KR20210039179A - Etchant for etching Ti-W film - Google Patents
Etchant for etching Ti-W film Download PDFInfo
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- KR20210039179A KR20210039179A KR1020190121692A KR20190121692A KR20210039179A KR 20210039179 A KR20210039179 A KR 20210039179A KR 1020190121692 A KR1020190121692 A KR 1020190121692A KR 20190121692 A KR20190121692 A KR 20190121692A KR 20210039179 A KR20210039179 A KR 20210039179A
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- hydrogen peroxide
- chelating agent
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- 238000005530 etching Methods 0.000 title claims description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000002738 chelating agent Substances 0.000 claims abstract description 26
- 239000004065 semiconductor Substances 0.000 claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 15
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 7
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 4
- HJMZMZRCABDKKV-UHFFFAOYSA-N carbonocyanidic acid Chemical compound OC(=O)C#N HJMZMZRCABDKKV-UHFFFAOYSA-N 0.000 claims description 4
- LJOQGZACKSYWCH-LHHVKLHASA-N (s)-[(2r,4s,5r)-5-ethyl-1-azabicyclo[2.2.2]octan-2-yl]-(6-methoxyquinolin-4-yl)methanol Chemical compound C1=C(OC)C=C2C([C@H](O)[C@H]3C[C@@H]4CCN3C[C@@H]4CC)=CC=NC2=C1 LJOQGZACKSYWCH-LHHVKLHASA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 3
- 239000000920 calcium hydroxide Substances 0.000 claims description 3
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims description 3
- LJOQGZACKSYWCH-UHFFFAOYSA-N dihydro quinine Natural products C1=C(OC)C=C2C(C(O)C3CC4CCN3CC4CC)=CC=NC2=C1 LJOQGZACKSYWCH-UHFFFAOYSA-N 0.000 claims description 3
- 229960004251 hydroquinine Drugs 0.000 claims description 3
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims description 3
- 239000000347 magnesium hydroxide Substances 0.000 claims description 3
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 2
- LKLLNYWECKEQIB-UHFFFAOYSA-N 1,3,5-triazinane Chemical compound C1NCNCN1 LKLLNYWECKEQIB-UHFFFAOYSA-N 0.000 claims description 2
- WREVVZMUNPAPOV-UHFFFAOYSA-N 8-aminoquinoline Chemical compound C1=CN=C2C(N)=CC=CC2=C1 WREVVZMUNPAPOV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 abstract description 23
- 239000002184 metal Substances 0.000 abstract description 23
- 229910001080 W alloy Inorganic materials 0.000 abstract description 16
- 230000003628 erosive effect Effects 0.000 abstract description 16
- 239000008367 deionised water Substances 0.000 abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 14
- -1 hydroxide ions Chemical class 0.000 abstract description 13
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 230000004888 barrier function Effects 0.000 description 13
- 239000010949 copper Substances 0.000 description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 11
- 229910052802 copper Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 239000002585 base Substances 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 6
- 239000006172 buffering agent Substances 0.000 description 6
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001039 wet etching Methods 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 150000002466 imines Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JHMYHHQGZIXONQ-UHFFFAOYSA-N NC=1C=CC=C2C=CC=NC12.NC=1C=CC=C2C=CC=NC12 Chemical compound NC=1C=CC=C2C=CC=NC12.NC=1C=CC=C2C=CC=NC12 JHMYHHQGZIXONQ-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- XAHAOEIIQYSRHJ-UHFFFAOYSA-N benzene-1,2-diamine Chemical compound NC1=CC=CC=C1N.NC1=CC=CC=C1N XAHAOEIIQYSRHJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
- 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
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- ing And Chemical Polishing (AREA)
- Weting (AREA)
Abstract
Description
본 발명은 반도체 기판의 가공에 관한 것으로, 보다 상세하게는 땜납 공정에서 확산 방지를 위한 베리어 금속층으로 사용되는 Ti-W 필름을 식각하기 위한 식각조성물에 관한 것이다.The present invention relates to processing of a semiconductor substrate, and more particularly, to an etching composition for etching a Ti-W film used as a barrier metal layer for preventing diffusion in a soldering process.
땜납 공정에서 확산 방지 기능을 하는 베리어 금속층은 상부 금속 물질과의 접착력과 전도성을 유지시켜주는 중요한 역할을 한다.The barrier metal layer that prevents diffusion in the soldering process plays an important role in maintaining adhesion and conductivity with the upper metal material.
