JP2021508308A - Surface-treated cerium oxide powder and polishing composition - Google Patents
Surface-treated cerium oxide powder and polishing composition Download PDFInfo
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- 229910000420 cerium oxide Inorganic materials 0.000 title claims abstract description 49
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000000843 powder Substances 0.000 title claims abstract description 49
- 238000005498 polishing Methods 0.000 title claims abstract description 28
- 239000000203 mixture Substances 0.000 title claims abstract description 14
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 13
- 238000005259 measurement Methods 0.000 claims abstract description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000005530 etching Methods 0.000 claims description 8
- XQXPVVBIMDBYFF-UHFFFAOYSA-N 4-hydroxyphenylacetic acid Chemical compound OC(=O)CC1=CC=C(O)C=C1 XQXPVVBIMDBYFF-UHFFFAOYSA-N 0.000 claims description 6
- YZXBAPSDXZZRGB-DOFZRALJSA-N arachidonic acid Chemical compound CCCCC\C=C/C\C=C/C\C=C/C\C=C/CCCC(O)=O YZXBAPSDXZZRGB-DOFZRALJSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- IPCSVZSSVZVIGE-UHFFFAOYSA-N hexadecanoic acid Chemical compound CCCCCCCCCCCCCCCC(O)=O IPCSVZSSVZVIGE-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 4
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 3
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005642 Oleic acid Substances 0.000 claims description 3
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021314 Palmitic acid Nutrition 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- DTOSIQBPPRVQHS-PDBXOOCHSA-N alpha-linolenic acid Chemical compound CC\C=C/C\C=C/C\C=C/CCCCCCCC(O)=O DTOSIQBPPRVQHS-PDBXOOCHSA-N 0.000 claims description 3
- 235000020661 alpha-linolenic acid Nutrition 0.000 claims description 3
- 235000021342 arachidonic acid Nutrition 0.000 claims description 3
- 229940114079 arachidonic acid Drugs 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 3
- 229960004488 linolenic acid Drugs 0.000 claims description 3
- KQQKGWQCNNTQJW-UHFFFAOYSA-N linolenic acid Natural products CC=CCCC=CCC=CCCCCCCCC(O)=O KQQKGWQCNNTQJW-UHFFFAOYSA-N 0.000 claims description 3
- WQEPLUUGTLDZJY-UHFFFAOYSA-N n-Pentadecanoic acid Natural products CCCCCCCCCCCCCCC(O)=O WQEPLUUGTLDZJY-UHFFFAOYSA-N 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 3
- 235000021313 oleic acid Nutrition 0.000 claims description 3
- IUGYQRQAERSCNH-UHFFFAOYSA-N pivalic acid Chemical compound CC(C)(C)C(O)=O IUGYQRQAERSCNH-UHFFFAOYSA-N 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000004441 surface measurement Methods 0.000 claims description 3
- 235000021122 unsaturated fatty acids Nutrition 0.000 claims description 3
- 150000004670 unsaturated fatty acids Chemical class 0.000 claims description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- -1 argon ions Chemical class 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 14
- 238000004381 surface treatment Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000012695 Ce precursor Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- OYHQOLUKZRVURQ-HZJYTTRNSA-N Linoleic acid Chemical compound CCCCC\C=C/C\C=C/CCCCCCCC(O)=O OYHQOLUKZRVURQ-HZJYTTRNSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 2
- 235000020778 linoleic acid Nutrition 0.000 description 2
- 229960004232 linoleic acid Drugs 0.000 description 2
- OYHQOLUKZRVURQ-IXWMQOLASA-N linoleic acid Natural products CCCCC\C=C/C\C=C\CCCCCCCC(O)=O OYHQOLUKZRVURQ-IXWMQOLASA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229960002969 oleic acid Drugs 0.000 description 2
- 229940098695 palmitic acid Drugs 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229960004274 stearic acid Drugs 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000012756 surface treatment agent Substances 0.000 description 2
- 229910002492 Ce(NO3)3·6H2O Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 1
- KQJQGYQIHVYKTF-UHFFFAOYSA-N cerium(3+);trinitrate;hydrate Chemical compound O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KQJQGYQIHVYKTF-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 235000003441 saturated fatty acids Nutrition 0.000 description 1
- 150000004671 saturated fatty acids Chemical class 0.000 description 1
- 239000005368 silicate glass Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000000992 sputter etching Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F17/00—Compounds of rare earth metals
- C01F17/20—Compounds containing only rare earth metals as the metal element
- C01F17/206—Compounds containing only rare earth metals as the metal element oxide or hydroxide being the only anion
- C01F17/224—Oxides or hydroxides of lanthanides
- C01F17/235—Cerium oxides or hydroxides
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
本発明は、有機物で表面処理された酸化セリウム粉末であって、Ｘ線光電子分光（ＸＰＳ）測定時のＯ−Ｃピーク面積がＯ−Ｃｅピーク面積よりもさらに大きい酸化セリウム粉末に関するもので、研磨速度に非常に優れる、表面処理された酸化セリウム粉末及びこれを含む研磨組成物を提供することができる。
The present invention relates to a cerium oxide powder surface-treated with an organic substance, the cerium oxide powder having an OC peak area larger than the O-Ce peak area at the time of X-ray photoelectron spectroscopy (XPS) measurement, and is polished. It is possible to provide a surface-treated cerium oxide powder and a polishing composition containing the same, which are extremely excellent in speed.
