CN102870197B - n型扩散层形成组合物、n型扩散层的制造方法和太阳能电池元件的制造方法 - Google Patents
n型扩散层形成组合物、n型扩散层的制造方法和太阳能电池元件的制造方法 Download PDFInfo
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- CN102870197B CN102870197B CN201180020190.8A CN201180020190A CN102870197B CN 102870197 B CN102870197 B CN 102870197B CN 201180020190 A CN201180020190 A CN 201180020190A CN 102870197 B CN102870197 B CN 102870197B
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Abstract
本发明的n型扩散层形成组合物含有:含给体元素并且寿命扼杀剂元素的总量为1000ppm以下的玻璃粉末;和分散介质。通过涂布该n型扩散层形成组合物,实施热扩散处理,从而制造n型扩散层和具有n型扩散层的太阳能电池元件。
Description
技术领域
本发明涉及太阳能电池元件的n型扩散层形成组合物、n型扩散层的制造方法和太阳能电池元件的制造方法,更详细地说,涉及能够在作为半导体基板的硅基板的特定的部分形成n型扩散层的技术。
背景技术
对以往的硅太阳能电池元件的制造工序进行说明。
首先,为了促进光封闭效果实现高效率化,准备形成了纹理结构的p型硅基板,接着在氧氯化磷(POCl3)、氮气、氧气的混合气体气氛中在800~900℃下进行数十分钟的处理,在基板上均匀地形成n型扩散层。对于该以往的方法,由于使用混合气体进行磷的扩散,因此不仅表面而且在侧面、背面也形成n型扩散层。因此,用于将侧面的n型扩散层除去的侧蚀刻工序是必要的。此外,背面的n型扩散层必须变换为p+型扩散层,在背面的n型扩散层上赋予铝糊剂,通过铝的扩散,从n型扩散层变换为p+型扩散层。
另一方面,在半导体的制造领域中,例如日本特开2002-75894号公报中公开那样,提出了通过含有五氧化磷(P2O5)或磷酸二氢铵(NH4H2PO4)等磷酸盐的溶液的涂布来形成n型扩散层的方法。但是,由于在该方法中使用溶液,与使用上述混合气体的气相反应法同样地,在侧面和背面也形成磷的扩散,以及不仅表面而且在侧面、背面也形成n型扩散层。
发明内容
发明要解决的课题
如上所述,n型扩散层形成时,对于使用了氧氯化磷的气相反应,不仅在本来需要n型扩散层的一面(通常为受光面、表面),而且在另一面(非受光面、背面)、侧面也形成n型扩散层。此外,对于涂布含有磷酸盐的溶液并使其热扩散的方法,与气相反应法同样地,在表面以外也形成n型扩散层。因此,为了作为元件具有pn结结构,在侧面必须进行蚀刻,在背面必须将n型扩散层变换为p型扩散层。一般地,在背面涂布作为第13族元素的铝的糊剂,进行烧成,将n型扩散层变换为p型扩散层。
本发明鉴于以上的以往的问题而研发的,其课题在于提供n型扩散层形成组合物、n型扩散层的制造方法和太阳能电池元件的制造方法,该n型扩散层形成组合物在使用了硅基板的太阳能电池元件的制造工序中,能够在没有形成不需要的n型扩散层的情况下,在特定的部分形成n型扩散层,在具有由此得到的n型扩散层的基板中载流子的寿命没有大幅度降低。
用于解决课题的手段
解决上述课题的手段如下所述。
<1>一种n型扩散层形成组合物,其含有:含给体元素,且寿命扼杀剂元素的总量为1000ppm以下的玻璃粉末;和分散介质。
<2>上述<1>所述的n型扩散层形成组合物,其中,所述给体元素为从P(磷)和Sb(锑)中选择的至少1种。
<3>上述<1>或<2>所述的n型扩散层形成组合物,其中,含所述给体元素的玻璃粉末含有从P2O3、P2O5和Sb2O3中选择的至少1种的含有给体元素的物质和从SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2和MoO3中选择的至少1种的玻璃成分物质。
<4>上述<1>~<3>中的任一项所述的n型扩散层形成组合物,其中,还含与所述玻璃粉末反应而结晶化的金属元素。
<5>上述<4>所述的n型扩散层形成组合物,其中,与所述玻璃粉末反应而结晶化的所述金属元素为从Ag(银)、Si(硅)和Zn(锌)中选择的至少1种。
<6>上述<1>~<5>中的任一项所述的n型扩散层形成组合物,其中,所述寿命扼杀剂元素为从Fe(铁)、Cu(铜)、Ni(镍)、Mn(锰)、Cr(铬)、W(钨)和Au(金)中选择的至少1种。
