CN1862839A - 半导体器件的制造方法及其中用到的导电组合物 - Google Patents
半导体器件的制造方法及其中用到的导电组合物 Download PDFInfo
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- CN1862839A CN1862839A CNA2006100748111A CN200610074811A CN1862839A CN 1862839 A CN1862839 A CN 1862839A CN A2006100748111 A CNA2006100748111 A CN A2006100748111A CN 200610074811 A CN200610074811 A CN 200610074811A CN 1862839 A CN1862839 A CN 1862839A
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Abstract
本发明涉及一种厚膜导电组合物,包含:分散在(d)有机介质中的(a)导电银粉;(b)含锰的添加剂;(c)玻璃料,其中所述玻璃料的软化点在300-600℃。本发明还涉及一种半导体器件以及从结构构件制造该半导体器件的方法,所述结构构件由具有p-n接面的半导体和形成在半导体主要表面上的绝缘薄膜组成。所述制造方法包括步骤(a)将如上所述的厚膜组合物施加在所述绝缘薄膜上;和(b)烧制所述半导体、绝缘薄膜和厚膜组合物以形成电极。
Description
技术领域
本发明主要涉及硅半导体器件。具体地说,本发明涉及用于太阳能电池器件前侧的导电银糊浆(silver paste)。
背景技术
本发明可用于多种半导体器件中,虽然它在光接收元件如光电二极管和太阳能电池中特别有效。下文将以太阳能电池作为现有技术的一个具体实例来对本发明的
背景技术进行描述。
具有p型基极(base)的传统太阳能电池结构有一个通常位于电池的前侧或太阳面的负电极,还有一个位于背侧正电极背侧。众所周知,落在半导体p-n接面上的合适波长的辐射是在半导体中产生空穴-电子对的外部能量源。因为在p-n接面上存在的电势差,空穴和电子以相反的方向移动穿过该接面,因此产生了电流的流动,这种流动可将电能传递给外电路。大多数太阳能电池是硅片形式,这些硅片是金属化的,即具有导电性的金属触点。
现在世界上所用的大多数发电的太阳能电池是硅太阳能电池。大规模生产的流程的目的一般是使程序最简单并且使生产成本最小。这种方法中所用的电极是通过例如丝网印刷的生产方法以形成金属糊浆来生产的。这种生产方法的一个例子在下文结合图1进行描述。图1所示为p型硅基片10。
图1(b)中,通过将磷(P)等热扩散来形成n型扩散层20,其为反向(reverse)导电型。通常用三氯氧化磷(POCl3)作为磷扩散源。不作任何特殊的改造,将扩散层20形成在硅基片10的整个表面上。该扩散层具有几十欧姆/方(Ω/□)的薄层电阻,其厚度约为0.3-0.5μm。
用抗蚀剂等保护该扩散层的一个表面之后,如图1(c)所示,用蚀刻的方法使扩散层20从大多数表面上去除从而使其只存在于一个主要表面上。然后用有机溶剂等将抗蚀剂去除。
接着,用等离子体化学气相沉积(CVD)等方法将氮化硅薄膜30以图1(d)所示的方式形成在n型扩散层20上,作为抗反射涂层,其厚度约为700-900。
如图1(e)所示,将用于正面电极的银糊浆500丝网印刷在氮化硅薄膜30上,然后干燥。此外,将背侧银糊浆或银/铝糊浆70以及铝糊浆60丝网印刷,然后在基片的背侧上干燥。然后,在红外加热炉中700-975℃下烧制,烧制时间从几分钟到几十分钟。
因此,如图1(f)所示,铝作为烧制中的掺杂物从铝糊浆扩散到硅基片10中,,形成含有高浓度的铝掺杂物的p+层40,。该层通常称为背侧场(BSF)层,有助于提高太阳能电池的能量转化效率。
通过烧制,铝糊浆从干燥状态60转化为背侧铝电极61。同时烧制背侧的银糊浆或银/铝糊浆,形成背侧银或银/铝电极71。烧制时,背侧的铝和背侧的银或银/铝的边界呈合金状态,且是电连接的。铝电极占了背电极的大部分面积,部分是因为需要形成p+层40。因为往铝电极上进行焊接是不可能的,所以通过铜代等将背侧银电极形成在背侧的多个部分上作为连接各太阳能电池的电极。此外,形成前侧电极的银糊浆500在烧制过程中烧结并且穿过氮化硅薄膜30,因此能够与n-型层20形成电接触。这种方法通常被称为“烧渗”(“fire through”)。这种“烧渗”的状态在图1(f)层501中很明显。
