KR20210130433A - Etchant composition for seed layer containing copper - Google Patents
Etchant composition for seed layer containing copper Download PDFInfo
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- KR20210130433A KR20210130433A KR1020200048628A KR20200048628A KR20210130433A KR 20210130433 A KR20210130433 A KR 20210130433A KR 1020200048628 A KR1020200048628 A KR 1020200048628A KR 20200048628 A KR20200048628 A KR 20200048628A KR 20210130433 A KR20210130433 A KR 20210130433A
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- etchant composition
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- seed layer
- tetrazole
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- 239000000203 mixture Substances 0.000 title claims abstract description 46
- 239000010949 copper Substances 0.000 title claims abstract description 31
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 28
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000005530 etching Methods 0.000 claims abstract description 44
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 38
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 27
- LRUDIIUSNGCQKF-UHFFFAOYSA-N 5-methyl-1H-benzotriazole Chemical compound C1=C(C)C=CC2=NNN=C21 LRUDIIUSNGCQKF-UHFFFAOYSA-N 0.000 claims abstract description 25
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000012964 benzotriazole Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000003536 tetrazoles Chemical class 0.000 claims abstract description 7
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000003002 pH adjusting agent Substances 0.000 claims description 13
- ULRPISSMEBPJLN-UHFFFAOYSA-N 2h-tetrazol-5-amine Chemical compound NC1=NN=NN1 ULRPISSMEBPJLN-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- MARUHZGHZWCEQU-UHFFFAOYSA-N 5-phenyl-2h-tetrazole Chemical compound C1=CC=CC=C1C1=NNN=N1 MARUHZGHZWCEQU-UHFFFAOYSA-N 0.000 claims description 7
- LQICKCWPFRQEFI-UHFFFAOYSA-N n-methyl-2h-tetrazol-5-amine Chemical compound CNC=1N=NNN=1 LQICKCWPFRQEFI-UHFFFAOYSA-N 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 3
- 238000012545 processing Methods 0.000 abstract description 7
- 230000000052 comparative effect Effects 0.000 description 24
- 235000012431 wafers Nutrition 0.000 description 19
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 12
- 239000004065 semiconductor Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 150000007524 organic acids Chemical class 0.000 description 6
- 230000004888 barrier function Effects 0.000 description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 229910001431 copper ion Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 150000007522 mineralic acids Chemical class 0.000 description 4
- 229960001124 trientine Drugs 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- NSPMIYGKQJPBQR-UHFFFAOYSA-N 4H-1,2,4-triazole Chemical compound C=1N=CNN=1 NSPMIYGKQJPBQR-UHFFFAOYSA-N 0.000 description 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910007637 SnAg Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- 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
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
- H05K3/067—Etchants
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
본 발명은 구리 함유 시드층의 식각액 조성물에 관한 것으로, 좀더 상세하게 설명하자면, 과산화수소 3~8 중량%; 구연산 2~5 중량%; 수산화칼륨, 모노에탄올 아민, 트리에틸렌 테트라민 중에서 선택된 pH 조절제 0.5~2 중량%; 테트라졸, 벤조트리아졸, 5-메틸벤조 트리아졸, 톨릴 트리아졸, 5-아미노 테트라졸, 5-페닐 테트라졸 중에서 선택된 식각조절제 0.01~0.1 중량%; 5-아미노 테트라졸 0.01~0.05 중량%; 그리고 잔량의 물로 이루어져 있어서, 과도한 에칭(etching)으로 인한 사이드 어택(side attack)이나 언더컷(undercut)의 발생을 최소화 할 수 있고, 웨이퍼(wafer)의 처리량이 증가하여도 안정성 및 에칭 성능을 오랫동안 유지할 수 있는 새로운 식각액 조성물에 관한 것이다.The present invention relates to an etchant composition for a copper-containing seed layer, and to be described in more detail, 3 to 8 wt% of hydrogen peroxide; 2-5% by weight of citric acid; 0.5 to 2% by weight of a pH adjusting agent selected from potassium hydroxide, monoethanolamine, and triethylenetetramine; 0.01 to 0.1 wt% of an etch control agent selected from tetrazole, benzotriazole, 5-methylbenzotriazole, tolyl triazole, 5-amino tetrazole, and 5-phenyl tetrazole; 5-amino tetrazole 0.01-0.05% by weight; And since it consists of a residual amount of water, it is possible to minimize the occurrence of side attack or undercut due to excessive etching, and to maintain stability and etching performance for a long time even if the throughput of the wafer is increased. It relates to a novel etchant composition that can be
