Methods for wet atomic layer etching of molybdenum
Systems and methods are provided for etching molybdenum in a wet ALE process. The methods disclosed herein use a wide variety of techniques and wet etch chemistries to oxidize a molybdenum surface and form a self-limiting, molybdenum oxide passivation layer in a surface modification step of the wet ALE process. For example, the methods use: (a) ultra-violet (UV) photolysis of peroxide oxidizers to create oxidizing radicals, which limit oxidation of the molybdenum surface and provide quasi-self-limiting oxidation behavior, (b) steric hinderance of oxidizers having large reactant molecules to achieve better self-limiting oxidation behavior, and/or (c) ligand-assisted oxidation to change the surface chemistry of the molybdenum oxide passivation layer and ensure self-limiting oxidation behavior. After forming the molybdenum oxide passivation layer using one or more of the oxidation techniques disclosed herein, the passivation layer is selectively removed in a dissolution step of the wet ALE process to etch the molybdenum surface.
1 . A method of etching, the method comprising:
receiving a substrate having a molybdenum (Mo) layer formed thereon, wherein a molybdenum surface is exposed on a surface of the substrate;
exposing the surface of the substrate to a surface modification solution comprising an oxidizer dissolved in a non-aqueous solvent, wherein the oxidizer reacts with the molybdenum surface to oxidize the molybdenum surface and form a molybdenum oxide passivation layer, which is self-limiting and insoluble in the non-aqueous solvent;
removing the surface modification solution from the surface of the substrate subsequent to forming the molybdenum oxide passivation layer;
exposing the surface of the substrate to a dissolution solution to selectively remove the molybdenum oxide passivation layer, wherein the dissolution solution reacts with the molybdenum oxide passivation layer to form soluble species that are dissolved by the dissolution solution, wherein the dissolution solution is an aqueous acidic solution, an aqueous basic solution or a non-aqueous ligand solution; and
removing the dissolution solution and the soluble species from the surface of the substrate to etch the molybdenum layer.
2 . The method of claim 1 , further comprising repeating said exposing the surface of the substrate to the surface modification solution, removing the surface modification solution, exposing the surface of the substrate to the dissolution solution, and removing the dissolution solution and the soluble species a number of times until a predetermined amount of the molybdenum layer is removed from the substrate.
3 . The method of claim 1 , wherein the surface modification solution further comprises a ligand species, which reacts with the molybdenum oxide passivation layer to change a surface chemistry of the molybdenum oxide passivation layer, and wherein changing the surface chemistry ensures that the molybdenum oxide passivation layer is self-limiting and insoluble in the non-aqueous solvent.
4 . The method of claim 3 , wherein the oxidizer comprises a peroxide oxidizer or a non-peroxide oxidizer, the ligand species comprises a carboxylic acid and the non-aqueous solvent comprises an organic solvent.
5 . The method of claim 3 , wherein the oxidizer comprises ammonium persulfate (APS), wherein the ligand species comprises oxalic acid, acetic acid, ascorbic acid, mandelic acid, malic acid, maleic acid or fumaric acid, and wherein the non-aqueous solvent comprises methanol (CH 3 OH), diethyl ether ((C 2 H 5 ) 2 O), acetonitrile (C 2 H 3 N), dimethyl sulfoxide (C 2 H 6 OS), isopropyl alcohol (IPA), another alcohol, a ketone or an acetate.
6 . The method of claim 1 , wherein the oxidizer comprises a large reactant molecule having a molecular size substantially greater than 2 angstroms and a smaller diffusion coefficient compared to a smaller reactant molecule having a molecular size less than 2 angstroms, wherein the smaller diffusion coefficient of the large reactant molecule reduces an oxidation rate at which the oxidizer oxidizes the molybdenum surface to form the molybdenum oxide passivation layer, and wherein reducing the oxidation rate improves self-limiting oxidation behavior of the oxidizer.
7 . The method of claim 6 , wherein the oxidizer comprises a non-peroxide oxidizer having the large reactant molecule, and wherein the non-aqueous solvent comprises an organic solvent.
8 . The method of claim 7 , wherein the non-peroxide oxidizer comprises ammonium persulfate (APS), ferric chloride (FeCl 3 ), an osmium tetroxide, a ruthenium tetroxide, a ruthenate, a manganate, a permanganate, a periodate, or a metal nitrate.
9 . The method of claim 7 , wherein the non-peroxide oxidizer comprises ammonium persulfate (APS), and wherein the non-aqueous solvent comprises methanol (CH 3 OH), diethyl ether ((C 2 H 5 ) 2 O), acetonitrile (C 2 H 3 N), dimethyl sulfoxide (C 2 H 6 OS), isopropyl alcohol (IPA), another alcohol, a ketone or an acetate.
10 . The method of claim 7 , wherein the non-peroxide oxidizer comprises ferric chloride (FeCl 3 ) and the non-aqueous solvent comprises isopropyl alcohol (IPA) or acetone, and wherein the ferric chloride reacts with the molybdenum surface to oxidize the molybdenum surface and form a molybdenum oxychloride passivation layer, which is self-limiting and insoluble in the non-aqueous solvent.
11 . The method of claim 6 , wherein the oxidizer comprises a peroxide oxidizer having the large reactant molecule, and wherein the non-aqueous solvent comprises an organic solvent.
12 . The method of claim 11 , wherein the peroxide oxidizer comprises di-tert-butyl peroxide (C 8 H 18 O 2 )) or tert-butyl peroxybenzoate (C 11 H 14 O 3 ), and wherein the non-aqueous solvent comprises methanol (CH 3 OH), diethyl ether ((C 2 H 5 ) 2 O), acetonitrile (C 2 H 3 N), dimethyl sulfoxide (C 2 H 6 OS), isopropyl alcohol (IPA), another alcohol, a ketone or an acetate.
