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Ryoichi Hashimoto, Wakayama (LP): a . C. S USOO7604751B2 (12) United States Patent (10) Patent No.: US 7,604,751 B2 Yoneda et al. (45) Date of Patent: Oct. 20, 2009 (54) POLISHING LIQUID COMPOSITION 5,741,765 A 4/1998 Leach ........................ 510,123 5,783,489 A * 7/1998 Kaufman et al. ............ 438,692 (75) Inventors: Yasuhiro Yoneda, Wakayama (JP); 5,916,855 A 6/1999 Avanzino et al. Ryoichi Hashimoto, Wakayama (LP): WW - A . C. S.allal Gal. m........... Toshiya Hagihara, Wakayama (JP) 6,136,711 A * 10/2000 Grumbine et al. ........... 438,692 6,383,240 B1 5, 2002 Nishimoto et al. (73) Assignee: Kao Corporation, Tokyo (JP) 6,447,563 B1* 9/2002 Mahulikar ................... 51.309 (*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS patent is extended or adjusted under 35 EP O 811 665 12/1997 U.S.C. 154(b) by 142 days. JP 11 116942 4f1999 JP 11-116948 A 4f1999 (21) Appl. No.: 11/434,074 JP 2000-252243 A 9, 2000 JP 2001-187877 T 2001 (22) Filed: May 16, 2006 WO WOOOOO561 A1 1, 2000 WO WOOO,398.44 T 2000 (65) Prior Publication Data OTHER PUBLICATIONS US 2006/024O672 A1 Oct. 26, 2006 U.S. Appl. No. 60/105.366, filed Oct. 23, 1998, by Malulikar, priority Related U.S. Application Data filing for USPN 6447,563, noted above.* Chemindustry.com; Synonyms for CAS Registry 6419-19-8; May 8, (62) Division of application No. 10/030,424, filed as appli 2005.* cation No. PCT/JP00/04571 on Jul. 7, 2000, now Pat. U.S. Appl. No. 1 1/544,694, filed Oct. 10, 2006, Yoneda, et al. No. 7,118,685. H. Duncan, et al., “Polishing composition for calcium fluoride—comprises acqueous iron(III) salt Sollution containing alco (30) Foreign Application Priority Data hol”, English Abstract of DD 249489A, May 26, 1986, 2 pp. Jul. 13, 1999 (JP) ................................. 11-198263 * cited by examiner Feb. 8, 2000 (JP) ............................. 2OOO-O3O477 Primary Examiner Keith D Hendricks (51) Int. Cl. Assistant Examiner—Patricia A George HOIL 2/302 (2006.01) (74) Attorney, Agent, or Firm Oblon, Spivak, McClelland, (52) U.S. Cl. ........................... 216/88; 216/89; 252/79.1 Maier & Neustadt, L.L.P. (58) Field of Classification Search ................. 438/692; (57) ABSTRACT 252/79.1, 79.4; 216/88 See application file for complete search history. A polishing liquid composition is applicable as a means of (56) References Cited forming embedded metal interconnections on a semiconduc tor Substrate. In a surface to be polished comprising an insu U.S. PATENT DOCUMENTS lating layer and a metal interconnection layer, the polishing liquid composition is capable of maintaining a polishing 2,892,796 A 6, 1959 McCune 4,141,850 A 2f1979 Readio et al. speed of the metal layer, of suppressing an etching speed, and 4,158,593. A 6, 1979 Allan et al. of preventing dishing of the metal layer. 5,209,820 A * 5/1993 Tytgatet al. ................ 216,108 5,496.485 A 3/1996 Maternaghan 12 Claims, No Drawings US 7,604,751 B2 1. 2 POLISHING LIQUID COMPOSITION layer made of copper or the like is polished, there arises Surface roughening of the copper Surface caused by ammo TECHNICAL FIELD nium polyacrylate. An object of the present invention is to provide a polishing The present invention relates to a polishing liquid compo 5 liquid composition capable of maintaining a polishing speed sition for polishing a surface to be polished comprising an of a metal film, Suppressing an etching speed, and having an insulating layer and a metal layer. More specifically, the excellent prevention effect such as dishing of the metal inter present invention relates to a polishing liquid composition connection layer, in a surface to be polished comprising an which is applicable as a means of forming embedded metal insulating layer and a metal layer, a process for polishing; and interconnection on a semiconductor Substrate, a process for 10 a process for manufacturing a semiconductor Substrate. polishing, and a process for manufacturing a semiconductor These objects and other objects of the present invention substrate. will be apparent from the following description. BACKGROUND ART DISCLOSURE OF INVENTION 15 In the process for manufacturing a semiconductor device, Specifically, the present invention relates to: comprising the steps of forming interconnection-shaped 1 a polishing liquid composition for polishing a surface to recesses on a Surface of the insulating film on a semiconduc be polished comprising an insulating layer and a metal tor Substrate, sedimenting a metal film made of copper or the layer, the polishing liquid composition comprising a com like on the insulating film having the recesses, and Subjecting pound having a structure in which each of two or more the metal film to polishing treatment by a polishing device adjacent carbonatoms has a hydroxyl