CN102369580A - 太阳能电池电极 - Google Patents
太阳能电池电极 Download PDFInfo
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- CN102369580A CN102369580A CN2010800158918A CN201080015891A CN102369580A CN 102369580 A CN102369580 A CN 102369580A CN 2010800158918 A CN2010800158918 A CN 2010800158918A CN 201080015891 A CN201080015891 A CN 201080015891A CN 102369580 A CN102369580 A CN 102369580A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- 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
- H01L31/02—Details
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- H—ELECTRICITY
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- 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
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
- H01L31/022441—Electrode arrangements specially adapted for back-contact solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- H01L31/0248—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 characterised by their semiconductor bodies
- H01L31/0352—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035272—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 characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions characterised by at least one potential jump barrier or surface barrier
- H01L31/03529—Shape of the potential jump barrier or surface barrier
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
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- 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 potential barriers
- 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 potential barriers 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 potential barriers 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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- 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
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
- H01L31/1804—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof comprising only elements of Group IV of the Periodic Table
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Abstract
本发明涉及用于太阳能电池中的电极以及用于制备此类电极的导电浆料,所述电极在N层和P层处显示具有良好的导电性。
Description
发明背景
发明领域
本发明涉及用于太阳能电池的电极。
发明背景
由于用于硅太阳能电池的电极需要具有低电阻以有利于提高效率。问题是具有较低电阻的银在与硅基板接触时获得高接触电阻。为了解决该问题,JP2006-93433公开了一种通过使用导电浆料在p型导电层上形成的电极,所述浆料包含银粉、有机载体、玻璃料和至少一种选自硼粉、无机硼化合物和有机硼化合物的物质。
JP2003-152200公开了一种用于太阳能电池电极的导电浆料,所述浆料包含银和TiO2。JPS59-11687公开了一种用于太阳能电池电极的导电浆料,所述浆料包含银和钛。JP2002-141520公开了一种太阳能电池的电极,所述电极包含钛、钴或锌的无机化合物。然而,即使这些电极能够降低由太阳能电池半导体N和P层构成的半导体中N层的接触电阻,但P层的电阻天然地居高不下。US 2008/0230119公开了一种包含银和钯的电极,该电极能够为n层和p层带来低接触电阻。然而,当导电浆料在高温下烧结时,电阻最终增大。根据以上问题,需要提供用于太阳能电池的电极,该电极在N层和P层中均提供良好的导电性,并且不会限制用于烧结该电极的烧结温度。
发明概述
本发明涉及通过烧结导电浆料而形成的太阳能电池电极,所述导电浆料包含(a)导电粉末,该导电粉末包含银粒子、钛粒子、或TiH2粒子,以及(i)选自锆、铬、钴、钼、锝、钌、铑、钯、钨、铼、锇、铱和铂的金属粒子,(ii)包含所述金属的合金粒子,或(iii)承载所述金属粒子的载体粒子;(b)玻璃料;以及(c)树脂基料。优选地,所述导电粉末包含30-98重量%的银粒子、1-70重量%的钛粒子或TiH2粒子,以及1-10重量%的(i)选自锆、铬、钴、钼、锝、钌、铑、钯、钨、铼、锇、铱和铂的金属粒子,(ii)包含所述金属的合金粒子,或(iii)承载所述金属粒子的载体粒子。
在本发明的另一方面,用于制备太阳能电池电极的方法包括以下步骤:在硅基板上施加用于太阳能电池电极的导电浆料,该导电浆料包含(a)导电粉末,该导电粉末包含银粒子、钛粒子、或TiH2粒子,以及(i)选自锆、铬、钴、钼、锝、钌、铑、钯、钨、铼、锇、铱和铂的金属粒子,(ii)包含所述金属的合金粒子,或(iii)承载所述金属粒子的载体粒子,(b)玻璃料,以及(c)树脂基料;烧结已施加到硅基板上的导电浆料。优选地,在450至900℃下对浆料进行烧结。
在本发明的另一方面,用于制备电极的方法包括以下步骤:在硅基板的n层和p层上均施加并烧结用于太阳能电池电极的导电浆料,所述导电浆料包含(a)导电粉末,该导电粉末包含银粒子、钛粒子、或TiH2粒子,以及(i)选自锆、铬、钴、钼、锝、钌、铑、钯、钨、铼、锇、铱和铂的金属粒子,(ii)包含所述金属的合金粒子,或(iii)承载所述金属粒子的载体粒子,(b)玻璃料,以及(c)树脂基料。
本发明的电极可用于在太阳能电池半导体层即P层和N层上获得低接触电阻。还防止了电极电阻在高温下烧结时增大。
附图简述
图1A为受本发明权利要求书保护的太阳能电池的一部分的横截面示意图,图1B为示出在与受本发明权利要求书保护的太阳能电池一部分的受光面相对面上的电极图案的顶视图;
图2A至2E为用于说明太阳能电池的生产过程的图片;
图3A至3E为用于说明太阳能电池的生产过程的图片;
图4A至4D为用于说明太阳能电池的生产过程的图片;
图5A至5C为用于说明太阳能电池的生产过程的图片;而
图6A至6E为用于说明P型基板太阳能电池的生产过程的图片。
图7A至7E为用于说明N型基板太阳能电池的生产过程的图片。
