CN112753093A - 通过合金化和蚀刻铂合金图案化铂 - Google Patents
通过合金化和蚀刻铂合金图案化铂 Download PDFInfo
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- CN112753093A CN112753093A CN201980063516.1A CN201980063516A CN112753093A CN 112753093 A CN112753093 A CN 112753093A CN 201980063516 A CN201980063516 A CN 201980063516A CN 112753093 A CN112753093 A CN 112753093A
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- platinum
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- metal
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 366
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 171
- 238000000059 patterning Methods 0.000 title claims abstract description 19
- 238000005530 etching Methods 0.000 title claims description 16
- 238000005275 alloying Methods 0.000 title claims description 15
- 229910001260 Pt alloy Inorganic materials 0.000 title claims description 3
- 238000000034 method Methods 0.000 claims abstract description 105
- 239000000758 substrate Substances 0.000 claims abstract description 63
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 59
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229920002120 photoresistant polymer Polymers 0.000 claims abstract description 51
- 239000004065 semiconductor Substances 0.000 claims abstract description 21
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 19
- 239000000956 alloy Substances 0.000 claims abstract description 19
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 37
- 238000000151 deposition Methods 0.000 claims description 16
- 238000004377 microelectronic Methods 0.000 claims description 15
- 238000001039 wet etching Methods 0.000 claims description 11
- 238000000137 annealing Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 239000007921 spray Substances 0.000 claims description 9
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000002739 metals Chemical class 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- XSBJUSIOTXTIPN-UHFFFAOYSA-N aluminum platinum Chemical compound [Al].[Pt] XSBJUSIOTXTIPN-UHFFFAOYSA-N 0.000 claims 8
- 238000004544 sputter deposition Methods 0.000 claims 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims 3
