CN103155164B - 太阳能电池的制造方法 - Google Patents
太阳能电池的制造方法 Download PDFInfo
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- CN103155164B CN103155164B CN201180048863.0A CN201180048863A CN103155164B CN 103155164 B CN103155164 B CN 103155164B CN 201180048863 A CN201180048863 A CN 201180048863A CN 103155164 B CN103155164 B CN 103155164B
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- 238000009792 diffusion process Methods 0.000 claims abstract description 103
- 239000000203 mixture Substances 0.000 claims abstract description 86
- 239000012535 impurity Substances 0.000 claims abstract description 57
- 239000011521 glass Substances 0.000 claims abstract description 56
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 239000000843 powder Substances 0.000 claims abstract description 37
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- 238000010438 heat treatment Methods 0.000 claims abstract description 10
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- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
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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
-
- 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
-
- 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
- H01L31/186—Particular post-treatment for the devices, e.g. annealing, impurity gettering, short-circuit elimination, recrystallisation
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Abstract
本发明提供一种太阳能电池的制造方法,其具有以下工序:对半导体基板的一个面上的部分区域给予含有含p型杂质的玻璃粉末及分散介质的第一用于形成p型扩散层的组合物的工序;对上述半导体基板的给予了上述第一用于形成p型扩散层的组合物的面上的、至少上述部分区域以外的区域,给予含有含p型杂质的玻璃粉末及分散介质、且p型杂质浓度比上述第一用于形成p型扩散层的组合物低的第二用于形成p型扩散层的组合物的工序;以及对给予了上述第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物的半导体基板进行热处理而形成p型扩散层的工序;在上述部分区域上形成电极的工序。
