CN116250063A - 用于移除硬掩模的方法 - Google Patents
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Abstract
本发明提供适用于蚀刻,即移除,已掺杂有例如硼、氯或氮的元素的非晶碳硬掩模的组合物及方法。所述组合物利用浓硫酸、水及至少一种氧化剂。在所述方法的操作中,即使在存在例如二氧化硅、氮化硅、氮化钽及多晶硅的层的情况下,所述组合物也以良好选择性来选择性地移除经掺杂硬掩模层。
Description
技术领域
本发明大体上涉及微电子装置制造的领域,且涉及用于蚀刻-即移除-掺硼非晶碳硬掩模的方法。
背景技术
处理半导体及微电子装置涉及沉积材料层并通过被称作“蚀刻”的化学工艺移除材料的各种步骤。通过蚀刻,将薄掩模层放置在经沉积材料层上方。接着在掩模中形成开口,且暴露衬底的选择部分。接着使经遮蔽衬底与蚀刻剂接触,所述蚀刻剂通过掩模中的开口接触底层衬底的材料且以化学方式降解及移除衬底的材料以在衬底中形成开口(三维空间)。
许多较新类型的衬底,例如用以制备三维存储器装置的衬底,经处理以形成具有高纵横比的开口,例如延伸到衬底中的深度显著地大于开口的宽度尺寸(例如直径)的开口。作为一个实例,3D NAND存储器装置的竖直延伸“通道孔”是通过在深度方向上将竖直延伸开口蚀刻到经沉积膜的许多层的堆叠中而形成。通道孔的深度可比通道孔的直径大二十倍、四十倍或五十倍,或更多。通过蚀刻而在微电子装置中形成此类型的高纵横比特征会需要高度专业化、准确且精确的蚀刻工艺。
对于此类型的蚀刻步骤,将抗化学腐蚀“硬掩模”放置在经沉积膜的多个层中的顶部层上方。有时被称作“膜堆叠”的膜层为存储器装置的功能材料,且可为经沉积氧化硅、氮化硅、多晶硅或类似物的层。硬掩模抵抗用以以化学方式降解及移除膜堆叠的材料以在衬底中形成高纵横比开口(例如通道孔)的蚀刻溶液。
一种常见类型的硬掩模为非晶碳硬掩模。此类型的硬掩模作为连续层被沉积到微电子装置衬底上,且接着经蚀刻以在硬掩模中形成开口。蚀刻底层衬底的后续步骤接着是通过将具有硬掩模的衬底暴露于能够以化学方式降解膜堆叠的材料的气态化学蚀刻剂来执行。气态蚀刻剂穿过硬掩模中的开口以接触并蚀刻掉-即移除-衬底的材料以在衬底中产生开口。在已视需要而蚀刻掉衬底材料之后,必须从衬底移除硬掩模以允许将衬底进一步处理为成品微电子装置。
产生展现高纵横比的精确形成且良好界定的衬底开口可极具挑战性。蚀刻工艺的常常被研究以用于改进整个工艺的一个组成部分为硬掩模,包含硬掩模的组合物以及应用及移除硬掩模的方法。
硬掩模可由厚非晶碳膜或能够耐受等离子体蚀刻工艺的多种类似材料组成。对于3DNAND结构,非晶碳为不完美的硬掩模材料,这是因为非晶碳在暴露于反应性等离子体达处理此类结构所需的时间长度时易遭受蚀刻。一种增加此类非晶碳膜的耐用性的方法包含使碳层掺杂有例如硼、氯及氮的抗蚀刻元素。在硼掺杂的情形中,使掩模硬化,由此形成碳化硼并使掩模类似于陶瓷形态且因此抵抗化学蚀刻剂。接着最终使用利用O2等离子体或O2等离子体结合H2等离子体的(干式)反应性离子蚀刻技术来移除此类掩模。(参见例如美国专利第9,229,581号)。
然而,需要用于移除已掺杂有例如硼的抗蚀刻元素的硬掩模的经改进方法。
发明内容
总体来说,本发明提供适用于蚀刻,即移除,已掺杂有例如硼、氯或氮的元素的非晶碳硬掩模的组合物及方法。所述组合物利用浓硫酸、水及至少一种氧化剂。在一个实施例中,所述氧化剂是选自例如碘酸盐及过碘酸的含碘氧化剂。所述组合物可进一步包括除硫酸之外的额外酸。在本发明的方法中,可将所述组合物施加到掩模,所述掩模合意地在高温下移除。在所述方法的操作中,即使在存在例如二氧化硅、氮化硅、氮化钽及多晶硅的层的情况下,所述组合物也以良好选择性来选择性地移除经掺杂硬掩模层。
