CN101055776B - 导电的厚膜组合物、电极和所形成的半导体设备 - Google Patents

导电的厚膜组合物、电极和所形成的半导体设备 Download PDF

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CN101055776B
CN101055776B CN200610074808XA CN200610074808A CN101055776B CN 101055776 B CN101055776 B CN 101055776B CN 200610074808X A CN200610074808X A CN 200610074808XA CN 200610074808 A CN200610074808 A CN 200610074808A CN 101055776 B CN101055776 B CN 101055776B
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Y·L·王
K·W·汉
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Abstract

本发明涉及一种导电厚膜组合物，包括：(a)导电金属粒子，选自(1)Al、Cu、Au、Ag、Pd和Pt；(2)Al、Cu、Au、Ag、Pd和Pt的合金；和(3)它们的混合物，(3)玻璃料，其中玻璃料不含铅；分散于(d)有机介质中，其中所述导电金属粒子的平均粒径在0.5-10.0微米范围内。本发明还涉及一种上述组合物形成的电极和包含所述电极的一种或多种半导体设备(如太阳能电池)。

Description

导电的厚膜组合物、电极和所形成的半导体设备
技术领域
本发明主要涉及一种厚膜组合物、电极和半导体设备。它还涉及一种硅半导体设备。具体地，它属于一种用于形成太阳能电池的厚膜电极的导电组合物。本发明还涉及一种用于太阳能电池的银的导电的厚膜组合物(糊)。
背景技术
本发明可广泛用于各类半导体设备，尽管它特别适用于光接收组件，例如光电二级管和太阳能电池。以下引用太阳能电池作为现有技术的具体例子，对本发明的背景进行具体描述。
常规的p-型基的太阳能电池结构具有负电极，它一般位于电池的正面或朝太阳面，以及位于背面的正电极。目前已知，波长合适的、落入半导体主体的p-n连接的辐射作为一种外能量源，以在该主体中产生孔-电子对。由于p-n连接处存在潜在差异，孔和电子以相反反向移经该连接，从而引起电流流动，能传递能量给外电路。多数太阳能电池是金属化的硅晶片的形式，即提供其具导电性的金属触点。
目前已有的多数产生电能的太阳能电池为硅太阳能电池。大规模生产的工艺流程一般旨在尽可能简化并最小化生产成本。特别是使用如丝网印刷的方法，自金属糊制造电极。
该生产方法的例子结合图1具体描述如下。
图1示p-型硅基材10。
在图1(b)中，n-型扩散层20，具反向的导电类型，通过磷(P)或类似物的热扩散形成。三氯氧化磷(POCl3)常用于磷扩散源。在不进行任何更改的情况下，扩散层20形成于整个硅基材10的表面。扩散层的表面电阻率为几十个欧姆每平方(W/o)，厚度约0.3至0.5μm。
当用保护层或类似物保护扩散层的正面之后，如图1(c)所示，通过蚀刻将扩散层20从其余表面除去，从而保护层仅留下正面。然后用有机溶剂或类似物将保护层除去。
然后，在n-型扩散层20上形成减反射涂层氮化硅膜30，厚度约700-900
Figure 10003_0
，如图1(d)所示，使用如等离子体化学气相沉淀(CVD)等方法。
如图1(e)所示，用于正面电极的银糊500经丝网印刷干燥于氮化硅膜30上。此外，一背面银或银/铝糊70以及铝糊60经丝网印刷依次干燥于基材背面。然后，在红外线炉中，约700-950℃下，用一般方法进行烧制几分钟至几十分钟的时间。
然后，如图1(f)所示，铝从铝糊扩散至硅基材10，在烧制时作为掺和剂，形成p+层40，包含高浓度的铝掺和剂。该层一般称为背称面区域(BSF)层，并有助于提高太阳能电池的能转化效率。