13 . The method of claim 1 , wherein the dissolution solution is an aqueous acidic solution comprising hydrochloric acid (HCl), nitric acid or sulfuric acid, an aqueous basic solution comprising ammonium hydroxide (NH 4 OH), tetramethylammonium hydroxide (TMAH), potassium hydroxide (KOH) or calcium hydroxide (Ca(OH) 2 ), or a non-aqueous ligand solution comprising alpha-benzoin oxime in acetone, dimethyl sulfoxide (DMSO), methyl-ethyl ketone (MEK) or another ketone.
14 . A method of etching a substrate using a wet atomic layer etching (ALE) process, the method comprising:
receiving the substrate, the substrate having a molybdenum (Mo) layer formed thereon, wherein a molybdenum surface is exposed on a surface of the substrate; and
selectively etching the molybdenum layer by performing multiple cycles of the wet ALE process, wherein each cycle comprises:
exposing the molybdenum surface to a first etch solution comprising an oxidizer and a ligand species in a non-aqueous solvent to form a chemically modified Mo surface layer that is self-limiting and insoluble in the non-aqueous solvent;
rinsing the substrate with a first purge solution to remove the first etch solution from the surface of the substrate;
exposing the chemically modified Mo surface layer to a second etch solution to dissolve the chemically modified Mo surface layer, wherein the second etch solution is an aqueous acidic solution, an aqueous basic solution or a non-aqueous ligand solution; and
rinsing the substrate with a second purge solution to remove the second etch solution from the surface of the substrate.
15 . The method of claim 14 , wherein the oxidizer reacts with the molybdenum surface to oxidize the molybdenum surface and form the chemically modified Mo surface layer, wherein the ligand species reacts with the chemically modified Mo surface layer to change a surface chemistry of the chemically modified Mo surface layer, and wherein changing the surface chemistry ensures that the chemically modified Mo surface layer is self-limiting and insoluble in the non-aqueous solvent.
16 . The method of claim 14 , wherein the oxidizer comprises ammonium persulfate (APS), ferric chloride (FeCl 3 ), an osmium tetroxide, a ruthenium tetroxide, a ruthenate, a manganate, a permanganate, a periodate, a metal nitrate, hydrogen peroxide (H 2 O 2 ), or another peroxide.
17 . The method of claim 14 , wherein the ligand species comprises a carboxylic acid and the non-aqueous solvent comprises an organic solvent.
18 . The method of claim 14 , wherein the ligand species comprises oxalic acid, acetic acid, ascorbic acid, mandelic acid, malic acid, maleic acid or fumaric acid, and wherein the non-aqueous solvent comprises methanol (CH 3 OH), diethyl ether ((C 2 H 5 ) 2 O), acetonitrile (C 2 H 3 N), dimethyl sulfoxide (C 2 H 6 OS), isopropyl alcohol (IPA), another alcohol, a ketone or an acetate.
19 . The method of claim 14 , wherein the second etch solution is an aqueous acidic solution comprising hydrochloric acid (HCl), nitric acid or sulfuric acid, an aqueous basic solution comprising hydroxide ammonium (NH 4 OH), tetramethylammonium hydroxide (TMAH), potassium hydroxide (KOH) or calcium hydroxide (Ca(OH) 2 ), or a non-aqueous ligand solution comprising alpha-benzoin oxime in acetone, dimethyl sulfoxide (DMSO), methyl-ethyl ketone (MEK) or another ketone.
20 . A method of etching, the method comprising:
receiving a substrate having a molybdenum (Mo) layer formed thereon, wherein a molybdenum surface is exposed on a surface of the substrate;
exposing the surface of the substrate to a surface modification solution comprising an oxidizer dissolved in a non-aqueous solvent, wherein the oxidizer reacts with the molybdenum surface to oxidize the molybdenum surface and form a molybdenum oxide passivation layer, which is self-limiting and insoluble in the non-aqueous solvent;
removing the surface modification solution from the surface of the substrate subsequent to forming the molybdenum oxide passivation layer;
exposing the surface of the substrate to a dissolution solution to selectively remove the molybdenum oxide passivation layer, wherein the dissolution solution reacts with the molybdenum oxide passivation layer to form soluble species that are dissolved by the dissolution solution; and
removing the dissolution solution and the soluble species from the surface of the substrate to etch the molybdenum layer;
wherein during said exposing the surface of the substrate to the surface modification solution, the method further comprises:
exposing the surface of the substrate to ultra-violet (UV) radiation to photolyze the oxidizer and create oxidizing radicals, which react with the molybdenum surface to oxidize the molybdenum surface and form the molybdenum oxide passivation layer, wherein a lifetime of the oxidizing radicals limits oxidation of the molybdenum oxide passivation layer to provide quasi-self-limiting oxidation behavior.
21 . The method of claim 20 , wherein the oxidizer comprises a peroxide oxidizer and the non-aqueous solvent comprises an organic solvent.
22 . The method of claim 20 , wherein the oxidizer comprises hydrogen peroxide (H 2 O 2 ), a symmetric organic peroxide, an asymmetric organic peroxide, a monoperoxide, or a peroxy acid, and wherein the non-aqueous solvent comprises methanol (CH 3 OH), diethyl ether ((C 2 H 5 ) 2 O), acetonitrile (C 2 H 3 N), dimethyl sulfoxide (C 2 H 6 OS), isopropyl alcohol (IPA), another alcohol, a ketone or an acetate.