CN112410036B - 一种低选择性的bpsg和peteos薄膜的蚀刻液 - Google Patents
一种低选择性的bpsg和peteos薄膜的蚀刻液 Download PDFInfo
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Abstract
本发明公开了一种低选择性的BPSG和PETEOS薄膜的蚀刻液，主要成分包括氢氟酸、有机溶剂、含氟化合物、胺类。本发明的蚀刻液中氢氟酸用于蚀刻BPSG和PETEOS薄膜；有机溶剂用于降低蚀刻液对BPSG和PETEOS薄膜的蚀刻速率，使蚀刻反应易于控制；含氟化合物作为氟离子缓释剂，提供氟离子，稳定蚀刻液的蚀刻速率和延长蚀刻液的使用寿命；胺类用于降低BPSG薄膜的蚀刻速率，使BPSG和PETEOS薄膜的蚀刻速率选择比接近于1。本发明所述的蚀刻液能够使BPSG和PETEOS薄膜的蚀刻速率选择比稳定在1.1±0.2。
Description
技术领域
本发明涉及半导体制造工业中介电层的蚀刻加工技术领域，更具体的说涉及一种低选择性的BPSG和PETEOS薄膜的蚀刻液。
背景技术
在半导体制造工业中，介电层薄膜的生长是一种添加制程，使金属层与金属层之间，金属层与有源器件之间提供可靠地绝缘保护。当有源器件在晶圆的表面制作完成后，在金属沉积前，会沉积介电层，一般介电层ILD的形成层次为①SiON层沉积(用来避免上层B、P渗入器件)；②BPSG(掺有硼、磷的硅玻璃即硼磷硅玻璃)层沉积；③PETEOS(等离子体增强正硅酸乙酯)层沉积；最后再经ILD Oxide CMP(SiO2的化学机械研磨)来做平坦化。
在使用蚀刻液进行蚀刻时(见附图1)，由于BPSG的蚀刻速率比PETEOS快，随着蚀刻的进行BPSG层会出现侧掏现象(见附图2)，影响后续的金属沉积制程。本发明为了解决BPSG侧掏问题，开发了一种蚀刻液，能够使BPSG和PETEOS的蚀刻速率选择比接近于1，使BPSG和PETEOS以等同的蚀刻速率进行蚀刻，蚀刻效果见附图3，同时也能稳定控制蚀刻液的蚀刻速率、延长蚀刻液的使用寿命。
发明内容
本发明所要解决的技术问题是提供一种能够降低BPSG薄膜的蚀刻速率，使BPSG和PETEOS薄膜的蚀刻速率选择比接近于1的蚀刻液，解决由于BPSG层蚀刻过快而出现的侧掏问题。
本发明涉及一种BPSG和PETEOS薄膜的蚀刻液，所述蚀刻液的组成包括：占蚀刻液总重量0.01-3％的氢氟酸、10-50％的有机溶剂、1-20％的含氟化合物、0.01-2％的胺类。
进一步地，本发明涉及上述蚀刻液，氢氟酸原始浓度为48-50％。
进一步地，本发明涉及上述蚀刻液，有机溶剂为选自甲醇、乙醇、异丙醇、乙二醇、1,2-丙二醇、1,3-丁二醇、丙三醇、二乙二醇、三乙二醇、环己醇、乙二醇单甲醚、乙二醇单乙醚、乙二醇单正丁醚、乙烯乙二醇醚等中的至少一种。
进一步地，本发明涉及上述蚀刻液，含氟化合物为选自氟化氢铵、氟化铵、氟硼酸、四甲基氟化铵、全氟辛酸、氟硼酸铵、三氟乙酸乙酯、对氟苯乙烯等中的至少一种。
进一步地，本发明涉及上述蚀刻液，胺类为选自二烯丙基胺、二正丙胺、二异丁胺、二正丁胺、2-乙基己胺、二异丙胺、1,2-二甲基丙胺、仲丁胺、1,5-二甲基己胺、甲酰胺、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、三乙烯二胺、吗啡啉、环己胺等中的至少一种。