铝糊通过烧制，从干燥状态60变为铝背电极61。背面的银或银/铝糊70在同时进行烧制，形成银或银/铝背电极71。烧制时，背面铝和背面银或银/铝间的边界设定为合金状态，并作电学连接。铝电极占背电极的大部分区域，部分地由于需要形成p+层40。由于不可能对铝电极进行焊接，银或银/铝背面电极通过铜带或类似物的方式，作为互连太阳能电池的电极，形成于背面(一般为5-6mm宽的母线)部分。此外，正面成电极银糊500，在烧制时，烧结并透过氮化硅膜30，从而能电连接n-型层20。这类工艺一般称为“烧透(firing through)”。该烧透状态在图1(f)的层501上很明显。
如上所述，使用在焊接过程中来互连太阳能电池的背面电极可包括银或银/铝组合物。当使用现有技术中的银组合物时，它们可提供较好的焊接力和粘附力。然而，由于银组合物不能产生背称面区域，太阳能电池的转化效率不佳。另外，当使用银/铝组合物时，粘附强度通常会降低，并影响长期的可靠性。这是由于加入铝一般会伤害焊接能力，并影响粘附。
此外，人们目前正在努力提供一种组合物，它们不含铅，同时保持设备的电学性能及其它相关特征。本发明发明者提供新型含银/铝组合物及能提供如无铅系统等的同时保持电学性质并提高粘附力的半导体设备。本发明提供这样的组合物和设备。此外，本发明的组合物在本发明某些实施例中可提供低的弯度。
发明简述
本发明涉及一种导电厚膜组合物，包括：
(a)导电金属粒子选自(1)Al、Cu、Au、Ag、Pd和Pt；(2)Al、Cu、Au、Ag、Pd和Pt的合金；和(3)混合物；
(b)玻璃料，其中所示玻璃料无铅；分散于
(c)一种有机介质，且其中所述导电金属粒子的平均粒径在0.5-10.0微米范围内。本发明还涉及由所述组合物形成的电极，如上的详述，以及涉及包含所述电极的半导体装置。
附图说明
图1为过程流程图，显示半导体装置的制造。图1中所示的编号解释如下。
10：p-型硅基材
20：n-型扩散层
30：氮化硅膜、氧化钛膜或氧化硅膜
40：p+层(背面区域，BSF)
60：形成于背面的铝糊
61：铝背面电极(通过燃烧背面铝糊获得)
70：形成于背面的银/铝糊
71：银/铝背面电极(通过燃烧背面的银/铝糊获得)
500：形成于正面的银糊
501：银正面电极(通过燃烧背面银糊形成)
图2(a)-(d)解释使用本发明的导电性糊体制造太阳能电池的制造过程。图2中所示的编号解释如下。
102      硅基材
104      光接收面侧电极
106      用于第一电极的糊组合物
108      用于第二电极的导电糊
110      第一电极
112      第二电极
发明详述
本发明的导电的厚膜组合物(糊)提供由所述糊形成电极的能力，其中该电极具有对硅基材的高粘附度、高背面区域和低弯度。
为了达到上述目的，本发明为一种导电厚膜组合物，尤其是银/铝导电糊，所述糊包括银和铝粒子、玻璃粒子、任选的无机添加剂和有机载体，并应用于这样的电池：它连接太阳能电池硅基材上的背面端。该情形的特征是，所述银/铝粒子的平均粒径为0.5-10.0微米。本发明中，优选包括以糊总重量计40-93wt％的银粒子、以糊总重量计1-5wt％的铝、以糊总重量计2-0wt％的玻璃粒子、为以糊总重量计0-2wt％的无机添加剂，以及以糊总重量计5-50wt％的有机载体。此外，优选在银导电糊中包括玻璃粉末，从而获得300-550℃的软化温度。
本发明的导电糊可直接接触硅基材使用或印刷于Al膜顶部使用。
本发明的导电厚膜糊的每种组分详细解释如下。
1.导电金属
本发明中，导电相最优选银(Ag)/铝(Al)；然而，除了银/铝外的导电金属，也可使用如Cu、Au、Ag、Pd、Pt、Al、Ag-Pd、Pt-Au等。事实上，导电金属粒子可选自(1)Al、Cu、Au、Ag、Pd和Pt；(2)Al、Cu、Au、Ag、Pd和Pt的合金；以及(3)它们的混合物。
一般地，本发明的导电糊内可用的导电金属，银(Ag)和铝(Al)将用作本发明组合物的导电相。银和铝粒子优选为片状或球状(有时称作粉末)形式。使用银以有助于高导电度和可焊接能力；使用铝以有助于其诱导背面区域的能力，从而转变效能。
优选银和铝具有高纯度(99+％)；尽管如此，具有低纯度的物质也可用于响应电极模式的电需求。
2.无机粘合剂
