KR20010031136A - Ammonium borate containing compositions for stripping residues from semiconductor substrates - Google Patents

Ammonium borate containing compositions for stripping residues from semiconductor substrates Download PDF

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KR20010031136A
KR20010031136A KR1020007004029A KR20007004029A KR20010031136A KR 20010031136 A KR20010031136 A KR 20010031136A KR 1020007004029 A KR1020007004029 A KR 1020007004029A KR 20007004029 A KR20007004029 A KR 20007004029A KR 20010031136 A KR20010031136 A KR 20010031136A
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wafer
group
ammonium
range
formulation
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윌리암 에이. 요트자크
조지 구안
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바누치 유진 지.
어드밴스드 테크놀러지 머티리얼즈, 인코포레이티드
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    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
    • H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/02—Inorganic compounds
    • C11D7/04—Water-soluble compounds
    • C11D7/10—Salts
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3209—Amines or imines with one to four nitrogen atoms; Quaternized amines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3218—Alkanolamines or alkanolimines
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3281—Heterocyclic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/26—Processing photosensitive materials; Apparatus therefor
    • G03F7/42—Stripping or agents therefor
    • G03F7/422—Stripping or agents therefor using liquids only
    • G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
    • 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
    • H01L21/02041—Cleaning
    • 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
    • H01L21/02041—Cleaning
    • H01L21/02057—Cleaning during device manufacture
    • H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
    • H01L21/02063—Cleaning during device manufacture during, before or after processing of insulating layers the processing being the formation of vias or contact holes
    • C11D2111/22—
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • H01L21/32135—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 vapour etching only
    • H01L21/32136—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 vapour etching only using plasmas

Abstract

본 발명은 할로겐계 플라스마 금속 에칭에 이은 산소 플라스마 에싱으로부터 생기는 웨이퍼 잔류물을 스트리핑하는 제형을 포함한다. 제형은 15내지 60중량%의 유기 아민 또는 아민의 혼합물, 20내지 60중량%의 물, 9내지 20중량%의 사붕산 암모늄 또는 오붕산 암모늄 및 0내지 15중량%의 임의의 극성 유기 용매를 함유한다.The present invention includes formulations for stripping wafer residues resulting from halogen-based plasma metal etching followed by oxygen plasma ashing. The formulation contains 15 to 60% by weight of an organic amine or mixture of amines, 20 to 60% by weight of water, 9 to 20% by weight of ammonium tetraborate or ammonium pentaborate and 0 to 15% by weight of any polar organic solvent do.

Description

반도체 기판으로부터 잔류물을 스트리핑하는 조성물을 함유하는 붕산 암모늄 {AMMONIUM BORATE CONTAINING COMPOSITIONS FOR STRIPPING RESIDUES FROM SEMICONDUCTOR SUBSTRATES}Ammonium borate containing compositions for stripping residues from semiconductor substrates {AMMONIUM BORATE CONTAINING COMPOSITIONS FOR STRIPPING RESIDUES FROM SEMICONDUCTOR SUBSTRATES}

선행 기술은 감광성 내식막(photoresist) 에싱 단계후에 잔류물을 제거하고 웨이퍼를 청소하기 위한 다양한 화학 제형의 이용을 교시한다. 통상적으로는, 이 선행 기술분야의 화학 제형은 원하지 않는 무기 잔류물의 제거를 돕기 위하여 강산 또는 강염기와 같은 강한 시약을 포함한다. 그러나, 이러한 강한 시약은 웨이퍼상에 남아있는 금속 또는 절연층의 원하지 않는 제거를 추가로 일으킬 수 있어서 많은 경우 바람직하지 않다. 따라서, 레지스트 에싱 단계후에 잔류물을 효과적으로 제거하되 의도와는 달리 웨이퍼상에 남아 있어야 하는 섬세한 구조물을 공격하여 잠재적으로는 파괴시키지 않는 화학 제형이 필요하다.The prior art teaches the use of various chemical formulations to remove residues and clean wafers after a photoresist ashing step. Typically, chemical formulations of this prior art include strong reagents such as strong acids or strong bases to help remove unwanted inorganic residues. However, such strong reagents can further cause unwanted removal of metal or insulating layers remaining on the wafer, which is undesirable in many cases. Thus, there is a need for a chemical formulation that effectively removes residues after a resist ashing step but unexpectedly attacks and potentially destroys delicate structures that must remain on the wafer.