授予Shuichi等的JP-A 2001-313400教导了一种太阳能电池,通过在半导体基片的一个主要表面上形成具有其它类型的导电区域和在半导体基片的该主要表面上形成抗反射涂层来形成所述的太阳能电池。产生的太阳能电池具有涂覆有抗反射涂层并且经烧制的电极材料。所述电极材料包括,例如,铅、硼和硅,还包括软化点约为300-600℃的,以及选自钛、铋、钴、锌、锆、铁和铬的一种或多种粉末。这些粉末的平均粒径为0.1-5μm。Shuichi等教导,平均粒径小于0.1μm的粉末在电极中的扩散性将会很差,电极的粘附强度(抗张强度)不足。
虽然存在多种制造太阳能电池的方法和组合物,但是仍然在努力提高太阳能电池在应用中的电性能,同时改善其焊接粘附性。本发明是关于制造半导体器件的新组合物和方法,该方法同时改善太阳能电池的电学性能和焊接粘附性。
发明概述
本发明涉及厚膜导电组合物,包括扩散在(d)有机介质中的(a)导电银粉;(b)含有Mn的添加剂;(c)软化点在300-600℃范围内的玻璃料。
本发明还涉及一种半导体器件,以及从具有p-n接面的半导体和绝缘薄膜(形成在该半导体的主要表面上)的结构构件中制备所述半导体器件的方法,该方法包括步骤:(a)将如上所述的厚膜组合物施加到绝缘薄膜上;和(b)烧制所述半导体、绝缘薄膜和厚膜组合物以形成电极。
附图简述
图1是一个工艺流程图,表示半导体器件的制造。
下面解释了图1中的标号。
10:p型硅基片
20:n型扩散层
30:氮化硅薄膜、氧化钛薄膜或氧化硅薄膜
40:p+层(背侧电场,BSF)
60:在背侧上形成的铝糊浆
61:背侧铝电极(通过烧制背侧铝糊浆而获得)
70:在背侧上形成的银或银/铝糊浆
71:背侧银或银/铝电极(通过烧制背侧银糊浆而获得)
500:在前侧上形成的银糊浆
501:前侧银电极(通过烧制前侧银糊浆形成)
发明详述
厚膜导电体组合物的主要组分是扩散在有机介质中的具有电功能的银粉、含锌的添加剂以及玻璃料。其它的添加剂可包括金属、金属氧化物或在烧制过程中可产生这些金属氧化物的任何化合物。下面描述了这些组分。
I.无机组分
本发明的无机组分包括(1)具有电功能的银粉;(2)一种或多种含锰添加剂;(3)玻璃料;以及任选地(4)其它金属/金属氧化物添加剂,选自下列物质:(a)金属,所述金属选自Zn,Ti,Sn,Pb,Ru,Co,Fe,Cu和Cr;(b)金属氧化物,MOx,其中M选自Zn,Ti,Sn,Pb,Ru,Co,Fe,Cu和Cr;(c)烧制时可产生金属氧化物(b)的任何化合物;和(d)它们的混合物。
A.具有电功能的银粉
通常,厚膜组合物包含功能相,它使组合物具有合适的电功能性特性。功能相包括扩散在有机介质中的具有电功能的银粉,有机介质作为形成该组合物的功能相的载体。烧制组合物以烧尽有机相,活化无机粘合剂相并引入电功能性特性。
组合物的功能相可以是导电的涂覆或不涂覆的银颗粒。当银颗粒是涂覆的,它们至少部分被表面活性剂涂覆。表面活性剂可选自但不限于,硬脂酸、棕榈酸、硬脂酸盐、棕榈酸盐,及其混合物。其它可用的表面活性剂包括月桂酸、油酸、硬脂酸、癸酸、肉豆蔻酸和亚油酸。反离子可以是但不限于,氢、铵、钠、钾及其混合物。
虽然希望银的平均粒径不大于10微米,优选不大于5微米,但银的粒径不受任何具体的限制。银粉占糊浆状组合物的70-85%,一般占组合物固体(即不包括有机载体)的92-99wt%。
B.含锰的添加剂
本发明含锰的添加剂可选自(a)Mn,(b)Mn的金属氧化物,(c)烧制中可产生Mn的金属氧化物的任何化合物,和(d)它们的混合物。含锰的添加剂的平均粒径不是特别重要,但它必须与丝网印刷技术相容。通常,平均粒径小于10微米。
在一个实施方式中,所述含锰的添加剂是MnO2。在一个具体实施方式中,所述含锰的添加剂平均粒径为7纳米至小于100纳米。
C.玻璃料
可用于本发明的玻璃料组分的例子包括无定形、可部分结晶的硅酸铅玻璃组合分以及其它相容的玻璃料组分。在另一个实施方式中,这些玻璃料不含镉。可用于本发明的一些玻璃料组分详细列于表1中。
表1:玻璃料组分(占总玻璃组合物的重量百分比)
号码 | SiO2 | Al2O3 | PbO | B2O3 | CeO2 | ZnO | Na2O | Bi2O3 | Li2O | TiO2 | CaO | CdO |
123456 | 28.0026.0623.3722.9723.001.50 | 4.706.690.411.540.40 | 55.9050.9659.7560.6258.80 | 8.108.947.938.407.8014.90 | 0.10 | 2.792.312.46 | 1.0 | 81.5 | 0.041.0 | 3.304.566.204.026.10 | 3.90 |