- 230000035945 sensitivity Effects 0.000 claims 1
- 238000007740 vapor deposition Methods 0.000 claims 1
- 229910000838 Al alloy Inorganic materials 0.000 abstract description 15
- GIGQFSYNIXPBCE-UHFFFAOYSA-N alumane;platinum Chemical compound [AlH3].[Pt] GIGQFSYNIXPBCE-UHFFFAOYSA-N 0.000 abstract description 15
- 239000010410 layer Substances 0.000 description 98
- 230000015572 biosynthetic process Effects 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000010408 film Substances 0.000 description 8
- 239000012790 adhesive layer Substances 0.000 description 6
- 238000011109 contamination Methods 0.000 description 6
- 238000000231 atomic layer deposition Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- 239000010936 titanium Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000007654 immersion Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 platinum group metals Chemical class 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000001465 metallisation Methods 0.000 description 3
- 238000004886 process control Methods 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 229910000951 Aluminide Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000012864 cross contamination Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910001092 metal group alloy Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000206 photolithography Methods 0.000 description 2
- 238000005240 physical vapour deposition Methods 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000007704 wet chemistry method Methods 0.000 description 2
- VLJQDHDVZJXNQL-UHFFFAOYSA-N 4-methyl-n-(oxomethylidene)benzenesulfonamide Chemical compound CC1=CC=C(S(=O)(=O)N=C=O)C=C1 VLJQDHDVZJXNQL-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910020286 SiOxNy Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 101150110932 US19 gene Proteins 0.000 description 1
