KR102169835B1 - Polishing liquid, chemical mechanical polishing method - Google Patents
Polishing liquid, chemical mechanical polishing method Download PDFInfo
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- KR102169835B1 KR102169835B1 KR1020187036008A KR20187036008A KR102169835B1 KR 102169835 B1 KR102169835 B1 KR 102169835B1 KR 1020187036008 A KR1020187036008 A KR 1020187036008A KR 20187036008 A KR20187036008 A KR 20187036008A KR 102169835 B1 KR102169835 B1 KR 102169835B1
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- KR
- South Korea
- Prior art keywords
- polishing
- polishing liquid
- acid
- group
- polished
- Prior art date
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- 238000005498 polishing Methods 0.000 title claims abstract description 263
- 239000007788 liquid Substances 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000126 substance Substances 0.000 title claims abstract description 21
- 229920003169 water-soluble polymer Polymers 0.000 claims abstract description 40
- 150000007524 organic acids Chemical class 0.000 claims abstract description 25
- 239000006061 abrasive grain Substances 0.000 claims abstract description 15
- 229920002125 Sokalan® Polymers 0.000 claims description 25
- 239000007800 oxidant agent Substances 0.000 claims description 25
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- 239000004584 polyacrylic acid Substances 0.000 claims description 18
- 229920001577 copolymer Polymers 0.000 claims description 15
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 9
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- 235000005985 organic acids Nutrition 0.000 claims description 8
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 6
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- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000004397 aminosulfonyl group Chemical group NS(=O)(=O)* 0.000 description 3
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Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B37/00—Lapping machines or devices; Accessories
-
- 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
-
- 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
- C09K3/1454—Abrasive powders, suspensions and pastes for polishing
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
본 발명의 과제는, 면내 균일성이 우수한 피연마체를 부여할 수 있는 연마액을 제공하는 것이다. 또, 상기 연마액을 이용한 화학적 기계적 연마 방법을 제공하는 것이다.
본 발명의 연마액은, 화학적 기계적 연마에 이용되는 연마액으로서, 지립과, 유기산과, 수용성 고분자를 함유하고, 하기 식 (1)~식 (3)을 모두 충족시킨다.
식 (1): 1.5≤η100rpm/η1000rpm≤20
식 (2): 1.2≤η100rpm/η500rpm≤10
식 (3): η100rpm/η1000rpm>η100rpm/η500rpm
식 (1)~식 (3) 중, η100rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 100rpm으로 측정되는 상기 연마액의 점도이고, η500rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 500rpm으로 측정되는 상기 연마액의 점도이며, η1000rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 1000rpm으로 측정되는 상기 연마액의 점도이다.An object of the present invention is to provide a polishing liquid capable of providing an object to be polished having excellent in-plane uniformity. In addition, it is to provide a chemical mechanical polishing method using the polishing liquid.
The polishing liquid of the present invention is a polishing liquid used for chemical mechanical polishing, and contains abrasive grains, an organic acid, and a water-soluble polymer, and satisfies all of the following formulas (1) to (3).
Equation (1): 1.5≤η 100rpm / η 1000rpm ≤20
Equation (2): 1.2≤η 100rpm / η 500rpm ≤10
Equation (3): η 100rpm /η 1000rpm >η 100rpm /η 500rpm
In formulas (1) to (3), η 100 rpm is the viscosity of the polishing liquid measured at a rotational speed of 100 rpm by a rotational viscometer at 40%RH and 23°C, and η 500rpm is 40%RH, 23°C. Is the viscosity of the polishing liquid measured at a rotational speed of 500 rpm by a rotational viscometer, and η 1000rpm is the viscosity of the polishing liquid measured at a rotational viscometer at 40%RH and 23°C at a rotational speed of 1000 rpm.
Description
본 발명은, 화학적 기계적 연마에 이용되는 연마액, 및 화학적 기계적 연마 방법에 관한 것이다.The present invention relates to a polishing liquid used for chemical mechanical polishing, and a chemical mechanical polishing method.
반도체 디바이스의 개발에 있어서는, 소형화 및 고속화를 위하여, 최근, 배선의 미세화와 적층화에 의한 고밀도화 및 고집적화가 요구되고 있다. 이를 위한 기술로서 화학적 기계적 연마(Chemical Mechanical Polishing, 이하, "CMP"라고 기재함) 등의 다양한 기술이 이용되고 있다. 이 CMP는 층간 절연막 등의 피가공막의 표면 평탄화, 플러그 형성, 또는 매립 금속 배선의 형성 등을 행하는 경우에 필수인 기술이고, 피연마체의 평활화, 배선 형성 시의 여분의 금속 박막의 제거 또는 절연막 상의 여분의 배리어층의 제거를 행하고 있다.BACKGROUND ART In the development of semiconductor devices, in order to increase the size and speed of the semiconductor device, in recent years, high density and high integration by miniaturization and lamination of wiring are required. As a technique for this, various techniques such as chemical mechanical polishing (hereinafter, referred to as "CMP") have been used. This CMP is an essential technique when flattening the surface of a film to be processed such as an interlayer insulating film, forming a plug, or forming a buried metal wiring, and smoothing the object to be polished, removing an excess metal thin film during wiring, or an insulating film. The excess barrier layer of the image is removed.
CMP의 일반적인 방법은, 원형의 연마 정반(플래튼) 상에 연마 패드를 첩부하고, 연마 패드 표면을 연마액에 침지하며, 패드에 피연마체의 표면을 압압하고, 그 이면으로부터 소정의 압력(연마 압력)을 가한 상태에서, 연마 정반 및 피연마체의 쌍방을 회전시켜, 발생하는 기계적 마찰에 의하여 피연마체의 표면을 평탄화하는 것이다.The general method of CMP is to affix a polishing pad on a circular polishing base (platen), immerse the surface of the polishing pad in a polishing liquid, press the surface of the object to be polished to the pad, and apply a predetermined pressure (polishing Pressure) is applied to rotate both the polishing platen and the object to be polished to flatten the surface of the object to be polished by the mechanical friction generated.
예를 들면, 특허문헌 1에는, 연마 속도가 양호한 연마액으로서, "산화제, 산화 금속 용해제, 금속 방식제, 수용성 폴리머 및 물을 함유하고, 상기 수용성 폴리머가, 아크릴산과 메타크릴산의 공중합체이며, 그 공중합체에 있어서의 상기 메타크릴산의 공중합 비율이, 상기 아크릴산과 상기 메타크릴산의 합계를 기준으로 하여 1~20mol%이고, 25℃에 있어서의 점도가 0.5~3.5mPa·s인, 금속막용 연마액"을 개시하고 있다.For example, in
본 발명자들은, 특허문헌 1에 기재된 연마액을 이용하여, 산화 규소막 혹은 질화 규소막 등의 무기 절연막, 또는 Cu, 혹은 Ta 등을 주로 함유하는 금속막을 성막한 웨이퍼 등의 각종 피연마체의 CMP를 실시한바, 연마 후의 피연마체의 연마량의 면내 균일성(이하, 간단히 "면내 균일성"이라고 함)이 현재의 요구 레벨에 도달하고 있지 않은 것을 발견하기에 이르렀다.The present inventors use the polishing liquid described in
본 발명자는, 그 원인이, 연마 패드로부터 받는 전단력이, 피연마체(예를 들면 웨이퍼)의 평면 내의 위치에 따라 다른 것에 있는 것을 발견했다.The inventors of the present invention have found that the cause is that the shear force received from the polishing pad differs depending on the position in the plane of the object to be polished (for example, the wafer).
따라서, 본 발명은 면내 균일성이 우수한 피연마체를 부여할 수 있는 연마액을 제공하는 것을 과제로 한다.Accordingly, an object of the present invention is to provide a polishing liquid capable of imparting an object to be polished having excellent in-plane uniformity.
또, 본 발명은 상기 연마액을 이용한 화학적 기계적 연마 방법을 제공하는 것도 과제로 한다.Another object of the present invention is to provide a chemical mechanical polishing method using the polishing liquid.
본 발명자들은, 상기 과제를 달성하기 위하여 예의 검토한 결과, 회전 점도계로 측정한 점도비가 소정의 범위 내에 있어 의소성(擬塑性)을 갖는 연마액에 의하면 상기 과제를 해결할 수 있는 것을 발견하여, 본 발명을 완성시켰다.The present inventors, as a result of earnestly examining in order to achieve the above object, found that the above problem can be solved by a polishing liquid having pseudoplasticity because the viscosity ratio measured with a rotational viscometer is within a predetermined range. The invention was completed.
즉, 이하의 구성에 의하여 상기 목적을 달성할 수 있는 것을 발견했다.In other words, it has been found that the above object can be achieved by the following configuration.
(1) 화학적 기계적 연마에 이용되는 연마액으로서,(1) As a polishing liquid used for chemical mechanical polishing,
지립과, 유기산과, 수용성 고분자를 함유하고,It contains abrasive grains, organic acids, and water-soluble polymers,
하기 식 (1)~식 (3)을 모두 충족시키는, 연마액.A polishing liquid that satisfies all of the following formulas (1) to (3).
식 (1): 1.5≤η100rpm/η1000rpm≤20Equation (1): 1.5≤η 100rpm / η 1000rpm ≤20
식 (2): 1.2≤η100rpm/η500rpm≤10Equation (2): 1.2≤η 100rpm / η 500rpm ≤10
식 (3): η100rpm/η1000rpm>η100rpm/η500rpm Equation (3): η 100rpm /η 1000rpm >η 100rpm /η 500rpm
식 (1)~식 (3) 중, η100rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 100rpm으로 측정되는 상기 연마액의 점도이고, η500rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 500rpm으로 측정되는 상기 연마액의 점도이며, η1000rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 1000rpm으로 측정되는 상기 연마액의 점도이다.In formulas (1) to (3), η 100 rpm is the viscosity of the polishing liquid measured at a rotational speed of 100 rpm by a rotational viscometer at 40%RH and 23°C, and η 500rpm is 40%RH, 23°C. Is the viscosity of the polishing liquid measured at a rotational speed of 500 rpm by a rotational viscometer, and η 1000rpm is the viscosity of the polishing liquid measured at a rotational viscometer at 40%RH and 23°C at a rotational speed of 1000 rpm.
(2) 상기 수용성 고분자의 중량 평균 분자량이, 5000~100000인, (1)에 기재된 연마액.(2) The polishing liquid according to (1), wherein the weight average molecular weight of the water-soluble polymer is 5000 to 100,000.
(3) 상기 수용성 고분자가, 폴리아크릴산, 폴리메타크릴산 및, 폴리아크릴산과 폴리메타크릴산 중 적어도 1종을 함유하는 공중합체로 이루어지는 군으로부터 선택되는 적어도 어느 1종인, (1) 또는 (2)에 기재된 연마액.(3) the water-soluble polymer is at least one selected from the group consisting of polyacrylic acid, polymethacrylic acid, and a copolymer containing at least one of polyacrylic acid and polymethacrylic acid, (1) or (2) Polishing liquid described in ).
(4) 상기 수용성 고분자의 함유량이 0.5~4질량%인, (1) 내지 (3) 중 어느 하나에 기재된 연마액.(4) The polishing liquid according to any one of (1) to (3), wherein the content of the water-soluble polymer is 0.5 to 4% by mass.
(5) 상기 유기산이, 석신산, 말산, 말론산 및 시트르산으로 이루어지는 군으로부터 선택되는 적어도 어느 1종인, (1) 내지 (4) 중 어느 하나에 기재된 연마액.(5) The polishing liquid according to any one of (1) to (4), wherein the organic acid is at least any one selected from the group consisting of succinic acid, malic acid, malonic acid, and citric acid.
(6) 산화제를 더 함유하는, (1) 내지 (5) 중 어느 하나에 기재된 연마액.(6) The polishing liquid according to any one of (1) to (5), further containing an oxidizing agent.
(7) 상기 산화제의 함유량이, 연마액 전체 질량에 대하여 0.03질량% 이상인, (6)에 기재된 연마액.(7) The polishing liquid according to (6), wherein the content of the oxidizing agent is 0.03 mass% or more with respect to the total mass of the polishing liquid.
(8) 상기 산화제가, 과산화 수소인, (6) 또는 (7)에 기재된 연마액.(8) The polishing liquid according to (6) or (7), wherein the oxidizing agent is hydrogen peroxide.
(9) 지립의 함유량이 3질량% 이상인, (1) 내지 (8) 중 어느 하나에 기재된 연마액.(9) The polishing liquid according to any one of (1) to (8), wherein the abrasive content is 3% by mass or more.
(10) pH가, 2.0~6.0의 범위인, (1) 내지 (9) 중 어느 하나에 기재된 연마액.(10) The polishing liquid according to any one of (1) to (9), wherein the pH is in the range of 2.0 to 6.0.
(11) 연마 정반에 장착된 연마 패드에, (1) 내지 (10) 중 어느 하나에 기재된 연마액을 공급하면서, 피연마체의 피연마면을 상기 연마 패드에 접촉시키고, 상기 피연마체, 및 상기 연마 패드를 상대적으로 움직여 상기 피연마면을 연마하여 연마가 완료된 피연마체를 얻는 공정을 포함하는, 화학적 기계적 연마 방법.(11) While supplying the polishing liquid according to any one of (1) to (10) to a polishing pad mounted on a polishing table, a surface to be polished of an object to be polished is brought into contact with the polishing pad, and the object to be polished and the A chemical mechanical polishing method comprising a step of relatively moving a polishing pad to polish the surface to be polished to obtain a polished object.
