KR20130077699A - Cmp slurry composition and polishing method using the same - Google Patents
Cmp slurry composition and polishing method using the same Download PDFInfo
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- KR20130077699A KR20130077699A KR1020110146562A KR20110146562A KR20130077699A KR 20130077699 A KR20130077699 A KR 20130077699A KR 1020110146562 A KR1020110146562 A KR 1020110146562A KR 20110146562 A KR20110146562 A KR 20110146562A KR 20130077699 A KR20130077699 A KR 20130077699A
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- slurry composition
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- cmp slurry
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- 238000000034 method Methods 0.000 title claims abstract description 18
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- 150000004706 metal oxides Chemical class 0.000 claims abstract description 27
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- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000004065 semiconductor Substances 0.000 claims abstract description 8
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- 239000004473 Threonine Substances 0.000 claims description 3
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 3
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- 235000004279 alanine Nutrition 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- ODKSFYDXXFIFQN-UHFFFAOYSA-N arginine Natural products OC(=O)C(N)CCCNC(N)=N ODKSFYDXXFIFQN-UHFFFAOYSA-N 0.000 claims description 3
- 235000003704 aspartic acid Nutrition 0.000 claims description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 3
- 229960003237 betaine Drugs 0.000 claims description 3
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- ZDXPYRJPNDTMRX-UHFFFAOYSA-N glutamine Natural products OC(=O)C(N)CCC(N)=O ZDXPYRJPNDTMRX-UHFFFAOYSA-N 0.000 claims description 3
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 3
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- COLNVLDHVKWLRT-UHFFFAOYSA-N phenylalanine Natural products OC(=O)C(N)CC1=CC=CC=C1 COLNVLDHVKWLRT-UHFFFAOYSA-N 0.000 claims description 3
- ZDXPYRJPNDTMRX-VKHMYHEASA-N L-glutamine Chemical compound OC(=O)[C@@H](N)CCC(N)=O ZDXPYRJPNDTMRX-VKHMYHEASA-N 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 abstract description 26
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- 229960005261 aspartic acid Drugs 0.000 description 6
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- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 101100107923 Vitis labrusca AMAT gene Proteins 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
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- 235000001014 amino acid Nutrition 0.000 description 2
- 150000001413 amino acids Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
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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
- H01L21/04—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
- H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
- H01L21/304—Mechanical treatment, e.g. grinding, polishing, cutting
-
- 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
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
- C09K3/1409—Abrasive particles per se
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- 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
- C09K3/00—Materials not provided for elsewhere
- C09K3/14—Anti-slip materials; Abrasives
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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
- H01L21/04—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
- H01L21/3105—After-treatment
- H01L21/31051—Planarisation of the insulating layers
- H01L21/31053—Planarisation of the insulating layers involving a dielectric removal step
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- Condensed Matter Physics & Semiconductors (AREA)
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- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
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- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
Description
본 발명은 CMP 슬러리 조성물 및 이를 이용한 연마 방법에 관한 것으로서, 더욱 구체적으로는 양의 제타값을 갖는 금속 산화물 입자, 양쪽 이온성 화합물, 및 양이온성 계면활성제를 포함하는 CMP 슬러리 조성물 및 이를 이용한 연마 방법에 관한 것이다.
The present invention relates to a CMP slurry composition and a polishing method using the CMP slurry composition. More specifically, the present invention relates to a CMP slurry composition comprising a metal oxide particle having a positive zeta value, an ionic compound, and a cationic surfactant, .
최근의 초대규모 집적회로(ULSI)에서 미세 가공 기술이 개발되고 있어, 20 나노의 디자인 룰(rule)이 실현되고 있다. CMP 기술은 반도체 장치의 제조 공정에 있어서, PR(Photoresist)이 도포되어 노광이 진행되는 층을 평탄화하여 노광에 의한 패턴의 정밀도를 향상함으로써 최종적으로는 수율을 안정화시킬 수 있는 중요한 기술로 각광받고 있다. 특히 소자 분리의 STI(Shallow trench isolation) 공정은 가장 정밀한 디자인이 적용되는 반도체 가공의 최초 단계이기 때문에 STI 공정 후의 평탄화는 소자 형성의 핵심이라고 할 수 있다.Recently, micromachining technology has been developed in a very large scale integrated circuit (ULSI), and a design rule of 20 nanometers is being realized. In the manufacturing process of semiconductor devices, CMP technology has been spotlighted as an important technology that can stabilize the yield by finally flattening the layer on which exposure is applied by applying PR (Photoresist) to improve the precision of the pattern by exposure. . In particular, the shallow trench isolation (STI) process for device isolation is the first step in semiconductor fabrication to which the most precise design is applied. Therefore, planarization after the STI process can be said to be the core of device formation.