식각은 반도체 공정 중 웨이퍼에서 회로 패턴을 만들기 위해 화공 약품, 부식성 가스 등을 이용하여 불필요한 부분을 선택적으로 없애는 과정이며, 일반적으로 마스크로 가려진 부분을 남겨둔 채 나머지 부분을 부식 혹은 반응에 의해 제거하는 방식을 채택한다.Etching is a process of selectively removing unnecessary parts by using chemicals or corrosive gas to make a circuit pattern from a wafer during the semiconductor process, and generally removing the remaining parts by corrosion or reaction while leaving the part covered by a mask. Adopt.
화공 약품을 이용하는 식각을 습식 식각이라고 하고, 부식성 가스나 플라즈마 등을 이용하는 식각을 건식 식각이라고 한다. 습식 식각은 각 소재에 대한 높은 선택비, 낮은 표면 손상 등 소재에 대한 장점과 상대적으로 저렴한 약액 비용 등 경제적 장점을 가진다. 하지만 습식 식각은 경우에 따라 식각 용액이 마스크 하부로 유입되어 하부 침식이 발생하는 문제를 유발할 수 있으며, 이러한 하부 침식은 반도체 소자의 크기가 작아지는 추세에서 회로의 단선 혹은 제품의 신뢰도를 저하시키는 요인이 될 수 있다.Etching using chemicals is called wet etching, and etching using corrosive gas or plasma is called dry etching. Wet etching has economic advantages such as high selectivity and low surface damage for each material, and relatively low cost of chemicals. However, wet etching may in some cases lead to a problem in which the etching solution flows into the lower part of the mask, resulting in lower erosion, and this lower erosion is a factor that reduces circuit breakage or product reliability as the size of semiconductor devices decreases. Can be
Ti/Ti-W 합금은 땜납 범프 혹은 재배선층(RDL, Redistribution Layer)을 만들기 위한 확산 방지를 위한 베리어 금속층으로 사용된다. 기존의 공정은 베리어 금속층이 Ti인 구조에서 공정을 진행해 왔으나, 근래에 들어 PMIC, 인덕터 등 전력반도체 소자 등에 사용되는 Ti가 소자의 균열을 야기하는 문제로 인하여 베리어 금속층이 상대적으로 유연한 금속인 Ti-W 합금으로 변경되는 추세를 보이고 있다. Ti-W 합금은 상대적으로 우수한 접착 특성을 가지며 Cu 하부의 표면 거칠기를 감소시키는 역할도 한다.Ti/Ti-W alloy is used as a barrier metal layer to prevent diffusion to make solder bumps or redistribution layers (RDL). Conventional processes have been carried out in a structure in which the barrier metal layer is Ti, but in recent years, Ti, which is used for power semiconductor devices such as PMICs and inductors, causes cracks in the device, so that the barrier metal layer is a relatively flexible metal, Ti- There is a trend of changing to W alloy. Ti-W alloy has relatively excellent adhesion properties and also serves to reduce the surface roughness of the lower part of Cu.
일반적으로 티탄계 금속 식각에 불산 혹은 불산·질산, 과산화수소·불산 등 혼산이 사용되지만 이는 실리콘 기판 혹은 유리 기판의 식각과 알루미늄 배선 등의 부식을 초래하여 반도체 디바이스에 적용하기에 적합하지 않다. 또한 과산화수소·암모니아 혼합액 및 과산화수소·인산염 혼합액을 사용하고자 하는 시도가 있었으나, 티탄계 금속의 식각 속도가 느리고 또한 과산화수소의 분해가 빨라 안정한 에칭을 할 수 없으며 식각액의 발포가 심하기 때문에 기판 표면에 기포가 생겨 기포가 부착된 부분은 에칭이 진행되지 않는 단점이 있다.In general, a mixture of hydrofluoric acid, hydrofluoric acid, nitric acid, hydrogen peroxide, and hydrofluoric acid is used for etching titanium-based metals, but this causes etching of silicon substrates or glass substrates and corrosion of aluminum wiring, which is not suitable for application to semiconductor devices. In addition, there have been attempts to use a mixture of hydrogen peroxide and ammonia, and a mixture of hydrogen peroxide and phosphate, but the etching rate of titanium-based metals is slow and the decomposition of hydrogen peroxide is fast, so stable etching cannot be performed. There is a disadvantage that the etching does not proceed in the area where the air bubbles are attached.