以重量%表示的玻璃料组分示于表1。实施例中优选的不含镉的玻璃组合物包含组成比例如下所示的氧化物组分:SiO2 21-29,Al2O3 0.1-8,PbO50-62,B2O3 7-10,ZnO 0-4,Li2O 0-0.1,TiO2 2-7,以重量%计。更优选的玻璃料组合物是:SiO2 28.00,Al2O3 4.70,PbO 55.90,B2O3 8.1,TiO2 3.30,以重量%计。
此外,在另一个实施方式中,玻璃料组合物是不含铅的组合物。可用于本发明的不含铅的一些玻璃组合物包含组成比例如下所示的氧化物组分:SiO2 0.1-8,Al2O3 0-4,B2O3 8-25,CaO 0-1,ZnO 0-42,Na2O 0-4,Li2O 0-3.5,Bi2O3 28-85,Ag2O 0-3CeO2 0-4.5,SnO2 0-3.5,BiF3 0-15,以占总玻璃料组合物的重量百分比计。
本发明玻璃料的平均粒径在实际使用中为0.5-1.5μm,优选平均粒径为0.8-1.2μm。玻璃料的软化点(Tc:DTA的第二转变点)应在300-600℃范围内。玻璃料在总组合物中的量少于总组合物的4wt.%。
本文所述的玻璃是用制造玻璃的常规技术生产的。更具体地说,可如下所述制备玻璃。通常,制备玻璃的量为500-1000克。一般,称量各成分,然后以所需比例混合,在底部加料的炉中加热以在铂合金坩埚中形成熔体。通常,加热到峰值温度(1000-1200℃),并保持一段时间使熔体完全变成液体并且均一。然后,将玻璃熔体倒在反向旋转式不锈钢辊(rotating stainless steelrollers)上淬火以形成10-20mil厚的玻璃小板,或将熔体倒到水槽中淬火。将产生的玻璃小板或用水淬火得到的玻璃料碾碎以形成粉末,该粉末50%体积分布在1-5微米。产生的玻璃粉末与填料和介质制成厚膜糊浆或可浇铸的介电组合物。
D.其它的金属/金属氧化物添加剂
本发明其它的金属/金属氧化物添加剂可选自(a)金属,所述金属选自Zn,Ti,Sn,Pb,Ru,Co,Fe,Cu和Cr,(b)金属氧化物MOx,其中M选自Zn,Ti,Sn,Pb,Ru,Co,Fe,Cu和Cr,(c)烧制时可产生金属氧化物(b)的任何化合物,和(d)它们的混合物。
虽然希望所述其它的金属/金属氧化物添加剂的平均粒径不大于10微米,优选不大于5微米,但其粒径不受任何具体的限制。
在一个实施方式中,所述其它的金属/金属氧化物添加剂的粒径在7-125纳米(nm)范围内。具体地,粒径范围(d50)为7-125纳米(nm)的ZnO2和TiO2可用于本发明。
所述组合物中金属/金属氧化物添加剂和含锰添加剂的范围为总组合物的0.1wt.%-6wt.%。
氧化物如MnOx和Cu/CuOx以及其它氧化物也在一定程度上有助于粘附。
E.有机介质
通常,通过机械混合将无机组分与有机组分混合以形成的粘性组合物称为“糊浆”,所述糊浆具有适用于印刷的稠度和流变能力。多种惰性粘性物质可用作有机介质。所述有机介质必须可以使无机组分以适当程度的稳定性扩散于其中。该介质的流变性能必须使组合物具有好的应用性能,包括:固体的稳定扩散、用于丝网印刷的合适的粘性和搅溶性、基片和浆状固体的合适的可湿性、良好的干燥速率以及良好的烧制性能。用于本发明厚膜组合物中的有机载体优选是非水性惰性液体。可用多种有机载体中的任何一种,它可包含或不包含增稠剂、稳定剂和/或其它常用添加剂。有机介质通常是溶于溶剂中的聚合物溶液。此外,少量的添加剂,如表面活性剂可以是有机介质的一部分。用于此目的的最常用的聚合物是乙基纤维素。聚合物的其它例子包括乙基羟乙基纤维素、木松香、乙基纤维素和酚醛树脂的混合物、低级醇的聚甲基丙烯酸酯,也可用乙二醇单乙酸一丁醚。在厚膜组合物中使用最广的溶剂是酯醇和萜烯如α-或β-萜品醇或其与其它溶剂的混合物,所述其它溶剂如煤油、邻苯二甲酸二丁酯、丁基卡必醇、丁基卡必醇乙酸酯、己二醇和以及高沸点醇和醇酯。此外,载体中可包括挥发性液体,促进其施加到基片之后的快速固化。用这些以及其它溶剂的各种组合来调配以获得所需的粘附性和挥发性。
有机介质中存在的聚合物为总组合物的8wt.%-11wt.%。可用有机介质调节本发明的厚膜银组合物使其具有预设定的可丝网印刷的粘度。
厚膜组合物中的有机介质与扩散液中无机组分的比例取决于施加糊浆体的方法和所用有机介质的种类,该比例是可以变化的。通常,为了获得良好的湿润性,扩散液将含有70-95wt%的无机组分和5-30wt%的有机介质(载体)。
半导体器件制造方法的描述