본 발명은, 통상적으로는, 반도체 웨이퍼 제조에 사용되는 화학 제형에 관한 것이며, 구체적으로는, 레지스트 플라스마 에싱(ashing) 단계후에 웨이퍼로부터 잔류물을 제거하는데 이용되는 붕산 암모늄 화합물을 포함하는 화학 제형에 관한 것이다.FIELD OF THE INVENTION The present invention relates generally to chemical formulations used in semiconductor wafer fabrication, and specifically to chemical formulations comprising ammonium borate compounds used to remove residues from the wafer after a resist plasma ashing step. It is about.

발명의 요약Summary of the Invention

본 발명은 할로겐계 플라스마 금속 에칭에 이은 산소 플라스마 에싱으로부터 발생하는 웨이퍼 잔류물을 스트리핑하는 제형을 포함한다. 제형은 다음의 통상적인 성분(중량%)을 함유한다.The present invention includes formulations for stripping wafer residues resulting from halogen-based plasma metal etching followed by oxygen plasma ashing. The formulation contains the following conventional ingredients (% by weight).

유기 아민 또는 아민의 혼합물 15-60%Organic amines or mixtures of amines 15-60%

물 20-60%20-60% of water

사붕산 암모늄 또는 오붕산 암모늄 9-20%Ammonium tetraborate or ammonium pentaborate 9-20%

임의의 극성 유기 용매 0-15%Any polar organic solvent 0-15%

바람직한 아민은 다음과 같다.Preferred amines are as follows.

모노에탄올아민(MEA)Monoethanolamine (MEA)

펜타메틸디에틸렌트리아민(PMDETA)Pentamethyldiethylenetriamine (PMDETA)

트리에탄올아민(TEA)Triethanolamine (TEA)

바람직한 제형은Preferred formulations

하나 이상의 바람직한 아민 35-57%One or more preferred amines 35-57%

사붕산 암모늄 10-20%Ammonium tetraborate 10-20%

물 28-49%Water 28-49%

N-메틸피롤리돈 0-15%을 함유한다.N-methylpyrrolidone contains 0-15%.

바람직한 제형의 예는 다음과 같다.Examples of preferred formulations are as follows.

TEA 35.2%TEA 35.2%

사붕산 암모늄 11.4%Ammonium tetraborate 11.4%

물 39%39% of water

N-메틸피롤리돈 14.3%N-methylpyrrolidone 14.3%

MEA 35%MEA 35%

사붕산 암모늄 20%Ammonium tetraborate 20%

물 45%45% of water

본 발명은 플라스마 에싱 단계후에 무기 잔류물을 효과적으로 제거하는데 유리하다.The present invention is advantageous for effectively removing inorganic residues after the plasma ashing step.

본 발명은 플라스마 에싱후에 금속 할라이드 및 금속 산화물 잔류물을 효과적으로 제거하는데 또한 유리하다.The present invention is also advantageous for effectively removing metal halides and metal oxide residues after plasma ashing.

본 발명은 강산 또는 강염기를 함유하지 않고 플라스마 에싱후에 반도체 웨이퍼로부터 무기 잔류물을 효과적으로 제거하는데 더욱 유리하다.The present invention is further advantageous for effectively removing inorganic residues from semiconductor wafers after plasma ashing without containing strong acids or strong bases.

