TW201710458A - Polishing method and composition adjusting agent - Google Patents
Polishing method and composition adjusting agent Download PDFInfo
- Publication number
- TW201710458A TW201710458A TW105115551A TW105115551A TW201710458A TW 201710458 A TW201710458 A TW 201710458A TW 105115551 A TW105115551 A TW 105115551A TW 105115551 A TW105115551 A TW 105115551A TW 201710458 A TW201710458 A TW 201710458A
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- TW
- Taiwan
- Prior art keywords
- polishing
- composition
- polished
- water
- soluble polymer
- Prior art date
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- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229920000578 graft copolymer Polymers 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- QOSATHPSBFQAML-UHFFFAOYSA-N hydrogen peroxide;hydrate Chemical compound O.OO QOSATHPSBFQAML-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000001341 hydroxy propyl starch Substances 0.000 description 1
- 229920003063 hydroxymethyl cellulose Polymers 0.000 description 1
- 229940031574 hydroxymethyl cellulose Drugs 0.000 description 1
- GTTBQSNGUYHPNK-UHFFFAOYSA-N hydroxymethylphosphonic acid Chemical compound OCP(O)(O)=O GTTBQSNGUYHPNK-UHFFFAOYSA-N 0.000 description 1
- 239000001863 hydroxypropyl cellulose Substances 0.000 description 1
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 description 1
- 235000013828 hydroxypropyl starch Nutrition 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- BEGLCMHJXHIJLR-UHFFFAOYSA-N methylisothiazolinone Chemical compound CN1SC=CC1=O BEGLCMHJXHIJLR-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 150000004885 piperazines Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920005630 polypropylene random copolymer Polymers 0.000 description 1
- 239000011970 polystyrene sulfonate Substances 0.000 description 1
- 229960002796 polystyrene sulfonate Drugs 0.000 description 1
- 239000011496 polyurethane foam Substances 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 235000019448 polyvinylpyrrolidone-vinyl acetate copolymer Nutrition 0.000 description 1
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 1
- 235000015497 potassium bicarbonate Nutrition 0.000 description 1
- 239000011736 potassium bicarbonate Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 229940086066 potassium hydrogencarbonate Drugs 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000005621 tetraalkylammonium salts Chemical class 0.000 description 1
- 125000005497 tetraalkylphosphonium group Chemical group 0.000 description 1
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- SZWHXXNVLACKBV-UHFFFAOYSA-N tetraethylphosphanium Chemical compound CC[P+](CC)(CC)CC SZWHXXNVLACKBV-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- XOGCTUKDUDAZKA-UHFFFAOYSA-N tetrapropylphosphanium Chemical compound CCC[P+](CCC)(CCC)CCC XOGCTUKDUDAZKA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- B24B55/00—Safety devices for grinding or polishing machines; Accessories fitted to grinding or polishing machines for keeping tools or parts of the machine in good working condition
- B24B55/12—Devices for exhausting mist of oil or coolant; Devices for collecting or recovering materials resulting from grinding or polishing, e.g. of precious metals, precious stones, diamonds or the like
-
- 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
- B24B57/00—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents
- B24B57/02—Devices for feeding, applying, grading or recovering grinding, polishing or lapping agents for feeding of fluid, sprayed, pulverised, or liquefied grinding, polishing or lapping agents
-
- 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)
- Mechanical Engineering (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
- Mechanical Treatment Of Semiconductor (AREA)
- Grinding-Machine Dressing And Accessory Apparatuses (AREA)
Abstract
Description
本發明係關於研磨方法及組成調整劑。 The present invention relates to a grinding method and a composition adjusting agent.
研磨對象物之研磨中使用之研磨用組成物，基於減低研磨成本之目的，有將研磨中使用後予以回收再使用之情況。然而，由於研磨中使用，有使構成研磨用組成物之研磨粒、添加劑等成分消耗或損失之情況，故有研磨用組成物之組成產生變化之情況。其結果，使研磨用組成物之研磨性能降低，於使用回收之研磨用組成物進行之研磨對象物之研磨中，有研磨對象物之表面品質、研磨速度等之研磨結果不充分之虞。 The polishing composition used for polishing the object to be polished may be recovered and used after being used for polishing for the purpose of reducing the polishing cost. However, since it is used for polishing, the components such as abrasive grains and additives constituting the polishing composition are consumed or lost, and thus the composition of the polishing composition may be changed. As a result, the polishing performance of the polishing composition is lowered, and in the polishing of the object to be polished using the collected polishing composition, the polishing results such as the surface quality and the polishing rate of the object to be polished are insufficient.
[先前技術文獻] [Previous Technical Literature]
[專利文獻] [Patent Literature]
專利文獻1：日本國專利公報第5598607號 Patent Document 1: Japanese Patent Publication No. 5598607
因此，本發明係為解決如上述之以往技術所具有之問題點，其課題在於提供即使於回收研磨對象物之研磨中使用之研磨用組成物而再使用時亦可獲得優異研磨結果之研磨方法。且課題在於同時提供於回收研磨對象物之研磨中使用之研磨用組成物而再使用時添加於研磨用組成物中而使研磨用組成物之研磨性能恢復之組成調整劑。 Therefore, the present invention has been made to solve the problems of the prior art as described above, and an object of the present invention is to provide a polishing method capable of obtaining an excellent polishing result even when the polishing composition used for polishing the polishing object is recovered and reused. . In addition, the object of the present invention is to provide a composition adjusting agent which is added to the polishing composition and recovers the polishing performance of the polishing composition when the polishing composition used for the polishing of the object to be polished is recovered.
為解決前述課題，本發明之一樣態之研磨方法係使用含有水溶性高分子之研磨用組成物研磨研磨對象物之研磨方法，其主要具備下述步驟：邊將槽內之研磨用組成物供給至研磨對象物邊研磨研磨對象物之研磨步驟，回收研磨對象物之研磨中使用之研磨用組成物而循環回到槽之回收步驟，及將供給至研磨對象物之研磨用組成物中之水溶性高分子濃度調整為預先設定之範圍內之數值之組成調整步驟。 In order to solve the above problems, the polishing method of the present invention is a polishing method for polishing an object to be polished using a polishing composition containing a water-soluble polymer, and mainly includes a step of supplying a polishing composition in a tank. a polishing step of polishing the object to be polished to the object to be polished, recovering the polishing composition used for polishing the object to be polished, recycling the step back to the tank, and dissolving the water in the polishing composition supplied to the object to be polished The composition adjustment step of adjusting the concentration of the polymer to a value within a predetermined range.
又，本發明另一樣態之組成調整劑係於上述一樣態之研磨方法中使用之組成調整劑，主要含有水溶性高分子。 Further, the composition adjusting agent of another aspect of the present invention is a composition adjusting agent used in the polishing method of the above-described state, and mainly contains a water-soluble polymer.
依據本發明之研磨方法，即使於回收研磨對象物之研磨中使用之研磨用組成物而再使用時亦可獲得優異研磨結果。且依據本發明之組成調整劑，可使研磨對象 物之研磨中使用之研磨用組成物之研磨性能回復。 According to the polishing method of the present invention, excellent polishing results can be obtained even when the polishing composition used for polishing the object to be polished is recovered and reused. And according to the composition adjusting agent of the invention, the grinding object can be The polishing performance of the polishing composition used in the polishing of the object is recovered.
12‧‧‧壓盤 12‧‧‧ Platen
14‧‧‧研磨墊 14‧‧‧ polishing pad
19‧‧‧晶圓保持板 19‧‧‧ Wafer Holder
21‧‧‧槽 21‧‧‧ slots
22‧‧‧研磨用組成物供給管 22‧‧‧ polishing composition supply tube
31‧‧‧研磨用組成物承接盤 31‧‧‧Plastic composition receiving tray
41‧‧‧組成調整劑供給管 41‧‧‧ Composition adjuster supply tube
圖1為說明本發明一實施形態之研磨方法之概念圖。 BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a conceptual view for explaining a polishing method according to an embodiment of the present invention.
針對本發明一實施形態詳細說明。本實施形態之研磨方法係使用含有水溶性高分子之研磨用組成物研磨研磨對象物之研磨方法，其具備下述步驟：邊將槽內之研磨用組成物供給至研磨對象物邊研磨研磨對象物之研磨步驟，回收於研磨步驟中研磨對象物之研磨中使用之研磨用組成物而循環回到槽之回收步驟，及將於研磨步驟中供給至研磨對象物之研磨用組成物中之水溶性高分子濃度調整為預先設定之範圍內之數值之組成調整步驟。 An embodiment of the present invention will be described in detail. The polishing method of the present embodiment is a polishing method for polishing an object to be polished by using a polishing composition containing a water-soluble polymer, which comprises the steps of: polishing a polishing object while supplying the polishing composition in the groove to the object to be polished; The polishing step of the material, the recovery step of recycling the polishing composition used for polishing the object to be polished in the polishing step, and the water-soluble solution in the polishing composition supplied to the object to be polished in the polishing step The composition adjustment step of adjusting the concentration of the polymer to a value within a predetermined range.
依據此本實施形態之研磨方法，由於將研磨用組成物中之水溶性高分子濃度總是維持於預先設定之範圍內之數值，同時進行研磨對象物之研磨，故即使於回收研磨對象物之研磨中使用之研磨用組成物而再使用時，研磨對象物之表面品質(例如平坦性、平滑性)、研磨速度等之研磨結果亦優異。因此，並無必要於短時間內更換研磨用組成物，而可長期間循環使用研磨用組成物。 According to the polishing method of the present embodiment, since the concentration of the water-soluble polymer in the polishing composition is always maintained within a predetermined range and the polishing object is polished, the object to be polished is recovered. When the polishing composition used for polishing is reused, the surface quality (for example, flatness and smoothness) of the object to be polished and the polishing rate are excellent. Therefore, it is not necessary to replace the polishing composition in a short time, and the polishing composition can be recycled for a long period of time.