- 238000000441 X-ray spectroscopy Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000002318 adhesion promoter Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910021340 platinum monosilicide Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000004151 rapid thermal annealing Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- MAKDTFFYCIMFQP-UHFFFAOYSA-N titanium tungsten Chemical compound [Ti].[W] MAKDTFFYCIMFQP-UHFFFAOYSA-N 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- 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
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- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/32051—Deposition of metallic or metal-silicide layers
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- 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
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- G01K7/00—Measuring temperature based on the use of electric or magnetic elements directly sensitive to heat ; Power supply therefor, e.g. using thermoelectric elements
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Abstract
提供一种在衬底(101)上图案化铂的方法。铂层(103)沉积在衬底上,并且经图案化的光致抗蚀剂层(105)形成在铂层上方,留下铂层的部分暴露区域。铝层(109)沉积在铂层(103)的部分暴露区域上方。合金(111)由来自部分暴露区域的铝和铂形成。铂铝合金(111)被蚀刻掉,留下铂层(103)的剩余部分,以在衬底(101)上形成经图案化的铂层。优选地,在形成经图案化的光致抗蚀剂层(105)之前,在半导体衬底(101)上的铂层(103)上沉积薄硬掩模层(107)。
Description
技术领域
本公开总体上涉及金属薄膜,并且更具体地涉及在微电子设备和传感器中图案化金属薄膜。
背景技术
通常,在恶劣环境下的薄膜技术传感器需要长寿命和化学稳定性,并且将非常受益于铂和其他类似相对惰性的金属以进行半导体金属化。由于如特殊物理特性(如PT1000电阻温度计设备(RTD)中的电阻温度系数(TCR))的关键特征,因此对于需要铂、铂族金属或合金或含有大量铂族金属的复合材料的微电子传感器或类似设备尤其如此。然而,铂和其他类似金属的极高期望惰性品质使它们难以图案化。到目前为止,这种传感器通常以分立元件的形式出售。由于难以向大型半导体制造商的数字和模拟晶圆厂引入相对惰性的MEMS材料及其工艺,因此在工业级生产方面几乎看不到任何实际发展。
尽管铂在IC工业中用于形成PtSi,但并未像铝或铜那样用作金属。由于铂的催化行为,铂通常被认为是晶圆厂中的污染风险,因此要非常小心地进行处理。现有技术铂图案化工艺在污染方面具有严重的缺点,导致禁止大量生产。
对生物医学或生物微机电(bio-MEMS)设备的兴趣日益浓厚,导致铂作为薄膜电极材料的重要性日益提高。固有的耐腐蚀性、良好的导电性、高生物相容性和不透射线的特性使铂适合各种生物MEMS设备。铂还用于电容器和热敏电阻以及许多其他应用。它的惰性使Pt本质上难以图案化。对于厚膜(>100nm)尤其如此,该厚膜能够承受传感应用中的苛刻条件而不会损坏或退化。
发明内容
以下呈现简化的概述,以便提供对本公开的一个或多个方面的基本理解。该概述不是本公开的广泛概述,并且既不旨在标识本公开的关键或重要元素,也不旨在划定其范围。相反,概述的主要目的是以简化形式呈现本公开的一些概念,作为稍后呈现的更详细描述的序言。
根据本公开的第一方面,提供一种在衬底上图案化铂的方法。铂层沉积在衬底上,并且在铂层上方形成图案化的光致抗蚀剂层,留下铂层的部分暴露区域。牺牲铝层沉积在铂层的部分暴露区域上方。由来自部分暴露区域的铝和铂形成合金。蚀刻掉铂铝合金以及非合金铝,留下铂层的剩余部分,以在衬底上形成图案化的铂层。在一个实施例中,在形成图案化的光致抗蚀剂层之前,薄硬掩模层沉积在半导体衬底上的铂层上。通过SiO2的物理电化学气相沉积(PECVD)可以形成薄硬掩模层,并且执行湿法蚀刻工艺以根据图案化的光致抗蚀剂层对薄硬掩模进行图案化,并去除光致抗蚀剂层。