Description
本発明は、表面処理された酸化セリウム粉末及び研磨組成物に関する。 The present invention relates to surface-treated cerium oxide powder and polishing compositions.
半導体素子の高集積化に伴い、フォトリソグラフィーマージンを確保し且つ配線の長さを最小化するために、下部膜の平坦化技術が要求される。下部膜を平坦化するための方法として、ＢＰＳＧ（ＢｏｒｏＰｈｏｓｐｈｏｒｕｓ Ｓｉｌｉｃａｔｅ Ｇｌａｓｓ）リフロー、ＳＯＧ（Ｓｐｉｎ Ｏｎ Ｇｌａｓｓ）エッチバック（ｅｔｃｈ ｂａｃｋ）、化学機械研磨（Ｃｈｅｍｉｃａｌ Ｍｅｃｈａｎｉｃａｌ Ｐｏｌｉｓｈｉｎｇ、以下「ＣＭＰ」という）工程などがある。ＣＭＰ工程は、リフロー工程やエッチバック工程で達成できない広い空間領域の平坦化及び低温平坦化を達成することができるので、次世代の半導体素子で有力な平坦化技術として台頭している。 With the increasing integration of semiconductor elements, a flattening technique for the lower film is required in order to secure a photolithography margin and minimize the length of wiring. Methods for flattening the lower film include BPSG (BoroPhosphorus Silicate Glass) reflow, SOG (Spin On Glass) etching back (etch back), chemical mechanical polishing (hereinafter referred to as "CMP"), and the like. .. Since the CMP process can achieve flattening of a wide spatial region and low-temperature flattening that cannot be achieved by the reflow process or the etchback process, it is emerging as a promising flattening technology for next-generation semiconductor devices.
しかし、配線抵抗を低減するために配線の厚さを増加させるにつれて、金属間の電気的絶縁のための金属間絶縁層（ＩｎｔｅｒＭｅｔａｌ Ｄｉｅｌｅｃｔｒｉｃ ｌａｙｅｒ、以下「ＩＭＤ」という）のデポ量も相対的に増加することにより、ＣＭＰ段階で平坦化させるための絶対除去量が大幅に増加している。
ところが、従来のＣＭＰ用スラリーは、除去速度が遅いため、ＣＭＰ時間が非常に長くなることにより、工程生産性に劣るという問題点がある。
However, as the thickness of the wiring is increased to reduce the wiring resistance, the amount of depot of the intermetal insulating layer (Inter Metal Dielectric layer, hereinafter referred to as "IMD") for electrical insulation between metals also increases relatively. By doing so, the absolute removal amount for flattening at the CMP stage is greatly increased.
However, the conventional slurry for CMP has a problem that the removal rate is slow, so that the CMP time becomes very long, and the process productivity is inferior.
本発明は、研磨速度に非常に優れた、表面処理された酸化セリウム粉末及びこれを含む研磨組成物を提供することを目的とする。 An object of the present invention is to provide a surface-treated cerium oxide powder and a polishing composition containing the same, which are extremely excellent in polishing rate.