因此,本发明的方法的性能非常适于包含具有96个层及更多层的3D-NAND结构的应用。
具体实施方式
1.在第一方面中,本发明提供一种用于从微电子装置移除非晶碳硬掩模的方法,其中所述硬掩模已掺杂有选自硼、氯及氮的元素以形成经掺杂硬掩模,所述方法包括使所述微电子装置与包括以下各者的组合物接触:
a.按所述组合物的总重量计,约50重量百分比到约98重量百分比的H2SO4;
b.水;及
c.按所述组合物的总重量计,约0.1重量百分比到约30重量百分比的至少一种氧化剂。
在一个实施例中,所述元素为硼。
在某些实施例中,所述氧化剂是选自例如碘酸盐及过碘酸、硝酸、过氯酸及过锰酸盐以及过硫酸盐的氧化剂。在一个实施例中,所述氧化剂的存在量为约1重量百分比到约15重量百分比或约5重量百分比到10重量百分比。在另一实施例中,所述氧化剂为过碘酸,且所述氧化剂的存在量为约5%到约8%。在另一实施例中,所述氧化剂为过碘酸,且所述氧化剂的存在量为约5%到约6%。
在一个实施例中,所述含碘氧化剂是选自H5IO6、HIO4或其混合物。
在一个实施例中,所述组合物包括约65重量百分比到约85重量百分比的H2SO4。
在某些实施例中,所述组合物进一步包括除H2SO4之外的酸。在某些实施例中,除H2SO4之外的酸是选自甲磺酸、三氟甲磺酸、硼酸及磷酸。
在某些实施例中,所述组合物进一步包括至少一种表面活性剂。如本文中所使用,术语“表面活性剂”是指降低两种液体之间或液体与固体之间的表面张力(或界面张力)的有机化合物,典型地为含有疏水基(例如烃(例如烷基)“尾端”)及亲水基的有机两亲化合物。有利地,表面活性剂是热稳定的且在例如本发明的蚀刻工艺的条件的强酸性条件下保持离子性。实例包含全氟烷基磺酸及长链季铵化合物(例如十二烷基三甲基硫酸氢铵)。还可使用经氟化的非离子性表面活性剂,例如Chemours′FS-31/FS-35。还可使用非离子性的未经氟化的表面活性剂,例如聚(乙二醇)-聚(丙二醇)共聚物(“PEG-PPG”)。
蚀刻组合物中的表面活性剂的量可为结合蚀刻组合物的其它材料而将提供所需总体性能的量。举例来说,组合物可含有一定量的表面活性剂,按组合物的总重量计,所述量可在约0.001重量百分比到约10重量百分比的范围内,例如约0.01重量百分比到约0.5重量百分比、1重量百分比、2重量百分比、7重量百分比或7重量百分比的表面活性剂。
本发明的组合物因此可用以通过将此类组合物施加到微电子装置的表面来蚀刻或移除此类掺硼、氯或氮非晶硬掩模。取决于待移除膜的厚度,硫酸浓度及操作温度可变化且优化。在一个实施例中,施加组合物是在约100℃到170℃的环境中进行。在一个实施例中,施加组合物是在约140℃到170℃的环境中进行。
本发明的组合物可容易地调配为在使用时或在使用之前混合的单包装调配物或多部分调配物,例如,多部分调配物的个别部分可在工具处、在工具上游的存储槽中或在将经混合调配物直接递送到工具的装运包装中混合。举例来说,单一装运包装可包含可由用户在制造厂混合在一起的至少两个单独容器或囊袋,且经混合调配物可经直接递送到工具。至少两个容器或囊袋中的一者可包含可为固体的氧化剂,而至少两个容器中的另一者可包含硫酸溶液。在一个实施例中,至少两个容器或囊袋中的一者包含氧化剂,而至少两个容器或囊袋中的第二者包含硫酸。在另一实施例中,至少两个容器或囊袋中的一者包含氧化剂,而至少两个容器或囊袋中的第二者包含硫酸与除硫酸之外的另一酸的混合物。在每一情形中,如果将添加水,那么水可在离开制造商之前添加到一个及/或两个容器,可在使用之前在制造厂添加,或这两者的组合,如所属领域的技术人员容易确定。装运包装及所述包装的内部容器或囊袋必须适合于存储及装运所述组合物组分,例如由先进技术材料(Advanced Technology Materials)公司(美国康涅狄格州丹柏立(Danbury))提供的包装。