이러한 단점을 개선하기 위해 등록특허 10-0825844호에서 과산화수소·유기산염·유기산암모늄염·암모니아를 포함한 혼합액이 소개되었다. 그러나 이 식각액은 느린 식각 속도를 가질 뿐만 아니라 큰 재배선층 하부 침식을 유발하여 제품 신뢰도를 저하시키는 문제를 가진다.In order to improve these disadvantages, a mixed solution containing hydrogen peroxide, an organic acid salt, an organic acid ammonium salt, and ammonia was introduced in Patent No. 10-0825844. However, this etchant has a problem that not only has a slow etch rate, but also causes large erosion under the redistribution layer, thereby reducing product reliability.
본 발명이 해결하고자 하는 과제는 반도체 포장(package) 공정에서 구리 재배선층의 들뜸을 방지하고 하부층(베리어 금속층)과의 밀착성 확보를 위해 습식 식각 방식을 통해 별도의 부가적인 장비 투자 없이 1 ㎛ 미만의 언더컷을 구현할 수 있도록 하는 식각조성물을 제공하는 것이다.The problem to be solved by the present invention is to prevent lifting of the copper redistribution layer in the semiconductor packaging process and secure adhesion to the lower layer (barrier metal layer) through a wet etching method without additional equipment investment. It is to provide an etching composition that enables the undercut to be realized.
본 발명의 실시예에 따른 기판 상의 Ti-W 필름을 식각하기 위한 식각조성물은 과산화수소, 염기, 킬레이트제 및 탈이온수(DIW)를 함유한다.The etching composition for etching the Ti-W film on the substrate according to the embodiment of the present invention contains hydrogen peroxide, a base, a chelating agent, and DIW.
상기 염기는 수산화나트륨, 수산화칼륨, 수산화마그네슘, 수산화칼슘, 암모니아수 및 수산화테트라메틸암모늄 중 하나 이상을 포함할 수 있다.상기 킬레이트제는 이미노디아세트산, 니트릴로아세트산, 헥사하이드로-1,3,5-트리아진, 디하이드로퀴닌, 8-아미노퀴놀린, o-페난트롤린 및 o-페닐렌디아민 중 둘 이상을 포함할 수 있다.The base may include at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, aqueous ammonia, and tetramethylammonium hydroxide. The chelating agent is iminodiacetic acid, nitriloacetic acid, hexahydro-1,3,5- Triazine, dihydroquinine, 8-aminoquinoline, o-phenanthroline, and o-phenylenediamine.
본 발명의 실시예에 따른 식각조성물은 완충제를 더 포함할 수 있다.The etching composition according to an embodiment of the present invention may further include a buffering agent.
본 발명의 한 실시예에 따르면, 상기 과산화수소는 25 내지 35 중량%로 함유되고, 상기 염기는 0.02 내지 10 중량%로 함유되며, 상기 킬레이트제 0.05 내지 5 중량%로 함유될 수 있다.According to an embodiment of the present invention, the hydrogen peroxide may be contained in an amount of 25 to 35% by weight, the base may be contained in an amount of 0.02 to 10% by weight, and the chelating agent may be contained in an amount of 0.05 to 5% by weight.
한편, 본 발명의 다른 실시예에 따르면, 상기 과산화수소는 28 내지 33 중량%로 함유되고, 상기 염기는 5 내지 7 중량%로 함유되며, 상기 킬레이트제 0.05 내지 1 중량%로 함유될 수 있다.Meanwhile, according to another embodiment of the present invention, the hydrogen peroxide may be contained in an amount of 28 to 33% by weight, the base may be contained in an amount of 5 to 7% by weight, and the chelating agent may be contained in an amount of 0.05 to 1% by weight.
본 발명에 의하면, Ti-W 필름을 언더컷 1 ㎛ 미만으로 식각할 수 있기 때문에, 기존의 Ti 금속을 Ti-W 합금으로 변경하는데 있어 하부 침식 문제를 해결할 수 있고 그에 따라 Ti 금속의 문제로 알려진 크랙에 의한 제품 신뢰도 저하 문제를 해결할 수 있다.According to the present invention, since the Ti-W film can be etched with an undercut less than 1 μm, it is possible to solve the problem of lower erosion in changing the existing Ti metal to a Ti-W alloy, and accordingly, a crack known as a problem of the Ti metal. It can solve the problem of product reliability degradation caused by.
도 1은 실험에 사용된 기판의 층 구조 및 식각 후 하부침식을 개념적으로 도시한 도면이다.