반도체 장치에서 웨이퍼(wafer) 위에 금속 배선을 형성하는 과정은 일반적으로 스퍼터링 등에 의한 금속막 형성공정과, 포토레지스트의 도포, 노광 및 현상에 의한 포토레지스트 형성공정, 그리고 상기 포토레지스트를 마스크로 하여 선택적인 영역의 금속층만 남기고 나머지 부분을 제거하는 식각공정 등을 포함한다. 이때, 상기 금속층은 예컨대 티타늄(Ti)을 함유하는 배리어층(barrier layer)과, 구리(Cu)를 함유하는 시드층(seed layer)을 포함할 수 있고, 상기 시드층을 선택적으로 제거하기 위하여 특수한 식각액( ‘에칭액’ 또는 ‘부식액’ 이라고도 함)을 사용한다.The process of forming a metal wiring on a wafer in a semiconductor device is generally a process of forming a metal film by sputtering, etc., a process of forming a photoresist by coating, exposure and development of a photoresist, and selecting the photoresist as a mask. It includes an etching process that removes the rest of the metal layer, leaving only the metal layer in the negative area. In this case, the metal layer may include, for example, a barrier layer containing titanium (Ti) and a seed layer containing copper (Cu). An etchant (also called 'etchant' or 'etchant') is used.
최근 반도체의 고집적화 추세에 따라 회로의 패턴(pattern)이 차츰 미세화 되고 있으며, 따라서 상기 시드층에 대한 선택적인 에칭(etching)도 점점 정밀한 작업이 요구되고 있다. 특히 식각 과정에서 구리 패턴에 대한 사이드 어택(side attack)이나 언더컷(undercut), 또는 상기 배리어층과 시드층 사이에서 갈바닉 부식(galvanic corrosion)이 일어나면, 반도체의 기능에 심각한 장애를 초래할 수 있다. 그래서 종래에도 이러한 식각 불량을 최소화 할 수 있는 새로운 식각액 조성물을 개발하려는 노력들이 계속 시도되어 왔다.In accordance with the recent trend of high integration of semiconductors, circuit patterns are gradually being refined, and accordingly, selective etching of the seed layer is also required to be more precise. In particular, when a side attack or undercut on a copper pattern or galvanic corrosion occurs between the barrier layer and the seed layer during the etching process, the function of the semiconductor may be seriously impaired. So, even in the prior art, efforts to develop a new etchant composition capable of minimizing such etching defects have been continuously attempted.
종래에 사용되고 있는 구리 함유 시드층용 식각액 조성물은 과산화수소(H2O2)에 무기산이 포함된 식각액 조성물과, 과산화수소(H2O2)에 유기산이 포함된 식각액 조성물로 구분할 수 있다. 여기서 상기 무기산으로는 주로 인산(phosphoric acid)이 사용되고, 상기 유기산으로는 주로 구연산(citric acid)이 사용된다.Copper seed layer etching liquid composition used in the prior are can be divided into an etching liquid composition comprising an organic acid to the hydrogen peroxide (H 2 O 2) and the etching liquid composition, hydrogen peroxide (H 2 O 2) include a mineral acid in the. Here, phosphoric acid is mainly used as the inorganic acid, and citric acid is mainly used as the organic acid.
예컨대, 공개특허 제10-2017-0079522호(2017년 07월 10일)에는, 과산화수소 1~10 중량%와, 완충액 1~10 중량%, 그리고 무기산 0.3~1.0 중량%를 포함하며, pH가 5~7 인, 구리를 함유하는 금속막의 식각액 조성물이 소개되어 있다. 이러한 무기산계 식각용 조성물은 시드층에 대한 에칭속도가 빠르고, 웨이퍼 처리량이 증가하여도 식각액의 안정성이 오랫동안 유지되는 장점이 있으나, 처리시간이 너무 빠르고, 시드층에서 과도한 언더컷이 발생하여 범프 패턴(bump pattern)이 떨어질 우려가 있다. For example, in Patent Publication No. 10-2017-0079522 (July 10, 2017), 1 to 10% by weight of hydrogen peroxide, 1 to 10% by weight of a buffer, and 0.3 to 1.0% by weight of an inorganic acid, the pH is 5 An etchant composition for a metal film containing ~7 phosphorus, copper is introduced. Such an inorganic acid-based etching composition has advantages in that the etching rate for the seed layer is fast and the stability of the etchant is maintained for a long time even when the wafer throughput is increased, but the processing time is too fast and excessive undercut occurs in the seed layer, so that the bump pattern ( bump pattern) may fall off.
