US 201701 07460A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2017/0107460 A1 Liu et al. (43) Pub. Date: Apr. 20, 2017 (54) TIN HARD MASK AND ETCH RESIDUAL CLID 3/30 (2006.01) REMOVAL CLID 3/20 (2006.01) CLID 3/33 (2006.01) (71) Applicant: Air Products and Chemicals, Inc., HOIL 2L/02 (2006.01) Allentown, PA (US) CLID 3/00 (2006.01) CLID 3/37 (2006.01) (72) Inventors: Wen Dar Liu, Chupei City (TW); HOIL 2/3 II (2006.01) Yi-Chia Lee, Chupei City (TW); HOIL 2L/033 (2006.01) William Jack Casteel, JR., Fountain HOIL 2L/768 (2006.01) Hill, PA (US); Tianniu Chen, Westford, CLID 3/39 (2006.01) MA (US); Rajiv Krishan Agarwal, CLID 3/28 (2006.01) Malvern, PA (US); Madhukar (52) U.S. Cl. Bhaskara Rao, Carlsbad, CA (US) CPC ........ CIID II/0047 (2013.01); CIID 3/3947 A (2013.01): CIID 3/43 (2013.01): CIID 3/30 (73) Assignee: As Products and Chemicals, Inc., (2013.01): CIID 3/2086 (2013.01): CIID 3/33 Allentown, PA (US) (2013.01); CIID 3/28 (2013.01); CIID3/0073 (2013.01); CIID 3/3773 (2013.01); HOIL (21) Appl. No.: 15/138,835 21/3 IIII (2013.01): HOIL 21/0332 (2013.01); (22) Filed:1-1. Apr. 26, 2016 HOIL 21/76865 (2013.01); HOIL (2013.01)21/02068 Related U.S. Application Data (57) ABSTRACT (60) Provisional application No. 62/155,794, filed on May Composition, method and system for PVD TiN hard mask 1, 2015, provisional application No. 62/164.293, filed on May 20, 2015, provisional application No. 62/281, removal from 28/20 nm pattern wafers - have been disclosed. 658, filed on Jan. 21, 2016 The composition uses peroxide as oxidizing agent for PVD , Illed On Jan. ZT, TiN hard mask removal under slightly basic conditions. The Publication Classification composition comprises bulky or long chain organic amines or polyalkylamine to improve removal/etching selectivity of (51) Int. Cl. PVD TiN vs CVD TiN. The composition further comprises CLID II/00 (2006.01) long chain organic acids or amines to maintain Co compat CLID 3/43 (2006.01) ibility. Patent Application Publication Apr. 20, 2017. Sheet 1 of 6 US 2017/O107460 A1 I:? ? Patent Application Publication Apr. 20, 2017. Sheet 2 of 6 US 2017/O107460 A1 H2O2 stability 104.0% SE 102.0% OO.Oo 98.096 96.0% 94.09 92.096 90.096 O 20 40 60 8O OO 2O 140 hrs FIG. 2(a) O 2O 40 60 8O OO 2O 140 hrs FIG. 2(b) Patent Application Publication Apr. 20, 2017. Sheet 3 of 6 US 2017/O107460 A1 R a -5 : 2 : s U 8 c C. : S E f : Sl. i - O S.s Patent Application Publication Apr. 20, 2017. Sheet 4 of 6 US 2017/O107460 A1 pH s H2O2 remaini:g --0-111S- - - - - - - -R-111S- - - - - - - + 0.5g glycine isE 100%1.10% S. 90% 709. 60% 500. 40% Time (hr) Time (hr) Cu etch rate TiNetChrate -1115 at 111S+ 0.5g glycine 3 Time (hr) Time (hr) Patent Application Publication Apr. 20, 2017. Sheet 5 of 6 US 2017/O107460 A1 FIG. 5(b) Patent Application Publication Apr. 20, 2017. Sheet 6 of 6 US 2017/0107460 A1 Cu etch rate TiN etch rate ? C) (O FIG. 6(b) US 2017/01 07460 A1 Apr. 20, 2017 TN HARD MASK AND ETCH RESIDUAL least one buffering species, and water. The composition REMOVAL achieves highly efficacious cleaning of the residue material from the microelectronic device while simultaneously not CROSS-REFERENCE TO RELATED damaging the interlevel dielectric and metal interconnect APPLICATIONS material also present thereon. 0001. This application claims the benefit of priority under 0008 U.S. Pat. No. 7.928,046 discloses an aqueous, 35 U.S.C. S 119(e) to earlier filed U.S. patent application Ser. silicate free, cleaning compositions of about pH 9 or below No. 62/155,794 filed on May 1, 2015, to earlier filed U.S. and method of using the cleaning compositions for cleaning patent application Ser. No. 62/164.293 filed on May 20, microelectronic Substrates, which compositions are able to 2015, and to earlier filed U.S. patent application Ser. No. essentially completely clean Such substrates and produce 62/281,658 filed on Jan. 21, 2016, the disclosures of which essentially no metal corrosion of the metal elements of Such are incorporated herein by reference. Substrates. The aqueous cleaning compositions of present invention have (a) water, (b) at least one of ammonium and quaternary ammonium ions and (c) at least one of hypo BACKGROUND phosphite (H2PO) and/or phosphite (HPO) ions. The 0002. As scaling continues to ever smaller feature sizes, cleaning compositions also may contain fluoride ions. integrated circuit (IC) reliability is an increasing concern in Optionally, the composition may contain other components IC fabrication technology. The impact of trace interconnect Such as organic solvents, oxidizing agent, Surfactants, cor failure mechanisms on device performance and reliability rosion inhibitors and metal complexing agents. demand much more from integration schemes, interconnect 0009 US 2013/004.5908 discloses a semiconductor pro