图8A为用于测定使用本发明的导电浆料在硅基板上制成的电极的接触电阻的样本形状的图片,而图8B为用于说明在电极之间测得的电阻值的图片。
发明详述
本发明的第一实施方案涉及硅太阳能电池的电极。本发明的电极在以下段落中有详细说明。
1.导电粉末
银粒子:
将银(Ag)粒子用作导电金属。银粒子可呈薄片形状、球体形状,或它们可为无定形的。虽然从技术效果的角度来讲,对银粒子的粒径没有特定的限制,但如果被用作普通导电浆料,则粒径对银的烧结特性有影响,例如,具有大粒径的银粒子比具有小粒径的银粒子烧结起来速率更慢。因此,粒径(d50,由激光散射型粒度分布测量设备测定)优选地在0.1-20.0μm的范围内,更优选地在2.0至10.0μm的范围内。实际所用的银粒子的粒径根据烧结温度分布图确定。此外,银粒子还有必要具有适合于用于施加导电浆料的方法(例如,丝网印刷)的粒径。在本发明中,可将具有不同粒径的两种或更多种类型的银粒子用作混合物。
通常说来,银优选地具有大于98%的高纯度。然而,根据电极图案的电气要求可使用纯度较低的物质。
虽然对所提供的银含量没有特定的限制,但其应为可实现本发明的目的的量,如果是银粒子,银含量优选为导电粉末总重量的30-98重量%,更优选为50-90重量%。在本发明中,可将具有不同粒径和/或不同形状的两种或更多种类型的银粒子用作混合物。
钛粒子:
本发明的太阳能电池电极包含Ti(钛)粒子或TiH2(氢化钛)粒子。钛粒子或TiH2粒子可呈薄片形状、球体形状或无定形形式。虽然从技术效果的角度来讲,对钛或TiH2粒子的粒径没有特定的限制,但如果被用作普通导电浆料,则钛粒子或TiH2粒子的平均粒度(D50,由激光散射型粒度分布测量设备测定)优选为0.1-100μm,更优选为1-60μm,并且甚至更优选为3-40μm。0.1μm或更小的粒度可导致钛粒子氧化,因此通过添加氧化钛可防止达到足够的氧化效应。虽然对本发明所用钛粒子的纯度没有特定的限制,但该纯度优选为至少99%。钛粒子或TiH2粒子的含量相对于导电粉末的总重量优选为1.0-70.0重量%。为获得较低的接触电阻,粒子的最小含量更优选为5重量%,甚至更优选为15重量%。当同时使用钛粒子和TiH2粒子时,钛粒子和TiH2粒子的总含量相对于导电粉末的总重量优选为1.0-70.0重量%。为获得较低的接触电阻,粒子的最小含量更优选为5重量%,甚至更优选为15重量%。小于1.0重量%的含量可导致电极与晶片的接触电阻降低不充分。大于70.0重量%的含量可导致电极本身具有较高的电阻。不管钛粒子或TiH2粒子是单独使用或是组合使用,均可获得良好的电性能,但由于TiH2粒子具有的抗氧化性优于钛粒子,故优选地使用TiH2粒子。在本发明中,可将具有不同粒径的两种或更多种类型的钛或TiH2粒子用作混合物。
其他金属粒子:
在本发明中,将除所述银、钛、TiH2粒子外的其他金属粒子添加到银和钛粒子中作为导电粉末。将金属粒子限定为属于元素周期表第6至11族的3d或4d过渡金属,也就是说,添加了选自Zr(锆)、Cr(铬)、Co(钴)、Mo(钼)、Tc(锝)、Ru(钌)、Rh(铑)、Pd(钯)、W(钨)、Re(铼)、Os(锇)、Ir(铱)和Pt(铂)的金属粒子。金属粒子的组优选地包括锆、钴、钼、钌、铑、钯、钨和铂,更优选地包括钌、钯和铂,所述金属粒子的组在烧结时可以与晶片上存在的硅(硅化物)形成化合物。以导电粉末的形式加入这些金属粒子可将接触电阻始终保持在较低水平而无需调节烧结温度,即使是在p层和n层上均施加导电材料时。
在本发明中,也可优选地使用包含上述金属粒子的合金粒子或承载有上述金属粒子的粒子。包含金属(在本发明的描述中也称为添加的粒子)的合金的实例包括银/钯合金、钯/金合金、钯/钌合金、钯/铂合金、钛/钼合金、钛/镍合金、铝/钼合金、镍/钼合金、铁/钴合金、银/钨合金和铜/钨合金。
金属粒子可呈薄片形状、球体形状或无定形形式。在被用作普通导电浆料的情形中,虽然从技术效果的角度来讲,对添加的粒子的粒径没有特定的限制,但粒径对银的烧结特性有影响。例如,具有大直径的其他金属粒子比具有小粒径的银粒子烧结起来速率更慢。因此,虽然粒径(D50,由激光散射型粒度分布测量设备测定)优选地在0.1-10.0μm的范围内,但是实际所用的添加的粒子的粒径根据烧结温度分布图确定。此外,添加的粒子还有必要具有适合于用于施加导电浆料的方法(例如,丝网印刷)的粒径。