본 발명에 의하면, 면내 균일성이 우수한 피연마체를 부여할 수 있는 연마액을 제공할 수 있다. 또, 본 발명에 의하면, 상기 연마액을 이용한 화학적 기계적 연마 방법을 제공할 수 있다.According to the present invention, it is possible to provide a polishing liquid capable of providing an object to be polished having excellent in-plane uniformity. Further, according to the present invention, it is possible to provide a chemical mechanical polishing method using the polishing liquid.
도 1은, 피연마체인 웨이퍼에 대하여 연마 패드를 이용하여 CMP를 실시하는 공정 시에, 웨이퍼와 연마 패드의 상대 위치를 나타낸 모식도이다.
도 2는, 뉴턴성을 나타내는 연마액을 이용하여 CMP를 실시한 경우에 있어서, 웨이퍼의 평면 내에 있어서의 각 위치의 연마 속도(연마량)를 나타내는 도이다.
도 3은, 1.5≤η100rpm/η1000rpm≤20의 범위에 있는 연마액을 이용하여 CMP를 실시한 경우에 있어서의, 웨이퍼의 평면 내의 각 위치에서의 연마 속도(연마량)를 나타내는 도이다.
도 4는, η100rpm/η1000rpm>20의 연마액을 이용하여 CMP를 실시한 경우에 있어서의, 웨이퍼의 평면 내의 각 위치에서의 연마 속도(연마량)를 나타내는 도이다.1 is a schematic diagram showing a relative position between a wafer and a polishing pad in a step of performing CMP using a polishing pad on a wafer as a polishing target.
Fig. 2 is a diagram showing the polishing rate (amount of polishing) at each position in the plane of the wafer in the case of performing CMP using a polishing liquid showing Newtonian properties.
Fig. 3 is a diagram showing a polishing rate (amount of polishing) at each position in the plane of the wafer in the case of performing CMP using a polishing liquid in the range of 1.5≦η 100 rpm /η 1000 rpm ≦20.
Fig. 4 is a diagram showing a polishing rate (amount of polishing) at each position in the plane of the wafer in the case of performing CMP using a polishing liquid having η 100 rpm / η 1000 rpm >20.
이하, 본 발명의 연마액 및 화학적 기계적 연마 방법에 대하여 상세하게 설명한다.Hereinafter, the polishing liquid and the chemical mechanical polishing method of the present invention will be described in detail.
이하에 기재하는 구성 요건의 설명은, 본 발명의 대표적인 실시형태에 근거하여 이루어지는 경우가 있지만, 본 발명은 그와 같은 실시형태에 한정되는 것은 아니다.The description of the constitutional requirements described below may be made based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment.
또한, 본 명세서에 있어서, "~"를 이용하여 나타나는 수치 범위는, "~"의 전후에 기재되는 수치를 하한값 및 상한값으로서 포함하는 범위를 의미한다.In addition, in this specification, the numerical range shown using "~" means a range including numerical values described before and after "~" as a lower limit value and an upper limit value.
또, 본 발명에 있어서, 1rpm은, 1회전/분에 상당한다.In addition, in the present invention, 1 rpm corresponds to 1 rotation/minute.
또, 본 발명에 있어서, 1psi는, 6894.76Pa에 상당한다.In addition, in the present invention, 1 psi corresponds to 6894.76 Pa.
또, 본 발명에 있어서, 1cP는, 1×103Pa·s에 상당한다.Further, in the present invention, 1 cP corresponds to 1×10 3 Pa·s.
또, 본 발명에 있어서의 기(원자군)의 표기에 있어서, 치환 및 무치환을 기재하지 않은 표기는, 본 발명의 효과를 저해하지 않는 범위에서, 치환기를 갖지 않는 것과 함께 치환기를 갖는 것도 포함하는 것이다. 예를 들면, "탄화 수소기"란, 치환기를 갖지 않는 탄화 수소기(무치환 탄화 수소기)뿐만 아니라, 치환기를 갖는 탄화 수소기(치환 탄화 수소기)도 포함하는 것이다. 이것은, 각 화합물에 대해서도 동의이다.In addition, in the notation of the group (atom group) in the present invention, the notation that does not indicate substitution or unsubstituted includes not only having no substituent but also having a substituent within the range not impairing the effect of the present invention. Is to do. For example, the "hydrocarbon group" includes not only a hydrocarbon group not having a substituent (unsubstituted hydrocarbon group), but also a hydrocarbon group having a substituent (substituted hydrocarbon group). This is also synonymous with each compound.
〔연마액〕〔Abrasive solution〕
본 발명의 연마액은,The polishing liquid of the present invention,
화학적 기계적 연마에 이용되는 연마액으로서,As a polishing liquid used for chemical mechanical polishing,
지립과, 유기산과, 수용성 고분자를 함유하고,It contains abrasive grains, organic acids, and water-soluble polymers,
하기 식 (1)~식 (3)을 모두 충족시킨다.All of the following formulas (1) to (3) are satisfied.
식 (1): 1.5≤η100rpm/η1000rpm≤20Equation (1): 1.5≤η 100rpm / η 1000rpm ≤20
식 (2): 1.2≤η100rpm/η500rpm≤10Equation (2): 1.2≤η 100rpm / η 500rpm ≤10
식 (3): η100rpm/η1000rpm>η100rpm/η500rpm Equation (3): η 100rpm /η 1000rpm >η 100rpm /η 500rpm
식 (1)~식 (3) 중, η100rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 100rpm으로 측정되는 상기 연마액의 점도이고, η500rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 500rpm으로 측정되는 상기 연마액의 점도이며, η1000rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 1000rpm으로 측정되는 상기 연마액의 점도이다.In formulas (1) to (3), η 100 rpm is the viscosity of the polishing liquid measured at a rotational speed of 100 rpm by a rotational viscometer at 40%RH and 23°C, and η 500rpm is 40%RH, 23°C. Is the viscosity of the polishing liquid measured at a rotational speed of 500 rpm by a rotational viscometer, and η 1000rpm is the viscosity of the polishing liquid measured at a rotational viscometer at 40%RH and 23°C at a rotational speed of 1000 rpm.
도 1은, 피연마체인 웨이퍼에 대하여 연마 패드를 이용하여 CMP를 실시하는 공정 시에, 웨이퍼와 연마 패드의 상대 위치를 나타낸 모식도이다. 또, 도 2는, 뉴턴성을 나타내는 연마액을 이용하여 CMP를 실시한 경우에 있어서, 웨이퍼의 평면 내에 있어서의 각 위치(중심부(A)와, 둘레 가장자리부(B 및 C))의 연마 속도(연마량)를 나타내는 도이다. 도 1 및 도 2에 나타내는 바와 같이, 웨이퍼(1)의 평면에 있어서, 중심부(A)에 대하여 둘레 가장자리부(B 및 C)는 전단력을 받기 쉬워, 둘레 가장자리부(B 및 C)에서는 연마 속도가 빠르다. 이로 인하여, 피연마체는, 중심부(A)에 대하여 둘레 가장자리부(B 및 C)에 있어서 그 연마량이 보다 많아진다. 또한, 웨이퍼(1)의 회전에 의하여, 둘레 가장자리부(B 및 C)에서의 연마 속도의 차(전단력의 차)는 해소되어 있어, 둘레 가장자리부(B 및 C)에 있어서의 연마량은 대략 동일해진다.1 is a schematic diagram showing a relative position between a wafer and a polishing pad in a step of performing CMP using a polishing pad on a wafer as a polishing target. In addition, FIG. 2 shows the polishing rate at each position in the plane of the wafer (central portion (A) and peripheral edge portions (B and C)) in the case of performing CMP using a polishing liquid exhibiting Newtonian properties ( It is a diagram showing the amount of polishing). As shown in Figs. 1 and 2, in the plane of the
상기와 같이, 뉴턴성의 연마액을 이용하여 피연마체에 대하여 CMP를 실시한 경우, 피연마체는, 중심부에 대하여 둘레 가장자리부의 연마량이 커, 면내 균일성이 뒤떨어지는 것이 된다.As described above, when CMP is performed on an object to be polished using a Newtonian polishing liquid, the polishing amount of the peripheral edge portion of the object to be polished is large with respect to the central portion, resulting in inferior in-plane uniformity.
이것에 대하여, 본 발명의 연마액은, 상기 식 (1)~식 (3)을 모두 충족시키는 점에 특징이 있다. 이 특징에 의하여, 본 발명의 연마액을 이용하여 피연마체에 대하여 CMP를 실시한 경우, 웨이퍼(1)의 평면에 있어서, 둘레 가장자리부(B 및 C)일수록 연마액의 점도가 낮아진다. 즉, 연마액이 저점성인 것에 의하여, 연마 패드(2)로부터의 전단력이 완화되기 쉬워, 피연마체의 연마량이 작아진다.On the other hand, the polishing liquid of the present invention is characterized in that it satisfies all of the above formulas (1) to (3). Due to this feature, when CMP is performed on an object to be polished using the polishing liquid of the present invention, the viscosity of the polishing liquid decreases as the circumferential edges B and C in the plane of the
여기에서, 본 발명의 상기 식 (1)~식 (3)을 설명한다.Here, the above formulas (1) to (3) of the present invention will be described.
식 (1)에 있어서, η100rpm/η1000rpm<1.5이면, 연마액이 뉴턴성과 대략 동일한 거동을 나타내고, 상술과 같이, 면내 균일성이 뒤떨어지는 것이 된다(상기 도 2 참조). 한편, 식 (1)에 있어서, η100rpm/η1000rpm>20이면, 웨이퍼(1)의 평면에 있어서, 중심부(A)에 대하여, 둘레 가장자리부(B 및 C)의 연마액의 점도가 과도하게 낮아진다. 이 결과, 중심부(A)에 있어서의 연마량이 커져, 면내 균일성이 뒤떨어지는 것이 된다(상기 도 4 참조). 1.5≤η100rpm/η1000rpm≤20의 범위에 있는 경우, 면내 균일성이 우수하다(상기 도 3 참조).In the formula (1), when η 100 rpm / η 1000 rpm <1.5, the polishing liquid exhibits substantially the same behavior as Newtonian property, and as described above, the in-plane uniformity is inferior (see Fig. 2). On the other hand, in the formula (1), if η 100 rpm / η 1000 rpm >20, the viscosity of the polishing liquid at the peripheral edges (B and C) is excessive in the plane of the wafer (1) with respect to the center (A). Lowers. As a result, the amount of polishing in the central portion A increases, and the in-plane uniformity is inferior (see Fig. 4). Is in the range of 1.5≤η 100rpm / η ≤20 1000rpm, in-plane uniformity is excellent (see FIG. 3).
또, 면내 균일성의 관점에서는, 회전 점도계에 의하여 100rpm~1000rpm의 사이의 회전수로 측정되는 점도에 대해서도, 연마 속도(연마량)가 큰 개소일수록 그 값이 낮은 것이 바람직하고, 적어도 식 (2) 및 식 (3)을 충족시킬 필요가 있다.In addition, from the viewpoint of in-plane uniformity, the value of the viscosity measured at a rotational speed between 100 rpm and 1000 rpm by a rotational viscometer is preferably lower as the polishing rate (amount of polishing) is larger, and at least Equation (2) And Equation (3) needs to be satisfied.
식 (2)에 있어서, η100rpm/η500rpm<1.2인 경우, 연마액이 뉴턴성을 나타내고, 면내 균일성이 뒤떨어지는 것이 된다. 한편, 식 (2)에 있어서, η100rpm/η500rpm>10이면, 중심부(A)에 있어서의 연마량이 커져, 면내 균일성이 뒤떨어지는 것이 된다.In the formula (2), when η 100 rpm / η 500 rpm <1.2, the polishing liquid exhibits Newtonian properties, and the in-plane uniformity is inferior. On the other hand, in the formula (2), if η 100 rpm / η 500 rpm >10, the amount of polishing in the center A increases, and the in-plane uniformity is inferior.
또한, 본 명세서에 있어서 회전 점도계로 측정되는 점도란, 브룩필드형 회전 점도계에 의하여, 40%RH, 23℃에서 측정된 점도를 의미한다.In addition, in the present specification, the viscosity measured by a rotational viscometer means a viscosity measured at 40%RH and 23°C by a Brookfield type rotational viscometer.
이하, 본 발명의 연마액의 액성 및 각 성분에 대하여 상세하게 설명한다.Hereinafter, the liquidity and each component of the polishing liquid of the present invention will be described in detail.
<pH><pH>
상기 연마액의 pH는, 2.0~8.0인 것이 바람직하고, 피연마체의 재질에 따라 적절히 설정할 수 있다. 연마액의 pH는, pH 미터(예를 들면, 도아 덴파 고교 가부시키가이샤, HM-30G)를 이용하여 측정할 수 있다.The pH of the polishing liquid is preferably 2.0 to 8.0, and can be appropriately set according to the material of the object to be polished. The pH of the polishing liquid can be measured using a pH meter (eg, Toa Denpa Kogyo Co., Ltd., HM-30G).
예를 들면, 연마 대상이 후술하는 바와 같은 금속층인 경우에는, 연마 속도 및 면내 균일성을 더 향상시킬 수 있는 관점에서, 2.0~6.0이 보다 바람직하고, 2.0~5.0이 더 바람직하며, 2.0~4.0이 특히 바람직하다.For example, when the object to be polished is a metal layer as described later, from the viewpoint of further improving the polishing rate and in-plane uniformity, 2.0 to 6.0 are more preferable, 2.0 to 5.0 are more preferable, and 2.0 to 4.0 This is particularly preferred.