materials, and processes. An optimal low-k dielectric mate cessing composition and method for removing photoresist, rial and its related deposition, pattern lithography, etching polymeric materials, etching residues and copper oxide from and cleaning are required to form dual-damascene intercon a Substrate comprising copper, low-k dielectric material and nect patterns. A hard-mask Scheme approach of intercon TiN, TiNXOy or W wherein the composition includes water, nects-patterning wafer fabrication is the ability to transfer a Cu corrosion inhibitor, at least one halide anion selected patterns into under layers with tightest optimal dimension from Cl or Br, and, where the metal hard mask comprises control. TiN or TiNXOy, at least one hydroxide source. 0003. As technology nodes advance to nanotechnology, (0010 WO 2013/101907 A1 discloses compositions com metal hard-mask materials such as TIN are used to gain prising etchants including hexafluorosilicic acid and better etching/removal selectivity, better pattern retention hexafluorotitanate, at least one oxidant including high Valent and profile control to the low-k materials during the pattern metals, peroxide or high oxidation state species and at least etching process. one solvent. 0004 Compositions have been developed to pullback or (0011 US 2013/0157472 discloses a semiconductor pro remove these types of metal hard-masks from Substrates. cessing composition and method for removing photoresist, The following patents are representative. polymeric materials, etching residues and copper oxide from 0005 US 2006/0226122 discloses a wet etching compo a Substrate comprising copper, low-k dielectric material and sition including hydrogen peroxide; an organic onium TIN. TiNXOy or W wherein the composition includes water, hydroxide; and an acid. In another embodiment, the inven at least one halide anion selected from Cl or Br, and, tion relates to a method of wet etching metal nitride selec where the metal hard mask comprises only TiN or TiNXOy, tively to Surrounding structures comprising one or more of optionally at least one hydroxide source. silicon, silicon oxides, glass, PSG, BPSG, BSG, silicon (0012 US 2012/0058644 A1 (BASF) discloses a liquid oxynitride, silicon nitride and silicon oxycarbide and com composition free from N-alkylpyrrolidones and hydroxyl binations and mixtures thereof and/or photoresist materials, amine and its derivatives, having a dynamic shear viscosity including steps of providing a wet etching composition at 50° C. of from 1 to 10 mPas as measured by rotational including hydrogen peroxide, an organic onium hydroxide, Viscometry and comprising based on the complete weight of and an organic acid; and exposing a metal nitride to be the composition, (A) of from 40 to 99.95% by weight of a etched with the wet etching composition for a time and at a polar organic solvent exhibiting in the presence of dissolved temperature effective to etch the metal nitride selectively to tetramethylammonium hydroxide (B) a constant removal the Surrounding structures. rate at 50° C. for a 30 nm thick polymeric barrier anti 0006 US 2011/0147341 discloses an etching solution for reflective layer containing deep UV absorbing chro titanium-based metals, tungsten-based metals, titanium/ mophoric groups, (B) offrom 0.05 to <0.5% of a quaternary tungsten-based metals or their nitrides. The etching Solution anunonium hydroxide, and (C)<5% by weight of water; contains 10-40 mass % hydrogen peroxide, 0.1-15 mass % method for its preparation, a method for manufacturing of an organic acid salt, and water. electrical devices and its use for removing negative-tone and 0007 U.S. Pat. No. 7,922,824 discloses an oxidizing positive-tone photoresists and post etch residues in the aqueous cleaning composition and process for cleaning manufacture of DD Stacked Integrated Circuits and 3D post-plasma etch residue and/or hardmask material from a Wafer Level Packagings by way of patterning Through microelectronic device having said residue thereon. The Silicon Vias and/or by plating and bumping. oxidizing aqueous cleaning composition includes at least (0013 US 2009/0131295 A1 discloses compositions for one oxidizing agent, at least one oxidizing agent stabilizer removing and cleaning resist, etching residues, planarization comprising an amine species selected from the group con residues, metal fluorides and/or metal oxides from a sub sisting of primary amines, secondary amines, tertiary amines strate are provided, the composition including a metal ion and amine-N-oxides, optionally at least one co-solvent, free fluoride compound and water. The resist, etching resi optionally at least one metal-chelating agent, optionally at dues, planarization residues, metal fluorides and/or metal US 2017/01 07460 A1 Apr.