CN102958862A - 低熔点玻璃组合物及使用其的导电性糊剂材料 - Google Patents
低熔点玻璃组合物及使用其的导电性糊剂材料 Download PDFInfo
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Abstract
提供一种用于无铅导电性糊剂材料的低熔点玻璃组合物,在晶体硅太阳能电池用的导电性糊剂中所述糊剂材料可得到高集电效率。所述导电性糊剂材料的特征在于,其含有SiO2-B2O3-ZnO-RO-R2O系无铅低熔点玻璃,该玻璃以重量%计,含有:2~10%的SiO2、18~30%的B2O3、0~10%的Al2O3、0~25%的ZnO、20~50%的RO(MgO+CaO+SrO+BaO)、10~17%的R2O(Li2O+Na2O+K2O)。
Description
技术领域
本发明涉及一种无铅导电性糊剂材料中的良好的低熔点玻璃组合物,所述糊剂材料尤其在形成晶体硅太阳能电池的电极中可获得良好的电特性、并且与硅半导体基板的密合性良好。
背景技术
作为使用半导体硅基板的电子部件,已知有如图1所示的太阳能电池元件。如图1所示,太阳能电池元件在厚度为200μm左右的p型半导体硅基板1的光接收面侧形成n型半导体硅层2,在光接收面侧表面形成有用以提高光接收效率的氮化硅膜等抗反射膜3,进而在该抗反射膜3上形成有与半导体连接的表面电极4。另外,在p型半导体硅基板1的背面侧,同样地形成有铝电极层5。
该铝电极层5通常由如下方法形成:使用丝网印刷等涂布由铝粉末、玻璃粉、包含乙基纤维素、丙烯酸(酯)系树脂等粘结剂的有机赋形剂组成的铝糊剂材料,在600~900℃左右的温度下进行短时间焙烧。
在该铝糊剂的焙烧中,铝扩散到p型半导体硅基板1中,从而在铝电极层5与p型半导体硅基板1之间形成被称为BSF(BackSurface Field)层6的Si-Al共晶层,进而形成由于铝的扩散所形成的杂质层p+层7。
该p+层7具有抑制由p-n结的光伏效应所生成的载流子的再结合所致的损失的效果,有助于提高太阳能电池元件的转换效率。
关于该BSF效果,公开有通过使用含铅的玻璃作为铝糊剂所含的玻璃粉可获得高效果(例如参照专利文献1、2)。
现有技术文献
专利文献
专利文献1:日本特开2007-59380号公报
专利文献2:日本特开2003-165744号公报
发明内容
发明要解决的问题
然而,铅成分虽然在使玻璃为低熔点方面是重要的成分,但是对人体、环境造成的危害较大。上述日本特开2007-59380号公报、日本特开2003-165744号公报所公开的玻璃粉存在含有铅成分的问题。
用于解决问题的方案
本发明是一种导电性糊剂材料,其为在使用硅半导体基板的太阳能电池中使用的导电性糊剂,其特征在于,该糊剂中所含的低熔点玻璃是SiO2-B2O3-ZnO-RO-R2O系无铅低熔点玻璃,其组成为:实质上不含铅成分,且以重量%计,含有:2~10%的SiO2、18~30%的B2O3、0~10%的Al2O3、0~25%的ZnO、20~50%的RO(MgO+CaO+SrO+BaO)、10~17%的R2O(Li2O+Na2O+K2O)。
另外,本发明是一种上述导电性糊剂材料,其特征在于,所述无铅低熔点玻璃的30℃~300℃下的热膨胀系数为(100~150)×10-7/℃、软化点为400℃以上且550℃以下。
进而,本发明是一种太阳能电池元件,其特征在于,其使用上述导电性糊剂材料。
再者,本发明是一种电子材料用基板,其特征在于,其使用上述导电性糊剂材料。
发明的效果
通过使用本发明的含有无铅低熔点玻璃粉的导电性糊剂材料,可得到高BSF效果。另外,可得到与硅半导体基板的良好的密合性。并且,由于实质上不含铅成分,因而对人体、环境不造成危害。
附图说明
图1为普通的晶体硅太阳能电池单元的概略剖面图。
具体实施方式
本发明的导电性糊剂材料是一种SiO2-B2O3-ZnO-RO-R2O系无铅低熔点玻璃,其特征在于,该无铅低熔点玻璃含有铝粉末、和包含乙基纤维素、丙烯酸(酯)系树脂等粘结剂的有机赋形剂,还含有玻璃粉,该玻璃粉为实质上不含铅成分,且以重量%计,含有:2~10%的SiO2、18~30%的B2O3、0~10%的Al2O3、0~25%的ZnO、20~50%的RO(MgO+CaO+SrO+BaO)、10~17%的R2O(Li2O+Na2O+K2O)。
本发明的玻璃粉中,SiO2是玻璃形成成分,通过使其与作为其它玻璃形成成分的B2O3共存,可形成稳定的玻璃,所以以2~10%(重量%,下同)的范围含有SiO2。SiO2超过10%时,玻璃的软化点上升,成形性、作业性变得困难。SiO2更优选4~9%的范围。
B2O3是玻璃形成成分,其使玻璃熔融变得容易,抑制玻璃的热膨胀系数过度上升,且烧结时赋予玻璃适度的流动性,使玻璃的介电常数下降。玻璃中以18~30%的范围含有B2O3。B2O3低于18%时,玻璃的流动性变得不充分,烧结性受损。另外,B2O3超过30%时玻璃的安定性降低。B2O3更优选19~29%的范围。
Al2O3是抑制玻璃的结晶化而使其稳定化的成分。优选在玻璃中以0~10%的范围含有Al2O3。Al2O3超过10%时,玻璃的软化点上升,成形性、作业性变得困难。
ZnO是降低玻璃的软化点的成分,在玻璃中以0~25%的范围含有ZnO。ZnO超过25%时,玻璃变得不稳定易产生结晶。ZnO优选为0~23%的范围。