上記の課題を解決するための手段として、
本発明は、有機物で表面処理された酸化セリウム粉末であって、Ｘ線光電子分光（ＸＰＳ）測定時のＯ−Ｃピーク面積がＯ−Ｃｅピーク面積よりもさらに大きい酸化セリウム粉末を提供する。特に、Ｏ−Ｃピーク面積がＯ−Ｃｅピーク面積に対して１．１倍乃至４．０倍の範囲内である酸化セリウム粉末を提供する。
As a means to solve the above problems
The present invention provides a cerium oxide powder surface-treated with an organic substance, the cerium oxide powder having an OC peak area larger than the O-Ce peak area at the time of X-ray photoelectron spectroscopy (XPS) measurement. In particular, a cerium oxide powder having an OC peak area in the range of 1.1 times to 4.0 times the OC peak area is provided.
また、本発明は、有機物で表面処理された酸化セリウム粉末であって、アルゴンイオンで２ＫｅＶ、３００ｓの条件にて表面エッチングした後、ＸＰＳ測定時のＯ−Ｃｅピーク面積がＯ−Ｃピーク面積よりもさらに大きい酸化セリウム粉末を提供する。特に、ＯＣのピーク面積がＯ−Ｃｅピーク面積に対して０．１０倍乃至０．４０倍の範囲内である酸化セリウム粉末を提供する。 Further, the present invention is a cerium oxide powder surface-treated with an organic substance, and after surface etching with argon ions under the conditions of 2 KeV and 300 s, the OC peak area at the time of XPS measurement is larger than the OC peak area. Also provides a larger cerium oxide powder. In particular, a cerium oxide powder having an OC peak area in the range of 0.10 times to 0.40 times the O-Ce peak area is provided.
また、本発明は、有機物で表面処理された酸化セリウム粉末において、次の数式を満足する酸化セリウム粉末を提供する。 The present invention also provides a cerium oxide powder surface-treated with an organic substance, which satisfies the following mathematical formula.
４．０≦Ａ／Ｂ≦４０
Ａ：表面測定条件でのＸＰＳ測定時のＯ−Ｃピーク面積／Ｏ−Ｃｅピーク面積
Ｂ：エッチング測定条件でのＸＰＳ測定時のＯ−Ｃピーク面積／Ｏ−Ｃｅピーク面積
4.0 ≤ A / B ≤ 40
A: OC peak area / O-Ce peak area during XPS measurement under surface measurement conditions B: OC peak area / O-Ce peak area during XPS measurement under etching measurement conditions
特に、次の数式を満足する酸化セリウム粉末を提供する。 In particular, a cerium oxide powder that satisfies the following formula is provided.
１０．０≦Ａ／Ｂ≦３５．０ 10.0 ≤ A / B ≤ 35.0
前記有機物は、酢酸、ギ酸、ピバル酸、プロピオン酸、４−ヒドロキシフェニル酢酸を含むカルボン酸、パルミチン酸、ステアリン酸、オレイン酸、アラキドン酸、リノール酸、リノレン酸を含む炭素数８〜２０の飽和または不飽和脂肪酸の中から選択でき、前記酸化セリウム粉末は、研磨剤の用途に使用できる。 The organic matter is saturated with 8 to 20 carbon atoms including carboxylic acid including acetic acid, formic acid, pivalic acid, propionic acid and 4-hydroxyphenylacetic acid, palmitic acid, stearic acid, oleic acid, arachidonic acid, linoleic acid and linolenic acid. Alternatively, it can be selected from unsaturated fatty acids, and the cerium oxide powder can be used as an abrasive.
また、本発明は、研磨剤及び溶剤を含む研磨組成物であって、前記研磨剤は、前記酸化セリウム粉末を含む研磨組成物を提供する。 The present invention also provides a polishing composition containing an abrasive and a solvent, wherein the polishing agent provides a polishing composition containing the cerium oxide powder.
上述した構成的特徴を有する本発明は、研磨速度に非常に優れた、表面処理された酸化セリウム粉末及びこれを含む研磨組成物を提供することができる。 The present invention having the above-mentioned structural features can provide a surface-treated cerium oxide powder and a polishing composition containing the same, which are extremely excellent in polishing rate.
以下、実施例によって本発明をより詳細に説明する。下記の説明は、本発明の具体的な一例についてのものであるので、たとえ断定的、限定的な表現があっても、特許請求の範囲から定められる権利範囲を限定するものではない。 Hereinafter, the present invention will be described in more detail by way of examples. Since the following description is for a specific example of the present invention, even if there is an assertive or limited expression, it does not limit the scope of rights defined by the claims.