在本发明中,还可优选地使用由任何类型的导电粒子承载的上述其他金属粒子。由于小直径的金属粒子具有强内聚力,因此金属粒子的量可通过由具有相对大直径的粒子来承载而减小。例如,廉价的碳粒子或铝粒子(Al2O3)可用作承载其他金属的粒子。更具体地讲,用于本发明的碳粒子为如下的碳:其由在惰性气氛中经过热处理的有机前体制成,例如,由凯琴黑(Ketchen black)、炭黑、活性炭、焦炭、石墨制成。碳粒子的粒径(D50)优选地在1.0-10.0μm的范围内。由碳粒子承载的金属粒子的粒径(D50)优选地在0.01-0.2μm的范围内。按碳粒子的总重量计,金属粒子的含量优选地在1-10重量%的范围内。
按导电粉末的总重量计,金属粒子的量在1至5重量%的范围内。如果添加的粒子的量过低,则不能获得效果。此外,如果添加的粒子的量过高,则导体电阻会增大,可烧结性降低并且成本会升高。
如上所述,理想的金属粒子为钌、钯和铂,但这些金属都很昂贵。通常主要用作导电粉末的银粉也很昂贵。由于添加了比较便宜的钛粒子或TiH2粒子来控制此类昂贵的银粉和金属粒子的含量,因此本发明可降低电极材料的成本。
2.玻璃料
导电浆料优选地包含呈玻璃料形式的无机基料。由于在本发明中玻璃料的化学组成并不重要,因此可使用任何玻璃料,前提条件是其应为电子材料的导电浆料中所用的玻璃料。例如,优选使用硼硅酸铅玻璃。从软化点和玻璃粘附性范围的角度来讲,在本发明中,硼硅酸铅玻璃为优异的材料。此外,也可使用无铅玻璃,诸如硅酸铋无铅玻璃。玻璃料具有350-600℃的软化点。
虽然对所提供的呈玻璃料形式的无机基料的含量没有具体限制,但其应为可实现本发明的目的的量。按浆料的重量计,其优选为0.5-20.0重量%,更优选为1.0-15.0重量%。如果无机基料的量低于0.5重量%,则粘合强度可能会不够。如果无机基料的量超过15.0重量%,则可能由于浮置玻璃等原因而在后续的焊接步骤中发生问题。此外,作为导体的电阻值也会增大。
3.树脂基料
用以制造本发明的电极的导电浆料包含树脂基料。在本发明中,可使用任意的树脂基料。作为一种有机树脂,本文提及了(例如)环氧树脂、聚酯树脂,乙烯-乙酸乙烯酯共聚物,以及改性纤维素,例如聚氯乙烯-乙酸酯共聚物、酚醛树脂、丙烯酸类树脂、乙基纤维素、硝化纤维。在本发明中,优选使用具有良好溶剂溶解度的乙基纤维素。按浆料的重量计,树脂基料的含量优选为10-50重量%。
4.溶剂
在本发明中,必要时可将溶剂附加地用作粘度调节剂。可使用任意溶剂。溶剂的实例包括芳香族溶剂、酮、酯、醚、乙二醇类、乙二醇醚和乙二醇酯。如果采用丝网印刷,则优选使用高沸点溶剂,例如乙基卡必醇醋酸酯、丁基溶纤剂醋酸酯、环己酮、苄醇、萜品醇。
5.添加剂
可将或可不将增稠剂和/或稳定剂和/或其他典型的添加剂添加到用以制造本发明的电极的导电浆料中。可添加的其他典型的添加剂包括分散剂和粘度调节剂。根据最终所需的导电浆料的特性确定添加剂的量。添加剂的量可适宜地由本领域的普通技术人员来确定。此外,也可添加多种类型的添加剂。如下所述,本发明的导电浆料具有在预定范围内的粘度。必要时可添加粘度调节剂以向导电浆料赋予合适的粘度。虽然添加的粘度调节剂的量可根据最终的导电浆料的粘度而有变化,但其可适宜地由本领域的普通技术人员来确定。
用导电浆料制造电极:
下文提供了使用电极浆料制造电极的说明。可通过如下方式生产用于制造本发明的电极的导电浆料:用辊压混碾机或旋转式搅拌机等来混合上述组分中的每一种。虽然本发明的导电浆料优选通过丝网印刷来印刷到太阳能电池的硅晶片上,但在用此类印刷方法进行印刷的情形中,浆料优选地具有预定的粘度范围。在使用14号锭子和Brookfield HBT粘度计的情形下,使用效用杯在10rpm和25℃下测量,导电浆料的粘度优选为50至350Pa.S。虽然所添加的粘度调节剂的量根据最终的导电浆料的粘度而变化,但它可适宜地由本领域的普通技术人员来确定。将丝网印刷的浆料在大约150℃下干燥3至10分钟。将干燥的浆料在450至900℃、优选在500℃至800℃下烧结10至60秒。在低于900℃的温度下进行烧结提供了如下优点:减小对P-N结的损伤;减小因热损伤而发生破坏的可能性;并降低成本。
背接触式PV的制造:
在一个实施方案中,本发明的电极可用于在背面具有N层和P层的背接触式太阳能电池。下文提供了背接触式太阳能电池的说明,以及如图1所示的作为本发明实例的背接触式太阳能电池电极的生产过程的说明,同时还提供了制造太阳能电池的实例的说明。
图1A为背接触式太阳能电池的一部分的横截面图,而图1B为示出受光面相对面上的电极图案的一部分的顶视图。背接触式太阳能电池100由受光部分102、载流子生成部分104和电极部分106构成。受光部分102具有纹理化结构,并且其表面覆盖有减反射膜108。减反射膜108是由例如二氧化钛(TiO2)和二氧化硅(SiO2)构成的薄膜。因为具有纹理化结构的受光部分102被这种减反射膜108覆盖,所以更多的入射光进入载流子生成部分104,从而可提高太阳能电池100的转换效率。
载流子生成部分104由半导体110构成。当来自受光部分102的光(尤其是能量等于或大于半导体110带隙能的光)进入该半导体110时,价带电子被激发到导带,在导带中形成自由电子,并在价带中形成自由空穴。这些自由电子和自由空穴被称为载流子。如果这些载流子先于在载流子生成部分104中重组时通过扩散到达电极部分106,则可从电极部分106获得电流。因此,为提高太阳能电池100的转换效率,优选使用削弱载流子重组(即,具有较长的载流子寿命)的半导体。为此,载流子生成部分104中所用的半导体110优选为例如结晶硅。
电极部分106为获得载流子生成部分104中形成的电流的部分。该电极部分106在半导体110的受光部分102面的相对面上形成。电极部分106具有阳极112和阴极114,并且这些阳极和阴极在半导体110的受光部分102面的相对面上交替形成。阳极和阴极分别以具有三角形横截面的V形凹槽116和118的形式形成。p层120在阳极的V形凹槽116中形成,而n层122在阴极的V形凹槽118中形成。受光部分102面的相对面表面覆盖有氧化膜124。此外,由导电浆料形成的电极126嵌入V形凹槽中。
接下来结合图2至5提供了本发明的背接触式太阳能电池电极的生产过程说明,以及背接触式太阳能电池的生产过程说明。
首先,结合图2至5提供了用于制造背接触式太阳能电池电极的背接触式太阳能电池基板的制造说明。
制备了硅基板202,在其两面上形成氧化膜204a和204b(图2A)。这些氧化膜可通过例如热氧化形成。接下来,通过光刻或激光蚀刻等移除硅基板一面上的氧化膜204a,以留下预定宽度(例如,100μm的宽度和300μm的间距)的条(图2B)。
随后,用氢氧化钾(KOH)或四甲基氢氧化铵(TMAH)在已移除一部分氧化膜的一面上进行各向异性蚀刻,以形成具有三角形横截面的条的形式的V形凹槽206(间距为例如300μm)(图2C)。
接下来,将其中已形成V形凹槽206的基板放入扩散炉进行磷扩散。上述步骤的结果是,在已形成V形凹槽206的硅部分上形成了n层208,如图2D所示。在扩散炉中,通过中断用作磷材料的气体,并仅引入氧气,V形凹槽206的表面可被氧化膜覆盖(图2E)。
然后,通过光刻或激光蚀刻氧化膜204a的V形凹槽206之间的部分(图3B)从以这种方式获得的基板(图3A)等间距地移除氧化膜。例如,在V形凹槽206之间的氧化膜部分具有300μm宽度的情况下,移除氧化膜使得该氧化膜部分的两面与V形凹槽206的距离均为100μm。
接下来,用氢氧化钾(KOH)或四甲基氢氧化铵(TMAH)等在已移除氧化膜的那些位置进行各向异性蚀刻,以形成具有三角形横截面的条的形式的V形凹槽302(宽度为例如100μm)(图3C)。
接下来,将其中已形成V形凹槽302的基板放入扩散炉进行硼扩散。因此,如图3D所示,在V形凹槽302的硅部分上形成了p层304。在扩散炉中,通过中断用作硼材料的气体,并仅引入氧气,V形凹槽302的表面可被氧化膜覆盖(图3E)。
在硅基板202(其中以这种方式形成了两种V形凹槽(图4A))的另一表面(在其上形成氧化膜204b的表面)上移除氧化膜后,用氢氧化钾(KOH)或四甲基氢氧化铵(TMAH)等进行各向异性蚀刻,以形成具有三角形横截面的条形式的纹理化结构402(图4B)。然后通过在扩散炉中进行干法氧化,在基板的另一面上形成氧化膜404(图4C)。
随后,通过溅射等在常温下将例如二氧化钛(TiO2)沉积到氧化膜404面(二氧化钛膜:406)。因此,在基板的另一面上形成了具有结构纹理化的减反射膜的受光面(图4D)。