RO(MgO+CaO+SrO+BaO)是降低玻璃的软化点、适度地赋予流动性的物质,在玻璃中以20~50%的范围含有RO。RO低于20%时,玻璃的软化点的下降不充分,烧结性受损。另外,RO超过50%时,玻璃的热膨胀系数变得过高。RO更优选为23~50%的范围。
R2O(Li2O、Na2O、K2O)是降低玻璃的软化点、适度地赋予流动性、并且将热膨胀系数调整为适当的范围内的物质,以10~17%的范围含有R2O。R2O低于10%时,玻璃的软化点的下降不充分,烧结性受损。另外,R2O超过17%时,使热膨胀系数过度上升。R2O更优选为12~17%的范围。
除此以外,也可添加通常以氧化物表示的CuO、TiO2、In2O3、Bi2O3、SnO2、TeO2等。
由于实质上不含PbO,因此不存在对人体、环境的影响。此处,所谓实质上不含PbO是指,PbO在玻璃原料中为作为杂质混入的程度的量。例如,在低熔点玻璃中PbO如果为0.3质量%以下的范围,则几乎不存在前述的危害,即不存在对人体、环境的影响以及对绝缘特性等的影响,实质上不受PbO的影响。
本发明是一种导电性糊剂材料,其特征在于,前述低熔点玻璃的30℃~300℃下的热膨胀系数为(100~150)×10-7/℃、软化点为400℃以上且500℃以下。热膨胀系数在(100~150)×10-7/℃范围外时,在电极形成时发生剥离、基板的翘曲等问题。30℃~300℃下的热膨胀系数优选为(105~145)×10-7/℃的范围。另外,软化点超过500℃时,因为焙烧时不能充分地流动,所以发生与硅半导体基板的密合性变差等问题。软化点优选为400℃以上且480℃以下。
另外,本发明是一种太阳能电池元件,其特征在于,其使用上述导电性糊剂材料。
进而,本发明是一种电子材料用基板,其特征在于,其使用上述导电性糊剂材料。
实施例
以下,基于实施例,对本发明进行说明。
(导电性糊剂材料)
首先,对于玻璃粉末,按照实施例中记载的特定组成的方式称量各种无机原料并混合,制备原料母料。将该原料母料投入铂坩埚,在电加热炉内以1000~1300℃加热熔融1~2小时,得到如表1的实施例1~5、表2的比较例1~4所示的组成的玻璃。玻璃的一部分流入模具内,形成块状,供热物性(热膨胀系数、软化点)测定使用。其余的玻璃利用急冷双辊成形机形成片状,通过粉碎装置制粒为平均粒径1~4μm、最大粒径低于10μm的粉末状。
接着,在由α-松油醇和丁基卡必醇乙酸酯组成的糊状油(paste oil)中,以特定比例混合作为粘结剂的乙基纤维素和上述玻璃粉、及作为导电性粉末的铝粉末,制备粘度为500±50泊左右的导电性糊剂。
需要说明的是,软化点使用热分析装置TG-DTA(RigakuCorporation制造)测定。另外,热膨胀系数是使用热膨胀计以5℃/分钟升温时通过在30~300℃下的伸长量求出的。
接着,准备p型半导体硅基板1,在其上部丝网印刷上述制备得到的导电性糊剂。将这些试验片利用140℃的干燥机进行10分钟干燥,接着,通过用电炉在800℃条件下焙烧1分钟,得到在p型半导体硅基板1上形成有铝电极层5和BSF层6的结构。
针对这样得到的样品,利用4探针式表面电阻测定器测定对电极间的欧姆电阻有影响的铝电极层5的表面电阻。
接着,为调查铝电极层5与p型半导体硅基板1的密合性,将修补胶带(Nichiban制造)贴到铝电极层5上,目测评价剥离时的铝电极层5的剥落状态。
然后,将形成有铝电极层5的p型半导体硅基板1浸渍到氢氧化钠水溶液中,蚀刻铝电极层5和BSF层6而使p+层7露出到表面,利用4探针式表面电阻测定器测定p+层7的表面电阻。
p+层7的表面电阻和BSF效果相关,p+层7的表面电阻越低,则BSF效果越高,作为太阳能电池元件的转换效率越高。此处,将p+层7的表面电阻的目标值设为25Ω/□以下。
(结果)
无铅低熔点玻璃组成和各种试验结果示出在表中。
[表1]
[表2]
如表1中的实施例1~5所示,在本发明的组成范围内,软化点为400℃~500℃,具有适宜的热膨胀系数(100~150)×10-7/℃,与p型半导体硅基板1的密合性也良好。进而与太阳能电池元件的转换效率相关的p+层7的电阻值也低,适合作为晶体硅太阳能电池用的导电性糊剂。
另一方面,超出本发明的组成范围的表2中的比较例1~4,不能获得与p型半导体硅基板1的良好的密合性,p+层7的电阻值高,或熔解后玻璃显示出潮解性等,不适合作为晶体硅太阳能电池用的导电性糊剂。
附图标记说明
1 p型半导体硅基板
2 n型半导体硅层
3 抗反射膜
4 表面电极
5 铝电极层
6 BSF层
7 P+层
Claims (5)
1.一种SiO2-B2O3-ZnO-RO-R2O系无铅低熔点玻璃,其为在使用硅半导体基板的太阳能电池中使用的导电性糊剂中所含的低熔点玻璃,其特征在于,该玻璃的组成为实质上不含铅成分,且以质量%计,含有:
2~10%的SiO2、18~30%的B2O3、0~10%的Al2O3、0~25%的ZnO、20~50%的RO、以及10~17%的R2O,
其中,RO是指选自MgO、CaO、SrO、BaO中的一种以上的总和,R2O是指选自Li2O、Na2O、K2O中的一种以上的总和。
2.根据权利要求1所述的无铅低熔点玻璃,其特征在于,其在30℃~300℃下的热膨胀系数为(100~150)×10-7/℃、软化点为400℃以上且550℃以下。
3.一种导电性糊剂,其特征在于,其使用权利要求1或权利要求2的无铅低熔点玻璃。
4.一种太阳能电池元件,其特征在于,其使用权利要求1或权利要求2的无铅低熔点玻璃。