因此,本发明提供一种新的组合物,它可用于制造半导体器件。可如下述方法从结构构件制造半导体器件,所述结构构件由带有接面的半导体基片和在该基片主要表面上形成的氮化硅绝缘薄膜组成。该制造半导体器件的方法包括以下步骤:将本发明的可穿透绝缘薄膜的导电厚膜组合物以预设形状施加(通常为涂覆和印刷)到绝缘薄膜上的预设位置,然后烧制使该导电厚膜组合物熔化并穿过绝缘薄膜,实现与硅基片的电接触。如本文所述,导电厚膜组合物是一种厚膜糊浆状组合物,由扩散在有机载体中的银粉、含锰的添加剂、软化点为300-600℃的玻璃或玻璃混合物以及任选地其它金属/金属氧化物添加剂制成。
组合物中的玻璃料末含量占总组合物的<5重量%,含锰的添加剂加上任选的金属/金属氧化物添加剂的含量在总组合物中不多于6重量%。本发明还提供用同样方法制造的半导体器件。
本发明还有一个特点是采用氮化硅薄膜或氧化硅薄膜作为绝缘薄膜。通常用等离子体化学气相沉积(CVD)或热CVD方法形成氮化硅薄膜。通常用热氧化、热CFD或等离子体CFD形成氧化硅薄膜。
该制造半导体器件的方法其特点还可以是,从结构构件制造半导体器件,所述结构构件由带有接面的半导体基片和在该基片主要表面上形成的氮化硅绝缘薄膜组成,其中该绝缘层选自氧化钛、氮化硅、SiNx:H、氧化硅和氧化硅/氧化钛薄膜,该方法包括以下步骤:使可与绝缘薄膜反应并穿透绝缘薄膜的金属糊浆状物以预设的形状形成在绝缘薄膜上预设的位置,与硅基片形成电接触。通常将含钛的有机液体材料涂覆在半导体基片上并烧制来形成氧化钛薄膜,或用热CVD来形成氧化钛薄膜。通常用PECVD(等离子体增强型化学气相沉积)来形成氮化硅薄膜。本发明还提供用同样方法制造的半导体器件。
通常在优选由氧气和氮气的混合气体组成的气氛中烧制由本发明的导电厚膜组合物形成的电极。该烧制过程将导电厚膜组合物中的有机介质去除并将玻璃料和银粉烧结。半导体基片通常是单晶或多晶硅。
图1(a)表示一个步骤,其中通常将可减少光反射的带纹理的表面提供给单晶硅或多晶硅基片。在太阳能电池中,基片常常由拉制(pulling)或铸造方法形成的结晶块切片而成。通常用碱水溶液如氢氧化钾水溶液或氢氧化钠水溶液或用氢氟酸和硝酸的混合物蚀刻掉约10-20μm厚的基片表面,从而去除由工具如用于切割的钢丝锯造成的基片表面损伤以及晶片切割步骤造成的污染。此外,可加入用盐酸和过氧化氢的混合物洗涤基片的步骤,去除粘附在基片表面的重金属如铁。然后,有时用碱水溶液如氢氧化钾水溶液或氢氧化钠水溶液形成抗反射的带纹理的表面。这样形成了基片,10。
接着,参照图1(b),当所用基片是p型基片时,形成n型层以产生p-n接面。用于形成该n型层的方法可以是用三氯氧化磷(POCl3)进行磷(P)扩散。这种情况下可以通过控制扩散温度和时间来改变扩散层的深度,扩散层的深度一般约为0.3-0.5μm。用这种方法形成的n型层见图中的标号20。接着,可用本发明背景技术中所述的方法在前侧和背侧上进行p-n分离。当用某种方法如旋转涂覆将含磷的液体涂覆材料如磷硅酸盐玻璃(PSG)施加到基片的仅仅一个表面时,常常不需要这些步骤,扩散是通过在合适的条件下退火来实现的。当然,当有在基片的背侧也形成n型层的危险时,可采用本发明背景技术中详述的步骤来增加完善的程度。
接着,在图1(d)中在上述n型扩散层20上形成氮化硅薄膜或其它绝缘薄膜(包括SiNx:H(即包含用于钝化用的氢的绝缘薄膜)薄膜、氧化钛薄膜以及氧化硅薄膜,30,作为抗反射涂层)。氮化硅薄膜30降低太阳能电池对入射光的表面反射,使太阳能电池产生的电流有可能大大增加。氮化硅薄膜30的厚度取决于其折射率,虽然对于约1.9-2.0的折射率合适的厚度约为700-900。可用例如低压CVD、等离子体CVD或热CVD等方法形成该氮化硅薄膜。当采用热CVD时,起始材料常常是二氯甲硅烷(SiCl2H2)和氨气(NH3),在至少700℃形成膜。当采用等离子体CVD时,起始材料的高温分解使得氮化硅薄膜中几乎不含氢,Si3N4中硅和氮的组成比率几乎是等当量的。折射率基本在1.96-1.98范围内。因此,这种氮化硅薄膜是一种非常密集的膜,其特性如厚度和折射率甚至在后续步骤中进行热处理时仍保持不变。当用等离子体CVD形成薄膜时原料气体通常是SiH4和NH3的混合气体。用等离子体将原料气体分解,在300-550℃形成膜。因为在等离子体CVD方法中膜形成时的温度比热CVD中所用的温度低,所以原料气体中存在的氢也存在于得到的氮化硅薄膜中。同样,因为用等离子体分解气体,该方法的另外一个不同特点是其能够大大改变硅和氮的组成比率。具体地,通过改变原料气体的流速比率以及膜形成时的压力和温度等条件,形成的氮化硅薄膜的硅、氮和氢的组成比例可以变化,折射率在1.8-2.5范围内。当在后续步骤中对具有这些性能的薄膜进行热处理时,因为电极烧制步骤中去除氢等原因在薄膜形成之前和之后其折射率可能会有所变化。这种情况下,可通过首先考虑由于后续步骤的热处理而发生的膜质量的改变来选择膜形成条件,从而获得太阳能电池中所需的氮化硅薄膜。
