CN109642159B - 非水性钨相容性金属氮化物选择性蚀刻剂和清洁剂 - Google Patents
非水性钨相容性金属氮化物选择性蚀刻剂和清洁剂 Download PDFInfo
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- CN109642159B CN109642159B CN201780019489.9A CN201780019489A CN109642159B CN 109642159 B CN109642159 B CN 109642159B CN 201780019489 A CN201780019489 A CN 201780019489A CN 109642159 B CN109642159 B CN 109642159B
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- metal nitride
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Abstract
因此,本文提供了一种新型酸性氟化物活化的清洁化学品。本发明包括新型酸性氟化物活化的、独特的基于有机溶剂的微电子选择性蚀刻剂/清洁剂组合物,其具有高金属氮化物蚀刻和广泛、优异的相容性(包括与钨(W)和低k材料)。其不使用W不相容性氧化剂如过氧化氢或产生颗粒的腐蚀抑制剂。
Description
相关申请的交叉引用
本申请要求于2016年3月24日提交的美国临时申请序列号62/312,689的优先权,所述临时申请通过引用并如本文。
背景技术
本发明涉及用于在金属导体和绝缘体材料(即低k电介质)存在下选择性地清洁和蚀刻微电子基材(包括金属氮化物和/或光刻胶蚀刻残留物)的组合物和方法。
微电子和纳米电子器件生产的最新进展导致需要新的剥离和清洁组合物,其具有前段制程(FEOL)和后段制程(BEOL)二者的剥离或清洁能力。迄今为止通常使用的清洁组合物已被发现不适用于微电子或纳米电子平台生产中所使用的新材料。先前使用的剥离或清洁组合物过于具有侵蚀性和/或不够具有选择性。用于生产这些新型微电子或纳米电子器件的新用材料为诸如以下材料:低-k(<3)和高-k(>20)和多孔电介质、铜敷金属、含氟聚合物抗反射涂层(ARC)、特殊硬质掩模(如由Ti和TiN构成的那些)、Si/Ge或Ge的应变晶片、以及金属盖层(如CoWP和CoWB的那些)。这些新材料给设备制造商带来了新的困难挑战。
例如,光刻胶掩模通常用于半导体工业中以图案化诸如半导体或电介质的材料。在一种应用中,光刻胶掩模用于双镶嵌工艺中以在微电子器件的后端金属化中形成互连。双镶嵌工艺涉及在覆盖金属导体层(如铜层)的低k介电层上形成光刻胶掩模。然后根据该光刻胶掩模蚀刻低k介电层,以形成暴露金属导体层的通孔和/或沟槽。通常称为双镶嵌结构的通孔和沟槽通常使用两个光刻步骤来定义。然后在将导电材料沉积到通孔和/或沟槽中以形成互连之前,从低k介电层去除该光刻胶掩模。
随着微电子器件尺寸的减小,实现通孔和沟槽的临界尺寸变得更加困难。因此,将金属硬掩模用于提供对通孔和沟槽的更好的轮廓控制。金属硬掩模可以由钛或氮化钛制成,并且在形成双镶嵌结构的通孔和/或沟槽之后通过湿蚀刻工艺去除。重要的是,湿蚀刻工艺使用去除化学品,所述去除化学品有效地去除金属硬掩模和/或光刻胶蚀刻残留物而不影响下面的金属导体层和低k电介质材料。换言之,要求去除化学品对金属导体层和低k介电层具有高选择性。