본 기술분야의 숙련가는 하기 바람직한 양태의 상세한 설명을 참조하면 본 발명의 이러한 특성 및 기타 다른 특성과 장점을 이해하게 될 것이다.Those skilled in the art will appreciate these and other features and advantages of the present invention by reference to the following detailed description of the preferred embodiments.

바람직한 양태의 상세한 설명Detailed Description of the Preferred Embodiments

반도체 웨이퍼의 제조에서의 통상적인 단계는 금속화된 층 또는 이 위에 형성된 패턴화된 레지스트 층을 가지는 절연층의 형성을 포함한다. 그리고 나서, 이러한 웨이퍼를 플라스마(예, 할로겐계 플라스마)에 노출시켜서 노출된 금속 또는 절연체를 제거한다. 따라서, 웨이퍼로부터 남이있는 레지스터를 제거하여(통상적으로는, 산소계 플라스마를 사용하여) 플라스마 에싱 단계를 수행한다.Typical steps in the manufacture of semiconductor wafers include the formation of an insulating layer having a metallized layer or a patterned resist layer formed thereon. This wafer is then exposed to plasma (eg, halogen-based plasma) to remove the exposed metal or insulator. Thus, the remaining resistors are removed from the wafer (usually using oxygen-based plasma) to perform the plasma ashing step.

통상적으로는, 이러한 연속적인 단계로 잔류물이 생기게 되어 추가의 제조 단계전에 웨이퍼로부터 제거되어야 한다. 플라스마 에싱 단계후의 잔류물은 주로 금속 할라이드 및 금속 산화물과 같은 무기 화합물로 이루어져 있다.Typically, these successive steps result in residue that must be removed from the wafer before further manufacturing steps. The residue after the plasma ashing step consists mainly of inorganic compounds such as metal halides and metal oxides.

현재, 무기 화합물 잔류물을 제거하기 위한 다양한 화학 제형이 사용되고 있다. 이 제형은, 통상적으로는, 레지스트 플라스마 에싱 기술이 소개되기 전에 사용되었던 과거의 반도체 제조 습식 화학 레지스터 제거 공정으로부터의 잔존물이다. 그래서, 선행 제형은 통상적으로는 잔류물을 제거하기 위하여 강산 또는 강염기를 함유한다. 본 발명은 무기 화합물 잔류물의 제거를 위한 화학 제형을 포함하며, 이 제형은 선행 기술분야 제형의 강산 또는 강염기를 함유하지 않는다.Currently, various chemical formulations are used to remove inorganic compound residues. This formulation is typically a residue from past semiconductor fabrication wet chemical register removal processes that were used before the resist plasma ashing technique was introduced. Thus, prior formulations typically contain strong acids or strong bases to remove residues. The present invention includes chemical formulations for the removal of inorganic compound residues, which do not contain strong acids or strong bases of the prior art formulations.

본 발명은 고밀도 플라스마 금속 에칭에 이은 플라스마 에싱으로부터 생기는 웨이퍼 잔류물을 스트리핑하는 새로운 제형을 포함한다. 제형의 주성분은 아민, 붕산 암모늄 및 물 또는 또 다른 용매이다.The present invention includes new formulations for stripping wafer residues resulting from high density plasma metal etching followed by plasma ashing. The main components of the formulation are amine, ammonium borate and water or another solvent.

바람직한 제형은 하기 통상적인 성분(중량%)을 이용한다.Preferred formulations employ the following conventional ingredients (% by weight).

유기 아민 또는 아민의 혼합물 15-60%Organic amines or mixtures of amines 15-60%

물 20-60%20-60% of water

사붕산 암모늄 또는 오붕산 암모늄 9-20%Ammonium tetraborate or ammonium pentaborate 9-20%

임의의 극성 유기 용매 0-15%Any polar organic solvent 0-15%

바람직한 아민은 다음과 같다.Preferred amines are as follows.

