CN114369461B - 一种氮化铝和硅的高选择性蚀刻液 - Google Patents
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- 238000005530 etching Methods 0.000 title claims abstract description 53
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 title claims abstract description 27
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 21
- 239000010703 silicon Substances 0.000 title claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 8
- 150000001367 organochlorosilanes Chemical class 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 7
- 239000004115 Sodium Silicate Substances 0.000 claims description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 4
- 235000019795 sodium metasilicate Nutrition 0.000 claims description 4
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 4
- KEZYHIPQRGTUDU-UHFFFAOYSA-N 2-[dithiocarboxy(methyl)amino]acetic acid Chemical compound SC(=S)N(C)CC(O)=O KEZYHIPQRGTUDU-UHFFFAOYSA-N 0.000 claims description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 235000003270 potassium fluoride Nutrition 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 239000011775 sodium fluoride Substances 0.000 claims description 2
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- -1 sodium metasilicate heptahydrate Chemical class 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 2
- 229920002554 vinyl polymer Chemical group 0.000 claims description 2
- 239000000758 substrate Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 17
- 235000012431 wafers Nutrition 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229940096017 silver fluoride Drugs 0.000 description 1
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 description 1
- 238000010897 surface acoustic wave method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching
- H01L21/30604—Chemical etching
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Abstract
本发明公开了一种氮化铝和硅的高选择性蚀刻液,该蚀刻液的主要成分包括占蚀刻液液5‑40质量%碱、0.2‑0.5质量%氟化物、0.1‑0.5质量%有机氯硅烷,1‑5质量%硅酸盐,其余为水。该蚀刻液能将氮化铝层快速清洗干净,不会有晶格残留,且对Si基底的选择比可达1000以上。
Description
技术领域
本发明属于电子化学品领域。
背景技术
由于AlN带隙宽、极化强,禁带宽度为6.2eV,其制备的氮化铝薄膜材料具有很多优异的物理化学性质,如高的击穿场强、高热导率、高电阻率、高化学和热稳定性以及良好的光学及力学性能。高质量的AlN薄膜还具有极高的超声传输速度、较小的声波损耗、相当大的压电耦合常数,与Si、GaAs相近的热膨胀系数等特点,独特的性质使它在机械、微电子、光学以及电子元器件、声表面波器件制造和高频宽带通信等领域有着广阔的应用前景。
由于氮化铝薄膜材料具有优良的吸能,在半导体中有广阔的应用前景。但目前氮化铝的蚀刻存在以下问题:采用酸性蚀刻液蚀刻氮化铝,蚀刻制程温度高,蚀刻速率低,工艺时间长;采用碱性蚀刻液可以避免上述问题,但碱性蚀刻液的各向异性蚀刻会造成氮化硅蚀刻晶体残留以及对基底硅的破坏。
现有文献已公开的蚀刻液或多或少存在一些缺点:CN107829114A选用熔融NaOH-KOH低共融混合物作为腐蚀液来侵蚀氮化铝晶体的表面,腐蚀前后采用有机溶剂清洗,腐蚀后采用浓酸洗去熔融碱。使用熔融NaOH-KOH温度高(170-400℃),工艺复杂,蚀刻后有晶体残留,且未考虑对Si的影响;
CN112384597公开了一种水性蚀刻组合物包含:含氟化物源的蚀刻剂;和金属腐蚀抑制剂;其中所述组合物的pH在3到8范围内。但其对AlN的蚀刻速率仅50A/min左右。
发明内容
本发明针对现有氮化铝蚀刻技术中的不足,目的在于提供一种蚀刻速率快、无蚀刻残留,且对硅基底具有高蚀刻选择性的氮化铝蚀刻液。
为实现上述发明目的,本发明采用的技术方案为:
本发明公开了一种氮化铝和硅的高选择性蚀刻液,该蚀刻液的主要成分包括占蚀刻液液5-40质量%碱、0.2-0.5质量%氟化物、0.1-0.5质量%有机氯硅烷,1-5质量%硅酸盐,其余为水。
上述方案中,所述的碱为氢氧化钾、氢氧化钠、四甲基氢氧化铵中的一种或几种的混合物,优选氢氧化钾与氢氧化钠,浓度为5-40wt%,优选10-20wt%。
上述方案中,所述的氟化物为氟化钠、氟化钾、氟化铵、氟化银中的一种或几种的混合物。
其中,R为氢、甲基、乙烯基、烷基、苯基、乙基或丙基。
上述方案中,所述无机硅为偏硅酸钠、偏硅酸钾、五水偏硅酸钠、七水偏硅酸钠中的一种或几种的混合物。
本发明的有益效果:
(1)本发明的蚀刻液中的氟化物可以加速蚀刻液对氮化铝晶格的破坏,使得蚀刻液可以有效地对氮化铝进行蚀刻,蚀刻后硅基底表面不会有氮化铝的晶体残留。
(2)本发明的蚀刻液中的有机氯硅烷水解后可与硅基底的硅羟基结合,起到保护下层硅不被蚀刻的作用,有机氯硅烷水解形成的氯化物有能促进氮化硅的蚀刻,起到提高氮化铝和硅的蚀刻选择比的作用。
(3)本发明的蚀刻液中硅酸盐可以降低蚀刻液对基底硅的蚀刻速率,提高蚀刻液对氮化铝和硅的蚀刻选择比,起到保护基底硅的作用。
附图说明
图1为氮化铝与硅的层状结构图。
图2为蚀刻后有大量氮化铝晶格残留的SEM图。
图3为蚀刻后有少量氮化铝晶格残留的SEM图。
图4为蚀刻后无氮化铝晶格残留的SEM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,但本发明的内容不仅仅局限于下面的实施例。
实施例1-15及对比例1-3:
符合本发明所构思实施例与对比例的各组分含量列于表1,余量为水。
表1
氮化铝和硅的高选择性蚀刻液按以下方式制备并使用:
1.按照上述表格中的原料种类与数量取原料备用;
2.在碱液中依次加入水、氟化物、硅酸盐和有机氯硅烷;
3.将上述混合液搅拌均匀并超声分散制成氮化铝和硅的高选择性蚀刻液;
4.将AlN与Si的晶圆切成1*1cm的小片,水洗并用氮气吹干后使用椭偏仪测量两种晶圆的初始厚度;
5.将步骤3制备的高选择性蚀刻液水浴加热至45℃,300r/min搅拌速率下进行蚀刻,AlN片蚀刻10s、Si片蚀刻2min;
6.蚀刻结束后立刻用水冲洗、氮气吹干后使用椭偏仪测量两种晶圆的蚀刻后厚度,通过蚀刻前后厚度差与蚀刻时间计算蚀刻速率、结果列于表2.
表2
对比上述实施例与对比例,数据显示,本发明的高选择性蚀刻液能进行氮化铝层的快速蚀刻,不会有晶格残留,且对Si基底的选择比可达1000以上。
显然,上述实施例仅是为清楚地说明所作的实例,而并非对实施方式的限制。对于所属领域的普通技术人员来说,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。
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