尽管它们很受欢迎,但特别是当使用基于酸性氟化物的化学品作为选择性金属氮化物蚀刻时存在许多困难。这样的清洁剂和蚀刻剂具有广泛的基材和金属(包括W和低k介电材料)相容性是特别重要的;特别是对使用金属氮化物如氮化钛(TiN)、氮化钽(TaN)和氮化钨(WN)而言。
目前的金属氮化物蚀刻化学品包括例如基于碱性过氧化氢的化学品(例如5:1:1的H2O-30%NH4OH-30%H2O2)。然而,这样的组合物是W不相容的。基于氢氟酸的化学品如10:1或100:1稀释的HF水溶液。然而,它们具有非常低的TiN蚀刻速率和与普通基材如氧化硅(例如TEOS)的不良基材相容性。
大多数金属氮化物蚀刻技术是水基配方。通常使用腐蚀抑制剂。它们均具有以下一个或多个缺点:低金属氮化物蚀刻速率、由组合物产生颗粒(可能涉及腐蚀抑制添加剂)以及与基材或敷金属(metallization)(包括W)的不良或有限相容性。
因此,本发明的一个目的是提供用于清洁和蚀刻微电子基材的改进的组合物和方法。希望提供具有高金属氮化物蚀刻和广泛、优异的相容性(包括与(W)和低k电介质材料)的组合物。我们的发明描述了用于先进技术节点中的微电子器件制造的酸性金属氮化物选择蚀刻剂/清洁剂
发明内容
本发明涉及用于相对于存在的金属导体层和低k介电层选择性地蚀刻硬掩模层和/或光刻胶蚀刻残留物的组合物和方法。更具体地,本发明涉及用于相对于铜、钨和低k介电层选择性地蚀刻氮化钛和/或光刻胶蚀刻残留物的组合物和方法。
本发明包括用于微电子应用的非水性清洁组合物,其包含约0.01%至约5.0%重量的氟化物活化剂、约0.01%至约20%重量的至少一种氧化剂、约80.00%至约99.90%重量的无水有机溶剂,其中所述清洁组合物的pH等于或小于5.5,并且其中所述氧化剂不是过氧化氢。
在一个实施方式中,非水性清洁组合物还具有蚀刻能力。非水性清洁还与钨和低κ介电基材相容。
在一个实施方式中,非水性清洁组合物包含约0.05%至约1.00%重量的氟化物活化剂、约0.01%至约5.00%重量的至少一种氧化剂、和约85.00%至约99.90%重量的无水有机溶剂。在另一个实施方式中,非水性清洁组合物包含约0.10%至约0.50%重量的氟化物活化剂、约0.01%至约2.00%重量的至少一种氧化剂、和约90.00%至约99.00%重量的无水有机溶剂。
在另一个实施方式中,本发明的非水性清洁组合物还包含共溶剂。在另一个实施方式中,非水性清洁组合物包含一种或多种选自以下的成分:pH调节剂、胺、酸、腐蚀控制剂和表面活性剂。
在又一个实施方式中,所述清洁组合物的氟化物活化剂选自氟化氢、氟化铵、氟化钾、碱金属氟化物、四烷基氟化铵、氟硼酸、四氟硼酸铵、碱金属四氟硼酸盐、四氟硼酸四烷基铵和四氟硼酸三甲基氧鎓。在另一个实施方式中,所述至少一种氧化剂选自硝酸、硫酸、磺酸、高碘酸、过硫酸铵、过氧单硫酸、过硼酸盐、过碳酸盐、过硫酸盐、臭氧和臭氧化物。
在一个实施方式中,所述清洁组合物的无水有机溶剂选自砜类、硫化物类、碳酸酯类、醇类、二醇类和酰胺类。在一个优选的实施方式中,所述无水有机溶剂是环丁砜。
本文还提供了清洁微电子基材的方法。所述方法包括使微电子基材与清洁组合物接触,所述清洁组合物包含约0.01%至约5.0%重量的氟化物活化剂、约0.01%至约20%重量的至少一种氧化剂、约80.00%至约99.90%重量的无水有机溶剂,其中所述清洁组合物的pH等于或小于5.5,并且其中所述氧化剂不是过氧化氢。
为了更好地理解本发明,连同其他和进一步的目的和优点,结合所附实施例而参照以下详细描述,并且本发明的范围将在随附的权利要求书中指出。以下详细描述并非旨在通过上述优点来限制本发明的范围。
附图说明
图1显示了氮化程度对蚀刻速率的影响。
具体实施方式