在一个实施例中,使用湿法蚀刻浸浴工具和稀王水(3HCL:HNO3+H2O)去除铂铝合金。一个实施例可以在氮气(N2)气氛中将铂与铝退火形成合金。
在进一步的实施例中,使用湿法蚀刻工艺去除铂铝合金,该湿法蚀刻工艺采用喷涂蚀刻工具和3:1HCl:H2O2+H2O的稀蚀刻溶液。
在另一个实施例中,铂与铝的合金化包括在氮气(N2)气氛中退火以在铂层的暴露区域处形成铂铝合金。
在又一个实施例中,铝层被溅射沉积在铂层和暴露区域上方。在另一个实施例中,铂层被溅射沉积在半导体衬底上方。在又一个实施例中,在沉积铂层之前,粘合层形成在半导体衬底上方。粘合层可以包含氧化铝(Al2O3)。在又一个实施例中,铂层的厚度为4000nm。在另一个实施例中,铝层的厚度为8000nm。在又一个实施例中,通过在HF或BHF中执行短浸来去除薄硬掩模层。
根据本公开的另一方面,提供一种微电子设备。在微电子设备的衬底上形成铂层,并且在铂层上方形成图案化的光致抗蚀剂层,留下铂层的部分暴露区域。铝层沉积在铂层的部分暴露区域上方。由来自部分暴露区域的铝和铂形成合金。从衬底剥离铂铝合金以及非合金铝,留下铂层的剩余部分以在衬底上形成图案化的铂层。在一个实施例中,使用高度选择性的湿法蚀刻化学去除铂铝合金。铂与铝的合金化可以包括在氮气(N2)气氛中退火。
在本公开的另一方面,提供一种微电子设备,该微电子设备包括半导体衬底和在该衬底的顶表面上的铂电极,其中该铂电极的厚度≥0.1μm。铂电极的厚度可以≥0.4μm。在一个实施例中,铂电极的厚度在≥0.1μm到lμm的范围内。
在本公开的又一方面,一种电化学传感器包括微电子设备,该微电子设备包括衬底和在该衬底的顶表面上的铂电极,其中该铂电极的厚度≥0.1μm。
在本公开的又一方面,一种电阻温度计设备(RTD)包括微电子设备,该微电子设备包括衬底和在衬底的顶表面上的铂电极,其中该铂电极的厚度≥0.1μm。
附图说明
图1A至图1H是在示例性形成方法的连续阶段中描绘的具有铂层的微电子设备的局部截面图。
图2示出示例性形成方法的图1G所描绘的步骤之后的测试结构的掩模布局与实际SEM图像的对比。
图3是示例性形成方法的图1E所描绘的Pt和Al合金化步骤之后的横截面的SEM图像。
图4是另一示例性形成方法的铂测试结构的SEM俯视图图像和横截面。
图5A至图5E是示出根据又一示例性形成方法的FSI汞批量酸喷涂蚀刻工具的均匀性改善的晶片检查图像。
图6是在另一示例性形成方法的工艺阶段期间形成的铂铝合金的EDX图。
图7A和图7B是示出根据又一示例性形成方法的用于去除铂铝合金的两种蚀刻工艺的比较的示图。
图8A和图8B是又一示例性形成方法的快速热退火步骤之前(在图8A中示出)和之后(在图8B中示出)的铂结构的SEM俯视图图像。
图9是根据微电子设备的另一示例性形成方法的激光修整的铂结构的图像。
具体实施方式
参考附图描述本发明。附图未按比例绘制,并且提供附图仅用于说明本发明。下面参考用于说明的示例性应用来描述本发明的几个方面。应当理解,阐述了许多具体细节、关系和方法以提供对本发明的理解。本发明不受所图示的动作或事件的顺序的限制,因为一些动作可以以不同的顺序发生和/或与其他动作或事件同时发生。此外,并非所有示出的动作或事件都是实施根据本发明的方法所必需的。
根据本公开的至少一个实施例,公开一种在衬底上图案化铂的方法。在该实施例中,在衬底上的铂层上方形成图案化的光致抗蚀剂层或掩模,留下铂的暴露区域,并且暴露的铂与牺牲金属层合金化。选择牺牲金属,以使其在对工业半导体工具有利的温度下易于与铂形成合金,并且相比于铂以及相对于所得的铂牺牲金属合金,具有选择性地良好的蚀刻。从衬底上蚀刻与牺牲金属合金化的铂和牺牲金属层,留下铂层的剩余部分,以在衬底上形成图案化的铂层。在一个实施例中,使用高度选择性的湿法蚀刻化学去除铂牺牲金属合金。
对于铂膜,没有可靠工业水平的与IC兼容的图案化工艺。关于半导体环境中的大量生产,先前设想的Pt图案化工艺均具有明显的缺点,在半导体环境中,交叉污染会导致重大问题。最突出的示例将在下文说明。
将Pt沉积到光致抗蚀剂上(优选具有负侧壁)并随后去除光致抗蚀剂是一种常见的实验室方法,但是由于光致抗蚀剂的严重工具污染,因此在IC工业中被排除。发明人等实现用除光致抗蚀剂以外的牺牲材料作为提离层,但由于牺牲层侧壁处的良好的Pt台阶覆盖,发现该工艺难以控制。提离后的Pt突起被留为所谓的“耳”。美国专利申请公开号US2018/0204767A1中详细描述了该工艺。
对于厚度大于100nm的膜,干法蚀刻铂是困难的。由于其惰性,几乎没有发生对Pt的化学蚀刻,因此仅对其进行物理蚀刻(例如,被Ar离子蚀刻)。对硬掩模和粘合层的低选择性以及长蚀刻时间,会导致侧壁重新沉积。继而,这使得难以去除硬掩模,而长时间的过蚀刻导致跨较大直径的晶片均匀性低。而且,蚀刻工具被催化活性的Pt污染会引起不希望的副作用。
