CN112458542B - 应用于热电器件的p型碲化铋基材料的表面处理剂及方法 - Google Patents
应用于热电器件的p型碲化铋基材料的表面处理剂及方法 Download PDFInfo
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Abstract
本发明公开了一种p型碲化铋基材料的表面处理剂,包括粗化液和除灰液两部分;所述粗化液的组成按体积百分比计包括:5~50%盐酸、5~40%双氧水、5~10%硝酸、余量为水;所述除灰液的组成按体积百分比计包括:5~50%氢氟酸、5~20%盐酸、5~10%硝酸、余量为水。该表面处理剂在使用时,粗化液和除灰液配合使用,洁净的p型碲化铋基晶片先浸入粗化液中,再浸入除灰液中,即可完成预处理,后续直接通过电镀或化学镀方式进行金属化连接。本发明提出的p型碲化铋基材料的表面处理剂及方法,避免了传统喷砂‑电弧喷涂处理较薄p型碲化铋基晶片时,容易导致晶片破损的问题,同时可以减少生产环节,提高成品率及生产效率,降低生产成本。
Description
技术领域
本发明涉及热电器件领域,尤其涉及一种应用于热电器件的p型碲化铋基材料的表面处理剂及方法。
背景技术
随着工业技术水平的提高,越来越多的电子设备趋向微型化和柔性化方向发展。热电技术作为一种可实现热能与电能之间直接相互转换的新型能源技术,在目前的石油危机之后,越来越受到人们的广泛关注。热电器件具有结构简单、无噪音、无传动部件和响应速度快等一系列优点,同时可实现发电和致冷两种功能。目前,热电器件同样趋于微型化方向发展,更多的用于激光通信、电子工业、生物医疗及航空航天等领域,比如激光器的精确控温、物联网的节点电源、可穿戴电子设备的供能等。
传统的p型碲化铋基晶片表面处理分为两个阶段,预处理阶段和电镀处理阶段。其中预处理阶段又可称为电镀前处理阶段,传统方式为喷砂结合电弧喷涂镍,喷砂起粗化片材表面作用,电弧喷涂镍起预先沉积作用,便于后续电镀处理阶段的进行,这种处理方式一般用于常规热电器件的制作,而常规热电器件所需p型碲化铋基晶片厚度均超过1mm,然而对于微型热电器件来说,其所用p型碲化铋基晶片厚度小于1mm,甚至达到0.2mm。采用传统表面处理方式,会在喷砂过程中产生高压环境,在电弧喷涂过程中产生高温环境,极易造成p型碲化铋基晶片的破损,降低成品率和生产效率,同时增加生产环节和生产成本。因此,发展一种新型的p型碲化铋基晶片表面处理方式迫在眉睫。
发明内容
本发明所要解决的技术问题是针对上述现有技术存在的不足而提供一种应用于热电器件的p型碲化铋基材料的表面处理剂及方法,处理工艺简便、对晶片不造成破损,尤其适宜规模化处理的应用于微型热电器件的p型碲化铋基材料的表面处理。
本发明为解决上述提出的问题所采用的技术方案为:
一种应用于热电器件的p型碲化铋基材料的表面处理方法,包括以下步骤:
配置p型碲化铋基晶片粗化溶液,粗化液包括5~50%盐酸(体积)、5~50%双氧水(体积)、5~10%硝酸(体积)、余量为水;
配置p型碲化铋基晶片除灰溶液,除灰液包括5~50%氢氟酸(体积)、5~20%盐酸(体积)、5~10%硝酸(体积)、余量为水;
将洁净的p型碲化铋基晶片浸入粗化液中进行粗化;
再将经过粗化后的p型碲化铋基晶片浸入除灰液中进行除灰;
除灰后的p型碲化铋基晶片即完成表面处理,可直接通过电镀或化学镀方式进行金属化连接。
按上述方案,所述洁净的p型碲化铋基晶片为预先经过水洗以及丙酮和无水乙醇等溶剂洗涤的p型碲化铋基晶片,除去了表面的油脂等污物或杂质。
按上述方案,所述硝酸为分析纯,浓度65~68%;盐酸为分析纯,浓度35~40%;双氧水为分析纯,浓度25~35%;氢氟酸为分析纯,浓度35~45%。
优选地,p型碲化铋基晶片粗化液,所述盐酸10%(体积),所述双氧水40%(体积),所述硝酸5%(体积)、余量为水。
优选地,p型碲化铋基晶片粗化所需温度为30℃,粗化时间为5min。
优选地,p型碲化铋基晶片除灰液,所述氢氟酸50%(体积)、所述盐酸10%(体积)、所述硝酸5%(体积)、余量为水。
优选地,p型碲化铋基晶片除灰所需温度为25℃,除灰时间5min。
以上述内容为基础,在不脱离本发明基本技术思想的前提下,根据本领域的普通技术知识和手段,对其内容还可以有多种形式的修改、替换或变更。比如p型碲化铋基晶片的制备方式包括区熔和粉末冶金等,本发明不限定p型碲化铋基晶片的制备方式。