本発明による一実施例は、有機物で表面処理された酸化セリウム粉末であって、Ｘ線光電子分光（ＸＰＳ）測定時のＯ−Ｃピーク面積がＯ−Ｃｅピーク面積よりもさらに大きい酸化セリウム粉末を提供する。特に、Ｏ−Ｃピーク面積がＯ−Ｃｅピーク面積に対して１．１倍乃至４．０倍の範囲内である酸化セリウム粉末を提供する。 One embodiment according to the present invention is a cerium oxide powder surface-treated with an organic substance, which has an OC peak area larger than the O-Ce peak area at the time of X-ray photoelectron spectroscopy (XPS) measurement. provide. In particular, a cerium oxide powder having an OC peak area in the range of 1.1 times to 4.0 times the OC peak area is provided.
本発明に係る別の一実施例は、有機物で表面処理された酸化セリウム粉末であって、２ＫｅＶ、３００ｓの条件で表面エッチングした後、ＸＰＳ測定時のＯ−Ｃｅピーク面積がＯ−Ｃピーク面積よりもさらに大きい酸化セリウム粉末を提供する。特に、Ｏ−Ｃピーク面積がＯ−Ｃｅピーク面積に対して０．１０倍乃至０．４０倍の範囲内である酸化セリウム粉末を提供する。 Another embodiment of the present invention is a cerium oxide powder surface-treated with an organic substance, and after surface etching under the conditions of 2 KeV and 300 s, the OC peak area at the time of XPS measurement is the OC peak area. Provides an even larger cerium oxide powder. In particular, a cerium oxide powder having an OC peak area in the range of 0.10 to 0.40 times the OC peak area is provided.
本発明に係る別の一実施例は、有機物で表面処理された酸化セリウム粉末であって、次の数式を満足する酸化セリウム粉末を提供する。 Another embodiment according to the present invention provides a cerium oxide powder surface-treated with an organic substance, which satisfies the following mathematical formula.
４．０≦Ａ／Ｂ≦４０
Ａ：表面測定条件でのＸＰＳ測定時のＯ−Ｃピーク面積／Ｏ−Ｃｅピーク面積
Ｂ：エッチング測定条件でのＸＰＳ測定時のＯ−Ｃピーク面積／Ｏ−Ｃｅピーク面積
4.0 ≤ A / B ≤ 40
A: OC peak area / O-Ce peak area during XPS measurement under surface measurement conditions B: OC peak area / O-Ce peak area during XPS measurement under etching measurement conditions
特に、次の数式を満足する酸化セリウム粉末を提供する。 In particular, a cerium oxide powder that satisfies the following formula is provided.
１０．０≦Ａ／Ｂ≦３５．０ 10.0 ≤ A / B ≤ 35.0
本発明者は、酸化セリウム粉末の表面処理が研磨速度に関連することを確認した。特に、どのように表面処理が施されたかによって、研磨速度性能に大きな影響を及ぼし、ＸＰＳ測定時に上記の範囲を満足すればこそ研磨速度が著しく向上することを見出し、後述する実施例から分かるように、上記の範囲内で研磨速度に非常に優れることを確認した。 The present inventor has confirmed that the surface treatment of cerium oxide powder is related to the polishing rate. In particular, it has been found that the polishing speed performance is greatly affected by how the surface treatment is applied, and the polishing speed is remarkably improved only when the above range is satisfied at the time of XPS measurement, as can be seen from the examples described later. It was confirmed that the polishing speed was very excellent within the above range.