又，藉由循環使用研磨用組成物，由於可削減作為廢液而排出之研磨用組成物之量，故可減低環境負 荷。再者，由於可減低所使用之研磨用組成物之量，故可抑制研磨對象物之研磨所需之製造成本。 Further, by recycling the polishing composition, since the amount of the polishing composition discharged as the waste liquid can be reduced, the environmental negative can be reduced. Lotus. Further, since the amount of the polishing composition to be used can be reduced, the manufacturing cost required for polishing the object to be polished can be suppressed.
組成調整步驟亦可為將於研磨步驟中供給至研磨對象物之研磨用組成物中之水溶性高分子濃度以成為預先設定之範圍內之數值之方式，對於以研磨步驟中供給至研磨對象物之研磨用組成物添加含有水溶性高分子之組成調整劑之步驟。 The composition adjustment step may be such that the concentration of the water-soluble polymer supplied to the polishing composition in the polishing step in the polishing step is a value within a predetermined range, and is supplied to the object to be polished in the polishing step. The step of adding a composition adjusting agent containing a water-soluble polymer to the polishing composition.
或者，組成調整步驟亦可為將於研磨步驟中藉由研磨用組成物之供給而供給至研磨對象物之水溶性高分子量以研磨對象物表面每1mm2成為0.0004mg/min以上且0.0030mg/min以下之方式，對於以研磨步驟中供給至研磨對象物之研磨用組成物添加含有水溶性高分子之組成調整劑之步驟。於研磨步驟中藉由研磨用組成物之供給而供給至研磨對象物之水溶性高分子之量較好係研磨對象物表面每1mm2為0.0006mg/min以上且0.0024mg/min以下，更好係研磨對象物表面每1mm2為0.0009mg/min以上且0.0020mg/min以下， 亦即，本實施形態之研磨方法之組成調整步驟所使用之組成調整劑係含有水溶性高分子之組成物，藉由添加於研磨對象物之研磨中使用後回收之研磨用組成物中，而調整該研磨用組成物之組成(將消耗或損失之水溶性高分子補給於研磨用組成物中)，可恢復該研磨用組成物之研磨性能。 Alternatively, the composition adjustment step may be such that the water-soluble high molecular weight supplied to the object to be polished by the supply of the polishing composition in the polishing step is 0.0004 mg/min or more and 0.0030 mg/min per 1 mm 2 of the surface of the object to be polished. In the method of the following, a step of adding a composition adjusting agent containing a water-soluble polymer to the polishing composition supplied to the object to be polished in the polishing step is added. The amount of the water-soluble polymer to be supplied to the object to be polished by the supply of the polishing composition in the polishing step is preferably 0.0006 mg/min or more and 0.0024 mg/min or less per 1 mm 2 of the object to be polished. The surface of the object to be polished is 0.0009 mg/min or more and 0.0020 mg/min or less per 1 mm 2 , that is, the composition adjusting agent used in the composition adjustment step of the polishing method of the present embodiment contains a composition of a water-soluble polymer. By adding the polishing composition recovered after polishing to the object to be polished, the composition of the polishing composition (replenishing the water-soluble polymer consumed or lost in the polishing composition) can be restored. The polishing performance of the polishing composition.
又，本實施形態之組成調整劑為了對研磨用 組成物補給因研磨對象物之研磨中使用而消耗或損失之水溶性高分子，故而含有水溶性高分子，但組成調整劑所含有之水溶性高分子之種類可與研磨用組成物所含有之水溶性高分子之種類同種，但若於研磨對象物之研磨中能發揮同樣作用效果則亦可為不同種。 Further, the composition adjusting agent of the present embodiment is used for polishing The composition replenishes the water-soluble polymer which is consumed or lost by use in the polishing of the object to be polished, and therefore contains a water-soluble polymer, but the type of the water-soluble polymer contained in the composition adjusting agent may be contained in the polishing composition. Although the type of the water-soluble polymer is the same, it may be different if it can exhibit the same effect in the polishing of the object to be polished.
且，本實施形態之組成調整劑亦可含有水溶性高分子以外之其他成分。亦即，研磨用組成物除了水溶性高分子以外，亦可含有研磨粒、添加劑等其他成分，但研磨粒、添加劑等之其他成分亦有於研磨對象物之研磨中使用而被消耗或損失之情況，必須注意尤其是添加劑中之鹼性化合物之減少。因此，本實施形態之組成調整劑為了對研磨用組成物補給研磨粒、添加劑等之其他成分之一部分或全部，亦可含有水溶性高分子以外之研磨粒、添加劑(尤其是鹼性化合物)等之其他成分。 Further, the composition adjusting agent of the present embodiment may contain other components than the water-soluble polymer. In other words, the polishing composition may contain other components such as abrasive grains and additives in addition to the water-soluble polymer, but other components such as abrasive grains and additives may be consumed or lost in the polishing of the object to be polished. In this case, attention must be paid, in particular, to the reduction of basic compounds in the additive. Therefore, the composition adjusting agent of the present embodiment may contain abrasive grains, additives (especially basic compounds), etc. other than the water-soluble polymer, in order to supply part or all of other components such as abrasive grains and additives to the polishing composition. Other ingredients.
以下，針對本實施形態之研磨方法、該研磨方法中使用之研磨用組成物及組成調整劑詳細說明。又，以下說明之各種操作或物性測定只要未特別說明，則為在室溫(20℃以上25℃以下)、相對濕度40%以上50%以下之條件進行者。 Hereinafter, the polishing method of the present embodiment, the polishing composition and the composition adjusting agent used in the polishing method will be described in detail. In addition, the various operations or physical properties described below are carried out under the conditions of room temperature (20° C. or higher and 25° C. or lower) and relative humidity of 40% or more and 50% or less unless otherwise specified.
1.研磨對象物 1. Grinding object
研磨步驟中研磨之研磨對象物種類並未特別限制，但舉例為單體矽、矽化合物、金屬等。單體矽及矽化合物為具有含有含矽材料之層之研磨對象物。 The type of the object to be polished which is polished in the polishing step is not particularly limited, and examples thereof include a monomer ruthenium, a ruthenium compound, a metal, and the like. The monomer ruthenium and ruthenium compound are polishing objects having a layer containing a ruthenium-containing material.
作為單體矽舉例為例如單晶矽、多晶矽(polysilicone)、非晶矽等。且作為矽化合物舉例為例如氮化矽、二氧化矽(例如使用四乙氧基矽烷(TEOS)形成之二氧化矽層間絕緣膜)、碳化矽等。 The monomer hydrazine is exemplified by, for example, a single crystal germanium, a polysilicone, an amorphous germanium or the like. Further, examples of the antimony compound include cerium nitride, cerium oxide (for example, a cerium oxide interlayer insulating film formed using tetraethoxy decane (TEOS)), tantalum carbide, and the like.
再者，作為金屬舉例為例如鎢、銅、鋁、鉿、鈷、鎳、鈦、鉭、金、銀、鉑、鈀、鍺、釕、銥、鋨等。該等金屬亦可包含合金或金屬化合物之形態。 Further, examples of the metal include, for example, tungsten, copper, aluminum, ruthenium, cobalt, nickel, titanium, rhodium, gold, silver, platinum, palladium, rhodium, ruthenium, osmium, iridium, and the like. The metals may also comprise the form of an alloy or a metal compound.
該等中，於具備由單晶或多晶之矽所成之表面之研磨對象物之研磨時，本實施形態之研磨方法有效，使用單晶矽作為研磨對象物之研磨中最有效。 In the polishing of the object to be polished which is formed of a single crystal or a polycrystalline crucible, the polishing method of the present embodiment is effective, and the use of single crystal germanium as the polishing target is most effective.
2.研磨用組成物 2. Grinding composition
研磨用組成物之組成(成分及濃度)並未特別限制，可為含有研磨粒、水溶性高分子及液狀介質之漿料。 The composition (ingredient and concentration) of the polishing composition is not particularly limited, and may be a slurry containing abrasive grains, a water-soluble polymer, and a liquid medium.
2-1研磨粒 2-1 abrasive grain
研磨粒種類並未特別限制，無機粒子、有機粒子、有機無機複合粒子之任一者均可使用。無機粒子之具體例舉例為由氧化矽、氧化鋁、氧化鈰、氧化鈦、氧化鉻等之金屬氧化物所成之粒子，或由氮化矽、碳化矽、氮化硼等陶瓷所成之粒子。且，有機粒子之具體例舉例為聚甲基丙烯酸甲酯(PMMA)粒子。該等研磨粒可單獨使用1種，亦可混合2種以上使用。且，該等研磨粒中，較好為膠體氧化矽、發煙氧化矽、溶凝膠法氧化矽等之氧化矽，更好為膠 體氧化矽。 The type of the abrasive grains is not particularly limited, and any of inorganic particles, organic particles, and organic-inorganic composite particles can be used. Specific examples of the inorganic particles are particles formed of a metal oxide such as cerium oxide, aluminum oxide, cerium oxide, titanium oxide or chromium oxide, or particles formed of ceramics such as tantalum nitride, tantalum carbide or boron nitride. . Further, specific examples of the organic particles are exemplified by polymethyl methacrylate (PMMA) particles. These abrasive grains may be used alone or in combination of two or more. Further, among the abrasive grains, ruthenium oxide such as colloidal cerium oxide, fuming cerium oxide, sol-gel cerium oxide or the like is preferable, and more preferably Body bismuth oxide.