또, 예를 들면 연마 대상이, 후술하는 바와 같은, 무기 절연층인 경우에는, 면내 균일성을 더 향상시킬 수 있는 관점에서, 2.0~6.0이 보다 바람직하다.Further, for example, when the object to be polished is an inorganic insulating layer as described later, from the viewpoint of further improving the in-plane uniformity, 2.0 to 6.0 are more preferable.
<점도><viscosity>
상술과 같이, 연마액의 점도는, 상기 식 (1)~(3)의 관계를 충족시킨다.As described above, the viscosity of the polishing liquid satisfies the relationship of the formulas (1) to (3).
보다 면내 균일성을 향상시키는 관점에서, η100rpm/η1000rpm은, 1.5~10이 바람직하고, 1.5~5가 보다 바람직하다. 또, 보다 면내 균일성을 향상시키는 관점에서, η100rpm/η500rpm은, 1.2~5가 바람직하고, 1.2~3이 보다 바람직하다.From the viewpoint of further improving the in-plane uniformity, η 100 rpm / η 1000 rpm is preferably 1.5 to 10, more preferably 1.5 to 5. In addition, from the viewpoint of further improving the in-plane uniformity, η 100 rpm / η 500 rpm is preferably 1.2 to 5, and more preferably 1.2 to 3.
연마 속도 및 면내 균일성을 보다 양호하게 하는 관점에서, η100rpm은, 1.0~10.0cP가 바람직하고, 1.2~5.0cP가 보다 바람직하다. 또, 연마 속도 및 면내 균일성을 보다 양호하게 하는 관점에서, η500rpm은, 1.0~8.0cP가 바람직하고, 1.2~4.0cP가 보다 바람직하다. 또, 연마 속도 및 면내 균일성을 보다 양호하게 하는 관점에서, η1000rpm은, 0.8~5.0cP가 바람직하고, 1.0~3.5cP가 보다 바람직하다.From the viewpoint of making the polishing rate and in-plane uniformity more favorable, η 100 rpm is preferably 1.0 to 10.0 cP, and more preferably 1.2 to 5.0 cP. Moreover, from the viewpoint of making the polishing rate and in-plane uniformity more favorable, η 500 rpm is preferably 1.0 to 8.0 cP, and more preferably 1.2 to 4.0 cP. Moreover, from a viewpoint of making the polishing rate and in-plane uniformity more favorable, η 1000 rpm is preferably 0.8 to 5.0 cP, and more preferably 1.0 to 3.5 cP.
<지립><Grain>
상기 연마액은, 지립을 함유한다.The polishing liquid contains abrasive grains.
상기 지립으로서는 특별히 제한되지 않고, 공지의 지립을 이용할 수 있다.The abrasive grains are not particularly limited, and known abrasive grains can be used.
지립으로서는 예를 들면, 실리카, 알루미나, 지르코니아, 세리아, 타이타니아, 저마니아, 및 탄화 규소 등의 무기물 지립; 폴리스타이렌, 폴리아크릴, 및 폴리 염화 바이닐 등의 유기물 지립을 들 수 있다. 그 중에서도, 연마액 중에서의 분산 안정성이 우수한 점, 및 CMP에 의하여 발생하는 스크래치의 발생수가 적은 점에서, 지립으로서는 실리카 입자 또는 세리아 입자가 바람직하고, 실리카 입자가 보다 바람직하다.Examples of the abrasive include inorganic abrasives such as silica, alumina, zirconia, ceria, titania, germania, and silicon carbide; And organic abrasive grains such as polystyrene, polyacrylic, and polyvinyl chloride. Among them, silica particles or ceria particles are preferable as abrasive grains, and silica particles are more preferable because of the excellent dispersion stability in the polishing liquid and the small number of scratches generated by CMP.
실리카 입자로서는 특별히 제한되지 않고, 예를 들면 침강 실리카, 흄드 실리카, 및 콜로이달 실리카 등을 들 수 있다. 그 중에서도, 콜로이달 실리카가 바람직하다.The silica particles are not particularly limited, and examples thereof include precipitated silica, fumed silica, and colloidal silica. Among them, colloidal silica is preferred.
지립의 평균 일차 입경은 특별히 제한되지 않지만, 연마액이 보다 우수한 분산 안정성을 갖는 점에서, 1~100nm가 바람직하다. 또한, 상기 평균 일차 입경은, 제조 회사의 카탈로그 등에 의하여 확인할 수 있다.The average primary particle diameter of the abrasive grains is not particularly limited, but is preferably 1 to 100 nm in view of the polishing liquid having more excellent dispersion stability. In addition, the average primary particle diameter can be confirmed by a catalog of a manufacturer or the like.
상기 지립의 시판품으로서는, 예를 들면 콜로이달 실리카로서, PL-1, PL-3, PL-7, 및 PL-10H 등(모두 상품명, 후소 가가쿠 고교사제)을 들 수 있다.As a commercial item of the said abrasive grain, PL-1, PL-3, PL-7, PL-10H, etc. (all a brand name, the product made by Fuso Chemical Co., Ltd.) are mentioned, for example as colloidal silica.
지립의 함유량으로서는 특별히 제한되지 않고, 연마액 전체 질량에 대하여 0.01~10질량%가 바람직하다. 상기 범위 내이면, 연마액을 CMP에 적용한 경우, 연마 속도가 우수한 것 외에, 면내 균일성을 더 향상시킬 수 있다. 면내 균일성을 보다 향상시키는 관점에서, 지립의 함유량의 하한은, 연마액 전체 질량에 대하여, 0.1질량% 이상이 보다 바람직하고, 3질량% 이상이 더 바람직하다.The content of the abrasive is not particularly limited, and is preferably 0.01 to 10% by mass relative to the total mass of the polishing liquid. Within the above range, when the polishing liquid is applied to CMP, in addition to excellent polishing speed, in-plane uniformity can be further improved. From the viewpoint of further improving the in-plane uniformity, the lower limit of the content of the abrasive grains is more preferably 0.1% by mass or more, and still more preferably 3% by mass or more with respect to the total mass of the polishing liquid.
또한, 지립은 1종을 단독으로 이용해도 되고, 2종 이상을 병용해도 된다. 2종 이상의 지립을 병용하는 경우에는, 합계 함유량이 상기 범위 내인 것이 바람직하다.In addition, the abrasive grains may be used alone or in combination of two or more. When using two or more kinds of abrasive grains together, it is preferable that the total content is within the above range.
<유기산><Organic acid>
상기 연마액은, 유기산을 함유한다. 유기산은, 후술하는 산화제와는 다른 화합물이고, 금속의 산화 촉진, 연마액의 pH 조정, 및 완충제로서의 작용을 갖는다.The polishing liquid contains an organic acid. The organic acid is a compound different from the oxidizing agent described later, and has an effect of promoting metal oxidation, adjusting the pH of the polishing liquid, and acting as a buffering agent.
유기산으로서는, 수용성의 유기산이 바람직하다.As the organic acid, a water-soluble organic acid is preferable.
유기산으로서는, 특별히 제한되지 않고, 공지의 유기산을 이용할 수 있다.The organic acid is not particularly limited, and a known organic acid can be used.
유기산으로서는, 예를 들면 폼산, 아세트산, 프로피온산, 뷰티르산, 발레르산, 2-메틸뷰티르산, n-헥산산, 3,3-다이메틸뷰티르산, 2-에틸뷰티르산, 4-메틸펜탄산, n-헵탄산, 2-메틸헥산산, n-옥탄산, 2-에틸헥산산, 벤조산, 글라이콜산, 살리실산, 글리세린산, 옥살산, 말론산, 석신산, 글루타르산, 아디프산, 피멜산, 말레산, 프탈산, 말산, 타타르산, 시트르산, 락트산, 하이드록시에틸이미노 이아세트산, 이미노 이아세트산과, 이들의 암모늄염 및/또는 알칼리 금속염 등의 염을 들 수 있다. 그 중에서도, 석신산, 말산, 말론산 및 시트르산으로 이루어지는 군으로부터 선택되는 적어도 어느 1종인 것이 보다 바람직하다.Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, valeric acid, 2-methylbutyric acid, n-hexanoic acid, 3,3-dimethylbutyric acid, 2-ethylbutyric acid, 4-methylpentanoic acid, n-heptanoic acid, 2-methylhexanoic acid, n-octanoic acid, 2-ethylhexanoic acid, benzoic acid, glycolic acid, salicylic acid, glyceric acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, blood And salts such as melic acid, maleic acid, phthalic acid, malic acid, tartaric acid, citric acid, lactic acid, hydroxyethylimino diacetic acid, imino diacetic acid and ammonium salts and/or alkali metal salts thereof. Especially, it is more preferable that it is at least any 1 type selected from the group consisting of succinic acid, malic acid, malonic acid, and citric acid.
유기산의 함유량으로서는 특별히 제한되지 않고, 연마액 전체 질량에 대하여, 0.001질량% 이상이 바람직하며, 0.01질량% 이상이 보다 바람직하고, 0.1질량% 이상이 더 바람직하다. 연마 속도 및 면내 균일성을 보다 향상시키는 관점에서, 유기산의 함유량은, 연마액 전체 질량에 대하여, 10질량% 이하가 바람직하고, 5질량% 이하가 보다 바람직하며, 3질량% 이하가 더 바람직하다.The content of the organic acid is not particularly limited, and is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, and still more preferably 0.1% by mass or more with respect to the total mass of the polishing liquid. From the viewpoint of further improving the polishing rate and in-plane uniformity, the content of the organic acid is preferably 10% by mass or less, more preferably 5% by mass or less, and more preferably 3% by mass or less based on the total mass of the polishing liquid. .
또한, 유기산은 1종을 단독으로 이용해도 되고, 2종 이상을 병용해도 된다. 2종 이상의 유기산을 병용하는 경우에는, 합계 함유량이 상기 범위 내인 것이 바람직하다.In addition, organic acids may be used singly or in combination of two or more. When using two or more types of organic acids together, it is preferable that the total content is within the above range.
<수용성 고분자><Water-soluble polymer>
본 발명의 연마액은, 수용성 고분자를 함유한다. 수용성 고분자는, 연마액의 점도 조정제로서의 작용을 갖는다.The polishing liquid of the present invention contains a water-soluble polymer. The water-soluble polymer has an action as a viscosity modifier of the polishing liquid.
수용성 고분자로서는, 카복실기를 갖는 모노머를 기본 구성 단위로 하는 폴리머 및 그 염과, 그들을 포함하는 공중합체를 들 수 있다. 구체적으로는, 폴리아크릴산 및 그 염과, 그들을 포함하는 공중합체; 폴리메타크릴산 및 그 염과, 그들을 포함하는 공중합체; 폴리아마이드산 및 그 염과, 그들을 포함하는 공중합체; 폴리말레산, 폴리이타콘산, 폴리푸마르산, 폴리(p-스타이렌카복실산), 및 폴리글리옥실산 등의 폴리카복실산 및 그 염과, 그들을 포함하는 공중합체를 들 수 있다.Examples of the water-soluble polymer include a polymer having a monomer having a carboxyl group as a basic structural unit, a salt thereof, and a copolymer containing them. Specifically, polyacrylic acid and its salts, and copolymers containing them; Polymethacrylic acid and salts thereof, and copolymers containing them; Polyamide acids and salts thereof, and copolymers containing them; Polycarboxylic acids such as polymaleic acid, polyitaconic acid, polyfumaric acid, poly(p-styrenecarboxylic acid), and polyglyoxylic acid, and salts thereof, and copolymers containing them.
또, 상기 외에, 폴리바이닐알코올, 폴리바이닐피롤리돈 및 폴리아크롤레인 등의 바이닐계 폴리머를 들 수 있다.In addition to the above, vinyl-based polymers such as polyvinyl alcohol, polyvinylpyrrolidone and polyacrolein may be mentioned.
단, 적용하는 피연마체가 반도체 집적 회로용 실리콘 기판 등인 경우는 알칼리 금속, 알칼리 토류 금속 및/또는 할로젠화물 등에 의한 오염은 바람직하지 않기 때문에, 수용성 고분자가 산인 경우는, 산인 채로 이용하거나, 혹은, 그의 암모늄염 상태로 이용하는 것이 바람직하다.However, when the object to be polished is a silicon substrate for semiconductor integrated circuits, contamination by alkali metals, alkaline earth metals and/or halides is not preferable. Therefore, when the water-soluble polymer is an acid, it is used as an acid, or , It is preferable to use it in its ammonium salt state.
