TWI597857B - Solar cell and fabrication method thereof - Google Patents
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- TWI597857B TWI597857B TW104108569A TW104108569A TWI597857B TW I597857 B TWI597857 B TW I597857B TW 104108569 A TW104108569 A TW 104108569A TW 104108569 A TW104108569 A TW 104108569A TW I597857 B TWI597857 B TW I597857B
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- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 238000000034 method Methods 0.000 title claims description 19
- 239000010410 layer Substances 0.000 claims description 286
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 159
- 229910052732 germanium Inorganic materials 0.000 claims description 157
- 239000013078 crystal Substances 0.000 claims description 64
- 239000000758 substrate Substances 0.000 claims description 63
- 239000000463 material Substances 0.000 claims description 25
- 239000002070 nanowire Substances 0.000 claims description 20
- 239000011241 protective layer Substances 0.000 claims description 19
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 17
- 229910052707 ruthenium Inorganic materials 0.000 claims description 17
- 238000010248 power generation Methods 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011810 insulating material Substances 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 5
- 229910001936 tantalum oxide Inorganic materials 0.000 claims description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
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- 230000005684 electric field Effects 0.000 description 8
- 229910052715 tantalum Inorganic materials 0.000 description 7
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- 238000005468 ion implantation Methods 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910004298 SiO 2 Inorganic materials 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 230000006866 deterioration Effects 0.000 description 3
- 244000126211 Hericium coralloides Species 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 238000003491 array Methods 0.000 description 2
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- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
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- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
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- 230000003287 optical effect Effects 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/072—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type
- H01L31/0745—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells
- H01L31/0747—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN heterojunction type comprising a AIVBIV heterojunction, e.g. Si/Ge, SiGe/Si or Si/SiC solar cells comprising a heterojunction of crystalline and amorphous materials, e.g. heterojunction with intrinsic thin layer or HIT® solar cells; solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/043—Mechanically stacked PV cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
- H01L31/0682—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by at least one potential-jump barrier or surface barrier the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells back-junction, i.e. rearside emitter, solar cells, e.g. interdigitated base-emitter regions back-junction cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/548—Amorphous silicon PV cells
Description
本發明係關於太陽能電池技術，更詳細而言，係關於光電轉換效率較先前之太陽能電池高之矽太陽能電池及其製造方法。 The present invention relates to solar cell technology, and more particularly to a solar cell having a higher photoelectric conversion efficiency than the prior solar cell and a method of manufacturing the same.
於太陽能電池之領域中，已知一種串接式(多接面式)太陽能電池，其層積有複數之光電轉換部，藉由對寬頻域之太陽光進行光電轉換以圖提高光電轉換效率(例如，參照專利文獻1~3)。為了進一步提高此種串接式太陽能電池之光電轉換效率，需要進一步增加光之利用效率來提高輸出電流。 In the field of solar cells, a series-connected (multi-junction) solar cell is known which is laminated with a plurality of photoelectric conversion sections to improve photoelectric conversion efficiency by photoelectrically converting sunlight in a wide frequency domain ( For example, refer to Patent Documents 1 to 3). In order to further improve the photoelectric conversion efficiency of such a tandem solar cell, it is necessary to further increase the utilization efficiency of light to increase the output current.
作為使用單晶矽晶圓之太陽能電池，目前已實現高光電轉換效率者，係將非晶矽沉積於單晶矽晶圓之兩面的異質接面太陽能電池、及於入射光側之相反側的面形成有射極及背面電場區域(BSF區域)之背接觸式太陽能電池。 As a solar cell using a single crystal germanium wafer, a high photoelectric conversion efficiency has been achieved by depositing amorphous germanium on a heterojunction solar cell on both sides of a single crystal germanium wafer, and on the opposite side of the incident light side. A back contact solar cell in which an emitter and a back electric field region (BSF region) are formed on the surface.
為了進一步提高串接式矽太陽能電池之光電轉換效率，對結晶矽層內之奧杰復合的抑制成為重要之課題。作為用以解決此問題之方法之一，具有將結晶矽 層之厚度減薄的方法，於研究層級上將結晶矽層減薄至100μm左右能獲得較高之光電轉換效率的太陽能電池。 In order to further improve the photoelectric conversion efficiency of the tandem-type tantalum solar cell, suppression of the Auger composite in the crystalline germanium layer becomes an important issue. As one of the methods for solving this problem, there is a crystallization 矽 In the method of thinning the thickness of the layer, a solar cell having a higher photoelectric conversion efficiency can be obtained by thinning the crystalline germanium layer to about 100 μm at the research level.
專利文獻1：日本特開平10-335683號公報 Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 10-335683
專利文獻2：日本特開2001-267598號公報 Patent Document 2: Japanese Laid-Open Patent Publication No. 2001-267598
專利文獻3：日本特開平2009-260310號公報 Patent Document 3: Japanese Patent Laid-Open Publication No. 2009-260310
如上述，為了進一步提高串接式矽太陽能電池之光電轉換效率，將結晶矽層之厚度減薄，對抑制結晶矽層內之奧杰復合相當有效。然而，相反若將結晶矽層之厚度減薄，則會因光吸收長度變短，而招致短路電流密度之減少，若對太陽能電池整體進行評價，則有無法達到所希望之光電轉換效率的問題。而且，於太陽能電池之製造步驟中，還要求開發用以不使薄結晶矽層破損之方法。 As described above, in order to further improve the photoelectric conversion efficiency of the tandem-type solar cell, the thickness of the crystallization layer is reduced, which is effective for suppressing the Auger recombination in the crystallization layer. On the other hand, if the thickness of the crystallization layer is reduced, the light absorption length is shortened, and the short-circuit current density is reduced. If the entire solar cell is evaluated, the desired photoelectric conversion efficiency cannot be achieved. . Moreover, in the manufacturing steps of solar cells, it is also required to develop a method for not damaging the thin crystalline germanium layer.
本發明係鑑於此種問題而完成者，其目的在於提供一種將上部電池之結晶矽層減薄，抑制結晶矽層內之奧杰復合，且於製造步驟中也不會使薄結晶矽層破損，且光電轉換效率高之串接式矽太陽能電池及其製造方法。 The present invention has been made in view of such a problem, and an object thereof is to provide a thinning of a crystalline germanium layer of an upper battery, suppressing Auger recombination in a crystalline germanium layer, and not causing damage to a thin crystalline germanium layer in a manufacturing step. And a tandem-type tantalum solar cell with high photoelectric conversion efficiency and a method of manufacturing the same.
為了解決上述問題，本發明之太陽能電池， 其特徵在於：上部電池設於基體之主面上，該上部電池包括自光入射側起依序具有透明導電層、第1導電型非晶矽材料層、與該第1導電型相反之第2導電型結晶矽層、第2導電型非晶矽層之層積構造，且於該上部電池之表面設置有受光面電極，於該基體設置有背面電極，該上部電池之第2導電型結晶矽層的厚度為30μm以下。 In order to solve the above problems, the solar cell of the present invention, The upper battery is provided on a main surface of the substrate, and the upper battery includes a transparent conductive layer, a first conductive type amorphous germanium material layer from the light incident side, and a second opposite to the first conductive type. a laminated structure of a conductive type crystalline germanium layer and a second conductive type amorphous germanium layer, wherein a light receiving surface electrode is provided on a surface of the upper battery, and a back surface electrode is provided on the substrate, and a second conductive type crystalline germanium of the upper battery The thickness of the layer is 30 μm or less.
較佳構成為，該上部電池之第2導電型結晶矽層的厚度為3μm~30μm。 Preferably, the thickness of the second conductive type crystalline germanium layer of the upper battery is 3 μm to 30 μm.
此外，較佳構成為，該上部電池之第2導電型結晶矽層的厚度為4μm~20μm。 Further, it is preferable that the thickness of the second conductive type crystalline ruthenium layer of the upper battery is 4 μm to 20 μm.
較佳構成為，該上部電池之第2導電型結晶矽層的厚度為5μm~10μm。 Preferably, the thickness of the second conductive type crystalline germanium layer of the upper battery is 5 μm to 10 μm.
一形態中，該上部電池係於該第1導電型非晶矽材料層與第2導電型結晶矽層之間具備i型非晶矽材料層。 In one aspect, the upper battery includes an i-type amorphous germanium material layer between the first conductive type amorphous germanium material layer and the second conductive type crystalline germanium layer.
此外，一形態中，該上部電池係於該第2導電型結晶矽層與第2導電型非晶矽層之間具備i型非晶矽層。 Further, in one aspect, the upper battery includes an i-type amorphous germanium layer between the second conductive type crystalline germanium layer and the second conductive type amorphous germanium layer.
並且，一形態中，於該上部電池與該基體之間具備絕緣性透明保護層。 Further, in one aspect, an insulating transparent protective layer is provided between the upper battery and the substrate.
較佳構成為，該絕緣性透明保護層係由矽氧化物或鋁氧化物構成之層。 Preferably, the insulating transparent protective layer is a layer composed of tantalum oxide or aluminum oxide.
例如，該基體係由單晶矽構成。 For example, the base system is composed of single crystal germanium.
一形態中，該基體係由單晶矽構成，於該上部電池與該基體之間具備由氧化銦錫(ITO)構成的層。 In one embodiment, the base system is composed of a single crystal germanium, and a layer made of indium tin oxide (ITO) is provided between the upper battery and the substrate.
此外，一形態中，該基體係由單晶矽構成之 下部電池，該上部電池側係第2導電型區域，於其下方形成有第1導電型區域，於該下部電池之背面設置有該背面電極且被串接。 In addition, in one form, the base system is composed of single crystal germanium. In the lower battery, the upper battery side is a second conductive type region, and a first conductive type region is formed under the battery, and the back surface electrode is provided on the back surface of the lower battery and connected in series.
並且，一形態中，該下部電池係於該第2導電 型區域之該上部電池側具備施體濃度較該第2導電型區域高的第2導電型層。 Moreover, in one aspect, the lower battery is tied to the second conductive The upper battery side of the type region has a second conductivity type layer having a higher donor concentration than the second conductivity type region.