本发明描述了新的酸性氟化物活化的、独特的基于有机溶剂的微电子选择性蚀刻剂/清洁剂组合物,其具有高金属氮化物蚀刻和广泛、优异的相容性(包括与钨(W)和低k材料)。其不使用W不相容性氧化剂例如过氧化氢或产生颗粒的腐蚀抑制剂。
前述化学品可以配制成高度非水性至半水性的溶液或浆料。它们可用于选择性地去除金属氮化物。它们还可提供对于以下的有效性和/或适用性:剥离ARC和光刻胶;清洁来自等离子体工艺产生的有机、有机金属和无机化合物的残留物;清洁来自平面化工艺(如化学机械抛光)的残留物;以及在平面化浆料/液体中用作添加剂。
一般而言,本发明还涉及用于相对于存在的金属导体层和低k介电层选择性地蚀刻硬掩模层和/或光刻胶蚀刻残留物的半水性组合物和方法。更具体地,本发明涉及用于相对于铜、钨和低k介电层选择性地蚀刻氮化钛和/或光刻胶蚀刻残留物的半水性组合物和方法。可存在于微电子器件上的其他材料不应被所述组合物所实质性除去或腐蚀。
如本文所用,术语“微电子器件”是指半导体基材、平板显示器、相变存储器件、太阳能板和其他产品,包括经制造用于微电子、集成电路、能量收集或计算机芯片应用中的太阳能电池器件、光伏器件和微机电系统(MEMS)。应理解,术语“微电子器件”、“微电子基材”和“微电子器件结构”并不意味着以任何方式进行限制,并且包括最终将成为微电子器件或微电子组件的任何基材或结构。微电子器件可以为图案化、覆盖的控制和/或测试装置。
如本文所用,术语“氮化钛”和“TiNx”是指纯氮化钛以及不纯的氮化钛,包括不同的化学计量和氧含量(TiOxNy)。
如本文所用,术语“约”是指所述值的±5%。
如本文所用,术语“低k电介质材料”是指用作分层微电子器件中的电介质材料的任何材料,其中所述材料具有小于约3.5的介电常数。
优选地,低k电介质材料包括低极性材料如含硅有机聚合物、含硅杂化有机/无机材料、有机硅酸盐玻璃(OSG)、TEOS、氟化硅酸盐玻璃(FSG)、二氧化硅和碳掺杂氧化物(CDO)玻璃。应理解,低k电介质材料可具有不同的密度和不同的孔隙率。
如本文所用,术语“非水性”是指主要为有机组合物,组合物中仅含有微量水,使得水不会导致微电子基材的损坏。在一个实施方式中,组合物可具有5%重量或更少的水。在一个优选的实施方式中,该组合物将具有3%重量或更少的水。
已发现本发明的组合物和方法具有以下有益效果:
对金属氮化物蚀刻速率和其他相容性的预料不到的显著溶剂效应:
a)有机溶剂效应:将所有其他组分保持在相同的含量,唯一的变量是有机溶剂含量:除了使用环丁砜作为有机溶剂的实施例20之外(其在>50-100X水平下表现出预料不到的高TiN蚀刻速率(65℃下85℃下)),所有配方显示出低TiN蚀刻速率(65℃时85℃时)这种显著的溶剂效应通常是不能预期的。完全水性组合物(例如实施例104)也具有高度升高的Al蚀刻速率[参见表1A和1B]。
b)水含量对蚀刻速率的高影响:与许多常见的水基蚀刻剂相比,我们的发明使用几乎无水至高度非水性的基质。水含量对蚀刻速率和相容性显示出异常高的影响(表2A和2B)。当添加额外的2%或更多的水时,已发现W蚀刻速率的不利增加。
同时异常高的金属氮化物蚀刻速率和广泛基材相容性:
a)氮化对TiN蚀刻速率的影响:钛的氮化(%氮)增加Ti硬度并使TiN抵抗蚀刻。当氮化水平增加,TiN蚀刻变得更加困难。表3A和图1证明了这样的影响。可以通过100:1DHF蚀刻具有较低氮化含量的商业TiN样品(例如来自Advantiv的PVD TiN#1)。然而,具有较高氮化水平的常见TiN样品(其通常用于诸如20nm或更低节点的先进技术中)根本不能被100:1DHF所蚀刻。这凸显了开发新型金属氮化物蚀刻化学品的需求。