수용성 고분자로서는, 상기 중에서도, 폴리아크릴산, 폴리메타크릴산, 폴리말레산, 폴리아크릴아마이드, 폴리아크릴산 암모늄염, 폴리바이닐알코올, 폴리바이닐피롤리돈 혹은 폴리에틸렌글라이콜 또는 이들을 포함하는 공중합체, 또는 폴리옥시에틸렌-폴리옥시프로필렌 블록 폴리머가 바람직하다. 그 중에서도, 폴리아크릴산, 폴리메타크릴산 및, 폴리아크릴산과 폴리메타크릴산 중 적어도 1종을 함유하는 공중합체(상기 폴리아크릴산 및 폴리메타크릴산 중 적어도 1종을 함유하는 공중합체란, 아크릴산에서 유래하는 구조 단위를 함유하는 공중합체, 메타크릴산에서 유래하는 구조 단위를 함유하는 공중합체, 또는 아크릴산에서 유래하는 구조 단위 및 메타아크릴산에서 유래하는 구조 단위를 함유하는 공중합체를 의도함)로 이루어지는 군으로부터 선택되는 적어도 어느 1종이 더 바람직하다.As a water-soluble polymer, among the above, polyacrylic acid, polymethacrylic acid, polymaleic acid, polyacrylamide, polyacrylic acid ammonium salt, polyvinyl alcohol, polyvinylpyrrolidone or polyethylene glycol, or a copolymer containing these, or poly Oxyethylene-polyoxypropylene block polymers are preferred. Among them, a copolymer containing at least one of polyacrylic acid, polymethacrylic acid, and polyacrylic acid and polymethacrylic acid (a copolymer containing at least one of polyacrylic acid and polymethacrylic acid is an acrylic acid Consisting of a copolymer containing a structural unit derived from, a copolymer containing a structural unit derived from methacrylic acid, or a copolymer containing a structural unit derived from acrylic acid and a structural unit derived from methacrylic acid) At least any one selected from the group is more preferable.
수용성 고분자의 중량 평균 분자량으로서는, 연마액의 점도가 적절히 조정되어, 양호한 면내 균일성을 달성하는 관점에서, GPC(젤 침투 크로마토그래피)법에 의한 폴리스타이렌 환산값으로서, 취급성의 관점에서, 통상, 3000~100000이 바람직하고, 5000~100000이 보다 바람직하며, 10000~50000이 더 바람직하고, 15000~30000이 특히 바람직하다. 또한, GPC법은, HLC-8020GPC(도소(주)제)를 이용하여, 칼럼으로서 TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000(도소(주)제, 4.6mmID×15cm)을, 용리액으로서 THF(테트라하이드로퓨란)를 이용하는 방법에 근거한다.As the weight average molecular weight of the water-soluble polymer, the viscosity of the polishing liquid is appropriately adjusted, from the viewpoint of achieving good in-plane uniformity, as a polystyrene conversion value by GPC (gel permeation chromatography) method, from the viewpoint of handling properties, usually 3000 -100000 are preferable, 5000--100000 are more preferable, 10000-50000 are more preferable, and 15000-30000 are especially preferable. In the GPC method, HLC-8020GPC (manufactured by Tosoh Corporation) was used as a column, TSKgel SuperHZM-H, TSKgel SuperHZ4000, TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6mmID×15cm) as an eluent, and THF ( It is based on a method using tetrahydrofuran).
수용성 고분자의 함유량으로서는 특별히 제한되지 않고, 연마액 전체 질량에 대하여, 0.01~10질량%가 바람직하다. 수용성 고분자의 함유량이, 0.01질량% 이상이면, 면내 균일성이 보다 양호해진다. 또, 수용성 고분자의 함유량이 10질량% 이하이면, 연마 속도가 우수한 것 외에, 면내 균일성이 보다 양호해진다. 면내 균일성을 보다 향상시키는 관점에서, 수용성 고분자의 함유량의 하한은, 연마액 전체 질량에 대하여, 0.1질량% 이상이 보다 바람직하고, 0.5질량% 이상이 더 바람직하다. 또, 면내 균일성을 보다 향상시키는 관점에서, 수용성 고분자의 함유량의 상한은, 연마액 전체 질량에 대하여, 5질량% 이하가 보다 바람직하고, 4질량% 이하가 더 바람직하다.The content of the water-soluble polymer is not particularly limited, and is preferably 0.01 to 10% by mass based on the total mass of the polishing liquid. When the content of the water-soluble polymer is 0.01% by mass or more, the in-plane uniformity becomes more favorable. Moreover, when the content of the water-soluble polymer is 10% by mass or less, the polishing rate is excellent, and the in-plane uniformity is more favorable. From the viewpoint of further improving the in-plane uniformity, the lower limit of the content of the water-soluble polymer is more preferably 0.1% by mass or more and even more preferably 0.5% by mass or more with respect to the total mass of the polishing liquid. In addition, from the viewpoint of further improving the in-plane uniformity, the upper limit of the content of the water-soluble polymer is more preferably 5% by mass or less, and still more preferably 4% by mass or less with respect to the total mass of the polishing liquid.
또한, 수용성 고분자는 1종을 단독으로 이용해도 되고, 2종 이상을 병용해도 된다. 2종 이상의 수용성 고분자를 병용하는 경우에는, 합계 함유량이 상기 범위 내인 것이 바람직하다.In addition, water-soluble polymers may be used singly or in combination of two or more. When two or more water-soluble polymers are used in combination, it is preferable that the total content is within the above range.
<그 외의 성분><Other ingredients>
(산화제)(Oxidant)
상기 연마액은, 배선 형성 시의 여분의 금속 박막의 제거의 CMP 용도에 적용하는 경우에는, 산화제를 함유하는 것이 바람직하다. 산화제는, 피연마체의 피연마면에 존재하는 연마 대상이 되는 금속을 산화시키는 기능을 갖는다.It is preferable that the polishing liquid contains an oxidizing agent when applied to a CMP application for removing an excess metal thin film during wiring formation. The oxidizing agent has a function of oxidizing a metal to be polished present on the surface to be polished of the object to be polished.
산화제로서는 특별히 제한되지 않고, 공지의 산화제를 이용할 수 있다.The oxidizing agent is not particularly limited, and a known oxidizing agent can be used.
산화제로서는, 예를 들면 과산화 수소, 과산화물, 질산, 질산염, 아이오딘산염, 과아이오딘산염, 차아염소산염, 아염소산염, 염소산염, 과염소산염, 과황산염, 중크로뮴산염, 과망가니즈산염, 오존수, 은(II)염, 및 철(III)염 등을 들 수 있다. 그 중에서도, 과산화 수소가 바람직하다.Examples of the oxidizing agent include hydrogen peroxide, peroxide, nitric acid, nitrate, iodate, periodate, hypochlorite, chlorite, chlorate, perchlorate, persulfate, dichromate, permanganate, ozonated water, silver ( II) salt, and iron (III) salt, etc. are mentioned. Among them, hydrogen peroxide is preferable.
상기 연마액이 산화제를 함유하는 경우, 그 함유량으로서는 특별히 제한되지 않지만, 연마액 전체 질량에 대하여, 0.005~10질량%가 바람직하다. 산화제의 함유량이 0.005질량% 이상이면, 연마액을 CMP에 적용한 경우에, 보다 우수한 연마 속도가 얻어진다. 산화제의 함유량이 10질량% 이하이면, 연마액을 CMP에 적용한 경우에, 피연마면에 디싱이 보다 발생하기 어렵다.When the polishing liquid contains an oxidizing agent, the content is not particularly limited, but is preferably 0.005 to 10 mass% with respect to the total mass of the polishing liquid. When the content of the oxidizing agent is 0.005% by mass or more, a more excellent polishing rate can be obtained when the polishing liquid is applied to CMP. When the content of the oxidizing agent is 10% by mass or less, when the polishing liquid is applied to CMP, dishing is more difficult to occur on the surface to be polished.
면내 균일성을 보다 향상시키는 관점에서, 산화제의 함유량의 하한은, 연마액 전체 질량에 대하여, 0.03질량% 이상이 보다 바람직하고, 1질량% 이상이 더 바람직하다. 또, 면내 균일성을 보다 향상시키는 관점에서, 산화제의 함유량의 상한은, 연마액 전체 질량에 대하여, 5질량% 이하가 보다 바람직하다.From the viewpoint of further improving the in-plane uniformity, the lower limit of the content of the oxidizing agent is more preferably 0.03% by mass or more and even more preferably 1% by mass or more with respect to the total mass of the polishing liquid. Further, from the viewpoint of further improving the in-plane uniformity, the upper limit of the content of the oxidizing agent is more preferably 5% by mass or less with respect to the total mass of the polishing liquid.
또한, 산화제는 1종을 단독으로 이용해도 되고, 2종 이상을 병용해도 된다. 2종 이상의 산화제를 병용하는 경우에는, 합계 함유량이 상기 범위 내인 것이 바람직하다.In addition, an oxidizing agent may be used individually by 1 type, and may use 2 or more types together. When using two or more types of oxidizing agents together, it is preferable that the total content is within the above range.
(물)(water)
상기 연마액은, 물을 함유하는 것이 바람직하다. 상기 연마액이 함유하는 물로서는, 특별히 제한되지 않지만, 이온 교환수, 또는 순수 등을 이용할 수 있다.It is preferable that the polishing liquid contains water. The water contained in the polishing liquid is not particularly limited, but ion-exchanged water or pure water can be used.
물의 함유량으로서는 특별히 제한되지 않지만, 연마액 전체 질량 중, 통상 80~99질량%가 바람직하다.Although it does not specifically limit as content of water, 80-99 mass% is usually preferable with respect to the total mass of a polishing liquid.
(아졸 화합물)(Azole compound)
상기 연마액은, 배선 형성 시의 여분의 금속 박막의 제거 등의 CMP 용도에 적용하는 경우에는, 아졸 화합물을 함유하는 것이 바람직하다. 아졸 화합물은, 상술한 임의 성분인 산화제에 의한 산화 작용을 향상시킬 뿐만 아니라, 피연마체 표면에 흡착하여 피막을 형성하고, 금속 표면의 부식을 제어하기 때문에, 디싱 또는 이로전(erosion)의 발생을 억제할 수 있다.When the polishing liquid is applied to a CMP application such as removal of an excess metal thin film during wiring formation, it is preferable to contain an azole compound. The azole compound not only improves the oxidation action by the oxidizing agent, which is an optional component described above, but also forms a film by adsorbing to the surface of the object to be polished, and controls corrosion of the metal surface, thereby preventing the occurrence of dishing or erosion. Can be suppressed.
본 명세서에 있어서, 아졸 화합물이란, 질소 원자를 1개 이상 함유하는 복소 오원환을 함유하는 화합물을 의도하고, 질소 원자수로서는 1~4개가 바람직하다. 또, 아졸 화합물은 질소 원자 이외의 원자를 헤테로 원자로서 함유해도 된다.In the present specification, the azole compound means a compound containing a hetero five-membered ring containing one or more nitrogen atoms, and the number of nitrogen atoms is preferably 1 to 4. Moreover, the azole compound may contain an atom other than a nitrogen atom as a hetero atom.
또, 상기 유도체는, 상기 복소 오원환이 함유할 수 있는 치환기를 갖는 화합물을 의도한다.Further, the derivative is intended to be a compound having a substituent that the hetero five membered ring may contain.
상기 아졸 화합물로서는, 예를 들면 피롤 골격, 이미다졸 골격, 피라졸 골격, 아이소싸이아졸 골격, 아이소옥사졸 골격, 트라이아졸 골격, 테트라졸 골격, 싸이아졸 골격, 옥사졸 골격, 싸이아다이아졸 골격, 옥사다이아졸 골격, 및 테트라졸 골격을 갖는 화합물 등을 들 수 있다.Examples of the azole compound include a pyrrole skeleton, imidazole skeleton, pyrazole skeleton, isothiazole skeleton, isoxazole skeleton, triazole skeleton, tetrazole skeleton, thiazole skeleton, oxazole skeleton, and thiadiazole skeleton. , Compounds having an oxadiazole skeleton, and a tetrazole skeleton.
상기 아졸 화합물로서는, 상기의 골격에 축합환을 함유하는 다환 구조를 더 함유하는 아졸 화합물이어도 된다. 상기 다환 구조를 함유하는 아졸 화합물로서는 예를 들면, 인돌 골격, 퓨린 골격, 인다졸 골격, 벤즈이미다졸 골격, 카바졸 골격, 벤즈옥사졸 골격, 벤조싸이아졸 골격, 벤조싸이아다이아졸 골격, 및 나프토이미다졸 골격을 함유하는 화합물 등을 들 수 있다.The azole compound may be an azole compound further containing a polycyclic structure containing a condensed ring in the skeleton. Examples of the azole compound containing the polycyclic structure include an indole skeleton, a purine skeleton, an indazole skeleton, a benzimidazole skeleton, a carbazole skeleton, a benzoxazole skeleton, a benzothiazole skeleton, a benzothiadiazole skeleton, and And compounds containing a naphthoimidazole skeleton.