接下来,使用导电浆料形成电极(本发明生产过程的步骤(1))。在此步骤中,将导电浆料502嵌入采用上述方法获得的基板(图5A)的V形凹槽中(图5B)。导电浆料的嵌入可通过图案化方法进行,例如丝网印刷、孔版印刷或分配器施加。
接下来,将由导电浆料填充的基板(图5A)置于预定温度(例如450至900℃)下焙烧(图5C)(本发明生产过程的步骤(2))。从而形成电极504。
在本发明中,在氧化膜于n层208和p层304上形成的情况下,通过在电极形成过程中焙烧导电浆料以烧透氧化膜,可将电极材料直接偶联到半导体并形成电接触。
本发明的背接触式太阳能电池电极按照图2-5所示的过程生产。
p型基板PV的制造:
在本发明的另一个实施方案中,本发明的电极可用于p型基板太阳能电池(其中将p型硅层用作基板)中,并且所述电极位于基板的受光面即其表面和反面上。下文通过使用具有图1所示的结构的太阳能电池的实施例来提供对使用本发明电极的硅型太阳能电池的说明和对该硅型太阳能电池的生产过程的说明。
图6A显示p型硅基板601。
在图6B中,反向导电型的n层602通过磷(P)等的热扩散而形成。通常将三氯氧化磷(POCl3)用作磷扩散源。在不作任何特定变型的情况下,将n层602形成在硅基板601的整个表面上。硅片包括p型基板601,并且n层602通常具有大约几十欧姆每平方(Ω/°)的薄片电阻率。在使用抗蚀剂等保护住n层的一个表面之后,如图6C所示,通过蚀刻将n层602从大部分表面上移除,使得n层只保留在一个主表面上。然后使用有机溶剂等将抗蚀剂移除。接下来,如图6D所示,通过诸如等离子体化学气相沉积(CVD)的方法在n层602上形成减反射涂层603。然后如图6E所示,将用于正面电极604的导电浆料丝网印刷到氮化硅膜上并干燥,其中氮化硅膜为减反射涂层603。可将本发明施用于正面电极604。然后将导电浆料丝网印刷在基板601的背面上以形成背面电极605,并且后续地使其干燥。本发明不仅可施用于正面电极,还可施用于背面电极605。背面导电层可为分别包括不同金属的两个层。然后在大约450℃至900℃温度范围内的红外线加热炉中进行焙烧,持续几分钟至几十分钟。
n型基板PV的制造:在本发明的另一个实施方案中,本发明的电极可用于n型基板太阳能电池(其中将n型硅层用作基板)中,并且在基板的受光面(即正面)和基板的反面(即背面)上存在电极。图7A显示n型硅基板701。在图7B中,通过硼(B)等的热扩散形成反向导电型的p层702。通常将三溴化硼(BBr3)用作硼扩散源。在不作任何特定变型的情况下,将p层702形成在n型硅基板701的整个表面上。硅片包括n型基板701,并且p层702通常具有大约几十欧姆每平方(Ω/℃)的薄片电阻率。在使用抗蚀剂等保护住p层的一个表面之后,如图7C所示,通过蚀刻将p层702从大部分表面上移除,使得p层只保留在一个主表面上。然后使用有机溶剂等将抗蚀剂移除。接下来,如图7D所示,通过诸如等离子体化学气相沉积(CVD)的方法在p层702上形成减反射涂层703。如图7E所示,将用于正面电极704的导电浆料丝网印刷在氮化硅膜703上。可将本发明施用于正面电极704。此外,然后还将导电浆料丝网印刷在n型硅基板701的背面上,并且后续地使其干燥。本发明不仅可施用于正面电极,还可施用于背面电极705。该导电层可为分别包括不同金属的两个层。然后在大约450℃至900℃温度范围内的红外线加热炉中进行焙烧,持续几分钟至几十分钟。
对于p型基板和n型基板太阳能电池,例如,当半导体被用作光催化剂并且受到能量大于半导体的带隙能的光照射时,价带中的电子被光激进导带中而在导带中产生自由电子,并且与此相反地在价带中产生正空穴。在被称为载流子的那些自由电子和正空穴重组之前,到达电极的电子越多,则获得的电流就越大。因此,减少重组可有效地提升太阳能电池的效率。
实施例
本发明是通过下列实施例来说明,但不限于下列实施例。
(I)导电浆料材料
导电浆料使用下列材料制成。
(i)导电粉末
-银粒子:薄片粉末[D50 2.7μm,由激光散射型粒度分布测量设备测定]
-钛粒子:无定形粉末[D50 27μm,由激光散射型粒度分布测量设备测定](TIE06PB,纯度99.9%,KOJUNDO ChemicalLaboratory Co.,Ltd.)