替代地,所述组合物的浓缩物可在一个容器中调配及包装以用于装运且用于在使用之前及/或期间与现场硫酸及任选地除硫酸之外的酸混合,其中本文中描述所述使用方法。举例来说,所述浓缩物可包括至少一种氧化剂、水,且其中按浓缩物的总重量计,所述氧化剂的浓度可在约0.1wt%到约30wt%或约1wt%到约15wt%的范围内。当存在时,所述浓缩物中的硫酸的量按浓缩物的总重量计可在约50wt%到约96wt%的范围内。在优选实施例中,用于与现场酸组合的浓缩物包括以下各者、由以下各者组成或基本上由以下各者组成:至少氧化剂、水及任选地除硫酸之外的至少一种酸。在另一实施例中,用于与现场酸组合的浓缩物包括以下各者、由以下各者组成或基本上由以下各者组成:至少一种含碘氧化剂、水及除硫酸之外的至少一种酸。所属领域的技术人员在知晓低pH组合物中需要多少氧化剂且浓缩物中存在多少酸的情况下会容易确定浓缩物对现场酸的比率。
另一方面涉及一种试剂盒,所述试剂盒在一或多个容器中包含适用于形成如本文中所描述的任一方面的组合物的一或多种组分。试剂盒的容器必须适合于存储及装运所述组合物,例如容器(先进技术材料公司,美国康涅狄格州丹柏立)。容纳本文中所描述的组合物的组分的一或多个容器优选地包含用于使所述一或多个容器中的组分处于流体连通以用于掺合及施配的构件。举例来说,参看/>容器,可向所述一或多个容器中的衬垫的外部施加气体压力,以使所述衬垫的内容物的至少一部分排放且因此使能够进行流体连通以用于掺合及施配。替代地,可向常规可加压容器的顶部空间施加气体压力,或可使用泵以使能够进行流体连通。另外,系统优选地包含施配端口以用于将经掺合移除组合物施配到处理工具。
大致上化学惰性、无杂质、柔性及弹性聚合膜材料,例如PTFE或PTFA,优选地用以制造用于所述一或多个容器的衬垫。处理合意的衬垫材料,而无需共挤出或阻障层,且无需可不利地影响对于待安置于衬垫中的组分的纯度要求的任何颜料、UV抑制剂或处理剂。合意的衬垫材料的列表包含包括原始聚四氟乙烯(PTFE)、PFA、等等的膜。在某些实施例中,此类衬垫材料的厚度在约5密耳(0.005英寸)到约30密耳(0.030英寸)的范围内,例如20密耳(0.020英寸)的厚度。
关于试剂盒的容器,以下专利及专利申请案的公开内容的相应全文特此以引用的方式并入本文中:名为“用于最小化超纯液体中的粒子产生的设备及方法(APPARATUS ANDMETHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS)”的美国专利第7,188,644号;名为“可回收且可重复使用的桶中袋式流体存储及施配容器系统(RETURNABLE AND REUSABLE,BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINERSYSTEM)”的美国专利第6,698,619号;2008年5月9日以约翰E.Q.休斯(John E.Q.Hughes)的名义申请的名为“用于材料掺合及分配的系统及方法(SYSTEMS AND METHODS FORMATERIAL BLENDING AND DISTRIBUTION)”的国际申请案第PCT/US08/63276号;及2008年12月8日以约翰E.Q.休斯(John E.Q.Hughes)等人的名义申请的名为“用于递送含流体工艺材料组合的系统及方法(SYSTEMS AND METHODS FOR DELIVERY OF FLUID-CONTAININGPROCESS MATERIAL COMBINATIONS)”的国际申请案第PCT/US08/85826号。
因此,在另一方面中,本发明提供一种试剂盒,所述试剂盒在一或多个容器中包括上文所叙述的一或多种组分a.、b.及c.,其经调适以形成本发明的组合物,如本文中所描述。
