CN114369460B - 一种提高凹型沟槽结构二氧化硅蚀刻均匀性的蚀刻液 - Google Patents
一种提高凹型沟槽结构二氧化硅蚀刻均匀性的蚀刻液 Download PDFInfo
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Abstract
本发明公开了一种提高凹型沟槽结构二氧化硅蚀刻均匀性的蚀刻液，主要成分包括氢氟酸、氟化铵、抑制剂、非离子型表面活性剂和超纯水。本发明的蚀刻液中通过加入抑制剂，提高蚀刻液的粘度，增加传质阻力，降低二氧化硅的蚀刻速率；非离子型表面活性剂则用于降低蚀刻液表面张力，提高浸润性，减小凹型沟槽结构上、中、下层二氧化硅蚀刻速率的差异。本发明所述的蚀刻液能够使凹型沟槽结构的上、中、下层蚀刻速率差异降低，保持上、中、下层的二氧化硅蚀刻速率基本一致。
Description
技术领域
本发明涉及半导体制造工业中一种二氧化硅的蚀刻液，更具体的说涉及一种凹型沟槽结构二氧化硅的蚀刻液。
背景技术
在半导体制造工业中，SiO2的主要作用一是作为掺杂阻挡层，SiO2能够形成阻挡保护层，防止掺杂物(例如硼、磷、砷等)向半导体中扩散；二是作为隔离层，在集成电路中，器件与器件之间的隔离可以有PN结隔离和SiO2介质隔离，SiO2介质隔离比PN结隔离的效果好，它采用一个厚的场氧化层来完成；三是作为缓冲层，但Si3N4直接沉积在Si衬底上时，界面存在较大的应力与极高的界面态密度，因此多采用Si3N4/SiO2/Si结构，可以清除Si3N4和衬底Si之间的应力；四是作为绝缘层，在芯片集成度越来越高的情况下就需要多层金属布线，它们之间需要用绝缘性能良好的介电材料加以隔离，SiO2就能充当这种隔离材料；五是作为保护器件和电路的钝化层，在集成电路芯片制作完成后，为了防止机械性的损伤，或接触含有水汽的环境太久而造成器件失效，通常在IC制造工艺结束后在表面沉积一层钝化层，掺磷的SiO2薄膜常用作这一用途。
SiO2在半导体制造工艺中是一个重要的组成部分，通常通过湿法蚀刻的方式，来获得所需的结构或起到所需的作用。一般SiO2蚀刻使用稀释的HF或HF+NH4F组合物来实现，稀释的HF或HF+NH4F组合物仅能用于处理无结构的SiO2，对于特定结构的SiO2，特别是对于深沟槽的结构，需要蚀刻液的表面张力低，才能有效渗透至深沟槽中SiO2层，进行有效蚀刻。
发明内容
本发明所要解决的技术问题是提供一种提高凹型沟槽结构二氧化硅蚀刻均匀性的蚀刻液，降低凹型沟槽结构的上、中、下层二氧化硅的蚀刻速率差异，保持上、中、下层蚀刻速率基本一致。
本发明涉及一种提高凹型沟槽结构二氧化硅蚀刻均匀性的蚀刻液，所述蚀刻液的组成包括：占蚀刻液总重量1-8％的氢氟酸、16-20％的氟化铵、0.1-5％的抑制剂、0.001-0.1％的非离子型表面活性剂，剩余为超纯水。
进一步地，本发明涉及上述蚀刻液，抑制剂为选自醇类、醇胺类、纤维素类、聚氨酯类中的至少一种。
进一步地，本发明涉及上述蚀刻液中的抑制剂，醇类抑制剂优选乙二醇、丙三醇、环己醇、二乙二醇、三乙二醇、聚乙二醇200、聚乙二醇300、聚乙二醇400、聚乙二醇600；醇胺类抑制剂优选乙醇胺、三乙醇胺、二甘醇胺、异丙醇胺、N-甲基二乙醇胺；纤维素类抑制剂优选甲基纤维素、羟丙基甲基纤维素、羟乙基纤维素、羟丙基纤维素、聚阴离子纤维素；聚氨酯类抑制剂优选水性聚氨酯。
进一步地，本发明涉及上述蚀刻液，非离子型表面活性剂为选自甘油椰油酸酯、椰子油脂肪酸二乙醇酰胺、油酰二乙醇胺、脂肪酸聚氧乙烯酯、聚乙二醇月桂酸酯、聚乙二醇硬脂酸脂、脂肪醇聚氧乙烯醚中的至少一种。
进一步地，本发明涉及上述蚀刻液，所述的氢氟酸起到蚀刻的作用，氟化铵提供氟离子起到稳定蚀刻速率和延长lifetime的作用；抑制剂用于提高蚀刻液的粘度，增加传质阻力，起到降低二氧化硅蚀刻速率的作用；非离子型表面活性剂用于降低蚀刻液表面张力，提高浸润性，减小凹型沟槽结构上、中、下层二氧化硅蚀刻速率的差异。