一形態中，該上部電池具有設於該第2導電型 非晶矽層之下側的第2透明導電層。 In one aspect, the upper battery has a second conductivity type a second transparent conductive layer on the lower side of the amorphous germanium layer.
並且，一形態中，該上部電池係自上方觀察 時，該第2透明導電層之表面呈具有匯流排部及自該匯流排部延伸之複數個手指部的梳齒狀而露出。 And, in one form, the upper battery system is viewed from above The surface of the second transparent conductive layer is exposed in a comb shape having a bus bar portion and a plurality of finger portions extending from the bus bar portion.
一形態中，於該上部電池之表面設置有電性 連接於該透明導電層之第1梳齒狀的受光面電極、及電性連接於該第2透明導電層之第2梳齒狀的受光面電極。 In one form, electrical properties are provided on the surface of the upper battery The first comb-shaped light-receiving surface electrode connected to the transparent conductive layer and the second comb-shaped light-receiving surface electrode electrically connected to the second transparent conductive layer.
並且，一形態中，於該下部電池之背面側形 成有該第1導電型區域及第2之第2導電型區域，該第1導電型區域係形成為具有匯流排部及自該匯流排部延伸的複數個手指部之梳齒狀，該第2之第2導電型區域係形成為具有匯流排部及自該匯流排部延伸之複數個手指部的梳齒狀，且施體濃度較該第2導電型區域高，該第1導電型區域之手指部與該第2之第2導電型區域的手指部係以既定間隔交互配置。 And, in one form, on the back side of the lower battery The first conductive type region and the second second conductive type region are formed, and the first conductive type region is formed in a comb shape having a bus bar portion and a plurality of finger portions extending from the bus bar portion. The second conductive type region of the second conductive type region is formed by a comb-shaped portion having a bus bar portion and a plurality of finger portions extending from the bus bar portion, and the donor concentration is higher than the second conductive type region, and the first conductive type region is formed. The finger portion and the finger portion of the second second conductivity type region are alternately arranged at a predetermined interval.
一較佳形態中，於該下部電池之背面設置有 電性連接於該第1導電型區域之第1梳齒狀的背面電極、及電性連接於該第2之第2導電型區域的第2梳齒狀之背 面電極。 In a preferred embodiment, the back side of the lower battery is provided with a first comb-shaped back electrode electrically connected to the first conductive type region and a second comb-shaped back electrically connected to the second second conductive type region Surface electrode.
又，一較佳形態中，當自上方觀察該太陽能 電池時，該第1梳齒狀之受光面電極的匯流排部與該第2梳齒狀之背面電極的匯流排部係於一端側位於平行之位置，該第2梳齒狀之受光面電極的匯流排部與該第1梳齒狀之背面電極的匯流排部係於另一端側位於平行之位置。 Also, in a preferred embodiment, when the solar energy is viewed from above In the case of the battery, the bus bar portion of the first comb-shaped light-receiving surface electrode and the bus bar portion of the second comb-shaped back electrode are located at one end side in parallel with each other, and the second comb-shaped light-receiving surface electrode The bus bar portion and the bus bar portion of the first comb-shaped back electrode are located at the other end side in parallel.
例如，設於該上部電池之透明導電層係氧化 銦錫(ITO)。 For example, the transparent conductive layer provided on the upper battery is oxidized Indium tin (ITO).
較佳構成為，設於該上部電池之光入射側的 透明導電層係兼作反射防止層。 Preferably, it is provided on the light incident side of the upper battery The transparent conductive layer also serves as an antireflection layer.
較佳構成為，該上部電池之該第2導電型結晶 矽層，係設計為該上部電池與該下部電池之發電電流相同之厚度。 Preferably, the second conductivity type crystal of the upper battery The ruthenium layer is designed to have the same thickness as the power generation current of the upper battery.
並且，較佳構成為，於自上方觀察該太陽能 電池時，該上部電池具備之具有透明導電層、第1導電型非晶矽材料層、第2導電型結晶矽層、第2導電型非晶矽層的層積構造，係具有被劃分成以既定間隔2維排列之複數條奈米線或壁面對齊於既定的方向且以既定間隔2維排列之複數個壁狀的奈米牆之陣列構造，該奈米線之直徑或該奈米牆的厚度，於該第2導電型結晶矽層的部位上為10nm以下。 Moreover, it is preferably configured to observe the solar energy from above In the case of a battery, the upper battery includes a laminated structure having a transparent conductive layer, a first conductive type amorphous germanium material layer, a second conductive type crystalline germanium layer, and a second conductive type amorphous germanium layer, and is divided into a plurality of wall-shaped nano-wall arrays arranged in a two-dimensional arrangement at a predetermined interval and aligned in a predetermined direction and arranged in two dimensions at a predetermined interval, the diameter of the nanowire or the nano-wall The thickness is 10 nm or less at the portion of the second conductivity type crystalline ruthenium layer.
較佳構成為，相互鄰接之該奈米線或該奈米 牆係由絕緣性物質隔離。 Preferably, the nanowire or the nanometer adjacent to each other is The wall is isolated by an insulating material.
本發明之太陽能電池的製造方法，係於基體 上具備上部電池之太陽能電池的製造方法，該製造方法 包含：第1步驟，其以400℃以下之溫度使第1之第2導電型矽結晶基板與該基體的表面彼此貼合，該第1之第2導電型矽結晶基板係於表面區域形成有第2導電型非晶矽層，且於該第2導電型非晶矽層上設置有透明導電層，該基體係於表面形成有透明導電層或絕緣性透明保護層；及第2步驟，其自背面將該第1之第2導電型矽結晶基板薄化至厚度30μm以下，作為該上部電池之第2導電型結晶矽層。 The method for manufacturing a solar cell of the present invention is based on a substrate Manufacturing method of solar cell with upper battery, the manufacturing method In the first step, the first second conductivity type germanium crystal substrate and the surface of the substrate are bonded to each other at a temperature of 400 ° C or lower, and the first second conductivity type germanium crystal substrate is formed on the surface region. a second conductive type amorphous germanium layer, wherein a transparent conductive layer is formed on the second conductive type amorphous germanium layer, and the base system has a transparent conductive layer or an insulating transparent protective layer formed on the surface; and a second step The first second conductivity type germanium crystal substrate is thinned to a thickness of 30 μm or less from the back surface to serve as a second conductivity type crystalline germanium layer of the upper battery.
較佳構成為，該基體係於表面區域形成有施 體濃度較塊狀體高之第2導電型層，且於該第2導電型層上設置有絕緣性透明保護層之第2之第2導電型矽結晶基板。 Preferably, the base system is formed on the surface region The second conductive type crystal substrate having the second conductive type layer having a bulk density higher than the bulk and having the insulating transparent protective layer on the second conductive type layer.
較佳構成為，該第1步驟具備對該第1之第2 導電型矽結晶基板的表面及該基體之表面的至少一者實施表面活化處理之次步驟。 Preferably, the first step includes the first and second At least one of the surface of the conductive germanium crystal substrate and the surface of the substrate is subjected to a surface activation treatment.
例如，該表面活化處理係以電漿處理或臭氧 處理之至少一者執行。 For example, the surface activation treatment is treated with plasma or ozone. At least one of the processes is performed.
例如，該透明導電層係氧化銦錫(ITO)，該絕 緣性透明保護層係由矽氧化物或鋁氧化物構成之層。 For example, the transparent conductive layer is indium tin oxide (ITO), which is absolutely The edge transparent protective layer is a layer composed of tantalum oxide or aluminum oxide.
一形態中，具備於該第1步驟之前朝該第1之 第2導電型矽結晶基板的表面區域植入既定配量之氫而形成氫離子植入層的步驟，於該第2步驟中，藉由對該氫離子植入層施加機械或熱衝擊，使第2導電型結晶矽層自該第1之第2導電型矽結晶基板剝離，而作為該上部電池之第2導電型結晶矽層。 In one aspect, the first step is performed before the first step a step of implanting a predetermined amount of hydrogen to form a hydrogen ion implantation layer in a surface region of the second conductivity type germanium crystal substrate, and applying mechanical or thermal shock to the hydrogen ion implantation layer in the second step The second conductive type crystalline germanium layer is peeled off from the first second conductive type germanium crystal substrate, and serves as a second conductive type crystalline germanium layer of the upper battery.
此外，一形態中，於該第2步驟之後，具備於 該第2導電型結晶矽層之上方形成與第2導電型相反之第1導電型非晶矽材料層的第3步驟。 Further, in one form, after the second step, A third step of forming a first conductive type amorphous germanium material layer opposite to the second conductive type is formed above the second conductive type crystalline germanium layer.
並且，一形態中，該第3步驟具備於該第1導 電型非晶矽材料層的形成之前，將該第2導電型結晶矽層劃分為奈米線或奈米牆的次步驟，其中該奈米線係以既定間隔2維排列之複數條奈米線，且是於該第2導電型結晶矽層的部位上直徑為10nm以下者，該奈米牆係壁面對齊於既定方向且以既定間隔2維排列之複數個壁狀的奈米牆且是於該第2導電型結晶矽層的部位上厚度為10nm以下者。 Further, in one aspect, the third step is provided in the first guide Before the formation of the electrically amorphous bismuth material layer, the second conductivity type crystalline ruthenium layer is divided into a sub-step of a nanowire or a nano wall, wherein the nanowire is a plurality of nanometers arranged at two intervals at a predetermined interval a line having a diameter of 10 nm or less at a portion of the second conductivity type crystal ruthenium layer, wherein the wall surface of the nano wall system is aligned with a predetermined number of wall-shaped nanowalls arranged at two intervals at a predetermined interval and is The thickness of the portion of the second conductivity type crystalline ruthenium layer is 10 nm or less.