在微型热电器件中,半导体与金属间的连接一直是关键技术问题。连接技术的好坏直接影响器件的发电与致冷性能,器件服役性能与可靠性。本发明采用化学粗化和除灰进行p型碲化铋基晶片表面处理,后续直接通过电镀或化学镀方式进行金属化连接,提升了界面结合强度,有效降低了界面接触电阻和界面接触热阻,这对于制备高性能微型热电器件是非常有益处的。
与现有技术相比,本发明的有益效果是:
1.本发明在不损伤晶片完整性的前提下,提高p型碲化铋基热电晶片的表面粗糙度,提升后续镍层与p型碲化铋基晶片的界面结合强度,有效降低了界面接触电阻和界面接触热阻,使热电器件的使用寿命,循坏次数及性能得到优化;
2.本发明溶液配置简便,方便操作,由于化学法除去表面轻微的氧化膜,使得片材表面活性提高,可减少电弧喷涂预先沉积镍这一工艺流程,可通过定期分析检测进行溶液管理,适合规模化生产。
因此,本发明提出的p型碲化铋基材料的表面处理剂及方法,避免了传统喷砂-电弧喷涂处理较薄p型碲化铋基晶片时,容易导致晶片破损的问题,同时可以减少生产环节,提高成品率及生产效率,降低生产成本理。
附图说明
图1为实施例1中步骤1)所用p型碲化铋基晶片照片;
图2为实施例1中步骤1)所用p型碲化铋基晶片的粗糙度测试结果;
图3为实施例1中步骤2)所得p型碲化铋基晶片的粗糙度测试结果;
图4为实施例1中步骤3)所得镀镍镀金后的p型碲化铋基晶片照片;
图5为实施例1中步骤4)中p型碲化铋基晶片的百格刀试验结果;
图6为实施例1中步骤5)所制作出的微型热电器件;
图7为实施例2中步骤1)所用p型碲化铋基晶片的表面SEM形貌图;
图8为实施例2中步骤2)所得化学处理完后的p型碲化铋基晶片的表面SEM形貌图。
具体实施方式
为了更好地理解本发明,下面结合实施例进一步阐明本发明的内容,但本发明不仅仅局限于下面的实施例。
下述实施例中,所用硝酸AR分析纯,浓度65~68%;浓盐酸为AR分析纯,浓度36~38%;双氧水为AR分析纯,浓度30%;氢氟酸为AR分析纯,浓度40%。
实施例1
一种p型碲化铋基材料的表面处理方法,它包括以下步骤:
1)直径30mm,厚度0.3mm的半圆形p型碲化铋基晶片,经丙酮洗涤脱脂除去表面污染物、无水乙醇脱水、干燥后采用OLS5000激光扫描显微镜进行表面粗糙度测试,其面粗糙度Sa为0.197μm,随后浸入粗化液(粗化液的组成为盐酸10%(体积)、双氧水40%(体积)、硝酸5%(体积)、余量为水)中,粗化温度30℃,粗化时间5min;
2)将步骤1)中粗化后的p型碲化铋基晶片转入除灰液(除灰液的组成为氢氟酸50%(体积)、盐酸10%(体积)、硝酸5%(体积)、余量为水)中进行除灰处理,除灰温度25℃,除灰时间5min,随后采用OLS5000激光扫描显微镜进行表面粗糙度测试,其面粗糙度Sa为0.649μm;
3)将步骤2)中除灰后的p型碲化铋基晶片放入电镀液中预先电镀镍,随后进行化学镀镍、电镀金,其中,
电镀镍的具体条件如下:硫酸镍200g/L;氯化镍45g/L;硼酸45g/L,8000#A半光亮镍开缸剂10mL/L,8000#B半光亮镍补充剂0.8mL/L,低泡润湿剂1mL/L,pH值4.0,温度55℃,阴极电流密度3A/dm2,3min;
化学镀镍的具体条件如下:硫酸镍0.095mol/L,次磷酸钠0.227mol/L,琥珀酸0.135mol/L,苹果酸0.179mol/L,pH 6,温度90℃,40min;
电镀金的具体条件如下:金氰化钾15g/L,柠檬酸35g/L,柠檬酸钾55g/L,pH 4.5,温度50℃,阴极电流密度1.3A/dm2,10min;
4)将步骤3)中得到的镀镍镀金的p型碲化铋基晶片进行QFH-A百格刀试验(根据ISO2409-1992标准设计制造,适用于GB/T9286-98、BS 3900E6、ASTM D3359),以“ISO/ASTM等级”评价镀层结合强度,其百格刀试验结果显示达到1/4B级别,在切口的相交处有小片剥落,划格区内实际破损不超过5%;
5)将步骤3)中得到的镀镍镀金的p型碲化铋基晶片进行一个8×8mm2微型热电器件的组装,并测试其致冷性能。
图1为实施例1中步骤1)所用p型碲化铋基晶片照片,可以看到表面有明显切割痕迹;