进一步地，本发明涉及上述蚀刻液，所述的氢氟酸用于蚀刻BPSG和PETEOS薄膜；有机溶剂用于降低蚀刻液对BPSG和PETEOS薄膜的蚀刻速率，使蚀刻反应易于控制；含氟化合物作为氟离子缓释剂，提供氟离子稳定蚀刻液的蚀刻速率和延长蚀刻液的使用寿命；胺类用于降低BPSG薄膜的蚀刻速率，使BPSG和PETEOS薄膜的蚀刻速率选择比接近于1。
进一步地，本发明涉及上述蚀刻液，其蚀刻速率选择比为1.1±0.2。
进一步地，本发明涉及上述蚀刻液，蚀刻温度为15-30℃，蚀刻时间为1-8min。
本发明中蚀刻速率的验证使用椭圆偏振光谱仪对蚀刻前后的膜层厚度进行量测，根据{(蚀刻前厚度-蚀刻后厚度)/蚀刻时间}计算蚀刻速率，通过公式①计算蚀刻速率选择比。
由于BPSG掺杂有硼和磷，而氮和硼具有配位亲和，因此本发明的蚀刻液中通过加入胺类物质使其吸附在BPSG薄膜上，从而降低BPSG薄膜的蚀刻速率，实现BPSG和PETEOS薄膜的蚀刻速率选择比接近于1，不出现侧掏现象影响后续的金属沉积制程，如图3所示。
附图说明
图1为蚀刻液进行蚀刻时的工作状态图。
图2为蚀刻液进行蚀刻过程中BPSG层会出现的侧掏现象图。
图3为本实施例中BPSG和PETEOS以等同的蚀刻速率进行蚀刻的现象图。
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。为了验证本发明蚀刻液的效果，具体实施例中使用单层的BPSG晶圆片和PETEOS晶圆片进行蚀刻实验，其中使用的BPSG晶圆片中硼(B)含量为4％、磷(P)含量为5％。
将BPSG和PETEOS晶圆片均切割成3cm×3cm大小的样片，使用超纯水清洗和氮气吹干后，利用椭圆偏振光谱仪量测BPSG和PETEOS样片的初始厚度，即蚀刻前厚度；待蚀刻液温度稳定在20℃后，将BPSG和PETEOS样片一起放入蚀刻液中蚀刻3min后取出，使用超纯水清洗和氮气吹干，再利用椭圆偏振光谱仪量测BPSG和PETEOS样片的蚀刻后厚度；根据{(蚀刻前厚度-蚀刻后厚度)/蚀刻时间}计算出BPSG和PETEOS的蚀刻速率，再根据上述公式①计算出蚀刻速率选择比。
实施例1
蚀刻液1的组成：0.5wt％氢氟酸、45wt％乙二醇、3wt％对氟苯乙烯、0.1wt％吗啡啉。
实施例2
蚀刻液2的组成：1wt％氢氟酸、42wt％1,3-丁二醇、3wt％四甲基氟化铵、0.1wt％1,5-二甲基己胺。
实施例3
蚀刻液3的组成：1wt％氢氟酸、35wt％丙三醇、2wt％三氟乙酸乙酯、0.2wt％二异丁胺。
实施例4
蚀刻液4的组成：0.8wt％氢氟酸、30wt％二乙二醇、2wt％氟硼酸铵、0.15wt％2-乙基己胺。
实施例5
蚀刻液5的组成：1wt％氢氟酸、42wt％1,3-丁二醇、5wt％四甲基氟化铵、0.1wt％1,5-二甲基己胺。
实施例6
蚀刻液6的组成：1wt％氢氟酸、42wt％1,3-丁二醇、8wt％四甲基氟化铵、0.1wt％1,5-二甲基己胺。
实施例7
蚀刻液7的组成：0.5wt％氢氟酸、45wt％乙二醇、3wt％对氟苯乙烯、0.15wt％吗啡啉。
实施例8
蚀刻液8的组成：0.5wt％氢氟酸、45wt％乙二醇、3wt％对氟苯乙烯、0.2wt％吗啡啉。
比较例1
比较例1的组成：1wt％氢氟酸、42wt％1,3-丁二醇、0.2wt％四甲基氟化铵、0.1wt％1,5-二甲基己胺。