优选本发明的导电糊包括无机粘合剂。本发明中可用的无机粘合剂为具有优选软化温度在300-550℃的玻璃料，从而使导电糊可在700-950℃下进行烧制，适当地进行烧结并湿润，并适当地粘附至硅基材。若软化温度低于300℃，玻璃可能过早熔化并移至电极表面，干扰焊接。另一方面，若软化温度高于550℃，玻璃将没有足够时间烧结软化并湿润导电相，且不能产生足够的粘附强度，且有时候并不能促进银的液相烧结。可理解，若加工中使用的烧制温度范围变化了，则最佳玻璃料的软化点温度范围也会变化。
此处，“软化温度”通过ASTM C338-57的纤维伸长法获得。本发明中玻璃化学成份，不仅对粘附强度、还对弧状弯曲和电性能有作用。此外，本发明限于无铅玻璃。本发明中有用的玻璃包括铋基玻璃。一些典型的玻璃组合物包括下列物质(以总玻璃组合物的重量百分数计)：SiO2：0.5-35％；Al2O3：0-5％；B2O3：1-15％；ZnO：0-15％；Bi2O3：55-90％。所选的玻璃组合物列入表1。
并不对玻璃料作为无机粘合剂的含量作具体限制，只要它的含量足以达到本发明的发明目的；尽管如此，该含量一般为，以导电糊总重量计，1-10wt％，优选2-6wt％。
如果无机粘合剂的量小于1wt％，则有时粘附强度会不足，电性能会受影响，而如果无机粘合剂的量高于10wt％，焊接可能变得十分难。此外，当玻璃含量的百分比增加时，也可不利地影响弯度。
3.任选的无机添加剂
本发明组合物中使用的玻璃料(无机粘合剂)提供粘附，然而，可加入总导电组合物的无机玻璃结合剂的总量受弯度和焊接力条件的限制。因此附加的无机添加剂可任选地加入，从而提高增加性能。这些附加任选添加剂可选自(1)TiB2、Cu、Ti、Al、Sn、Sb、Cr、Fe、Mn、Co、Ni、Ru、B和Bi；(2)可生成选自Cu、Ti、Al、Sn、Sb、Cr、Fe、Mn、Co、Ni、Ru、B和Bi等金属元素的化合物；(3)Cu、Ti、Al、Sn、Sb、Cr、Fe、Mn、Co、Ni、Ru、B和Bi的氧化物；以及(4)它们的组合物。
本发明发明者发现，少量的任选添加剂，如铜粉或金属氧化物，Bi2O3、TiO2、TiB2、Al2O3、B2O3、SnO2、Sb2O5、Cr2O3、Fe2O3、CuO、Cu2O、MnO2、Co2O3、NiO、RuO2等，可帮助提高粘附特性，同时不影响电学性能和弯度。
任选的无机添加剂的平均粒径在0.5-10.0μm范围内，或在添加剂为有机金属化合物形式时，分散至分子水平。
4.有机介质
无机组分一般通过机械混合与有机介质混合，从而形成粘性组合物，称作“糊”，具有适合印刷的稠度和流变学特性。可将各种惰性粘滞材料用作有机介质。有机介质须是这样的：无机组分以适合稳定度分散于其中。介质的流变学特性必需使其赋予组合物较好的应用特性，包括：固体的稳定分散性、适合于丝网印刷的的粘度和触变性、基材和糊固体的适合的可湿性、较好的干燥速率、以及较好的烧制特性。本发明的厚膜组合物所使用的有机载体优选非水性惰性液体。可使用各类有机载体的任一种，它们可包括或可不包括增稠剂、稳定剂和/或其它常用添加剂。有机介质一般为聚合物在溶剂中的溶液。此外，少量添加剂，例如表面活性剂，可作为有机介质的一部分。最常见的用于此用途的聚合物是乙基纤维素。其它聚合物的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，也可使用乙烯乙二醇一醋酸酯的单丁基醚。最常用于厚膜组合物的溶剂为酯醇类和萜，例如α-或β-萜品醇或其同其它溶剂的混合物，例如煤油、邻苯二甲酸二丁酯、丁基卡必醇、丁基卡必醇醋酸酯、己二醇和高沸腾醇和醇酯。此外，挥发性体可包括用于促进施用于基材后使快速硬化的挥发性液体。配制这些和其它溶剂的组合以获得所需的粘度和挥发性。
在有机介质中的聚合物占总组合物的8-11wt％。本发明的厚膜组合物可与有机介质调节至预定的、可丝网印刷的粘度。
厚膜组合物中有机介质和分散系中无机成份的比例依赖于施加糊的方法和所使用的有机介质种类，且可变化。一般分散系会包含70 95wt％的无机组分和5 30wt％的有机介质(载体)，以达得良好的湿润。
本发明的导电糊一般由动力混合方便地制得，是一种等同于传统辊轴碾磨机的分散技术。本发明的导电糊优选通过丝网印刷散布于太阳能电池背面的所需部分；在使用该方法散布的同时，优选具有预定范围内的粘度。本发明的导电糊粘度优选80-200PaS，这是用Brookfield HBT粘度计和14号轴的通用杯子在10rpm和25℃下测量的。