本發明之太陽能電池係採用較先前技術的構成明顯地將上部電池之第2導電型結晶矽層減薄之構造。其結果，與將第2導電型結晶矽層設定為100μm之構成比較，上部電池之開路電壓變得高出0.1V以上，可利用高電壓擷取電流，因而可提高光電轉換效率。 The solar cell of the present invention has a structure in which the second conductivity type crystalline ruthenium layer of the upper battery is remarkably thinned by the configuration of the prior art. As a result, compared with the configuration in which the second conductivity type crystalline germanium layer is set to 100 μm, the open circuit voltage of the upper battery is increased by 0.1 V or more, and the current can be extracted by the high voltage, so that the photoelectric conversion efficiency can be improved.
此外，於將本發明設為串接式太陽能電池之情況下，由於可自上部電池及下部電池分別獨立地取出輸出，因此，不需要取得串聯連接型串接式電池中所需要之發電電流的匹配。 Further, in the case where the present invention is a tandem solar cell, since the output can be taken out independently from the upper battery and the lower battery, it is not necessary to obtain the power generation current required in the series-connected series battery. match.
而且，本發明之太陽能電池的製造方法，係應用所謂「貼合」技術，於400℃以下進行上部電池與基體或下部電池的「貼合」，因此無氫自氫化非晶矽層脫離而使膜質降低之情況，也不會對結晶矽層產生新的缺 陷。因此，於將本發明設為串接式太陽能電池之情況下，不會產生伴隨串接化之異質接面電池的劣化。 Further, in the method for producing a solar cell of the present invention, the so-called "bonding" technique is applied, and the upper battery is "bonded" to the substrate or the lower battery at 400 ° C or lower. Therefore, hydrogen is not detached from the hydrogenated amorphous layer. If the film quality is reduced, there will be no new defects in the crystallization layer. trap. Therefore, in the case where the present invention is a tandem solar cell, deterioration of the heterojunction battery accompanying the series connection does not occur.
10‧‧‧第1之n型矽結晶基板 10‧‧‧1st n-type crystalline substrate
20‧‧‧第2之n型矽結晶基板 20‧‧‧2nd n-type crystalline substrate
100‧‧‧上部電池 100‧‧‧Upper battery
110‧‧‧透明導電層 110‧‧‧Transparent conductive layer
120‧‧‧p型非晶矽層 120‧‧‧p-type amorphous layer
130‧‧‧n型結晶矽層 130‧‧‧n type crystalline layer
140‧‧‧n型非晶矽層 140‧‧‧n type amorphous layer
150‧‧‧第2透明導電層 150‧‧‧2nd transparent conductive layer
160‧‧‧絕緣性透明保護層 160‧‧‧Insulating transparent protective layer
200‧‧‧下部電池 200‧‧‧lower battery
210‧‧‧n型區域 210‧‧‧n type area
220‧‧‧作為發射極層之p型區域 220‧‧‧ p-type region as the emitter layer
230‧‧‧施體濃度高之n型層 230‧‧‧N-type layer with high body concentration
240‧‧‧施體濃度高之第2之n型層 240‧‧‧The second n-type layer with high body concentration
250‧‧‧絕緣性膜 250‧‧‧Insulating film
260‧‧‧第1背面電極 260‧‧‧1st back electrode
270‧‧‧第2背面電極 270‧‧‧2nd back electrode
280‧‧‧導電性材料 280‧‧‧Electrical materials
300‧‧‧太陽能電池 300‧‧‧ solar cells
第1圖為用於說明本發明之串接式矽太陽能電池的基本構造之概要的剖面圖。 Fig. 1 is a cross-sectional view for explaining an outline of a basic structure of a tandem-type tantalum solar cell of the present invention.
第2圖為顯示光電轉換效率之上部電池n型結晶矽層的厚度依賴性之圖。 Fig. 2 is a graph showing the thickness dependence of the n-type crystalline germanium layer in the upper portion of the photoelectric conversion efficiency.
第3圖為顯示上部電池之開路電壓的n型結晶矽層之厚度依賴性的模擬結果之圖。 Fig. 3 is a graph showing the simulation results of the thickness dependence of the n-type crystalline germanium layer showing the open circuit voltage of the upper battery.
第4圖為用於說明本發明之太陽能電池具備的受光面電極的形態之圖。 Fig. 4 is a view for explaining the form of a light-receiving surface electrode provided in the solar cell of the present invention.
第5圖為說明自本發明之太陽能電池的光入射側(上方)觀察時之受光面電極的形態之圖(第5(A)圖)、及說明自背面側(下方)觀察時之背面電極的形態之圖(第5(B)圖)。 Fig. 5 is a view showing the form of the light-receiving surface electrode when viewed from the light incident side (upper side) of the solar cell of the present invention (Fig. 5(A)), and the back electrode when viewed from the back side (bottom). Figure of the form (Fig. 5(B)).
第6圖為顯示設為2端子串接式電池構造時之，第5(A)圖及第5(B)圖之圖中的虛線顯示部分之剖面構造的概要之圖。 Fig. 6 is a view showing an outline of a cross-sectional structure of a broken line display portion in the fifth (A) and fifth (B) views when the two-terminal tandem battery structure is used.
第7圖為製造本發明之太陽能電池的製程例之流程圖。 Fig. 7 is a flow chart showing an example of a process for producing the solar cell of the present invention.
第8圖為用於說明上部電池為被劃分為以既定間隔2維排列之複數個壁狀的奈米牆之陣列構造的情況之串接式太陽能電池的構成之立體示意圖。 Fig. 8 is a perspective view showing the configuration of a tandem solar cell in the case where the upper battery is divided into an array structure of a plurality of wall-shaped nanowalls arranged at two intervals at a predetermined interval.
第9圖為觀察具有被劃分為以既定間隔2維排列之複 數個壁狀的矽之奈米牆的陣列構造之上部電池的一部分之穿透式電子顯微鏡圖像。 Figure 9 shows that the observation has a division that is divided into two dimensions at a predetermined interval. A number of wall-shaped arrays of 矽Nylon walls are constructed with a transmission electron microscope image of a portion of the upper cell.
第10圖為顯示被劃分為奈米牆之陣列構造(A)的反射率、及於奈米牆相互間埋入絕緣性物質即SiO2之陣列構造(B)的反射率之波長依賴性之圖。 Fig. 10 is a graph showing the reflectance of the array structure (A) divided into nanowalls and the wavelength dependence of the reflectance of the array structure (B) of SiO 2 in which insulating materials are embedded between the nanowalls. Figure.
下面，參照圖式對本發明之太陽能電池及其製造方法進行說明。再者，之後之說明中，設第1導電型為p型，且設第2導電型為n型進行說明，但也可為相反之關係，亦即設第1導電型為n型，且設第2導電型為p型。此外，之後之說明中，將「非晶矽材料層」作為非晶矽層進行說明，除此以外，也可作為非結晶SiO層或非結晶SiN層等。 Hereinafter, a solar cell of the present invention and a method of manufacturing the same will be described with reference to the drawings. In the following description, the first conductivity type is a p-type and the second conductivity type is an n-type. However, the reverse conductivity may be employed, that is, the first conductivity type is an n-type, and The second conductivity type is p-type. In the following description, the "amorphous germanium material layer" will be described as an amorphous germanium layer, and may be an amorphous SiO layer or an amorphous SiN layer.
之後，對本發明之太陽能電池為串接式太陽能電池的情況進行說明，但不一定要為串接式。本發明之太陽能電池也可為不具備下部電池，於基體上設置有上部電池之太陽能電池。亦即，「下部電池」不一定要作為太陽能電池發揮作用。 Hereinafter, the case where the solar cell of the present invention is a tandem solar cell will be described, but it is not necessarily required to be a tandem type. The solar cell of the present invention may be a solar cell in which an upper battery is provided on a substrate without a lower battery. That is, the "lower battery" does not have to function as a solar cell.
〔本發明之串接式太陽能電池的基本構造之概要〕 [Summary of Basic Structure of Tandem Solar Cell of the Present Invention]
第1圖為用於說明本發明之串接式矽太陽能電池的基本構之概要的剖面圖。太陽能電池300係將設於光入射側(圖之上側)之上部電池100、及設於該上部電池100之下方的下部電池200層積而成的串接式太陽能電池。 Fig. 1 is a cross-sectional view for explaining an outline of a basic structure of a tandem-type tantalum solar cell of the present invention. The solar cell 300 is a tandem solar cell in which a battery 100 provided on the light incident side (on the upper side of the drawing) and a lower battery 200 provided below the upper battery 100 are stacked.
上部電池100係使用第1之n型矽結晶基板10 ，且藉由後述的製程例而製造。該上部電池100係自光入射側起依序具備透明導電層110、作為p型非結晶材料層的p型非晶矽層120、n型結晶矽層130、n型非晶矽層140。第1圖所示之例子中，於n型非晶矽層140之下側設置有第2透明導電層150，藉由將透明導電層110及第2透明導電層150作為2個電極層，可與下部電池200獨立地取出上部電池100之輸出。透明導電層110例如由氧化銦錫(ITO)構成，也能使其兼作反射防止層。再者，關於設在上部電池100之表面的受光面電極(未圖示)，容待後述。 The upper battery 100 uses the first n-type germanium crystal substrate 10 And it is manufactured by the process example mentioned later. The upper battery 100 is provided with a transparent conductive layer 110, a p-type amorphous germanium layer 120 as a p-type amorphous material layer, an n-type crystalline germanium layer 130, and an n-type amorphous germanium layer 140 in this order from the light incident side. In the example shown in FIG. 1, the second transparent conductive layer 150 is provided on the lower side of the n-type amorphous germanium layer 140, and the transparent conductive layer 110 and the second transparent conductive layer 150 are used as two electrode layers. The output of the upper battery 100 is taken out independently of the lower battery 200. The transparent conductive layer 110 is made of, for example, indium tin oxide (ITO), and can also serve as an antireflection layer. In addition, the light-receiving surface electrode (not shown) provided on the surface of the upper battery 100 is to be described later.