本发明可进一步通过其优选实施例的以下实例进行说明,但应理解,除非另有特定指示,否则仅出于说明的目的而包含这些实例且这些实例不旨在限制本发明的范围。
实例
调配物实例1到3:
*DIW=去离子水
*MSA=甲磺酸
*BHM=硼硬掩模
以下实例1描述用于制备及测试调配物实例1到3的通用方法。
实例A-蚀刻组合物的制备
将H5IO6的50重量%样本与水及甲磺酸组合。向此混合物中缓慢添加96%H2SO4,其中用于冷却的冰水浴作为控制放热反应的方式。烧杯测试的总溶液重量在250ml的三颈玻璃瓶中为300g。用加热包加热所得溶液,同时将温度控制为155℃。始终将搅拌维持在360rpm。
实例B-试件测试:
将晶片切割成1.5×3cm2大小,且通过TeflonTM带将试件紧固在TeflonTM(聚四氟乙烯)样本固持器上。毯覆式晶片的处理时间为30min到60min,且图案晶片(50%过度蚀刻)为120min。在蚀刻工艺之后,用去离子水洗涤试件达1分钟且用氮气将其吹干。通过椭圆计来测量膜损失,且通过扫描电子显微术(SEM)来检查图案晶片。
下表比较实例3的调配物的掺硼非晶形膜的蚀刻速率与其它表面组合物的蚀刻速率:
在155℃下进行测试达30分钟,同时用磁性搅拌棒以360rpm进行搅拌。使用椭圆计来测量膜损失。
BPSG=硼磷硅玻璃
经掺杂多晶硅=掺硼多晶硅
在如此描述了本公开的若干说明性实施例的情况下,所属领域的技术人员将容易了解,可在此处随附的权利要求书的范围内制作及使用另外其它实施例。此文件所涵盖的本公开的诸多优点已在前文描述中进行阐述。然而,应理解,本公开在许多方面中仅是说明性的。在不超出本公开的范围的情况下,可进行细节改变,尤其是在部分的形状、大小及布置方面。当然,本公开的范围是以表达随附权利要求书的语言进行界定。
Claims (17)
1.一种用于从微电子装置移除非晶碳硬掩模的方法,其中所述硬掩模已掺杂有选自硼、氯及氮的元素以形成经掺杂硬掩模,所述方法包括使所述微电子装置与包括以下各者的组合物接触:
a.按所述组合物的总重量计,约50重量百分比到约98重量百分比的H2SO4;
b.水;及
c.按所述组合物的总重量计,约0.1重量百分比到约30重量百分比的至少一种氧化剂。
根据权利要求1所述的方法,其中所述元素为氯或氮。
2.根据权利要求1所述的方法,其中所述元素为硼。
3.根据权利要求1所述的方法,其中氧化剂为含碘氧化剂。
4.根据权利要求1所述的方法,其中含碘氧化剂是选自H5IO6、HIO4或其混合物。
5.根据权利要求1所述的方法,其中所述氧化剂在约1重量百分比到约15重量百分比的范围内使用。
6.根据权利要求1所述的方法,其中所述氧化剂在约5重量百分比到约10重量百分比的范围内使用。
7.根据权利要求1所述的方法,其中所述氧化剂是选自过硫酸盐、硝酸、过氯酸及过锰酸盐。
8.根据权利要求1所述的方法,其中所述组合物包括约65重量百分比到约85重量百分比的H2SO4。
9.根据权利要求1所述的方法,其进一步包括除H2SO4之外的酸。
10.根据权利要求1所述的方法,其进一步包括除含碘氧化剂之外的氧化剂。
11.根据权利要求10所述的方法,其中酸选自甲磺酸、三氟甲磺酸、硼酸及磷酸。
12.根据权利要求10所述的方法,其中所述氧化剂为H5IO6。
13.根据权利要求1所述的方法,其进一步包括至少一种表面活性剂。
14.根据权利要求1所述的方法,其中所述微电子装置为3D-NAND存储装置。
15.根据权利要求1所述的方法,其中所述装置及所述组合物经加热到约100℃到170℃的温度。
16.根据权利要求1所述的方法,其中所述装置及所述组合物经加热到约140℃到170℃的温度。
17.一种试剂盒,其在一或多个容器中包括一或多种组分
a.H2SO4;
b.水;及
c.至少一种氧化剂。
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