本发明的导电糊可直接接触硅晶片使用或印刷于干燥铝膜顶部使用。Ag/Al膜可与Al在称为共加热的过程中进行共同烧制。此外，结合附图(图2)解释使用本发明的导电糊(银/铝导电糊)制备太阳能电池的例子。
首先，制备硅基材102。在硅基材的光接收侧面(表面)，安装电极(如主要由Ag组成的电极)104(图2(a))。在基材背面，通过丝网印刷等散布，用作太阳能电池背面电极的铝糊106(尽管只要将其用作太阳能电池，就并不受到特别限制，如PV333，PV322(购自E.I.du Pont de Nemours and Company))然后干燥(图2(b))。然后将本发明的导电糊以部分重叠的方式同铝糊一起散布并干燥，事先将铝糊印刷并干燥(图2(c))。每种糊体的干燥温度优选150℃或更低。而且，铝糊优选干燥膜厚度为40-60μm，且本发明银/铝厚导电糊的度优选15-25μm。同时，铝糊和银/铝导电糊的重叠部分优选约0.5-2.5mm。
接下来，获得的基材在700-950℃温度下烧制，如烧制约1-15分钟，从而获得所需的太阳能电池(图2(d))。自本发明的组合物形成一种电极，其中所述组合物经烧制以除去有机介质并烧结玻璃料。
使用本发明的导电糊获得的太阳能电池，如图2(d)所述，具在基材(如硅基材)102的光接收面(表面)的电极104，在背面，有铝电极110主要包含铝，银/铝电极112主要包含Ag和Al。
实施例
下面结合具体实施例，进一步阐述本发明。在以下的实施例中，本发明银/铝导电糊的一个制造实施例、和一个银/铝导电糊在太阳能电池制造过程中用作硅基材的背面的电极材料的实施例在以下进行描述。
实施例1
以下具体描述实施例1。
将合适量的有机介质、玻璃料、无机添加剂和Ag/Al，在真空搅拌机中混合15-30分钟。通过粉末混合器或辊碾机传送混合物，以使成份充分分散。分散度通过研磨细度(FOG)来衡量。当分散充分后，配制糊体以形成所需的固体含量和粘度值。
太阳能电池的制造
本发明可用于宽范围的半导体设备，尽管它特别适用于光接收组件，例如光电二级管和太阳能电池。下面描述怎样使用本发明组合物形成太阳能电池。
使用获得的银/铝导电糊，以以下顺序形成太阳能电池。
(1)在正面具有银电极的硅基材的背面，印刷新发明的Ag/Al糊，并干燥。典型的干燥厚度在15至25微米范围内。用于太阳能电池(如购自E.I.du Pontde Nemours and Company的PV333)背面电极的铝糊，以40-60微米的干燥膜厚度进行丝网印刷。Ag/Al以5-6mm宽的母线印刷，且铝膜两边都与Ag/Al母线重叠lmm，从而确保导电的连续性。在一些应用中，整个背面可以用Ag/Al网格线覆盖，且在这些情形下，无须印刷Al糊。
(2)然后依据炉尺寸和温度值，将最高温度设置为700至950℃，在炉内烧制印刷薄片1-10分钟。烧制后形成太阳能电池。
测试步骤-效能
将依据上述方法制造的太阳能电池置于商用IV测试器以测量效能。IV测试器内的灯泡以已知密度模拟太阳光，并照射电池正面，将印刷于电池正面的母线与测试器的多个探针连接，电信号通过探针传送至计算机，从而计算效能。
测试步骤-粘附
烧制后，焊料带(涂有62Sn/36Pb/2Ag的铜)焊接至印刷于电池背面的母线。焊接条件一般为345℃下5秒。使用的焊剂为MF200。焊接区域约为2mm×2mm。粘附强度这样获得：以与电池表面呈90度角的方式拉所述带。粘附强度评估为低、适中或好，评估基于这样的假设：小于200g的粘附强度认为“低”，在200-300g的范围内的值为“适中”，在300-400内或更高的值为“好”。
由于本发明仅包含无铅玻璃作为玻璃料，我们用无铅焊料和含铅焊料测试了粘附度。使用的无铅焊料是96.5Sn/3.5Ag。无铅焊料的焊接温度在345-375℃范围，焊料时间为5-7秒。所用焊剂为MF200。
弯曲度判断标准如下：＞1mm为“高”，0.6-1mm为中等，＜0.6mm为“低”。
实施例的组合物列入表2。表2所述的玻璃组合物具体描述于表1中。实施例的性能特征列于表3。
Figure G06174808X20060515D000091