그리고 공개특허 제10-2015-32424호(2015년 03월 26일)에는, 과산화수소 0.1~10 중량%와, 구연산 염을 포함하는 완충액 0.1~10 중량%를 포함하며, pH가 4.0~7.0인, 구리를 함유 하는 금속막의 식각에 사용되는 액체 조성물이 소개되어 있다. And Patent Publication No. 10-2015-32424 No. 10-2015-32424 (March 26, 2015), contains 0.1 to 10% by weight of hydrogen peroxide and 0.1 to 10% by weight of a buffer containing citrate, the pH is 4.0 to 7.0, A liquid composition used for etching a metal film containing copper is introduced.
이러한 유기산계 식각액 조성물은 상기 무기산계 식각액 조성물에 비해 과도한 언더컷이 발생하는 문제는 어느 정도 개선되었으나, 피치가 15㎛ 이하인 미세 패턴에 대한 재배선(RDL) 처리 시에는 여전히 사이드 어택 및 언더컷이 발생하는 문제가 있고, 식각공정의 처리시간을 줄이면 구리 잔사가 남는 불량이 발생할 우려가 있으며 공정 처리시간에 대한 마진(margin)이 적다는 문제점이 있다. The organic acid-based etchant composition has improved the problem of excessive undercutting compared to the inorganic acid-based etchant composition to some extent, but side attack and undercut still occur during redistribution (RDL) processing for fine patterns having a pitch of 15 μm or less. There is a problem, and if the processing time of the etching process is reduced, there is a possibility that a defect in which a copper residue remains may occur, and there is a problem that a margin for the processing time is small.
또한, 식각 대상이 되는 웨이퍼의 처리량, 즉 처리매수가 많아지면, 식각액에 용해되는 구리 이온의 농도가 증가하고 그로 인해 과산화수소가 분해됨으로서 결과적으로 식각액의 안정성이 저하되고 에칭 성능이 저하되는 문제점이 있다.In addition, if the throughput of the wafer to be etched, that is, the number of processing sheets increases, the concentration of copper ions dissolved in the etchant increases, and thus hydrogen peroxide is decomposed. As a result, the stability of the etchant is reduced and the etching performance is reduced .
이에 본 발명이 해결하고자 하는 과제는, 미세한 범프(bump)와 회로 패턴(pattern)이 구비된 반도체 웨이퍼(wafer) 상에서 구리를 함유하는 시드층을 잔사 없이 균일하고 깨끗하게 제거할 수 있고, 과도한 에칭으로 인한 사이드 어택 및 언더컷의 발생을 최소화 할 수 있는 구리 함유 시드층의 식각액 조성물을 제공하는 것이다.Accordingly, the problem to be solved by the present invention is that the seed layer containing copper can be uniformly and cleanly removed without residue on a semiconductor wafer having fine bumps and circuit patterns, and can be etched through excessive etching. To provide an etchant composition for a copper-containing seed layer capable of minimizing the occurrence of side attack and undercut due to the side attack.
또한 본 발명이 해결하고자 하는 다른 과제는, 웨이퍼의 처리량이 증가하여도 안정성 및 에칭 성능이 오랫동안 유지되는 구리 함유 시드층의 식각액 조성물을 제공하는 것이다.Another problem to be solved by the present invention is to provide an etchant composition for a copper-containing seed layer in which stability and etching performance are maintained for a long time even when the throughput of the wafer is increased.
본 발명에 따른 구리 함유 시드층의 식각액 조성물은, 과산화수소 3~8 중량%; 구연산 2~5 중량%; 수산화칼륨, 모노에탄올 아민, 트리에틸렌 테트라민 중에서 선택된 pH 조절제 0.5~2 중량%; 테트라졸, 벤조트리아졸, 5-메틸벤조 트리아졸, 톨릴 트리아졸, 5-메틸아미노 테트라졸, 5-페닐 테트라졸 중에서 선택된 식각조절제 0.01~0.1 중량%; 5-아미노 테트라졸 0.01~0.05 중량%; 그리고 잔량의 물 로 이루어지는 것을 특징으로 한다.The etchant composition of the copper-containing seed layer according to the present invention includes 3 to 8 wt% of hydrogen peroxide; 2-5% by weight of citric acid; 0.5 to 2% by weight of a pH adjusting agent selected from potassium hydroxide, monoethanolamine, and triethylenetetramine; 0.01 to 0.1 wt% of an etch control agent selected from tetrazole, benzotriazole, 5-methylbenzotriazole, tolyl triazole, 5-methylamino tetrazole, and 5-phenyl tetrazole; 5-amino tetrazole 0.01-0.05% by weight; And it is characterized in that it consists of the remaining amount of water.