-钯粒子:球状粉末[D50 0.8μm,由激光散射型粒度分布测量设备测定]
(ii)玻璃料:硼硅酸铅玻璃(软化点:440℃)
(iii)树脂基料:乙基纤维素
(iv)溶剂:萜品醇
(II)导电浆料的制备
将乙基纤维素树脂和萜品醇混合、加热并溶解,然后将混合物冷却至室温,生成树脂浓度为16重量%的萜品醇溶液。称取68.0重量%的银粒子粉末、7.0重量%的玻璃料和25.0重量%的萜品醇溶液并按以下比例混合,然后用三辊研磨机处理混合物,得到银浆。然后相似地将65.3重量%的银粉、2.7重量%的钯粉、7.0重量%的玻璃料和25.0重量%的萜品醇溶液用作制备银-钯混合物浆料的材料。再称取50.0重量%的钛粒子和50.0重量%的萜品醇溶液并混合,然后将混合物置于熟知的旋转式搅拌器中处理2分钟,得到钛浆。将所得的银浆、银-钯浆和钛浆按表1给定的比例混合,然后将混合物置于旋转式搅拌器中处理30秒。导电浆料组合物1-11包含如表1所示的不同含量的银浆、钯浆和钛浆。在每种浆料中银粒子、钛粒子和钯粒子相对于导电粉末的总重量的重量百分比示于表2中。
表1
(III)测试工件的制造
将通过上述方法获得的导电浆料以1mm的电极(10mm长、1mm宽、20μm厚)802间距丝网印刷在N型基板和P型基板的硅晶片(25mm×25mm)801上(图8A)。也就是说,将导电浆料印刷到n型基板硅晶片中的p层上,并印刷到p型基板硅晶片中的n层上。将印刷到晶片上的导电浆料置于对流烘箱中于150℃下干燥5分钟。然后在红外线加热型带式炉中以不同的温度设置(650℃、700℃和725℃)进行烧结,从而获得电极。烧结期间的传送带速度为370cpm。
(IV)测量电阻
使用数字源表(2420,Keithley Instruments Inc.)测量电极间的电阻(衬垫间的电阻(Ω))。如图8B所示,测得的衬垫间的电阻为硅晶片电阻、电极本身的电阻以及硅晶片与电极之间的接触面处的接触电阻的总和。与其他电阻相比,电极电阻相对来说非常低。硅晶片的电阻在样本间几乎一致。因为使用了相同的硅晶片,所以衬垫间的电阻均具有相同的硅晶片电阻。众所周知,电极的固有电阻相对较低。因此,衬垫间的电阻大小代表接触电阻的大小。
(V)结果
表2示出了使用不同导电浆料形成的电极衬垫间的电阻的测量结果。不管烧结温度是多少,使用导电浆料7-11形成的电极衬垫间的电阻在n层上不超过2.0Ω,在p层上不超过20Ω。也就是说,不管烧结温度是多少,衬垫间的电阻可保持在较低水平,即使是在n层和p层上均形成了含有银、钛和钯的浆料时。
表2
(VI)TiH
2
的用途
然后以与上述相同的方法制备浆料12-19,不同的是将用于含银、钛和钯的浆料4-10的组合物中的钛粒子更换为氢氧化钛(TiH2)粒子(TII04PB,Kojundo Chemical Laboratory Co.,Inc.)。浆料中包含的银、钛和钯的含量示于表3中。所用的TiH2的平均粒径(D50)为5-10μm。以与上述相同的方法测量使用这些浆料12-19获得的衬垫间的电阻(表3)。
不管烧结温度是多少,使用导电浆料12-19形成的电极衬垫间的电阻在n层上不超过2.0Ω,在p层上不超过20.0Ω。也就是说,不管烧结温度是多少,衬垫间的电阻可保持在较低水平,即使是在n层和p层上均形成了包含65.3至92.2重量%的银、4至32重量%的TiH2和2.7至3.8重量%的钯的浆料时。
表3
过去,在衬垫间具有低电阻的导电浆料存在于n层上,但本发明的电极在n层和p层上使用时均可获得衬垫间的低电阻。因此,没有必要根据基板类型使用不同的导电浆料,从而使得本发明成为用于在一面既具有n层又具有p层的背接触式太阳能电池的理想选择。此外,由于即使在高温下烧结电阻也不会增大,因此可在不调节烧结温度的情况下将电阻保持在较低水平。也就是说,在过去必须将烧结温度设置为与导电浆料相符,但在使用本发明的导电浆料时,可设置的烧结温度范围更大,从而允许在太阳能电池中一致地形成具有低电阻的电极。
Claims (6)
1.通过烧结导电浆料形成的太阳能电池电极,所述导电浆料包含:
(a)导电粉末,所述导电粉末包含银粒子、钛粒子、或TiH2粒子,以及(i)选自锆、铬、钴、钼、锝、钌、铑、钯、钨、铼、锇、铱和铂的金属粒子,(ii)包含所述金属的合金粒子,或(iii)承载所述金属粒子的载体粒子;