도 2는 본 발명의 실시예에 따른 Ti-W 합금 식각액을 통하여 1 ㎛ 이내로 하부침식을 최소화한 주사전자현미경 이미지이다.1 is a diagram conceptually showing a layer structure of a substrate used in an experiment and a bottom erosion after etching.
2 is a scanning electron microscope image in which bottom erosion is minimized to within 1 μm through a Ti-W alloy etchant according to an embodiment of the present invention.
이하에서 첨부된 도면을 참조하여 본 발명의 실시예에 대해 상세히 설명한다.Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.
본 발명의 실시예에 따른 식각조성물은 과산화수소, 염기, 킬레이트제(chelating agent) 및 탈이온수(DIW)를 함유할 수 있으며, 나아가 완충제를 선택적으로 함유할 수 있다.The etching composition according to an embodiment of the present invention may contain hydrogen peroxide, a base, a chelating agent, and deionized water (DIW), and may optionally contain a buffering agent.
본 발명의 한 실시예에 따른 식각조성물은 과산화수소 25 내지 35 중량%, 염기 0.02 내지 10 중량%, 킬레이트제 0.05 내지 5 중량% 및 여분의 탈이온수를 포함할 수 있으며, 선택적으로 완충제를 포함할 수 있다. 이때 탈이온수는 67 내지 72 중량%로 함유될 수 있다. 본 발명의 다른 실시예에 따른 식각조성물은 과산화수소 28 내지 33 중량%, 염기 5 내지 7 중량%, 킬레이트제 0.05 내지 5 중량% 및 여분의 탈이온수를 포함할 수 있으며, 선택적으로 완충제를 포함할 수 있다.The etching composition according to an embodiment of the present invention may contain 25 to 35% by weight of hydrogen peroxide, 0.02 to 10% by weight of a base, 0.05 to 5% by weight of a chelating agent, and extra deionized water, and optionally a buffer. have. In this case, the deionized water may be contained in an amount of 67 to 72% by weight. The etching composition according to another embodiment of the present invention may contain 28 to 33% by weight of hydrogen peroxide, 5 to 7% by weight of a base, 0.05 to 5% by weight of a chelating agent, and extra deionized water, and may optionally include a buffering agent. have.
염기는 수산화나트륨, 수산화칼륨, 수산화마그네슘, 수산화칼슘, 암모니아수, 수산화테트라메틸암모늄 중 하나 이상을 함유할 수 있다.The base may contain one or more of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, aqueous ammonia, and tetramethylammonium hydroxide.
킬레이트제는 금속이온에 킬레이트 역할을 하여 과산화수소의 라디칼 생성을 억제하는 기능을 한다. 킬레이트제는 고리 구조를 갖는 이민(imine)계 유기 이온, 및 금속이온과 결합하여 고리 형태의 구조를 이루는 아미노(amino)계 유기 이온 중 어느 하나 이상을 포함할 수 있다. 킬레이트제는 이미노디아세트산(iminodiacetic acid), 니트릴로아세트산(nitrilotriacetic acid), 헥사하이드로-1,3,5-트리아진(hexahydro-1,3,5-triazinane), 디하이드로퀴닌(dihydroquinine), 8-아미노퀴놀린(8-aminoquinoline), o-페난트롤린(o-phenanthroline), 및 o-페닐렌디아민(o-phenylenediamine) 중 둘 이상이 조합된 혼합물일 수 있다.The chelating agent acts as a chelating agent for metal ions and functions to inhibit the generation of radicals of hydrogen peroxide. The chelating agent may include any one or more of imine-based organic ions having a cyclic structure, and amino-based organic ions forming a cyclic structure by bonding with metal ions. Chelating agents iminodiacetic acid, nitrilotriacetic acid, hexahydro-1,3,5-triazinane, dihydroquinine, 8 -Aminoquinoline (8-aminoquinoline), o-phenanthroline (o-phenanthroline), and may be a mixture of two or more of o-phenylenediamine (o-phenylenediamine).