本實施形態之研磨用組成物所含有之研磨粒之一次粒徑亦可為20nm以上，較好為30nm以上，更好為40nm以上。研磨粒之平均一次粒徑若為上述範圍內，則可提高研磨用組成物對研磨對象物之研磨速度。另一方面，本實施形態之研磨用組成物所含有之研磨粒之平均一次粒徑亦可為150nm以下，較好為100nm以下，更好為70nm以下。研磨粒之平均一次粒徑若為上述範圍內，則可容易藉由研磨獲得表面粗糙度良好之被研磨面。又，研磨粒之平均一次粒徑可藉由例如以氮氣吸附法(BET法)測定之比表面積而算出。研磨粒之比表面積之測定可使用例如Micrometrix公司製之「Flow SorbII 2300」進行。 The primary particle diameter of the abrasive grains contained in the polishing composition of the present embodiment may be 20 nm or more, preferably 30 nm or more, more preferably 40 nm or more. When the average primary particle diameter of the abrasive grains is within the above range, the polishing rate of the polishing composition to the object to be polished can be increased. On the other hand, the average primary particle diameter of the abrasive grains contained in the polishing composition of the present embodiment may be 150 nm or less, preferably 100 nm or less, more preferably 70 nm or less. When the average primary particle diameter of the abrasive grains is within the above range, the surface to be polished having a good surface roughness can be easily obtained by polishing. Further, the average primary particle diameter of the abrasive grains can be calculated, for example, by the specific surface area measured by a nitrogen gas adsorption method (BET method). The measurement of the specific surface area of the abrasive grains can be carried out, for example, using "Flow Sorb II 2300" manufactured by Micrometrix.
本實施形態之研磨用組成物中之研磨粒含量宜為0.1質量%以上，較好為0.5質量%以上，更好為1質量%以上。研磨粒含量若為上述範圍內，則可提高研磨用組成物對研磨對象物之研磨速度。另一方面，研磨用組成物中之研磨粒含量宜為5質量%以下，較好為3質量%以下，更好為2質量%以下。研磨粒含量若為上述範圍內，則可減低研磨用組成物之製造成本。且，可減低研磨後之研磨對象物表面上殘存之研磨粒量，提高研磨對象物之表面清淨性。 The content of the abrasive grains in the polishing composition of the present embodiment is preferably 0.1% by mass or more, preferably 0.5% by mass or more, more preferably 1% by mass or more. When the content of the abrasive grains is within the above range, the polishing rate of the polishing composition to the object to be polished can be increased. On the other hand, the content of the abrasive grains in the polishing composition is preferably 5% by mass or less, preferably 3% by mass or less, more preferably 2% by mass or less. When the content of the abrasive grains is within the above range, the production cost of the polishing composition can be reduced. Further, the amount of abrasive grains remaining on the surface of the object to be polished after polishing can be reduced, and the surface cleanability of the object to be polished can be improved.
研磨粒之形狀(外形)可為球形，亦可為非球形。較好為非球形之形狀。作為非球形之形狀之例，舉例有例如中間部具有縮頸之橢圓體形狀之所謂繭型形狀、於 表面具有複數突起之球形形狀、橄欖球形狀等。且研磨粒亦可具有2個以上一次粒子締合之構造。 The shape (outer shape) of the abrasive grains may be spherical or non-spherical. It is preferably a non-spherical shape. As an example of the shape of the non-spherical shape, for example, a so-called 茧-shaped shape having an ellipsoid shape in which the neck portion is constricted, The surface has a spherical shape of a plurality of protrusions, a football shape, and the like. Further, the abrasive grains may have a structure in which two or more primary particles are associated.
研磨粒之一次粒子之長徑/短徑比之平均值(平均縱橫比)並未特別限制，原理上為1.0以上，較好為1.1以上，更好為1.2以上。藉由增大研磨粒之平均縱橫比，可實現更高之研磨速度。且，研磨粒之平均縱橫比，基於擦痕減低等之觀點，較好為4.0以下，更好為3.0以下，又更好為2.5以下。 The average value (average aspect ratio) of the major axis/short diameter ratio of the primary particles of the abrasive grains is not particularly limited, and is preferably 1.0 or more in principle, preferably 1.1 or more, more preferably 1.2 or more. Higher grinding speeds can be achieved by increasing the average aspect ratio of the abrasive particles. Further, the average aspect ratio of the abrasive grains is preferably 4.0 or less, more preferably 3.0 or less, still more preferably 2.5 or less, from the viewpoint of the reduction of scratches and the like.
上述研磨粒之形狀(外形)或平均縱橫比可藉由例如電子顯微鏡觀察而掌握。掌握平均縱橫比之具體順序可使用例如掃描型電子顯微鏡(SEM)，針對可辨識獨立粒子形狀之特定個數(例如200個)研磨粒粒子，描繪與各粒子圖像外切之最小長方形。接著，對於各粒子圖像描繪之長方形，算出將其長邊之長度(長徑值)除以短邊長度(短徑值)之值作為長徑/短徑比(縱橫比)。藉由對上述特定個數之研磨粒子之縱橫比進行算術平均，可求得平均縱橫比。 The shape (outer shape) or the average aspect ratio of the above abrasive grains can be grasped by, for example, observation by an electron microscope. The specific order in which the average aspect ratio is grasped can be, for example, a scanning electron microscope (SEM), for a specific number (for example, 200) of abrasive particles that can recognize the shape of the individual particles, and a minimum rectangle that is circumscribed to each particle image is drawn. Next, for the rectangle drawn by each particle image, a value obtained by dividing the length (long diameter value) of the long side by the short side length (short diameter value) is calculated as the long diameter/short diameter ratio (aspect ratio). The average aspect ratio can be obtained by arithmetically averaging the aspect ratio of the above specific number of abrasive particles.
2-2水溶性高分子 2-2 water soluble polymer
研磨用組成物中之水溶性高分子可藉由疏水性吸附於研磨對象物表面而提高階差消除性，故提高研磨後之研磨對象物之平坦性。 The water-soluble polymer in the polishing composition can be adsorbed on the surface of the object to be polished by hydrophobicity to improve the step-eliminating property, thereby improving the flatness of the object to be polished after polishing.
作為水溶性高分子舉例為纖維素衍生物、澱粉衍生物、含氧伸烷基單位之聚合物、含氮原子之聚合物、及乙烯醇系聚合物。 The water-soluble polymer is exemplified by a cellulose derivative, a starch derivative, a polymer of an oxygen-containing alkylene unit, a polymer containing a nitrogen atom, and a vinyl alcohol polymer.
纖維素衍生物之具體例舉例為羥甲基纖維素、羥乙基纖維素、羥丙基纖維素、羧甲基纖維素等。該等中，較好為羥乙基纖維素。 Specific examples of the cellulose derivative are hydroxymethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, carboxymethylcellulose, and the like. Among these, hydroxyethyl cellulose is preferred.
又，作為澱粉衍生物之具體例舉例為澱粉、羥丙基澱粉等。 Further, specific examples of the starch derivative are starch, hydroxypropyl starch, and the like.
再者，作為含氧伸烷基單元之聚合物之具體例舉例為聚乙二醇、聚環氧乙烷、聚環氧丙烷、環氧乙烷與環氧丙烷之無規共聚物或嵌段共聚物等。 Further, specific examples of the polymer as the oxygen-containing alkylene unit are polyethylene glycol, polyethylene oxide, polypropylene oxide, random copolymer or block of ethylene oxide and propylene oxide. Copolymers, etc.
再者，作為含氮原子之聚合物之具體例舉例為聚乙烯吡咯啶酮、聚乙烯吡咯啶酮聚丙烯酸共聚物、聚乙烯吡咯啶酮乙酸乙烯酯共聚物等之吡咯啶酮系聚合物、或聚丙烯醯基嗎啉、聚丙烯醯胺等。該等中，較好為聚乙烯吡咯啶酮。 Further, specific examples of the polymer containing a nitrogen atom are pyrrolidone polymers such as polyvinylpyrrolidone, polyvinylpyrrolidone polyacrylic acid copolymer, and polyvinylpyrrolidone vinyl acetate copolymer. Or polypropylene decylmorpholine, polypropylene decylamine, and the like. Among these, polyvinylpyrrolidone is preferred.
再者，聚乙烯醇系聚合物之具體例舉例為聚乙烯醇、陽離子改性之聚乙烯醇、陰離子改性聚乙烯醇等。該等中，較好為聚乙烯醇。 Further, specific examples of the polyvinyl alcohol-based polymer are polyvinyl alcohol, cationically modified polyvinyl alcohol, and anion-modified polyvinyl alcohol. Among these, polyvinyl alcohol is preferred.
作為該等以外之水溶性高分子之例舉例為聚異戊二烯磺酸、聚乙烯磺酸、聚烯丙基磺酸、聚伸異戊基磺酸、聚苯乙烯磺酸鹽、聚丙烯酸鹽、聚乙酸乙烯酯等。 Examples of the water-soluble polymer other than the above are polyisoprenesulfonic acid, polyvinylsulfonic acid, polyallylsulfonic acid, polyisoamylsulfonic acid, polystyrenesulfonate, polyacrylic acid. Salt, polyvinyl acetate, and the like.
該等水溶性高分子可單獨使用1種亦可組合2種以上使用。 These water-soluble polymers may be used alone or in combination of two or more.
又，水溶性高分子可為均聚物亦可為共聚物。共聚物可為無歸共聚物、交替共聚物、嵌段共聚物、接枝共聚物之任一類型共聚物。 Further, the water-soluble polymer may be a homopolymer or a copolymer. The copolymer may be any type of copolymer of a non-return copolymer, an alternating copolymer, a block copolymer, and a graft copolymer.