<7>一种n型扩散层的制造方法,其具有:涂布上述<1>~<6>中的任一项所述的n型扩散层形成组合物的工序;和实施热扩散处理的工序。
<8>一种太阳能电池元件的制造方法,其具有:在半导体基板上涂布上述<1>~<6>中的任一项所述的n型扩散层形成组合物的工序;实施热扩散处理,形成n型扩散层的工序;和在已形成的所述n型扩散层上形成电极的工序。
发明的效果
根据本发明,在使用了硅基板的太阳能电池元件的制造工序中,能够在没有形成不需要的n型扩散层的情况下在特定的部分形成n型扩散层,形成了n型扩散层的基板中的载流子的寿命没有大幅度地降低。
附图说明
图1为示意性地表示本发明的太阳能电池元件的制造工序的一例的剖面图。
图2A为从表面观察太阳能电池元件的俯视图。
图2B为将图2A的一部分放大表示的立体图。
具体实施方式
首先,对本发明的n型扩散层形成组合物进行说明,其次,对使用n型扩散层形成组合物的n型扩散层和太阳能电池元件的制造方法进行说明。
需要说明的是,本说明书中“工序”的用语不仅是指独立的工序,即使在与其他工序不能明确地区分的情况下如果能实现该工序的所期望的作用的情况,则也包含在本用语中。
此外,本说明书中“~”,表示包含其前后记载的数值分别作为最小值和最大值的范围。
此外,本说明书中提及组合物中的各成分的量的情况下,在组合物中存在多种与各成分相当的物质的情况下,只要无特别说明,则意味着组合物中存在的该多种物质的合计量。
本发明的n型扩散层形成组合物含有:至少含给体元素且寿命扼杀剂元素的总量为1000ppm以下的玻璃粉末(以下有时简称为“玻璃粉末”)和分散介质,进而考虑涂布性等,可根据需要含有其他的添加剂。
其中,所谓n型扩散层形成组合物,是指如下材料:含有给体元素,例如,通过在硅基板涂布后进行热扩散处理(烧成),从而能够使该给体元素热扩散,形成n型扩散层的材料。通过使用本发明的n型扩散层形成组合物,从而只在赋予了n型扩散层形成组合物的所需的部位形成n型扩散层,在没有赋予n型扩散层形成组合物的背面、侧面不会形成不需要的n型扩散层。
因此,如果应用本发明的n型扩散层形成组合物,则以往广泛采用的气相反应法中必需的侧蚀刻工序变得不需要,使工序变得简单。此外,将在背面形成的n型扩散层变换为p+型扩散层的工序也变得不需要。因此,对背面的p+型扩散层的形成方法,背面电极的材质、形状和厚度没有限制,应用的制造方法、材质、形状的选择范围变宽。此外,详细情况将后述,因背面电极的厚度而造成在硅基板内产生内部应力的情况得到抑制,硅基板的翘曲也得以抑制。
此外,本发明的n型扩散层形成组合物,由于其中所含的玻璃粉末中的寿命扼杀剂元素的总量为1000ppm以下,因此形成了n型扩散层的基板中的载流子的寿命不会大幅度降低。寿命扼杀剂元素的详细情况将后述。
需要说明的是,本发明的n型扩散层形成组合物中含有的玻璃粉末通过烧成而熔融,在n型扩散层上形成玻璃层。但是,在以往的气相反应法、涂布含有磷酸盐的溶液的方法中也在n型扩散层上形成了玻璃层。因此,本发明中生成的玻璃层与以往的方法同样地,能够采用蚀刻除去。因此,本发明的n型扩散层形成组合物与以往的方法相比,没有产生不需要的生成物,也没有使工序增加。
此外,玻璃粉末中的给体成分在烧成中也难以挥散,因此由于挥散气体的发生而造成使n型扩散层不仅在表面形成而且甚至在背面、侧面也形成的情况得以抑制。
作为其理由,认为是给体成分与玻璃粉末中的元素结合,或者进入玻璃中,因此难以挥散。
这样,本发明的n型扩散层形成组合物,能够在所需的部位形成所需的浓度的n型扩散层,因此能够形成n型掺杂剂浓度高的选择性区域。另一方面,采用作为n型扩散层的一般的方法的气相反应法、使用含有磷酸盐的溶液的方法,一般难以形成n型掺杂剂浓度高的选择性区域。
对本发明涉及的含有给体元素的玻璃粉末,详细地说明。
所谓给体元素,是指通过在硅基板中掺杂而能够形成n型扩散层的元素。作为给体元素,能够使用第15族的元素,可列举例如P(磷)、Sb(锑)、Bi(铋)和As(砷)等。从安全性、玻璃化的容易性等的观点出发,优选P或Sb。
作为用于将给体元素导入玻璃粉末的含有给体元素的物质,可列举P2O3、P2O5、Sb2O3、Bi2O3和As2O3,优选使用从P2O3、P2O5和Sb2O3中选择的至少1种。
此外,对于玻璃粉末,通过根据需要调节成分比率,能够控制熔融温度、软化点、玻璃化转变温度、化学耐久性等。优选还含有以下所述的成分。
