CN1203205A - 硅酸盐的选择性刻蚀 - Google Patents
硅酸盐的选择性刻蚀 Download PDFInfo
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- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
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- 239000011521 glass Substances 0.000 claims 1
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- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 2
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/3105—After-treatment
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Abstract
采用含化合物的氟化物和某些有机溶剂的混合物刻蚀硅酸盐玻璃。较佳考虑的刻蚀混合物也包含水。
Description
本发明涉及硅酸盐的选择性刻蚀,尤其涉及刻蚀速率大于二氧化硅刻蚀速率的硅酸盐选择性刻蚀。此外,本发明也涉及某些刻蚀混合物,它们适合用于刻蚀速率大于二氧化硅刻蚀速率的硅酸盐选择性刻蚀。
在微电子元件的制造中,其中很多步骤是刻蚀过程,如集成电路芯片的制备,以及固定和保护芯片的封装过程。因此,很多年来,发展了大量不同的清除材料(有时在某些选定的区域)的刻蚀过程,这些过程在不同程度上被利用着。而且,不同层(如构成最后集成电路芯片的不同层)的刻蚀步骤是最关键和决定性的步骤。
一种广泛采用的刻蚀方法是:用合适的掩模覆盖被刻蚀的表面,然后把表面及掩模浸入能溶解被刻蚀表面的化学溶液中,同时掩模完整无损,只最小限度地刻蚀物体的其他材料。
但当二氧化硅和硅酸盐玻璃同时出现在一个器件,并且暴露在用来刻蚀硅酸盐玻璃的混合物中,此时选择性的问题就很严重。因此在刻蚀同时含有硅酸盐玻璃和二氧化硅的材料时,要求更高级的清洁和刻蚀方法,这些方法具有特别高的选择性。
所以有必要提供一种具有选择性的刻蚀方法,这种方法不仅对硅酸盐有很高的选择性,而且能获得很好的清除效果。
本发明涉及选择性刻蚀硅酸盐玻璃的方法。本发明的工艺包含以下的过程,用刻蚀混合物接触含有硅酸盐玻璃和二氧化硅的制品,刻蚀混合物包含大约0.05到3克分子的含化合物的氟化物和有机溶剂,从而使得选择性刻蚀硅酸盐玻璃的速率大于二氧化硅的刻蚀速率。
此外,本发明涉及某些优选的刻蚀混合物,使得硅酸盐玻璃的选择性刻蚀速率大于二氧化硅的刻蚀速率。这些优选的混合物包含大约0.05到3克分子的含化合物的氟化物,有机溶剂和大约0.05到3克分子的水。
本发明采用的有机溶剂通常是具有相对高的燃点和低粘度的混合物。合适的溶剂包括环丁砜,氧杂环戊烷,酯,酮,醛,内酯,卤化的碳氢化合物,一羟基的醇,胺和酰亚胺。
以下将通过简单地阐明本发明的最佳模式来描述本发明的实施方式。这里的描述仅仅局限于几种常用的实施方式。从这些详细的描述中将会看到,对于熟练的技术人员,本发明的其他目的和优势是十分明显的。必须指出的是,本发明还有其他的和不同的实施方式,并且一些细节在很多明显的方面能够修正而不偏离本发明。因此,附图及其描述事实上只是示例性的说明,而不是限制性的。
本发明涉及硅酸盐玻璃的选择性刻蚀,特别是掺硼,砷,锑和(或者)磷的硅酸盐玻璃的选择性刻蚀。根据本发明,被刻蚀的掺杂硅酸盐玻璃,一般包含的掺杂物在重量上占大约0.5%到10%,最好是大约在3%到7%。而且,硅酸盐可以出现在同时包含二氧化硅的制品中,此时,硅酸盐和二氧化硅同时和刻蚀混合物接触。本发明提供硅酸盐玻璃的选择性刻蚀速率至少约为二氧化硅的刻蚀速率的100倍。二氧化硅的较佳选择是高密度的二氧化硅。高密度的二氧化硅是指热生长的二氧化硅,或者是化学汽相淀积(CVD)和物理汽相淀积(PVD)后再热退火的二氧化硅。
根据本发明,采用的刻蚀混合物包括含氟化物的化合物和有机溶剂。刻蚀混合物中含化合物的氟化物的容量大约为0.05到3克分子,较佳选择大约为0.2到2.5克分子,最佳选择大约为0.25到1.5克分子。