그 중에서 세리아 입자를 포함하는 CMP 슬러리는 GATE 생성 자리에 STI 패턴 마스크로 300~500Å의 두께로 적층되는 질화 실리콘 (Si3N4)과 분리(Trench isolation) 영역과 질화 실리콘 위로 적층(deposioton)된 실리콘 산화막(SiO2) 간의 연마 속도 선택성을 조절하는 주요 소재로 각광받고 있다.Among them, the CMP slurry containing ceria particles is formed by depositing silicon nitride (Si 3 N 4 ) and silicon nitride (Si 3 N 4 ) layers stacked at a thickness of 300-500 Å in an STI pattern mask at the GATE generation site, Has been attracting attention as a main material for controlling the polishing rate selectivity between silicon oxide films (SiO 2 ).
도 1은 STI 공정을 도시한 것이다. STI 공정에서 소자 생성 자리에 질화막 마스크가 도포되고 소자 분리를 위하여 트렌치(Trench)에 채워지는 산화물은 완전한 충진을 위하여 질화막 위로 7,000Å까지 과적층(Over deposition)되기도 한다.Figure 1 shows an STI process. In the STI process, a nitride mask is applied to a device generation site, and an oxide filled in a trench for device isolation may be over-deposited up to 7,000Å over the nitride film for complete filling.
이때 질화막 위로 적층된 산화막과 2,000~2,500Å의 트렌치에 과적층되는 산화막 간에는 2,000~3,000Å의 단차가 발생한다. 따라서 STI CMP는 질화막 위의 과적층 산화막(볼록부)과 트렌치 상의 산화막(오목부)간의 단차를 제거하는 1차 연마, 질화막 상의 산화물을 제거하는 2차 연마, 및 질화막 위의 잔류 산화막을 완전 제거하기 위하여 과연마(overpolishing)하는 3차 연마의 세 단계로 이루어지고 있다(도1).At this time, a step of 2,000 to 3,000 angstroms occurs between the oxide film stacked over the nitride film and the oxide film over-deposited on the trench of 2,000 to 2,500 angstroms. Therefore, the STI CMP can be used for the first polishing that removes the step between the overburden oxide film (convex portion) on the nitride film and the oxide film (concave portion) on the trench, the second polishing for removing oxide on the nitride film, And a third polishing step for overpolishing the wafer (Fig. 1).
1차 연마는 생산성을 고려하여 빠르게 산화막 단차를 제거하고, 2차 연마는 질화막이 연마되지 않고 트렌치의 산화막이 질화막 층 이하 높이로 연마되는 것을 방지하기 위하여 질화막 층 위로 500~1000Å 정도까지만 연마하여 평탄한 표면을 만든다. 3차 연마는 질화막상의 산화막이 완전히 제거되도록 질화막이 약 100Å 이하로 연마되도록 과연마하는데 이때 트렌치의 산화막 손실(디싱, dishing)이 최소화되어야 한다.The primary polishing removes the oxide step quickly in consideration of the productivity, and the secondary polishing flattens the surface of the nitride layer by 500 to 1000Å to prevent the nitride layer from being polished and the oxide layer of the trench to be polished to a height below the nitride layer. Make a surface. In the third polishing, the oxide film on the nitride film is completely removed so that the nitride film is polished to about 100 Å or less. At this time, the oxide film loss (dishing) of the trench should be minimized.
세리아 연마제는 산화막과의 강한 반응성으로 인하여 1% 이하의 적은 농도로도 10% 이상의 농도가 필요한 실리카 연마제보다 2배 이상의 연마 속도를 발휘할 수 있다. 최근에는 입자의 직경이 100nm로 작아지는 등 CMP 결함을 감소시키는 방향으로 개발되고 있다.Ceria abrasives can exhibit twice as much polishing speed as silica abrasives requiring concentrations of 10% or more, even at low concentrations of less than 1% due to their strong reactivity with the oxide film. Recently, it has been developed in the direction of reducing CMP defects such as the diameter of the particles is reduced to 100nm.
그러나, 질화막 상층에 존재하는 산화막에 대한 연마 속도를 3000Å/분 이상으로 유지하면서, 질화막 층에 대한 트렌치 상층의 산화막에 대한 연마 속도의 비를 10 이상으로 유지함과 동시에 트렌치 상층의 산화막 상의 디싱을 최소화하고 전체 피 연마층 상의 파임 결함을 최소화한 CMP 슬러리 조성물은 아직 개발되지 않았으며, 이에 대한 요구가 절실한 실정이다.
However, while the polishing rate for the oxide film existing in the upper layer of the nitride film is maintained at 3000 A / min or more, the ratio of the polishing rate to the oxide film in the trench upper layer relative to the nitride film layer is maintained at 10 or more, , And a CMP slurry composition which minimizes pitting defects on the whole polishing layer has not yet been developed, and there is a strong demand for the CMP slurry composition.
본 발명의 목적은 질화막 상층에 존재하는 산화막에 대한 연마 속도를 3000Å 이상으로 유지하면서, 질화막 층에 대한 트렌치 상층의 산화막에 대한 연마 속도의 비를 10 이상으로 유지함과 동시에 트렌치 상층의 산화막 상의 디싱을 최소화하고 전체 피 연마층 상의 파임 결함을 최소화한 CMP 슬러리 조성물을 제공하는 것이다.An object of the present invention is to maintain the polishing rate of the oxide film in the trench upper layer relative to the nitride film layer at 10 or more while maintaining the polishing rate for the oxide film existing in the upper layer of the nitride film to 3000 angstroms or more, And minimizing pitting defects on the entire polishing layer.