上記の範囲を満足する酸化セリウム粉末と研磨組成物の製造方法は、制限されず、様々な方法で製造できる。酸化セリウム粉末は、湿式酸化法、ゾルゲル（Ｓｏｌ Ｇｅｌ）法、水熱合成法、か焼法などを使用することができ、後述する実施例で望ましい方法を提示する。つまり、セリウム前駆体と塩基性物質とを混合してセリウム前駆体を酸化させて酸化セリウムを得ることができる。その後、洗浄及び乾燥を行い、粉砕した後、熱処理して有機物で表面処理した後、水で希釈して酸化セリウム粉末を含む研磨組成物を得ることができる。本発明の一実施例に係る酸化セリウム粉末を得るために、有機物の種類や有機物の含有量などが重要な因子として作用できるが、実施例を介して具体的に例示している。セリウム前駆体としては、特に制限されず、好ましくは塩の形態であり得る。その非制限的な例としては硝酸セリウム（ｃｅｒｉｕｍ ｎｉｔｒａｔｅ）、酢酸セリウム（ｃｅｒｉｕｍ ａｃｅｔａｔｅ）、これらの水和物などがあり、これらは単独で或いは２種以上組み合わせて使用できる。 The method for producing the cerium oxide powder and the polishing composition that satisfy the above range is not limited, and can be produced by various methods. As the cerium oxide powder, a wet oxidation method, a sol-gel method, a hydrothermal synthesis method, a calcination method and the like can be used, and a desirable method will be presented in Examples described later. That is, cerium oxide can be obtained by mixing the cerium precursor and the basic substance and oxidizing the cerium precursor. Then, it is washed and dried, pulverized, heat-treated, surface-treated with an organic substance, and then diluted with water to obtain a polishing composition containing cerium oxide powder. In order to obtain the cerium oxide powder according to one embodiment of the present invention, the type of organic substance, the content of the organic substance, and the like can act as important factors, but the examples are specifically exemplified. The cerium precursor is not particularly limited and may be preferably in the form of a salt. Non-limiting examples thereof include cerium nitrate, cerium acetate, and hydrates thereof, which can be used alone or in combination of two or more.
酸化セリウム粉末を表面処理するために使用する有機物は、制限されないが、酢酸、ギ酸、ピバル酸、プロピオン酸、４−ヒドロキシフェニル酢酸などのカルボン酸、パルミチン酸、ステアリン酸、オレイン酸、アラキドン酸、リノール酸、リノレン酸などの炭素数８〜２０の飽和または不飽和脂肪酸などを挙げることができる。表面処理方法としては、粉末を別個の分散機を用いて表面処理剤でコーティングする方法があり、この他にも、表面処理は、水に酸化セリウム粉末と表面処理剤を仕込んで撹拌することにより研磨組成物を製造する過程において行われてもよいが、これに限定されない。 The organics used to surface treat the cerium oxide powder are not limited to carboxylic acids such as acetic acid, formic acid, pivalic acid, propionic acid, 4-hydroxyphenylacetic acid, palmitic acid, stearic acid, oleic acid, arachidonic acid, etc. Examples thereof include saturated or unsaturated fatty acids having 8 to 20 carbon atoms such as linoleic acid and linolenic acid. As a surface treatment method, there is a method of coating the powder with a surface treatment agent using a separate disperser. In addition to this, the surface treatment is performed by adding cerium oxide powder and a surface treatment agent to water and stirring the mixture. It may be performed in the process of producing the polishing composition, but is not limited to this.
酸化セリウム粉末を含む研磨組成物は、溶剤として、水を使用してもよく、有機溶剤を一部混合して使用してもよい。この他にも、多様な添加剤、例えば、分散剤、欠陥抑制剤、酸化剤、研磨促進剤、ｐＨ調整剤などが含まれ得る。
以下、実施例についてより詳細に説明する。
In the polishing composition containing the cerium oxide powder, water may be used as the solvent, or an organic solvent may be partially mixed and used. In addition, various additives such as dispersants, defect inhibitors, oxidizing agents, polishing accelerators, pH adjusters and the like can be included.
Hereinafter, examples will be described in more detail.