根据本发明,提供氟化物源的一般化合物是氢氟酸,氟化铵,氟硼酸盐,氟硼酸,二氟化锡,氟化锑,四丁铵四氟硼酸盐,以及六氟化铝。同时,可使用脂肪族的伯胺氟化物盐,仲胺氟化物盐或叔胺氟化物盐。这些化合物有如下的表达式:R1N(R3)R2。其中R1,R2,R3分别代表H或者烷基。一般地,R1,R2,R3基团中碳原子的总数等于或小于12。含化合物的氟化物较佳选择是氟化氢和氟化铵。
氟化氢一般用作49%重量比的水溶液。
合适的有机化合物的例子包括氧杂环戊烷(四氢呋喃),环丁砜,酯,酮,醛,内酯,卤化溶剂,胺,酰亚胺和一羟基的醇。合适的酯有碳酸酯,苯(甲)酸酯,酞酸(苯二酸)酯,异酞酸酯,对酞酸酯,特别是C1-C6烷基酯。优选的有机溶剂有碳酸丙烯,N-甲基吡咯烷酮,γ-丁内酯,二氯甲烷,苯甲醇,N-甲酰吗啉,N-甲酰哌啶,环己酮,环戊酮,苯甲酸甲酯,二甘醇二甲醚,2-甲基四氢呋喃,以及酞酸(苯二酸)、异酞酸和对酞酸的甲基酯和乙基酯。根据本发明,溶剂的较佳选择是碳酸丙烯,N-甲基吡咯烷酮和γ-丁内酯,最好为碳酸丙烯。
本发明中采用有机溶剂是为了提供低粘度的刻蚀混合物,从而最终使得刻蚀混合物更有效和刻蚀更均匀。这在使用多元醇(如丙三醇、乙二醇)时效果尤其显著。
根据本发明的各种理想选择,混合物还可以包含水。一般地,如果混合物含水,其容量大约为0.05到3.5克分子,较佳选择是大约0.2到2.9克分子,最好是大约0.1到1.7克分子。然而,应该说明的是,本发明的刻蚀混合物并不要求水。
本发明的刻蚀过程一般是在约为20℃到90℃的温度下进行,较佳的温度约为30℃到70℃。刻蚀温度的增加,会导致硅酸盐和二氧化硅的刻蚀速率增加。但对于硅酸盐玻璃和二氧化硅,由于温度增加而引起的刻蚀速率的增加是不同的,硅酸盐玻璃的刻蚀速率增加更多些,因而就增加了硅酸盐玻璃刻蚀的选择性。
下面以实例来进一步阐明本发明,但本发明并不局限于这些实例。
实例1:刻蚀混合物是在碳酸丙烯中混合重量百分比为49%的氢氟酸水溶液,两者体积比是28∶1,从而形成碳酸丙烯和1克分子的氢氟酸水溶液的刻蚀混合物。在硅晶片上热生长一层二氧化硅,二氧化硅层上是一层氮化硅,氮化硅层上是掺硼(重量上为6%)的硅酸盐玻璃。硅晶片和刻蚀混合物接触,被刻蚀的物质通过下面的层,如氮化硅层和二氧化硅层,其层壁暴露在刻蚀剂中。刻蚀在室温下进行。对于这种刻蚀液,掺硼硅酸盐玻璃的刻蚀速率是每分钟125纳米,而二氧化硅的刻蚀速率只有0.6纳米/分钟。因此,掺硼硅酸盐玻璃的刻蚀相对二氧化硅刻蚀的选择性超过200∶1。
实例2:例1中的氢氟酸溶液中水含量增加一倍,其他各项条件保持不变。这时掺硼硅酸盐玻璃的刻蚀速率是每分钟140纳米,而二氧化硅的刻蚀速率是每分钟1.2纳米。相应地,掺硼硅酸盐玻璃的刻蚀相对二氧化硅刻蚀的选择性大约是115∶1。
实例3:例1中的其他各项条件保持不变,刻蚀混合物中碳酸丙烯与重量比为49%的氢氟酸水溶液的体积比变成115∶1,刻蚀在60℃下进行。此时硅酸盐玻璃的刻蚀速率是每分钟615埃,二氧化硅的刻蚀速率是每分钟3.6埃。相应的刻蚀选择性大约是170∶1。
本文仅公开说明和描述了本发明的优选实施方式。但如前所述,本发明能应用在其他不同的组合和环境中,能在本文表达的发明概念范围内对它进行更改和修正。
Claims (31)
1.选择性刻蚀硅酸盐玻璃的方法,包括用刻蚀混合物接触含有所述硅酸盐玻璃和二氧化硅的制品,刻蚀混合物由大约0.05到3克分子的含化合物的氟化物和有机溶剂组成,所述溶剂选自环丁砜,氧杂环戊烷(四氢呋喃),酯,酮,醛,内酯,卤化的碳氢化合物,一羟基的醇,胺和酰亚胺,从而使得选择性刻蚀所述硅酸盐玻璃的速率大于所述二氧化硅的刻蚀速率
2.权利要求1的方法,其特征在于所述硅酸盐玻璃至少掺有硼,砷,锑和磷元素的一种。
3.权利要求1的方法,其特征在于所述硅酸盐玻璃是掺硼的玻璃。
4.权利要求1的方法,其特征在于所述有机溶剂选碳酸丙烯,N-甲基吡咯烷酮,γ-丁内酯,二氯甲烷,苯甲醇,N-甲酰吗啉,N-甲酰哌啶,环己酮,环戊酮,苯甲酸甲酯,二甘醇二甲醚,2-甲基四氢呋喃,以及酞酸(苯二酸)、异酞酸和对酞酸的甲基酯和乙基酯。
5.权利要求1的方法,其特征在于所述有机溶剂选自碳酸丙烯,N-甲基吡咯烷酮和γ-丁内酯。
6.权利要求1的方法,其特征在于所述溶剂是碳酸丙烯。