发明人已经发现在王水(3:1HCl:HNO3)中湿法蚀刻铂是不均匀的,这是由于如此所沉积的Pt表面的局部不均匀氧化,这导致蚀刻抑制。常见方法不能解决此问题。即使如美国专利申请(公开号US2018/0204734)中详述的,通过在Pt的顶部上原位沉积铝来解决,王水也是一种危险且高反应性的化学物质。在浸没工具中蚀刻时,必须定期刷新混合物以确保工艺控制。
根据本公开的其他方面,本文所公开的公开方法和技术可以用于图案化其他相对惰性且难于蚀刻的金属。然后根据本文详述的原理,相应地选择用于与这些金属合金化的合适的牺牲金属。
本公开的实施例利用铝作为用于与铂合金化的牺牲金属层。该方法利用以下事实:Pt和Al在相对低的温度下形成合金,该温度从200℃以上开始,并且更优选从250℃及以上开始。发明人已经发现,如此形成的合金以高达纯Pt的100倍的速率蚀刻。当Pt被消耗时,在Pt-Al界面上,最主要的共存相为Pt/PtAl2/Pt5Al21/Pt8Al21/Al。形成是扩散受控制的,并遵循抛物线时间相关性。因此,为了快速将Pt合金化到衬底底部,需要铝与铂的化学计量比至少为1:2。考虑到理想的Pt和Al密度,这意味着厚度比为1:2.2。
在一个实施例中,类似于大多数湿法蚀刻工艺,通过扩散来控制合金化工艺。给定的工艺提供了更好的特征尺寸/长宽比,因为它可以进行高度的工艺控制,因为与湿化学法相比,可以更加严格地控制扩散的材料量和持续时间。以这种方式,该方法可以被描述为固态湿法蚀刻工艺。已经发现有两种方法效果很好。
参考图1A至图1G,描述了根据本公开的实施例的通过合金化来图案化铂的第一方法。参考图1A,衬底101用作用于形成铂结构的基底。衬底可以包括诸如晶片或晶片的一部分的半导体结构,并且可以由硅、锗或其他合适的材料制成。在衬底上待被图案化的铂可以用于多种目的中的任何一种,包括但不限于,形成电阻器、形成电容器、形成用于传感器的电极、形成电阻温度设备(RTD)或金属化目的。衬底101可能已经包括在其上形成的结构,因此可能不是完全平坦的。在一个实施例中,对铂进行图案化以便在集成电路的不同电子部件之间传导电流。在一个可替代实施例中,在对衬底101上的铂进行图案化之后,形成其他集成电路部件。
仍然参考图1A,粘合层102沉积在衬底101的顶部上。粘合层102可以用于促进其他层到衬底的附着。例如,粘合层102可以由适合于将铂附着到硅衬底的材料制成。在一些实施例中,粘合层102包括钛、氮化钛或钛钨。可以使用多种技术中的任何一种来将粘合层102沉积在衬底101上。具体技术可以取决于用作粘合层的材料的类型。例如,可以使用物理气相沉积(PVD)、化学气相沉积(CVD)、电化学沉积(ECD)或其他合适的方法中的任何一种来沉积粘合层。在一个示例中,粘合层102包括溅射在衬底101的顶部上的钛层。粘合层的厚度可以是大约但是在其他实施方式中可以更薄或更厚。
在其他实施例中,粘合层102可以包括例如由Ta2O5、TaN、TiO2或氧化铝制成的陶瓷层。在一个实施例中,粘合层102包括氧化铝(Al2O3)的原子层沉积(ALD)。在一个实施例中,粘合层102包括大约12.5nm厚的氧化铝的ALD。
尽管图1A至图1G中所示的实施例说明粘合层102的使用,但是其他实施例可以避免使用粘合层。在这些后者的实施例中,铂结构可以直接形成在衬底101的表面上。例如,在一个实施例中,衬底101可以是蓝宝石衬底(Al2O3)。在该实施例中,可以在没有中间粘合层的情况下将铂层沉积在蓝宝石衬底上。在一个可替代实施例中,衬底101的表面经过使用氩的溅射蚀刻工艺以改善表面的粘合性。
再次参考图1A,将厚度大约为400nm的铂膜或铂层103溅射沉积在12.5nmALD氧化铝(Al2O3)粘合层102的顶部上。在一些实施例中,在铂层103上形成薄硬掩模层107。尽管厚度在10nm至100nm之间的PECVD SiO2硬掩模提供了更好的性能,但是诸如Ti、TiN、氮氧化物、SiOxNy或Si3N4的不同材料可以用于形成薄硬掩模层107。在薄硬掩模107的上方形成光致抗蚀剂层105,然后通过例如光刻技术对其进行图案化,从而在光致抗蚀剂层中形成掩模。例如,光致抗蚀剂层105可以暴露于深紫外线(DUV)光以便形成图案。在实施例中,在薄硬掩模层107的顶部上施加i线光致抗蚀剂105并将其图案化。在另一个实施例中,使用负性光致抗蚀剂,其中光致抗蚀剂的暴露于光的部分变得不溶于光致抗蚀剂显影剂(即,光致抗蚀剂的未曝光部分将被溶解)。随后,光致抗蚀剂显影剂溶液去除光致抗蚀剂层的未被曝光的部分,并且被曝光的抗蚀剂保留在薄硬掩模的表面上。因此,形成包括反图案的抗蚀剂掩模。尽管图1A至图1G中所示的实施例说明使用薄硬掩模层,但是其他实施例可以避免使用薄硬掩模层107,并且光致抗蚀剂层105可以直接形成在铂层103的表面上,在铂层中留下暴露区域;