比较例2
比较例2的组成：0.5wt％氢氟酸、45wt％乙二醇、3wt％对氟苯乙烯、0.005wt％吗啡啉。
比较例3
比较例3的组成：0.5wt％氢氟酸、45wt％乙二醇、3wt％对氟苯乙烯、3wt％吗啡啉。
比较例4
比较例4的组成：0.8wt％氢氟酸、30wt％二乙二醇、2wt％氟硼酸铵、0.15wt％三乙胺。
比较例5
比较例5的组成：1wt％氢氟酸、42wt％1,3-丁二醇、3wt％四甲基氟化铵。
比较例6
比较例6的组成：0.5wt％氢氟酸、45wt％乙二醇、0.1wt％吗啡啉。
实验结果见下表1。
表1蚀刻速率及选择比数据表
由表1的评价结果表明，实施例1-8的配方条件下的蚀刻液组合物的蚀刻速率选择比均在1.1±0.2范围内，在蚀刻过程中呈现如图3所示的蚀刻过程。而对比例2、5出现严重的侧掏现象，对比例4出现较弱的侧掏现象。
比较例1中蚀刻速率选择比为1.04，含氟化合物添加量低于1％，BPSG和PETEOS两者的蚀刻速率均低于实施例2，且蚀刻液在循环蚀刻3次后，BPSG和PETEOS两者的蚀刻速率降至
和
蚀刻速率下降明显，不利于稳定蚀刻。比较例2中的胺类物质低于0.01％，由结果可知，BPSG的蚀刻速率抑制不明显，与PETEOS的蚀刻速率差异较大，导致蚀刻速率选择比高于1.3。比较例3中的胺类物质高于2％，BPSG的蚀刻速率抑制明显，导致蚀刻速率选择比低于0.9。
比较例5不含胺类物质，BPSG和PETEOS两者的蚀刻速率存在明显差异。比较例4中添加的胺类物质三乙胺不是选自权利要求5中列出的胺类物质，虽然蚀刻速率选择比低于比较例5，但BPSG的蚀刻速率抑制效果差于实施例中添加的胺类物质，故并不是任一种胺类物质均能使蚀刻速率选择比控制在1.1±0.2范围内。
比较例6虽然蚀刻速率差异不明显，但对比实施例1，分别循环蚀刻5次后，比较例6中BPSG和PETEOS的蚀刻速率降为
和
(蚀刻速率选择比为.35)，而实施例1中BPSG和PETEOS的蚀刻速率为
和
(蚀刻速率选择比为1.05)，结果说明含氟化合物的加入能够稳定蚀刻液的蚀刻速率和延长蚀刻液的使用寿命。
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 (3)
1.一种低选择性的BPSG和PETEOS薄膜的蚀刻液，其特征在于，所述的蚀刻液成分包括占蚀刻液总重量0.01-3%的氢氟酸、10-50%的有机溶剂、1-20%的含氟化合物、0.01-2%的胺类，所述的有机溶剂选自甲醇、乙醇、异丙醇、乙二醇、1,2-丙二醇、1,3-丁二醇、丙三醇、二乙二醇、三乙二醇、环己醇中的至少一种，所述蚀刻液成分中的含氟化合物选自氟化氢铵、氟化铵、氟硼酸、四甲基氟化铵、氟辛酸、氟硼酸铵、三氟乙酸乙酯、对氟苯乙烯中的至少一种，所述的胺类选自二异丁胺、2-乙基己胺、1,5-二甲基己胺、吗啡啉中的至少一种。
2.根据权利要求1所述的一种低选择性的BPSG和PETEOS薄膜的蚀刻液，其特征在于，所述蚀刻液成分中的氢氟酸原始浓度为48-50%。
3.根据权利要求1所述的一种低选择性的BPSG和PETEOS薄膜的蚀刻液，其特征在于，所述蚀刻液蚀刻BPSG和PETEOS薄膜后的速率选择比为1.1±0.2。
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