再者，p型非結晶材料層也可設為p型非結晶 SiO層及p型非結晶SiN層，以取代該p型非晶矽層120。此外，也可於p型非晶矽層120與n型結晶矽層130之間設置作為i型非結晶材料層的i型非晶矽層，也可取代i型非晶矽層，而設置i型非結晶SiO層或i型非結晶SiN層。 Furthermore, the p-type amorphous material layer can also be set to p-type amorphous The SiO layer and the p-type amorphous SiN layer are substituted for the p-type amorphous germanium layer 120. In addition, an i-type amorphous germanium layer as an i-type amorphous material layer may be disposed between the p-type amorphous germanium layer 120 and the n-type crystalline germanium layer 130, or may be replaced by an i-type amorphous germanium layer. A type of amorphous SiO layer or an i-type amorphous SiN layer.
再者，該p型非晶矽層120、i型非晶矽層、n 型非晶矽層140，於多數情況下皆被設為被氫化之非結晶層。這點於p型非晶矽層120及i型非晶矽層為上述其他非晶矽材料層的情況時也同樣。 Furthermore, the p-type amorphous germanium layer 120, the i-type amorphous germanium layer, n The amorphous ruthenium layer 140 is, in many cases, an amorphous layer that is hydrogenated. This is also the case when the p-type amorphous germanium layer 120 and the i-type amorphous germanium layer are the other amorphous germanium material layers described above.
下部電池200係使用第2之n型矽結晶基板20 ，且藉由後述之製程例而製造。此下部電池200係由單晶矽構成，上部電池側係n型區域210，於其下方(亦即太陽能電池之背面側)設置有作為發射極層的p型區域220。 The lower battery 200 is a second n-type germanium crystal substrate 20 And it is manufactured by the process example mentioned later. The lower battery 200 is composed of a single crystal crucible, and the upper battery side is an n-type region 210, and a p-type region 220 as an emitter layer is provided below (that is, on the back side of the solar cell).
此外，於該圖所示之例子中，於下部電池200 之n型區域210的上部電池側設置有施體濃度較作為塊狀體之n型區域高的n型層230，而作為表面電場層(FSF)。 並且，與作為發射極層之p型區域220鄰接形成有施體濃度較作為塊狀體的n型區域高的第2之n型層240，而作為背面電場層(BSF)。 In addition, in the example shown in the figure, the lower battery 200 The upper battery side of the n-type region 210 is provided with an n-type layer 230 having a higher donor concentration than the n-type region as a bulk, and serves as a surface electric field layer (FSF). Further, a second n-type layer 240 having a higher donor concentration than the n-type region as a bulk is formed adjacent to the p-type region 220 as the emitter layer, and serves as a back surface electric field layer (BSF).
第1背面電極260及第2背面電極270經由絕緣 性膜250電性連接於發射極層即p型區域220及第2之n型層240之各者，藉由將發射極層即p型區域220及第2之n型層240作為2個電極層，可與上部電池100獨立地取出下部電池200之輸出。 The first back surface electrode 260 and the second back surface electrode 270 are insulated The film 250 is electrically connected to each of the emitter layer, that is, the p-type region 220 and the second n-type layer 240, and the emitter layer, that is, the p-type region 220 and the second n-type layer 240 are used as two electrodes. The layer can take out the output of the lower battery 200 independently of the upper battery 100.
再者，後述之形態中，將p型區域220形成為 具有匯流排部及自該匯流排部延伸之複數個手指部的梳齒狀，並且第2之n型區域240也同樣形成為具有匯流排部及自該匯流排部延伸之複數個手指部的梳齒狀，且使p型區域220之手指部與第2之n型區域240的手指部以既定間隔交互地配置。 Furthermore, in the form described later, the p-type region 220 is formed as The bus bar portion has a comb shape of a plurality of finger portions extending from the bus bar portion, and the second n-type region 240 is also formed to have a bus bar portion and a plurality of finger portions extending from the bus bar portion. The comb-tooth shape is such that the finger portion of the p-type region 220 and the finger portion of the second n-type region 240 are alternately arranged at a predetermined interval.
在此，該p型區域220中的匯流排部，不一定 要為p型之導電型，但為方便起見，將該匯流排部也包含在內稱為「p型區域」。同樣，該第2之n型區域240中的匯流排部，也不一定要為n型之導電型，但為方便起見，將該匯流排部也包含在內稱為「n型區域」。換言之，p型區域220之手指部及第2之n型區域240的手指部分別為「p型」及「n型」」，也可使這些手指部以既定間隔呈條紋狀交互配置。 Here, the busbar portion in the p-type region 220 is not necessarily It is a p-type conductivity type, but for convenience, the bus bar portion is also referred to as a "p-type region". Similarly, the bus bar portion in the second n-type region 240 does not necessarily have to be an n-type conductivity type, but for convenience, the bus bar portion is also referred to as an "n-type region". In other words, the finger portions of the p-type region 220 and the finger portions of the second n-type region 240 are "p-type" and "n-type", respectively, and these finger portions can be alternately arranged in stripes at predetermined intervals.
設於上部電池100與下部電池200之間的以符 號160所示之層，係絕緣性透明保護層，且是於後述之製造製程中用於貼合的層。絕緣性透明保護層160例如為由 矽氧化物、鋁氧化物構成的層。 a symbol between the upper battery 100 and the lower battery 200 The layer shown by the numeral 160 is an insulating transparent protective layer and is a layer for bonding in a manufacturing process to be described later. The insulating transparent protective layer 160 is, for example, composed of A layer composed of cerium oxide or aluminum oxide.
上部電池100之各層的組成及厚度等，例如按 下述方式進行設計。透明導電層110係0.1μm左右的ITO，p型非晶矽層120與i型非晶矽層的總厚為0.01μm左右，n型結晶矽層130之厚度為30μm以下，i型非晶矽層與n型非晶矽層140之總厚為0.01μm左右，第2透明導電層150係0.1μm左右的ITO。再者，上部電池之n型結晶矽層的厚度，較佳為3μm~30μm，更佳為4μm~20μm，最佳為5μm~10μm。關於其理由容待後述。 The composition and thickness of each layer of the upper battery 100, for example, Designed in the following manner. The transparent conductive layer 110 is ITO of about 0.1 μm, the total thickness of the p-type amorphous germanium layer 120 and the i-type amorphous germanium layer is about 0.01 μm, and the thickness of the n-type crystalline germanium layer 130 is 30 μm or less, i-type amorphous germanium. The total thickness of the layer and the n-type amorphous germanium layer 140 is about 0.01 μm, and the second transparent conductive layer 150 is about 0.1 μm of ITO. Further, the thickness of the n-type crystalline germanium layer of the upper battery is preferably 3 μm to 30 μm, more preferably 4 μm to 20 μm, and most preferably 5 μm to 10 μm. The reasons for this are to be described later.
由單晶矽構成之下部電池200的各層之厚度 等，例如可按下述方式進行設計。作為塊狀體的n型區域210，其厚度為200~500μm左右且比電阻為1Ωcm左右，作為發射極層之p型區域220，其受體濃度為5×1019cm-3左右，且厚度為2~3μm左右，作為表面電場層(FSF)之n型層230，其施體濃度為1×1019cm-3左右，且厚度為0.1~1μm左右，作為背面電場層(BSF)之第2之n型層240，其施體濃度為5×1019cm-3~1×1020cm-3左右，且厚度為1~2μm左右。 The thickness of each layer of the lower battery 200 composed of single crystal germanium can be designed, for example, as follows. The n-type region 210 as a bulk has a thickness of about 200 to 500 μm and a specific resistance of about 1 Ωcm, and the p-type region 220 as an emitter layer has a receptor concentration of about 5 × 10 19 cm -3 and a thickness. The n-type layer 230, which is a surface electric field layer (FSF), has a donor concentration of about 1×10 19 cm -3 and a thickness of about 0.1 to 1 μm as a back surface electric field layer (BSF). The n-type layer 240 of 2 has a donor concentration of about 5×10 19 cm −3 to 1×10 20 cm −3 and a thickness of about 1 to 2 μm.
再者，作為絕緣性膜250可適宜使用SiO2。此 外，SiO2也能適宜地使用於設於上部電池100與下部電池200之間的絕緣性透明保護層160，其厚度例如為0.1μm左右。 Further, as the insulating film 250, SiO 2 can be suitably used. Further, SiO 2 can be suitably used for the insulating transparent protective layer 160 provided between the upper battery 100 and the lower battery 200, and has a thickness of, for example, about 0.1 μm.
此外，後述之受光面電極或該背面電極260 、270，係利用濺鍍及蒸鍍對形成於全面之金屬(例如，Al或Ag等)進行圖案處理而形成，或使用Al、Ag等的糊 膏進行網版印刷後燒結形成。 Further, a light-receiving surface electrode or a back surface electrode 260 which will be described later 270, which is formed by patterning a metal (for example, Al or Ag) formed by sputtering or vapor deposition, or using a paste of Al, Ag, or the like. The paste is formed by sintering after screen printing.
第2圖為顯示光電轉換效率之上部電池n型結晶矽層的厚度依賴性之模擬結果的圖。於該模擬中，設下部電池之厚度為300μm，且將上部電池之n型結晶矽層的厚度作為參數求取光電轉換效率。根據該結果，上部電池之n型結晶矽層的厚度為100μm之情況時的光電轉換效率，與n型結晶矽層之厚度為1μm的情況大致相等(23.5%)，若厚度超過100μm，則該值下降。 Fig. 2 is a graph showing the results of simulation of the thickness dependence of the n-type crystalline germanium layer on the upper portion of the photoelectric conversion efficiency. In this simulation, the thickness of the lower battery was set to 300 μm, and the photoelectric conversion efficiency was obtained by taking the thickness of the n-type crystalline germanium layer of the upper battery as a parameter. According to the results, the photoelectric conversion efficiency when the thickness of the n-type crystalline germanium layer of the upper battery is 100 μm is substantially equal to the case where the thickness of the n-type crystalline germanium layer is 1 μm (23.5%), and when the thickness exceeds 100 μm, the thickness is more than 100 μm. The value drops.
n型結晶矽層之厚度為30μm以下，可獲得24%以上之光電轉換效率，若n型結晶矽層之厚度在3~30μm的範圍，則可獲得24%以上之光電轉換效率。此外，於n型結晶矽層之厚度為4μm~20μm的範圍內可獲得超過24.1%之光電轉換效率，於5μm~10μm之範圍內可獲得超過24.2%的光電轉換效率。 The thickness of the n-type crystalline germanium layer is 30 μm or less, and a photoelectric conversion efficiency of 24% or more can be obtained. When the thickness of the n-type crystalline germanium layer is in the range of 3 to 30 μm, a photoelectric conversion efficiency of 24% or more can be obtained. Further, a photoelectric conversion efficiency of more than 24.1% can be obtained in the range of 4 μm to 20 μm in the thickness of the n-type crystalline germanium layer, and a photoelectric conversion efficiency of more than 24.2% can be obtained in the range of 5 μm to 10 μm.
