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(12) Patent Application Publication (10) Pub. No.: US 2015/0048053 A1 Cordonier Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2015/0048053 A1 Cordonier Et Al US 20150.048053A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2015/0048053 A1 Cordonier et al. (43) Pub. Date: Feb. 19, 2015 (54) SELECTIVEETCHING METHOD Publication Classification (51) Int. C. (75) Inventors: Christopher Cordonier, Kanagawa C09K I3/02 (2006.01) (JP); Mitsuhiro Nabeshima, Kanagawa C23F L/40 (2006.01) (JP); Shingo Kumagai, Kanagawa (JP); C23F I/44 (2006.01) Naoki Takahashi, Kanagawa (JP) C23F I/38 (2006.01) (52) U.S. C. CPC. C09K 13/02 (2013.01); C23H 1/38 (2013.01); (73) Assignee: JCUCORPORATION, Tokyo (JP) C23F I/40 (2013.01); C23H I/44 (2013.01) USPC ............... 216/97: 216/99: 216/105: 216/100; (21) Appl. No.: 14/385,007 252/79.5; 562/476; 562/584; 562/477; 562/585 (22) PCT Fled: Sep. 3, 2012 (57) ABSTRACT A layer of a metal selected from titanium, niobium, tungsten, (86) PCT NO.: PCT/UP2012/072301 molybdenum, ruthenium, rhodium, arsenic, aluminum and S371 (c)(1), gallium, an oxide of the metal, a nitride of the metal, silicon (2), (4) Date: Sep. 12, 2014 nitride, hafnium nitride, tantalum nitride, or an alloy of these metals, the layer being provided on an underlying base mate (30) Foreign Application Priority Data rial selected from glass, silicon, copper and nickel, is selec tively etched with an alkaline etching solution containing a Mar. 12, 2012 (JP) ..................... PCT/JP2012/056315 predefined complexing agent. Patent Application Publication Feb. 19, 2015 Sheet 1 of 2 US 2015/0048053 A1 Patent Application Publication Feb. 19, 2015 Sheet 2 of 2 US 2015/0048053 A1 383 &sage 8: Si w88: US 2015/0048053 A1 Feb. 19, 2015 SELECTIVE ETCHING METHOD glass, silicon, copper and nickel, and the present inventors completed the present invention. TECHNICAL FIELD 0009 Specifically, the present invention relates to an etch 0001. The present invention relates to a method for selec ing method, including: bringing a layer of a metal selected tively etching a layer of a metal selected from titanium, nio from titanium, niobium, tungsten, molybdenum, ruthenium, bium, tungsten, molybdenum, ruthenium, rhodium, arsenic, rhodium, arsenic, aluminum and gallium, an oxide of the aluminum and gallium, an oxide of the metal, a nitride of the metal, a nitride of the metal, silicon nitride, hafnium nitride, metal, silicon nitride, hafnium nitride, tantalum nitride, oran tantalum nitride, or an alloy of these metals, the layer being alloy of these metals, the layer being provided on an under provided on an underlying base material selected from glass, lying base material selected from glass, silicon, copper and silicon, copper and nickel, into contact with an etching solu nickel, in preference to the underlying base material. tion which consists essentially of at least one complexing agent selected from compounds shown by Formulas (I) and BACKGROUND ART (II) and which is alkaline, thereby selectively etching the 0002. In general, when etching of titanium is carried out, a metal selected from titanium, niobium, tungsten, molybde hydrofluoric acid-based etching solution is used. However, num, ruthenium, rhodium, arsenic, aluminum and gallium, when Such a hydrofluoric acid-based etching solution is used, the oxide of the metal, the nitride of the metal, silicon nitride, the underlying base material will also be etched in cases hafnium nitride, tantalum nitride, or the alloy of these metals, where the underlying base material is nickel or glass. 0003. Furthermore, when etching of titanium is carried out, a sodium hydroxide solution may be used. However, Chemical Formula 1 titanium will hardly be etched with such an etching solution (I) alone, and the etching rate is very slow even when hydrogen peroxide is combined with the etching solution to improve the etching rate. Therefore, this etching solution is impracticable. R2 OH 0004. In recent years, as for etching solutions for titanium, a method in which EDTA is used as a complexing agent has been known, and, specifically, a method in which an alkaline etching solution containing EDTA and hydrogen peroxide is used has been known (Patent Document 1). wherein R' to R may be identical to or different from one 0005. However, while titanium deposited on lithium nio another, and are -R, OR, OOR, COOR, bate (LiNbO) can be selectively etched by this method, there COOOR, CHCOOR, CHCOOOR3, CRO or is a problem of slow etching rate. Furthermore, in this —CHCHCH, where R to R' may be identical to or different method, Some Substances (metals) cannot be etched, and the from one another, and are hydrogen, a C1 to C10 Saturated underlying base material may be adversely affected depend aliphatic group, a C1 to C10 unsaturated aliphatic group, oran ing on the type of the underlying base material. For example, aryl group, and since the