图2为实施例1中步骤1)所用p型碲化铋基晶片的粗糙度测试结果,粗糙度Sa为0.197μm;
图3为实施例1中步骤2)所得p型碲化铋基晶片的粗糙度测试结果,经表面酸洗后,粗糙度增大到0.649μm;
图4为实施例1中步骤3)所得镀镍镀金后的p型碲化铋基晶片照片;
图5为实施例1中步骤4)中p型碲化铋基晶片的百格刀试验结果,为1/4B等级,满足微电子行业标准;
图6为实施例1中步骤5)所制作出的微型热电器件;
表1为实施例1中步骤5)所制作出的微型热电器件的致冷性能,最大制冷温差达58℃。
表2为采用传统方式制作出的微型热电器件的致冷性能。传统方式的制备过程是喷砂+电弧喷涂+电镀镍+化学镀镍+化学镀金,即没有采用实施例1步骤(1)和(2)进行表面处理,而是采用喷砂+电弧喷涂镍的预处理方式(喷砂采用320目球型玻璃珠磨料,压力0.05MPa;电弧喷涂工艺:采用Φ1.2 mm镍丝,工作电压25V,工作电流90A,空气压力0.65MPa,喷枪电压9V),后续处理工艺一致。
由表1和表2对比,可以看到传统方式制作出的器件,电阻增加0.445Ω,主要由接触电阻贡献,最大制冷温差为55℃,减小3℃。因此,本发明所述表面处理方法,在不损伤晶片完整性的前提下,有效降低了界面接触电阻,说明表面处理后的p型碲化铋基晶片与后续镍层的界面接触性能提高了。
表1
表2
实施例2
一种p型碲化铋基材料的表面处理方法,它包括以下步骤:
1)直径30mm,厚度0.3mm的半圆形p型碲化铋基晶片,经丙酮洗涤脱脂除去表面污染物、无水乙醇脱水、干燥后采用SEM进行形貌观察,随后浸入粗化液(粗化液的组成为盐酸20%(体积)、双氧水30%(体积)、硝酸5%(体积)、余量为水)中,粗化温度30℃,粗化时间10min;
2)将步骤1)中粗化后的p型碲化铋基晶片转入除灰液(除灰液的组成为氢氟酸40%(体积)、盐酸10%(体积)、硝酸5%(体积)、余量为水)中进行除灰处理,除灰温度25℃,除灰时间10min,随后采用SEM继续形貌观察;
3)将步骤2)中除灰后的p型碲化铋基晶片放入电镀液中预先电镀镍,随后进行化学镀镍、电镀金(电镀镍、化学镀镍、电镀金的具体条件与实施例1相同);
4)将步骤3)中得到的镀镍镀金的p型碲化铋基晶片进行QFH-A百格刀试验,其百格刀试验结果显示达到1/4B级别,在切口的相交处有小片剥落,划格区内实际破损不超过5%;
5)将步骤3)中得到的镀镍镀金的p型碲化铋基晶片进行一个8×8mm2微型热电器件的组装,并测试其致冷性能。
图7为实施例2中步骤1)所用p型碲化铋基晶片SEM形貌图,可以看到表面有明显切割划痕;
图8为实施例2中步骤2)所得化学处理完后的p型碲化铋基晶片的SEM形貌图,可以看到化学处理后切割划痕消失;
表3为实施例2中步骤5)所制作出的微型热电器件的致冷性能,最大制冷温差达57.8℃。
表3
以上所述仅是本发明的优选实施方式,应当指出,对于本领域的普通技术人员来说,在不脱离本发明创造构思的前提下,还可以做出若干改进和变换,这些都属于本发明的保护范围。
Claims (4)
1.一种p型碲化铋基材料的表面处理剂,其特征在于包括粗化液和除灰液两部分;所述粗化液的组成按体积百分比计包括:5~20%盐酸、20~40%双氧水、5~10%硝酸、余量为水;所述除灰液的组成按体积百分比计包括:30~50%氢氟酸、5~20%盐酸、5~10%硝酸、余量为水;
所述硝酸的质量百分浓度为60~70%;盐酸的质量百分浓度为30~40%;双氧水的质量百分浓度为20~40%;氢氟酸的质量百分浓度为30~50%。
2.一种p型碲化铋基材料的表面处理方法,其特征在于采用权利要求1所述的表面处理剂对p型碲化铋基晶片进行预处理,首先将洁净的p型碲化铋基晶片先浸入粗化液中,再浸入除灰液中,即可完成预处理,后续直接通过电镀或化学镀方式进行金属化连接。
3.根据权利要求2所述的一种p型碲化铋基材料的表面处理方法,其特征在于p型碲化铋基晶片浸入粗化液中,粗化液温度为20~35℃,粗化时间为1~15min。
4.根据权利要求2所述的一种p型碲化铋基材料的表面处理方法,其特征在于将经过粗化液处理的p型碲化铋基晶片浸入除灰液中,除灰液温度为20~30 ℃,除灰时间1~10 min。
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