Description
技术领域
本发明涉及一种太阳能电池的制造方法。
背景技术
在以往的具有pn结的太阳能电池单元的制造中,例如在硅等n型半导体基板上扩散p型杂质而形成p型扩散层,由此形成pn结。
尤其是作为以提高转换效率为目的的太阳能电池单元的结构,已知有使电极正下方以外的部分的区域中的杂质浓度比电极正下方的杂质浓度低的选择性发射极(selective emitter)结构(参照例如L.Debarge,M.Schott,J.C.Muller,R.Monna、Solar Energy Materials&Solar Cells74(2002)71-75)。在该结构中,由于在电极正下方形成杂质浓度高的区域(以下,将该区域也称为“选择性发射极”),因此可以降低金属电极与硅的接触电阻。另一方面,在金属电极部分以外,杂质浓度变低,可以提高太阳能电池的转换效率。
为了形成如上述那样的选择性发射极结构,需要将多次扩散和利用掩模的部分蚀刻等组合的复杂的工序(例如参照日本特开2004-193350号公报)。
此外,还提出了利用喷墨法将多种杂质浓度的扩散剂分开涂于基板、扩散杂质的方法(例如参照日本特开2004-221149号公报)。
发明内容
发明要解决的课题
但是,在日本特开2004-193350号公报记载的方法中,为了形成选择性发射极结构而需要用于形成图案、蚀刻的工序,存在工序数增多的倾向。此外,在日本特开2004-221149号公报记载的喷墨法中,需要具有多个喷头的专用装置,来自各喷头的喷射的控制也变得复杂。
本发明的课题在于,提供一种太阳能电池的制造方法,其无需复杂的装置而利用简便的方法即可制造具有选择性发射极结构的太阳能电池。
用于解决课题的手段
本发明包含以下技术方案。
<1>一种太阳能电池的制造方法,其具有以下工序:对半导体基板的一个面上的部分区域给予含有含p型杂质的玻璃粉末及分散介质的第一用于形成p型扩散层的组合物的工序;对上述半导体基板的给予上述第一用于形成p型扩散层的组合物的面上的、且至少上述部分区域以外的区域,给予含有含p型杂质的玻璃粉末及分散介质、且p型杂质浓度比上述第一用于形成p型扩散层的组合物低的第二用于形成p型扩散层的组合物的工序;对给予了上述第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物的半导体基板进行热处理而形成p型扩散层的工序;以及在上述部分区域上形成电极的工序。
<2>根据上述<1>所述的太阳能电池的制造方法,其中,上述p型杂质包含选自B(硼)、Al(铝)及Ga(镓)中的至少1种元素。
<3>根据上述<1>或<2>所述的太阳能电池的制造方法,其中,上述含p型杂质的玻璃粉末含有:选自B2O3、Al2O3及Ga2O3中的至少1种含p型杂质的物质;以及选自SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、V2O5、SnO、ZrO2、TiO2及MoO3中的至少1种玻璃成分物质。
发明效果
根据本发明,能够提供一种太阳能电池的制造方法,其无需复杂的装置而利用简便的方法即可制造具有选择性发射极结构的太阳能电池。
具体实施方式
本说明书中,“工序”这一用语不仅为独立的工序,即使在无法与其他工序明确区分的情况下,只要能达成该工序的预期作用,也包含在本用语中。此外,本说明书中,使用“~”表示的数值范围表示包含“~”的前后记载的数值分别作为最小值及最大值的范围。进而,本说明书中,在组合物中属于各成分的物质存在多种时,只要无特别说明,组合物中的各成分的量均指组合物中存在的该多种物质的总量。
本发明的太阳能电池的制造方法包含以下工序而构成,即,对半导体基板的一个面上的部分区域给予含有含p型杂质的玻璃粉末及分散介质的第一用于形成p型扩散层的组合物的工序;对给予了上述第一用于形成p型扩散层的组合物的半导体基板的面上的、至少上述部分区域以外的区域,给予含有含p型杂质的玻璃粉末及分散介质、且p型杂质浓度比上述第一用于形成p型扩散层的组合物低的第二用于形成p型扩散层的组合物的工序;对给予了上述第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物的半导体基板进行热处理而形成p型扩散层的工序;在上述部分区域上形成电极的工序;以及根据需要而包含的其他工序。