(b)玻璃料;以及
(c)树脂基料。
2.根据权利要求1的太阳能电池电极,其中所述导电粉末包含30-98重量%的银粒子、1-70重量%的钛粒子或TiH2粒子,以及1-10重量%的(i)选自锆、铬、钴、钼、锝、钌、铑、钯、钨、铼、锇、铱和铂的金属粒子,(ii)包含所述金属的合金粒子,或(iii)承载所述金属粒子的载体粒子。
3.制备太阳能电池电极的方法,所述方法包括:
在硅基板上施加用于太阳能电池电极的导电浆料的步骤,所述导电浆料包含:
(a)导电粉末,所述导电粉末包含银粒子、钛粒子、或TiH2粒子,以及(i)选自锆、铬、钴、钼、锝、钌、铑、钯、钨、铼、锇、铱和铂的金属粒子,(ii)包含所述金属的合金粒子,或(iii)承载所述金属粒子的载体粒子,(b)玻璃料,和
(c)树脂基料;以及
烧结所述已施加的导电浆料的步骤。
4.根据权利要求3的用于制备太阳能电池电极的方法,其中在450至900摄氏度下烧结所述浆料。
5.根据权利要求3的用于制备太阳能电池电极的方法,其中所述导电粉末包含30-98重量%的银粒子、1-70重量%的钛粒子或TiH2粒子,以及1-10重量%的(i)选自锆、铬、钴、钼、锝、钌、铑、钯、钨、铼、锇、铱和铂的金属粒子,(ii)包含所述金属的合金粒子,或(iii)选自承载所述金属粒子的粒子的附加粒子。
6.用于制备太阳能电池电极的方法,所述方法包括:在硅基板的n层和p层上均施加并烧结用于太阳能电池电极的导电浆料,所述导电浆料包含:
(a)导电粉末,所述导电粉末包含银粒子、钛粒子、或TiH2粒子,以及(i)选自锆、铬、钴、钼、锝、钌、铑、钯、钨、铼、锇、铱和铂的金属粒子,(ii)包含所述金属的合金粒子,或(iii)承载所述金属粒子的载体粒子,
(b)玻璃料,和
(c)树脂基料。
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Application Number | Priority Date | Filing Date | Title |
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US16763609P | 2009-04-08 | 2009-04-08 | |
US61/167,636 | 2009-04-08 | ||
PCT/US2010/030069 WO2010118004A1 (en) | 2009-04-08 | 2010-04-06 | Solar cell electrode |
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2010
- 2010-04-06 CN CN2010800158918A patent/CN102369580A/zh active Pending
- 2010-04-06 US US12/754,655 patent/US8263858B2/en active Active
- 2010-04-06 WO PCT/US2010/030069 patent/WO2010118004A1/en active Application Filing
- 2010-04-06 EP EP10712869A patent/EP2417607A1/en not_active Withdrawn
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US20100258182A1 (en) | 2010-10-14 |
US8263858B2 (en) | 2012-09-11 |
EP2417607A1 (en) | 2012-02-15 |
WO2010118004A1 (en) | 2010-10-14 |
JP2012523696A (ja) | 2012-10-04 |
KR20110135880A (ko) | 2011-12-19 |
TW201101337A (en) | 2011-01-01 |
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