第3圖為顯示上部電池之開路電壓Voc的n型結晶矽層之厚度依賴性的模擬結果之圖，圖中以圓符號顯示假定為塊狀體之矽而獲得的開路電壓Voc的值。第3(A)圖顯示n型結晶矽層之厚度在1~100μm的範圍內之開路電壓，第3(B)圖顯示n型結晶矽層之厚度在1~10μm的範圍內之開路電壓。 Fig. 3 is a graph showing the simulation results of the thickness dependence of the n-type crystalline germanium layer of the open circuit voltage Voc of the upper battery, in which the value of the open circuit voltage Voc obtained assuming the blockiness of the bulk is indicated by a circle symbol. . Fig. 3(A) shows an open circuit voltage in which the thickness of the n-type crystalline germanium layer is in the range of 1 to 100 μm, and Fig. 3(B) shows an open circuit voltage in which the thickness of the n-type crystalline germanium layer is in the range of 1 to 10 μm.
根據這些圖所示之結果，於n型結晶矽層之厚度為10~20μm附近，開路電壓確有提高，特別是在n型結晶矽層之厚度為10μm以下，開路電壓明顯提高，能獲得0.8V以上之值。這表示藉由將n型結晶矽層之厚度減薄 ，結晶矽層內之載體的奧杰復合明顯被抑制。 According to the results shown in these figures, the open circuit voltage is improved in the vicinity of the thickness of the n-type crystalline germanium layer of 10 to 20 μm, especially in the case where the thickness of the n-type crystalline germanium layer is 10 μm or less, and the open circuit voltage is remarkably improved, and 0.8 can be obtained. Value above V. This means that the thickness of the n-type crystalline germanium layer is thinned. The Auger complex of the carrier in the crystalline ruthenium layer was significantly inhibited.
根據第3圖所示之結果，於n型結晶矽層之厚 度為10μm以下，開路電壓確有明顯提高，另一方面，根據第2圖所示之結果，考慮到若n型結晶矽層之厚度變得較5μm更薄則光電轉換效率逐漸下降之事實，可認為最佳之n型結晶矽層的厚度範圍為5μm~10μm。 According to the results shown in Figure 3, the thickness of the n-type crystalline germanium layer When the degree is 10 μm or less, the open circuit voltage is remarkably improved. On the other hand, according to the result shown in Fig. 2, considering the fact that the photoelectric conversion efficiency is gradually lowered if the thickness of the n-type crystalline germanium layer becomes thinner than 5 μm, The thickness of the n-type crystalline germanium layer which is optimal is considered to be in the range of 5 μm to 10 μm.
第4圖為用於說明本發明之太陽能電池具備的受光面電極的形態之圖。該形態中，於上部電池100之表面設置有電性連接於該透明導電層110之第1受光面電極170、及電性連接於第2透明導電層150之第2受光面電極180，藉由將透明導電層110及第2透明導電層150作為2個電極層，可與下部電池200獨立地取出上部電池100之輸出。 Fig. 4 is a view for explaining the form of a light-receiving surface electrode provided in the solar cell of the present invention. In this embodiment, the first light-receiving surface electrode 170 electrically connected to the transparent conductive layer 110 and the second light-receiving surface electrode 180 electrically connected to the second transparent conductive layer 150 are provided on the surface of the upper battery 100. The transparent conductive layer 110 and the second transparent conductive layer 150 are used as two electrode layers, and the output of the upper battery 100 can be taken out independently of the lower battery 200.
再者，如已說明者，下部電池200之輸出也可藉由將發射極層即p型區域220與第2之n型層240作為2個電極層，而可與上部電池100獨立地取出下部電池200之輸出。 Furthermore, as already explained, the output of the lower battery 200 can also be taken out independently of the upper battery 100 by using the emitter layer, that is, the p-type region 220 and the second n-type layer 240 as two electrode layers. The output of the battery 200.
第5(A)及第5(B)圖分別為說明自太陽能電池300之光入射側(上方)觀察時之受光面電極的形態之圖(第5(A)圖)、及說明自太陽能電池300之背面側(下方)觀察時之背面電極的形態之圖(第5(B)圖)。 5(A) and 5(B) are diagrams for explaining the form of the light-receiving surface electrode when viewed from the light incident side (upper side) of the solar cell 300 (Fig. 5(A)), and the description from the solar cell A view of the form of the back electrode when viewed on the back side (lower side) of 300 (Fig. 5(B)).
如第5(A)圖所示，自上方觀察時，於上部電池100設置有第1梳齒狀之受光面電極170及第2梳齒狀的受光面電極180。並且，上部電池100之第2透明導電層150 的表面係呈具有匯流排部及自該匯流排部延伸之複數個手指部的梳齒狀而露出，第1梳齒狀的受光面電極170電性連接於透明導電層110，第2梳齒狀之受光面電極180電性連接於第2透明導電層150。 As shown in Fig. 5(A), when viewed from above, the upper battery 100 is provided with a first comb-shaped light-receiving surface electrode 170 and a second comb-shaped light-receiving surface electrode 180. And, the second transparent conductive layer 150 of the upper battery 100 The surface is exposed by a comb-shaped portion having a bus bar portion and a plurality of finger portions extending from the bus bar portion, and the first comb-shaped light-receiving surface electrode 170 is electrically connected to the transparent conductive layer 110, and the second comb tooth The light-receiving surface electrode 180 is electrically connected to the second transparent conductive layer 150.
亦即，上部電池100於自上方觀察時，第2透 明導電層150之表面呈具有匯流排部及自該匯流排部延伸之複數個手指部的梳齒狀而露出，且設置有電性連接於透明導電層110之第1梳齒狀的受光面電極170、及電性連接於第2透明導電層150之第2梳齒狀的受光面電極180，藉此，可與下部電池200獨立地取出上部電池100之輸出。 That is, when the upper battery 100 is viewed from above, the second through The surface of the conductive layer 150 is exposed in a comb shape having a bus bar portion and a plurality of finger portions extending from the bus bar portion, and is provided with a first comb-shaped light receiving surface electrically connected to the transparent conductive layer 110. The electrode 170 and the second comb-shaped light-receiving surface electrode 180 electrically connected to the second transparent conductive layer 150 can take out the output of the upper battery 100 independently of the lower battery 200.
此外，本形態中，於下部電池200之背面側形 成有p型區域220及第2之n型區域240，該p型區域220係形成為具有匯流排部及自該匯流排部延伸之複數個手指部的梳齒狀，該第2之n型區域240係形成為具有匯流排部及自該匯流排部延伸之複數個手指部的梳齒狀，且施體濃度較作為塊狀體的n型區域210高，p型區域220之手指部及第2之n型區域240的手指部係以既定間隔交互地配置。 Further, in the present embodiment, the back side of the lower battery 200 is shaped A p-type region 220 and a second n-type region 240 are formed, and the p-type region 220 is formed in a comb shape having a bus bar portion and a plurality of finger portions extending from the bus bar portion, and the second n-type The region 240 is formed in a comb shape having a bus bar portion and a plurality of finger portions extending from the bus bar portion, and has a donor concentration higher than that of the n-type region 210 as a block body, and a finger portion of the p-type region 220 and The finger portions of the second n-type region 240 are alternately arranged at predetermined intervals.
並且，於下部電池200之背面設置有電性連接 於p型區域220的第1梳齒狀之背面電極260、及電性連接於第2之n型區域240的第2梳齒狀之背面電極270，藉此，可與上部電池100獨立地取出下部電池200之輸出。 Moreover, an electrical connection is provided on the back surface of the lower battery 200. The first comb-shaped back surface electrode 260 of the p-type region 220 and the second comb-shaped back surface electrode 270 electrically connected to the second n-type region 240 can be taken out independently of the upper battery 100. The output of the lower battery 200.
此種形態之受光面電極的構造，對無法忽視 因上部電池100之透明導電層(110、150)的膜電阻高而造成的損失之情況尤其有效。並且，由於能獨立地取出上 部電池100之輸出及下部電池200的輸出，因此，不需要像電性串聯連接之2端子串接式電池那樣取得兩者的發電電流之匹配，從而可減少電池設計之限制。 The structure of the light-receiving electrode of this form cannot be ignored The loss due to the high film resistance of the transparent conductive layer (110, 150) of the upper battery 100 is particularly effective. And because it can be taken out independently Since the output of the battery 100 and the output of the lower battery 200 are not required to match the power generation currents of the two-terminal series battery electrically connected in series, the limitation of the battery design can be reduced.
此外，於該形態中，由於上部電池100之輸出 端子位於入射光面側，下部電池200之輸出端子位於背面側，因此於藉由組入幾片電池來製作模組之情況下，將上部電池彼此或下部電池彼此串聯連接，且模組之端子係設為4端子。 In addition, in this form, due to the output of the upper battery 100 The terminal is located on the side of the incident light surface, and the output terminal of the lower battery 200 is located on the back side. Therefore, in the case of forming a module by assembling a plurality of batteries, the upper battery or the lower battery are connected in series to each other, and the terminals of the module are connected. Set to 4 terminals.
再者，也可藉由調整上部電池100之結晶矽層 130的厚度，以使上部電池100及下部電池200之發電電流變得相同。該情況下還能實現2端子化。例如，可串聯連接上部電池及下部電池之輸出而組入模組中，也可於模組之端子箱內串聯連接來自上部電池的輸出及來自下部電池的輸出而設為2端子。 Furthermore, the crystallization layer of the upper battery 100 can also be adjusted. The thickness of 130 is such that the generated currents of the upper battery 100 and the lower battery 200 become the same. In this case, 2-terminalization can also be achieved. For example, the output of the upper battery and the lower battery may be connected in series to be incorporated into the module, or the output from the upper battery and the output from the lower battery may be connected in series in the terminal box of the module to be a two-terminal.