＜実施例１＞
硝酸セリウム水和物（Ｃｅ（ＮＯ３）３・６Ｈ２Ｏ）２．５ｋｇを水３．５ｋｇに溶解した後、１時間撹拌して前駆体溶液を製造した。アンモニア水３．２ｋｇを０．４ｋｇ／ｍｉｎの流量で前駆体溶液に投入し、前駆体溶液は攪拌した。アンモニア水の投入が完了した後、８０℃に昇温し、圧力を２ｂａｒに昇圧して攪拌しながら１２時間反応させた。得られた酸化セリウムをフィルタープレスで濾過、洗浄し、２００℃で１２時間乾燥させた後、粉砕し、ベルト炉にて９００℃で９０分間熱処理を行った。その後、酢酸を酸化セリウム粉末に対して１０重量％添加して分散機で分散させて表面処理し、０．３μｍのノミナル（ｎｏｍｉｎａｌ）フィルターで濾過し、希釈して酸化セリウムスラリーを製造した。
粉末の表面処理特性を分析するために、次の条件でＸ線光電子分光（ＸＰＳ）を行って粉末の表面を測定し、その結果を表２に示した。
<Example 1>
After cerium nitrate hydrate (Ce (NO 3) 3 · 6H 2 O) 2.5kg was dissolved in water 3.5 kg, was prepared precursor solution is stirred for 1 hour. 3.2 kg of aqueous ammonia was added to the precursor solution at a flow rate of 0.4 kg / min, and the precursor solution was stirred. After the addition of ammonia water was completed, the temperature was raised to 80 ° C., the pressure was increased to 2 bar, and the reaction was carried out for 12 hours with stirring. The obtained cerium oxide was filtered with a filter press, washed, dried at 200 ° C. for 12 hours, pulverized, and heat-treated at 900 ° C. for 90 minutes in a belt furnace. Then, 10% by weight of acetic acid was added to the cerium oxide powder, dispersed by a disperser, surface-treated, filtered through a 0.3 μm nominal filter, and diluted to produce a cerium oxide slurry.
In order to analyze the surface treatment characteristics of the powder, the surface of the powder was measured by performing X-ray photoelectron spectroscopy (XPS) under the following conditions, and the results are shown in Table 2.
＜測定条件＞
１．ＸＰＳ装備名／メーカー：Ｋ−Ａｌｐｈａ＋／ＴｈｅｒｍｏＦｉｓｈｅｒ Ｓｃｉｅｎｔｉｆｉｃ製
<Measurement conditions>
1. 1. XPS Equipment Name / Manufacturer: K-Alpha + / Thermo Fisher Scientific
２．測定条件
１）Ｘ線源：Ｍｏｎｏｃｈｒｏｍａｔｅｄ Ａｌ Ｘ−Ｒａｙ ｓｏｕｒｃｅｓ（Ａｌ Ｋα ｌｉｎｅ：１４８６．６ｅＶ）
２）Ｘ線電源：１２ｋＶ、１０ｍＡ
３）サンプリングエリア：４００μｍ（直径）
４）ナロースキャン：パスエネルギー（ｐａｓｓ ｅｎｅｒｇｙ）４０ｅＶ、ステップサイズ０．０５ｅＶ
５）真空：３ｘ１０−９ｍｂａｒ
６）キャリブレーション：Ｎｏ
７）フラッドガンは電荷補償に使用される(Flood gun is used for charge compensation)：ＯＮ
2. Measurement conditions 1) X-ray source: Monochromated Al X-Ray sources (Al Kα line: 1486.6 eV)
2) X-ray power supply: 12kV, 10mA
3) Sampling area: 400 μm (diameter)
4) Narrow scan: pass energy 40 eV, step size 0.05 eV
5) Vacuum: 3x10-9mbar
6) Calibration: No
7) Flood gun is used for charge compensation: ON
また、粉末表面の一部を下記の条件でエッチングし、上記の条件でＸＰＳを行い、その結果を表２に示した。 Further, a part of the powder surface was etched under the following conditions, XPS was performed under the above conditions, and the results are shown in Table 2.
＜エッチング条件＞
Ａｒイオンエッチング：２ｋｅＶ、６００ｓｅｃ、ラスターサイズ２ｘ２ｍｍ
また、酸化セリウムスラリーの研磨テストのために、下記の条件でテストし、その結果を表２に示した。
<Etching conditions>
Ar ion etching: 2keV, 600sec, raster size 2x2mm
In addition, for the polishing test of the cerium oxide slurry, the test was performed under the following conditions, and the results are shown in Table 2.
研磨テスト：ＣＭＰ装備（モデル名：斗山ＵＮＩＰＬＡ２３１）
パッド：ＩＣ１０００ＴＭ Ａ２ ＰＡＤ ２０‘＊１．１８’ ＡＣＡＯ：１Ｙ１０
時間：６０秒
スピンドル速度：８５ｒｐｍ
ウエハー圧力：５ｐｓｉ
スラリーフローレート：２００ｃｃ／ｍｉｎ
ウエハー：８ｉｎｃｈ（ＰＥＴＥＯＳ）
ウエハー厚さ：１２０００Å
Polishing test: CMP equipment (model name: Doosan UNIPLA231)
Pad: IC1000TM A2 PAD 20'* 1.18' ACAO: 1Y10
Time: 60 seconds Spindle speed: 85 rpm
Wafer pressure: 5psi
Slurry flow rate: 200cc / min
Wafer: 8 inch (PETEOS)
Wafer thickness: 12000 Å
＜実施例２＞乃至＜実施例５＞
実施例１において下記表１に提示した条件以外は実施例１と同様にして行った。
<Example 2> to <Example 5>
In Example 1, the conditions were the same as in Example 1 except for the conditions presented in Table 1 below.