b)高金属氮化物蚀刻速率:对于酸性氟化物活化的蚀刻化学品,存在很大的问题和挑战---使用常规/标准蚀刻剂(如DHF溶液)时的低金属氮化物蚀刻速率,参见以上2a部分中的讨论。我们的化学品提供了优异的蚀刻速率,易于高过选择的配方超过(表4)。
c)相比普通清洁剂/蚀刻剂的优异的区分选择性:SC-1化学品如5:1:1H2O-29%NH4OH-30%H2O2能够提供良好的TiN蚀刻速率,但与W不相容。HF基化学品如10:1DHF具有低TiN蚀刻速率和不可接受的高氧化硅(TEOS)蚀刻速率(表4)。我们选择的蚀刻化学品不仅提供高金属氮化物蚀刻速率,而且还提供与W、TEOS和其他基材的优异相容性。
d)TiN硬掩模(HM)和W-塞/填的TiN衬里之间独特的蚀刻选择性:将来自我们化学平台的选定组合物与电化学设计进一步相结合以提供优异的电控制,使W金属旁没有或具有最小的TiN蚀刻,例如用于W塞的TiN衬里。实例是IB、4A和6(参见表5)。
e)我们选择的蚀刻化学平台的其他实例-参见表6、7和8。
注意:一些组合物包含优异的Al相容性(例如实施例1)。
在我们的发明中,我们指定选择使用特殊的溶剂基质、氧化剂和选定的氟化物的金属氮化物蚀刻清洁剂/蚀刻剂,以提供令人惊奇的高效金属氮化物蚀刻、与敷金属和基材(包括W、TEOS、低k材料等)的广泛和优异的相容性。
本发明描述了酸性、基于有机溶剂的微电子选择性蚀刻剂/清洁剂组合物,其具有高金属氮化物蚀刻和广泛、优异的相容性(包括与钨(W)和低k材料)。它们包含:
(A)作为主要氟化物活化剂的氟化物化合物,其量为0.01-5%重量。优选0.05-1%重量,更优选0.1-0.5%重量。它们包括氟化氢、氟化铵、氟化钾、碱金属氟化物、四烷基氟化铵、氟硼酸、四氟硼酸铵、碱金属四氟硼酸盐、四氟硼酸四烷基铵、四氟硼酸三甲基氧鎓等。
(B)一种或多种氧化剂,不包括过氧化氢。氧化剂包括硝酸、硫酸、磺酸、高碘酸、过硫酸铵、过氧单硫酸、过硼酸盐、过碳酸盐、过硫酸盐、臭氧和臭氧化物;其量为0.01-20%重量;优选0.01-5%重量;且更优选0.01-2%重量。
(C)低水或无水有机溶剂。可以使用一种或多种有机溶剂。用量为80-99.9%重量。优选85-99.9%重量,更优选90-99%重量。有机溶剂选自砜类、硫化物类、碳酸酯类、醇类、二醇类和酰胺类。最优选砜类,例如环丁砜和二甲基砜。砜类可以用作唯一的有机溶剂,或作为主要溶剂与其他共溶剂组合使用。其他合适的溶剂或共溶剂包括碳酸亚丙酯、卡必醇、乙二醇、二甲基亚砜、N-甲基吡咯烷酮(NMP)等。
醇、醇-醚和醚可用作任选的共溶剂。优选地,它们用作次要共溶剂。含量为0至49%重量。优选0-25%重量,更优选0-20%重量。实例:乙二醇、丙二醇、甘油、二甘醇(DEG)、卡必醇、聚乙二醇(PEG)、丁基二甘醇、四甘醇、乙二醇丁醚(EGBE;蒸发率0.07)、二乙二醇单乙醚(DEGME;蒸发率0.02)、卡必醇、丁基二甘醇、四甘醇、二丙二醇甲基醚(DPGME)。
(D)低水组合物。本发明组合物的含水量控制在10%或更少的量。优选地,其量为5%或更少。最优选地,其量为3%或更少。
(E)pH(10%稀释水溶液的pH或表观pH)应等于或小于5.5,更优选等于或小于5.0,最优选等于或小于4。
(F)我们的发明不需要额外的腐蚀抑制剂。这消除了添加的腐蚀抑制剂所产生的颗粒。
(G)任选的:pH调节剂、胺(例如单乙醇胺)、酸(例如盐酸、乙酸)、腐蚀控制剂(例如苯并三唑、四唑、柠檬酸、儿茶酚)和表面活性剂(两性、阳离子和阴离子和非离子表面活性剂)如Surfynol-61、Surfynol-465和Du Pont Zonyl FSH。任何上述添加剂必须与我们的基本组合物相容,并且没有(不希望的)颗粒生成。