参考图1B,去除薄硬掩模层107的未被光致抗蚀剂层104覆盖(并因此暴露)的部分。已经发现短的湿法蚀刻工艺在薄硬掩模层107上再现光致抗蚀剂层105的图案,而特征尺寸没有显著损失。在本公开的其他实施例中,代替地使用干法蚀刻工艺。适当地图案化的薄硬掩模层107在铂层中留下暴露区域;
参考图1C,在一些实施例中,在去除图1B中所示的光致抗蚀剂105之后,将铝层109溅射沉积到现在部分暴露的铂(如图1C中的铂层103中的暴露区域所示)上。在一个实施例中,沉积的铝层109的厚度大于0.8μm
参考图1D,随后在氮气(N2)气氛中退火在与铝层109接触的铂层的暴露区域中形成铂-铝合金111。在一个实施例中,在N2气氛中,在350℃的温度下执行退火2小时。在其他实施例中,用于使铂与铝合金化的退火工艺在≥250℃的温度下执行。在其他实施例中,退火工艺可以在环境气氛、O2气氛、H2气氛中执行,或者可以是高真空退火工艺。
图3是在图1D所说明的铂与铝合金化后的实际截面的扫描电子显微镜(SEM)图像。在图3中,薄硬掩膜不可见。
参考图1E,通过使用HCl执行湿法蚀刻工艺来去除铝层的非合金区域。37%HCl的化学蚀刻剂本身不会蚀刻铂-铝合金铂铝化物。该去除步骤是可选的,并且在一些实施例中,可以省略用于剥离铝的湿法蚀刻工艺。
参考图1F,在一些实施例中,通过使用稀释的铂蚀刻化学物质(如王水或3:1HCl:H2O2)执行湿法蚀刻工艺,从晶片上剥离铂-铝合金111。通过稀释铂蚀刻化学物质(如王水或3:1HCl:H2O2),铂对其合金铂铝化合物的选择性进一步提高。即使稀释,当温度升高到50℃以上时,H2O2的浓度也低至0.5%就足够了。因此,通过进行如图5所描述的某些工艺调整,甚至可以采用固有地非均匀批量喷涂工具来去除(剥离)牺牲铂-铝合金层111。在诸如FSIMercury或Semitool SST的喷涂工具中,蚀刻化学物质与溶解的材料一起被排出。
图7A描绘湿法蚀刻喷涂工具工艺,并且图7B描绘湿法蚀刻浸没工具。浸没工具湿法蚀刻工艺会遭受交叉污染,以及蚀刻化学物质的老化。在图2的测试结构的SEM图像中看到的喷涂图案是由于科里奥利力作用在由静态中央喷柱喷出的雾化化学物质上引起的。
参考图1G,通过短浸在氢氟酸HF或缓冲氢氟酸BHF中来去除硬掩模,氢氟酸HF或缓冲氢氟酸BHF两者都不侵蚀铂。图2示出最终铂结构的SEM图像。
在图3中,可以看到由硬掩模边缘下方的横向铝扩散引起的固有过蚀刻。从图2至图4中所示的横截面的TEM图像和SEM图像,从铂侧壁斜率可以明显看出,所公开的方法具有与湿法蚀刻类似的各向同性性质。在本公开的一些实施例中,过蚀刻可以通过Pt:Al的化学计量比以及合金化时间来控制,这允许比湿法蚀刻更大的工艺控制。
结合图1A至图1G描述的工艺被验证为达到1μm的铂厚度。发明人已经发现,在铂-铝铂铝化物合金形成期间,控制硬掩模弯曲的难度越来越大,这可能最终导致Pt厚度的上限。Al/Pt/Al三明治结构或采用壕沟状的拓扑结构可以能够形成更厚的铂膜。此外,该工艺不需要平坦化。类似于湿法蚀刻,只要Al的台阶覆盖率可以接受,拓扑结构就不阻碍Pt-Al合金化。发明人已经验证其可以在小于120°的角度下工作。
根据本公开的另一方面,描述了在衬底上图案化铂的第二方法。该衬底用作用于形成铂结构的基底。衬底可以包括诸如晶片或晶片的一部分的半导体结构,并且可以由硅、锗或其他合适的材料制成。在衬底上待被图案化的铂可以用于多种目的中的任何一种。铂层沉积在衬底的上方,并且铝层沉积在铂层上。在一个实施例中,铝层被原位沉积在毯状铂晶片的顶部上。
在铝层上方形成光致抗蚀剂层,并且通过光刻技术将光致抗蚀剂层图案化,从而在光致抗蚀剂层中形成掩模。在一些实施例中,在晶片上施加期望的Pt图案的负性光致抗蚀剂。使用负性光致抗蚀剂,其中光致抗蚀剂的暴露于光的部分变得不溶于光致抗蚀剂显影剂(即,光致抗蚀剂的未曝光部分将被溶解)。随后,光致抗蚀剂显影剂溶液去除光致抗蚀剂层的未曝光部分,并且曝光的抗蚀剂保留在牺牲层的表面上。因此,形成包括反图案的抗蚀剂掩模。
蚀刻铝层以在铂层的顶部上形成Al图案。由于干法蚀刻带来污染风险,因此用铝浸出材料对铝进行湿法蚀刻,在一个实施例中,该铝浸出材料是磷酸、乙酸和硝酸的混合物。由于必要的过蚀刻,这导致特征尺寸有所减小,取决于铂层(以及铝)的厚度。在去除抗蚀剂之后,在一个实施例中,在氧气环境中使铂和铝合金化,其中暴露的作为有益副作用的铂也被氧化。在一些实施例中,通过执行稀释的铂蚀刻湿化学工艺来去除铂-铝合金。
图6示出所形成的铂-铝合金PtAl2的能量X射线光谱(EDX)。