图1(d)中,可在n型扩散层20上形成氧化钛薄膜代替氮化硅薄膜30,作为抗反射涂层。通过将含钛的有机液体材料涂覆在n型扩散层20上,烧制,或通过热CVD,形成该氧化钛薄膜。在图1(d)中,还可能在n型扩散层20上形成氧化硅薄膜代替氮化硅薄膜30,作为抗反射层。用热氧化、热CVD或等离子体CVD形成氧化硅薄膜。
然后,用类似于图10(e)和(f)中的步骤来形成电极。即,如图1(e)所示,将铝糊浆60和背侧银糊浆70丝网印刷到基片10的背侧上,如图1(e)所示,然后干燥。此外,将形成前侧电极的银糊浆丝网印刷到氮化硅薄膜30上,方法与丝网印刷到基片10的背侧上相同,然后在红外加热炉中干燥和烧制,温度通常为700-975℃,时间为几分钟至十多分钟,同时,使氧气和氮气的混合气流穿过该炉。
如图1(f)所示,在烧制过程中,铝作为杂质从铝糊浆扩散到硅基片10的背侧中,因此形成p+层,40,其中铝掺杂物的浓度很高。烧制将干燥的铝糊浆60转换为背侧铝电极61。同时烧制背侧银糊浆70,使它成为背侧银电极71。烧制过程中,背侧铝和背侧银之间的边界呈合金状态,因此可实现电连接。背侧电极的大部分区域被铝电极占据,部分由于需要形成p+层40。同时,由于在铝电极上焊接是不可能的,背侧银或银/铝电极形成在背侧有限区域上,作为用铜带等连接各太阳能电池的电极。
在前侧,本发明的前侧电极银糊浆500由银、含锰的添加剂、玻璃料、有机介质和任选的金属氧化物组成,在烧制过程中可与氮化硅薄膜30反应并穿透氮化硅薄膜30,实现与n型层20的电接触(烧渗)。这种烧渗的状态,即前侧电极银糊浆熔化并穿过氮化硅薄膜30的程度取决于氮化硅薄膜30的质量和厚度、前侧电极银糊浆的组成以及烧制条件。
太阳能电池的转化效率和抗潮的可靠性很大程度上取决于这种烧渗状态。
实施例
下面实施例1-25描述了本发明的厚膜组合物。
玻璃制备
实施例中所用的玻璃组合物描述于下表2中,在表3中进行区分。
表2 玻璃组分在总玻璃组合物中所占的重量百分比
Li2OPbOB2O3 | 玻璃组分的重量百分比Bi2O3 | ASTM软化点(℃)SiO2CeO2 | TMA开始(℃)Na2OAl2O3 | |||||||||
TiO2 | ZnO | 玻璃I | 28.0 | 4.70 | 55.90 | |||||||
8.10 | 3.30 | 600 | 502 | 玻璃II | 6.00 | 80.50 | ||||||
12.00 | 1.50 | 430 | 365 | 玻璃III | 1.64 | 1.73 | 85.76 | |||||
10.86 | 362 | 322 | 玻璃IV | 9.10 | 1.40 | 77.0 | ||||||
12.50 | 395 | 361 | 玻璃V | 1.77 | 82.32 | |||||||
8.73 | 1.18 | 6.00 | - | 340 | 玻璃VI | 1.50 | 1.0 | 1.0 | 81.5 | 0.10 | ||
糊浆状物的制备
通常,糊浆状物的制备可通过以下过程完成:称取适量的溶剂、介质和表面活性剂,然后在混合罐中混合15分钟,然后加入玻璃料和金属添加剂并再混合15分钟。由于Ag是本发明固体中的主要部分,将其递增加入以确保更好的润湿。当充分混合时,以从0到400psi的压力将糊浆状物通过3-辊轧机几次。将辊的间距调整到1mil。通过磨粉细度(FOG)来测定扩散程度。用于导体的典型FOG值通常等于或低于20/15。
表3:实施例1-25的银和玻璃组分占总组合物的重量百分比
实施例编号 | Ag(wt%) | 玻璃I(wt%) | 玻璃II(wt%) | 玻璃III(wt%) | 玻璃IV(wt%) | 玻璃VI |
1 | 80 | 2.0 | 0 | 0 | 0 | 0 |
2 | 80.95 | 2.0 | 0 | 0 | 0 | 0 |
3 | 80 | 0.5 | 0 | 0 | 0 | |
4 | 80.95 | 1.5 | 0.5 | 0 | 0 | 0 |
5 | 79.5 | 2.0 | 0.5 | 0 | 0 | 0 |
6 | 80 | 2.0 | 0 | 0 | 0 | 0 |
7 | 80 | 2.0 | 0 | 0 | 0 | 0 |
8 | 80 | 2.0 | 0 | 0 | 0 | 0 |
9 | 80.45 | 0 | 2.5 | 0 | 0 | 0 |
10 | 80.35 | 0 | 2.5 | 0 | 0 | 0 |