본 발명의 또 다른 목적은 상기 CMP 슬러리 조성물을 이용한 연마 방법을 제공하는 것이다.
Still another object of the present invention is to provide a polishing method using the CMP slurry composition.
본 발명의 CMP 슬러리 조성물은 양의 제타 전위를 갖는 금속 산화물 입자, 양쪽 이온성 화합물, 양이온성 계면활성제, 및 초순수를 포함하는 것이다.The CMP slurry composition of the present invention comprises a metal oxide particle having a positive zeta potential, an ionic compound, a cationic surfactant, and ultrapure water.
상기 금속 산화물 입자는 하소(calcination) 또는 화염 산화(flame oxidation) 또는 수열 합성(thermal synthesis)으로 제조한 것일 수 있다.The metal oxide particles may be prepared by calcination, flame oxidation, or thermal synthesis.
상기 양의 제타 전위를 갖는 금속 산화물 입자는 세리아(CeO2) 입자, 실리카(SiO2) 입자, 알루미나(Al2O3) 입자, 티타니아(TiO2) 입자, 및 지르코니아(ZrO2) 입자로 이루어진 군에서 선택되는 적어도 어느 하나일 수 있다. Metal oxide particles having a zeta potential of both is composed of ceria (CeO 2) particles, and silica (SiO 2) particles, alumina (Al 2 O 3) particles, titania (TiO 2) particles, and zirconia (ZrO 2) particles Lt; RTI ID = 0.0 > and / or < / RTI >
상기 양의 제타 전위를 갖는 금속 산화물 입자는 평균 입경이 70~150nm이고, 비표면적이 10~50m2/g일 수 있다.The metal oxide particles having positive zeta potential may have an average particle diameter of 70 to 150 nm and a specific surface area of 10 to 50 m 2 / g.
상기 양의 제타 전위를 갖는 금속 산화물 입자는 세리아 입자일 수 있다.The metal oxide particles having the positive zeta potential may be ceria particles.
상기 양쪽 이온성 화합물은 알라닌(alanine), 페닐알라닌(phenylalanine), 프롤린(proline), 글리신(glycine), 히스티딘(histidine), 리신(lysine), 아르기닌(arginine), 트레오닌(threonine), 아스파르트산(aspartic acid), 트립토판(tryptophan), 글루타민(glutamine), 베타인(betaine), 코코미도프로필베테인(cocomidopropylbetaine), 라우릴프로필베테인(laurylpropylbetaine)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 아미노산일 수 있다.The ampholytic compounds may be selected from the group consisting of alanine, phenylalanine, proline, glycine, histidine, lysine, arginine, threonine, aspartic acid, wherein the amino acid is at least one selected from the group consisting of an acid, a tryptophan, a glutamine, a betaine, a cocomidopropylbetaine, and laurylpropylbetaine. .
상기 양이온성 계면활성제는 트리에틸렌테트라민(triethylenetetramine), N,N-디에틸에탄올아민(N,N-Diethylethanolamine), N,N-디이소프로필아민(N,N-Diisopropylamine), N,N-디터셔리부틸아닐린(N,N-ditertiarybutylaniline), 및 루파졸(Lupasol)로 이루어진 군에서 선택되는 적어도 어느 하나일 수 있다. The cationic surfactant may be selected from the group consisting of triethylenetetramine, N, N-diethylethanolamine, N, N-diisopropylamine, N, N- At least one selected from the group consisting of N, N-ditertiarybutylaniline, and Lupasol.
상기 양이온성 계면활성제는 하기의 화학식 1의 구조식을 가질 수 있다.
The cationic surfactant may have the following structural formula (1).
[화학식 1] [Formula 1]
여기서, EO는 ethylene oxide, PO는 propylene oxide, m은 0 내지 50, n은 10 내지 50, x는 0 내지 15, y는 0 내지 1이다. EO is ethylene oxide, PO is propylene oxide, m is 0 to 50, n is 10 to 50, x is 0 to 15, and y is 0 to 1.
x가 0일 경우에는 N과 N이 직접 연결된 것을 의미한다. When x is 0, it means that N and N are directly connected.
상기 화학식 1의 양이온성 계면활성제의 중량 평균 분자량은 1,000g/mol 내지 100,000g/mol일 수 있다. The weight average molecular weight of the cationic surfactant of Formula 1 may range from 1,000 g / mol to 100,000 g / mol.
상기 CMP 슬러리 조성물은 금속 산화물 입자 0.01~1 중량%, 양쪽 이온성 화합물 0.001~1 중량%, 양이온성 계면활성제 0.001~1 중량%, 및 잔량으로서 초순수를 포함할 수 있다.The CMP slurry composition may include 0.01 to 1 wt% of metal oxide particles, 0.001 to 1 wt% of an amphoteric compound, 0.001 to 1 wt% of a cationic surfactant, and ultrapure water as a balance.