5.一种电子材料用基板,其特征在于,其使用权利要求1或权利要求2的无铅低熔点玻璃。
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PCT/JP2011/063590 WO2012002143A1 (ja) | 2010-06-29 | 2011-06-14 | 低融点ガラス組成物及びそれを用いた導電性ペースト材料 |
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104464878A (zh) * | 2014-12-26 | 2015-03-25 | 常熟联茂电子科技有限公司 | 一种电阻浆料 |
CN106927677A (zh) * | 2017-03-07 | 2017-07-07 | 陕西科技大学 | 一种利用碎玻璃制备仿玉石玻璃的方法 |
CN110066108A (zh) * | 2018-01-23 | 2019-07-30 | Agc株式会社 | 玻璃、玻璃的制造方法、导电糊剂和太阳能电池 |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104703936A (zh) * | 2012-09-28 | 2015-06-10 | 丹麦技术大学 | 用于作为密封剂使用的玻璃组合物 |
WO2014175013A1 (ja) * | 2013-04-25 | 2014-10-30 | 株式会社村田製作所 | 導電性ペーストおよび積層セラミック電子部品 |
EP3040320A1 (en) * | 2014-12-31 | 2016-07-06 | Heraeus Precious Metals North America Conshohocken LLC | Glass composition for electroconductive paste compositions |
KR102323215B1 (ko) | 2015-05-20 | 2021-11-08 | 삼성전자주식회사 | 전극 활물질, 이를 포함하는 전극 및 에너지 저장장치, 및 상기 전극 활물질의 제조방법 |
JP6825948B2 (ja) * | 2017-03-17 | 2021-02-03 | 東洋アルミニウム株式会社 | 太陽電池用ペースト組成物 |
WO2019183931A1 (zh) * | 2018-03-30 | 2019-10-03 | 深圳市首骋新材料科技有限公司 | 晶硅太阳能电池正面导电浆料及其制备方法和太阳能电池 |
CN114822910B (zh) * | 2022-05-20 | 2022-12-06 | 上海银浆科技有限公司 | 导电银铝浆、制备方法、电极及电池 |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5738343A (en) * | 1980-08-18 | 1982-03-03 | Fuji Photo Optical Co Ltd | Acid leachable glass for manufacturing flexible optical fiber strand |
US6362119B1 (en) * | 1999-06-09 | 2002-03-26 | Asahi Glass Company, Limited | Barium borosilicate glass and glass ceramic composition |
WO2008001631A1 (fr) * | 2006-06-28 | 2008-01-03 | Panasonic Corporation | panneau d'affichage plasma ET SON PROCÉDÉ DE FABRICATION |
Family Cites Families (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4400214A (en) * | 1981-06-05 | 1983-08-23 | Matsushita Electric Industrial, Co., Ltd. | Conductive paste |
JP2707010B2 (ja) * | 1991-06-21 | 1998-01-28 | 株式会社オハラ | 光学ガラス |
US5376596A (en) * | 1992-08-06 | 1994-12-27 | Murata Manufacturing Co., Ltd. | Conductive paste |
JP3120703B2 (ja) * | 1995-08-07 | 2000-12-25 | 株式会社村田製作所 | 導電性ペースト及び積層セラミック電子部品 |
US5998037A (en) * | 1997-12-22 | 1999-12-07 | Ferro Corporation | Porcelain enamel composition for electronic applications |
JP2001139345A (ja) | 1999-11-10 | 2001-05-22 | Asahi Glass Co Ltd | 無鉛低融点ガラスおよびガラスフリット |