본 발명의 바람직한 실시예에 따른 구리 함유 시드층의 식각액 조성물은, 과산화수소 5 중량%; 구연산 2.2 중량%; 모노에탄올 아민 0.9 중량%; 5-메틸벤조 트리아졸 0.05 중량%; 5-아미노 테트라졸 0.01 중량%; 그리고 잔량의 물로 이루어지고, pH가 4.0인 것을 특징으로 한다.The etchant composition of the copper-containing seed layer according to a preferred embodiment of the present invention comprises: 5 wt% of hydrogen peroxide; 2.2% by weight of citric acid; 0.9% by weight of monoethanolamine; 0.05% by weight of 5-methylbenzotriazole; 0.01% by weight of 5-amino tetrazole; And it consists of a residual amount of water, characterized in that the pH is 4.0.
본 발명에 따른 구리 함유 시드층의 식각액 조성물은, 과도한 에칭으로 인한 사이드 어택이나 언더컷의 발생을 억제하여 반도체 제조공정상 시간적 마진을 안정적으로 확보함으로써 반도체 집적회로의 생산수율을 개선할 수 있는 효과가 있다. The etchant composition of the copper-containing seed layer according to the present invention suppresses the occurrence of side attacks or undercuts due to excessive etching, thereby stably securing a temporal margin in the semiconductor manufacturing process, thereby improving the production yield of semiconductor integrated circuits. .
또한 본 발명에 따른 식각액 조성물은, 웨이퍼의 처리량이 증가하여도 과산화수소의 분해율이 적고 식각액의 안정성과 에칭 성능이 통상적인 식각액에 비해 3배 정도 유지되기 때문에 반도체 집적회로를 제조하는데 소요되는 비용을 크게 절감할 수 있는 효과가 있다.In addition, the etchant composition according to the present invention has a low decomposition rate of hydrogen peroxide even when the processing amount of the wafer is increased, and the stability and etching performance of the etchant are maintained three times compared to a conventional etchant, so the cost required for manufacturing a semiconductor integrated circuit is greatly increased There is a saving effect.
이하, 첨부한 도면을 이용하여 본 발명을 상세하게 설명한다. 다만, 첨부 도면은 본 발명의 바람직한 실시예를 예시한 것이므로 이들 실시예에 의해서 본 발명의 권리범위가 제한되는 것은 아니다. 또한 본 발명을 실시하는데 꼭 필요한 구성이라 하더라도 종래기술에 소개되어 있거나, 통상의 기술자가 공지기술로부터 용이하게 실시할 수 있는 사항에 대해서는 구체적인 설명을 생략한다.Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. However, since the accompanying drawings illustrate preferred embodiments of the present invention, the scope of the present invention is not limited by these embodiments. In addition, even if it is a necessary configuration for carrying out the present invention, a detailed description of the matters introduced in the prior art or that can be easily implemented by those skilled in the art from the known technology will be omitted.
본 발명의 식각액 조성물의 작용 및 효과를 이해하기 위해서는 본 발명의 식각액 조성물이 사용되는 반도체 제조공정을 충분히 이해해야 하는데, 이점에 대해서는 앞서 배경기술로 소개한 공개특허 제10-2015-32424호 및 공개특허 제10-2017-0079522호 등에 소상하게 설명되어 있으므로 본 발명에서는 구체적인 설명을 생략한다.In order to understand the action and effect of the etchant composition of the present invention, it is necessary to fully understand the semiconductor manufacturing process in which the etchant composition of the present invention is used. Since it is described in detail in No. 10-2017-0079522 and the like, a detailed description thereof will be omitted in the present invention.
본 발명에 따른 식각액 조성물은 미세회로용 구리 함유 시드층을 에칭하는 데 사용되는 것으로, 과산화수소와, 구연산, pH 조절제, 식각조절제, 5-아미노 테트라졸, 그리고 잔량의 물을 포함하여 구성되며, pH는 3.5~4.5이다.The etchant composition according to the present invention is used to etch a copper-containing seed layer for microcircuits, and comprises hydrogen peroxide, citric acid, a pH adjuster, an etchant adjuster, 5-amino tetrazole, and the remainder of water, the pH is 3.5 to 4.5.