研磨用組成物中之水溶性高分子濃度可為0.000001質量%以上，較好為0.00001質量%以上，更好為0.0001質量%以上。水溶性高分子濃度較高時，可使研磨對象物表面更平坦。且，研磨用組成物中之水溶性高分子濃度，基於提高研磨速度等之觀點，較好為0.01質量%以下，更好為0.001質量%以下，又更好為0.0005質量%以下。 The concentration of the water-soluble polymer in the polishing composition may be 0.000001% by mass or more, preferably 0.00001% by mass or more, more preferably 0.0001% by mass or more. When the concentration of the water-soluble polymer is high, the surface of the object to be polished can be made flat. In addition, the concentration of the water-soluble polymer in the polishing composition is preferably 0.01% by mass or less, more preferably 0.001% by mass or less, and still more preferably 0.0005% by mass or less, from the viewpoint of improving the polishing rate and the like.
2-3添加劑 2-3 additives
研磨用組成物中，為了提高其研磨性能，根據需要亦可添加水溶性高分子以外之各種添加劑。作為添加劑舉例為鹼性化合物、螯合劑、界面活性劑、防黴劑、防腐劑等。惟，較好實質上不含氧化劑。 In order to improve the polishing performance of the polishing composition, various additives other than the water-soluble polymer may be added as needed. The additive is exemplified by a basic compound, a chelating agent, a surfactant, an antifungal agent, a preservative, and the like. Preferably, it is preferably substantially free of oxidizing agents.
2-3-1鹼性化合物 2-3-1 basic compound
研磨用組成物亦可含有鹼性化合物。鹼性化合物由於對矽晶圓等之研磨對象物表面賦予化學作用而化學性研磨(化學蝕刻)，故容易提高研磨對象物研磨時之研磨速度。 The polishing composition may also contain a basic compound. Since the basic compound chemically polishes (chemically etches) by chemically applying the surface of the object to be polished such as a ruthenium wafer, it is easy to increase the polishing rate at the time of polishing the object to be polished.
作為鹼性化合物可為有機鹼性化合物，且亦可為鹼金屬氫氧化物、鹼金屬碳酸氫鹽、鹼金屬碳酸鹽、氨等之無機鹼性化合物。該等鹼性化合物可單獨使用1種，亦可組合2種以上使用。 The basic compound may be an organic basic compound, and may be an inorganic basic compound such as an alkali metal hydroxide, an alkali metal hydrogencarbonate, an alkali metal carbonate or ammonia. These basic compounds may be used alone or in combination of two or more.
鹼金屬氫氧化物之種類並未特別限制，舉例為例如氫氧化鈉、氫氧化鉀。且，鹼金屬碳酸氫鹽之種類 並未特別限制，舉例為例如碳酸氫鈉、碳酸氫鉀。進而，鹼金屬碳酸鹽種類並未特別限制，舉例為例如碳酸鈉、碳酸鉀。 The kind of the alkali metal hydroxide is not particularly limited, and examples thereof include sodium hydroxide and potassium hydroxide. And the type of alkali metal hydrogencarbonate It is not particularly limited and is exemplified by, for example, sodium hydrogencarbonate or potassium hydrogencarbonate. Further, the type of the alkali metal carbonate is not particularly limited, and examples thereof include sodium carbonate and potassium carbonate.
作為有機鹼性化合物之例舉例為四烷基銨鹽等之四級銨鹽。上述銨鹽之陰離子可為例如OH-、F-、Cl-、Br-、I-、ClO4-、BH4-等。較好可使用例如膽鹼、氫氧化四甲基銨、氫氧化四乙基銨、氫氧化四丙基銨、氫氧化四丁基銨等之四級銨鹽。該等中，更好為氫氧化四甲基銨。 As an example of the organic basic compound, a quaternary ammonium salt such as a tetraalkylammonium salt is exemplified. The anion of the above ammonium salt may be, for example, OH - , F - , Cl - , Br - , I - , ClO 4- , BH 4- or the like. A quaternary ammonium salt such as choline, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide can be preferably used. Among these, tetramethylammonium hydroxide is more preferred.
作為有機鹼性化合物之其他例舉例為四烷基鏻鹽等之四級鏻鹽。上述鏻鹽中之陰離子可為例如OH-、F-、Cl-、Br-、I-、ClO4-、BH4-等。較好可使用例如四甲基鏻、四乙基鏻、四丙基鏻、四丁基鏻等之鹵化物、氫氧化物。 As another example of the organic basic compound, a quaternary phosphonium salt such as a tetraalkylphosphonium salt is exemplified. The anion in the above onium salt may be, for example, OH - , F - , Cl - , Br - , I - , ClO 4- , BH 4- or the like. A halide or a hydroxide such as tetramethylguanidine, tetraethylphosphonium, tetrapropylphosphonium or tetrabutylphosphonium can be preferably used.
作為有機鹼性化合物之其他例舉例為胺類(例如甲胺、二甲胺、三甲胺、乙胺、二乙胺、三乙胺、乙二胺、單乙醇胺、N-(β-胺基乙基)乙醇胺、六亞甲二胺、二伸乙三胺、三伸乙四胺)、哌嗪類(例如哌嗪、1-(2-胺基乙基)哌嗪、N-甲基哌嗪)、唑類(例如咪唑、***)、二氮雜雙環烷類(例如1,4-二氮雜雙環[2.2.2]辛烷、1,8-二氮雜雙環[5.4.0]十一碳-7-烯、1,5-二氮雜雙環[4.3.0]-5-壬烯)、其他環狀胺類(例如哌啶、胺基吡啶)、胍等。 Other examples of the organic basic compound are exemplified by amines (for example, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, ethylenediamine, monoethanolamine, N-(β-amino group B). Base) ethanolamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine), piperazines (eg piperazine, 1-(2-aminoethyl)piperazine, N-methylpiperazine) ), azoles (eg imidazole, triazole), diazabicycloalkanes (eg 1,4-diazabicyclo[2.2.2]octane, 1,8-diazabicyclo[5.4.0] ten Monocarb-7-ene, 1,5-diazabicyclo[4.3.0]-5-pinene, other cyclic amines (such as piperidine, aminopyridine), hydrazine, and the like.
本實施形態中之研磨用組成物中之鹼性化合物含量亦可為0.001質量%以上，較好為0.01質量%以上，更好為0.05質量%以上。鹼性化合物含量若為上述範 圍內，則可提高研磨用組成物對研磨對象物之研磨速度。另一方面，研磨用組成物中之鹼性化合物含量亦可為5質量%以下，較好為3質量%以下，更好為1.5質量%以下。鹼性化合物含量若為上述範圍內，則可減低研磨用組成物之製造成本。 The content of the basic compound in the polishing composition in the present embodiment may be 0.001% by mass or more, preferably 0.01% by mass or more, more preferably 0.05% by mass or more. If the basic compound content is the above In the periphery, the polishing rate of the polishing target to the object to be polished can be increased. On the other hand, the content of the basic compound in the polishing composition may be 5% by mass or less, preferably 3% by mass or less, more preferably 1.5% by mass or less. When the content of the basic compound is within the above range, the production cost of the polishing composition can be reduced.
2-3-2螯合劑 2-3-2 chelating agent
本實施形態之研磨用組成物亦可添加螯合劑。螯合劑係藉由捕捉研磨系中之金屬雜質成分形成錯合物而抑制矽基板之金屬汙染。螯合劑之具體例舉例為葡萄糖酸之羧酸系螯合劑，乙二胺、二伸乙三胺、三甲基四胺等之胺系螯合劑，乙二胺四乙酸、氮基三乙酸、羥基乙基乙二胺三乙酸、三伸乙四胺六乙酸、二伸乙三胺五乙酸等之聚胺聚羧酸系螯合劑、2-胺基乙基膦酸、1-羥基亞乙基-1,1-二膦酸、胺基三(亞甲基膦酸)、乙二胺四(亞甲基膦酸)、二伸乙三胺五(亞甲基膦酸)、乙烷-1,1-二膦酸、乙烷-1,1,2-三膦酸、乙烷-1-羥基-1,1-二膦酸、乙烷-1-羥基-1,1,2-三膦酸、乙烷-1,2-二羧基-1,2-二膦酸、甲烷羥基膦酸、2-膦基丁烷-1,2-二羧酸、1-膦基丁烷-2,3,4-三羧酸等之有機膦酸系螯合劑，酚衍生物、1,3-二酮等。該等螯合劑中，有機膦酸系螯合劑尤其較好使用乙二胺四(亞甲基膦酸)。該等螯合劑可單獨使用一種，亦可組合兩種以上使用。 A chelating agent may be added to the polishing composition of the present embodiment. The chelating agent inhibits metal contamination of the ruthenium substrate by capturing a metal impurity component in the polishing system to form a complex. Specific examples of the chelating agent are carboxylic acid-based chelating agents of gluconic acid, amine-based chelating agents such as ethylenediamine, diethylenetriamine, and trimethyltetramine, ethylenediaminetetraacetic acid, nitrogen triacetic acid, and hydroxyl group. Polyamine polycarboxylic acid chelating agent, 2-aminoethylphosphonic acid, 1-hydroxyethylidene, such as ethylethylenediaminetriacetic acid, triamethylenetetraamine hexaacetic acid, diamethylenetriaminepentaacetic acid, etc. 1,1-diphosphonic acid, aminotris(methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid), diethylenetriamine penta (methylenephosphonic acid), ethane-1, 1-diphosphonic acid, ethane-1,1,2-triphosphonic acid, ethane-1-hydroxy-1,1-diphosphonic acid, ethane-1-hydroxy-1,1,2-triphosphonic acid , ethane-1,2-dicarboxy-1,2-diphosphonic acid, methane hydroxyphosphonic acid, 2-phosphinobutane-1,2-dicarboxylic acid, 1-phosphinobutane-2,3, An organic phosphonic acid-based chelating agent such as 4-tricarboxylic acid, a phenol derivative or a 1,3-diketone. Among these chelating agents, ethylenediaminetetrakis (methylenephosphonic acid) is particularly preferably used as the organic phosphonic acid-based chelating agent. These chelating agents may be used alone or in combination of two or more.