본 발명의 연마 방법은 상기의 CMP 슬러리 조성물을 사용하여 반도체 웨이퍼를 연마하는 단계를 포함하는 것이다.
The polishing method of the present invention includes polishing a semiconductor wafer using the CMP slurry composition.
본 발명은 질화막 상층에 존재하는 산화막에 대한 연마 속도를 3000Å 이상으로 유지하면서, 질화막 층에 대한 트렌치 상층의 산화막에 대한 연마 속도의 비를 10 이상으로 유지함과 동시에 트렌치 상층의 산화막 상의 디싱을 최소화하고 전체 피 연마층 상의 파임 결함을 최소화한 CMP 슬러리 조성물을 제공한다.
Disclosed is a method for manufacturing a semiconductor device, which is capable of maintaining a polishing rate to an oxide film in a trench upper layer relative to a nitride film layer at 10 or more and at the same time minimizing dishing on an oxide film in a trench upper layer while maintaining a polishing rate for an oxide film existing in an upper layer of the nitride film to 3000 Å or more The present invention provides a CMP slurry composition that minimizes pitting defects on the entire layer to be polished.
도 1은 본 발명의 조성물이 적용되는 일 구체예인 STI 공정의 개략적인 공정도이다.
도 2는 2차 연마 후 피 연마층 상에 형성되는 파임 결함을 AFM(Atomic Force Microscope)으로 측정한 프로파일이다.1 is a schematic process diagram of an STI process, which is one embodiment of the composition of the present invention.
FIG. 2 is a profile obtained by AFM (Atomic Force Microscope) measurement of a flaw defect formed on a layer to be polished after secondary polishing.
본 발명의 CMP 슬러리 조성물은 양의 제타 전위를 갖는 금속 산화물 입자, 양쪽 이온성 화합물, 양이온성 계면활성제, 및 초순수를 포함하는 것이다.The CMP slurry composition of the present invention comprises a metal oxide particle having a positive zeta potential, an ionic compound, a cationic surfactant, and ultrapure water.
금속 산화물 입자Metal oxide particles
본 발명의 CMP 슬러리 조성물은 양의 제타 전위를 갖는 금속 산화물 입자를 포함한다.The CMP slurry composition of the present invention comprises metal oxide particles having a positive zeta potential.
상기 양의 제타 전위를 갖는 금속 산화물 입자로는 하소(calcination) 또는 화염 산화(flame oxidation) 또는 수열 합성(thermal synthesis)으로 제조한 것을 사용하는 것이 바람직하다.The metal oxide particles having positive zeta potential are preferably those prepared by calcination, flame oxidation, or thermal synthesis.
상기 양의 제타 전위를 갖는 금속 산화물 입자로는 세리아(CeO2) 입자, 실리카(SiO2) 입자, 알루미나(Al2O3) 입자, 티타니아(TiO2) 입자, 및 지르코니아(ZrO2) 입자로 이루어진 군에서 선택되는 적어도 어느 하나를 사용하는 것이 바람직하다.A metal oxide particle having a zeta potential of both the ceria (CeO 2) particles, and silica (SiO 2) particles, alumina (Al 2 O 3) particles, titania (TiO 2) particles, and zirconia (ZrO 2) particles It is preferable to use at least one selected from the group consisting of
상기 양의 제타 전위를 갖는 금속 산화물 입자는 산화막에 대한 연마 속도를 확보하고, 질화막에 대한 연마 속도를 억제하기 위하여 평균 입경이 70~150nm이고, 비표면적이 10~50m2/g인 것을 사용하는 것이 바람직하다. The metal oxide particles having positive zeta potential have an average particle diameter of 70 to 150 nm and a specific surface area of 10 to 50 m 2 / g in order to secure a polishing rate for the oxide film and to suppress the polishing rate for the nitride film .
상기 양의 제타 전위를 갖는 금속 산화물 입자는 세리아 입자일 수 있으며, 상기 양의 제타 전위를 갖는 금속 산화물 입자로 수열 합성으로 제조한 세리아 입자를 사용하는 경우에는 분산제를 사용하지 않아도 되기 때문에 분산제에 의한 제타 전위 값의 변화 없이 세리아 본연의 양의 제타 전위를 유지하게 되어 산화막 연마에 효과가 크다.The metal oxide particles having positive zeta potential may be ceria particles, and in the case of using ceria particles prepared by hydrothermal synthesis with metal oxide particles having the positive zeta potential, there is no need to use a dispersant, The zeta potential of the original amount of ceria is maintained without changing the value of the zeta potential, which is effective for polishing the oxide film.
상기 양의 제타 전위를 갖는 금속 산화물 입자는 0.01~1 중량%로 사용하는 것이 바람직하며, 0.1~0.7 중량%로 사용하는 것이 보다 바람직하다.
The metal oxide particles having a positive zeta potential are preferably used in an amount of 0.01 to 1% by weight, more preferably 0.1 to 0.7% by weight.