作为玻璃成分物质,可列举SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、V2O5、SnO、ZrO2、MoO3、La2O3、Nb2O5、Ta2O5、Y2O3、TiO2、ZrO2、GeO2、TeO2和Lu2O3等,优选使用从SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2和MoO3中选择的至少1种。
作为含给体元素的玻璃粉末的具体例,可列举含上述含有给体元素的物质和上述玻璃成分物质这两者的体系,可列举P2O5-SiO2系(按含有给体元素的物质-玻璃成分物质的顺序记载,下同)、P2O5-K2O系、P2O5-Na2O系、P2O5-Li2O系、P2O5-BaO系、P2O5-SrO系、P2O5-CaO系、P2O5-MgO系、P2O5-BeO系、P2O5-ZnO系、P2O5-CdO系、P2O5-PbO系、P2O5-CeO2系、P2O5-SnO系、P2O5-GeO2系、P2O5-TeO2系等含P2O5作为含有给体元素的物质的体系的玻璃粉末、代替上述的含P2O5的体系的P2O5而含Sb2O3作为含有给体元素的物质的体系的玻璃粉末。
此外,可以是如P2O5-Sb2O3系、P2O5-As2O3系等那样含2种以上的含有给体元素的物质的玻璃粉末。
上述中例示了含2成分的复合玻璃,也可以是P2O5-SiO2-CeO2、P2O5-SiO2-CaO等根据需要的3种以上的复合玻璃。
使载流子的寿命降低的元素(寿命扼杀剂元素)在玻璃粉末中的总量为1000ppm以下,优选500ppm以下,更优选100ppm以下,进一步优选10ppm以下。
作为寿命扼杀剂元素,可列举Fe、Cu、Ni、Mn、Cr、W和Au等。这些的元素量能够采用ICP质量分析装置、ICP光谱分析装置、原子吸收光谱分析装置分析。此外,载流子的寿命能够采用微波光导电衰减法(μ-PCD法)测定。
玻璃粉末中的玻璃成分物质的含有比率,希望考虑熔融温度、软化温度、玻璃化转变温度、化学耐久性而适当设定,一般地,优选为0.1质量%以上95质量%以下,更优选为0.5质量%以上90质量%以下。
玻璃粉末的软化温度,从扩散处理时的扩散性、液体低垂的观点出发,优选为200℃~1000℃,更优选为300℃~900℃。需要说明的是,玻璃粉末的软化温度,能够采用公知的差示热分析装置(DTA),由其吸热峰容易地测定。
作为玻璃粉末的形状,可列举大致球状、扁平状、块状、板状和鳞片状等,从形成n型扩散层形成组合物时的对基板的涂布性、均一扩散性的方面出发,希望为大致球状、扁平状或板状。
玻璃粉末的粒径,希望为100μm以下。使用了具有100μm以下的粒径的玻璃粉末的情况下,容易获得平滑的涂膜。而且,玻璃粉末的粒径更希望为50μm以下。需要说明的是,对下限并无特别限制,优选为0.01μm以上。
其中,玻璃的粒径表示平均粒径,能够采用激光散射衍射法粒度分布测定装置等测定。
含给体元素的玻璃粉末按以下的顺序制作。
最初,秤量原料,填充到坩埚。作为坩埚的材质,可列举铂、铂-铑、铱、氧化铝、石英、碳等,考虑熔融温度、气氛、与熔融物质的反应性等来适当选择。
接下来,用电炉在根据玻璃组成的温度下加热,形成熔融液。此时,为了使熔融液均匀,希望进行搅拌。
接着,将得到的熔融液浇铸到氧化锆基板、碳基板等上,使熔融液成为玻璃。
最后,将玻璃粉碎而成为粉末状。对于粉碎,可应用喷射磨机、珠磨机、球磨机等公知的方法。
n型扩散层形成组合物中的含给体元素的玻璃粉末的含有比率,考虑涂布性、给体元素的扩散性等而决定。一般地,n型扩散层形成组合物中的玻璃粉末的含有比率优选为0.1质量%以上95质量%以下,更优选为1质量%以上90质量%以下。
接下来,对分散介质进行说明。
所谓分散介质,是指在组合物中使上述玻璃粉末分散的介质。具体而言,作为分散介质,采用粘结剂、溶剂等。
作为粘结剂,例如,可适当选择(甲基)丙烯酸二甲基氨基乙酯聚合物、聚乙烯醇、聚丙烯酰胺类、聚乙烯基酰胺类、聚乙烯基吡咯烷酮、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、瓜尔胶及瓜尔胶衍生物、硬葡聚糖及硬葡聚糖衍生物、黄蓍胶及黄蓍胶衍生物、糊精及糊精衍生物、丙烯酸树脂、丙烯酸酯树脂、丁二烯树脂、苯乙烯树脂、及它们的共聚物、以及二氧化硅等。这些可单独使用1种,或者将2种以上组合使用。
对粘结剂的分子量并无特别限制,希望考虑作为组合物的所需的粘度来适当调节。