表1A-显示出对蚀刻速率和相容性的溶剂效应的组合物
实施例编号 | 溶剂/wt% | 70%HNO3,wt% | 49%HF,wt% | H2SO4,wt% |
100 | DMSO 96.2 | 1 | 0.8 | 2 |
101 | CAR 96.2 | 1 | 0.8 | 2 |
102 | EGBE 96.2 | 1 | 0.8 | 2 |
103 | NMP 96.2 | 1 | 0.8 | 2 |
104 | H2O 96.2 | 1 | 0.8 | 2 |
20 | SFL 96.2 | 1 | 0.8 | 2 |
表2A.证明水对蚀刻速率影响的组合物。
表2B.水对蚀刻速率的影响。显示了对W蚀刻速率的高度影响。
晶片描述 | 2D | 2D-A | 2D-B | 2D-C | 2D-D |
PVD TiN | 32 | 29 | 27 | 32 | 27 |
SiCN | 1.4 | 1.4 | 0. | 0.8 | 0.8 |
W | 4 | 3.8 | 5 | 8.4 | 10.2 |
WN | 9 | 8 | 5 | 9 | 5 |
TEOS | 4.8 | 5.2 | 4.8 | 5 | 3.8 |
热氧化物 | 1.6 | 1.4 | 1.2 | 1.8 | 1.2 |
表3A.氮化对TiN蚀刻速率的影响。
XM-7=实施例20。
PVD TiN#1样品-来自Advantiv,在此比较中用作“标准”。
%N=24.3重量%;52.3原子%
表4.选择金属氮化物蚀刻---蚀刻速率比较
·SC-1:有效TiN、WN蚀刻;低TaN蚀刻;W不相容
·10:1DHF:低TiN蚀刻;W-相容;TEOS不相容
·实施例3、2A、2B、2D和2E蚀刻:高TiN、TaN或WN蚀刻;W-相容
·除SC-1外,所有化学品均不含过氧化物
表5.蚀刻速率(ER)、腐蚀电位(ΔEcorr)和选择TiN蚀刻组成
表6.选择蚀刻组成和蚀刻速率
表7.选择蚀刻组成和蚀刻速率
表8.选择金属氮化物蚀刻剂/清洁剂的蚀刻速率
表9-本发明的组合物
因此,虽然已经描述了目前被认为是本发明的优选实施方式的内容,但是本领域技术人员将认识到,在不脱离本发明的精神的情况下,可以对其进行改变和修饰,并且旨在要求保护所有这些落入本发明的真实范围的改变和修饰。
Claims (7)
1.一种用于微电子应用的非水性清洁组合物,包含0.01%至5.0%重量的氟化物活化剂、0.01%至20.00%重量的至少一种氧化剂、80.00%至99.90%重量的无水有机溶剂,其中所述清洁组合物的pH等于或小于5.5,其中所述氧化剂是硝酸,所述无水有机溶剂是环丁砜,并且所述氟化物活化剂是氟化氢(HF)或氟硼酸(HBF4)。
2.根据权利要求1所述的非水性清洁组合物,其中所述清洁组合物还具有蚀刻能力。
3.根据权利要求1所述的非水性清洁组合物,其中所述清洁组合物与钨和低κ电介质基材相容。
4.根据权利要求1所述的非水性清洁组合物,其包含0.05%至1.00%重量的氟化物活化剂、0.01%至5.00%重量的至少一种氧化剂、和85.00%至99.90%重量的无水有机溶剂。
5.根据权利要求1所述的非水性清洁组合物,其包含0.10%至0.50%重量的氟化物活化剂、0.01%至2.00%重量的至少一种氧化剂、和90.00%至99.00重量%的无水有机溶剂。
6.根据权利要求1所述的非水性清洁组合物,其还包含共溶剂。
7.根据权利要求1所述的非水性清洁组合物,其还包含一种或多种选自以下的成分:pH调节剂、胺、酸、腐蚀控制剂和表面活性剂。
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