进一步地，本发明涉及上述蚀刻液，能够使凹型沟槽结构的上、中、下层二氧化硅的蚀刻速率差异降低，保持上、中、下层蚀刻速率基本一致。
本发明的有益效果
本发明的优点和有益效果在于：在本发明中，通过抑制剂和非离子型表面活性剂的协同作用，可以降低二氧化硅的蚀刻速率，且使凹型沟槽结构上、中、下层二氧化硅的蚀刻速率差异减小，基本保持一致，为后续制程提供所需的结构。
附图说明
图1为二氧化硅的凹型沟槽结构图，上层、中层、下层的蚀刻速率验证位点如图所示，蚀刻液从凹型沟槽结构中进入蚀刻。
具体实施方式
下面结合具体实施例，进一步阐述本发明。对本发明做进一步详细的说明，但不限于这些实施例。实施例中使用的蚀刻温度为23℃、蚀刻时间为4min、蚀刻方式为静置浸泡蚀刻。二氧化硅凹型结构wafer的上、中、下层蚀刻差异性使用扫描电子显微镜(SEM)进行结构层图片拍摄，通过剩余上、中、下层二氧化硅层厚度，计算上、中、下层的蚀刻厚度和蚀刻速率。实施例中各组分与含量见表1。
表1为实施例与对比例的组分及含量
实验结果见下表2。
表2凹型结构top、middle、bottom二氧化硅蚀刻速率
由表2的评价结果表明，实施例蚀刻液组合物的表面张力均＜33mN/m，凹型结构的上、中、下二氧化硅层的蚀刻速率差异不明显，上层和下层的
蚀刻速率保持基本一致。
比较例1-6中上层和下层的
比较例1中不含抑制剂和表面活性剂，故蚀刻液表面张力大、蚀刻速率偏快且差异性最大；比较例4-6中分别选择了阳离子表面活性剂、阴离子表面活性剂和两性表面活性剂与非离子表面活性剂进行对比，经验证虽然蚀刻液的表面张力有明显降低，但上、中、下层的蚀刻速率差异并没有减小，不能起到降低蚀刻速率差异的作用。
本发明所述的抑制剂用于提高蚀刻液的粘度，增加传质阻力，起到降低二氧化硅蚀刻速率的作用；非离子型表面活性剂用于降低蚀刻液表面张力，提高浸润性，减小凹型沟槽结构上、中、下层二氧化硅蚀刻速率的差异。
所述的蚀刻液能够使凹型沟槽结构的上、中、下层二氧化硅的蚀刻速率差异降低，保持上、中、下层蚀刻速率基本一致。
显然，上述实施例和比较例仅仅是为了清楚地说明所作的实例，而并非对实施方式的限制。对于所属领域的技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动，这里无需也无法对所有的实施方式予以穷举。而因此所引申的显而易见的变化或变动仍处于本发明创造的保护范围之内。
Claims (4)
1.一种提高凹型沟槽结构二氧化硅蚀刻均匀性的蚀刻液，其特征在于，所述的蚀刻液成分包括占蚀刻液总重量1-8%的氢氟酸、16-20%的氟化铵、0.1-5%的抑制剂、0.001-0.1%的非离子型表面活性剂，剩余为超纯水，所述蚀刻液成分中的抑制剂为纤维素类，纤维素类选自甲基纤维素、羟丙基甲基纤维素、羟乙基纤维素、羟丙基纤维素、聚阴离子纤维素中的至少一种，所述蚀刻液成分中的非离子型表面活性剂选自甘油椰油酸酯、椰子油脂肪酸二乙醇酰胺、油酰二乙醇胺、脂肪酸聚氧乙烯酯、聚乙二醇月桂酸酯、聚乙二醇硬脂酸脂、脂肪醇聚氧乙烯醚中的至少一种。
2.根据权利要求1所述的一种提高凹型沟槽结构二氧化硅蚀刻均匀性的蚀刻液，其特征在于，所述蚀刻液成分中的抑制剂还可以为醇类、聚氨酯类中的至少一种。
3.根据权利要求2所述的一种提高凹型沟槽结构二氧化硅蚀刻均匀性的蚀刻液，其特征在于，所述醇类选自乙二醇、丙三醇、环己醇、二乙二醇、三乙二醇、聚乙二醇200、聚乙二醇300、聚乙二醇400、聚乙二醇600中的至少一种。
4.根据权利要求2所述的一种提高凹型沟槽结构二氧化硅蚀刻均匀性的蚀刻液，其特征在于，聚氨酯类选自水性聚氨酯。
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