먼저 과산화수소(H2O2)는 산화제로서 반도체 웨이퍼 상에서 마스크 밖으로 노출되는 시드층(seed layer)에 포함되어 있는 구리(Cu)를 산화시키는 기능을 한다. 그래서 상기 식각액과 접촉하는 시드층의 표면에는 산화구리막(CuO)이 형성된다.First, hydrogen peroxide (H 2 O 2 ) is an oxidizing agent and functions to oxidize copper (Cu) included in a seed layer exposed outside a mask on a semiconductor wafer. Therefore, a copper oxide film (CuO) is formed on the surface of the seed layer in contact with the etchant.
본 발명의 식각액 조성물에서 과산화수소의 함량이 3 중량% 미만이면 구리에 대한 산화력이 미약하여 에칭 성능이 감소하고, 반대로 8 중량%를 초과하면 구리 대한 산화력이 너무 강해지고 에칭 속도가 증가하여 범프 구조상에서 구리 시드층에 대한 사이드 어택 및 언더컷이 발생하는 문제가 있다. If the content of hydrogen peroxide in the etchant composition of the present invention is less than 3% by weight, the oxidizing power to copper is weak and the etching performance is reduced. There is a problem in that a side attack and undercut to the copper seed layer occur.
다음으로 구연산은 유기산으로서, 실질적으로 산화된 시드층을 부식시켜서 제거하는 기능을 한다. 본 발명에서 상기 구연산의 함량이 2 중량% 미만이면 pH 조절제와 중화 반응 후 남는 유기산의 농도가 너무 낮아져서, 산화된 시드층의 표면에 대한 에칭 불량이 발생하는 문제가 있고, 5 중량%를 초과하면 에칭 속도가 너무 증가하여 사이드 어택 및 언더컷이 발생하는 문제가 있다. Next, citric acid is an organic acid, which substantially corrodes and removes the oxidized seed layer. In the present invention, when the content of the citric acid is less than 2% by weight, the concentration of the organic acid remaining after the neutralization reaction with the pH adjuster is too low, so there is a problem that etching defect occurs on the surface of the oxidized seed layer, and when it exceeds 5% by weight There is a problem in that the etching rate is increased too much to cause side attack and undercut.
다음으로 pH 조절제는 본 발명에 따른 식각액 조성물의 pH를 조절하여 상기 시드층이 제거될 때 배리어층과 시드층 사이에서 일어나는 갈바닉 부식(galvanic corrosion)을 억제하는 기능을 한다.Next, the pH adjuster controls the pH of the etchant composition according to the present invention to inhibit galvanic corrosion occurring between the barrier layer and the seed layer when the seed layer is removed.
상기 pH 조절제의 함량이 0.5 중량% 미만이면, 식각액 조성물의 pH가 너무 낮아져서 에칭 속도가 증가하여 갈바닉 부식이 발생할 우려가 있고, 반대로 2 중량%를 초과하면 에칭 속도가 감소하여 충분한 에칭이 달성되지 않을 우려가 있다. If the content of the pH adjuster is less than 0.5% by weight, the pH of the etchant composition is too low to increase the etching rate to cause galvanic corrosion, and conversely, if it exceeds 2% by weight, the etching rate is reduced and sufficient etching may not be achieved. There are concerns.
상기 pH 조절제로는, 수산화칼륨(KOH), 모노에탄올 아민(MEA), 트리에틸렌 테트라민(TETA) 중에서 선택된 어느 하나 이상을 사용할 수 있고, 이중에서 모노에탄올 아민(MEA)이 가장 바람직하다. As the pH adjusting agent, any one or more selected from potassium hydroxide (KOH), monoethanol amine (MEA), and triethylene tetramine (TETA) may be used, and among them, monoethanol amine (MEA) is most preferred.