11 | 80.75 | 1.5 | 0.5 | 0 | 0 | 0 |
12 | 79.5 | 0 | 2.5 | 0 | 0 | 0 |
13 | 79.0 | 2.0 | 0 | 0 | 0 | 0 |
14 | 79.45 | 0 | 2.5 | 0 | 0 | 0 |
15 | 80.35 | 0 | 0 | 2.5 | 0 | 0 |
16 | 81.95 | 0 | 0 | 0 | 0 | 0 |
17 | 84.45 | 0 | 0 | 0 | 2 | 0 |
18 | 80.0 | 0 | 2.0 | 0 | 0 | |
19 | 80 | 2.0 | 0 | 0 | 0 | 0 |
20 | 80.45 | 2.0 | 0.5 | 0 | 0 | 0 |
21 | 79 | 0 | 0 | 0 | 0 | 1.4 |
22 | 80 | 2.0 | 0 | 0 | 0 | 0 |
23 | 80 | 2.0 | 0 | 0 | 0 | 0 |
24 | 80 | 2.0 | 0 | 0 | 0 | 0 |
25 | 80 | 2.0 | 0 | 0 | 0 | 0 |
*实施例1-25各含有12wt.%的溶剂(Texanol),1.1wt.%的乙基纤维素和0.8wt.%的表面活性剂(大豆卵磷脂)。
表4:实施例1-21的金属、金属树脂酸盐组分在总组合物中的重量百分比
实施例编号 | ZnO | ZnO细粒 | Zn金属 | TiO2 | TiO2细粒 | MnO2 | Tyzor | 树脂酸锰 | 树脂酸锌 | Cu | 效率% | 粘附性 |
1 | 4.45 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 15.3 | 良好 |
2 | 0 | 3.50 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 15.6 | 良好 |
3 | 4.45 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 15.4 | 良好 |
4 | 0 | 3.50 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 15.4 | 良好 |
5 | 4.45 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 15.4 | 良好 |
6 | 4.45 | 0 | 0 | 1.0 | 0 | 0 | 0 | 0 | 0 | 0 | 153 | 足够 |
7 | 4.45 | 0 | 0 | 0 | 0 | 0 | 1.0 | 0 | 0 | 0 | 15.4 | 良好 |
8 | 4.45 | 0 | 0 | 0 | 0 | 0 | 0 | 1.0 | 0 | 0 | 15.1 | 良好 |
9 | 0 | 3.50 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 15.4 | 很好 |
10 | 0 | 3.50 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 | 0 | >15.6 | 良好 |
11 | 0 | 3.50 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0.2 | 15.6 | 优良 |
12 | 4.45 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 2 | 0 | >15.3 | 良好 |
13 | 4.45 | 0 | 0 | 0 | 0 | 1.0 | 0 | 0 | 0 | 0 | >15 | 良好 |
14 | 0 | 0 | 0 | 0 | 0 | 4.50 | 0 | 0 | 0 | 0 | >15 | 良好 |
15 | 0 | 3.5 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 | 0 | ~15 | 很好 |
16 | 0 | 3.5 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 1.0 | >10 | 足够 |
17 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ~4 | NT |
18 | 4.45 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ~15 | 良好 |