为了将公开的铂图案化工艺无缝地集成到现有的晶圆厂工艺或回路中,在铂结构形成之前和之后都必须考虑粘合问题以及污染问题。众所周知,铂在大多数表面上都不能很好地粘合。已经发现Ti和ALD沉积的Al2O3是优异的粘合促进剂。后者对于单金属工艺流程是优选的,因为铂和Ti始于大约400℃的温度形成合金。为了将铂图案化工艺集成到半导体流中,将Al2O3用作合适的(干法)蚀刻停止层,以形成用于平坦化的通孔,或者用于在钝化层沉积之后打开铂。已经开发出一种特殊的无氧无氩干法蚀刻工艺,该工艺允许在厚度仅为3nm的A12O3层上着陆,然后可以通过短暂的湿法蚀刻将其去除。该工艺在也由申请人提交的PCT专利申请号PCT/US19/24381中进行了详细描述。证明这种能力的测试结构在图4中示出,其中光致抗蚀剂没有显示侧壁再沉积或聚合的迹象。Al2O3/Pt/Al2O3的三明治结构允许在IC制造的每个阶段中实现铂金属化的无污染集成。关于粘合力,根据本公开的一些实施例的图案化铂膜通过了透明胶带测试,并且即使当用强力刮擦表面时也几乎没有粘合力损失或没有粘合力损失。
贯穿以下描述和权利要求书,使用某些术语来指代特定***部件。不同的公司可以通过不同的名称来指代部件。本文档无意区分名称不同但功能相同的部件。在以下讨论和权利要求中,术语“包括”和“包含”以开放式方式使用,因此应解释为表示“包括但不限于”。
尽管上面已经描述了本发明的各种实施例,但是应当理解,它们仅是通过示例而非限制的方式给出。可以组合不同示例的各种元素以提供本发明的不同方面。在不脱离本发明的精神或范围的情况下,可以根据本文的公开内容对所公开的实施例进行多种改变。因此,本发明的广度和范围不应受到任何上述实施例的限制。而是,本发明的范围应根据所附权利要求及其等同物来限定。
Claims (32)
1.一种图案化铂的方法,其包括:
在半导体衬底上沉积铂层;
在所述铂层上方形成经图案化的光致抗蚀剂层,留下所述铂层中的暴露区域;
在所述铂层和所述暴露区域上方沉积铝层;
在所述铂层的所述暴露区域中形成铝和铂的合金;和
在所述铂层的所述暴露区域处蚀刻所述铝层以及合金化的铝铂,从而留下所述铂层的剩余部分以在所述衬底上形成经图案化的铂层。
2.根据权利要求1所述的方法,其中在所述铂层的所述暴露区域中蚀刻所述铝层以及所述合金化的铝铂包括使用稀王水即3HCL:HNO3+H2O蚀刻剂的湿法蚀刻浸浴工艺。
3.根据权利要求1所述的方法,其中在所述铂层的所述暴露区域中蚀刻所述铝层以及所述合金化的铝铂包括使用3:1HCl:H2O2的稀蚀刻剂的湿法蚀刻喷涂工具工艺。
4.根据权利要求1所述的方法,进一步包括:
在形成所述经图案化的光致抗蚀剂层之前,在所述半导体衬底上的所述铂层上形成薄硬掩模层。
5.根据权利要求4所述的方法,其中所述薄硬掩模层通过SiO2的物理电化学气相沉积即PECVD形成,并且
执行湿法蚀刻,以根据所述经图案化的光致抗蚀剂层对所述薄硬掩模进行图案化,并去除所述光致抗蚀剂层。
6.根据权利要求1所述的方法,其中在所述铂层和所述暴露区域上方沉积铝层包括执行溅射沉积工艺。
7.根据权利要求1所述的方法,其中在所述铂层的所述暴露区域处形成铝和铂的合金包括在氮气气氛中退火以在所述铂层的所述暴露区域处形成所述合金。
8.根据权利要求1所述的方法,进一步包括在沉积所述铂层之前,在所述半导体衬底上方形成粘合层。
9.根据权利要求8所述的方法,其中所述粘合层包括氧化铝即Al2O3。
10.根据权利要求1所述的方法,其中在所述衬底上沉积所述铂层包括执行溅射沉积工艺。
11.根据权利要求10所述的方法,其中所述铂层的厚度为0.4μm。
12.根据权利要求6所述的方法,其中所述铝层的厚度为0.8μm或更厚。
13.根据权利要求5所述的方法,进一步包括通过在HF或BHF中执行短浸来去除所述薄硬掩模层。
14.一种图案化铂的方法,其包括:
在所述半导体衬底上方沉积粘合层;
在半导体衬底上溅射沉积铂层;
在所述铂层上方形成经图案化的光致抗蚀剂层,留下所述铂层中的暴露区域;
在所述铂层和所述暴露区域上溅射沉积铝层;
通过在氮气气氛中退火,在所述铂层的所述暴露区域处形成铝和铂的合金,以在所述铂层的所述暴露区域处形成PtAl2合金;和
通过使用稀王水即3HCL:HNO3+H2O蚀刻剂执行湿法蚀刻浸浴工艺,在所述铂层的所述暴露区域处蚀刻所述铝层以及合金化的铝铂,从而留下所述铂层的剩余部分以在所述衬底上形成经图案化的铂层。
15.根据权利要求14所述的方法,进一步包括:
在形成所述经图案化的光致抗蚀剂层之前,在所述半导体衬底上的所述铂层上形成薄硬掩模层,根据所述经图案化的光致抗蚀剂层通过执行湿法蚀刻以对所述薄硬掩模进行图案化并去除所述光致抗蚀剂层。
16.根据权利要求14所述的方法,其中所述薄硬掩模层通过SiO2的物理电化学气相沉积即PECVD形成。
17.根据权利要求15所述的方法,其中通过在HF或BHF中执行短浸来去除所述薄硬掩模层。
18.根据权利要求14所述的方法,其中所述铂层的厚度为0.4μm,并且所述铝层的厚度为0.8μm。
19.一种图案化铂的方法,其包括:
在半导体衬底上沉积铂层;
在所述铂层上方形成经图案化的光致抗蚀剂层,留下所述铂层中的暴露区域;
在所述铂层和所述暴露区域上方沉积铝层;
通过在氮气气氛中退火,在所述铂层的所述暴露区域处形成铝和铂的合金,以在所述铂层的所述暴露区域处形成PtAl2合金;和