아졸 화합물이 함유할 수 있는 치환기로서는 특별히 제한되지 않지만, 예를 들면 할로젠 원자(불소 원자, 염소 원자, 브로민 원자, 또는 아이오딘 원자), 알킬기(직쇄, 분기 또는 환상의 알킬기이고, 바이사이클로알킬기와 같이 다환 알킬기여도 되고, 활성 메타인기를 포함해도 됨), 알켄일기, 알카인일기, 아릴기, 헤테로환기(치환하는 위치는 불문함), 아실기, 알콕시카보닐기, 아릴옥시카보닐기, 헤테로환 옥시카보닐기, 카바모일기(치환기를 갖는 카바모일기로서는, 예를 들면 N-하이드록시카바모일기, N-아실카바모일기, N-설폰일카바모일기, N-카바모일카바모일기, 싸이오카바모일기, 및 N-설파모일카바모일기 등을 들 수 있음), 카바조일기, 카복실기 또는 그 염, 옥살일기, 옥사모일기, 사이아노기, 카본이미도일기, 폼일기, 하이드록시기, 알콕시기(에틸렌옥시기 또는 프로필렌옥시기를 반복 단위로서 포함하는 기를 포함함), 아릴옥시기, 헤테로환 옥시기, 아실옥시기, 카보닐옥시기, 카바모일옥시기, 설폰일옥시기, 아미노기, 아실아미노기, 설폰아마이드기, 유레이도기, 싸이오유레이도기, N-하이드록시유레이도기, 이미드기, 카보닐아미노기, 설파모일아미노기, 세미카바자이드기, 싸이오세미카바자이드기, 하이드라지노기, 암모니오기, 옥사모일아미노기, N-(알킬 또는 아릴)설폰일유레이도기, N-아실유레이도기, N-아실설파모일아미노기, 하이드록시아미노기, 나이트로기, 4급화된 질소 원자를 포함하는 헤테로환기(예를 들면, 피리디니오기, 이미다졸리오기, 퀴놀리니오기, 및 아이소퀴놀리니오기를 들 수 있음), 아이소사이아노기, 이미노기, 머캅토기, (알킬, 아릴, 또는 헤테로환)싸이오기, (알킬, 아릴, 또는 헤테로환)다이싸이오기, (알킬 또는 아릴)설폰일기, (알킬 또는 아릴)설핀일기, 설포기 또는 그 염, 설파모일기(치환기를 갖는 설파모일기로서는, 예를 들면 N-아실설파모일기, 및 N-설폰일설파모일기를 들 수 있음) 또는 그 염, 포스피노기, 포스핀일기, 포스핀일옥시기, 포스핀일아미노기, 및 실릴기 등을 들 수 있다.The substituent that the azole compound may contain is not particularly limited, but for example, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (a straight chain, branched or cyclic alkyl group, and a bicyclo It may be a polycyclic alkyl group such as an alkyl group, or an active metaine group), alkenyl group, alkynyl group, aryl group, heterocyclic group (regardless of the position to be substituted), acyl group, alkoxycarbonyl group, aryloxycarbonyl group, Heterocyclic oxycarbonyl group, carbamoyl group (as a carbamoyl group having a substituent, for example, N-hydroxycarbamoyl group, N-acylcarbamoyl group, N-sulfonylcarbamoyl group, N-carbamoylcarbamo Diary, thiocarbamoyl group, and N-sulfamoylcarbamoyl group, etc.), carbazoyl group, carboxyl group or salt thereof, oxalyl group, oxamoyl group, cyano group, carbonimidoyl group, formil group , A hydroxy group, an alkoxy group (including a group containing an ethyleneoxy group or a propyleneoxy group as a repeating unit), an aryloxy group, a heterocyclic oxy group, an acyloxy group, a carbonyloxy group, a carbamoyloxy group, a sulfonyloxy group, Amino group, acylamino group, sulfonamide group, ureido group, thiourido group, N-hydroxyureido group, imide group, carbonylamino group, sulfamoylamino group, semicarbazide group, thiosemicarbazide group, hydrazino group, Heterocyclic groups including ammonio groups, oxamoylamino groups, N-(alkyl or aryl)sulfonylureido groups, N-acylureido groups, N-acylsulfamoylamino groups, hydroxyamino groups, nitro groups, and quaternized nitrogen atoms (For example, a pyridini group, an imidazoli group, a quinolini group, and an isoquinolini group may be mentioned), isocyano group, imino group, mercapto group, (alkyl, aryl, or heterocycle) Thio group, (alkyl, aryl, or heterocyclic) dithio group, (alkyl or aryl) sulfonyl group, (alkyl or aryl) sulfinyl group, sulfo group or a salt thereof, sulfamoyl group (as a sulfamoyl group having a substituent, For example, N-acylsulfamoyl group and N-sulfonylsulfamoyl group may be mentioned) or salts thereof, phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, etc. Can be mentioned.
그 중에서도, 할로젠 원자(불소 원자, 염소 원자, 브로민 원자, 또는 아이오딘 원자), 알킬기(직쇄, 분기 또는 환상의 알킬기이고, 바이사이클로알킬기와 같이 다환 알킬기여도 되며, 활성 메타인기를 포함해도 됨), 알켄일기, 알카인일기, 아릴기, 또는 헤테로환기(치환하는 위치는 불문함)가 바람직하다.Among them, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom), an alkyl group (a linear, branched or cyclic alkyl group, may be a polycyclic alkyl group such as a bicycloalkyl group, or an active metaphosphoric group) ), an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group (regardless of the position to be substituted) is preferable.
또한, 여기에서, "활성 메타인기"란, 2개의 전자 구인성기로 치환된 메타인기를 의미한다. "전자 구인성기"란, 예를 들면 아실기, 알콕시카보닐기, 아릴옥시카보닐기, 카바모일기, 알킬설폰일기, 아릴설폰일기, 설파모일기, 트라이플루오로메틸기, 사이아노기, 나이트로기, 또는 카본이미도일기를 의도한다. 또, 2개의 전자 구인성기는 서로 결합하여 환상 구조를 취하고 있어도 된다. 또, "염"이란 알칼리 금속, 알칼리 토류 금속, 및 중금속 등의 양이온; 암모늄 이온, 및 포스포늄 이온 등의 유기의 양이온을 의도한다.In addition, as used herein, the "active metaphosphoric group" means a metaphosphoric group substituted with two electron withdrawing groups. "Electron withdrawing group" is, for example, acyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, alkylsulfonyl group, arylsulfonyl group, sulfamoyl group, trifluoromethyl group, cyano group, nitro group , Or carbon imidoyl group. Further, the two electron withdrawing groups may be bonded to each other to have a cyclic structure. In addition, "salt" means cations such as alkali metals, alkaline earth metals, and heavy metals; Organic cations such as ammonium ions and phosphonium ions are intended.
아졸 화합물로서는, 구체적으로는, 5-메틸벤조트라이아졸, 5-아미노벤조트라이아졸, 벤조트라이아졸, 5,6-다이메틸벤조트라이아졸, 3-아미노-1,2,4-트라이아졸, 1,2,4-트라이아졸, 3,5-다이메틸피라졸, 피라졸, 및 이미다졸 등을 들 수 있다.As an azole compound, specifically, 5-methylbenzotriazole, 5-aminobenzotriazole, benzotriazole, 5,6-dimethylbenzotriazole, 3-amino-1,2,4-triazole, 1 ,2,4-triazole, 3,5-dimethylpyrazole, pyrazole, and imidazole.
또, 벤조트라이아졸 화합물(벤조트라이아졸 골격을 함유하는 화합물)과, 벤조트라이아졸 화합물과는 다른 화합물(벤조트라이아졸 골격을 함유하지 않는 화합물)을 함유해도 된다. 벤조트라이아졸 골격을 함유하는 화합물은 산화제에 의하여 산화된 구리에 강하게 배위하기 쉽다. 한편, 아졸 화합물이더라도, 벤조트라이아졸 골격을 함유하지 않는 화합물은, 산화된 구리에 비교적 약하게 배위하기 쉽다. 이들을 병용함으로써, 연마 속도를 보다 빠르게 하는 효과가 얻어진다.Moreover, you may contain a benzotriazole compound (a compound containing a benzotriazole skeleton) and a compound different from a benzotriazole compound (a compound not containing a benzotriazole skeleton). Compounds containing a benzotriazole skeleton are likely to strongly coordinate with copper oxidized by an oxidizing agent. On the other hand, even if it is an azole compound, a compound which does not contain a benzotriazole skeleton tends to be relatively weakly coordinated with oxidized copper. By using these together, the effect of increasing the polishing rate is obtained.
상기 벤조트라이아졸 골격을 함유하지 않는 화합물로서는, 특별히 제한되지 않지만, 연마 속도를 보다 향상시키는 관점에서, 3-아미노-1,2,4-트라이아졸, 1,2,4-트라이아졸, 또는 이미다졸이 바람직하다.The compound not containing the benzotriazole skeleton is not particularly limited, but from the viewpoint of further improving the polishing rate, 3-amino-1,2,4-triazole, 1,2,4-triazole, or already Dazole is preferred.
상기 아졸 화합물의 함유량으로서는, 특별히 제한되지 않지만, 연마 속도를 보다 향상시키는 관점에서, 연마액 전체 질량에 대하여 0.001~5질량%가 바람직하고, 0.001~2질량%가 보다 바람직하다.The content of the azole compound is not particularly limited, but from the viewpoint of further improving the polishing rate, it is preferably 0.001 to 5% by mass and more preferably 0.001 to 2% by mass with respect to the total mass of the polishing liquid.
아졸 화합물을 2종 이상 이용하는 경우는, 그 합계량이 상기 범위 내에 포함되는 것이 바람직하다.When two or more types of azole compounds are used, it is preferable that the total amount is contained within the above range.
(유기 용제)(Organic solvent)
상기 연마액은, 유기 용제를 함유해도 된다. 유기 용제로서는 특별히 제한되지 않고, 공지의 유기 용제를 이용할 수 있다. 그 중에서도, 수용성의 유기 용제가 바람직하다.The polishing liquid may contain an organic solvent. The organic solvent is not particularly limited, and a known organic solvent can be used. Among them, a water-soluble organic solvent is preferable.
유기 용제로서는, 예를 들면 케톤계 용제, 에터계 용제, 알코올계 용제, 글라이콜계 용제, 글라이콜에터계 용제 및 아마이드계 용제 등을 들 수 있다.Examples of the organic solvent include ketone-based solvents, ether-based solvents, alcohol-based solvents, glycol-based solvents, glycol ether-based solvents, and amide-based solvents.
보다 구체적으로는, 예를 들면 아세톤, 메틸에틸케톤, 테트라하이드로퓨란, 다이옥세인, 다이메틸아세트아마이드, N-메틸피롤리돈, 다이메틸설폭사이드, 아세토나이트릴, 메탄올, 에탄올, 1-프로판올, 2-프로판올, 1-뷰탄올, 에틸렌글라이콜, 프로필렌글라이콜, 및 에톡시에탄올 등을 들 수 있다.More specifically, for example, acetone, methyl ethyl ketone, tetrahydrofuran, dioxane, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetonitrile, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, ethylene glycol, propylene glycol, and ethoxyethanol.
그 중에서도, 메틸에틸케톤, 테트라하이드로퓨란, 다이옥세인, N-메틸피롤리돈, 메탄올, 에탄올, 또는 에틸렌글라이콜 등이 바람직하다.Among them, methyl ethyl ketone, tetrahydrofuran, dioxane, N-methylpyrrolidone, methanol, ethanol, or ethylene glycol are preferable.
유기 용제를 함유하는 경우, 그 함유량으로서는 특별히 제한되지 않지만, 연마액 전체 질량에 대하여, 0.001~5.0질량%가 바람직하고, 0.01~2.0질량%가 보다 바람직하다.When the organic solvent is contained, the content is not particularly limited, but is preferably 0.001 to 5.0% by mass, and more preferably 0.01 to 2.0% by mass, based on the total mass of the polishing liquid.
유기 용제의 함유량이 0.01~2.0질량%의 범위 내이면, 연마 속도의 안정성이 보다 우수한 연마액이 얻어진다.When the content of the organic solvent is in the range of 0.01 to 2.0% by mass, a polishing liquid having more excellent polishing rate stability can be obtained.
또한 유기 용제는 1종을 단독으로 이용해도 되고, 2종 이상을 병용해도 된다. 2종 이상의 유기 용제를 병용하는 경우에는, 합계 함유량이 상기 범위 내인 것이 바람직하다.Moreover, organic solvents may be used individually by 1 type, and may use 2 or more types together. When using two or more types of organic solvents together, it is preferable that the total content is within the above range.
(연마 촉진제)(Polishing accelerator)
무기 절연층의 CMP에 적용하는 경우에는, 연마액은, 연마 촉진제를 함유하는 것이 바람직하다. 연마 촉진제를 함유함으로써, 피연마체의 표면의 무기 절연층의 면내 균일성을 보다 향상시키기 쉽다. 연마 촉진제로서는, 설폰산 화합물, 포스폰산 화합물을 들 수 있고, 설포기(-SO3H) 및 아미노기(-NH2, -NHR 또는 -NRR')를 분자 중에 갖는 화합물인 것이 바람직하다. 또한, 상기 R 및 R'은, 각각 독립적으로, 알킬기, 아릴기, 또는 각각의 치환체를 나타낸다.In the case of applying to the CMP of the inorganic insulating layer, the polishing liquid preferably contains a polishing accelerator. By containing the polishing accelerator, it is easy to further improve the in-plane uniformity of the inorganic insulating layer on the surface of the object to be polished. Examples of the polishing accelerator include a sulfonic acid compound and a phosphonic acid compound, and a compound having a sulfo group (-SO 3 H) and an amino group (-NH 2 , -NHR or -NRR') in a molecule is preferable. In addition, the above R and R'each independently represent an alkyl group, an aryl group, or each substituent.