為了設為2端子串接式電池構造，例如，可採 用如下之電極間連接關係。 In order to be a 2-terminal series battery structure, for example, Use the following electrode connection relationship.
第6圖為顯示第5(A)圖及第5(B)圖之圖中的 虛線顯示部分之剖面構造的概要之圖。首先，調整上部電池100之結晶矽130層的厚度，以使上部電池100及下部電池200之最適動作電流大致相等。然後，以於電池之厚度方向上橫切下部電池200之端部的形式，由導電性材料280連接用以取出來自下部電池200之發射極的輸出之梳齒電極260的母線、及電性連接於設在上部電池100之n型非晶矽層側的第2透明導電層150之梳齒電極180的母線。 Figure 6 is a view showing the 5th (A) and 5th (B) The dotted line shows a schematic view of the cross-sectional structure of the portion. First, the thickness of the layer of the crystallization 130 of the upper battery 100 is adjusted so that the optimum operating currents of the upper battery 100 and the lower battery 200 are substantially equal. Then, in the form of crossing the end of the lower battery 200 in the thickness direction of the battery, the bus bar for connecting the comb-shaped electrode 260 for outputting the emitter from the lower battery 200 and the electrical connection are connected by the conductive material 280. The bus bar of the comb-shaped electrode 180 of the second transparent conductive layer 150 provided on the n-type amorphous germanium layer side of the upper battery 100.
該情況下，以成為電池之相同端部邊緣之方 式預先配置欲連接的梳齒電極之母線彼此。亦即，於自上方觀察太陽能電池100時，使第2梳齒狀之受光面電極即第2透明導電層150的匯流排部與第1梳齒狀之背面電極即第1背面電極260之匯流排部於另一端側位於平行之位置。另一方面，第1梳齒狀之受光面電極即第1透明導電層110的匯流排部與第2梳齒狀之背面電極即第2背面電極270之匯流排部係於另一端側位於平行之位置。 In this case, to become the same edge of the battery The bus bars of the comb-shaped electrodes to be connected are pre-configured with each other. In other words, when the solar cell 100 is viewed from above, the confluence of the busbar portion of the second transparent conductive layer 150, which is the second comb-shaped light-receiving surface electrode, and the first back electrode 260, which is the first comb-shaped back electrode. The rows are located in parallel at the other end side. On the other hand, the busbar portion of the first transparent conductive layer 110, which is the first comb-shaped light-receiving surface electrode, and the busbar portion of the second back electrode 270, which is the second comb-shaped back surface electrode, are parallel to each other. The location.
當進行此種之電極間的連接時，以發電電流 引起之電壓下降變得充分小之方式進行。於電池背面之絕緣性膜250為由熱氧化或電漿CVD形成的氧化膜之情況下，若考慮到電池之端面也由此種絕緣性膜250被覆，而且電池之厚度為數百μm之情況，則以使用厚度為數μm以上之Ag糊膏等的導電性糊膏為較佳。若使用此種導電性糊膏，只要以接觸於上述兩母線之方式塗佈於電池之端部且進行燒結，即可使發電電流產生之該連接部位的電壓下降較發電電壓充分地小。 When such an electrode connection is made, the current is generated The resulting voltage drop becomes sufficiently small. In the case where the insulating film 250 on the back surface of the battery is an oxide film formed by thermal oxidation or plasma CVD, it is considered that the end surface of the battery is covered by such an insulating film 250, and the thickness of the battery is several hundred μm. Further, a conductive paste such as an Ag paste having a thickness of several μm or more is preferably used. When such a conductive paste is used, if it is applied to the end portion of the battery so as to be in contact with the above-mentioned two bus bars and sintered, the voltage drop at the connection portion where the generated current is generated can be sufficiently smaller than the generated voltage.
以下，藉由例示對該構造之本發明的太陽能電池之製造方法的概要進行說明。再者，下述實施例中，設第1導電型為p型，且設第2導電型為n型，但也可為相反之關係，亦即設第1導電型為n型，且設第2導電型為p型，這點誠如已作之敘述。此外，「非晶矽材料層」還可不作為非晶矽層，而是作為非結晶SiO層或非結晶SiN層等，這點也誠如已作之敘述。 Hereinafter, an outline of a method of manufacturing a solar cell of the present invention having such a structure will be described. Further, in the following embodiments, the first conductivity type is a p-type and the second conductivity type is an n-type, but the opposite relationship may be employed, that is, the first conductivity type is an n-type, and 2 Conductive type is p-type, as it has been described. Further, the "amorphous germanium material layer" may not be used as an amorphous germanium layer, but as an amorphous SiO layer or an amorphous SiN layer, etc., as will be described.
第7圖為製造本發明之太陽能電池的製程例之流程圖。首先，準備該2片之n型單晶矽基板(10、20)。對矽基板之厚度無特別之限制，一般為200~500μm。第1之n型矽結晶基板10係上部電池製作用者，第2之n型矽結晶基板20係下部電池製作用者。下述之實施例中，第1之n型矽結晶基板10可使用單面鏡面加工者亦無妨，但第2之n型矽結晶基板20係使用雙面鏡面加工者。此外，矽基板之比電阻值為太陽能電池的設計事項，在此採用1Ωcm左右者。 Fig. 7 is a flow chart showing an example of a process for producing the solar cell of the present invention. First, the two n-type single crystal germanium substrates (10, 20) are prepared. There is no particular limitation on the thickness of the tantalum substrate, and it is generally 200 to 500 μm. The first n-type germanium crystal substrate 10 is used for the production of an upper cell, and the second n-type germanium crystal substrate 20 is a lower cell manufacturer. In the following embodiments, the first n-type germanium crystal substrate 10 may be a single-sided mirror-finished substrate. However, the second n-type germanium crystal substrate 20 is a double-sided mirror-finished processor. Further, the specific resistance value of the tantalum substrate is a design matter of the solar cell, and is used here to be about 1 Ωcm.
於第1之n型矽結晶基板10的表面形成n型氫化非晶矽層140(S101)，並且於該n型氫化非晶矽層140上形成由ITO構成之透明導電層150(S102)。 An n-type hydrogenated amorphous germanium layer 140 is formed on the surface of the first n-type germanium crystal substrate 10 (S101), and a transparent conductive layer 150 made of ITO is formed on the n-type hydrogenated amorphous germanium layer 140 (S102).
另一方面，於第2之n型矽結晶基板20的背面，呈條紋狀(或梳子狀)形成n+區域(磷濃度1019~1020cm-3左右)及p+區域(硼濃度1019~1020cm-3左右的p+層)，且將這些設為作為背面電場層(BSF)之第2之n型層240及作為發射極層的p型區域220(S201)。這些n+區域及p+區域係藉由離子植入法、熱擴散法或激光摻雜法等形成。 On the other hand, in the back surface of the second n-type germanium crystal substrate 20, an n + region (phosphorus concentration of about 10 19 to 10 20 cm -3 ) and a p + region (boron concentration of 10) are formed in a stripe shape (or a comb shape). These are p + layers of about 19 to 10 20 cm -3 , and these are referred to as the second n-type layer 240 as the back surface electric field layer (BSF) and the p-type region 220 as the emitter layer (S201). These n + regions and p + regions are formed by ion implantation, thermal diffusion or laser doping.
接著，於第2之n型矽結晶基板20的表面形成作為表面電場層(FSF)之n型層230(磷濃度1019cm-3左右的n+層)(S202)。此FSF層係藉由熱擴散法及離子植入法形成。 Next, an n-type layer 230 (n + layer having a phosphorus concentration of about 10 19 cm -3 ) as a surface electric field layer (FSF) is formed on the surface of the second n-type germanium crystal substrate 20 (S202). This FSF layer is formed by a thermal diffusion method and an ion implantation method.
接著，於作為表面電場層(FSF)之n型層230的上面形成絕緣性透明保護層160(S203)。該保護膜係熱氧化膜、CVD之沉積氧化膜、電漿CVD或熱絲CVD形成 之氫化非結晶SiO膜等。 Next, an insulating transparent protective layer 160 is formed on the upper surface of the n-type layer 230 as a surface electric field layer (FSF) (S203). The protective film is formed by a thermal oxide film, a deposited oxide film of CVD, plasma CVD or hot filament CVD. A hydrogenated amorphous SiO film or the like.
接著，對第1之n型矽結晶基板10的表面(即， 由ITO構成之透明導電層150)及第2之n型矽結晶基板20的表面(即，絕緣性透明保護層160)之至少一者實施表面活化處理(S301)。此表面活化處理例如為電漿處理或臭氧處理。 Next, the surface of the first n-type germanium crystal substrate 10 (ie, At least one of the transparent conductive layer 150 made of ITO and the surface of the second n-type germanium crystal substrate 20 (that is, the insulating transparent protective layer 160) is subjected to a surface activation treatment (S301). This surface activation treatment is, for example, a plasma treatment or an ozone treatment.
接續該表面活化處理，應用已公知之半導體 基板間的貼合技術，使第1之n型矽結晶基板的表面(即，由ITO構成之透明導電層150)與第2之n型矽結晶基板的表面(即，由矽氧化物或鋁氧化物等構成之絕緣性透明保護層160)彼此貼合(S302)。再者，該貼合係於400℃以下的溫度下進行。這是為了抑制上部電池之因氫自氫化非晶矽層的脫離而引起之膜質降低、及朝上部電池之結晶矽層的缺陷導入，不使串接化時之太陽能電池特性產生劣化。 Continuing the surface activation treatment, applying a well-known semiconductor The bonding technique between the substrates is such that the surface of the first n-type germanium crystal substrate (that is, the transparent conductive layer 150 made of ITO) and the surface of the second n-type germanium crystal substrate (that is, the tantalum oxide or aluminum) The insulating transparent protective layer 160 made of an oxide or the like is bonded to each other (S302). Further, the bonding is carried out at a temperature of 400 ° C or lower. This is to suppress the deterioration of the film quality due to the detachment of hydrogen from the hydrogenated amorphous germanium layer in the upper battery, and to introduce defects into the crystalline germanium layer of the upper battery, and to deteriorate the solar cell characteristics when the tandem is formed.