作为溶剂,可列举例如丙酮、甲基乙基酮、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、乙二醇二甲醚、乙二醇二乙醚、乙二醇二正丙醚、乙二醇二丁醚、二甘醇二甲醚、二甘醇二乙醚、二甘醇甲基乙基醚、二甘醇甲基正丙基醚、二甘醇甲基正丁基醚、二甘醇二正丙醚、二甘醇二正丁醚、二甘醇甲基正己基醚、三甘醇二甲醚、三甘醇二乙醚、三甘醇甲基乙基醚、三甘醇甲基正丁基醚、三甘醇二正丁基醚、三甘醇甲基正己基醚、四甘醇二甲醚、四甘醇二乙醚、四甘醇甲基乙基醚、四甘醇甲基正丁基醚、二甘醇二正丁醚、四甘醇甲基正己基醚、四甘醇二正丁醚、丙二醇二甲醚、丙二醇二乙醚、丙二醇二正丙醚、丙二醇二丁醚、二丙二醇二甲醚、二丙二醇二乙醚、二丙二醇甲基乙基醚、二丙二醇甲基正丁基醚、二丙二醇二正丙醚、二丙二醇二正丁醚、二丙二醇甲基正己基醚、三丙二醇二甲醚、三丙二醇二乙醚、三丙二醇甲基乙基醚、三丙二醇甲基正丁基醚、三丙二醇二正丁醚、三丙二醇甲基正己基醚、四丙二醇二甲醚、四丙二醇二乙醚、四丙二醇甲基乙基醚、四丙二醇甲基正丁基醚、二丙二醇二正丁醚、四丙二醇甲基正己基醚、四丙二醇二正丁醚等醚系溶剂;醋酸甲酯、醋酸乙酯、醋酸正丙酯、醋酸异丙酯、醋酸正丁酯、醋酸异丁酯、醋酸仲丁酯、醋酸正戊酯、醋酸仲戊酯、醋酸3-甲氧基丁酯、醋酸甲基戊酯、醋酸2-乙基丁酯、醋酸2-乙基己酯、醋酸2-(2-丁氧基乙氧基)乙酯、醋酸苄酯、醋酸环己酯、醋酸甲基环己酯、醋酸壬酯、乙酰乙酸甲酯、乙酰乙酸乙酯、醋酸二甘醇单甲醚、醋酸二甘醇单乙醚、醋酸二甘醇单正丁醚、醋酸二丙二醇单甲醚、醋酸二丙二醇单乙醚、二醋酸乙二醇酯、醋酸甲氧基三甘酯、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、乳酸正戊酯、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、二甘醇甲基醚乙酸酯、二甘醇乙基醚乙酸酯、二甘醇正丁基醚乙酸酯、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、二丙二醇甲基醚乙酸酯、二丙二醇乙基醚乙酸酯、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、二甘醇、二丙二醇、三甘醇、三丙二醇等醇系溶剂;乙二醇甲基醚、乙二醇乙基醚、乙二醇单苯基醚、二甘醇单甲基醚、二甘醇单乙基醚、二甘醇单正丁基醚、二甘醇单正己基醚、乙氧基三甘醇、四甘醇单正丁基醚、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-萜品烯、α-萜品醇、月桂烯、别罗勒烯、柠檬烯、二茂烯、α-蒎烯、β-蒎烯、萜品醇、香芹酮、罗勒烯、水茴香烯等萜烯系溶剂;水等。这些可单独使用1种,或者将2种以上组合使用。
制成n型扩散层形成组合物的情况下,从对基板的涂布性的观点出发,作为优选的溶剂,可列举α-萜品醇、二甘醇单正丁醚、醋酸2-(2-丁氧基乙氧基)乙酯。
n型扩散层形成组合物中的分散介质的含有比率,考虑涂布性、给体浓度而决定。
n型扩散层形成组合物的粘度,考虑涂布性,优选为10mPa·S以上1000000mPa·S以下,更优选为50mPa·S以上500000mPa·S以下。
此外,n型扩散层形成组合物可含有其他的添加剂。作为其他的添加物,可列举例如容易与上述玻璃粉末反应的金属。
将n型扩散层形成组合物涂布到半导体基板上,在高温下进行热处理,从而形成n型扩散层,但此时在表面形成玻璃。该玻璃通过浸渍于氢氟酸等酸而除去,因玻璃的种类不同,也有难以除去的玻璃。这种情况下,通过预先添加容易与玻璃结晶化的Ag、Zn、Si等金属,能够在酸洗涤后容易地将玻璃除去。这些中,优选使用从Ag、Si和Zn中选择的至少1种。
容易与玻璃粉末反应的金属的含有比率,希望根据玻璃的种类、该金属的种类适当地调整,一般地,相对于上述玻璃粉末,优选为0.01质量%以上10质量%以下。
需要说明的是,上述玻璃粉末中的寿命扼杀剂元素的总量为1000ppm以下的情况下,n型扩散层形成粗组合物中的寿命扼杀剂元素的总量大约为1100ppm以下。因此,上述n型扩散层形成粗组合物中的寿命扼杀剂元素的总量优选为500ppm以下,更优选为100ppm以下。
接下来,参照图1对本发明的n型扩散层和太阳能电池元件的制造方法进行说明。图1是示意性地表示本发明的太阳能电池元件的制造工序的一例的剖面示意图。以后的附图中,对共同的构成要素标注相同的附图标记。
图1(1)中,对作为p型半导体基板10的硅基板给予碱溶液,将损伤层除去,通过蚀刻得到纹理结构。
详细地说,用20质量%苛性钠将从锭上切片下来时产生的硅表面的损伤层除去。接下来,利用1质量%苛性钠和10质量%异丙醇的混合液进行蚀刻,形成纹理结构(图中,省略了纹理结构的记载)。太阳能电池元件,通过在受光面(表面)侧形成纹理结构,促进光封闭效果,实现高效率化。