모노에탄올아민(MEA)Monoethanolamine (MEA)

펜타메틸디에틸렌트리아민(PMDETA)Pentamethyldiethylenetriamine (PMDETA)

트리에탄올아민(TEA)Triethanolamine (TEA)

효과적인 다른 아민은 다음과 같다.Other effective amines are as follows.

N-메틸디에탄올아민N-methyldiethanolamine

디글리콜아민Diglycolamine

디에틸에탄올아민Diethylethanolamine

하이드록시에틸모르폴린Hydroxyethyl morpholine

바람직한 제형은Preferred formulations

하나 이상의 바람직한 아민 35-57%One or more preferred amines 35-57%

사붕산 암모늄 10-20%Ammonium tetraborate 10-20%

물 28-49%Water 28-49%

N-메틸피롤리돈 0-15%을 함유한다.N-methylpyrrolidone contains 0-15%.

아민과 함께 금속 킬레이트제로서의 붕산염의 이용은 본 발명의 독특한 특징이다. 이 제형은 우수한 스트리핑 성능을 제공하여 아민 및 다른 킬레이트제를 함유하는 전통적인 제형보다 상당히 낮은 부식성을 제공한다. 붕산염/아민 조합물은 공지되지 않아서 상업적인 스트리퍼에서 이용된 적이 없다.The use of borate salts as metal chelating agents with amines is a unique feature of the present invention. This formulation provides good stripping performance, providing significantly lower corrosiveness than traditional formulations containing amines and other chelating agents. Borate / amine combinations are not known and have never been used in commercial strippers.

바람직한 제형의 예는 다음과 같다.Examples of preferred formulations are as follows.

TEA 35.2%TEA 35.2%

사붕산 암모늄 11.4%Ammonium tetraborate 11.4%

물 39%39% of water

N-메틸피롤리돈 14.3%N-methylpyrrolidone 14.3%

MEA 35%MEA 35%

사붕산 암모늄 20%Ammonium tetraborate 20%

물 45%45% of water

본 발명자들은 밀접하게 관련된 다른 성분들이 바람직한 제형에서 이용된 것과 대등한 성능을 보일 것으로 예측하였다.We predicted that other closely related components would perform comparable to those used in the preferred formulations.

이것은this is

A. 다른 유기 아민이 적합하다고 예측되었고,A. Other organic amines were predicted to be suitable,

B. 다른 극성 유기 용매가 적합하다고 예측되었고,B. Other polar organic solvents were predicted to be suitable,

C. 또한, 계면 활성제, 안정제, 부식 억제제, 완충제 및 보조 용매와 같은 임의의 성분들의 함유가 본 기술분야에서 실시되는 첨가물에 대한 분명한 첨가물을 구성한다고 예측되었다.C. It was also predicted that the inclusion of any ingredients such as surfactants, stabilizers, corrosion inhibitors, buffers and co-solvents constitute a clear addition to the additives practiced in the art.

본 발명의 제형은 염소 또는 불소 함유 플라스마로 에칭된 후에 산소 플라스마 에싱되는 웨이퍼상에서 특히 유용하다. 이러한 유형의 공정에 의해 생성된 잔류물은 통상적으로는 알루미늄 산화물 및 티타늄 산화물과 같은 무기 금속을 함유하며, 이 무기 금속으로 한정되는 것은 아니다. 이러한 잔류물은 종종 효과적인 장치 성능에 요구되는 금속 및 티타늄 질화물의 특징을 손상시킴 없이 완전히 용해시키기가 곤란하다.The formulations of the invention are particularly useful on wafers that are oxygen plasma ashed after being etched with chlorine or fluorine containing plasma. Residues produced by this type of process typically contain inorganic metals such as aluminum oxide and titanium oxide, and are not limited to these inorganic metals. Such residues are often difficult to dissolve completely without compromising the characteristics of the metal and titanium nitrides required for effective device performance.