首先,对本发明的第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物(以下,也统称为“用于形成p型扩散层的组合物”)进行说明,接着,对使用这些用于形成p型扩散层的组合物的选择性发射极结构的形成方法进行说明。
上述用于形成p型扩散层的组合物含有至少1种的含p型杂质的玻璃粉末和至少1种的分散介质,还可以考虑涂布性等而根据需要含有其他添加剂。
在此,用于形成p型扩散层的组合物是指含有p型杂质、且通过涂布于硅基板后使该p型杂质热扩散而能够形成p型扩散层的材料。通过使用用于形成p型扩散层的组合物,能够在所预期的部位形成p型扩散层。
此外,玻璃粉末中的p型杂质即使在烧成中也难以挥散,因此因挥散气体的产生的不仅在给予了用于形成p型扩散层的组合物的部分形成p型扩散层,而且就连背面、侧面也会形成p型扩散层的现象能得到抑制。作为该理由,可认为是由于p型杂质与玻璃粉末中的元素结合或进入到玻璃中而难以挥散。
(玻璃粉末)
上述玻璃粉末中所含的p型杂质是指能够通过扩散于硅基板中而形成p型扩散层的元素。作为p型杂质,可以使用第13族元素,可举出例如B(硼)、Al(铝)、及Ga(镓)等。
作为含p型杂质的物质,可举出B2O3、Al2O3、及Ga2O3,优选使用选自B2O3、Al2O3及Ga2O3中的至少1种。
此外,玻璃粉末可以通过根据需要调整成分比率来控制熔融温度、软化点、玻璃化转变点、化学耐久性等。进而,优选含有以下记载的玻璃成分物质。
作为玻璃成分物质,可举出SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、Tl2O、V2O5、SnO、WO3、MoO3、MnO、La2O3、Nb2O5、Ta2O5、Y2O3、TiO2、ZrO2、GeO2、TeO2及Lu2O3等,优选使用选自SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、V2O5、SnO、ZrO2、TiO2、及MoO3中的至少1种。
作为含p型杂质的玻璃粉末的具体例,可举出含有上述含p型杂质的物质和上述玻璃成分物质双方的玻璃粉末,可举出B2O3-SiO2系(以含p型杂质的物质-玻璃成分物质的顺序记载,下同)、B2O3-ZnO系、B2O3-PbO系、B2O3单独系等含有B2O3作为含p型杂质的物质的体系;Al2O3-SiO2系等含有Al2O3作为含p型杂质的物质的体系;Ga2O3-SiO2系、系等含有Ga2O3作为含p型杂质的物质的体系等的玻璃粉末。
此外,可以是如Al2O3-B2O3系、Ga2O3-B2O3系等那样,含有2种以上的含p型杂质的物质的玻璃粉末。
上述例示出含有1种成分的玻璃或2种成分的复合玻璃,但也可以是B2O3-SiO2-Na2O等含有3种成分以上的物质的玻璃粉末。
玻璃粉末中的玻璃成分物质的含有比率理想的是考虑熔融温度、软化点、玻璃化转变点、化学耐久性等进行适当设定,一般而言,优选为0.1质量%~95质量%,更优选为0.5质量%~90质量%。
从扩散处理时的扩散性、液体滴落的观点出发,玻璃粉末的软化点优选为200℃~1000℃,更优选为300℃~900℃。
作为玻璃粉末的形状,可举出大致球状、扁平状、块状、板状及鳞片状等,从制成用于形成n型扩散层的组合物时对基板的涂布性、均匀扩散性的方面出发,理想的是大致球状、扁平状或板状。玻璃粉末的平均粒径理想的是100μm以下。在使用具有100μm以下的平均粒径的玻璃粉末的情况下,容易得到平滑的涂膜。进而,玻璃粉末的平均粒径更理想的是50μm以下,进一步理想的是10μm以下。另外,下限没有特别的限制,优选为0.01μm以上。