다음으로 상기 식각조절제는, 식각 속도를 억제하여 구리 패턴에 대한 사이드 어택이나 언더컷을 방지하는 기능을 하는 것으로, 테트라졸, 벤조 트리아졸(BTA), 5-메틸벤조 트리아졸(5-MBTA), 톨릴 트리아졸(TTZ), 5-메틸아미노 테트라졸(5-MTZ), 5-페닐 테트라졸(5-PTZ) 중에서 선택된 어느 하나를 사용할 수 있고, 이 중에서 5-메틸벤조 트리아졸(5-MBTA)이 가장 바람직하다.Next, the etch control agent functions to prevent side attack or undercut on the copper pattern by suppressing the etch rate, tetrazole, benzotriazole (BTA), 5-methylbenzotriazole (5-MBTA), Any one selected from tolyl triazole (TTZ), 5-methylamino tetrazole (5-MTZ), and 5-phenyl tetrazole (5-PTZ) may be used, and among these, 5-methylbenzotriazole (5-MBTA) ) is most preferred.
상기 식각조절제의 함량이 0.01 중량% 미만이면, 구리 패턴에 대한 사이드 어택이나 언더컷이 발생할 우려가 없고, 반대로 0.1 중량% 초과하면 구리 시드층에 대한 에칭 불량이 발생할 우려가 있다. If the content of the etch control agent is less than 0.01 wt %, there is no fear of side attack or undercut on the copper pattern, and on the contrary, if it exceeds 0.1 wt %, there is a risk of poor etching of the copper seed layer.
마지막으로 상기 5-아미노 테트라졸은, 구리 패턴에 대한 사이드 어택과 언더컷의 발생을 억제함과 동시에, 특히 식각액 조성물의 안정성을 오랫동안 유지하는 기능을 한다. 일반적으로 식각액 조성물은 웨이퍼 처리량이 증가함에 따라 구리 이온의 농도가 점점 높아지게 되고, 이러한 구리 이온이 과산화수소를 분해함으로써 에칭능력이 점차 저해시키게 된다. Lastly, the 5-amino tetrazole functions to suppress the occurrence of side attacks and undercuts on the copper pattern and, in particular, to maintain stability of the etchant composition for a long time. In general, in the etching solution composition, the concentration of copper ions gradually increases as the wafer throughput increases, and the copper ions decompose hydrogen peroxide, thereby gradually inhibiting the etching ability.
그런데 본 발명에서는 상기 5-아미노 테트라졸에 포함되어 있는 질소(N) 분자가 식각 과정에서 식각액 속으로 용해되어 나오는 구리 이온과 배위결합 하여 상기 과산화수소의 분해를 방지함으로써 식각액 자체의 안정성 및 에칭 능력을 오랫동안 유지시켜 주는 기능을 한다. However, in the present invention, the nitrogen (N) molecules contained in the 5-aminotetrazole are coordinated with copper ions that are dissolved into the etchant during the etching process to prevent the decomposition of the hydrogen peroxide, thereby improving the stability and etching ability of the etchant itself. It functions to keep it for a long time.
상기 5-아미노 테트라졸의 함량이 0.01 중량% 미만이면, 웨이퍼 처리량이 증가함에 따라 식각액의 안정성이 저하되는 문제가 있고, 0.05 중량% 초과하면 구리 시드층에 대한 에칭 불량이 발생할 우려가 있다If the content of 5-amino tetrazole is less than 0.01 wt %, there is a problem in that the stability of the etchant decreases as the wafer throughput increases, and if it exceeds 0.05 wt %, there is a risk of poor etching of the copper seed layer.
본 발명에 따른 식각액 조성물은 상기 과산화수소와, 구연산, pH 조절제, 식각조절제 및 5-아미노 테트라졸에 더하여 추가적으로 그 잔량(중량%)에 해당하는 물을 포함한다. The etching solution composition according to the present invention includes hydrogen peroxide, citric acid, a pH control agent, an etching control agent, and water corresponding to the remaining amount (wt%) in addition to 5-amino tetrazole.
이하, 본 발명에 대한 실시예 및 비교예를 들어보면 다음과 같다.Hereinafter, examples and comparative examples for the present invention are given as follows.
[실시예][Example]
다음 [표 1] 와 같은 구성성분 및 함량에 따라 본 발명에 따른 식각액 조성물을 제조하였다. 제조방법은 반응기에다 먼저 식각조절제와 5-ATZ를 투입하고, 이어서 과산화수소(H2O2)를 투입 및 교반하여 상기 식각조절제와 5-ATZ를 용해한 다음, 구연산과 잔량(중량%)의 정제수를 투입하고, 마지막으로 pH 조절제를 투입한 후 충분히 교반하였다.An etchant composition according to the present invention was prepared according to the components and contents shown in Table 1 below. In the manufacturing method, an etch control agent and 5-ATZ are first added to the reactor, and then hydrogen peroxide (H 2 O 2 ) is added and stirred to dissolve the etch control agent and 5-ATZ, and then citric acid and purified water of the remaining amount (wt%) and finally, a pH adjuster was added, followed by sufficient stirring.
