CN112708495B - 一种GaAs晶圆切割液 - Google Patents

一种GaAs晶圆切割液 Download PDF

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CN112708495B
CN112708495B CN202011598241.2A CN202011598241A CN112708495B CN 112708495 B CN112708495 B CN 112708495B CN 202011598241 A CN202011598241 A CN 202011598241A CN 112708495 B CN112708495 B CN 112708495B
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侯军
褚雨露
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Abstract

一种GaAs晶圆切割液，属于光电子器件的表面精密加工领域。该切割液包括低聚皂化合物、润湿剂、分散剂、螯合剂、增溶剂、抑菌剂与酸碱调节剂，其中低聚皂化合物在溶液中电离形成负电荷基团，具有类似表面活性剂的两亲性结构，使其能够在晶圆表面形成定向排列的吸附层，其带有负电荷的基团朝外，与带有负电荷的硅碎屑之间形成斥力；从而阻挡硅碎屑与晶圆表面直接接触，避免了硅碎屑对晶圆造成污染。

Description

一种GaAs晶圆切割液
技术领域
本发明涉及一种GaAs晶圆切割液，属于光电子器件的表面精密加工领域。
背景技术
GaAs是一种重要的半导体材料，GaAs可以制成电阻率比硅、锗高3个数量级以上的半绝缘高阻材料，用来制作集成电路衬底、红外探测器、γ光子探测器等；用GaAs制成的半导体器件具有高频、高温、低温性能好、噪声小、抗辐射能力强等优点。
在GaAs芯片制备工艺中，需要将经过光刻、镀膜、减薄等工艺制程后的整个芯片分割成所需求尺寸的单一晶粒，是半导体发光二极管芯片制备工艺中不可或缺的一道工序。GaAs晶圆切割过程：将晶圆固定在切割台上，用晶片切割机的刀片从晶圆上切出砷化镓芯片，在切割GaAs晶圆时，切割工艺过程中产生的残渣颗粒，会粘附到晶圆表面和侧壁。这些残渣颗粒一旦与晶圆接触，则很难在后续的清洗工艺中去除，会导致芯片产品良率下降。目前普遍使用的残渣清洁方法是：在切割过程中，将去离子水高压喷洒在切割区域和高速旋转的刀片上，将切割过程中产生的残渣冲掉。然而，利用这种方法仅能够将较大的残渣颗粒冲走，仍有一些细小的残渣无法被冲走。
发明内容
为了解决上述技术问题，本发明提供一种晶圆切割液，用于半导体晶圆切割制程，降低细小残渣的残留，提高晶圆切割过程中的清洁效果。
本发明采用的技术方案为：一种GaAs晶圆切割液，该切割液的组分及其质量分数如下：
Figure BDA0002868640560000011
余量为超纯水；
所述低聚皂化合物为低聚皂化合物的结构通式为：
Figure BDA0002868640560000021
其中：4≤n≤18。
所述润湿剂为烷基酚聚氧乙烯醚、C12-C16仲烷基磺酸钠、脂肪醇硫酸盐、仲烷基苯磺酸纳，2,5,8,11-四甲基-6-十二碳炔-5,8-二醇聚氧乙烯醚或2,5,8,11-四甲基-5-癸炔-5,8-二醇聚氧乙烯醚。
所述分散剂为马来酸/丙烯酸共聚物、马来酸/烯烃共聚物、改性聚丙烯酸钠盐、改性聚丙烯酸、阳离子聚乙烯胺亚胺、苯乙烯/丙烯酸共聚物、聚乙烯吡咯烷酮、羧甲基纤维素、羟丙基纤维素或羟乙基纤维素。
所述螯合剂为柠檬酸、葡萄糖酸、戊二酸、乙二胺四乙酸、N-羟乙基乙胺三乙酸、氨基三亚甲基膦酸、氨基三甲叉膦酸。
所述增溶剂为乙二醇丙醚、二乙二醇甲醚、乙二醇丁醚、二乙二醇丁醚、丙二醇甲醚、二丙二醇甲醚、二乙二醇乙醚或二乙二醇己醚。
所述抑菌剂为苯氧乙醇、苯酚、卡松或季铵盐型阳离子表面活性剂。
所述酸碱调节剂为氢氧化钾、氨水、三乙醇胺、单乙醇胺、二甘醇胺或三乙胺。
本发明的有益效果为：在GaAs晶圆切割过程中，刀片高速旋转与晶圆表面剧烈摩擦，由于使用的水为18兆欧超纯水，因此摩擦产生的静电荷可以在晶片上累积。切割产生的碎屑也会由于静电吸引而牢牢吸附在晶圆表面，导致后续无法清洗干净，因此在切割过程中将静电电荷释放掉是十分重要的。
通过控制pH在8-9，使切割产生硅碎屑表面具有负电荷，该切割液使用的低聚皂化合物在溶液中电离形成负电荷基团，其同时还具有类似表面活性剂的两亲性结构，使其能够在晶圆表面形成定向排列的吸附层，其带有负电荷的基团朝外，与带有负电荷的硅碎屑之间形成斥力，从而阻挡硅碎屑与晶圆表面直接接触，避免了硅碎屑对晶圆造成的污染。
附图说明
图1是实施例1中切割液切割后GaAs晶圆颗粒残留图，(图中无颗粒残留)。
图2是对比例1中切割液切割后GaAs晶圆颗粒残留图，(圈中为颗粒残留)。
具体实施方式
下面通过具体实施例对本发明作进一步说明，但本发明并不受以下实施例所限定。
表1实施例1-14切割液的组分及含量
Figure BDA0002868640560000031
Figure BDA0002868640560000041
Figure BDA0002868640560000051
实施例1-14的制备方法为：将一定量超纯水加入反应釜中，开动搅拌；按质量比加入低聚皂类化合物，搅拌3-5分钟；按质量比加入分散剂，搅拌5分钟；按质量比加入润湿剂，搅拌5分钟；按质量比加入螯合剂，搅拌5分钟；按质量比加入增溶剂，搅拌5分钟；按质量比加入抑菌剂，搅拌5分钟；按质量比加入酸碱调节剂，搅拌至透明，即得晶圆切割液。
对比例1
Figure BDA0002868640560000052
对比例1的制备方法为在超纯水中依次按比例加入壬基酚局氧乙烯醚、氧化聚乙烯(分子量50万)、柠檬酸、乙二醇甲醚、苯氧乙醇、二甘醇胺，搅拌至透明即得。
对比例2
Figure BDA0002868640560000053
对比例2的制备方法为在超纯水中依次按比例加入仲烷基苯磺酸、羧甲基纤维素(分子量10万)、柠檬酸、乙二醇甲醚、苯氧乙醇、二甘醇胺，搅拌至透明即得。
实施例15颗粒残留检测
以下实施例的效果检测均采用以下方法：以Disco 322晶圆切割机切割4寸GaAs晶圆，切割液稀释倍数为2000倍，以金相显微镜观察切割后的晶圆表面是否有颗粒残留；取切割后的废水样品，以ICP检测其中金属离子含量。
表2实施例1-10与对比例1的颗粒残留结果
Figure BDA0002868640560000061
其中：ICP最低检出限为0.2ppm，低于检出限结果记为N.D.
切割后有无颗粒残留对比图如图1和图2所示，图1是实施例1中切割液切割后金相显微镜观察切割后的晶圆表面，图中可见晶圆表面干净无颗粒残留；图2是对比例1中切割液切割后的晶圆表面，图中圈出的部分有颗粒残留。