일반적으로 과산화수소는 금속이온 및 불순물에 의해 불안정해지며 산소이온을 방출하고 라디칼을 형성한다. 다량의 금속 물질을 식각하는 공정에서 과산화수소는 급속도로 분해되어 사용시간 단축뿐만 아니라 성능 저하를 유발한다. 본 발명의 실시예에서 킬레이트제가 메탈 이온과 결합하여 이에 의해 과산화수소 분해 반응을 예방한다. 본 발명의 실시예에서 고리 구조를 갖는 이민(imine)계 킬레이트제는 2가 혹은 3가 금속에 대하여 결합할 수 있고 식각을 통해 이온화된 금속과 결합하여 과산화수소의 안정성을 높인다. 또한 본 발명에서 아미노(amino)계 유기이온을 리간드 형성을 통해 이민계 킬레이트제보다 다양한 금속이온과 결합할 수 있어 범용적으로 적용될 수 있으나 첨가할 수 있는 양이 제한적이다.In general, hydrogen peroxide is unstable by metal ions and impurities, and releases oxygen ions and forms radicals. In the process of etching a large amount of metal, hydrogen peroxide is rapidly decomposed, causing not only shortening of use time but also performance degradation. In an embodiment of the present invention, the chelating agent binds to metal ions to thereby prevent hydrogen peroxide decomposition reaction. In an exemplary embodiment of the present invention, an imine-based chelating agent having a cyclic structure can bind to a divalent or trivalent metal and bind to an ionized metal through etching to increase the stability of hydrogen peroxide. In addition, in the present invention, amino-based organic ions can be combined with various metal ions than imine-based chelating agents through ligand formation, and thus can be applied universally, but the amount that can be added is limited.
선택적으로 함유되는 완충제는 pH를 일정 범위로 유지하기 위해 사용된다. 완충제는 특별한 제한 없이 일반적으로 사용되는 것일 수 있으며, 예를 들어 염화암모늄, 질산암모늄 등 무기산 암모늄염이 바람직하다. 이와 달리 나트륨, 칼륨, 리튬 등의 알칼리 금속염이 완충제로 사용될 수도 있으며, 본 발명에서는 알칼리 금속염이 직접 사용되는 것이 바람직하다. 본 발명의 실시예에 따른 식각조성물은 수산화 이온을 필요로 하지만 알칼리 조건보다 산 혹은 중성 조건을 가지는 것이 바람직하다.An optionally contained buffering agent is used to maintain the pH in a certain range. The buffering agent may be generally used without particular limitation, and for example, inorganic acid ammonium salts such as ammonium chloride and ammonium nitrate are preferable. Alternatively, alkali metal salts such as sodium, potassium, and lithium may be used as a buffering agent, and in the present invention, it is preferable that alkali metal salts are used directly. The etching composition according to the exemplary embodiment of the present invention requires hydroxide ions, but it is preferable to have acid or neutral conditions rather than alkaline conditions.
본 발명의 실시예에 따른 식각조성물은 pH가 일반적으로 4.5 내지 10, 바람직하게는 5 내지 7의 범위가 되도록 유지된다. 완충제로 알칼리 금속염이 사용되는 경우 완충제의 농도는 0.01 내지 20 중량%, 바람직하게는 0.02 내지 10 중량%, 더욱 바람직하게는 0.03 내지 5 중량%일 수 있다.The etch composition according to the embodiment of the present invention is maintained so that the pH is generally in the range of 4.5 to 10, preferably 5 to 7. When an alkali metal salt is used as the buffer, the concentration of the buffer may be 0.01 to 20% by weight, preferably 0.02 to 10% by weight, and more preferably 0.03 to 5% by weight.
탈이온수는 다른 구성 성분들을 용해시키는 용매로 작용한다. 탈이온수의 양에 따라 점도, pH 등 물성의 변화가 나타나며, 탈이온수의 양은 전체적인 용해도를 고려하여 적절하게 조절될 수 있다.Deionized water acts as a solvent to dissolve other constituents. Depending on the amount of deionized water, changes in physical properties such as viscosity and pH appear, and the amount of deionized water can be appropriately adjusted in consideration of the overall solubility.
이하에서 실시예 및 비교예를 들어 본 발명을 더 상세히 설명한다. 본 발명은 실시예들에 한정되지 않는다는 것을 인지해야 한다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. It should be appreciated that the invention is not limited to the embodiments.