再者，為了提高該貼合之強度的目的，也可 於上部電池側之由ITO構成的透明導電層150上面再預先沉積氫化非結晶SiO膜。 Furthermore, in order to increase the strength of the bonding, it is also possible A hydrogenated amorphous SiO film was previously deposited on the upper surface of the transparent conductive layer 150 made of ITO on the upper battery side.
於該貼合之後，除去第1之n型矽結晶基板的 背面側之結晶部分，薄化至厚度30μm以下(一般為10μm以下)，形成上部電池之n型結晶矽層130(S303)。 After the bonding, the first n-type germanium crystal substrate is removed. The crystal portion on the back side is thinned to a thickness of 30 μm or less (generally 10 μm or less) to form an n-type crystalline germanium layer 130 of the upper battery (S303).
該薄化步驟除機械研磨第1之n型矽結晶基板 的背面側以外，也可藉由所謂「智能切割法」等之手法進行。 The thinning step except mechanically grinding the first n-type germanium crystal substrate In addition to the back side, it can also be carried out by a method such as "smart cutting method".
於智能切割法之情況下，於步驟S101之前， 在第1之n型矽結晶基板的表面區域植入既定配量之氫而預先形成氫離子植入層，於步驟S303中，藉由對該氫離子植入層施加機械或熱衝擊以使n型結晶矽層自第1之n型矽結晶基板剝離而作為上部電池的n型結晶矽層。 In the case of the smart cutting method, before step S101, Depositing a predetermined amount of hydrogen in a surface region of the first n-type germanium crystal substrate to form a hydrogen ion implantation layer in advance, and applying mechanical or thermal shock to the hydrogen ion implantation layer to make n in step S303 The type of crystalline ruthenium layer is peeled off from the n-type ruthenium crystal substrate of the first type and serves as an n-type crystallization layer of the upper battery.
於此種薄化步驟之後，根據需要進行研磨損傷層之蝕刻去除，將結晶矽層之厚度調整至希望的值。 After such a thinning step, the etching damage of the polishing damage layer is performed as needed to adjust the thickness of the crystalline germanium layer to a desired value.
此後，於光入射面側依序沉積氫化i型非晶矽層、氫化p型非晶矽層120、由ITO構成之透明導電層110(S304~S306)。 Thereafter, a hydrogenated i-type amorphous germanium layer, a hydrogenated p-type amorphous germanium layer 120, and a transparent conductive layer 110 made of ITO are sequentially deposited on the light incident surface side (S304 to S306).
接著，如第4圖所示，藉由光微影技術使第2透明導電層150之一部分露出(S307)，形成受光面電極170、180(S308)。藉此，第1受光面電極170電性連接於透明導電層110，第2受光面電極180電性連接於第2透明導電層150，進而完成上部電池。 Next, as shown in FIG. 4, one of the second transparent conductive layers 150 is partially exposed by photolithography (S307), and the light-receiving surface electrodes 170 and 180 are formed (S308). Thereby, the first light-receiving surface electrode 170 is electrically connected to the transparent conductive layer 110, and the second light-receiving surface electrode 180 is electrically connected to the second transparent conductive layer 150, thereby completing the upper battery.
最後，於第2之n型矽結晶基板的背面側形成接觸孔，形成如第4圖所示之背面電極260、270(S309)，完成上部電池並完成太陽能電池。 Finally, a contact hole is formed on the back side of the second n-type germanium crystal substrate, and the back electrodes 260 and 270 as shown in Fig. 4 are formed (S309), and the upper battery is completed to complete the solar cell.
如已說明者，藉由像本發明之太陽能電池那樣將上部電池的結晶矽層之厚度減薄，可提高開路電壓。另一方面，若上部電池之結晶矽層的厚度變薄，則上部電池之光吸收長度(光路長)變短，其結果，短路電流密度變小，輸出功率與結晶矽層厚之電池比較而下降。然而，由於本發明之太陽能電池為串接式構造，因此在上部電池不能吸收之光可由下部電池吸收，從而能提供發電。其結果，與以下部電池單體進行發電之情況比較 ，可改善相當於能以高電壓能擷取上部電池的發電電流的部分之轉換效率。 As described above, the open circuit voltage can be increased by thinning the thickness of the crystalline germanium layer of the upper battery like the solar cell of the present invention. On the other hand, when the thickness of the crystallization layer of the upper battery is reduced, the light absorption length (optical path length) of the upper battery is shortened, and as a result, the short-circuit current density is small, and the output is compared with the battery having a thick crystallization layer. decline. However, since the solar cell of the present invention has a tandem configuration, light that cannot be absorbed by the upper battery can be absorbed by the lower battery, thereby providing power generation. As a result, compared with the case where the following battery cells are used for power generation It is possible to improve the conversion efficiency equivalent to the portion of the power generation current that can capture the upper battery at a high voltage.
如此，本發明之太陽能電池係採用較先前之 構成明顯將上部電池的第2導電型結晶矽層減薄的構造。其結果，與將第2導電型結晶矽層設為100μm之構成比較，由於上部電池之開路電壓增高0.1V以上，可以高電壓擷取電流，因此可提高光電轉換效率。 Thus, the solar cell of the present invention adopts the previous one. A structure in which the second conductivity type crystalline ruthenium layer of the upper battery is significantly thinned is formed. As a result, compared with the configuration in which the second conductivity type crystalline ruthenium layer is set to 100 μm, since the open circuit voltage of the upper battery is increased by 0.1 V or more, the current can be drawn at a high voltage, so that the photoelectric conversion efficiency can be improved.
此外，由於可自上部電池及下部電池分別獨 立地取出輸出，因此不需要取得串聯連接型串接式電池所需要之發電電流的匹配。 In addition, since it can be separately from the upper battery and the lower battery The output is taken out at the stand-up, so there is no need to match the power generation current required for the series-connected series-connected battery.
並且，由於本發明之太陽能電池的製造方法 係應用所謂「貼合」技術，且於400℃以下進行上部電池與下部電池的「貼合」，因此無氫自氫化非晶矽層脫離而使膜質降低之情況，也不會對結晶矽層產生新的缺陷，因此，不會產生伴隨串接化之異質接面電池的劣化。 Moreover, the method of manufacturing the solar cell of the present invention The so-called "bonding" technology is applied, and the "bonding" between the upper battery and the lower battery is performed at 400 ° C or lower. Therefore, no hydrogen is removed from the hydrogenated amorphous germanium layer to lower the film quality, and the crystalline layer is not formed. New defects are generated, and therefore, deterioration of the heterojunction battery accompanying the series connection does not occur.
至此，對本發明之太陽能電池為串接式太陽 能電池的情況進行了說明。然而，本發明之太陽能電池不一定要為串接式，也可為不具備下部電池，於基體上設置有該上部電池之太陽能電池。亦即，上述「下部電池」不一定要作為太陽能電池發揮作用。 So far, the solar cell of the present invention is a tandem solar The case of the battery can be explained. However, the solar cell of the present invention does not have to be a tandem type, and may be a solar cell in which the upper battery is not provided on the substrate. That is, the above "lower battery" does not necessarily have to function as a solar cell.
於不將該「下部電池」作為太陽能電池而為 所謂基體之情況，本發明之太陽能電池，其特徵在於：上部電池設於基體之主面上，該上部電池係具有自光入射側起依序具有透明導電層、第1導電型非晶矽材料層、與該第1導電型相反之第2導電型結晶矽層、第2導電型非 晶矽層的層積構造，且於該上部電池之表面設置有受光面電極，於該基體設置有背面電極，該上部電池之第2導電型結晶矽層的厚度為30μm以下。 I will not use the "lower battery" as a solar cell. In the case of a substrate, the solar cell of the present invention is characterized in that the upper battery is provided on the main surface of the substrate, and the upper battery has a transparent conductive layer and a first conductive amorphous material from the light incident side. a layer, a second conductivity type crystalline layer opposite to the first conductivity type, and a second conductivity type The laminated structure of the wafer layer is provided with a light-receiving surface electrode on the surface of the upper battery, and a back surface electrode is provided on the substrate, and the thickness of the second-conductivity-type crystalline germanium layer of the upper battery is 30 μm or less.
作為該情況下之基體，例如可使用單晶矽。 此外，於基體由單晶矽構成之情況，也可為於上部電池與基體之間具有由氧化銦錫(ITO)構成的層之形態。 As the substrate in this case, for example, single crystal germanium can be used. Further, in the case where the substrate is composed of single crystal germanium, it may be in the form of a layer composed of indium tin oxide (ITO) between the upper battery and the substrate.
並且，該基體也可為於表面區域形成有施體 濃度較塊狀體高之第2導電型層，且於該第2導電型層上設置有絕緣性透明保護層的第2之第2導電型矽結晶基板的形態。 Moreover, the substrate may also have a donor body formed on the surface region. The second conductivity type layer of the second conductivity type layer having a higher concentration than the bulk material, and the second second conductivity type germanium crystal substrate having the insulating transparent protective layer on the second conductivity type layer.
該情況下，於太陽能電池之製造時，也可於 該步驟S303(貼合之後，除去第1之n型矽結晶基板的背面側之結晶部分，減薄至厚度30μm以下，形成上部電池之n型結晶矽層130的步驟)之後，具備於第2導電型結晶矽層之上方形成與第2導電型相反之第1導電型非晶矽材料層的步驟。 In this case, at the time of manufacture of the solar cell, In the step S303 (after the bonding, the crystal portion on the back side of the first n-type germanium crystal substrate is removed, and the thickness is reduced to 30 μm or less to form the n-type crystalline germanium layer 130 of the upper cell), and then the second portion is provided. A step of forming a first conductivity type amorphous germanium material layer opposite to the second conductivity type is formed above the conductive crystal layer.