在此,玻璃的平均粒径表示体积平均粒径,可以利用激光散射衍射法粒度分布测定装置等来进行测定。
含p型杂质的玻璃粉末可以按以下步骤来制作。
最初,称量原料,填充于坩埚中。作为坩埚的材质,可举出铂、铂-铑、铱、氧化铝、石英、碳等,可考虑熔融温度、气氛、与熔融物质的反应性、杂质的混入等进行适当选择。
接着,用电炉在与玻璃组成相应的温度下加热,制成熔融液。此时理想的是进行搅拌使熔融液变得均匀。
接着将得到的熔融液流出到氧化锆基板、碳基板等上,使熔融液玻璃化。
最后,将玻璃粉碎,制成粉末状。粉碎可以应用喷射式磨机(jet mill)、珠磨机、球磨机等公知的方法。
用于形成p型扩散层的组合物中的含p型杂质的玻璃粉末的含有比率可以考虑涂布性、p型杂质的扩散性等来确定。一般而言,用于形成p型扩散层的组合物中的玻璃粉末的含有比率优选为0.1质量%~95质量%,更优选为1质量%~90质量%,进一步优选为1.5质量%~85质量%,特别优选为2质量%~80质量%。
(分散介质)
接着,对分散介质进行说明。
分散介质是指组合物中分散上述玻璃粉末的介质。具体而言,作为分散介质,采用粘结剂(binder)、溶剂等。
-粘结剂-
作为粘结剂,例如可适当选择聚乙烯醇、聚丙烯酰胺类、聚乙烯酰胺类、聚乙烯吡咯烷酮、聚(甲基)丙烯酸类、聚环氧乙烷类、聚磺酸、丙烯酰胺烷基磺酸、纤维素醚类、纤维素衍生物、羧甲基纤维素、羟乙基纤维素、乙基纤维素、明胶、淀粉及淀粉衍生物、海藻酸钠类、黄原胶(xanthan)及黄原胶衍生物、瓜尔胶(guar gum)及瓜尔胶衍生物、硬葡聚糖(scleroglucan)及硬葡聚糖衍生物、黄蓍胶(Tragacanth)及黄蓍胶衍生物、糊精及糊精衍生物、(甲基)丙烯酸树脂、(甲基)丙烯酸树脂、(甲基)丙烯酸酯树脂(例如(甲基)丙烯酸烷基酯树脂、(甲基)丙烯酸二甲基氨基乙酯树脂等)、丁二烯树脂、苯乙烯树脂、及它们的共聚物、以及硅氧烷树脂等。它们可以单独使用1种或组合使用2种以上。
粘结剂的分子量没有特别的限制,理想的是鉴于作为组合物的所预期的粘度进行适当调整。
-溶剂-
作为溶剂,可举出例如丙酮、甲乙酮、甲基正丙基酮、甲基-异丙基酮、甲基正丁基酮、甲基异丁基酮、甲基正戊基酮、甲基-正己基酮、二乙基酮、二丙基酮、二异丁基酮、三甲基壬酮、环己酮、环戊酮、甲基环己酮、2,4-戊二酮、丙酮基丙酮等酮系溶剂;二乙基醚、甲基乙基醚、甲基-正丙基醚、二异丙基醚、四氢呋喃、甲基四氢呋喃、二噁烷、二甲基二噁烷、乙二醇二甲基醚、乙二醇二乙基醚、乙二醇二正丙基醚、乙二醇二丁基醚、二乙二醇二甲基醚、二乙二醇二乙基醚、二乙二醇甲基乙基醚、二乙二醇甲基-正丙基醚、二乙二醇甲基-正丁基醚、二乙二醇二正丙基醚、二乙二醇二正丁基醚、二乙二醇甲基-正己基醚、三乙二醇二甲基醚、三乙二醇二乙基醚、三乙二醇甲基乙基醚、三乙二醇甲基-正丁基醚、三乙二醇二正丁基醚、三乙二醇甲基-正己基醚、四乙二醇二甲基醚、四乙二醇二乙基醚、四(二乙二醇)甲基乙基醚、四乙二醇甲基-正丁基醚、二乙二醇二正丁基醚、四乙二醇甲基-正己基醚、四乙二醇二正丁基醚、丙二醇二甲基醚、丙二醇二乙基醚、丙二醇二正丙基醚、丙二醇二丁基醚、二丙二醇二甲基醚、二丙二醇二乙基醚、二丙二醇甲基乙基醚、二丙二醇甲基-正丁基醚、二丙二醇二正丙基醚、二丙二醇二正丁基醚、二丙二醇甲基-正己基醚、三丙二醇二甲基醚、三丙二醇二乙基醚、三丙二醇甲基乙基醚、三丙二醇甲基-正丁基醚、三丙二醇二正丁基醚、三丙二醇甲基-正己基醚、四丙二醇二甲基醚、四丙二醇二乙基醚、四(二丙二醇)甲基乙基醚、四丙二醇甲基-正丁基醚、二丙二醇二正丁基醚、四丙二醇甲基-正己基醚、四丙二醇二正丁基醚等醚系溶剂;乙酸甲酯、乙酸乙酯、乙酸正丙酯、乙酸异丙酯、乙酸正丁酯、乙酸异丁酯、乙酸仲丁酯、乙酸正戊酯、乙酸仲戊酯、乙酸3-甲氧基丁酯、乙酸甲基戊酯、乙酸2-乙基丁酯、乙酸2-乙基己酯、乙酸2-(2-丁氧基乙氧基)乙酯、乙酸苄酯、乙酸环己酯、乙酸甲基环己酯、乙酸壬酯、乙酰乙酸甲酯、乙酰乙酸乙酯、二乙二醇甲基醚乙酸酯、二乙二醇乙基醚乙酸酯、二丙二醇甲基醚乙酸酯、二丙