본 발명의 실시예의 평가는 30℃ 조건을 유지하며 평가 시편을 약액에 침지하는 형태로 진행되었다. 도 1을 참조하면, 평가 시편은 실리콘 웨이퍼(150), 그리고 그 위에 차례로 형성되는 Ti-W 합금 베리어 금속층(110), 구리 씨앗층(120), 구리 재배선층(130) 및 금(Au)(140)을 포함한다.The evaluation of the examples of the present invention was conducted in the form of immersing the evaluation specimen in a chemical solution while maintaining the condition at 30°C. Referring to FIG. 1, the evaluation specimen includes a
실시예1 및 2에서는 과산화수소의 분해를 억제하기 위하여 한 가지 킬레이트제를 첨가하여 사용한 경우에 대한 평가가 이루어졌다. 실시예3 및 4에서는 두 가지 킬레이트제를 조합하여 사용할 경우의 결과를 비교하기 위해 평가가 이루어졌다. 실시예5 및 6에서는 알칼리 금속염의 함량에 따른 결과를 비교하기 위한 평가가 이루어졌다. 실시예1 내지 실시예6은 표1과 같다.In Examples 1 and 2, evaluation was made on the case where one chelating agent was added and used in order to suppress the decomposition of hydrogen peroxide. In Examples 3 and 4, evaluation was made in order to compare the results when the two chelating agents were used in combination. In Examples 5 and 6, evaluation was made to compare the results according to the content of the alkali metal salt. Examples 1 to 6 are shown in Table 1.
(중량%)Hydrogen peroxide
(weight%)
(중량%)Potassium hydroxide
(weight%)
(중량%)Chelating agent/radical inhibitor
(weight%)
(중량%)o-phenanthroline
(weight%)
(중량%)DIW
(weight%)
본 발명의 실시예와의 비교를 위해 다음과 같은 비교예에 따른 식각액 조성물을 제조하여 실험을 하였다. 비교예1 내지 비교예3은 실시예와 동일한 방식으로 평가를 수행하되 다음 표2에 나타난 바와 같이 첨가되는 수산화 이온과 킬레이트제의 양을 2배, 3배로 증가시켜 평가를 진행하였다.For comparison with the examples of the present invention, an etchant composition according to the following comparative example was prepared and tested. In Comparative Examples 1 to 3, evaluation was performed in the same manner as in Examples, but as shown in Table 2 below, the amount of added hydroxide ions and chelating agent was increased by two or three to perform evaluation.
(중량%)Hydrogen peroxide
(weight%)
(중량%)Potassium hydroxide
(weight%)
(중량%)Chelating agent/radical inhibitor
(weight%)
(중량%)o-phenanthroline
(weight%)
(중량%)DIW
(weight%)
상기한 실시예1 내지 실시예6, 비교예1 내지 비교예3에 의해 제조된 식각액을 Ti-W 합금을 베리어 금속층으로 하는 재배선층 공정의 패턴 웨이퍼에서 실험을 진행하였다. 각 식각액의 식각 성능을 평가하기 위해 실리콘 웨이퍼, Ti-W 베리어 금속층, 구리 씨앗층, 구리 재배선층으로 구성된 시편에서 30℃ 조건으로 각각 용액에 침지하였다. 용액 별 하부 실리콘 웨이퍼가 드러날 때까지 침지하였으며 성능에 따른 침지 시간은 상이하게 진행하였다. 이후 탈이온수로 3분 동안 세척하고 질소가스를 이용하여 시편을 건조시켰다. 실시예들 및 비교예들에 따른 각 식각액의 성능을 평가하기 위해 실험 결과를 하기 표3 및 표4에 나타내었다.The etchant prepared in Examples 1 to 6 and Comparative Examples 1 to 3 was tested on a pattern wafer of a redistribution layer process using Ti-W alloy as a barrier metal layer. In order to evaluate the etching performance of each etchant, a specimen composed of a silicon wafer, a Ti-W barrier metal layer, a copper seed layer, and a copper redistribution layer was immersed in each solution at 30°C. Each solution was immersed until the lower silicon wafer was exposed, and the immersion time according to the performance was different. After washing for 3 minutes with deionized water, the specimen was dried using nitrogen gas. In order to evaluate the performance of each etchant according to Examples and Comparative Examples, the experimental results are shown in Tables 3 and 4 below.