19 | 0 | 4.45 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 14.7 | 足够 | |
20 | 0 | 3.5 | 0 | 0 | 0.1 | 0 | 0 | 0 | 0 | 0.2 | 15.7 | 很好 |
21 | 6.5 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | 0 | ~15 | 很好 |
实施例1-21各含有12wt.%的溶剂(Texanol),1.1wt.%的乙基纤维素和0.8wt.%的表面活性剂大豆卵磷脂。
**ZnO细粒以商业途径从US Zinc Corporation获得,平均粒径为7-30nm。
***树脂酸锌以商业途径从OMG Americas获得,商品名为ZINCTEN-CEM。
表5:实施例22-25,金属氧化物组分在总组合物中的重量百分比以及它们的太阳能电池性能
实施例 | TiO2 | Co3O4 | Fe2O3 | Cr2O3 | 效率% | 粘附性 |
22 | 4.45 | <5 | NT | |||
23 | 4.45 | <5 | NT | |||
24 | 4.45 | <5 | NT | |||
25 | 4.50 | <5 | NT | |||
NT:未测试
测试方法——效率
将根据上述方法制成的太阳能电池置于市售的IV测试器中,以测定效率。IV测试器中的灯泡模拟强度已知的阳光并照射电池的前侧。将印刷在电池前侧的母线与IV测试器的多个探棒连接,电信号通过探棒传输到计算机中以计算效率。
测试方法——粘附性
烧制后,将焊条(用62Sn/36Pb/2Ag涂覆的铜)焊接到印刷在电池前侧的母线上。焊接条件通常是345℃5秒钟。所用的助熔剂是轻度活化的α-611或未活化的多中心(multicenter)100。焊接面积约为2mm×2mm。通过与电池表面成90°角牵引焊条来获得粘附强度。将小于400g的粘附强度设定为不良,400g至小于600g设定为足够的粘附强度,等于或大于600g设定为良好、很好或优良的粘附强度,基于这些假定将对粘度强度的评价分为足够、良好、很好或优良。
此外,牵引后,用显微镜检查焊接点的破裂方式。如果不多于50%的焊接区域显示为Si断裂,认为是好的破裂方式。
对于采用不含Pb的玻璃料的组合物,用不含Pb的焊接剂和含Pb的焊接剂测试粘附性。所用的不含Pb的焊接剂是96.5Sn/3.5Ag。对于不含Pb的焊接剂,焊接温度为375℃,焊接时间是5-7秒。所用助溶剂是MF200。获得的粘附性通常大于600g。
Claims (14)
1.一种厚膜导电组合物,其包含:
分散在(d)有机介质中的:
a)导电银粉;
b)含锰的添加剂;
c)玻璃料,其中所述玻璃料的软化点为300-600℃。
2.如权利要求1所述的组合物,其还包含选自下列物质的其它金属/金属氧化物添加剂:(a)金属,所述金属选自Zn,Ti,Sn,Pb,Ru,Co,Fe,Cu和Cr;(b)金属氧化物,MOx,其中M选自Zn,Ti,Sn,Pb,Ru,Co,Fe,Cu和Cr;(c)烧制时可产生金属氧化物(b)的任何化合物;和(d)它们的混合物。
3.如权利要求1所述的组合物,其特征在于,所述含锰的添加剂是MnO2。
4.如权利要求1所述的组合物,其特征在于,所述含锰的添加剂是锰的有机金属化合物。
5.如权利要求1所述的组合物,其特征在于,所述含锰的添加剂是在烧制条件下可产生MnO2的化合物。
6.如权利要求1所述的组合物,其特征在于,所述含锰的添加剂其粒径在7纳米到小于100纳米范围内,并且所述含锰的添加剂是粉末形式的。
7.如权利要求1所述的组合物,其特征在于,基于总玻璃料组合物的重量百分比,所述玻璃料组合物包含:SiO2 21-29,Al2O3 0.1-8,PbO 50-62,B2O37-10,ZnO 0-4,Li2O 0-0.1以及TiO2 2-7。
8.如权利要求1所述的组合物,其特征在于,所述玻璃料是不含铅的玻璃料,基于总玻璃料组合物的重量百分比,其包含:SiO2 0.1-8,Al2O3 0-4,B2O38-25,CaO 0-1,ZnO 0-42,Na2O 0-4,Li2O 0-3.5,Bi2O3 28-85,Ag2O 0-3 CeO20-4.5,SnO2 0-3.5以及BiF3 0-15。
9.一种含有权利要求1所述组合物的基片,所述组合物已经过处理除去了所述有机介质,并且烧结了所述玻璃料和银粉。
10.一种由权利要求1的组合物形成的电极,所述组合物已经过处理除去了所述有机介质,并且烧结了所述玻璃料和银粉。