본 발명의 제형을 사용하여 바이어스를 함유하는 2가지 유형의 상업적으로 생산된 웨이퍼를 평가하였다. 각각의 경우에, 플라스마 에칭 및 에싱후에 웨이퍼를 50내지 60℃에서 30분 동안 제형 욕내에 침지시킨 다음, 탈이온수로 세척하고 질소 기류로 건조시킴으로써 잔류물을 웨이퍼로부터 제거하였다. 발명자들은 자동화된 분무 기구에서 웨이퍼위에 분무후 물 세정에 의해서도 제형을 적용시킬 수 있을 것으로 예측하였다.The formulations of the invention were used to evaluate two types of commercially produced wafers containing bias. In each case, the residue was removed from the wafer by immersing the wafer in the formulation bath at 50 to 60 ° C. for 30 minutes after plasma etching and ashing, then washing with deionized water and drying with a stream of nitrogen. The inventors predicted that the formulation could also be applied by water rinsing after spraying onto wafers in an automated spray apparatus.

실시예 1Example 1

웨이퍼는 직경이 1.6 micron이며, 3층의 바이어스는 티타늄 질화물 상부층(40nm 두께), 실리콘 산화물의 제2층(1.3 microns 두께), 및 알루미늄/구리 합금의 바닥층으로 구성된다. 기판은 실리콘 산화물이다.The wafer is 1.6 microns in diameter, and the three layers of bias consist of a titanium nitride top layer (40 nm thick), a second layer of silicon oxide (1.3 microns thick), and a bottom layer of aluminum / copper alloy. The substrate is silicon oxide.

시험된 제형의 예는 다음과 같다.Examples of formulations tested are as follows.

TEA 35.2%TEA 35.2%

사붕산 암모늄 11.4%Ammonium tetraborate 11.4%

물 39%39% of water

N-메틸피롤리돈 14.3%N-methylpyrrolidone 14.3%

MEA 35%MEA 35%

사붕산 암모늄 20%Ammonium tetraborate 20%

물 45%45% of water

실시예 2Example 2

웨이퍼는 직경이 1 micron이며, 3층의 바이어스는 실리콘 산화물 상부층(7000 angstroms 두께), 티타늄 질화물의 제2층(1200 angstroms 두께), 및 알루미늄의 바닥층으로 구성된다. 기판은 실리콘 산화물이다.The wafer is 1 micron in diameter and the bias of the three layers consists of a silicon oxide top layer (7000 angstroms thickness), a second layer of titanium nitride (1200 angstroms thickness), and a bottom layer of aluminum. The substrate is silicon oxide.

시험된 제형의 예는 다음과 같다.Examples of formulations tested are as follows.

TEA 35.2%TEA 35.2%

사붕산 암모늄 11.4%Ammonium tetraborate 11.4%

물 39%39% of water

N-메틸피롤리돈 14.3%N-methylpyrrolidone 14.3%

MEA 35%MEA 35%

사붕산 암모늄 20%Ammonium tetraborate 20%

물 45%45% of water

본 발명의 제형을 상대적인 스트리핑 효율성 및 부식성에 대하여 평가하였다. 바람직한 제형은 최고점을 기록하였으며 스트리핑 효율성과 낮은 부식성을 기초로 하는 전체적인 성능에서 대략적으로는 동등하였다.The formulation of the invention was evaluated for relative stripping efficiency and corrosion. Preferred formulations scored highest and were approximately equivalent in overall performance based on stripping efficiency and low corrosiveness.

본 발명은 특히 바람직한 양태를 참조로 하여 예시하고 기재하였기 때문에, 본 발명의 숙련가는 본 발명을 이해한 후에 본 발명의 다른 추가의 변형 및 변경을 이해하게 될 것이다. 따라서, 하기 청구항은 본 발명의 사상 및 범위내에 있는 이러한 모든 변형 및 변경을 포함한다.Since the present invention has been illustrated and described with reference to particularly preferred embodiments, those skilled in the art will understand other additional variations and modifications of the invention after understanding the invention. Accordingly, the following claims are intended to cover all such modifications and variations as fall within the spirit and scope of the invention.