图1(2)中,在p型半导体基板10的表面即成为受光面的面,涂布上述n型扩散层形成组合物,形成n型扩散层形成组合物层11。本发明中,对涂布方法并无限制,例如,有印刷法、旋涂法、刷毛涂布、喷涂法、刮刀法、辊式涂布机法、喷墨法等。
作为上述n型扩散层形成组合物的涂布量,并无特别限制。例如,作为玻璃粉末量,可设为0.01g/m2~100g/m2,优选为0.1g/m2~10g/m2。
需要说明的是,根据n型扩散层形成组合物的组成,在涂布后,可设置用于使组合物中所含的溶剂挥发的干燥工序。这种情况下,在80~300℃左右的温度下,使用热板的情况下用1~10分钟,使用干燥机等的情况下用10~30分钟左右使其干燥。该干燥条件依赖于n型扩散层形成组合物的溶剂组成,本发明中,并不特别限定于上述条件。
此外,使用本发明的制造方法的情况下,背面的p+型扩散层(高浓度电场层)14的制造方法,并不限定于采用利用铝的由n型扩散层向p型扩散层的变换的方法,能够采用以往公知的任何方法,制造方法的选择范围变宽。因此,例如,赋予含B(硼)等第13族元素的组合物13,能够形成高浓度电场层14。
作为上述含B(硼)等第13族元素的组合物13,例如,可列举代替含给体元素的玻璃粉末而使用含受体元素的玻璃粉末,与n型扩散层形成组合物同样地构成的p型扩散层形成组合物。受体元素为第13族元素即可,例如,可列举B(硼)、Al(铝)和Ga(镓)等。此外,含受体元素的玻璃粉末优选含从B2O3、Al2O3和Ga2O3中选择的至少1种。
此外,将p型扩散层形成组合物赋予硅基板的背面的方法与已述的将n型扩散层形成组合物涂布到硅基板上的方法相同。
通过对赋予背面的p型扩散层形成组合物,与后述的n型扩散层形成组合物中的热扩散处理同样地进行热扩散处理,从而可在背面形成高浓度电场层14。需要说明的是,p型扩散层形成组合物的热扩散处理优选与n型扩散层形成组合物的热扩散处理同时地进行。
接下来,将形成了上述n型扩散层形成组合物层11的半导体基板10在600~1200℃下进行热扩散处理。通过该热扩散处理,如图1(3)中所示,给体元素向半导体基板中扩散,形成n型扩散层12。对于热扩散处理,能够应用公知的连续炉、间歇炉等。此外,热扩散处理时的炉内气氛也能够适当地调节为空气、氧气、氮气等。
热扩散处理时间可根据n型扩散层形成组合物中所含的给体元素的含有率等适当选择。例如,可为1分钟~60分钟,更优选为5分钟~30分钟。
由于在形成的n型扩散层12的表面形成了磷酸玻璃等玻璃层(未图示),因此通过蚀刻将该玻璃层除去。作为蚀刻,能够应用浸渍于氢氟酸等酸的方法、浸渍于苛性钠等碱的方法等公知的方法。
在图1(2)和(3)中所示的、使用本发明的n型扩散层形成组合物11形成n型扩散层12的本发明的n型扩散层的形成方法中,只在所需的部位形成n型扩散层12,在背面、侧面没有形成不需要的n型扩散层。
因此,采用以往广泛采用的气相反应法形成n型扩散层的方法中,用于将在侧面形成的不需要的n型扩散层除去的侧蚀刻工序是必需的,但根据本发明的制造方法,侧蚀刻工序变得不需要,使工序变得简单。
此外,对于以往的制造方法,必须将在背面形成的不需要的n型扩散层变换为p型扩散层,作为该变换方法,采用了如下方法:将作为第13族元素的铝的糊剂涂布于背面的n型扩散层,进行烧成,使铝向n型扩散层扩散,变换为p型扩散层。该方法中为了使向p型扩散层的变换充分,而且形成p+型扩散层的高浓度电场层,铝量达到某程度以上是必需的,因此必须形成厚的铝层。但是,铝的热膨胀率与用作基板的硅的热膨胀率的差异大,因此在烧成和冷却的过程中在硅基板中产生大的内部应力,成为了硅基板的翘曲的原因。
该内部应力对结晶的晶粒间界给予损伤,存在电力损失变大的课题。此外,翘曲在模块工序中的太阳能电池元件的搬送、与称为极耳线的铜线的连接中,容易使电池破损。近年来,由于切片加工技术的提高,因此硅基板的厚度不断薄型化而且太阳能电池元件倾向于容易断裂。
但是,根据本发明的制造方法,由于在背面没有形成不需要的n型扩散层,因此不必进行从n型扩散层向p型扩散层的变换,没有使铝层变厚的必然性。其结果,能够抑制硅基板内的内部应力的发生、翘曲。结果,能够抑制电力损失的增大、太阳能电池元件的破损。
此外,使用本发明的制造方法的情况下,背面的p+型扩散层(高浓度电场层)14的制造方法并不限定于采用利用铝的由n型扩散层向p型扩散层的变换的方法,能够采用以往公知的任何方法,制造方法的选择范围变宽。
例如,优选代替含给体元素的玻璃粉末而使用含受体元素的玻璃粉末,将与n型扩散层形成组合物同样地构成的p型扩散层形成组合物涂布于硅基板的背面(涂布了n型扩散层形成组合物的面的相反侧的面),进行烧成处理,从而在背面形成p+型扩散层(高浓度电场层)14。