Claims (4)

1.一种GaAs晶圆切割液，其特征在于：该切割液的组分及其质量分数如下：
低聚皂化合物 1.0-10.0%
润湿剂 0.5-2.0%
分散剂 1.5-5.0%
螯合剂 0.5-1.0%
增溶剂 2.0-5.0%
抑菌剂 0.1-0.5%
酸碱调节剂 0.1-2.0%
余量为超纯水；
所述低聚皂化合物的结构通式为：
Figure 32070DEST_PATH_IMAGE002
，其中：4≤n≤18；
所述切割液的pH值为8-9；
所述润湿剂为烷基酚聚氧乙烯醚、C12-C16仲烷基磺酸钠、脂肪醇硫酸盐、仲烷基苯磺酸纳，2,5,8,11-四甲基-6-十二碳炔-5,8-二醇聚氧乙烯醚或2,5,8,11-四甲基-5-癸炔-5,8-二醇聚氧乙烯醚；
所述分散剂为马来酸/丙烯酸共聚物、马来酸/烯烃共聚物、改性聚丙烯酸钠盐、改性聚丙烯酸、苯乙烯/丙烯酸共聚物、聚乙烯吡咯烷酮、氧化聚乙烯、羧甲基纤维素、羟丙基纤维素或羟乙基纤维素，其分子量为10-20万；
所述增溶剂为乙二醇丙醚、二乙二醇甲醚、乙二醇丁醚、二乙二醇丁醚、丙二醇甲醚、二丙二醇甲醚、二乙二醇乙醚或二乙二醇己醚。
2.根据权利要求1所述的一种GaAs晶圆切割液，其特征在于：所述螯合剂为柠檬酸、葡萄糖酸、戊二酸、乙二胺四乙酸、N-羟乙基乙胺三乙酸、氨基三亚甲基膦酸、氨基三甲叉膦酸。
3.根据权利要求1所述的一种GaAs晶圆切割液，其特征在于：所述抑菌剂为苯氧乙醇、苯酚、卡松或季铵盐型阳离子表面活性剂。
4.根据权利要求1所述的一种GaAs晶圆切割液，其特征在于：所述酸碱调节剂为氢氧化钾、氨水、三乙醇胺、单乙醇胺、二甘醇胺或三乙胺。
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