상기 표3 및 표4에서 식각률(etch rate)은 Ti-W 합금의 분당 식각 두께를 나타내며 숫자가 클수록 식각 속도가 빠름을 의미한다. 하부침식(under-cut)은 Ti-W 베리어 금속층과 접해있는 구리 씨앗층으로부터 안쪽으로 식각된 깊이를 의미한다. 그 정도의 측정은 Ti-W 합금의 식각이 일어남에 따라 구리 씨앗층과 수직으로 일치하는 지점을 최종 식각 시간이라 정하고, 그 시간으로부터 50%의 시간을 추가하여 식각할 때의 하부침식 깊이를 측정하였다. 안정성은 Ti-W 합금을 식각함에 따라 약액 내 금속이온 농도가 증가하게 되고 과산화수소의 안정성이 떨어짐에 따라 기포발생 및 발연반응이 진행된다. 그 정도는 기호로 표시되었으며, '◎'는 매우 양호(1L 당 4매 이상 처리 시 용액에 기포발생 및 발열반응 시작), '○'는 양호(1L 당 3매 이상 4매 미만 처리 시 용액에 기포발생 및 발열반응 시작), '△'는 보통(1L 당 2매 이상 3매 미만 처리 시 용액에 기포발생 및 발열반응 시작), 'X'는 불량(1L 당 1매 미만 처리 시 용액에 기포발생 및 발열반응 시작)을 나타낸다.In Tables 3 and 4, the etch rate represents the etching thickness per minute of the Ti-W alloy, and the larger the number, the faster the etching rate. Under-cut refers to the depth etched inward from the copper seed layer in contact with the Ti-W barrier metal layer. As the Ti-W alloy is etched, the point vertically coinciding with the copper seed layer is determined as the final etching time, and 50% of the time is added to measure the depth of erosion at the time of etching. I did. As for the stability, as the Ti-W alloy is etched, the concentration of metal ions in the chemical solution increases, and as the stability of hydrogen peroxide decreases, bubbles and fuming reactions proceed. The degree is indicated by a symbol, and'◎' is very good (bubbles are generated in the solution and exothermic reaction starts when 4 or more sheets are processed per 1L), and'○' is good (when processing 3 or more sheets or less than 4 sheets per 1L, the solution is Bubbles are generated and exothermic reaction starts),'△' is normal (bubbles are generated in the solution when 2 or more sheets per 1 L and less than 3 sheets are treated),'X' is poor (bubbles in the solution when less than 1 sheet is processed per 1 L) Occurrence and initiation of an exothermic reaction).
표3을 참고하면, 실시예5 및 실시예6에서 가장 안정적으로 식각이 진행되었지만 실시예5에서는 최종 목표인 하부침식 1 ㎛ 이내의 목표를 달성되지 못했다. 표 3을 참고하여 하부침식이 최초 목표인 1 ㎛ 이내를 달성하고 안정성 측면에서 가장 우수한 실시예6에 첨가되는 수산화이온, 킬레이트제의 양을 2배, 3배로 증가시켜 성능을 비교하였으나, 약액 안정성 측면에서 실시예6이 가장 좋은 결과를 보여줬다.Referring to Table 3, etching was most stably performed in Examples 5 and 6, but in Example 5, the final goal of lower erosion within 1 μm was not achieved. The performance was compared by increasing the amount of hydroxide ions and chelating agents added to Example 6, which is the most excellent in terms of stability, to within 1 μm, which is the initial goal of lower erosion, with reference to Table 3, but chemical solution stability From the side, Example 6 showed the best results.
본 발명의 실시예에 따른 식각액을 통해 Ti-W 필름을 식각한 결과를 도 1 및 도 2에 나타내었다. 도 1은 실험에 사용된 기판의 층 구조 및 식각 후 하부침식을 개념적으로 도시한 도면이며, Ti-W 합금 베리어 금속층(110)의 하부침식(160) 및 구리 씨앗층(120)과 구리 재배선층(130)의 침식(170)이 개념적으로 도시되어 있다. 도 2는 Ti-W 합금 식각액을 통하여 1 ㎛ 이내로 하부침식을 최소화한 주사전자현미경 이미지이다. The results of etching the Ti-W film through the etching solution according to the embodiment of the present invention are shown in FIGS. 1 and 2. 1 is a diagram conceptually showing the layer structure of the substrate used in the experiment and the bottom erosion after etching, the
이상에서 설명한 바와 같이 본 발명의 실시예에 따른 식각액을 이용함으로써 베리어 금속층의 Ti-W 합금에 대한 언더컷을 1 ㎛ 이내로 확보할 수 있으며 그에 따라 제품 불량률을 최소화할 수 있고 최종 제품에 대한 신뢰도를 확보할 수 있다.As described above, by using the etchant according to the embodiment of the present invention, the undercut for the Ti-W alloy of the barrier metal layer can be secured within 1 µm, thereby minimizing product defect rates and securing reliability for the final product. can do.
이상에서 본 발명의 실시예를 설명하였으나, 본 발명의 권리범위는 이에 한정되지 아니하며 본 발명의 실시예로부터 본 발명이 속하는 기술분야에서 통상의 지식을 가진 자에 의해 용이하게 변경되어 균등한 것으로 인정되는 범위의 모든 변경 및 수정을 포함한다.Although the embodiments of the present invention have been described above, the scope of the present invention is not limited thereto, and the embodiments of the present invention are easily changed by those of ordinary skill in the technical field to which the present invention pertains and are recognized as equivalent. It includes all changes and modifications to the extent that it is.