2-3-3界面活性劑 2-3-3 surfactant
研磨用組成物中亦可添加界面活性劑。界面活性劑由於具有對研磨後之研磨對象物之研磨表面賦予親水性之作用，故使研磨後之研磨對象物之洗淨效率良好，可抑制汙物附著等。作為界面活性劑可使用陰離子性界面活性劑、陽離子性界面活性劑、兩性界面活性劑、及非離子性界面活性劑之任一者。 A surfactant may also be added to the polishing composition. Since the surfactant has a function of imparting hydrophilicity to the polishing surface of the object to be polished after polishing, the cleaning efficiency of the object to be polished after polishing is good, and adhesion of dirt and the like can be suppressed. As the surfactant, any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant, and a nonionic surfactant can be used.
作為陰離子性界面活性劑之具體例舉例為聚氧乙烯烷基醚乙酸、聚氧乙烯烷基硫酸酯、烷基硫酸酯、聚氧乙烯烷基硫酸、烷基硫酸、烷基苯磺酸、烷基磷酸酯、聚氧乙烯烷基磷酸酯、聚氧乙烯磺基琥珀酸、烷基磺基琥珀酸、烷基萘磺酸、烷基二苯基醚二磺酸或該等之鹽。 Specific examples of the anionic surfactant are polyoxyethylene alkyl ether acetic acid, polyoxyethylene alkyl sulfate, alkyl sulfate, polyoxyethylene alkyl sulfate, alkyl sulfuric acid, alkylbenzenesulfonic acid, and alkane. Phosphate, polyoxyethylene alkyl phosphate, polyoxyethylene sulfosuccinic acid, alkyl sulfosuccinic acid, alkyl naphthalene sulfonic acid, alkyl diphenyl ether disulfonic acid or the like.
又，作為陽離子性界面活性劑之具體例舉例為烷基三甲基銨鹽、烷基二甲基銨鹽、烷基苄基二甲基銨鹽、烷基銨鹽。 Further, specific examples of the cationic surfactant are alkyltrimethylammonium salts, alkyldimethylammonium salts, alkylbenzyldimethylammonium salts, and alkylammonium salts.
再者，兩性界面活性劑之具體例舉例為烷基甜菜鹼、烷基胺氧化物。 Further, specific examples of the amphoteric surfactant are exemplified by alkyl betaines and alkylamine oxides.
再者，作為非離子性界面活性劑之具體例舉例為聚氧乙烯烷基醚、聚氧伸烷基烷基醚、山梨糖醇酐脂肪酸酯、甘油脂肪酸酯、聚氧乙烯脂肪酸酯、聚氧乙烯烷基胺、烷基烷醇胺。 Further, specific examples of the nonionic surfactant are polyoxyethylene alkyl ether, polyoxyalkylene alkyl ether, sorbitan fatty acid ester, glycerin fatty acid ester, and polyoxyethylene fatty acid ester. , polyoxyethylene alkylamine, alkyl alkanolamine.
該等界面活性劑可單獨使用一種，亦可組合兩種以上使用。 These surfactants may be used alone or in combination of two or more.
2-3-4防黴劑、防腐劑 2-3-4 anti-mold agent, preservative
研磨用組成物中亦可添加防黴劑、防腐劑。防黴劑、防腐劑之具體例舉例為異噻唑啉系防腐劑(例如2-甲基-4-異噻唑啉-3-酮、5-氯-2-甲基-4-異噻唑啉-3-酮)、噁唑啉系防腐劑(例如噁唑啉-2,5-二酮)、對羥基苯甲酸酯類、苯氧基乙醇。該等防黴劑、防腐劑可單獨使用一種，亦可組合兩種以上使用。 An antifungal agent or a preservative may be added to the polishing composition. Specific examples of the fungicide and the preservative are exemplified by an isothiazoline-based preservative (for example, 2-methyl-4-isothiazolin-3-one, 5-chloro-2-methyl-4-isothiazoline-3) a ketone), an oxazoline-based preservative (for example, oxazoline-2,5-dione), a paraben, or a phenoxyethanol. These antifungal agents and preservatives may be used alone or in combination of two or more.
2-3-5氧化劑 2-3-5 oxidant
本文揭示之研磨用組成物較好實質上不含氧化劑。其理由為於研磨用組成物中含有氧化劑時，因該研磨用組成物供給至研磨對象物(例如矽晶圓)而使該研磨對象物表面氧化產生氧化膜，藉此會使所需研磨時間變長。此處作為氧化劑之具體例舉例為過氧化氫(H2O2)、過硫酸鈉、過硫酸銨、過錳酸鉀、二氯異氰尿酸鈉等。 The polishing composition disclosed herein preferably contains substantially no oxidizing agent. The reason for this is that when the polishing composition contains an oxidizing agent, the polishing composition is supplied to an object to be polished (for example, a tantalum wafer), and the surface of the object to be polished is oxidized to form an oxide film, thereby causing a required polishing time. lengthen. Specific examples of the oxidizing agent herein include hydrogen peroxide (H 2 O 2 ), sodium persulfate, ammonium persulfate, potassium permanganate, and sodium dichloroisocyanurate.
所謂研磨用組成物較好實質上不含氧化劑意指至少不含刻意之氧化劑。因此，不可避免地含有源自原料或製法等之微量(例如研磨用組成物中之氧化劑莫耳濃度為0.0005莫耳/L以下，較好為0.0001莫耳/L以下，更好為0.00001莫耳/L以下，特佳為0.000001莫耳/L以下)之氧化劑而成的研磨用組成物，係可包含於此處所稱之實質上不含氧化劑之研磨用組成物之概念中。 The polishing composition preferably contains substantially no oxidizing agent means at least no deliberate oxidizing agent. Therefore, it is inevitable to contain a trace amount derived from a raw material, a production method, etc. (for example, the oxidizing agent molar concentration in the polishing composition is 0.0005 mol/L or less, preferably 0.0001 mol/L or less, more preferably 0.00001 mol. The polishing composition obtained by oxidizing the oxidizing agent of /L or less, particularly preferably 0.000001 mol/L or less, may be included in the concept of a polishing composition substantially free of an oxidizing agent.
2-4液狀介質 2-4 liquid medium
液狀介質係作為用以分散或溶解研磨用組成物之各成分(研磨粒、水溶性高分子、其他添加劑等)之分散介質或溶劑而發揮功能。作為液狀介質舉例為水、有機溶劑，可單獨使用一種，亦可混合兩種以上使用，較好含有水。惟，基於防止阻礙各成分作用之觀點，叫好使用儘可能不含雜質之水。具體而言，較好為以離子交換樹脂去除雜質離子後通過過濾器去除異物之純水或超純水，或者蒸餾水。 The liquid medium functions as a dispersion medium or a solvent for dispersing or dissolving each component (abrasive grain, water-soluble polymer, other additives, etc.) of the polishing composition. The liquid medium may, for example, be water or an organic solvent, and may be used singly or in combination of two or more. It preferably contains water. However, based on the idea of preventing the effects of the various components, it is desirable to use water that is as free of impurities as possible. Specifically, it is preferably pure water or ultrapure water or distilled water which removes foreign matter by an ion exchange resin and removes foreign matter through a filter.
3.研磨用組成物之製造方法 3. Method for producing polishing composition
研磨用組成物之製造方法並未特別限制。可藉由將研磨粒、水溶性高分子與根據需要之各種添加劑於水等之液狀介質中攪拌、混合而製造。例如，將研磨粒、水溶性高分子、界面活性劑等之添加劑於水中攪拌、混合而製造。混合時之溫度並未特別限制，但較好為10℃以上40℃以下，為了提高溶解速度亦可加熱。且混合時間亦未特別限制。 The method for producing the polishing composition is not particularly limited. It can be produced by stirring and mixing the abrasive grains, the water-soluble polymer, and various additives as needed in a liquid medium such as water. For example, an additive such as abrasive grains, a water-soluble polymer, or a surfactant is produced by stirring and mixing in water. The temperature at the time of mixing is not particularly limited, but is preferably 10 ° C or more and 40 ° C or less, and may be heated in order to increase the dissolution rate. The mixing time is also not particularly limited.
4.組成調整劑 4. Composition adjuster
本實施形態之組成調整劑可含有水溶性高分子，但亦可僅由水溶性高分子構成，亦可以水等之液狀介質與水溶性高分子構成，亦可以水等之液狀介質與水溶性高分子與其他成分(例如研磨粒、添加劑)構成。組成調整劑中之水溶性高分子之濃度並未特別限制，可根據研磨用組成物之 組成、研磨用組成物中之水溶性高分子濃度(前述預先設定之濃度)、研磨對象物種類、研磨條件等適當設定即可。 The composition adjusting agent of the present embodiment may contain a water-soluble polymer, but may be composed only of a water-soluble polymer, or may be composed of a liquid medium such as water or a water-soluble polymer, or may be dissolved in a liquid medium such as water or water. The polymer is composed of other components (for example, abrasive grains and additives). The concentration of the water-soluble polymer in the composition adjusting agent is not particularly limited, and may be based on the composition for polishing. The composition of the composition, the water-soluble polymer concentration in the polishing composition (the predetermined concentration), the type of the object to be polished, the polishing conditions, and the like may be appropriately set.