연마 촉진제로서는, 예를 들면 3-아미노벤젠설폰산, 4-아미노벤젠설폰산(설파닐산), 아미노메테인설폰산, 1-아미노에테인설폰산, 2-아미노-1-에테인설폰산(타우린), 1-아미노프로페인-2-설폰산 등의 아미노설폰산류, 아마이드 황산(설팜산), N-메틸설팜산, 페닐설팜산, 및 N-사이클로헥실설팜산 등의 설팜산류 등을 들 수 있다. 그 중에서도, 일급 아미노기(-NH2)를 갖는 것이 바람직하고, 3-아미노벤젠설폰산, 혹은 4-아미노벤젠설폰산 등의 벤젠설폰산류, 또는 아마이드 황산이 보다 바람직하며, 4-아미노벤젠설폰산 또는 아마이드 황산이 더 바람직하다.As a polishing accelerator, for example, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid (sulfanyl acid), aminomethanesulfonic acid, 1-aminoethanesulfonic acid, 2-amino-1-ethanesulfonic acid (taurine), And aminosulfonic acids such as 1-aminopropane-2-sulfonic acid, amide sulfuric acid (sulfamic acid), N-methylsulfamic acid, phenylsulfamic acid, and sulfamic acids such as N-cyclohexylsulfamic acid. Among them, those having a primary amino group (-NH 2 ) are preferred, benzenesulfonic acids such as 3-aminobenzenesulfonic acid or 4-aminobenzenesulfonic acid, or amide sulfuric acid are more preferred, and 4-aminobenzenesulfonic acid Or amide sulfuric acid is more preferable.
연마 촉진제를 함유하는 경우, 그 함유량으로서는 특별히 제한되지 않지만, 면내 균일성 및 연마 속도를 보다 양호하게 하는 관점에서, 연마액 전체 질량에 대하여, 0.001~5질량%가 바람직하고, 0.01~3질량%가 보다 바람직하다.When a polishing accelerator is contained, the content thereof is not particularly limited, but from the viewpoint of improving the in-plane uniformity and polishing rate, 0.001 to 5% by mass is preferable, and 0.01 to 3% by mass, based on the total mass of the polishing liquid. Is more preferable.
또한, 연마 촉진제는 1종을 단독으로 이용해도 되고, 2종 이상을 병용해도 된다. 2종 이상의 연마 촉진제를 병용하는 경우에는, 합계 함유량이 상기 범위 내인 것이 바람직하다.In addition, the polishing accelerator may be used singly or in combination of two or more. When two or more types of polishing accelerators are used in combination, it is preferable that the total content is within the above range.
(pH 조정제 및/또는 pH 완충제)(pH adjusting agent and/or pH buffering agent)
상기 연마액은, 소정의 pH로 하기 위하여, pH 조정제 및/또는 pH 완충제를 더 함유해도 된다. pH 조정제 및/또는 pH 완충제로서는, 산제 및/또는 알칼리제를 들 수 있다. 또한, pH 조정제 및 pH 완충제는, 상기 유기산과는 다른 화합물이다.The polishing liquid may further contain a pH adjusting agent and/or a pH buffering agent in order to obtain a predetermined pH. As the pH adjusting agent and/or the pH buffering agent, a powder and/or an alkali agent can be mentioned. In addition, the pH adjusting agent and the pH buffering agent are compounds different from the above organic acids.
산제로서는, 특별히 제한되지 않지만, 무기산이 바람직하다. 무기산으로서는, 예를 들면 황산, 질산, 붕산, 및 인산 등을 들 수 있다. 그 중에서도 황산 또는 질산이 보다 바람직하다.Although it does not specifically limit as a powder, Inorganic acid is preferable. As an inorganic acid, sulfuric acid, nitric acid, boric acid, phosphoric acid, etc. are mentioned, for example. Among them, sulfuric acid or nitric acid is more preferable.
알칼리제로서는, 특별히 제한되지 않지만, 암모니아; 수산화 암모늄 및 유기 수산화 암모늄(예를 들면 수산화 테트라뷰틸암모늄); 다이에탄올아민, 트라이에탄올아민, 및 트라이아이소프로판올아민 등의 알칸올아민류; 수산화 나트륨, 수산화 칼륨, 및 수산화 리튬 등의 알칼리 금속 수산화물; 탄산 나트륨 등의 탄산염; 인산 삼나트륨 등의 인산염; 붕산염, 및 사붕산염; 하이드록시벤조산염 등을 들 수 있다.Although it does not specifically limit as an alkali agent, Ammonia; Ammonium hydroxide and organic ammonium hydroxide (eg tetrabutylammonium hydroxide); Alkanolamines such as diethanolamine, triethanolamine, and triisopropanolamine; Alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide; Carbonates such as sodium carbonate; Phosphates such as trisodium phosphate; Borate, and tetraborate; Hydroxybenzoate and the like.
pH 조정제 및/또는 pH 완충제의 함유량으로서는, pH가 원하는 범위로 유지되는 데에 필요한 양이면 특별히 제한되지 않고, 통상, 연마액 전체 질량 중, 0.01~1질량%가 바람직하다.The content of the pH adjusting agent and/or the pH buffering agent is not particularly limited as long as it is an amount necessary for maintaining the pH in a desired range, and is usually preferably 0.01 to 1% by mass with respect to the total mass of the polishing liquid.
〔화학적 기계적 연마 방법〕[Chemical mechanical polishing method]
본 발명의 연마액을 이용한 화학적 기계적 연마 방법은, 특별히 한정되지 않고, 공지의 화학적 기계적 연마 방법을 적용할 수 있다.The chemical mechanical polishing method using the polishing liquid of the present invention is not particularly limited, and a known chemical mechanical polishing method can be applied.
본 발명의 연마액을 이용할 수 있는 일 실시형태에 관한 화학적 기계적 연마 방법으로서, 연마 정반에 장착된 연마 패드에, 상기 연마액을 공급하면서, 피연마체의 피연마면을 연마 패드에 접촉시키고, 피연마체, 및 연마 패드를 상대적으로 움직여 피연마면을 연마하여 연마가 완료된 피연마체를 얻는 공정을 포함하는, 화학적 기계적 연마 방법(이하 "CMP 방법"이라고도 함)을 들 수 있다.As a chemical mechanical polishing method according to an embodiment in which the polishing liquid of the present invention can be used, while supplying the polishing liquid to a polishing pad mounted on a polishing table, a surface to be polished of an object to be polished is brought into contact with the polishing pad, and And a chemical mechanical polishing method (hereinafter also referred to as a "CMP method") including a step of obtaining a polished object by polishing a surface to be polished by relatively moving a horse body and a polishing pad.
<피연마체><Object to be polished>
상기 실시형태에 관한 CMP 방법을 적용할 수 있는 피연마체로서는, 특별히 제한되지 않는다. 피연마체의 일례로서, 표면에, 금속층 및 무기 절연층으로 이루어지는 군으로부터 선택되는 적어도 1종을 갖는 기판을 들 수 있다. 즉, 상기 실시형태에 관한 CMP 방법에 의하여, 상술한 금속층 또는 무기 절연층이 연마된다. 또한, 이들 층은 적층되어 있어도 된다.The object to be polished to which the CMP method according to the above embodiment can be applied is not particularly limited. As an example of the object to be polished, a substrate having at least one type selected from the group consisting of a metal layer and an inorganic insulating layer is mentioned on the surface. That is, the above-described metal layer or inorganic insulating layer is polished by the CMP method according to the above embodiment. In addition, these layers may be laminated.
기판이란, 특별히 한정되지 않지만, 예를 들면 단층으로 이루어지는 반도체 기판, 및 다층으로 이루어지는 반도체 기판이 포함된다.The substrate is not particularly limited, but includes, for example, a semiconductor substrate made of a single layer and a semiconductor substrate made of multiple layers.
단층으로 이루어지는 반도체 기판을 구성하는 재료는 특별히 한정되지 않고, 일반적으로, 실리콘, 실리콘저마늄, GaAs와 같은 제III-V족 화합물, 또는 그들의 임의의 조합으로 구성되는 것이 바람직하다.The material constituting the single-layer semiconductor substrate is not particularly limited, and in general, it is preferably composed of a III-V group compound such as silicon, silicon germanium, or GaAs, or any combination thereof.
다층으로 이루어지는 반도체 기판인 경우에는, 그 구성은 특별히 한정되지 않고, 예를 들면 상술한 실리콘 등의 반도체 기판 상에 금속선 및 유전 재료와 같은 상호 접속 구조(interconnect features) 등이 노출된 집적 회로 구조를 갖고 있어도 된다.In the case of a multi-layered semiconductor substrate, the configuration is not particularly limited, and for example, an integrated circuit structure in which interconnect features such as metal wires and dielectric materials are exposed on the semiconductor substrate such as silicon described above. You may have it.
금속층이란, 특별히 한정되지 않지만, 배선을 형성할 수 있는 배선층 및 배리어 금속층 등을 들 수 있다. 배선을 형성할 수 있는 배선층에 포함되는 금속 성분이란, 예를 들면 구리계 금속(구리 또는 구리 합금 등)을 들 수 있다. 또, 배리어 금속층을 구성하는 메탈 재료로서는, 특별히 제한되지 않고, 공지의 저저항의 메탈 재료를 이용할 수 있다. 저저항의 메탈 재료로서는, 예를 들면 TiN, TiW, Ta, TaN, W, 또는 WN이 바람직하고, 그 중에서도 Ta, 또는 TaN이 보다 바람직하다.The metal layer is not particularly limited, and examples thereof include a wiring layer and a barrier metal layer capable of forming a wiring. The metal component contained in the wiring layer capable of forming a wiring includes, for example, a copper-based metal (copper or copper alloy, etc.). In addition, the metal material constituting the barrier metal layer is not particularly limited, and a known low-resistance metal material can be used. As a low-resistance metal material, for example, TiN, TiW, Ta, TaN, W, or WN is preferable, and among them, Ta or TaN is more preferable.
무기 절연층을 구성하는 재료로서는, 특별히 한정되지 않지만, 예를 들면 산화 규소, 질화 규소, 탄화 규소, 탄질화 규소, 산화 탄화 규소, 및 산질화 규소 등을 들 수 있다. 그 중에서도, 산화 규소, 또는 질화 규소가 바람직하다.The material constituting the inorganic insulating layer is not particularly limited, and examples thereof include silicon oxide, silicon nitride, silicon carbide, silicon carbonitride, silicon oxide carbide, and silicon oxynitride. Among them, silicon oxide or silicon nitride is preferable.
<연마 장치><Polishing device>
연마 장치로서는 특별히 제한되지 않고, 상기 실시형태에 관한 CMP 방법을 적용할 수 있는 공지의 화학적 기계적 연마 장치(이하 "CMP 장치"라고도 함)를 이용할 수 있다.The polishing apparatus is not particularly limited, and a known chemical mechanical polishing apparatus (hereinafter also referred to as "CMP apparatus") to which the CMP method according to the above embodiment can be applied can be used.
CMP 장치로서는, 예를 들면 피연마면을 갖는 피연마체(예를 들면, 반도체 기판 등)를 유지하는 홀더와, 연마 패드를 첩부한(회전수가 변경 가능한 모터 등이 장착되어 있는) 연마 정반을 구비하는 일반적인 CMP 장치를 이용할 수 있다. 시판품으로서는, 예를 들면 FREX300(에바라 세이사쿠쇼제)을 이용할 수 있다.As a CMP device, for example, a holder for holding an object to be polished (e.g., a semiconductor substrate, etc.) having a surface to be polished, and a polishing plate with a polishing pad attached to it (with a motor that can change the number of rotations) are provided. You can use a general CMP device. As a commercial item, FREX300 (made by Ebara Seisakusho) can be used, for example.
<연마 압력><Polishing pressure>
상기 실시형태에 관한 CMP 방법에서는, 연마 압력, 즉, 피연마면과 연마 패드의 접촉면에 발생하는 압력 3000~25000Pa로 연마를 행하는 것이 바람직하고, 6500~14000Pa로 연마를 행하는 것이 보다 바람직하다.In the CMP method according to the above embodiment, it is preferable to perform polishing at a polishing pressure, that is, a pressure generated on the contact surface between the surface to be polished and the polishing pad, between 3000 and 25000 Pa, and more preferably at 6500 to 14000 Pa.
<연마 정반의 회전수><The number of revolutions of the grinding wheel>
상기 실시형태에 관한 CMP 방법에서는, 연마 정반의 회전수 50~200rpm으로 연마를 행하는 것이 바람직하고, 60~150rpm으로 연마를 행하는 것이 보다 바람직하다.In the CMP method according to the above embodiment, it is preferable to perform polishing at a rotational speed of 50 to 200 rpm of the polishing platen, and more preferably at 60 to 150 rpm.
또한, 연마체 및 연마 패드를 상대적으로 움직이기 위하여, 홀더를 더 회전 및/또는 요동시켜도 되고, 연마 정반을 유성 회전시켜도 되며, 벨트 형상의 연마 패드를 장척 방향의 일 방향으로 직선 형상으로 움직여도 된다. 또한, 홀더는 고정, 회전, 또는 요동 중 어느 상태여도 된다. 이들 연마 방법은, 연마체 및 연마 패드를 상대적으로 움직인다면, 피연마면 및/또는 연마 장치에 의하여 적절히 선택할 수 있다.In addition, in order to relatively move the polishing body and the polishing pad, the holder may be further rotated and/or swung, the polishing plate may be planetary rotation, and the belt-shaped polishing pad may be moved in a straight line in one direction in the long direction. . In addition, the holder may be in any state of being fixed, rotated, or swung. These polishing methods can be appropriately selected depending on the surface to be polished and/or the polishing apparatus as long as the polishing body and the polishing pad are relatively moved.