양쪽 이온성 화합물Zwitterionic compound
본 발명의 CMP 슬러리 조성물은 질화막의 연마를 막기(stopping) 위하여 양쪽 이온성 화합물을 포함한다. The CMP slurry composition of the present invention includes both ionic compounds to stop polishing the nitride film.
상기 양쪽 이온성 화합물은 알라닌(alanine), 페닐알라닌(phenylalanine), 프롤린(proline), 글리신(glycine), 히스티딘(histidine), 리신(lysine), 아르기닌(arginine), 트레오닌(threonine), 아스파르트산(aspartic acid), 트립토판(tryptophan), 글루타민(glutamine), 베타인(betaine), 코코미도프로필베테인(ccocomidopropylbetaine), 라우릴프로필베테인(laurylpropylbetaine)으로 이루어진 군에서 선택되는 적어도 어느 하나를 포함하는 아미노산일 수 있다.The ampholytic compounds may be selected from the group consisting of alanine, phenylalanine, proline, glycine, histidine, lysine, arginine, threonine, aspartic acid, wherein the amino acid is at least one selected from the group consisting of acid, tryptophan, glutamine, betaine, cococidopropylbetaine, laurylpropylbetaine, .
상기 양쪽 이온성 화합물은 산화막에 대한 연마 속도를 확보하고, 질화막에 대한 연마 속도를 억제하며, 전체 피 연마층 상의 파임 결함을 최소화하기 위하여 0.001~1 중량%로 사용하는 것이 바람직하고, 0.005~0.7 중량%로 사용하는 것이 보다 바람직하며, 0.01~0.4 중량%로 사용하는 것이 가장 바람직하다.
The amphoteric compound is preferably used in an amount of 0.001 to 1 wt%, more preferably 0.005 to 0.7 wt%, in order to secure a polishing rate for an oxide film, to suppress a polishing rate for a nitride film, More preferably, it is used in an amount of 0.01 to 0.4% by weight.
양이온성Cationic 계면활성제 Surfactants
본 발명의 CMP 슬러리 조성물은 산화막에 대한 연마 속도를 조절하여 연마 프로파일을 개선하고 트렌치 상층의 산화막 상의 디싱을 최소화하고 전체 피 연마층 상의 파임 결함을 최소화하기 위하여 양이온성 계면활성제를 포함한다.The CMP slurry composition of the present invention comprises a cationic surfactant to improve the polishing profile by controlling the polishing rate for the oxide film, minimize dishing on the oxide film of the trench upper layer, and minimize pitting defects on the entire polishing layer.
상기 양이온성 계면활성제는 트리에틸렌테트라민(triethylenetetramine), N,N-디에틸에탄올아민(N,N-Diethylethanolamine), N,N-디이소프로필아민(N,N-Diisopropylamine), N,N-디터셔리부틸아닐린(N,N-ditertiarybutylaniline), 및 루파졸(Lupasol)로 이루어진 군에서 선택되는 적어도 어느 하나일 수 있다. The cationic surfactant may be selected from the group consisting of triethylenetetramine, N, N-diethylethanolamine, N, N-diisopropylamine, N, N- At least one selected from the group consisting of N, N-ditertiarybutylaniline, and Lupasol.
상기 양이온성 계면활성제는 하기의 화학식 1의 구조식을 가질 수 있다.
The cationic surfactant may have the following structural formula (1).
[화학식 1][Formula 1]
여기서, EO 는 ethylene oxide, PO 는 propylene oxide , m은 0 내지 50, n은 10 내지 50, x는 0 내지 15, y는 0 내지 1이다. EO is ethylene oxide, PO is propylene oxide, m is 0 to 50, n is 10 to 50, x is 0 to 15, and y is 0 to 1.
x가 0일 경우에는 N과 N이 직접 연결된 것을 의미한다. When x is 0, it means that N and N are directly connected.
상기 화학식 1의 양이온성 계면활성제의 중량 평균 분자량은 1,000g/mol 내지 100,000g/mol인 것이 바람직하며, 점도는 0.9 내지 2.0cP인 것이 바람직하다. The weight average molecular weight of the cationic surfactant of Formula 1 is preferably 1,000 g / mol to 100,000 g / mol, and the viscosity is preferably 0.9 to 2.0 cP.
본 발명에서는 상기 양이온성 계면활성제를 상기 양쪽 이온성 화합물과 동시에 사용함으로써 트렌치 상층의 산화막 상의 디싱을 최소화하고 전체 피 연마층 상의 파임 결함을 최소화할 수 있다. In the present invention, by using the cationic surfactant simultaneously with the amphoteric compound, it is possible to minimize dishing on the oxide film in the trench upper layer and to minimize breakdown defects on the entire layer to be polished.