此外，也可將上部電池之構造作為陣列排列 有奈米線及奈米牆的形態者。藉由設為此種奈米構造者，可提高量子效應，提高太陽能電池之光電轉換效率。 In addition, the configuration of the upper battery can also be arranged as an array. There are nanowires and the shape of the nano wall. By setting it as such a nanostructure, the quantum effect can be improved and the photoelectric conversion efficiency of a solar cell can be improved.
具備此種構造之上部電池的太陽能電池，為 具有以下之構造的太陽能電池，亦即，具有該上部電池具備之透明導電層、第1導電型非晶矽材料層、第2導電型結晶矽層、第2導電型非晶矽層之層積構造，於自上方觀察該太陽能電池時，具有以既定間隔2維排列之複數條奈米線或壁面對齊於既定方向且被劃分為以既定間隔2 維排列的複數個壁狀之奈米牆的陣列構造，該奈米線之直徑或該奈米牆的厚度，係於該第2導電型結晶矽層的部位上為10nm以下。 A solar cell having such a top battery is constructed A solar cell having a structure in which a transparent conductive layer provided in the upper battery, a first conductive type amorphous germanium material layer, a second conductive type crystalline germanium layer, and a second conductive type amorphous germanium layer are laminated The structure is such that when the solar cell is viewed from above, a plurality of nanowires or walls arranged in two dimensions at a predetermined interval are aligned in a predetermined direction and are divided into predetermined intervals 2 The array structure of a plurality of wall-shaped nanowalls arranged in a dimension, the diameter of the nanowire or the thickness of the nanowall is 10 nm or less at a portion of the second conductivity type crystalline layer.
於採用此形態之情況下，以相互鄰接之該奈米線或該奈米牆，係藉由絕緣性物質隔離為較佳。 In the case of adopting such a form, it is preferable that the nanowires or the nanowalls adjacent to each other are separated by an insulating material.
此外，於作為奈米構造之上部電池時，於在第2導電型結晶矽層之上方形成與第2導電型相反的第1導電型非晶矽材料層的步驟中，較佳為具備於第1導電型非晶矽材料層的形成之前，將第2導電型結晶矽層劃分為奈米線或奈米牆的次步驟，其中該奈米線係以既定間隔2維排列之複數條奈米線，且是於該第2導電型結晶矽層的部位上直徑為10nm以下者，該奈米牆係壁面對齊於既定方向且以既定間隔2維排列之複數個壁狀的奈米牆且是於該第2導電型結晶矽層的部位上厚度為10nm以下者。 Further, in the case of forming the upper battery of the nanostructure, the step of forming the first conductivity type amorphous germanium material layer opposite to the second conductivity type above the second conductivity type crystalline germanium layer is preferably provided in the first step. Before the formation of the conductive amorphous germanium material layer, the second conductive type crystalline germanium layer is divided into a sub-step of a nanowire or a nanowall, wherein the nanowire is a plurality of nanometers arranged at two intervals at a predetermined interval. a line having a diameter of 10 nm or less at a portion of the second conductivity type crystal ruthenium layer, wherein the wall surface of the nano wall system is aligned with a predetermined number of wall-shaped nanowalls arranged at two intervals at a predetermined interval and is The thickness of the portion of the second conductivity type crystalline ruthenium layer is 10 nm or less.
第8圖為用於說明上部電池為被劃分為以既定間隔2維排列之複數個壁狀的奈米牆之陣列構造的情況之串接式太陽能電池的構成之立體示意圖。 Fig. 8 is a perspective view showing the configuration of a tandem solar cell in the case where the upper battery is divided into an array structure of a plurality of wall-shaped nanowalls arranged at two intervals at a predetermined interval.
已知矽的帶隙於塊狀體中為1.1eV左右，但於作為奈米級之牆及線的情況下，若其大小較10nm小則會變大。並且，藉由改變奈米牆及奈米線之尺寸(寬度)，可藉由量子封閉效應進行帶隙控制。亦即，藉由將上部電池設為使此種大小的奈米牆或奈米線2維排列之構造者，積極地利用量子封閉效應，能提高作為太陽能電池之性能。 It is known that the band gap of ruthenium is about 1.1 eV in the bulk, but in the case of a wall and a wire of a nanometer, if the size is smaller than 10 nm, it becomes large. Moreover, by changing the size (width) of the nano wall and the nanowire, the band gap control can be performed by the quantum confinement effect. In other words, by using the upper battery as a structure in which nano-walls or nanowires of such a size are arranged in two dimensions, the quantum sealing effect is actively utilized, and the performance as a solar cell can be improved.
假定為奈米牆，理論上若將牆的厚度縮小至 2nm，則實效之帶隙約為1.6eV，較塊狀體之矽的帶隙(約1.1eV)擴大了45%左右之帶隙，從而能期待高效率化。 Assuming a nano wall, theoretically reduce the thickness of the wall to At 2 nm, the effective band gap is about 1.6 eV, which is wider than the band gap (about 1.1 eV) of the bulk of the block, and the band gap is increased by about 45%, so that high efficiency can be expected.
第9圖為觀察具有被劃分為以既定間隔2維排 列之複數個壁狀的矽之奈米牆的陣列構造之上部電池的一部分之穿透式電子顯微鏡圖像。奈米牆之尺寸為10nm以下，於該圖所示之例子中約為2nm。此外，於奈米牆相互間埋入絕緣性物質(SiO2或Al2O3)。 Fig. 9 is a view showing a transmission electron microscope image of a part of an upper cell of an array structure having a plurality of wall-shaped nano-walls divided into a plurality of walls arranged at a predetermined interval. The size of the nano wall is 10 nm or less, which is about 2 nm in the example shown in the figure. Further, an insulating substance (SiO 2 or Al 2 O 3 ) is buried between the nano walls.
第10圖為顯示被劃分為奈米牆之陣列構造 (A)的反射率、及於奈米牆相互間埋入絕緣性物質即SiO2之陣列構造(B)的反射率的波長依賴性之圖。 Fig. 10 is a graph showing the wavelength dependence of the reflectance of the array structure (A) divided into nanowalls and the reflectivity of the array structure (B) of SiO 2 in which insulating materials are embedded between the nanowalls. Figure.
由該圖可知，藉由於奈米牆相互間埋入絕緣 性物質，將反射率抑制地較低，可提高太陽光之利用效率。 It can be seen from the figure that the insulation is buried between the nano walls. Sexual substances, which have a low reflectance, can improve the utilization efficiency of sunlight.
此種奈米牆例如可藉由下述之製程進行製作 。首先，藉由使用浸液光微影之圖案處理形成數十nm寬度之牆。藉此，例如能形成寬度75nm左右，高度1μm左右的牆。再者，若設作為基材之矽的主面為(1,1,0)面，例如(1,-1,1)面直接移至(1,1,0)面，因而可將壁面為(1,-1,1)面之牆垂直地形成於主面。接著，藉由反復地進行氧化處理及蝕刻處理，形成寬度為數nm之奈米牆。 Such a nano wall can be produced, for example, by the following process . First, a wall having a width of several tens of nm is formed by patterning using a immersion liquid lithography. Thereby, for example, a wall having a width of about 75 nm and a height of about 1 μm can be formed. Further, if the main surface of the crucible as the substrate is a (1, 1, 0) plane, for example, the (1, -1, 1) plane is directly moved to the (1, 1, 0) plane, so that the wall surface can be The wall of the (1, -1, 1) surface is formed vertically on the main surface. Next, a nanowall having a width of several nm is formed by repeatedly performing an oxidation treatment and an etching treatment.
再者，當然不用再作解釋，即使取代上述牆 ，而設為被劃分為以既定之間隔2維排列的複數條奈米線的陣列構造，且將奈米線之直徑設為10nm以下的尺寸者，也可獲得同樣之量子效應。 Furthermore, of course, no need to explain, even if the above wall is replaced In addition, the same quantum effect can be obtained by an array structure in which a plurality of nanowires are arranged in two dimensions at a predetermined interval, and the diameter of the nanowire is set to be 10 nm or less.
根據本發明，提供一種將上部電池之結晶矽層減薄，抑制結晶矽層內之奧杰復合，且於製造步驟中也不會使薄結晶矽層破損，且光電轉換效率高的矽太陽能電池及其製造方法。 According to the present invention, there is provided a tantalum solar cell in which the crystal layer of the upper battery is thinned, the Auger composite in the crystalline germanium layer is suppressed, and the thin crystalline germanium layer is not damaged in the manufacturing step, and the photoelectric conversion efficiency is high. And its manufacturing method.
10‧‧‧第1之n型矽結晶基板 10‧‧‧1st n-type crystalline substrate
20‧‧‧第2之n型矽結晶基板 20‧‧‧2nd n-type crystalline substrate
100‧‧‧上部電池 100‧‧‧Upper battery
110‧‧‧透明導電層 110‧‧‧Transparent conductive layer
120‧‧‧p型非晶矽層 120‧‧‧p-type amorphous layer
130‧‧‧n型結晶矽層 130‧‧‧n type crystalline layer
140‧‧‧n型非晶矽層 140‧‧‧n type amorphous layer
150‧‧‧第2透明導電層 150‧‧‧2nd transparent conductive layer
160‧‧‧絕緣性透明保護層 160‧‧‧Insulating transparent protective layer
200‧‧‧下部電池 200‧‧‧lower battery
210‧‧‧n型區域 210‧‧‧n type area
220‧‧‧作為發射極層之p型區域 220‧‧‧ p-type region as the emitter layer
230‧‧‧施體濃度高之n型層 230‧‧‧N-type layer with high body concentration
240‧‧‧施體濃度高之第2之n型層 240‧‧‧The second n-type layer with high body concentration
250‧‧‧絕緣性膜 250‧‧‧Insulating film
260‧‧‧第1背面電極 260‧‧‧1st back electrode
270‧‧‧第2背面電極 270‧‧‧2nd back electrode
300‧‧‧太陽能電池 300‧‧‧ solar cells
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