表2.组合物实施例(总组合物计重量百分比)
  实施例 玻璃 玻璃II 玻璃III 玻璃IV 玻璃V 银 铝 TiB2 Bi2O3 Cu 有机
  1   5.12   68.98   2.47   0.20   23.23
  2   5.12   68.98   2.47   0.20   23.23
  3   5.12   68.98   2.47   0.20   23.23
  4   5.12   68.98   2.47   0.20   23.23
  5   5.12   68.98   2.47   0.20   23.23
  6   2.66   68.98   2.47   0.75   1.0   23.23
表3.实施例组合物的性能特征
Figure G06174808X20060515D000101

Claims (9)

1.一种导电厚膜组合物，包含：
(a)导电金属粒子，它包括银粒子和铝粒子的混合物；
(b)玻璃料，所述玻璃料不含Pb；分散于
(c)有机介质中；
所述导电金属粒子的平均粒径在0.5-10.0微米范围内；
所述玻璃料包含，以玻璃料组合物总重量百分比计的下列物质：SiO2 0.5-35，Al2O3 0-5，B2O3 1-15，ZnO 0-15和Bi2O3 55-90；
所述组合物还包含
(d)一种或多种无机添加剂，所述无机添加剂选自：(1)Cu和Bi；(2)能产生Cu和Bi的化合物；以及(4)它们的混合物。
2.如权利要求1所述的组合物，其特征在于所述能产生Cu和Bi的化合物各自为Cu的氧化物和Bi的氧化物。
3.如权利要求1所述的组合物，其特征在于它还包括一种或多种无机添加剂，该无机添加剂选自：(1)TiB2、Ti、Al、Sn、Sb、Cr、Fe、Mn、Co、Ni、Ru和B；(2)能产生选自以下的金属元素的化合物：Ti、Al、Sn、Sb、Cr、Fe、Mn、Co、Ni、Ru和B；以及(4)它们的混合物。
4.如权利要求3所述的组合物，其特征在于所述能产生Ti、Al、Sn、Sb、Cr、Fe、Mn、Co、Ni、Ru和B金属元素的化合物是Ti、Al、Sn、Sb、Cr、Fe、Mn、Co、Ni、Ru和B各自的氧化物。
5.如权利要求1所述的组合物，包含，以组合物总重量计：
40-68.98重量百分数的Ag粒子，
2-10重量百分数的所述玻璃料，
1-5重量百分数的Al粒子，
0.2-2重量百分数的无机添加剂，和
23.23-50重量百分数的有机介质。
6.如权利要求1所述的组合物，其特征在于所述导电金属粒子为选自下列的形式：(1)片状、(2)球状、和(3)它们的混合物。
7.如权利要求1所述的组合物，其特征在于所述玻璃料的软化温度在300-550℃范围。
8.由权利要求1所述的组合物形成的电极，其特征在于，所述组合物经过燃烧，以除去有机介质，并烧结所述玻璃料。
9.一种包含权利要求8所述电极的半导体设备。
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KR20060108552A (ko) 2006-10-18
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US20090140217A1 (en) 2009-06-04
US20120119165A1 (en) 2012-05-17
EP1713094A2 (en) 2006-10-18
EP1713094A3 (en) 2007-03-07
US20110006268A1 (en) 2011-01-13
KR100890866B1 (ko) 2009-03-27
AU2006201557A1 (en) 2006-11-02
JP2006313744A (ja) 2006-11-16
CN101055776A (zh) 2007-10-17
US20060231803A1 (en) 2006-10-19
US8123985B2 (en) 2012-02-28
US7494607B2 (en) 2009-02-24

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