通过使用3:1HCl:H2O2稀蚀刻剂执行湿法蚀刻喷涂工具工艺,在所述铂层的所述暴露区域处蚀刻所述铝层以及合金化的铝铂,从而留下所述铂层的剩余部分以在所述衬底上形成经图案化的铂层。
20.根据权利要求19所述的方法,其包括:
在形成所述经图案化的光致抗蚀剂层之前,在所述半导体衬底上的所述铂层上形成薄硬掩模层,根据所述经图案化的光致抗蚀剂层通过执行湿法蚀刻以对所述薄硬掩模进行图案化并去除所述光致抗蚀剂层。
21.根据权利要求20所述的方法,其中所述铂层通过溅射沉积工艺沉积并且具有0.4μm的厚度,并且所述铝层通过溅射沉积工艺沉积并且具有0.8μm的厚度。
22.一种图案化铂的方法,其包括:
在半导体衬底上沉积铂层;
在所述铂层上方沉积铝层;
在所述铝层上方形成经图案化的光致抗蚀剂层,留下所述铝层中的暴露区域;
通过执行湿法蚀刻工艺来蚀刻所述铝层的所述暴露区域;
去除所述光致抗蚀剂层;
在氧气环境中,在所述铝层的所述暴露区域处形成铂和铝的合金;和
通过使用稀释的铂蚀刻化学蚀刻剂执行湿法蚀刻工艺来蚀刻合金化的铝铂,从而留下所述铂层的剩余部分以在所述衬底上形成经图案化的铂层。
23.根据权利要求22所述的方法,其中用于蚀刻所述铝层的所述暴露区域的所述湿法蚀刻工艺使用包括磷酸的蚀刻剂材料。
24.根据权利要求22所述的方法,其中使用稀释的铂蚀刻化学蚀刻剂来蚀刻所述合金化的铝铂的所述湿法蚀刻工艺是使用3:1HCl:H2O2的稀蚀刻剂的湿法蚀刻喷涂工具工艺。
25.根据权利要求22所述的方法,其中使用稀释的铂蚀刻化学蚀刻剂来蚀刻所述合金化的铝铂的所述湿法蚀刻工艺是使用稀王水即3HCL:HNO3+H2O蚀刻剂的湿法蚀刻浸浴工艺。
26.一种微电子设备,其包括:
半导体衬底;和
在所述衬底的顶表面上的铂电极,
其中所述铂电极的厚度≥0.1μm。
27.根据权利要求26所述的微电子设备,其中所述铂电极的厚度≥0.4μm。
28.根据权利要求26所述的微电子设备,其中所述铂电极的厚度在≥0.1μm到lμm的范围内。
29.一种电化学传感器,其包括根据权利要求26所述的微电子设备。
30.一种电阻温度计设备即RTD,其包括根据权利要求26所述的微电子设备。
31.一种形成微电子设备的方法,其包括:
提供具有顶表面的衬底;
在所述衬底的所述顶表面上形成第一金属的层;
在所述第一金属的层上方形成经图案化的光致抗蚀剂层,留下所述第一金属的层中的暴露区域;
在所述第一金属的层中的所述暴露区域上方形成第二金属的层;
在所述第一金属的层的所述暴露区域处形成所述第一金属和所述第二金属的合金;和
在所述第一金属的层的所述暴露区域处蚀刻所述第一金属的层以及合金化的第一金属和第二金属,从而留下所述第一金属的层的剩余部分,以在所述衬底上形成经图案化的第一金属的层;
其中所述第一金属是惰性金属,并且所述第二金属是易于与所述惰性金属形成可蚀刻合金的金属,并且
其中所述可蚀刻合金比所述惰性金属具有更大的蚀刻敏感性。
32.根据权利要求31所述的方法,其中蚀刻所述第一金属的层以及所述合金化的第一金属和第二金属的步骤是利用选择性湿法蚀刻工艺执行的。
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- 2019-07-29 CN CN201980063516.1A patent/CN112753093A/zh active Pending
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CN111945128A (zh) * | 2020-08-18 | 2020-11-17 | 江苏能华微电子科技发展有限公司 | 一种提高铂与衬底黏附性的方法及其产品 |
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US20200035500A1 (en) | 2020-01-30 |
KR20210035189A (ko) | 2021-03-31 |
EP3830862A4 (en) | 2021-12-29 |
US11011381B2 (en) | 2021-05-18 |
WO2020023953A1 (en) | 2020-01-30 |
EP3830862A1 (en) | 2021-06-09 |
KR102646859B1 (ko) | 2024-03-13 |
US20230253211A1 (en) | 2023-08-10 |
JP7476442B2 (ja) | 2024-05-01 |
KR20240038117A (ko) | 2024-03-22 |
US20210242029A1 (en) | 2021-08-05 |
US11658034B2 (en) | 2023-05-23 |
JP2024072836A (ja) | 2024-05-28 |
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