상기 양이온성 계면활성제는 산화막에 대한 연마 속도를 조절하여 연마 프로파일을 개선하고, 질화막에 대한 연마 속도를 억제하며, 트렌치 상층의 산화막 상의 디싱을 최소화하고 전체 피 연마층 상의 파임 결함을 최소화하기 위하여 0.001~1 중량%로 사용하는 것이 바람직하고, 0.005~0.8 중량%로 사용하는 것이 보다 바람직하며, 0.01~0.7 중량%로 사용하는 것이 가장 바람직하다.The cationic surfactant adjusts the polishing rate for the oxide film to improve the polishing profile, to suppress the polishing rate for the nitride film, to minimize dishing on the oxide layer of the trench upper layer and to minimize the defects on the entire polished layer. It is preferable to use it at -1 weight%, It is more preferable to use it at 0.005 to 0.8 weight%, It is most preferable to use it at 0.01 to 0.7 weight%.
본 발명의 연마 방법은 상기의 CMP 슬러리 조성물을 사용하여 반도체 웨이퍼를 연마하는 단계를 포함하는 것이다. 해당 공정은 ILD(Interlayer Dielectric) 공정 또는 STI(Shallow Trench Isolation) 공정일 수 있다. 이때, 본 발명의 CMP 슬러리 조성물은 패턴화된 산화막에 대한 연마 효율이 우수하기 때문에 연마 대상인 반도체 웨이퍼는 패턴화된 산화막을 포함하는 것이 바람직하다.The polishing method of the present invention includes a step of polishing a semiconductor wafer using the above CMP slurry composition. The process may be an interlayer dielectric (ILD) process or a shallow trench isolation (STI) process. At this time, since the CMP slurry composition of the present invention has excellent polishing efficiency for the patterned oxide film, it is preferable that the semiconductor wafer to be polished contains a patterned oxide film.
이하 실시예를 통하여 본 발명을 더욱 구체적으로 설명한다. 다만, 이는 설명을 위한 가능한 실시예일 뿐, 본 발명이 이에 한정되는 것은 아니다.The present invention will be described in more detail with reference to the following Examples. However, this is a possible embodiment for explanation, but the present invention is not limited thereto.
다음의 실시예 및 비교예에서 제조된 CMP 슬러리 조성물을 이용하여 하기 연마 조건에서 패턴 웨이퍼를 연마하였다. 연마에 의해 제거된 웨이퍼의 두께 변화를 측정하여 연마 속도를 산출하였고, 옵티프로브(ThermalWave 社, Optiprobe2600) 장비를 사용하여 측정하였다.
The pattern wafers were polished under the following polishing conditions using the CMP slurry compositions prepared in the following examples and comparative examples. The polishing rate was calculated by measuring the change in thickness of the wafer removed by polishing, and measured using an Optiprobe (ThermalWave, Optiprobe2600) equipment.
<연마 조건><Polishing Condition>
- 패턴 웨이퍼: 상용 슬러리(제일모직 SP7500)로 1차 연마한 200mm MIT (Massachusetts Institute of Technology) 패턴 웨이퍼.- Pattern Wafer: 200mm MIT (Massachusetts Institute of Technology) pattern wafers first polished with commercial slurry (Cheil Industries SP7500).
=> MIT의 full name을 기재하여 주시기 바랍니다.Please fill in the full name of MIT.
- 연마 설비 : AMAT Mirra (AMAT社)-Polishing facility: AMAT Mirra (AMAT company)
- 연마 패드 : IC1010 k-groove(Rodel社)- Polishing pad: IC1010 k-groove (Rodel)
- Polishing time : P1 60초 P2 30초, P3 40초- Polishing time: P1 60 seconds P2 30 seconds, P3 40 seconds
- Polishing Pressure : 3psi- Polishing Pressure: 3 psi
- Platen rpm : 103 rpmPlaten rpm: 103 rpm
- Head rpm : 97 rpmHead rpm: 97 rpm
- Flow rate : 200 ml/min- Flow rate: 200 ml / min
비교예 1Comparative Example 1
화학식 1에서 x=2이고, y=1이며, m/n은 1.5이며 중량 평균 분자량이 10,000g/mol인 양이온성 계면활성제(a) 0.5wt%와 평균 입경이 100nm(호리바 LA710 으로 측정)이고, 중량 평균 분자량이 10,000g/mol인 폴리아크릴산으로 수계 분산하여 제타 전위가 -30mV인 세리아 0.5wt를 초순수로 혼합하여 시료를 준비하였다. pH를 4.5로 맞추어 일액형 슬러리를 제작하였다. 상기 연마 조건에 따라 패턴 밀도가 50%이고 pitch size가 100 ㎛인 패턴 웨이퍼에 대하여 연마 성능을 평가하여 표 1과 같이 결과를 기술하였다.
0.5 wt% of a cationic surfactant (a) having x = 2, y = 1, m / n of 1.5 and a weight average molecular weight of 10,000 g / mol, and an average particle size of 100 nm (measured with HORIBA LA710) , 0.5 wt% of ceria having a zeta potential of -30 mV was dispersed in water with polyacrylic acid having a weight average molecular weight of 10,000 g / mol and mixed with ultrapure water to prepare a sample. and the pH was adjusted to 4.5 to prepare a one-component slurry. The polishing performance was evaluated on a patterned wafer having a pattern density of 50% and a pitch size of 100 탆 according to the above polishing conditions, and the results are shown in Table 1.