二醇乙基醚乙酸酯、二乙酸乙二醇酯、乙酸甲氧基三甘醇酯、丙酸乙酯、丙酸正丁酯、丙酸异戊酯、草酸二乙酯、草酸二正丁酯、乳酸甲酯、乳酸乙酯、乳酸正丁酯、乳酸正戊基、乙二醇甲基醚丙酸酯、乙二醇乙基醚丙酸酯、乙二醇甲基醚乙酸酯、乙二醇乙基醚乙酸酯、丙二醇甲基醚乙酸酯、丙二醇乙基醚乙酸酯、丙二醇丙基醚乙酸酯、γ-丁内酯、γ-戊内酯等酯系溶剂;乙腈、N-甲基吡咯烷酮、N-乙基吡咯烷酮、N-丙基吡咯烷酮、N-丁基吡咯烷酮、N-己基吡咯烷酮、N-环己基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜等非质子性极性溶剂;甲醇、乙醇、正丙醇、异丙醇、正丁醇、异丁醇、仲丁醇、叔丁醇、正戊醇、异戊醇、2-甲基丁醇、仲戊醇、叔戊醇、3-甲氧基丁醇、正己醇、2-甲基戊醇、仲己醇、2-乙基丁醇、仲庚醇、正辛醇、2-乙基己醇、仲辛醇、正壬基醇、正癸醇、仲十一烷醇、三甲基壬醇、仲十四烷醇、仲十七烷醇、苯酚、环己醇、甲基环己醇、苄醇、乙二醇、1,2-丙二醇、1,3-丁二醇、二乙二醇、二丙二醇、三乙二醇、三丙二醇等醇系溶剂;乙二醇单甲基醚、乙二醇单乙基醚、乙二醇单苯基醚、二乙二醇单甲基醚、二乙二醇单乙基醚、二乙二醇单正丁基醚、二乙二醇单正己基醚、乙氧基三甘醇、四乙二醇单正丁基醚、丙二醇单甲基醚、二丙二醇单甲基醚、二丙二醇单乙基醚、三丙二醇单甲基醚等二醇单醚系溶剂;α-萜烯、α-萜品醇、月桂烯(myrcene)、别罗勒烯(alloocimene)、柠檬萜、双戊烯、α-蒎烯(pinene)、β-蒎烯、松油醇、香芹酮(carvone)、罗勒烯、水芹烯等萜烯系溶剂;水。这些溶剂可以单独使用1种或组合使用2种以上。在制成用于形成p型扩散层的组合物时,从对基板的涂布性的观点出发,优选α-萜品醇、二乙二醇单-正丁基醚、乙酸2-(2-丁氧基乙氧基)乙酯。
用于形成p型扩散层的组合物中的分散介质的含有比率考虑涂布性、p型杂质浓度而确定。
考虑涂布性时,用于形成p型扩散层的组合物的粘度优选为10mPa·s~1000000mPa·s,更优选为50mPa·s~500000mPa·s。
本发明中使用p型杂质浓度不同的至少2种用于形成p型扩散层的组合物。本发明中,例如,对半导体基板的一个面上的电极形成区域给予p型杂质浓度高的第一用于形成p型扩散层的组合物,在同一面的电极形成区域以外的区域或整面给予p型杂质浓度低的第二用于形成p型扩散层的组合物。然后,通过加热处理使用于形成p型扩散层的组合物中的p型杂质扩散到半导体基板中,形成p型扩散层,由此可以在电极形成区域有效地形成p型杂质浓度高的选择性发射极。
有关上述第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物中的p型杂质的浓度,只要是在第一用于形成p型扩散层的组合物中更大,则没有特别的限制。从高浓度p型扩散层(选择性发射极)的形成效率、光发电效率的观点出发,第一用于形成p型扩散层的组合物中的p型杂质浓度与第二用于形成p型扩散层的组合物中的p型杂质浓度之比(第一用于形成p型扩散层的组合物/第二用于形成p型扩散层的组合物)优选为1.1~50,更优选为1.2~20。
另外,用于形成p型扩散层的组合物中的p型杂质浓度可以通过适当选择玻璃粉末的含有率、玻璃粉末中含有的p型杂质的含有率等来进行调整。
(太阳能电池的制造方法)
首先,使用酸性或碱性的溶液蚀刻除去在硅基板的表面上的破损层。
接着,在硅基板的一个表面形成由硅的氧化物膜或硅的氮化物膜形成的保护膜。在此,硅的氧化物膜可以利用例如使用硅烷气体和氧气的常压CVD法来形成。此外,硅的氮化物膜可以利用例如使用硅烷气体、氨气及氮气的等离子体CVD法来形成。
接着,在未形成硅基板的保护膜的一侧的表面形成被称作纹理(texture)结构的微细凹凸结构。纹理结构可以通过例如将形成有保护膜的硅基板浸渍在含有氢氧化钾和异丙醇(IPA)的约80℃左右的液体来形成。
接着,通过使硅基板浸渍于氢氟酸,从而蚀刻除去保护膜。