11.一种从结构构件制造半导体器件的方法,所述结构构件由具有p-n接面的半导体和形成在所述半导体主要表面上的绝缘薄膜组成,所述制造方法包括步骤(a)将权利要求1所述的厚膜组合物施加在绝缘薄膜上;和(b)烧制所述半导体、绝缘薄膜和厚膜组合物以形成电极。
12.如权利要求8所述的方法,其特征在于,所述绝缘薄膜选自氮化硅薄膜、氧化钛薄膜、SiNx:H薄膜、氧化硅薄膜和氧化硅/氧化钛薄膜。
13.一种用权利要求8所述的方法制造的半导体器件。
14.一种用权利要求1所述的组合物形成的半导体器件,所述组合物已经过处理除去了所述有机介质,并且烧结了所述玻璃料和银粉。
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- 2006-04-13 EP EP20060252077 patent/EP1713095B1/en not_active Revoked
- 2006-04-14 TW TW95113535A patent/TWI338308B/zh not_active IP Right Cessation
- 2006-04-14 CN CN2006100748111A patent/CN1862839B/zh not_active Expired - Fee Related
- 2006-04-14 JP JP2006112246A patent/JP5362946B2/ja not_active Expired - Fee Related
- 2006-04-14 KR KR1020060034126A patent/KR100887128B1/ko not_active IP Right Cessation
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CN102428568A (zh) * | 2009-05-20 | 2012-04-25 | E.I.内穆尔杜邦公司 | 在硅片正面上形成栅极的方法 |
CN102804389A (zh) * | 2009-06-26 | 2012-11-28 | E·I·内穆尔杜邦公司 | 在硅片正面上形成栅阴极的方法 |
CN102576580A (zh) * | 2009-09-08 | 2012-07-11 | E.I.内穆尔杜邦公司 | 用于光伏电池的导体 |
CN102667961A (zh) * | 2009-11-25 | 2012-09-12 | E·I·内穆尔杜邦公司 | 铝浆及其在钝化发射极以及背面接触硅太阳能电池生产中的用途 |
CN104810258A (zh) * | 2010-01-25 | 2015-07-29 | 日立化成工业株式会社 | 形成n型扩散层的组合物和方法,及制备光伏电池的方法 |
CN109994246A (zh) * | 2017-12-15 | 2019-07-09 | 住友金属矿山株式会社 | 厚膜导体形成用粉末组合物以及厚膜导体形成用浆料 |
CN109994246B (zh) * | 2017-12-15 | 2022-05-10 | 住友金属矿山株式会社 | 厚膜导体形成用粉末组合物以及厚膜导体形成用浆料 |
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US20060231800A1 (en) | 2006-10-19 |
EP1713095B1 (en) | 2011-08-03 |
CN1862839B (zh) | 2010-04-21 |
TW200731291A (en) | 2007-08-16 |
JP2006302891A (ja) | 2006-11-02 |
EP1713095A2 (en) | 2006-10-18 |
AU2006201555A1 (en) | 2006-11-02 |
EP1713095A3 (en) | 2007-03-07 |
TWI338308B (en) | 2011-03-01 |
US8313673B2 (en) | 2012-11-20 |
KR20060108551A (ko) | 2006-10-18 |
KR100887128B1 (ko) | 2009-03-04 |
US20090044858A1 (en) | 2009-02-19 |
US7462304B2 (en) | 2008-12-09 |
JP5362946B2 (ja) | 2013-12-11 |
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