is sufficient. Further, the second processing can be performed with the film substrate 1 remaining fixed to one stage, so that positioning of the film substrate 1 is unnecessary. Hence time to position the film substrate 1 is unnecessary, and the process is shortened.
Comparison of Cell Characteristics by Trial Manufacture
Table 2 below compares representative cell characteristics of Example and Comparative Examples 1 and 2, using three types of trial-manufactured cells (68 in series, cell area 1,720 cm2, aperture area 1,510 cm2).
From the experimental results shown in Table 2, it is seen that the output is lowest for Comparative Example 1, using the three-layer batch division processing method, and that the output improves in the order of Comparative Example 2 and Example, which use two-step division processing methods.
Further, in Example of this invention, although the output is high, the unit average leakage current is held low relative to the improvement in output, so that the unit average leakage current is lowest. Hence in Example of this invention, the intended advantageous effects are exhibited, crystallization at the processed end portions is suppressed, and the unit average leakage current can be held low.
Further, the reason for the higher unit average leakage current of the characteristics of Comparative Example 1 compared with Comparative Example 2 is thought to be the two phenomena of a greater extent of crystallization of the processed end portions, and an increase in alloying with the electrode, as results of processing with laser light at higher power.
Regarding the Amount of Absorption of Laser Light
From
As shown in
From these results, in the case of 532 nm, corresponding to the second harmonic of the YAG laser, as shown in
On the other hand, in the case of a krypton ion laser at 647 nm, as shown in
That is, it is seen that as the wavelength of the laser light lengthens, the light absorption amount becomes greater for the bottom cell B than for the top cell A, and moreover the fraction of change of light absorption attenuates exponentially to become substantially constant. The results are as in
On the other hand, an element determining the upper limit of the laser light wavelength is the absolute value of the bottom cell light absorption. As is seen from the graph in
If the Ge content of the a-SiGe tandem cell is increased, narrowing the band gap, then the absorption edge is shifted to longer wavelengths, so that when processing a triple cell with a Ge content of 40 to 50% in an a-SiGe tandem cell, the wavelength upper limit is thought to be approximately 900 nm. If microcrystalline silicon is used in the bottom cell, the processing wavelength upper limit is thought to be approximately 900 nm.
Further, in cases in which processability is a problem due to the wavelength, if the wavelength is longer than 900 nm, the heat processing element becomes more prominent and crystallization tends to occur; hence in order to avoid effects of heat processing, the wavelength must not be made to exceed 900 nm. Hence it is thought that a laser light wavelength of 900 nm or lower, and preferably 810 nm or lower, is reasonable.
A second embodiment of the invention concerns a method for manufacturing a substrate structure thin film solar cell in which serial connections are made without using series connection holes 2, collector holes 5 and other holes.
In the state shown in
Here, the photoelectric conversion layer 6 of this embodiment has a tandem structure with an a-SiGe bottom cell 6a and an a-Si top cell 6b; the lower portion of the transparent electrode 7 is formed so as to reach the metal electrode 3 via strip-shape cut-away portions of the photoelectric conversion layer 6.
In this state, as shown in
Thus by means of the second embodiment of the invention, crystallization of the end faces of the top cell 6b is suppressed, so that insulation of the transparent electrode 7 and metal electrode 3 in these portions is secured. Hence a thin film solar cell with little leakage and high efficiency is obtained.
In the above, embodiments of the invention have been described, but the invention is not limited to the embodiments described above, and various modifications and alterations are possible based on the technical concept of the invention. For example, this invention is not limited to a tandem stacked member having a top cell 6b on the side of the transparent electrode 7 and a bottom cell 6a on the side of the metal electrode 3, but can also be applied to a triple stacked member having a middle cell intermediate between a top cell 6b and a bottom cell 6a.
Thus, a thin film silicon solar cell with a substrate structure and a method of manufacturing the same have been described according to the present invention. Many modifications and variations may be made to the techniques and structures described and illustrated herein without departing from the spirit and scope of the invention. Accordingly, it should be understood that the devices and methods described herein are illustrative only and are not limiting upon the scope of the invention.
| Number | Date | Country | Kind |
|---|---|---|---|
| 2010-061883 | Mar 2010 | JP | national |
This application is a continuation of PCT/JP2011/50321, filed on Jan. 12, 2011, which is based on and claims priority to Japanese Patent Application 2010-061883, filed on Mar. 18, 2010. The disclosure of the Japanese priority application and the PCT application in their entirety, including the drawings, claims, and the specification thereof, are incorporated herein by reference.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/JP2011/050321 | Jan 2011 | US |
| Child | 13368466 | US |