接着,在n型硅基板上形成p型扩散层,从而形成pn结。本发明中具有以下特征:通过对将要形成受光面电极的电极形成区域(电极形成预定区域)给予用于形成p型扩散层的组合物,从而使电极形成区域中的杂质浓度高于电极形成区域以外的杂质浓度。
本发明中,杂质浓度高的电极形成区域的形状及大小可以根据所构成的太阳能电池的结构进行适当选择。作为形状,可以制成例如线状等。
本发明中,通过对n型硅基板上的将要形成受光面电极的电极形成区域给予上述第一用于形成p型扩散层的组合物的工序以及对至少上述电极形成区域以外的区域给予上述第二用于形成p型扩散层的组合物的工序,从而在n型硅基板上形成用于形成p型扩散层的组合物层。
对上述电极形成区域可以仅给予第一用于形成p型扩散层的组合物,也可以给予第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物两者。
此外,给予第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物的顺序没有特别的限制。即,可以在对电极形成区域给予第一用于形成p型扩散层的组合物后,对受光面整面或电极形成区域以外的区域给予第二用于形成p型扩散层的组合物,此外,也可以对受光面整面或电极形成区域以外的区域给予第二用于形成p型扩散层的组合物后,对电极形成区域给予第一用于形成p型扩散层的组合物。
第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物的给予方法没有特别的限制,可以使用通常使用的方法。可以使用例如丝网印刷法、凹版印刷法等印刷法、旋涂法、刷毛涂布、喷射法、刮刀法、辊涂法、喷墨法等来进行。进而,第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物的给予方法可以分别相同或不同。
作为上述第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物的给予量,没有特别的限制。例如,以玻璃粉末量计可以为0.01g/m2~100g/m2,优选为0.1g/m2~10g/m2。此外,第二用于形成p型扩散层的组合物的给予量与第一用于形成p型扩散层的组合物的给予量之比(第二用于形成p型扩散层的组合物/第一用于形成p型扩散层的组合物)没有特别的限制,可以按照使所形成的p型扩散层成为所需的杂质浓度的方式进行适当选择。
在硅基板上给予用于形成p型扩散层的组合物后,可以设置用于除去至少一部分的分散介质的加热工序。加热工序中,通过在例如100℃~200℃进行加热处理,从而可以使溶剂的至少一部分挥发。此外,通过在例如200℃~500℃进行加热处理,从而除去粘结剂的至少一部分。
接着,通过对给予了用于形成p型扩散层的组合物的硅基板进行热处理,从而形成p型扩散层。通过热处理而使p型杂质从用于形成p型扩散层的组合物扩散到硅基板中,在将要形成受光面电极的电极形成区域形成高浓度的p型扩散层,在其以外的区域形成低浓度的p型扩散层。
在此,热处理温度优选为800℃~1100℃,进一步优选为850℃~1100℃,更优选为900℃~1100℃。
按照上述方式在形成有p型扩散层的硅基板上会残留玻璃层,但优选除去该玻璃层。玻璃层的除去可以应用浸渍于氢氟酸等酸的方法、浸渍于苛性钠等碱中的方法等公知的方法。
接着,在形成有p型扩散层的受光面上形成防反射膜。在此,作为防反射膜,可以使用例如利用等离子体CVD法形成的氮化物膜。
接着,在基板背面及受光面形成电极。电极的形成可以没有特别限制地使用通常所用的方法。
例如,受光面电极(表面电极)可以如下形成:在上述电极形成区域上给予含有金属粒子及玻璃粒子的表面电极用金属糊剂,使其成为所预期的形状,对其进行烧成处理,由此可以在形成有高浓度的p型扩散层的电极形成区域上形成表面电极。
作为上述表面电极用金属糊剂,可以使用例如本技术领域中常用的银糊剂等。
此外,背面电极例如可以如下形成:将含有铝、银或铜等金属的背面电极用糊剂进行涂布,使其干燥,将其进行烧成处理,由此可以形成该背面电极。此时,为了模块化工序中的单元间的连接,还可以在背面的一部分设置银电极形成用银糊剂。