Claims (26)

반도체 제조에 있어서 플라스마 에싱후에 사용하기 위한 하기 중량%의 범위로 하기 성분을 포함하는 반도체 웨이퍼 청소 제형.A semiconductor wafer cleaning formulation comprising the following components in the range of the following weight percent for use after plasma ashing in semiconductor manufacturing. 하나 이상의 유기 아민 15-60%One or more organic amines 15-60% 물 20-60%20-60% of water 붕산 암모늄 화합물 9-20%Ammonium Borate Compound 9-20% 제 1항에 있어서, 붕산 암모늄 화합물이 사붕산 암모늄 및 오붕산 암모늄으로 구성된 군으로부터 선택됨을 특징으로 하는 청소 제형.The cleaning formulation of claim 1, wherein the ammonium borate compound is selected from the group consisting of ammonium tetraborate and ammonium pentaborate. 제 1항에 있어서, 0-15중량%의 범위로 극성 유기 용매를 추가로 포함함을 특징으로 하는 청소 제형.The cleaning formulation of claim 1, further comprising a polar organic solvent in the range of 0-15% by weight. 제 2항에 있어서, 0-15중량%의 범위로 극성 유기 용매를 추가로 포함함을 특징으로 하는 청소 제형.3. The cleaning formulation of claim 2, further comprising a polar organic solvent in the range of 0-15% by weight. 제 1항에 있어서, 유기 아민이The method of claim 1 wherein the organic amine is 모노에탄올아민(MEA),Monoethanolamine (MEA), 펜타메틸디에틸렌트리아민(PMDETA) 및Pentamethyldiethylenetriamine (PMDETA) and 트리에탄올아민(TEA)으로 구성된 군으로부터 선택됨을 특징으로 하는 청소 제형.Cleaning formulation, characterized in that it is selected from the group consisting of triethanolamine (TEA). 제 2항에 있어서, 유기 아민이The method of claim 2 wherein the organic amine is 모노에탄올아민(MEA),Monoethanolamine (MEA), 펜타메틸디에틸렌트리아민(PMDETA) 및Pentamethyldiethylenetriamine (PMDETA) and 트리에탄올아민(TEA)으로 구성된 군으로부터 선택됨을 특징으로 하는 청소 제형.Cleaning formulation, characterized in that it is selected from the group consisting of triethanolamine (TEA). 제 3항에 있어서, 유기 아민이The method of claim 3 wherein the organic amine is 모노에탄올아민(MEA),Monoethanolamine (MEA), 펜타메틸디에틸렌트리아민(PMDETA) 및Pentamethyldiethylenetriamine (PMDETA) and 트리에탄올아민(TEA)으로 구성된 군으로부터 선택됨을 특징으로 하는 청소 제형.Cleaning formulation, characterized in that it is selected from the group consisting of triethanolamine (TEA). 제 2항에 있어서, 유기 아민이The method of claim 2 wherein the organic amine is N-메틸디에탄올아민,N-methyldiethanolamine, 디글리콜아민,Diglycolamine, 디에틸에탄올아민 및Diethylethanolamine and 하이드록시에틸모르폴린으로 구성된 군으로부터 선택됨을 특징으로 하는 청소 제형.A cleaning formulation, characterized in that it is selected from the group consisting of hydroxyethyl morpholine. 제 1항에 있어서, 계면 활성제, 안정제, 부식 억제제, 완충제 및 보조 용매로 구성된 군으로부터 선택된 하나 이상의 화합물을 추가로 함유함을 특징으로 하는 청소 제형.The cleaning formulation of claim 1, further comprising at least one compound selected from the group consisting of surfactants, stabilizers, corrosion inhibitors, buffers and auxiliary solvents. 