비교예 2Comparative Example 2
비교예 1의 세리아 대신에 평균 입경이 100nm(호리바 LA710 으로 측정)이고, 제타 전위가 +40mV인 세리아를 사용한 것을 제외하고, 비교예 1과 동일하게 시료를 준비하고 연마 성능을 평가하여 표 1에 기재하였다.
A sample was prepared in the same manner as in Comparative Example 1 except that ceria having an average particle size of 100 nm (measured by Horiba LA710) and a zeta potential of +40 mV was used instead of ceria in Comparative Example 1, and the polishing performance was evaluated. .
비교예 3Comparative Example 3
양이온성 계면활성제(a) 대신에 x=2이고, y=1이며, m은 0이며, 중량 평균 분자량이 10,000g/mol인 양이온성 계면활성제(b)를 사용한 것을 제외하고, 비교예 2와 동일하게 시료를 준비하고 연마 성능을 평가하여 표 1에 기재하였다.
Except that the cationic surfactant (b) was used in place of the cationic surfactant (a), x = 2, y = 1, m = 0 and a weight average molecular weight of 10,000 g / mol. Samples were prepared in the same manner, and polishing performance was evaluated.
비교예 4Comparative Example 4
양이온성 계면활성제를 사용하지 않고, 양쪽 이온성 화합물인 L-아스파르트산(L-Aspartic acid)(c)을 0.2wt%로 사용한 것을 제외하고, 비교예 2와 동일하게 시료를 준비하고 연마 성능을 평가하여 표 1에 기재하였다.
A sample was prepared in the same manner as in Comparative Example 2, except that a cationic surfactant was not used and 0.2 wt% of L-aspartic acid (c), which is an ionic compound, was used. The results are shown in Table 1.
비교예 5Comparative Example 5
양쪽 이온성 화합물로 L-아스파르트산(L-Aspartic acid) 대신에 글리신(Glycine)(d)을 사용한 것을 제외하고, 비교예 4와 동일하게 시료를 준비하고 연마 성능을 평가하여 표 1에 기재하였다.
Samples were prepared in the same manner as in Comparative Example 4 except that glycine (d) was used instead of L-aspartic acid as both ionic compounds, and polishing performance was evaluated and shown in Table 1 .
비교예 6Comparative Example 6
양쪽 이온성 화합물로 L-아스파르트산(L-Aspartic acid) 대신에 리신(Lysine)(e)을 사용한 것을 제외하고, 비교예 4와 동일하게 시료를 준비하고 연마 성능을 평가하여 표 1에 기재하였다.
Samples were prepared in the same manner as in Comparative Example 4 except that Lysine (e) was used instead of L-Aspartic acid as both ionic compounds, and polishing performance was evaluated and shown in Table 1 .
실시예 1Example 1
양이온성 계면활성제(a)를 0.5wt%로 더 추가한 것을 제외하고, 비교예 4와 동일하게 시료를 준비하고 연마 성능을 평가하여 표 1에 기재하였다.
A sample was prepared in the same manner as in Comparative Example 4 except that the cationic surfactant (a) was further added in an amount of 0.5 wt%, and the polishing performance was evaluated.
실시예 2Example 2
L-아스파르트산(L-Aspartic acid)(c) 대신에 라우릴프로필베테인(laurylpropylbetaine)(f)를 0.05wt%로 사용한 것을 제외하고, 실시예 1과 동일하게 시료를 준비하고 연마 성능을 평가하여 표 1에 기재하였다.
A sample was prepared and polishing performance was evaluated in the same manner as in Example 1, except that laurylpropylbetaine (f) was used in an amount of 0.05 wt% instead of L-aspartic acid (c) Are shown in Table 1.
실시예 3Example 3
양이온성 계면활성제(a) 대신에 양이온성 계면활성제(b)를 사용한 것을 제외하고, 실시예 1과 동일하게 시료를 준비하고 연마 성능을 평가하여 표 1에 기재하였다.
Samples were prepared and polishing performance was evaluated in the same manner as in Example 1 except that the cationic surfactant (a) was replaced with the cationic surfactant (b).
실시예 4Example 4
양이온성 계면활성제(a) 대신에 양이온성 계면활성제(b)를 사용한 것을 제외하고, 실시예 2와 동일하게 시료를 준비하고 연마 성능을 평가하여 표 1에 기재하였다.
Samples were prepared and polishing performance was evaluated in the same manner as in Example 2 except that the cationic surfactant (a) was replaced with the cationic surfactant (b).
제타 전위Metal oxide particles
Zeta potential
계면활성제Cationic
Surfactants
Ox RRConvex portion
Ox RR
RR(α)Convex portion SiN
RR (?)
(β/α)Selectivity
(? /?)