JP2001163635A (ja) | 1999-12-06 | 2001-06-19 | Asahi Glass Co Ltd | 隔壁形成用無鉛低融点ガラスおよびガラスセラミックス組成物 |
JP4069559B2 (ja) * | 1999-12-20 | 2008-04-02 | 旭硝子株式会社 | 隔壁形成用低融点ガラスおよびプラズマディスプレイパネル |
JP3534684B2 (ja) * | 2000-07-10 | 2004-06-07 | Tdk株式会社 | 導電ペーストおよび外部電極とその製造方法 |
JP2003165744A (ja) | 2001-11-26 | 2003-06-10 | Murata Mfg Co Ltd | 導電性ペースト |
JP2005219942A (ja) * | 2004-02-03 | 2005-08-18 | Central Glass Co Ltd | 無鉛低融点ガラス |
US7771623B2 (en) | 2005-06-07 | 2010-08-10 | E.I. du Pont de Nemours and Company Dupont (UK) Limited | Aluminum thick film composition(s), electrode(s), semiconductor device(s) and methods of making thereof |
JP2007039269A (ja) * | 2005-08-02 | 2007-02-15 | Asahi Glass Co Ltd | 電極被覆用ガラスおよびプラズマディスプレイ装置 |
JP2008019145A (ja) | 2006-07-14 | 2008-01-31 | Nihon Yamamura Glass Co Ltd | 無鉛ガラス組成物 |
-
2010
- 2010-06-29 JP JP2010147806A patent/JP5609319B2/ja not_active Expired - Fee Related
-
2011
- 2011-06-14 CN CN201180031585.8A patent/CN102958862B/zh not_active Expired - Fee Related
- 2011-06-14 EP EP11800610.5A patent/EP2589577B1/en not_active Not-in-force
- 2011-06-14 WO PCT/JP2011/063590 patent/WO2012002143A1/ja active Application Filing
- 2011-06-14 US US13/634,727 patent/US8808582B2/en not_active Expired - Fee Related
- 2011-06-24 TW TW100122325A patent/TWI428303B/zh not_active IP Right Cessation
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5738343A (en) * | 1980-08-18 | 1982-03-03 | Fuji Photo Optical Co Ltd | Acid leachable glass for manufacturing flexible optical fiber strand |
US6362119B1 (en) * | 1999-06-09 | 2002-03-26 | Asahi Glass Company, Limited | Barium borosilicate glass and glass ceramic composition |
WO2008001631A1 (fr) * | 2006-06-28 | 2008-01-03 | Panasonic Corporation | panneau d'affichage plasma ET SON PROCÉDÉ DE FABRICATION |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104464878A (zh) * | 2014-12-26 | 2015-03-25 | 常熟联茂电子科技有限公司 | 一种电阻浆料 |
CN106927677A (zh) * | 2017-03-07 | 2017-07-07 | 陕西科技大学 | 一种利用碎玻璃制备仿玉石玻璃的方法 |
CN106927677B (zh) * | 2017-03-07 | 2019-10-01 | 陕西科技大学 | 一种利用碎玻璃制备仿玉石玻璃的方法 |
CN110066108A (zh) * | 2018-01-23 | 2019-07-30 | Agc株式会社 | 玻璃、玻璃的制造方法、导电糊剂和太阳能电池 |
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US20130119326A1 (en) | 2013-05-16 |
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