상기 [ 표 1 ]에 기재된 약자의 의미는 다음과 같다.The meanings of the abbreviations in [Table 1] are as follows.
- MEA : 모노에탄올 아민(Mono ethanol amine) - MEA: Mono ethanol amine
- KOH : 수산화칼륨- KOH: potassium hydroxide
- TETA: 트리에틸렌 테트라민(Triethylene tetramine) - TETA: Triethylene tetramine
- 5-MBTA : 5-메틸 벤조트리아졸(5-methyl benzotriazole)- 5-MBTA: 5-methyl benzotriazole
- TTZ : 톨릴 트리아졸(Tolyl triazole) - TTZ: Tolyl triazole
- BTA : 벤조 트리아졸(Benzo triazole) - BTA: Benzo triazole
- 5-MTZ : 5-메틸아미노 테트라졸(5-methyl amino tetrazole)- 5-MTZ : 5-methyl amino tetrazole
- 5-PTZ : 5-페닐 테트라졸(5-phenyl tetrazole)- 5-PTZ: 5-phenyl tetrazole
- 5-ATZ : 5-아미노 테트라졸(5-amino tetrazole)- 5-ATZ: 5-amino tetrazole
[비교예][Comparative example]
다음 [표 2] 와 같은 구성성분 및 함량에 따라 비교예로서의 식각액 조성물을 제조하였다. 제조방법은 상기 실시예와 동일하다. An etchant composition as a comparative example was prepared according to the components and contents shown in Table 2 below. The manufacturing method is the same as in the above embodiment.
상기 [표 2]에서 비교예 12의 pH 조절제로 사용된 ‘PEHA’은 Penta ethylene hexamine의 약자이다. In [Table 2], 'PEHA' used as the pH adjuster of Comparative Example 12 is an abbreviation of penta ethylene hexamine.
[성능시험 및 평가][Performance test and evaluation]
상기 실시예 및 비교예에 따라 제조된 식각액 조성물에 대하여 다음과 같은 방법으로 에칭성능을 시험하였다.Etching performance was tested in the following manner with respect to the etchant compositions prepared according to the Examples and Comparative Examples.
1) 에칭 성능 시험1) Etching performance test
Ni-SnAg의 구조인 범프가 형성되어 있고, 상기 범프의 하부 전극막은 배리어층과 시드층을 포함하는 웨이퍼를 준비한다. 상기 배리어층은 실리콘을 함유하고, 상기 시드층은 구리를 포함한다. 상기 웨이퍼를 약 2cm×2cm 크기로 잘라 준비하고, 상기 실시예 및 비교예에 따라 제조된 식각액 조성물에다 각각 상기 웨이퍼를 침지한 다음, 30℃의 온도에서 초당 1회 왕복 스윙(swing) 하면서 상기 시드층이 제거되는 시점을 육안 및 금속현미경으로 확인하였다. 시험 결과, 45초 이내에 시드층이 완전히 제거되면 ‘○’으로 평가하고, 45~50초 이면 ‘△’, 그리고 50초를 초과하면 ‘×’로 평가하였다.A wafer having a Ni-SnAg structure is formed, and the lower electrode layer of the bump includes a barrier layer and a seed layer. The barrier layer contains silicon and the seed layer contains copper. Prepare the wafer by cutting it into a size of about 2 cm × 2 cm, immersing the wafer in the etchant composition prepared according to the Examples and Comparative Examples, respectively, and then swinging the wafer once per second at a temperature of 30° C. while reciprocating the seed The time point at which the layer was removed was confirmed with the naked eye and a metallographic microscope. As a result of the test, if the seed layer was completely removed within 45 seconds, it was evaluated as ‘○’, if it was 45-50 seconds, it was evaluated as ‘△’, and if it exceeded 50 seconds, it was evaluated as ‘×’.