110: Ti-W 합금 베리어 금속층
120: 구리 씨앗층
130: 구리 재배선층
140: 금
150: 실리콘 웨이퍼110: Ti-W alloy barrier metal layer
120: copper seed layer
130: copper redistribution layer
140: gold
150: silicon wafer
Claims (6)
상기 염기는 수산화나트륨, 수산화칼륨, 수산화마그네슘, 수산화칼슘, 암모니아수 및 수산화테트라메틸암모늄 중 하나 이상을 포함하는 반도체 기판 상의 Ti-W 필름을 식각하기 위한 식각조성물.In claim 1,
The base is an etching composition for etching a Ti-W film on a semiconductor substrate containing at least one of sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, aqueous ammonia, and tetramethylammonium hydroxide.
상기 킬레이트제는 이미노디아세트산, 니트릴로아세트산, 헥사하이드로-1,3,5-트리아진, 디하이드로퀴닌, 8-아미노퀴놀린, o-페난트롤린 및 o-페닐렌디아민 중 둘 이상을 포함하는 반도체 기판 상의 Ti-W 필름을 식각하기 위한 식각조성물.In claim 1,
The chelating agent comprises at least two of iminodiacetic acid, nitriloacetic acid, hexahydro-1,3,5-triazine, dihydroquinine, 8-aminoquinoline, o-phenanthroline and o-phenylenediamine. An etching composition for etching a Ti-W film on a semiconductor substrate.
완충제를 더 포함하는 반도체 기판 상의 Ti-W 필름을 식각하기 위한 식각조성물.In claim 1,
An etching composition for etching a Ti-W film on a semiconductor substrate further comprising a buffer.
상기 과산화수소는 25 내지 35 중량%로 함유되고, 상기 염기는 0.02 내지 10 중량%로 함유되며, 상기 킬레이트제 0.05 내지 5 중량%로 함유되는
반도체 기판 상의 Ti-W 필름을 식각하기 위한 식각조성물.In any one of claims 1 to 4,
The hydrogen peroxide is contained in an amount of 25 to 35% by weight, the base is contained in an amount of 0.02 to 10% by weight, and the chelating agent is contained in an amount of 0.05 to 5% by weight.
An etching composition for etching a Ti-W film on a semiconductor substrate.
상기 과산화수소는 28 내지 33 중량%로 함유되고, 상기 염기는 5 내지 7 중량%로 함유되며, 상기 킬레이트제 0.05 내지 1 중량%로 함유되는
반도체 기판 상의 Ti-W 필름을 식각하기 위한 식각조성물.In any one of claims 1 to 4,
The hydrogen peroxide is contained in an amount of 28 to 33% by weight, the base is contained in an amount of 5 to 7% by weight, and the chelating agent is contained in an amount of 0.05 to 1% by weight.
An etching composition for etching a Ti-W film on a semiconductor substrate.
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| CN114854419A (en) * | 2022-04-13 | 2022-08-05 | 华中科技大学 | Alkaline etching solution for wet etching of phase-change material and application thereof |
| WO2022203405A1 (en) | 2021-03-25 | 2022-09-29 | 주식회사 엘지에너지솔루션 | Electrolyte material for all-solid-state battery and all-solid-state battery comprising same |
| CN116083910A (en) * | 2022-12-28 | 2023-05-09 | 湖北兴福电子材料股份有限公司 | Etching solution for titanium or titanium alloy |
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| KR101524782B1 (en) | 2013-11-18 | 2015-06-10 | 주식회사 익스톨 | Aqueous alkali composition with hydrogen peroxide comprising stabilizer for hydrogen peroxide |
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| WO2022203405A1 (en) | 2021-03-25 | 2022-09-29 | 주식회사 엘지에너지솔루션 | Electrolyte material for all-solid-state battery and all-solid-state battery comprising same |
| CN114854419A (en) * | 2022-04-13 | 2022-08-05 | 华中科技大学 | Alkaline etching solution for wet etching of phase-change material and application thereof |
| CN114854419B (en) * | 2022-04-13 | 2023-09-05 | 华中科技大学 | Alkaline etching solution for wet etching of phase-change material and application thereof |
| CN116083910A (en) * | 2022-12-28 | 2023-05-09 | 湖北兴福电子材料股份有限公司 | Etching solution for titanium or titanium alloy |
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