实施例
以下,利用实施例对本发明进行更具体地说明,但本发明不受这些实施例的限定。另外,只要没有特别说明,药品全部使用试剂。此外,“份”及“%”为质量基准。
[实施例1]
将粒子形状为大致球状、平均粒径为1.5μm、软化温度为约810℃的玻璃粉末(以B2O3、SiO2、CaO、MgO、BaO为主要成分,且分别为30%、40%、10%、10%、10%)、乙基纤维素、萜品醇分别以20g、8g、72g混合,进行糊剂化,制备成第一用于形成p型扩散层的组合物(组合物A)。此外,将粒子形状为大致球状、平均粒径为1.5μm、软化温度为约810℃的玻璃粉末(以B2O3、SiO2、CaO、MgO、BaO为主要成分,且分别为30%、40%、10%、10%、10%)、乙基纤维素、萜品醇分别以5g、6g、89g混合,进行糊剂化,制备成第二用于形成p型扩散层的组合物(组合物B)。
另外,使用(株)日立高科技制造的TM-1000型扫描型电子显微镜进行观察,从而判定玻璃粒子形状。玻璃的平均粒径使用BECKMANCOULTER(株)制造的LS13320型激光散射衍射法粒度分布测定装置(测定波长:632nm)来计算。玻璃的软化点使用(株)岛津制作所制造的DTG-60H型示差热·热重量同时测定装置,利用示差热(DTA)曲线来求得。
接着,利用丝网印刷将组合物A在n型硅基板的表面的一部分涂布成线状,在150℃干燥10分钟,接着,利用丝网印刷在硅基板相同表面的整面涂布组合物B,在150℃干燥10分钟。然后,在350℃进行3分钟的脱粘结剂处理。
接着,在大气中、950℃条件下热处理10分钟,使p型杂质扩散于硅基板中,形成p型扩散层。接着,利用氢氟酸将残留在硅基板表面的玻璃层除去。
涂布有组合物A的部分(电极形成区域)的薄膜电阻的平均值为58Ω/□、其以外的部分的薄膜电阻的平均值为127Ω/□、涂布有组合物A的部分被选择性地低电阻化。另外,薄膜电阻使用三菱化学(株)制造的Loresta-EP MCP-T360型低电阻率计并利用四探针法进行测定。
[太阳能电池的制作]
使用上述得到的形成有p型扩散层的硅基板,利用常规方法在表面形成防反射膜,在电极形成区域形成表面电极,在背面形成背面电极,制作太阳能电池单元。与不具有形成了高浓度的p型扩散层的电极形成区域(选择性发射极)的太阳能电池单元相比,所得的太阳能电池单元显示出良好的光转换特性。
对于日本专利申请2010-157169号的公开内容,作为参照将其全体并入本说明书中。本说明书中记载的全部的文献、专利申请及技术标准,与具体且分别记载了各个文献、专利申请和技术标准的情况,同程度地作为参照援引于本说明书中。
Claims (3)
1.一种太阳能电池的制造方法,其具有以下工序:
对半导体基板的一个面上的部分区域给予含有含p型杂质的玻璃粉末及分散介质的第一用于形成p型扩散层的组合物的工序;
对所述半导体基板的给予所述第一用于形成p型扩散层的组合物的面上的、至少所述部分区域以外的区域,给予含有含p型杂质的玻璃粉末及分散介质、且p型杂质浓度比所述第一用于形成p型扩散层的组合物低的第二用于形成p型扩散层的组合物的工序;
对给予了所述第一用于形成p型扩散层的组合物及第二用于形成p型扩散层的组合物的半导体基板进行热处理而形成p型扩散层的工序;以及
在所述部分区域上形成电极的工序。
2.根据权利要求1所述的太阳能电池的制造方法,其中,所述p型杂质包含选自硼B、铝Al及Ga镓中的至少1种元素。
3.根据权利要求1或权利要求2所述的太阳能电池的制造方法,其中,所述含p型杂质的玻璃粉末含有:
选自B2O3、Al2O3及Ga2O3中的至少1种含p型杂质的物质;以及
选自SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、V2O5、SnO、ZrO2、TiO2及MoO3中的至少1种玻璃成分物质。
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