7.权利要求1的方法,其特征在于所述含化合物的氟化物选自氢氟酸,氟化铵,氟硼酸盐,四丁铵四氟硼酸盐,氟硼酸,六氟化铝,二氟化锡,氟化锑,以及脂肪族的伯胺氟化物盐,仲胺氟化物盐和叔胺氟化物盐
8.权利要求1的方法,其特征在于所述含化合物的氟化物是氢氟酸或氟化铵。
9.权利要求1的方法,其特征在于所述含化合物的氟化物是氢氟酸。
10.权利要求1的方法,其特征在于所述二氧化硅是高密度的二氧化硅。
11.权利要求10的方法,其特征在于所述二氧化硅选自热生长的二氧化硅,化学汽相淀积再热退火的二氧化硅和物理汽相淀积再热退火的二氧化硅。
12.权利要求10的方法,其特征在于所述二氧化硅是热生长的二氧化硅。
13.权利要求1的方法,其特征在于所述混合物还包含水。
14.权利要求13的方法,其特征在于所述水的容量大约为0.05到3.5克分子。
15.权利要求13的方法,其特征在于所述水的容量大约为0.2到2.9克分子。
16.权利要求13的方法,其特征在于所述水的容量大约为0.25到1.7克分子。
17.权利要求1的方法,其特征在于所述氟化物的容量大约为0.2到2.5克分子。
18.权利要求1的方法,其特征在于所述氟化物的容量大约为0.25到1.5克分子。
19.权利要求1的方法,其特征在于和所述混合物接触是在约20℃到90℃下进行的。
20.权利要求1的方法,其特征在于和所述混合物接触是在约30℃到70℃下进行的。
21.刻蚀混合物,适合用于刻蚀速率大于二氧化硅刻蚀速率的硅酸盐玻璃的刻蚀,包含大约0.05到3.0克分子的含化合物的氟化物,有机溶剂和大约0.05到3.5克分子的水,其中有机溶剂选自环丁砜,氧杂环戊烷(四氢呋喃),酯,酮,醛,内酯,卤化的碳氢化合物,一羟基的醇,胺和酰亚胺。
22.权利要求21的刻蚀混合物,其特征在于所述有机溶剂选自碳酸丙烯,N-甲基吡咯烷酮,γ-丁内酯,二氯甲烷,苯甲醇,N-甲酰吗啉,N-甲酰哌啶,环己酮,环戊酮,苯甲酸甲酯,二甘醇二甲醚,2-甲基四氢呋喃,以及酞酸(苯二酸)、异酞酸和对酞酸的甲基酯和乙基酯。
23.权利要求21的刻蚀混合物,其特征在于所述有机溶剂选自碳酸丙烯,N-甲基吡咯烷酮和γ-丁内酯。
24.权利要求21的刻蚀混合物,其特征在于所述溶剂是碳酸丙烯。
25.权利要求21的刻蚀混合物,其特征在于所述含化合物的氟化物选自氢氟酸,氟化铵,氟硼酸盐,四丁铵四氟硼酸盐,氟硼酸,六氟化铝,二氟化锡,氟化锑,以及脂肪族的伯胺氟化物盐,仲胺氟化物盐和叔胺氟化物盐。
26.权利要求21的刻蚀混合物,其特征在于所述含化合物的氟化物是氢氟酸或者氟化铵。
27.权利要求21的刻蚀混合物,其特征在于所述含化合物的氟化物是氢氟酸。
28.权利要求21的刻蚀混合物,其特征在于所述水的容量大约为0.2到2.9克分子。
29.权利要求21的刻蚀混合物,其特征在于所述氟化物的容量大约为0.2到2.5克分子。
30.权利要求21的刻蚀混合物,其特征在于所述水的容量大约在0.25到1.7克分子。
31.权利要求21的刻蚀混合物,其特征在于所述氟化物的容量大约在0.25到1.5克分子。
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- 1998-05-14 KR KR1019980017437A patent/KR19990006448A/ko active Search and Examination
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CN102225874B (zh) * | 2006-08-21 | 2013-01-30 | 第一毛织株式会社 | 湿蚀刻溶液 |
CN113767075A (zh) * | 2019-03-05 | 2021-12-07 | 株式会社Nsc | 玻璃用蚀刻液及玻璃基板制造方法 |
CN113767075B (zh) * | 2019-03-05 | 2023-11-03 | 株式会社Nsc | 玻璃用蚀刻液及玻璃基板制造方法 |
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US6254796B1 (en) | 2001-07-03 |
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