此外,如后所述,用于背面的表面电极20的材料并不限定于第13族的铝,能够应用例如Ag(银)、Cu(铜)等,背面的表面电极20的厚度也能够比以往的厚度薄地形成。
图1(4)中,在n型扩散层12上形成防反射膜16。防反射膜16采用公知的技术形成。例如,防反射膜16为硅氮化膜的情况下,采用以SiH4和NH3的混合气体为原料的等离子体CVD法形成。此时,氢在结晶中扩散,不参与硅原子结合的轨道,即悬空键与氢结合,使缺陷失活(氢钝化)。
更具体而言,在上述混合气体流量比NH3/SiH4为0.05~1.0、反应室的压力为0.1~2Torr、成膜时的温度为300~550℃、用于等离子体的放电的频率为100kHz以上的条件下形成。
图1(5)中,在表面(受光面)的防反射膜16上,采用丝网印刷法将表面电极用金属糊剂印刷涂布,使其干燥,形成表面电极18。表面电极用金属糊剂以(1)金属粒子和(2)玻璃粒子为必要成分,根据需要含有(3)树脂粘结剂、(4)其他的添加剂等。
接下来,在上述背面的高浓度电场层14上也形成背面电极20。如前所述,在本发明中,对背面电极20的材质、形成方法并无特别限定。例如,可将含铝、银或铜等金属的背面电极用糊剂涂布,使其干燥,形成背面电极20。此时,在背面,为了模块工序中的电池间的连接,也可在一部分赋予银电极形成用银糊剂。
图1(6)中,将电极烧成,完成太阳能电池元件。如果在600~900℃的范围烧成数秒~数分钟,则在表面侧利用电极用金属糊剂中所含的玻璃粒子,作为绝缘膜的防反射膜16熔融,而且硅10表面也一部分熔融,糊剂中的金属粒子(例如银粒子)与硅基板10形成接触部,凝固。由此,使形成的表面电极18与硅基板10导通。将其称为烧通(フアイア一スル一)。
对表面电极18的形状进行说明。表面电极18由主栅线(bus bar)电极30和与该主栅线电极30交叉的指状电极32构成。图2A是对使表面电极18为由主栅线电极30和与该主栅线电极30交叉的指状电极32组成的构成的太阳能电池元件从表面看到的俯视图,图2B为将图2A的一部分放大表示的立体图。
这样的表面电极18,例如,能够采用上述的金属糊剂的丝网印刷、或电极材料的镀敷、利用高真空中的电子束加热的电极材料的蒸镀等手段形成。一般已使用由主栅线电极30和指状电极32组成的表面电极18作为受光面侧的电极,这些是公知的,可应用受光面侧的主栅线电极和指状电极的公知的形成手段。
上述中,对在表面形成n型扩散层,在背面形成p+型扩散层,而且在各个层上设置了表面电极和背面电极的太阳能电池元件进行了说明,但只要使用本发明的n型扩散层形成组合物,也能够制作背接触型的太阳能电池元件。
背接触型的太阳能电池元件是将电极全部设置在背面而使受光面的面积增大的太阳能电池元件。即,背接触型的太阳能电池元件中,必须在背面形成n型扩散部位和p+型扩散部位这两者,形成pn结结构。本发明的n型扩散层形成组合物能够只在特定的部位形成n型扩散部位,因此,适宜应用于背接触型的太阳能电池元件的制造。
需要说明的是,日本申请2010-100222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、专利申请和技术标准,以参照的形式将各个文献、专利申请和技术标准并入本说明书中,该情况下与具体地并且各自记载的情形相同程度地,作为参照并入本说明书中。
实施例
以下更具体地对本发明的实施例进行说明,但本发明并不限于这些实施例。需要说明的是,只要无特别记载,药品全部使用了试剂。此外,只要无特别说明,“%”意味着“mol%”。
需要说明的是,以下所示的“载流子的寿命”是用相对值表示的,是指实施例或比较例中制作的具有n型扩散层的p型硅基板的载流子的寿命相对于通过以往的气相扩散形成了n型扩散层的p型硅基板的载流子的寿命的相对值。载流子的寿命,从实用的观点出发,将70%以上作为合格。
[实施例1]
将粒子形状为大致球状、平均粒径为3.5μm的SiO2-P2O5-CaO系玻璃(SiO2:60mol%、P2O5:30mol%、CaO:10mol%、寿命扼杀剂元素970ppm)粉末10g和乙基纤维素4g、醋酸2-(2-丁氧基乙氧基)乙酯86g使用自动乳钵混炼装置进行混合而糊剂化,调制n型扩散层形成组合物。
需要说明的是,对于玻璃粉末中的寿命扼杀剂元素,使用高频电感耦合等离子体发光分光分析装置和高频电感耦合等离子体质量分析装置,对其含量和元素的种类进行分析。以下实施例中同样。玻璃粉末中,作为寿命扼杀剂元素,含有Fe、Cu、Ni。
此外,对于玻璃粒子形状,使用(株)日立高技术制TM-1000型扫描型电子显微镜进行观察来判定。对于玻璃的平均粒径,使用Beckmancoulter(株)制LS 13 320型激光散射衍射法粒度分布测定装置(测定波长:632nm)算出。