반도체 제조에 있어서 플라스마 에싱후에 사용하기 위한 하기 중량%의 범위로 하기 성분을 포함하는 반도체 웨이퍼 청소 제형.A semiconductor wafer cleaning formulation comprising the following components in the range of the following weight percent for use after plasma ashing in semiconductor manufacturing. TEA 35.2%TEA 35.2% 사붕산 암모늄 11.4%Ammonium tetraborate 11.4% 물 39%39% of water N-메틸피롤리돈 14.3%N-methylpyrrolidone 14.3% 제 10항에 있어서, 계면 활성제, 안정제, 부식 억제제, 완충제 및 보조 용매로 구성된 기로부터 선택된 하나 이상의 성분을 추가로 포함함을 특징으로 하는 청소 제형.The cleaning formulation of claim 10, further comprising at least one component selected from the group consisting of surfactants, stabilizers, corrosion inhibitors, buffers and auxiliary solvents. 반도체 제조에 있어서 플라스마 에싱후에 사용하기 위한 하기 중량%의 범위로 하기 성분을 포함하는 반도체 웨이퍼 청소 제형.A semiconductor wafer cleaning formulation comprising the following components in the range of the following weight percent for use after plasma ashing in semiconductor manufacturing. MEA 35%MEA 35% 사붕산 암모늄 20%Ammonium tetraborate 20% 물 45%45% of water 제 12항에 있어서, 계면 활성제, 안정제, 부식 억제제, 완충제 및 보조 용매로 구성된 기로부터 선택된 하나 이상의 성분을 추가로 포함함을 특징으로 하는 청소 제형.13. The cleaning formulation of claim 12, further comprising at least one component selected from the group consisting of surfactants, stabilizers, corrosion inhibitors, buffers and co-solvents. 웨이퍼의 표면으로부터 금속화된 층을 플라스마 에칭하는 단계,Plasma etching the metallized layer from the surface of the wafer, 금속 에칭 단계 후에 웨이퍼 표면으로부터 레지스트를 플라스마 에싱하는 단계 및Plasma ashing the resist from the wafer surface after the metal etching step; and 하기 중량%의 범위로 하기 성분을 포함하는 화학 제형을 사용하여 웨이퍼를 청소하는 단계를 포함하여 반도체 웨이퍼를 제조하는 방법.Cleaning the wafer using a chemical formulation comprising the following components in the range of the following weight percent: 하나 이상의 유기 아민 15-60%One or more organic amines 15-60% 물 20-60%20-60% of water 붕산 암모늄 화합물 9-20%Ammonium Borate Compound 9-20% 제 14항에 있어서, 붕산 암모늄 화합물이 사붕산 암모늄 및 오붕산 암모늄으로 구성된 군으로부터 선택됨을 특징으로 하는 방법.15. The method of claim 14, wherein the ammonium borate compound is selected from the group consisting of ammonium tetraborate and ammonium pentaborate. 제 14항에 있어서, 0-15중량%의 범위로 극성 유기 용매를 추가로 포함함을 특징으로 하는 방법.15. The method of claim 14, further comprising a polar organic solvent in the range of 0-15% by weight. 제 15항에 있어서, 0-15%의 중량% 범위로 극성 유기 용매를 추가로 포함함을 특징으로 하는 방법.16. The method of claim 15, further comprising a polar organic solvent in the range of 0-15% by weight. 제 14항에 있어서, 유기 아민이The method of claim 14 wherein the organic amine is 모노에탄올아민(MEA),Monoethanolamine (MEA), 펜타메틸디에틸렌트리아민(PMDETA) 및Pentamethyldiethylenetriamine (PMDETA) and 트리에탄올아민(TEA)으로 구성된 군으로부터 선택됨을 특징으로 하는 방법.Triethanolamine (TEA). 