5.研磨墊 5. Grinding pad
研磨對象物之研磨中亦可使用研磨墊。研磨墊之材質並未特別限定，可無特別限制地使用一般不織布、麂皮、聚胺基甲酸酯發泡體、聚乙烯發泡體、多孔質氟樹脂等。且，材質不同以外，亦可使用硬度或厚度等物性各種不同者。再者，可使用含研磨粒者、不含研磨粒者之任一者。再者，研磨墊之研磨面亦可設有溝槽以積存液狀之研磨用組成物。 A polishing pad can also be used for the polishing of the object to be polished. The material of the polishing pad is not particularly limited, and a general nonwoven fabric, a suede, a polyurethane foam, a polyethylene foam, a porous fluororesin or the like can be used without particular limitation. Further, in addition to the materials, various physical properties such as hardness and thickness may be used. Further, any one of those containing abrasive grains and containing no abrasive grains can be used. Further, the polishing surface of the polishing pad may be provided with a groove to accumulate a liquid polishing composition.
6.研磨對象物之研磨方法 6. Grinding method of grinding object
本實施形態之研磨方法對研磨對象物之研磨條件並未特別限定，可以一般條件進行研磨，適於研磨對象物之研磨之條件只要適當選擇即可。且，研磨中使用之研磨裝置亦未特別限制，可使用一般之研磨裝置，例如可使用單面研磨裝置或雙面研磨裝置。 In the polishing method of the present embodiment, the polishing conditions of the object to be polished are not particularly limited, and polishing can be performed under normal conditions, and the conditions suitable for polishing the object to be polished can be appropriately selected. Further, the polishing apparatus used in the polishing is not particularly limited, and a general polishing apparatus can be used, and for example, a single-side polishing apparatus or a double-side polishing apparatus can be used.
例如，使用單面研磨裝置對研磨對象物的矽晶圓進行研磨時，使用稱為載具之保持具保持矽晶圓，將貼附有研磨墊之壓盤壓抵於矽晶圓之單面邊供給研磨用組成物邊使壓盤旋轉，而研磨矽晶圓之單面。 For example, when a single-sided polishing apparatus is used to polish a wafer of a polishing object, a holder called a carrier is used to hold the wafer, and a pressure pad to which the polishing pad is attached is pressed against one side of the wafer. While the composition for polishing is supplied, the platen is rotated to polish one side of the wafer.
且，使用雙面研磨裝置研磨矽晶圓時，使用稱為載具 之保持具保持矽晶圓，將貼附有研磨墊之壓盤壓自矽晶圓之兩側分別壓抵矽晶圓兩面邊供給研磨用組成物邊使兩側之壓盤旋轉，而研磨矽晶圓之雙面。 Moreover, when a silicon wafer is polished using a double-side polishing apparatus, a carrier is used. The holding device holds the silicon wafer, and the pressure plate is attached with the polishing pad, and the two sides of the wafer are pressed against the two sides of the wafer to supply the polishing composition, and the pressure plates on both sides are rotated, and the polishing is performed. Both sides of the wafer.
使用任一研磨裝置時，均係藉由摩擦(研磨墊及研磨用組成物與矽晶圓之摩擦)之物理作用與研磨用組成物對矽晶圓帶來之化學作用而研磨矽晶圓。 When any of the polishing apparatuses is used, the silicon wafer is polished by the physical action of rubbing (friction of the polishing pad and the polishing composition with the germanium wafer) and the chemical action of the polishing composition on the wafer.
以下，邊參考圖1邊說明本實施形態之研磨方法之一例。首先，本實施形態之研磨方法中矽晶圓之研磨中使用之單面研磨裝置之構成加以說明。 Hereinafter, an example of the polishing method of the present embodiment will be described with reference to Fig. 1 . First, the configuration of the single-side polishing apparatus used for polishing the tantalum wafer in the polishing method of the present embodiment will be described.
研磨裝置11具備於上面貼附有研磨墊14之圓盤狀壓盤12。壓盤12設為可對於第1旋轉軸13一體地旋轉。於壓盤12之上方，設置至少一個晶圓固定器15。晶圓固定器15設為可對於第2旋轉軸16一體地旋轉。於晶圓固定器15之底面可卸下地安裝具有晶圓保持孔18之晶圓保持板19。 The polishing apparatus 11 is provided with a disk-shaped platen 12 to which the polishing pad 14 is attached. The platen 12 is configured to be rotatable integrally with the first rotating shaft 13 . Above the platen 12, at least one wafer holder 15 is disposed. The wafer holder 15 is configured to be rotatable integrally with respect to the second rotating shaft 16 . A wafer holding plate 19 having a wafer holding hole 18 is detachably mounted on the bottom surface of the wafer holder 15.
且，研磨裝置11進而於壓盤12之上方進而具備收容含有水溶性高分子之研磨用組成物之槽21。於槽21連結有將研磨用組成物供給至研磨墊14上之研磨用組成物供給管22，使研磨用組成物自研磨用組成物供給管22之前端噴嘴噴出於研磨墊14上。 Further, the polishing apparatus 11 further includes a groove 21 for containing a polishing composition containing a water-soluble polymer, above the platen 12. The polishing composition supply pipe 22 for supplying the polishing composition to the polishing pad 14 is connected to the groove 21, and the polishing composition is sprayed onto the polishing pad 14 from the front end nozzle of the polishing composition supply pipe 22.
再者，研磨裝置11於壓盤12之下方具備接收於矽晶圓研磨中使用後自壓盤12流下之研磨用組成物之研磨用組成物承接盤31。研磨用組成物承接盤31與槽21以送液管32連結，將於研磨用組成物承接盤31接收 之研磨用組成物藉由未圖示之送液泵送液至槽21。因此，研磨用組成物於槽21與研磨用組成物承接盤31之間循環。 Further, the polishing apparatus 11 is provided below the platen 12 with a polishing composition receiving disk 31 that receives the polishing composition that flows down from the platen 12 after use in the polishing of the enamel wafer. The polishing composition receiving tray 31 and the groove 21 are connected by the liquid supply tube 32, and are received by the polishing composition receiving tray 31. The polishing composition is pumped to the tank 21 by a liquid supply pump (not shown). Therefore, the polishing composition circulates between the groove 21 and the polishing composition receiving tray 31.
再者，研磨裝置11亦可具備將含有水溶性高分子之組成調整劑添加於槽21內之組成調整劑添加裝置(未圖示)。該組成調整劑添加裝置可基於預先藉由預備試驗或計算等求出之水溶性高分子之濃度、組成調整劑中之水溶性高分子之濃度、預先設定之水溶性高分子之濃度範圍(例如未使用之研磨用組成物中之水溶性高分子之濃度設為中央值之濃度範圍)，算出應添加於槽21內之研磨用組成物之組成調整劑之量。而且，算出之量的組成調整劑自組成調整劑添加裝置之組成調整劑供給管41噴出並供給至槽21。 Further, the polishing apparatus 11 may include a composition adjusting agent adding device (not shown) that adds a composition adjusting agent containing a water-soluble polymer to the tank 21. The composition adjusting agent adding device can be based on a concentration of a water-soluble polymer determined in advance by a preliminary test or calculation, a concentration of a water-soluble polymer in a composition adjusting agent, and a concentration range of a predetermined water-soluble polymer (for example, The concentration of the water-soluble polymer in the unused polishing composition is a concentration range of the central value, and the amount of the composition adjusting agent to be added to the polishing composition in the tank 21 is calculated. Further, the calculated amount of the composition adjusting agent is ejected from the composition adjusting agent supply pipe 41 of the composition adjusting agent adding device and supplied to the tank 21.
使用此研磨裝置11進行矽晶圓之研磨時，將欲研磨之矽晶圓吸引於晶圓保持孔18內並保持於晶圓固定器15。首先，開始晶圓固定器15及壓盤12之旋轉，自槽21對研磨墊14上連續供給研磨用組成物。接著，將矽晶圓壓抵於研磨墊14，使晶圓固定器15朝向壓盤12向下方移動。藉此，研磨與研磨墊14接觸之矽晶圓表面(被研磨面)(研磨步驟)。 When the polishing apparatus 11 is used to polish the wafer, the wafer to be polished is sucked into the wafer holding hole 18 and held by the wafer holder 15. First, the rotation of the wafer holder 15 and the platen 12 is started, and the polishing composition is continuously supplied from the groove 21 to the polishing pad 14. Next, the germanium wafer is pressed against the polishing pad 14 to move the wafer holder 15 downward toward the platen 12. Thereby, the surface of the wafer (the surface to be polished) which is in contact with the polishing pad 14 is polished (grinding step).
以研磨步驟研磨中使用之研磨用組成物自壓盤12流下並回收於研磨用組成物承接盤31。接著，研磨用組成物承接盤31內之研磨用組成物經由送液管32回到槽21(回收步驟)。 The polishing composition used for the polishing step is flowed down from the platen 12 and recovered in the polishing composition receiving tray 31. Then, the polishing composition in the polishing composition receiving tray 31 is returned to the tank 21 via the liquid supply tube 32 (recovering step).