接下来,将调制的糊剂(n型扩散层形成组合物)采用丝网印刷涂布于p型硅基板表面,在150℃的热板上使其干燥5分钟。接下来,用设定为1000℃的电炉进行10分钟热扩散处理,然后,为了将在表面形成的玻璃层除去,将基板浸渍于氢氟酸中5分钟,进行流水洗涤,然后进行干燥。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为50Ω/□,P(磷)扩散,形成了n型扩散层。背面的薄膜电阻为1000000Ω/□以上,不能测定,判断为实质上没有形成n型扩散层。此外,载流子的寿命为75%。
[实施例2]
除了将使用的玻璃粉末替换为SiO2-P2O5-CaO系玻璃粉末(SiO2:60mol%、P2O5:30mol%、CaO:10mol%、寿命扼杀剂元素550ppm、大致球状、平均粒径3.2μm)以外,与实施例1同样地进行n型扩散层形成。在玻璃粉末中,作为寿命扼杀剂元素,含有Fe、Cu、Ni。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为46Ω/□,P(磷)扩散,形成了n型扩散层。背面的薄膜电阻为1000000Ω/□以上,不能测定,判断为实质上没有形成n型扩散层。此外,载流子的寿命为80%。
[实施例3]
除了将使用的玻璃粉末替换为SiO2-P2O5-CaO系玻璃粉末(SiO2:60mol%、P2O5:30mol%、CaO:10mol%、寿命扼杀剂元素460ppm、大致球状、平均粒径3.1μm)以外,与实施例1同样地进行n型扩散层形成。在玻璃粉末中,作为寿命扼杀剂元素,含有Fe、Cu、Ni。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为51Ω/□,P(磷)扩散,形成了n型扩散层。背面的薄膜电阻为1000000Ω/□以上,不能测定,判断为实质上没有形成n型扩散层。此外,载流子的寿命为85%。
[实施例4]
除了将使用的玻璃粉末替换为SiO2-P2O5-CaO系玻璃粉末(SiO2:60mol%、P2O5:30mol%、CaO:10mol%、寿命扼杀剂元素110ppm、大致球状、平均粒径3.5μm)以外,与实施例1同样地进行n型扩散层形成。在玻璃粉末中,作为寿命扼杀剂元素,含有Fe、Cu、Ni。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为47Ω/□,P(磷)扩散,形成了n型扩散层。背面的薄膜电阻为1000000Ω/□以上,不能测定,判断为实质上没有形成n型扩散层。此外,载流子的寿命为90%。
[实施例5]
除了将使用的玻璃粉末替换为SiO2-P2O5-CaO系玻璃粉末(SiO2:60mol%、P2O5:30mol%、CaO:10mol%、寿命扼杀剂元素90ppm、大致球状、平均粒径3.3μm)以外,与实施例1同样地进行n型扩散层形成。在玻璃粉末中,作为寿命扼杀剂元素,含有Fe、Cu、Ni。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为47Ω/□,P(磷)扩散,形成了n型扩散层。背面的薄膜电阻为1000000Ω/□以上,不能测定,判断为实质上没有形成n型扩散层。此外,载流子的寿命为92%。
[实施例6]
除了将使用的玻璃粉末替换为SiO2-P2O5-CaO系玻璃粉末(SiO2:60mol%、P2O5:30mol%、CaO:10mol%、寿命扼杀剂元素20ppm、大致球状、平均粒径3.1μm)以外,与实施例1同样地进行n型扩散层形成。在玻璃粉末中,作为寿命扼杀剂元素,含有Fe、Cu、Ni。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为50Ω/□,P(磷)扩散,形成了n型扩散层。背面的薄膜电阻为1000000Ω/□以上,不能测定,判断为实质上没有形成n型扩散层。此外,载流子的寿命为97%。
[实施例7]
除了将使用的玻璃粉末替换为SiO2-P2O5-CaO系玻璃粉末(SiO2:60mol%、P2O5:30mol%、CaO:10mol%、寿命扼杀剂元素8ppm、大致球状、平均粒径3.2μm)以外,与实施例1同样地进行n型扩散层形成。在玻璃粉末中,作为寿命扼杀剂元素,含有Fe、Cu、Ni。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为50Ω/□,P(磷)扩散,形成了n型扩散层。背面的薄膜电阻为1000000Ω/□以上,不能测定,判断为实质上没有形成n型扩散层。此外,载流子的寿命为100%。