제 15항에 있어서, 유기 아민이16. The organic amine of claim 15 wherein the organic amine is 모노에탄올아민(MEA),Monoethanolamine (MEA), 펜타메틸디에틸렌트리아민(PMDETA) 및Pentamethyldiethylenetriamine (PMDETA) and 트리에탄올아민(TEA)으로 구성된 군으로부터 선택됨을 특징으로 하는 방법.Triethanolamine (TEA). 제 16항에 있어서, 유기 아민이The method of claim 16 wherein the organic amine is 모노에탄올아민(MEA),Monoethanolamine (MEA), 펜타메틸디에틸렌트리아민(PMDETA) 및Pentamethyldiethylenetriamine (PMDETA) and 트리에탄올아민(TEA)으로 구성된 군으로부터 선택됨을 특징으로 하는 방법.Triethanolamine (TEA). 제 16항에 있어서, 유기 아민이The method of claim 16 wherein the organic amine is N-메틸디에탄올아민,N-methyldiethanolamine, 디글리콜아민,Diglycolamine, 디에틸에탄올아민 및Diethylethanolamine and 하이드록시에틸모르폴린으로 구성된 군으로부터 선택됨을 특징으로 하는 방법.And hydroxyethyl morpholine. 제 14항에 있어서, 계면 활성제, 안정제, 부식 억제제, 완충제 및 보조 용매로 구성된 군으로부터 선택된 하나 이상의 화합물을 추가로 포함함을 특징으로 하는 방법.15. The method of claim 14, further comprising at least one compound selected from the group consisting of surfactants, stabilizers, corrosion inhibitors, buffers and auxiliary solvents. 웨이퍼의 표면으로부터 금속화된 층을 플라스마 에칭하는 단계,Plasma etching the metallized layer from the surface of the wafer, 금속 에칭 단계 후에 웨이퍼 표면으로부터 레지스트를 플라스마 에싱하는 단계 및Plasma ashing the resist from the wafer surface after the metal etching step; and 하기 중량%의 범위로 하기 성분을 함유하는 화학 제형을 사용하여 웨이퍼를 청소하는 단계를 포함하여 반도체 웨이퍼를 제조하는 방법.Cleaning the wafer using a chemical formulation containing the following components in the range of the following weight percent: TEA 35.2%TEA 35.2% 사붕산 암모늄 11.4%Ammonium tetraborate 11.4% 물 39%39% of water N-메틸피롤리돈 14.3%N-methylpyrrolidone 14.3% 제 23항에 있어서, 계면 활성제, 안정제, 부식 억제제, 완충제 및 보조 용매로 구성된 기로부터 선택된 하나 이상의 성분을 추가로 포함함을 특징으로 하는 방법.The method of claim 23, further comprising one or more components selected from the group consisting of surfactants, stabilizers, corrosion inhibitors, buffers, and auxiliary solvents. 웨이퍼의 표면으로부터 금속화된 층을 플라스마 에칭하는 단계,Plasma etching the metallized layer from the surface of the wafer, 금속 에칭 단계 후에 웨이퍼 표면으로부터 레지스트를 플라스마 에싱하는 단계 및Plasma ashing the resist from the wafer surface after the metal etching step; and 하기 중량%의 범위로 하기 성분을 함유하는 화학 제형을 사용하여 웨이퍼를 청소하는 단계를 포함하여 반도체 웨이퍼를 제조하는 방법.Cleaning the wafer using a chemical formulation containing the following components in the range of the following weight percent: MEA 35%MEA 35% 붕산 암모늄 20%Ammonium Borate 20% 물 45%45% of water 제 25항에 있어서, 제형 19가 계면 활성제, 안정제, 부식 억제제, 완충제 및 보조 용매로 구성된 기로부터 선택된 하나 이상의 성분을 추가로 포함함을 특징으로 하는 방법.The method of claim 25, wherein Formulation 19 further comprises one or more components selected from the group consisting of surfactants, stabilizers, corrosion inhibitors, buffers and co-solvents.
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