group in a molecule, and a polishing liquid, thereby allowing the metal layer to and water (hereinafter also referred to “the polishing liquid remain only in the recesses to form a metal interconnection composition 1-1'); layer, wherein Metal Chemical Mechanical Polishing (here 2 a polishing liquid composition for polishing a surface to inafter simply referred to as “metal CMP) is employed for 25 be polished comprising an insulating layer and a metal the process of polishing. layer, the polishing liquid composition comprising an ali However, in the metal CMP, there arise grooves so-called phatic carboxylic acid having 7 to 24 carbonatoms and/or dishing on the metal interconnection layer in the recesses of a salt thereof, an etching agent, and water (hereinafter also the insulating film, so that the cross-sectional area of the referred to “the polishing liquid composition 1-2); metal interconnection layer is reduced, thereby causing an 30 3 a polishing liquid composition for polishing a surface to increase in electric resistivity. This dishing is caused by more be polished comprising an insulating layer and a metal excessive polishing or etching of the Surface of the metal layer, the polishing liquid composition comprising an interconnection layer than that of the insulating film Surface amine compound represented by the following general for by the polishing liquid composition. Especially copper, one mula (II): of the main metal interconnection, has defects of being exces 35 sively etched by the polishing liquid composition, so that the dishing is likely to be caused. (II) Therefore, there has been desired a polishing liquid com position free from defects Such as dishing in the metal layer during the formation of interconnection, with retaining an 40 V etching action for polishing the metal film on the insulating film. As a conventional polishing liquid, for instance, Japanese wherein R is a linear or branched alkyl group having 4 to 18 Patent Laid-Open Nos. Hei 8-83780 and Hei 11-21546 each 45 carbon atoms, a linear or branched alkenyl group having 4 to discloses a polishing liquid comprising benzotriazole or a 18 carbon atoms, an aryl group having 6 to 18 carbon atoms, derivative thereofas a protective film-forming agent for the and an aralkyl group having 7 to 18 carbonatoms; each of R' metal surface in order to prevent the dishing. Since the formed and R, which may be identical or different, is hydrogenatom, protective film is rigid, when the metal layer is polished in the a linear alkyl group having 1 to 8 carbon atoms or a branched metal CMP, the polishing speed would become insufficient. 50 alkyl group having 3 to 8 carbon atoms, or a group repre In addition, Japanese Patent Laid-Open No. Hei 11-116942 sented by H-(OR), , wherein Risalinear alkylenegroup discloses a composition for polishing, comprising a com having 1 to 3 carbon atoms, or a branched alkylene group pound having 1 to 10 alcoholic hydroxyl groups, or a nitro gen-containing basic compound having 1 to 10 alcoholic having 3 carbon atoms; and Z is a number of 1 to 20, hydroxyl groups. This composition for polishing has a pur 55 and/or a salt thereof, an etching agent, and water (hereinafter pose of reducing particles deposited on a wafer Surface in also referred to “the polishing liquid composition 1-3); final polishing of the semiconductor wafer, so that the prob 4 the polishing liquid composition according to any one of lems to be solved are different. items 1 to 3 above, further comprising an oxidizing In addition, Japanese Patent Laid-OpenNo. Hei 10-44047 agent (hereinafter also referred to “the polishing liquid discloses a polishing liquid comprising an aqueous medium, 60 composition 2'); an abrasive, an oxidizing agent, and an organic acid. How 5the polishing liquid composition according to any one of ever, since the etching action is too strong, the prevention for items 1 to 4 above, further comprising an abrasive dishing would be insufficient. Further, Japanese Patent Laid (hereinafter also referred to “the polishing liquid compo Open No. Hei 11-195628 discloses a process for polishing in sition 3'); which a polishing liquid is used in combination with ammo 65 6 a process for polishing a semiconductor Substrate, com nium polyacrylate as a Substance for Suppressing oxidation prising polishing a surface to be polished comprising an and etching. However, in the metal CMP in which a metal insulating layer and a metal layer using the polishing liquid US 7,604,751 B2 3 4 composition of any one of items 1 to 5, thereby smooth which each of two or more adjacent carbon atoms has a ening the semiconductor Substrate; and hydroxyl group is present in the terminal portion of a mol 7 a process for manufacturing a semiconductor Substrate ecule.
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