於研磨步驟中研磨使用之研磨用組成物由於水溶性高分子被消耗或損失，故水溶性高分子濃度低於初期(未使用時)(研磨用組成物之組成產生變化)。如此之研磨用組成物回到槽21，與槽21內之研磨用組成物混合時，隨著研磨用組成物循環，槽21內之研磨用組成物之水溶性高分子濃度緩緩降低。若如此，則供給至研磨墊14上之研磨用組成物之研磨性能降低，有使矽晶圓之研磨結果例如研磨速度或被研磨面之研磨品質不充分之虞。 Since the polishing composition used for polishing in the polishing step is consumed or lost by the water-soluble polymer, the concentration of the water-soluble polymer is lower than that at the initial stage (when not used) (the composition of the polishing composition changes). When the polishing composition is returned to the groove 21 and mixed with the polishing composition in the groove 21, the concentration of the water-soluble polymer in the polishing composition in the groove 21 gradually decreases as the polishing composition circulates. In this case, the polishing performance of the polishing composition supplied onto the polishing pad 14 is lowered, and the polishing result of the silicon wafer, for example, the polishing rate or the polishing quality of the surface to be polished is insufficient.
因此，自組成調整劑添加裝置之組成調整劑供給管41對槽21供給組成調整劑，或以手動將必要量之組成調整劑供給至槽21中，邊使研磨用組成物循環(組成調整步驟)，藉由添加組成調整劑而補給消耗或損失之水溶性高分子進行研磨。 Therefore, the composition adjusting agent supply unit 41 of the composition adjusting agent addition device supplies the composition adjusting agent to the tank 21, or manually supplies the necessary amount of the composition adjusting agent to the tank 21, and circulates the polishing composition (composition adjustment step) The slurry is supplied by adding a composition adjusting agent to replenish the water-soluble polymer which is consumed or lost.
因此，由於可將研磨用組成物中之水溶性高分子濃度總是維持在預先設定之範圍內之數值並進行矽晶圓之研磨，故儘管回收並循環使用於研磨中使用之研磨用組成物，矽晶圓之表面品質、研磨速度等之研磨結果優異。 Therefore, since the concentration of the water-soluble polymer in the polishing composition can be maintained at a value within a predetermined range and the ruthenium wafer is polished, the polishing composition used in the polishing is recycled and recycled. The surface quality and polishing rate of the wafer are excellent.
又，本實施形態之研磨方法亦有可能應用於如進行鏡面加工等之精研磨之最終研磨步驟、或在最終研磨步驟之前進行預備研磨之預備研磨步驟等之研磨步驟，但對預備研磨步驟特別適用。 Further, the polishing method of the present embodiment may be applied to a polishing step such as a final polishing step for performing fine polishing such as mirror processing or a preliminary polishing step for performing preliminary polishing before the final polishing step, but the preliminary polishing step is particularly preferable. Be applicable.
於研磨對象物表面有賦予加工損傷或輸送時產生之傷痕之情況，該等傷痕於一個研磨步驟中鏡面化時需要花費較多時間故而不經濟，此外，有損及研磨對象物之表面平 坦性、平滑性之虞。因此，藉由預先以預備研磨步驟去除研磨對象物之表面傷痕，可縮短最終研磨步驟所需之研磨時間，可有效地獲得優異鏡面。 There is a case where the surface of the object to be polished is provided with scratches caused by processing damage or conveyance, and it takes time for the surface of the object to be mirrored in one polishing step, which is uneconomical, and the surface of the object to be polished is damaged. The nature of frankness and smoothness. Therefore, by removing the surface flaw of the object to be polished in advance by the preliminary polishing step, the polishing time required for the final polishing step can be shortened, and an excellent mirror surface can be effectively obtained.
[實施例] [Examples]
以下顯示實施例進一步具體說明本發明。使用研磨用組成物進行矽晶圓之研磨，評價矽晶圓之表面品質、研磨速度等之研磨結果。 The invention is further illustrated by the following examples. The polishing composition was polished using a polishing composition, and the polishing results of the surface quality and polishing rate of the silicon wafer were evaluated.
<研磨用組成物之調製> <Modulation of polishing composition>
混合研磨粒、水溶性高分子、鹼性化合物及超純水，製造研磨用組成物。 The abrasive composition, the water-soluble polymer, the basic compound, and ultrapure water are mixed to produce a polishing composition.
研磨粒為平均一次粒徑52nm之膠體氧化矽，研磨用組成物中之研磨粒濃度為0.6質量%。 The abrasive grains were colloidal cerium oxide having an average primary particle diameter of 52 nm, and the polishing particle concentration in the polishing composition was 0.6% by mass.
且，鹼性化合物為碳酸鉀及氫氧化四甲基銨。研磨用組成物中之碳酸鉀濃度為0.05質量%，研磨用組成物中之氫氧化四甲基銨濃度為0.08質量%。 Further, the basic compound is potassium carbonate and tetramethylammonium hydroxide. The concentration of potassium carbonate in the polishing composition was 0.05% by mass, and the concentration of tetramethylammonium hydroxide in the polishing composition was 0.08% by mass.
再者，水溶性高分子為重量平均分子量250000之聚乙烯吡咯啶酮(表1中記載為「PVP」)、重量平均分子量250000之羥乙基纖維素(表1中記載為「HEC」)或重量平均分子量13000之聚乙烯醇(表1中記載為「PVA」)，研磨用組成物中之水溶性高分子濃度為100a.u.(任意單位)或0a.u.。 Further, the water-soluble polymer is polyvinylpyrrolidone having a weight average molecular weight of 250,000 (described as "PVP" in Table 1) and hydroxyethylcellulose having a weight average molecular weight of 250,000 (described as "HEC" in Table 1) or The polyvinyl alcohol having a weight average molecular weight of 13,000 (described as "PVA" in Table 1) and the water-soluble polymer in the polishing composition have a concentration of 100 a.u. (arbitrary unit) or 0 a.u.
亦即，製造水溶性高分子種類不同之3種研磨用組成 物與不含水溶性高分子之1種研磨用組成物之合計4種研磨用組成物。 That is, three kinds of polishing compositions for producing different types of water-soluble polymers Four kinds of polishing compositions are combined with one polishing composition containing no water-soluble polymer.
<矽晶圓之研磨方法> <矽Wheeling method of wafer>
研磨對象物的矽晶圓之直徑為300mm，厚度為795μm，結晶方位為<100>。 The tantalum wafer of the object to be polished has a diameter of 300 mm, a thickness of 795 μm, and a crystal orientation of <100>.
研磨所用之研磨墊為NITTA HAAS股份有限公司製之HM-S15A，其厚度為0.8mm。又，研磨墊表面(研磨面)上並未設置用以積存液狀研磨用組成物之溝槽。 The polishing pad used for the polishing was HM-S15A manufactured by NITTA HAAS Co., Ltd., and had a thickness of 0.8 mm. Further, a groove for accumulating the liquid polishing composition is not provided on the polishing pad surface (polishing surface).
研磨所用之研磨機為SPEED FAM股份有限公司製之雙面研磨機DSM20B-5P-4D。且，載具之材質為似鑽石碳，厚度775μm。 The grinding machine used for the grinding was a double-side grinding machine DSM20B-5P-4D manufactured by SPEED FAM Co., Ltd. Moreover, the material of the carrier is diamond-like carbon and has a thickness of 775 μm.
以載具保持5片矽晶圓，使用上述研磨用組成物、研磨墊及研磨機，以如下述之研磨條件進行研磨。將此矽晶圓5片一起研磨之步驟設為1批次，結束1批次研磨之5片矽晶圓更換為未研磨品進行同樣研磨，以10批次連續進行。且，10批次連續研磨中於研磨用組成物中追加添加氫氧化鉀，將pH維持10.8以上且11.0以下。 Five wafers were held by a carrier, and the polishing composition, the polishing pad, and the polishing machine were used to perform polishing under the following polishing conditions. The steps of polishing the five wafers together were set to one batch, and the five wafers that had been polished in one batch were replaced with unpolished products and polished in the same manner, and were continuously carried out in 10 batches. Further, in 10 batches of continuous polishing, potassium hydroxide was additionally added to the polishing composition, and the pH was maintained at 10.8 or more and 11.0 or less.
(研磨條件) (grinding conditions)
研磨荷重：20kPa Grinding load: 20kPa
上下壓盤之相對旋轉速度：30rpm Relative rotation speed of upper and lower pressure plate: 30rpm
載具之自轉速度：10rpm Vehicle rotation speed: 10 rpm
研磨時間：使研磨掉之量成為20μm之時間 Grinding time: the amount of grinding is 20 μm
研磨用組成物(漿料)之溫度：20℃ Temperature of the polishing composition (slurry): 20 ° C
研磨用組成物之供給速度：4.5L/分鐘(循環使用) Feeding speed of the polishing composition: 4.5 L / min (recycling)
研磨用組成物邊與參考圖1說明之上述研磨方法同樣進行回收並在使用於研磨中。亦即，矽晶圓之研磨中使用後回收自壓盤流下之研磨用組成物，將該回收之研磨用組成物送液至收容用以對壓盤供給之研磨用組成物之槽中，循環使用研磨用組成物。 The polishing composition was recovered in the same manner as the above-described polishing method described with reference to Fig. 1 and used in polishing. In other words, after the polishing of the silicon wafer is used, the polishing composition that has flowed down from the pressure plate is recovered, and the recovered polishing composition is sent to a tank for containing the polishing composition for supplying the pressure plate, and the cycle is performed. A polishing composition is used.
循環使用研磨用組成物時，針對實施例1~7之研磨例，對供給至壓盤之研磨用組成物中適當添加組成調整劑，針對比較例1~3之研磨例，完全未進行組成調整劑之添加。 When the polishing composition was recycled, the composition adjusting agents were appropriately added to the polishing compositions supplied to the platen in the polishing examples of Examples 1 to 7, and the composition adjustment was not performed at all in the polishing examples of Comparative Examples 1 to 3. Addition of the agent.