＜比較例１＞乃至＜比較例３＞
実施例１において下記表１に提示した条件以外は実施例１と同様にして行った。
<Comparative Example 1> to <Comparative Example 3>
In Example 1, the conditions were the same as in Example 1 except for the conditions presented in Table 1 below.
表２より、Ａ／Ｂの値が高い場合には、研磨速度（ＲＲ）値が高いが、比較例２のようにＡ／Ｂの値が過度に高い場合には、むしろＲＲ値が低いことが分かった。このようにＡ／Ｂの値が研磨速度性能と深く関連していることを確認することができる。 From Table 2, when the A / B value is high, the polishing rate (RR) value is high, but when the A / B value is excessively high as in Comparative Example 2, the RR value is rather low. I found out. In this way, it can be confirmed that the A / B value is deeply related to the polishing speed performance.
また、Ａの値は１よりも高く、Ｂの値は１よりも低い場合には、ＲＲ値が高いことが分かった。 Further, it was found that when the value of A was higher than 1 and the value of B was lower than 1, the RR value was high.
また、Ｏ−Ｃピーク面積がＯ−Ｃｅピーク面積に対して１．１倍乃至４．０倍の範囲内である場合には研磨速度に優れており、Ｏ−Ｃピーク面積がＯ−Ｃｅピーク面積に対して０．１０倍乃至０．４０倍の範囲内である場合には研磨速度に優れていることを確認することができる。 Further, when the OC peak area is in the range of 1.1 to 4.0 times the O-Ce peak area, the polishing rate is excellent, and the O-C peak area is the O-Ce peak. When it is in the range of 0.10 times to 0.40 times the area, it can be confirmed that the polishing speed is excellent.
Claims (9)
Ｘ線光電子分光（ＸＰＳ）測定時のＯ−Ｃピーク面積がＯ−Ｃｅピーク面積よりもさらに大きい、酸化セリウム粉末。 Cerium oxide powder surface-treated with organic matter
Cerium oxide powder in which the OC peak area at the time of X-ray photoelectron spectroscopy (XPS) measurement is even larger than the O-Ce peak area.
アルゴンイオンで２ＫｅＶ、３００ｓの条件にて表面エッチングした後、ＸＰＳ測定時のＯ−Ｃｅピーク面積がＯ−Ｃピーク面積よりもさらに大きい、酸化セリウム粉末。 Cerium oxide powder surface-treated with organic matter
A cerium oxide powder in which the O-Ce peak area at the time of XPS measurement is further larger than the O-C peak area after surface etching with argon ions under the conditions of 2 KeV and 300 s.
下記の数式を満足する酸化セリウム粉末。
４．０≦Ａ／Ｂ≦４０
Ａ：表面測定条件でのＸＰＳ測定時のＯ−Ｃピーク面積／Ｏ−Ｃｅピーク面積
Ｂ：エッチング測定条件でのＸＰＳ測定時のＯ−Ｃピーク面積／Ｏ−Ｃｅピーク面積 In cerium oxide powder surface-treated with organic matter,
Cerium oxide powder that satisfies the following formula.
4.0 ≤ A / B ≤ 40
A: OC peak area / O-Ce peak area during XPS measurement under surface measurement conditions B: OC peak area / O-Ce peak area during XPS measurement under etching measurement conditions
１０．０≦Ａ／Ｂ≦３５．０ The cerium oxide powder according to claim 5, which satisfies the following formula.
10.0 ≤ A / B ≤ 35.0
前記研磨剤は請求項１乃至７のいずれか一項に記載の酸化セリウム粉末を含む、研磨組成物。 A polishing composition containing an abrasive and a solvent.
The polishing composition containing the cerium oxide powder according to any one of claims 1 to 7.
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