etching rate of titanium is slower than the etching rate of nickel, the underlying base material is dissolved prior Chemical Formula 2) to dissolution of titanium. (II) PRIOR ART DOCUMENT Patent Document 0006 Patent Document 1: U.S. Pat. No. 4,554,050 SUMMARY OF THE INVENTION Problems that the Invention is to Solve 0007 An objective of the present invention is to provide a wherein R* to R' may be identical to or different from one method for selectively etching not only titanium but also another, and are - R, OR, OOR, COOR', other metals at practical speed in preference to the underlying COOOR", CHCOOR", CHCOOOR, CRPO, base material. —CH2CHCH. —CN, NC, NO. —F. —Cl, —Br. —I, or -SOR where R to R may be identical to or different Means for Solving the Problems from one another, and are hydrogen, a C1 to C10 Saturated 0008. The present inventors conducted intensive studies to aliphatic group, a C1 to C10 unsaturated aliphatic group, oran solve the above-described problem. Consequently, the aryl group, and X is -OH,-COOH or -COOOH. present inventors found that an alkaline etching Solution con 0010 Furthermore, the present invention relates to an taining a specific complexing agent can selectively etch a etching Solution for a metal selected from titanium, niobium, metal selected from titanium, niobium, tungsten, molybde tungsten, molybdenum, ruthenium, rhodium, arsenic, alumi num, ruthenium, rhodium, arsenic, aluminum and gallium, an num and gallium, an oxide of the metal, a nitride of the metal, oxide of the metal, a nitride of the metal, silicon nitride, silicon nitride, hafnium nitride, tantalum nitride, or an alloy hafnium nitride, tantalum nitride, or an alloy of these metals, of these metals, provided on an underlying base material in preference to the underlying base material selected from selected from glass, silicon, copper and nickel, the etching US 2015/0048053 A1 Feb. 19, 2015 Solution consisting essentially of at least one complexing 0014 FIG. 2 shows SPM photos and Ra values of samples agent selected from compounds shown by Formulas (I) and which were etched under etching conditions of 80° C. and 5 (II) minutes by using the etching Solution of Example 6 in Test Example 4. (In this figure. (A) refers to the surface of Sample A: (B) refers to the surface of Sample B: (C) refers to the Chemical Formula 3 surface of Sample B which was subjected to etching; and (D) refers to the surface of Sample A which was subjected to (I) etching.) (0015 FIG.3 shows SEM photos (upside) and SPM photos (downside) of samples which were etched under etching con R2 OH ditions of 80° C. and 40 minutes by using the etching solution of Example 6 in Test Example 5. (In this figure, (A) refers to the surface of Sample A; (B) refers to the surface of Sample B: and (C) refers to the surface of Sample B which was subjected wherein R' to R may be identical to or different from one to etching.) another, and are -R, OR, —OOR, COOR, (0016 FIG. 4 shows SEM photos (upside) and SPM photos COOOR, CHCOOR, CHCOOOR3, CRO or (downside) of samples which were etched under etching con —CHCHCH, where R to R' may be identical to ordifferent ditions of 80° C. and 25 seconds by using the etching solution from one another, and are hydrogen, a C1 to C10 Saturated of Example 6 in Test Example 6. (In this figure, (A) refers to aliphatic group, a C1 to C10 unsaturated aliphatic group, oran the surface of Sample A; (B) refers to the surface of Sample B: aryl group, and and (C) refers to the surface of Sample B which was subjected to etching.) Chemical Formula 4 MODE FOR CARRYING OUT THE INVENTION (II) 0017. The method for selectively etching a metal selected from titanium, niobium, tungsten, molybdenum, ruthenium, rhodium, arsenic, aluminum and gallium, an oxide of the metal, a nitride of the metal, silicon nitride, hafnium nitride, tantalum nitride, or an alloy of these metals according to the present invention (hereinafter, simply referred to as “the method of the present invention') is carried out by bringing a layer of a metal selected from titanium, niobium, tungsten, molybdenum, ruthenium, rhodium, arsenic, aluminum and wherein R* to R' may be identical to or different from one gallium, an oxide of the metal, a nitride of the metal, silicon another, and are - R', -OR, —OOR', -COOR', nitride, hafnium nitride, tantalum nitride, or an alloy of these COOOR", CHCOOR", CHCOOOR, CRPO, metals, the layer being provided on an underlying base mate —CH2CHCH. —CN, NC, NO. —F. —Cl, —Br. —I, rial selected from glass, silicon, copper and nickel, into con or - SOR where R to R may be identical to or different tact with an etching solution which consists essentially of at from one another, and are hydrogen, a C1 to C10 Saturated least one complexing agent selected from compounds shown aliphatic group, a C1 to C10 unsaturated aliphatic group, oran by Formulas (I) and (II) and which is alkaline.
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