表1中，自左側之行起依序顯示研磨用組成物中含有之水溶性高分子之種類、研磨中未使用時之研磨用組成物中之水溶性高分子濃度(初期濃度)、添加之組成調整劑形態、組成調整劑中之水溶性高分子濃度、組成調整劑之添加頻度、以1次添加所加之組成調整劑之量(相對於循環使用之研磨用組成物全體之比例)。 In Table 1, the type of the water-soluble polymer contained in the polishing composition and the concentration of the water-soluble polymer (initial concentration) in the polishing composition when not used during polishing are sequentially displayed from the row on the left side, and added. The composition of the adjusting agent, the concentration of the water-soluble polymer in the composition adjusting agent, the frequency of addition of the composition adjusting agent, and the amount of the composition adjusting agent added in one time (relative to the ratio of the entire polishing composition for recycling).
又，水溶性高分子之濃度單位均為a.u.(任意單位)。且，作為組成調整劑之形態，有水溶性高分子之水溶液、含有與循環使用之研磨用組成物同樣成分之漿料(僅水溶性高分子濃度不同，其他成分濃度相同)，表1中將前者記為水溶液，將後者記為漿料。 Further, the concentration unit of the water-soluble polymer is a.u. (arbitrary unit). Further, as a form of the composition adjusting agent, there are an aqueous solution of a water-soluble polymer and a slurry containing the same components as the polishing composition to be recycled (only the concentration of the water-soluble polymer is different, and the concentrations of the other components are the same), and Table 1 will The former is referred to as an aqueous solution, and the latter is referred to as a slurry.
又，表1中，於右側之2行，顯示添加組成 調整劑之前之研磨用組成物中含有之水溶性高分子濃度與添加組成調整劑之後之研磨用組成物中含有之水溶性高分子濃度。10批次研磨間添加複數次組成調整劑之研磨例之情況下，表示複數次添加之平均值。又，水溶性高分子濃度單位均為a.u.(任意單位)。 Also, in Table 1, on the right side of the 2 lines, the display adds the composition. The concentration of the water-soluble polymer contained in the polishing composition before the conditioning agent and the concentration of the water-soluble polymer contained in the polishing composition after the composition adjusting agent is added. In the case of a polishing example in which a plurality of composition adjusting agents are added between 10 batches of grinding, the average value of the plurality of additions is shown. Further, the water-soluble polymer concentration unit is a.u. (arbitrary unit).
由該等結果可知，循環使用之研磨用組成物因研磨中使用而使水溶性高分子消耗或損失，但藉由添加組成調整劑，而使研磨用組成物中之水溶性高分子濃度恢復至初期值(未使用之研磨用組成物中之水溶性高分子濃度)。 From these results, it is understood that the polishing composition to be recycled is consumed or lost by the use of the water-soluble polymer during the polishing. However, by adding the composition adjusting agent, the concentration of the water-soluble polymer in the polishing composition is restored to Initial value (concentration of water-soluble polymer in the composition for polishing which is not used).
又，各批次之研磨結束後以超純水清洗。清洗中使用之超純水並未切換配管回收而廢棄。因此，此時由於一部分之研磨用組成物亦未回收而廢棄，故應補充廢棄量之研磨用組成物，將未使用之研磨用組成物追加於槽中。廢棄之研磨用組成物之量及追加之研磨用組成物之量為循環使用之研磨用組成物全體之5體積%。 Further, after the completion of the polishing of each batch, it was washed with ultrapure water. The ultrapure water used in the cleaning is not discarded by switching the piping. Therefore, at this time, since a part of the polishing composition is not recovered and discarded, the waste polishing composition is added and the unused polishing composition is added to the tank. The amount of the polishing composition to be discarded and the amount of the additional polishing composition were 5% by volume based on the entire polishing composition for recycling.
<研磨結果之評價> <Evaluation of grinding results>
針對實施例1~7及比較例1~3之研磨例，測定研磨速度、矽晶圓表面之平坦度、缺陷數、表面粗糙度。該等測定全部對10批次矽晶圓進行。測定結果示於表2。任一測定項目均顯示10批次全體中之最大值與最小值。又，各測定項目之數值係將比較例3之最小值設為100時之相對值。 With respect to the polishing examples of Examples 1 to 7 and Comparative Examples 1 to 3, the polishing rate, the flatness of the surface of the germanium wafer, the number of defects, and the surface roughness were measured. All of these measurements were performed on 10 batches of wafers. The measurement results are shown in Table 2. Any of the measurement items shows the maximum and minimum values of the entire 10 batches. Further, the numerical value of each measurement item is a relative value when the minimum value of Comparative Example 3 is set to 100.
研磨速度係自以黑田精工股份有限公司製之表面形狀測定裝置NANOMETRO 300TT測定之研磨前後之矽晶圓厚度與研磨時間而算出。 The polishing rate was calculated from the wafer thickness and the polishing time before and after the polishing measured by the surface shape measuring device NANOMETRO 300TT manufactured by Kuroda Seiko Co., Ltd.
平坦度係針對GBIR(Global Backside Ideal Range，總體背面理想範圍)與滑離(roll off)進行測定。GBIR係針對研磨後之矽晶圓，使用黑田精工股份有限公司製之表面形狀測定裝置NANOMETRO 300TT測定。且滑離係使用黑田精工股份有限公司製之表面形狀測定裝置NANOMETRO 300TT，針對研磨後之矽晶圓之複數部位測定SFQR(Site Front Least Squares Range，前側最小平方範圍)，算出全部部位中矽晶圓之上下左右之端部8部位之SFQR之平均值。又，部位之尺寸為邊長25mm之正方形。 The flatness is measured for GBIR (Global Backside Ideal Range) and roll off. The GBIR system was measured using a surface shape measuring device NANOMETRO 300TT manufactured by Kuroda Seiko Co., Ltd. for the polished tantalum wafer. In addition, the surface shape measuring device NANOMETRO 300TT manufactured by Kuroda Seiko Co., Ltd. was used to measure the SFQR (Site Front Least Squares Range) on the plurality of parts of the polished silicon wafer, and the entire part was calculated. The average value of the SFQR of the upper and lower end portions 8 of the wafer. Further, the size of the portion is a square having a side length of 25 mm.
針對缺陷數，將研磨後之矽晶圓進行SC-1洗淨後，使用KLA TENCOR公司製之晶圓表面檢查裝置Surfscan SP2，測定200nm以上尺寸之缺陷個數。又，洗淨液組成為氨水(氨濃度29質量%)：過氧化氫水(過氧化氫濃度31質量%)：超純水=1：3：30(體積比)。 After the polished wafer was subjected to SC-1 cleaning, the number of defects was measured using a wafer surface inspection apparatus Surfscan SP2 manufactured by KLA TENCOR Co., Ltd., and the number of defects of 200 nm or more was measured. Further, the composition of the cleaning liquid was ammonia water (ammonia concentration: 29% by mass): hydrogen peroxide water (hydrogen peroxide concentration: 31% by mass): ultrapure water = 1:3:30 (volume ratio).
關於表面粗糙度，係針對研磨後之矽晶圓，使用Schmitt測量系統公司(Schmitt Measurement Systems,Inc.)製之光散射式表面粗糙度測定裝置TMS-3000-WRC，測定算術平均粗糙度Ra。 Regarding the surface roughness, the arithmetic mean roughness Ra was measured using a light scattering type surface roughness measuring apparatus TMS-3000-WRC manufactured by Schmitt Measurement Systems, Inc. for the polished silicon wafer.
又，表2所示之測定結果，基於下述基準評價之結果示於表3。亦即，10批次全體中之最大值與最小值之差未 達5%時評價為「A」，為5%以上且未達10%時評價為「B」，為10%以上且未達15%時評價為「C」，為15%以上且未達20%時評價為「D」，為20%以上時評價為「E」。 Further, the measurement results shown in Table 2 are shown in Table 3 based on the results of the following standard evaluations. That is, the difference between the maximum and minimum values of the 10 batches is not When it is 5%, it is evaluated as "A". When it is 5% or more and less than 10%, it is evaluated as "B". When it is 10% or more and less than 15%, it is evaluated as "C", and it is 15% or more and less than 20%. When it is %, it is evaluated as "D", and when it is 20% or more, it is evaluated as "E".
由表2、3所示之結果可知，實施例1~7之研磨例中，由於藉由組成調整劑之添加，對研磨用組成物補給因研磨而消耗或損失之水溶性高分子，故使研磨用組成物之研磨性能恢復，獲得優異之研磨結果。 As is apparent from the results shown in Tables 2 and 3, in the polishing examples of Examples 1 to 7, the composition for polishing was supplied with the water-soluble polymer which was consumed or lost by polishing by the addition of the composition adjusting agent. The polishing performance of the polishing composition was restored, and excellent polishing results were obtained.
11‧‧‧研磨裝置 11‧‧‧ grinding device
12‧‧‧壓盤 12‧‧‧ Platen
13‧‧‧第1旋轉軸 13‧‧‧1st rotating shaft
14‧‧‧研磨墊 14‧‧‧ polishing pad
15‧‧‧晶圓固定器 15‧‧‧ Wafer holder
16‧‧‧第2旋轉軸 16‧‧‧2nd rotation axis
18‧‧‧晶圓保持孔 18‧‧‧ wafer holding hole
19‧‧‧晶圓保持板 19‧‧‧ Wafer Holder
21‧‧‧槽 21‧‧‧ slots
22‧‧‧研磨用組成物供給管 22‧‧‧ polishing composition supply tube
31‧‧‧研磨用組成物承接盤 31‧‧‧Plastic composition receiving tray
32‧‧‧送液管 32‧‧‧ Liquid supply tube
41‧‧‧組成調整劑供給管 41‧‧‧ Composition adjuster supply tube
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| WO2019189124A1 (en) * | 2018-03-28 | 2019-10-03 | 株式会社フジミインコーポレーテッド | Polishing composition |
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