※ 연마 속도 단위 : Å/분 ※ polishing speed unit: Å / minute
※ 파임 결함 : 산화막과 질화막 상에서 육안 식별되는 것으로 육안상 얼룩으로 관찰되며 AFM 측정 시 얼룩 부위는 주변대비 400Å~800Å의 단차로 측정됨. 파임 결함의 판정은 육안상으로 있음 혹은 없음으로 판별하였음.※ Detachment defect: It is visually recognized on the oxide film and nitride film, and it is observed with naked eye. In AFM measurement, the spot area is measured as a step of 400 ~ 800 Å from the surrounding area. The judgment of the defective defect was judged to be with or without the naked eye.
※ 볼록부 Ox RR이란 질화막 상층에 존재하는 산화막에 대한 연마 속도를 의미하고, 볼록부 SiN RR이란 질화막 층에 대한 연마 속도를 의미하며, 오목부 Ox RR이란 트렌치 상층의 산화막에 대한 연마 속도를 의미함※ convex Ox RR means the polishing rate for the oxide film existing in the upper layer of the nitride film, convex SiN RR means the polishing rate for the nitride film layer, and the concavity Ox RR means the polishing rate for the oxide film in the upper trench box
이상의 결과에서 알 수 있듯이, 본 발명의 CMP 슬러리 조성물은 질화막 상층에 존재하는 산화막에 대한 연마 속도를 3000Å 이상으로 유지하면서, 질화막 층에 대한 트렌치 상층의 산화막에 대한 연마 속도의 비를 10 이상으로 유지함과 동시에 전체 피 연마층 상의 파임 결함을 최소화한 CMP 슬러리 조성물을 제공한다.
As can be seen from the above results, the CMP slurry composition of the present invention maintains the ratio of the polishing rate to the oxide film in the trench upper layer relative to the nitride film layer at 10 or more while maintaining the polishing rate for the oxide film present in the upper layer of the nitride film to 3000 Å or more And at the same time, minimizes pitting defects on the entire layer to be polished.
Claims (10)
양쪽 이온성 화합물;
양이온성 계면활성제; 및
초순수;를 포함하는 CMP 슬러리 조성물.
Metal oxide particles having positive zeta potential;
Both ionic compounds;
Cationic surfactants; And
Ultra pure water.
The CMP slurry composition according to claim 1, wherein the metal oxide particles are prepared by calcination, flame oxidation or hydrothermal synthesis.
According to claim 1, wherein the metal oxide particles are ceria (CeO 2 ) particles, silica (SiO 2 ) particles, alumina (Al 2 O 3 ) particles, titania (TiO 2 ) particles, and zirconia (ZrO 2 ) particles. CMP slurry composition, characterized in that at least one selected from the group consisting of.
The CMP slurry composition according to claim 1, wherein the metal oxide particles having a positive zeta potential have an average particle size of 70 to 150 nm and a specific surface area of 10 to 50 m 2 / g.
The CMP slurry composition according to claim 1, wherein the metal oxide particles having positive zeta potential are ceria particles.
3. The composition of claim 1 wherein the ampholytic compound is selected from the group consisting of alanine, phenylalanine, proline, glycine, histidine, lysine, arginine, threonine, At least one selected from the group consisting of aspartic acid, tryptophan, glutamine, betaine, cocomidopropylbetaine, and laurylpropylbetaine. Lt; RTI ID = 0.0 > CMP < / RTI >
The method according to claim 1, wherein the cationic surfactant is selected from the group consisting of triethylenetetramine, N, N-diethylethanolamine, N, N-diisopropylamine And at least one selected from the group consisting of N, N-ditertiarybutylaniline, and Lupasol.
[화학식 1]
상기 화학식 1에서, EO 는 ethylene oxide, PO 는 propylene oxide , m은 0 내지 50, n은 10 내지 50, x는 0 내지 15, y는 0 내지 1이다.
2. The CMP slurry composition of claim 1, wherein the cationic surfactant has the following structural formula:
[Formula 1]
Wherein EO is ethylene oxide, PO is propylene oxide, m is 0 to 50, n is 10 to 50, x is 0 to 15, and y is 0 to 1.
The CMP slurry composition of claim 1, wherein the CMP slurry composition comprises 0.2-0.5 wt% metal oxide particles having positive zeta potential, 0.001-1.0 wt% zwitterionic compound, 0.0001-0.5 wt% cationic surfactant, ≪ / RTI >
A polishing method comprising polishing a semiconductor wafer using the CMP slurry composition of any one of claims 1 to 9.
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| WO2017043701A1 (en) * | 2015-09-08 | 2017-03-16 | 삼성에스디아이 주식회사 | Cmp slurry composition for polishing copper, and polishing method using same |
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| KR20200076991A (en) * | 2018-12-20 | 2020-06-30 | 주식회사 케이씨텍 | Polishing slurry composition for sti process |
| KR102213533B1 (en) * | 2020-04-24 | 2021-02-09 | 주식회사 케이씨텍 | Polishing slurry composition for sti process |
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| WO2017043701A1 (en) * | 2015-09-08 | 2017-03-16 | 삼성에스디아이 주식회사 | Cmp slurry composition for polishing copper, and polishing method using same |
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