2) 언더컷 시험2) Undercut test
상기 에칭 시험에 사용된 웨이퍼들에 대하여 주사전자 현미경(FE-SEM)으로 사이드 어택 및 언더컷의 발생 정도를 측정하였다. 측정 결과, Sp Cu가 제거된 시점을 기준으로 처리시간을 2배로 하였을 때, 편측 기준 0.3 ㎛ 이내이면 ‘○’으로 평가하고, 0.3~0.4 ㎛ 이면 ‘△’, 0.4 ㎛를 초과하면 ‘×’ 로 평가하였다.With respect to the wafers used in the etching test, the degree of occurrence of side attack and undercut was measured with a scanning electron microscope (FE-SEM). As a result of the measurement, when the treatment time is doubled based on the time when Sp Cu is removed, it is evaluated as '○' if it is within 0.3 µm of one side, 'Δ' if it is 0.3 to 0.4 µm, and '×' if it exceeds 0.4 µm. was evaluated as
3) 안정성 시험3) Stability test
상기 식각액 조성물에다 각각 구리(Cu)를 1000ppm의 농도로 용해하고, 30℃의 온도에서 하루 동안 방치한 다음, 과산화수소의 농도 변화와, 시드층 에칭능력 및 언더컷 발생정도를 시험 초기, 즉 방치 이전의 상태와 비교하였다. Each copper (Cu) was dissolved at a concentration of 1000 ppm in the etchant composition, left at a temperature of 30 ° C. for one day, and then the change in the concentration of hydrogen peroxide, the seed layer etching ability and the degree of undercutting were measured at the beginning of the test, that is, before leaving. status was compared.
시험 결과, 상기 식각액 조성물을 하루 동안 방치한 이후에도 시험 초기의 식각액 조성물에 비해 별다른 변화가 없으면 ‘○’으로 평가하고, 시험 초기에 비해 과산화수소의 농도 및 시드층 에칭능력이 저하되거나, 언더컷 불량이 발생하였으면 ‘×’로 평가하였다.As a result of the test, even after leaving the etchant composition for one day, if there is no significant change compared to the etchant composition at the beginning of the test, it is evaluated as '○', and the concentration of hydrogen peroxide and the etching ability of the seed layer are lowered compared to the initial stage of the test, or undercut defects occur If yes, it was evaluated as 'x'.
4) 시험 결과4) Test results
상기 시험항목에 대한 평가결과를 각 식각액 조성물의 pH와 함께 다음 [표 3] 및 [표 4]에 각각 수록하였다. The evaluation results for the test items were recorded in the following [Table 3] and [Table 4] together with the pH of each etchant composition, respectively.
상기 [표 3] 및 [표 4]에서 보는 바와 같이, 본 발명의 실시예에 따른 식각액 조성물은 비교예의 식각액 조성물에 비해, 구리함유 시드층에 대한 에칭 능력이 우수하고, 사이드 어택 및 언더컷의 발생이 거의 없으며, 나아가 웨이퍼의 처리량이 증가하여도 식각액의 안정성이 훨씬 우수한 것으로 나타났다. As shown in [Table 3] and [Table 4], the etchant composition according to the embodiment of the present invention has excellent etching ability for the copper-containing seed layer, compared to the etchant composition of the comparative example, and occurrence of side attack and undercut It was found that the stability of the etchant was much better even when the throughput of the wafer was increased.
특히 일반적인 식각액 조성물의 경우, 12인치 웨이퍼의 처리량이 약 100매/40L 정도인데 비해, 본 발명의 식각액 조성물은 12인치 웨이퍼의 처리량이 약 300매/40L 정도로서 종래 식각액에 비해 웨이퍼 처리량 및 식각액의 안정성이 약 3배 정도 개선된 것으로 확인되었다. In particular, in the case of a typical etchant composition, the throughput of a 12-inch wafer is about 100 sheets/40L, whereas the etchant composition of the present invention has a throughput of about 300 sheets/40L for a 12-inch wafer, compared to the conventional etchant, the wafer throughput and stability of the etchant It was confirmed that this improved about 3 times.
Claims (4)
3 to 8% by weight of hydrogen peroxide; 2-5% by weight of citric acid; 0.5 to 2% by weight of a pH adjusting agent selected from potassium hydroxide, monoethanolamine, and triethylenetetramine; 0.01 to 0.1 wt% of an etching modifier selected from tetrazole, benzotriazole, 5-methylbenzotriazole, tolyl triazole, 5-methylamino tetrazole, and 5-phenyl tetrazole; 5-amino tetrazole 0.01-0.05% by weight; And the etchant composition of the copper-containing seed layer, characterized in that consisting of the remaining amount of water.
The etchant composition of claim 1 , wherein the pH adjusting agent is monoethanolamine, and the pH is 3.5 to 4.5.
The etchant composition of claim 1 or 2, wherein the etch control agent is 5-methylbenzotriazole.
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