[比较例1]
将磷酸二氢铵(NH4H2PO4)粉末20g和乙基纤维素3g、醋酸2-(2-丁氧基乙氧基)乙酯7g混合而糊剂化,调制n型扩散层组合物。
接下来,将调制的糊剂采用丝网印刷涂布于p型硅基板表面,在150℃的热板上使其干燥5分钟。接着,用设定为1000℃的电炉进行10分钟热扩散处理,然后,为了将玻璃层除去,将基板浸渍于氢氟酸中5分钟,进行流水洗涤、干燥。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为14Ω/□,P(磷)扩散,形成了n型扩散层。但是,背面的薄膜电阻为50Ω/□,在背面也形成了n型扩散层。
[比较例2]
将磷酸二氢铵(NH4H2PO4)粉末1g和纯水7g、聚乙烯醇0.7g、异丙醇1.5g混合,调制溶液,调制n型扩散层组合物。
接下来,将调制的溶液用旋转涂布器(2000rpm、30秒)涂布于p型硅基板表面,在150℃的热板上使其干燥5分钟。接着,用设定为1000℃的电炉进行10分钟热扩散处理,然后为了将玻璃层除去,将基板浸渍于氢氟酸中5分钟,进行流水洗涤、干燥。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为10Ω/□,P(磷)扩散,形成了n型扩散层。但是,背面的薄膜电阻为100Ω/□,在背面也形成了n型扩散层。
[比较例3]
将粒子形状为大致球状、平均粒径为3.1μm的SiO2-P2O5-CaO系玻璃(SiO2:60mol%、P2O5:30mol%、CaO:10mol%、寿命扼杀剂元素1150ppm)粉末10g和乙基纤维素4g、醋酸2-(2-丁氧基乙氧基)乙酯86g混合而糊剂化,调制n型扩散层形成组合物。在玻璃粉末中,作为寿命扼杀剂元素,含有Fe、Cu、Ni。
接下来,将调制的糊剂(p型扩散层形成组合物)采用丝网印刷涂布于p型硅基板表面,在150℃的热板上使其干燥5分钟。接着,用设定为1000℃的电炉进行10分钟热扩散处理,然后为了将玻璃层除去,将基板浸渍于氢氟酸中5分钟,进行流水洗涤,然后,进行干燥。
涂布了n型扩散层形成组合物的一侧的表面的薄膜电阻为48Ω/□,P(磷)扩散,形成了n型扩散层。背面的薄膜电阻为1000000Ω/□以上,不能测定,没有形成n型扩散层。但是,载流子的寿命低至67%。
附图标记的说明
10 p型半导体基板
12 n型扩散层
14高浓度电场层
16防反射膜
18表面电极
20背面电极(电极层)
30主栅线电极
32指状电极
Claims (9)
1.一种n型扩散层形成组合物,其含有:含给体元素,且寿命扼杀剂元素的总量为1000ppm以下的玻璃粉末;和分散介质。
2.如权利要求1所述的n型扩散层形成组合物,其中,所述给体元素为从磷P和锑Sb中选择的至少1种。
3.如权利要求1或2所述的n型扩散层形成组合物,其中含所述给体元素的玻璃粉末含有:从P2O3、P2O5和Sb2O3中选择的至少1种的含有给体元素的物质;和从SiO2、K2O、Na2O、Li2O、BaO、SrO、CaO、MgO、BeO、ZnO、PbO、CdO、SnO、ZrO2和MoO3中选择的至少1种的玻璃成分物质。
4.如权利要求1所述的n型扩散层形成组合物,其中,还含有与所述玻璃粉末反应而结晶化的金属元素。
5.如权利要求4所述的n型扩散层形成组合物,其中,与所述玻璃粉末反应而结晶化的所述金属元素为从银Ag和锌Zn中选择的至少1种。
6.如权利要求1所述的n型扩散层形成组合物,其中,还含有与所述玻璃粉末反应而结晶化的硅Si。
7.如权利要求1所述的n型扩散层形成组合物,其中,所述寿命扼杀剂元素为从铁Fe、铜Cu、镍Ni、锰Mn、铬Cr、钨W和金Au中选择的至少1种。
8.一种n型扩散层的制造方法,其具有:涂布权利要求1~7中的任一项所述的n型扩散层形成组合物的工序;和实施热扩散处理的工序。
9.一种太阳能电池元件的制造方法,其具有:在半导体基板上涂布权利要求1~7中的任一项所述的n型扩散层形成组合物的工序;实施热扩散处理而形成n型扩散层的工序;和在已形成的所述n型扩散层上形成电极的工序。
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TWI603386B (zh) * | 2012-02-23 | 2017-10-21 | 日立化成股份有限公司 | n型擴散層形成組成物、具有n型擴散層的半導體基板的製造方法以及太陽電池元件的製造方法 |
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