<연마액의 공급 방법><How to supply polishing liquid>
상기 실시형태에 관한 CMP 방법에서는, 피연마면을 연마하는 동안, 연마 정반 상의 연마 패드에 연마액을 펌프 등으로 연속적으로 공급한다. 이 공급량에 제한은 없지만, 연마 패드의 표면이 항상 연마액으로 덮여 있는 것이 바람직하다. 또한, 연마액의 양태에 대해서는 상기와 같다.In the CMP method according to the above embodiment, while polishing the surface to be polished, the polishing liquid is continuously supplied to the polishing pad on the polishing table by a pump or the like. Although there is no limit to this supply amount, it is preferable that the surface of the polishing pad is always covered with a polishing liquid. In addition, the aspect of the polishing liquid is as described above.
실시예Example
이하에 실시예에 근거하여 본 발명을 더 상세하게 설명한다. 이하의 실시예에 나타내는 재료, 사용량, 비율, 처리 내용, 또는 처리 순서 등은, 본 발명의 취지를 일탈하지 않는 한 적절히 변경할 수 있다. 따라서, 본 발명의 범위는 이하에 나타내는 실시예에 의하여 한정적으로 해석되어야 할 것은 아니다.Hereinafter, the present invention will be described in more detail based on examples. The material, the amount used, the ratio, the treatment content, or the treatment sequence shown in the following examples can be appropriately changed without departing from the gist of the present invention. Therefore, the scope of the present invention should not be limitedly interpreted by the examples shown below.
〔원료 등의 정제〕〔Purification of raw materials, etc.〕
이하에 나타내는 각 실시예에서 사용되는 각 원료 및 각 촉매는, 순도 99% 이상의 고순도 그레이드를 이용하고, 또한 사전에 증류, 이온 교환, 또는 여과 등에 의하여 정제한 것이다.Each raw material and each catalyst used in each of the examples shown below were purified by distillation, ion exchange, or filtration in advance using a high purity grade of 99% or more.
1. 실시예 1~27, 비교예 1~4의 연마액의 조제 및 그 평가1. Preparation of polishing liquids of Examples 1 to 27 and Comparative Examples 1 to 4 and evaluation thereof
〔실시예 1〕[Example 1]
하기에 나타내는 각 성분을 혼합하여, 연마액을 조제했다. 또한 연마액의 pH가 표 1에 기재된 값이 되도록, 희황산 또는 수산화 칼륨을 적절히 첨가했다.Each component shown below was mixed and the polishing liquid was prepared. Further, dilute sulfuric acid or potassium hydroxide was appropriately added so that the pH of the polishing liquid became the value shown in Table 1.
·콜로이달 실리카(평균 일차 입자경: 35nm, 제품명 "PL3", 후소 가가쿠 고교사제, 지립에 해당함) 3.0질량%Colloidal silica (average primary particle diameter: 35 nm, product name "PL3", manufactured by Fuso Chemical Industry Co., Ltd., equivalent to abrasive grains) 3.0% by mass
·말산(유기산에 해당함) 0.5질량%・Malic acid (corresponding to organic acid) 0.5% by mass
·PAA(Mw25000)(중량 평균 분자량 25000의 폴리아크릴산, 수용성 고분자에 해당함) 1.0질량%PAA (Mw25000) (corresponds to polyacrylic acid and water-soluble polymer having a weight average molecular weight of 25000) 1.0% by mass
·과산화 수소(산화제에 해당함) 0.03질량%-Hydrogen peroxide (corresponding to oxidizing agent) 0.03% by mass
·메탄올(유기 용제에 상당함) 1.0질량%Methanol (equivalent to organic solvent) 1.0% by mass
·BTA(벤조트라이아졸, 벤조트라이아졸 골격을 함유하는 아졸 화합물에 해당함) 0.5질량%BTA (corresponds to benzotriazole and azole compounds containing a benzotriazole skeleton) 0.5% by mass
·물(초순수) 잔부(질량%)・Remaining water (ultra pure water) (mass%)
[각종 측정 및 평가][Various measurement and evaluation]
얻어진 실시예 1의 연마액에 대하여 하기의 평가를 행했다.The following evaluation was performed on the obtained polishing liquid of Example 1.
<회전 점도계에 의한 점도 측정><Viscosity measurement by rotating viscometer>
회전 점도계를 이용하여, 40%RH, 23℃에서의 각 회전수에 있어서의 점도(η100rpm, η500rpm, η1000rpm)를 측정했다. 또한, 회전 점도계로는, Brookfield사제 "LVDV-II"를 이용했다.Using a rotational viscometer, the viscosity (η 100 rpm , η 500 rpm , η 1000 rpm ) at 40% RH and 23° C. was measured. In addition, "LVDV-II" manufactured by Brookfield Corporation was used as a rotational viscometer.
점도 측정은, 회전을 개시한 후 점도가 안정될 때까지 2분간 회전시키고, 2분 후의 점도를 측정값으로 했다.The viscosity measurement was performed for 2 minutes until the viscosity stabilized after starting the rotation, and the viscosity after 2 minutes was taken as the measured value.
측정한 점도로부터, η100rpm/η1000rpm, 및 η100rpm/η500rpm의 각 값을 구했다.From the measured viscosity, each value of η 100 rpm / η 1000 rpm and η 100 rpm / η 500 rpm was determined.
<연마 속도의 평가><Evaluation of polishing speed>
이하의 조건으로 연마액을 연마 패드에 공급하면서 연마를 행하여, 연마 속도의 평가를 행했다.Polishing was performed while supplying the polishing liquid to the polishing pad under the following conditions, and the polishing rate was evaluated.
·연마 장치: FREX300(에바라 세이사쿠쇼제)・Polishing device: FREX300 (made by Ebara Seisakusho)
·피연마체(웨이퍼): · Object to be polished (wafer):
실리콘 기판 상에 두께 1.5μm의 Cu막을 형성한 12인치(또한, 1인치는 25.4mm에 상당함)의 블랭킷 웨이퍼 A 12-inch blanket wafer with a 1.5 μm-thick Cu film formed on a silicon substrate (1 inch is equivalent to 25.4 mm)
실리콘 기판 상에 두께 0.2μm의 Ta막을 형성한 12인치의 블랭킷 웨이퍼 12-inch blanket wafer with 0.2 μm-thick Ta film formed on a silicon substrate
·연마 패드: IC1400 XY-k-pad(로델·닛타 가부시키가이샤제)・Polishing pad: IC1400 XY-k-pad (Rodel Nitta Co., Ltd.)
·연마 조건: ·Polishing conditions:
연마 압력(피연마면과 연마 패드의 접촉 압력); 1.5psi Polishing pressure (contact pressure between the surface to be polished and the polishing pad); 1.5psi
연마액 공급 속도; 300ml/min Polishing liquid supply rate; 300ml/min
연마 정반 회전수; 112rpm Grinding plate rotation speed; 112rpm
연마 헤드 회전수; 113rpm Grinding head rotation speed; 113rpm
연마 속도의 산출: Calculation of polishing rate:
상기 블랭킷 웨이퍼를 60초간 연마하고, 웨이퍼면 상의 균등 간격의 49개소에 대하여, 접촉식의 막두께 측정기를 이용하여 연마 전후에서의 금속 막두께를 구하고, (연마 전의 막두께-연마 후의 막두께)를 연마 시간으로 나누어 구한 값의 평균값을 연마 속도(단위: nm/min)로 했다.The blanket wafer was polished for 60 seconds, and the metal film thickness before and after polishing was calculated using a contact-type film thickness meter for 49 equally spaced locations on the wafer surface (film thickness before polishing-film thickness after polishing). The average value of the value obtained by dividing by the polishing time was taken as the polishing rate (unit: nm/min).
결과를 표 1에 나타낸다.Table 1 shows the results.
<면내 균일성의 평가><Evaluation of in-plane uniformity>
상기 연마 후의 블랭킷 웨이퍼의 직경 방향의 막두께를 측정하여, 그 막두께 편차를 면내 균일성이라고 정의했다.The film thickness in the radial direction of the polished blanket wafer was measured, and the film thickness deviation was defined as in-plane uniformity.
구체적으로는, 상기 블랭킷 웨이퍼의 직경 방향으로 41점 등간격으로 측정점을 취하고, 접촉식의 막두께 측정기를 이용하여, 최대 막두께(Max)와 최소 막두께(min)를 측정하며, 하기에 나타내는 산출식으로부터 평가했다.Specifically, measuring points are taken at equal intervals of 41 points in the radial direction of the blanket wafer, and the maximum film thickness (Max) and the minimum film thickness (min) are measured using a contact-type film thickness measuring device, as shown below. It evaluated from the calculation formula.
면내 균일성=(최대 막두께(Max)-최소 막두께(min))/(최대 막두께(Max)+최소 막두께(min))×100(%) In-plane uniformity = (maximum film thickness (Max)-minimum film thickness (min))/(maximum film thickness (Max) + minimum film thickness (min))×100 (%)
또, 상기 블랭킷 웨이퍼의 외주 제외 영역(Edge Exclusion: EE)에 있어서의 면내 균일성에 대해서도 함께 평가했다.In addition, in-plane uniformity in the edge exclusion (EE) of the blanket wafer was also evaluated.
표 중, "EE 3mm"란, 블랭킷 웨이퍼의 외주 측 3mm의 영역을 제외한 면내 균일성을 의미하고, "EE 10mm"란, 블랭킷 웨이퍼의 외주 측 10mm의 영역을 제외한 면내 균일성을 의미한다.In the table, "EE 3mm" means in-plane uniformity excluding an area of 3 mm on the outer peripheral side of the blanket wafer, and "EE 10 mm" means in-plane uniformity excluding an area of 10 mm on the outer peripheral side of the blanket wafer.
결과를 표 1에 나타낸다.Table 1 shows the results.
〔실시예 2~27, 비교예 1~4〕(Examples 2 to 27, Comparative Examples 1 to 4)
각 성분의 배합량 또는 pH를 변경한 것 이외에는 상기 실시예 1과 동일한 방법에 의하여, 실시예 2~27, 비교예 1~4의 연마액을 조제하여, 동일한 평가를 행했다. 결과를 표 1에 나타낸다.The polishing liquids of Examples 2 to 27 and Comparative Examples 1 to 4 were prepared in the same manner as in Example 1, except that the compounding amount or pH of each component was changed, and the same evaluation was performed. Table 1 shows the results.
또한, 표 1에 있어서, 연마액 조성에 있어서의 각 성분량(질량%)은, 조성물 전체 질량에 대한 양을 의미한다.In addition, in Table 1, the amount of each component (mass%) in the polishing liquid composition means the amount with respect to the total mass of the composition.
또, 이하 표 1에서 이용되는 다른 성분을 나타낸다.In addition, other components used in Table 1 below are shown.
·PAA(Mw3000)(중량 평균 분자량 3000의 폴리아크릴산, 수용성 고분자에 해당함)PAA (Mw3000) (corresponds to polyacrylic acid with a weight average molecular weight of 3000, water-soluble polymer)
·PAA(Mw5000)(중량 평균 분자량 5000의 폴리아크릴산, 수용성 고분자에 해당함)PAA (Mw5000) (corresponds to polyacrylic acid and water-soluble polymer with a weight average molecular weight of 5000)
·PAA(Mw15000)(중량 평균 분자량 15000의 폴리아크릴산, 수용성 고분자에 해당함)PAA (Mw15000) (corresponds to polyacrylic acid and water-soluble polymer with a weight average molecular weight of 15000)
·PAA(Mw50000)(중량 평균 분자량 50000의 폴리아크릴산, 수용성 고분자에 해당함)PAA (Mw50000) (corresponds to polyacrylic acid with a weight average molecular weight of 50000, water-soluble polymer)
·PAA(Mw100000)(중량 평균 분자량 100000의 폴리아크릴산, 수용성 고분자에 해당함)PAA (Mw100000) (corresponds to polyacrylic acid with a weight average molecular weight of 100000, water-soluble polymer)
·PVA(Mw10000)(중량 평균 분자량 10000의 폴리바이닐알코올, 수용성 고분자에 해당함)PVA (Mw10000) (corresponds to polyvinyl alcohol with a weight average molecular weight of 10000, water-soluble polymer)
·CMC(Mw10000)(중량 평균 분자량 10000의 카복시메틸셀룰로스, 수용성 고분자에 해당함)CMC (Mw10000) (corresponds to carboxymethylcellulose with a weight average molecular weight of 10000, water-soluble polymer)
·5-MBTA(5-메틸벤조트라이아졸, 벤조트라이아졸 골격을 함유하는 아졸 화합물에 해당함)5-MBTA (corresponds to azole compounds containing 5-methylbenzotriazole and benzotriazole skeletons)
·1,2,4-트라이아졸(벤조트라이아졸 골격을 함유하지 않는 화합물에 해당함)1,2,4-triazole (corresponds to compounds that do not contain a benzotriazole skeleton)
·시트르산(유기산에 해당함)Citric acid (corresponds to organic acids)
·말론산(유기산에 해당함)Malonic acid (corresponds to organic acid)
[표 1][Table 1]
[표 2][Table 2]
표 1의 결과로부터, 실시예의 연마액을 이용한 경우, 면내 균일성이 우수한 것을 확인할 수 있다.From the results in Table 1, it can be seen that the in-plane uniformity is excellent when the polishing liquid of the example is used.
그 중에서도, 실시예 1, 5~9의 비교로부터, 수용성 고분자의 중량 평균 분자량이 5000~100000인 경우(바람직하게는 10000~50000, 보다 바람직하게는 15000~30000), 면내 균일성이 보다 우수한 것이 확인되었다.Among them, from the comparison of Examples 1 and 5 to 9, when the weight average molecular weight of the water-soluble polymer is 5000 to 100000 (preferably 10000 to 500,000, more preferably 15000 to 30000), the in-plane uniformity is more excellent. Confirmed.
실시예 1, 10~12의 비교로부터, 수용성 고분자의 함유량이 0.5~4질량%인 경우, 면내 균일성이 보다 우수한 것이 확인되었다.From the comparison of Examples 1 and 10 to 12, it was confirmed that when the content of the water-soluble polymer was 0.5 to 4% by mass, the in-plane uniformity was more excellent.
실시예 1, 15, 16의 비교로부터, 지립의 함유량이 3질량% 이상인 경우, 면내 균일성이 보다 우수한 것이 확인되었다.From the comparison of Examples 1, 15 and 16, it was confirmed that the in-plane uniformity was more excellent when the abrasive content was 3% by mass or more.
실시예 1, 22, 23의 비교로부터, 산화제의 함유량이 0.03질량% 이상인 경우, 면내 균일성이 보다 우수한 것이 확인되었다.From the comparison of Examples 1, 22 and 23, it was confirmed that the in-plane uniformity was more excellent when the content of the oxidizing agent was 0.03% by mass or more.
실시예 1, 24~26의 비교로부터, pH가 2.0~5.0(바람직하게는, 2.0~4.0)인 경우, 면내 균일성이 보다 우수한 것이 확인되었다.From the comparison of Examples 1 and 24 to 26, when the pH is 2.0 to 5.0 (preferably, 2.0 to 4.0), it was confirmed that the in-plane uniformity is more excellent.
실시예 1~4의 비교로부터, 유기산의 함유량이 3질량% 이하인 경우, 연마 속도가 보다 우수하고, 또, 특히 Cu막에 대하여 CMP를 할 때에, 면내 균일성이 보다 우수한 것이 확인되었다.From the comparison of Examples 1 to 4, it was confirmed that when the content of the organic acid was 3% by mass or less, the polishing rate was more excellent, and particularly, when performing CMP on the Cu film, the in-plane uniformity was more excellent.
실시예 1과, 실시예 13~14의 비교에 의하여, 수용성 고분자로서 폴리아크릴산을 이용한 경우, 특히 Cu막에 대하여 CMP를 할 때에, 보다 면내 균일성이 우수한 것이 확인되었다.By comparison between Example 1 and Examples 13 to 14, it was confirmed that in the case of using polyacrylic acid as a water-soluble polymer, particularly when performing CMP on a Cu film, more excellent in-plane uniformity.
실시예 27과, 실시예 1, 실시예 17~19와의 대비에 의하여, 유기산으로서 말산, 말론산 또는 시트르산을 이용한 경우, 특히 Cu막에 대하여 CMP를 할 때에, 보다 면내 균일성이 우수한 것이 확인되었다.By contrast between Example 27 and Examples 1 and 17 to 19, it was confirmed that when malic acid, malonic acid, or citric acid was used as the organic acid, particularly when performing CMP on the Cu film, the in-plane uniformity was more excellent. .
한편, 비교예의 연마액을 이용한 경우, 면내 균일성이 원하는 요구를 충족시키고 있지 않았다.On the other hand, when the polishing liquid of the comparative example was used, the in-plane uniformity did not satisfy the desired demand.
2. 실시예 28~42, 비교예 5의 연마액의 조제 및 그 평가2. Preparation of polishing liquid of Examples 28 to 42 and Comparative Example 5 and evaluation thereof
〔실시예 28〕(Example 28)
하기에 나타내는 각 성분을 혼합하여, 연마액을 조제했다. 또한 연마액의 pH가 표 2에 기재된 값이 되도록, 희황산 또는 수산화 칼륨을 적절히 첨가했다.Each component shown below was mixed and the polishing liquid was prepared. Further, dilute sulfuric acid or potassium hydroxide was appropriately added so that the pH of the polishing liquid became the value shown in Table 2.
세리아 입자(세리아 지립 분산액, 2차 입경: 350nm, 히타치 가세이 고교 가부시키가이샤제, 제품명 "GPX 시리즈", pH8~9, 지립에 해당함) 3.0질량%Ceria particles (ceria abrasive dispersion, secondary particle diameter: 350 nm, manufactured by Hitachi Kasei Kogyo Co., Ltd., product name "GPX series", pH 8~9, equivalent to abrasive) 3.0% by mass
·시트르산(유기산에 해당함) 0.5질량%Citric acid (corresponding to organic acid) 0.5% by mass
·PAA(Mw25000)(중량 평균 분자량 25000의 폴리아크릴산, 수용성 고분자에 해당함) 1.0질량%PAA (Mw25000) (corresponds to polyacrylic acid and water-soluble polymer having a weight average molecular weight of 25000) 1.0% by mass
·4-아미노벤젠설폰산(연마 촉진제에 해당함) 2.0질량%2.0% by mass of 4-aminobenzenesulfonic acid (corresponding to a polishing accelerator)
·물(초순수) 잔부(질량%)・Remaining water (ultra pure water) (mass%)
[각종 측정 및 평가][Various measurement and evaluation]
얻어진 실시예 28의 연마액에 대하여, 실시예 1과 동일하게, 회전 점도계에 의한 점도 측정을 실시했다. 또, 실시예 1과 동일하게, 연마 속도 평가, 및 면내 균일성 평가를 실시했다. 또한, 연마 속도 평가 및 면내 균일성 평가에 대해서는, 피연마체(웨이퍼)를 하기에 나타내는 블랭킷 웨이퍼로 하고, 또, 비접촉식의 막두께 측정기를 이용하여 연마 전후의 막두께를 측정했다.About the obtained polishing liquid of Example 28, in the same manner as in Example 1, viscosity measurement with a rotational viscometer was performed. Moreover, in the same manner as in Example 1, evaluation of a polishing rate and evaluation of in-plane uniformity were performed. In addition, for the evaluation of the polishing rate and the evaluation of the in-plane uniformity, the object to be polished (wafer) was a blanket wafer shown below, and the film thickness before and after polishing was measured using a non-contact film thickness measuring device.
실리콘 기판 상에 두께 1.5μm의 SiO2막을 형성한 직경 12인치의 블랭킷 웨이퍼 결과를 표 2에 나타낸다.Table 2 shows the results of a 12-inch-diameter blanket wafer in which a 1.5 μm-thick SiO 2 film was formed on a silicon substrate.
〔실시예 29~42, 비교예 5〕(Examples 29 to 42, Comparative Example 5)
각 성분의 배합량 또는 pH를 변경한 것 이외에는 상기 실시예 28과 동일한 방법에 의하여, 실시예 29~42, 비교예 5의 연마액을 조제하여, 동일한 평가를 행했다. 결과를 표 2에 나타낸다.The polishing liquids of Examples 29 to 42 and Comparative Example 5 were prepared in the same manner as in Example 28, except that the compounding amount or pH of each component was changed, and the same evaluation was performed. The results are shown in Table 2.
또한, 표 2에 있어서, 연마액 조성에 있어서의 각 성분량(질량%)은, 조성물 전체 질량에 대한 양을 의미한다. 또, 표 2에서 이용되는 다른 성분에 대해서는, 상기 표 1로 나타낸 것과 동일하다.In addition, in Table 2, the amount of each component (mass%) in the polishing liquid composition means the amount with respect to the total mass of the composition. In addition, other components used in Table 2 are the same as those shown in Table 1 above.
[표 3][Table 3]
표 2의 결과로부터, 실시예의 연마액을 이용한 경우, 면내 균일성이 우수한 것을 확인할 수 있다.From the results of Table 2, it can be confirmed that the in-plane uniformity was excellent when the polishing liquid of the example was used.
그 중에서도, 실시예 28~33의 비교로부터, 수용성 고분자의 중량 평균 분자량이 5000~100000인 경우(바람직하게는 10000~50000, 보다 바람직하게는 15000~30000), 면내 균일성이 보다 우수한 것이 확인되었다.Among them, from the comparison of Examples 28 to 33, it was confirmed that when the weight average molecular weight of the water-soluble polymer is 5000 to 100000 (preferably 10000 to 500,000, more preferably 15000 to 30000), the in-plane uniformity is more excellent. .
실시예 28, 34~36의 비교로부터, 수용성 고분자의 함유량이 0.5~4질량%인 경우, 면내 균일성이 보다 우수한 것이 확인되었다.From the comparison of Examples 28 and 34 to 36, it was confirmed that the in-plane uniformity was more excellent when the content of the water-soluble polymer was 0.5 to 4% by mass.
실시예 28, 37, 38의 비교로부터, 지립의 함유량이 3질량% 이상인 경우, 면내 균일성이 보다 우수한 것이 확인되었다.From the comparison of Examples 28, 37, and 38, it was confirmed that the in-plane uniformity was more excellent when the abrasive content was 3% by mass or more.
실시예 28, 40~42의 비교로부터, pH가 4.0~6.0인 경우, 면내 균일성이 보다 우수한 것이 확인되었다.From the comparison of Examples 28 and 40 to 42, it was confirmed that the in-plane uniformity was more excellent when the pH was 4.0 to 6.0.
한편, 비교예의 연마액을 이용한 경우, 면내 균일성이 원하는 요구를 충족시키고 있지 않았다.On the other hand, when the polishing liquid of the comparative example was used, the in-plane uniformity did not meet the desired demand.
1 웨이퍼(피연마체)
2 연마 패드1 wafer (object to be polished)
2 polishing pad
Claims (11)
지립과, 유기산과, 수용성 고분자를 함유하고,
하기 식 (1)~식 (3)을 모두 충족시키는, 연마액.
식 (1): 1.5≤η100rpm/η1000rpm≤5
식 (2): 1.2≤η100rpm/η500rpm≤5
식 (3): η100rpm/η1000rpm>η100rpm/η500rpm
식 (1)~식 (3) 중, η100rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 100rpm으로 측정되는 상기 연마액의 점도이고, η500rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 500rpm으로 측정되는 상기 연마액의 점도이며, η1000rpm은, 40%RH, 23℃에 있어서 회전 점도계에 의하여 회전수 1000rpm으로 측정되는 상기 연마액의 점도이다.As a polishing liquid used for chemical mechanical polishing,
It contains abrasive grains, organic acids, and water-soluble polymers,
A polishing liquid that satisfies all of the following formulas (1) to (3).
Equation (1): 1.5≤η 100rpm / η 1000rpm ≤5
Equation (2): 1.2≤η 100rpm / η 500rpm ≤5
Equation (3): η 100rpm /η 1000rpm >η 100rpm /η 500rpm
In formulas (1) to (3), η 100 rpm is the viscosity of the polishing liquid measured at a rotational speed of 100 rpm by a rotational viscometer at 40%RH and 23°C, and η 500rpm is 40%RH, 23°C. Is the viscosity of the polishing liquid measured at a rotational speed of 500 rpm by a rotational viscometer, and η 1000rpm is the viscosity of the polishing liquid measured at a rotational viscometer at 40%RH and 23°C at a rotational speed of 1000 rpm.
상기 수용성 고분자의 중량 평균 분자량이, 5000~100000인, 연마액.The method according to claim 1,
A polishing liquid having a weight average molecular weight of the water-soluble polymer of 5000 to 100,000.
상기 수용성 고분자가, 폴리아크릴산, 폴리메타크릴산 및, 폴리아크릴산과 폴리메타크릴산 중 적어도 1종을 함유하는 공중합체로 이루어지는 군으로부터 선택되는 적어도 어느 1종인, 연마액.The method according to claim 1 or 2,
The polishing liquid, wherein the water-soluble polymer is at least one selected from the group consisting of polyacrylic acid, polymethacrylic acid, and a copolymer containing at least one of polyacrylic acid and polymethacrylic acid.
상기 수용성 고분자의 함유량이 0.5~4질량%인, 연마액.The method according to claim 1 or 2,
A polishing liquid in which the content of the water-soluble polymer is 0.5 to 4% by mass.
상기 유기산이, 석신산, 말산, 말론산 및 시트르산으로 이루어지는 군으로부터 선택되는 적어도 어느 1종인, 연마액.The method according to claim 1 or 2,
The polishing liquid, wherein the organic acid is at least any one selected from the group consisting of succinic acid, malic acid, malonic acid, and citric acid.
산화제를 더 함유하는, 연마액.The method according to claim 1 or 2,
A polishing liquid further containing an oxidizing agent.
상기 산화제의 함유량이, 연마액 전체 질량에 대하여 0.03질량% 이상인, 연마액.The method of claim 6,
The polishing liquid, wherein the content of the oxidizing agent is 0.03 mass% or more with respect to the total mass of the polishing liquid.
상기 산화제가, 과산화 수소인, 연마액.The method of claim 6,
The polishing liquid, wherein the oxidizing agent is hydrogen peroxide.
지립의 함유량이 3질량% 이상인, 연마액.The method according to claim 1 or 2,
A polishing liquid having an abrasive content of 3% by mass or more.
pH가, 2.0~6.0의 범위인, 연마액.The method according to claim 1 or 2,
A polishing liquid having a pH in the range of 2.0 to 6.0.
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| CN109746771B (en) * | 2019-02-14 | 2020-11-20 | 南京航空航天大学 | CsPbX3Polishing method of inorganic perovskite crystal material |
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