Methods for wet atomic layer etching of tungsten
Various embodiments of methods are provided for etching tungsten in a wet ALE process. The methods disclosed herein use a wide variety of techniques and wet etch chemistries to: (a) oxidize a tungsten surface and form a self-limiting, tungsten oxide passivation layer in a surface modification step of the wet ALE process, and (b) selectively remove the tungsten oxide passivation layer in a dissolution step of the wet ALE process. In the embodiments disclosed herein, ligand-assisted dissolution is used to selectively remove the tungsten oxide passivation layer without removing the unmodified tungsten surface underlying the tungsten oxide passivation layer. The ligand added to the dissolution solution prevents the dissolution solution from attacking and removing the unmodified tungsten surface.
1 . A method of etching, the method comprising:
receiving a substrate having a tungsten (W) layer formed thereon, wherein a tungsten 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 tungsten surface to oxidize the tungsten surface and form a tungsten 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 tungsten oxide passivation layer;
exposing the surface of the substrate to a dissolution solution comprising a ligand to selectively remove the tungsten oxide passivation layer, wherein the dissolution solution reacts with the tungsten oxide passivation layer to form soluble species, which are dissolved by the dissolution solution to expose an unmodified tungsten surface underlying the tungsten oxide passivation layer, wherein the ligand prevents the dissolution solution from attacking and removing the unmodified tungsten surface; and
removing the dissolution solution and the soluble species from the surface of the substrate to etch the tungsten 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 tungsten layer is removed from the substrate.
3 . The method of claim 1 , wherein the ligand is a reducing agent that inhibits oxidation of the unmodified tungsten surface and prevents continuous etching of the tungsten layer to provide a post-etch surface roughness of the tungsten layer that is substantially equal to an initial surface roughness of the tungsten layer before etching.
4 . The method of claim 3 , wherein the ligand contains an ascorbate anion.
5 . The method of claim 4 , wherein the ligand is ascorbic acid, sodium ascorbate, calcium ascorbate or potassium ascorbate.
6 . The method of claim 3 , wherein the ligand is ascorbic acid.
7 . The method of claim 3 , wherein the ligand is oxalic acid, formic acid, acetic acid, ethylenediamine, ethylenediaminetetraacetic acid (EDTA) or iminodiacetic acid.
8 . The method of claim 1 , wherein the dissolution solution is an aqueous basic solution comprising: (i) the ligand, and (ii) ammonium hydroxide (NH 4 OH), tetramethylammonium hydroxide (TMAH), potassium hydroxide (KOH) or calcium hydroxide (Ca(OH) 2 ).
9 . The method of claim 1 , wherein the dissolution solution is an aqueous acidic solution comprising: (i) the ligand, and (ii) hydrochloric acid (HCl), nitric acid or sulfuric acid.
10 . The method of claim 1 , wherein the oxidizer reacts with the tungsten surface to oxidize the tungsten surface and form a tungsten trioxide (WO 3 ) passivation layer, which is self-limiting and insoluble in the non-aqueous solvent, and wherein a concentration of the oxidizer in the surface modification solution is selected to avoid substantially increasing a post-etch surface roughness of the tungsten layer compared to an initial surface roughness of the tungsten layer before etching.
11 . The method of claim 10 , wherein the oxidizer comprises ammonium persulfate (APS), wherein the non-aqueous solvent comprises methanol (CH 3 OH), and wherein a concentration of the ammonium persulfate in the surface modification solution ranges between 0.005% and 0.1%.
12 . The method of claim 10 , wherein the oxidizer comprises hydrogen peroxide (H 2 O 2 ), wherein the non-aqueous solvent comprises isopropyl alcohol (IPA), and wherein a concentration of the hydrogen peroxide in the surface modification solution ranges between 0.05% and 1%.
13 . The method of claim 10 , wherein said exposing the surface of the substrate to the surface modification solution comprises:
exposing the surface of the substrate to the surface modification solution at a temperature ranging between 25° C. and 65° C. to increase an etch rate of the tungsten layer.
14 . The method of claim 10 , wherein the dissolution solution is an aqueous basic solution comprising the ligand and a base, wherein the base removes the tungsten trioxide (WO 3 ) passivation layer to expose the unmodified tungsten surface underlying the tungsten trioxide (WO 3 ) passivation layer, and wherein the ligand prevents the base from removing the unmodified tungsten surface and increasing the post-etch surface roughness of the tungsten layer compared to the initial surface roughness of the tungsten layer before etching.
15 . The method of claim 14 , wherein the dissolution solution is an aqueous basic solution comprising 0 mM to 10 mM ascorbic acid dissolved in 0.05 mM to 1 M of ammonium hydroxide (NH 4 OH) and water.
16 . A method of etching a substrate using a wet atomic layer etching (ALE) process, the method comprising:
receiving the substrate, the substrate having a tungsten (W) layer formed thereon, wherein a tungsten surface is exposed on a surface of the substrate; and
selectively etching the tungsten layer by performing multiple cycles of the wet ALE process, wherein each cycle comprises:
exposing the tungsten surface to a first etch solution comprising an oxidizer in a non-aqueous solvent to form a chemically modified W 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 W surface layer to a second etch solution to selectively dissolve the chemically modified W surface layer and expose an unmodified tungsten surface underlying the chemically modified W surface layer, wherein the second etch solution comprises a ligand that inhibits oxidation of the unmodified tungsten surface and prevents continuous etching of the tungsten layer; and
rinsing the substrate with a second purge solution to remove the second etch solution from the surface of the substrate and etch the tungsten layer.
17 . The method of claim 16 , wherein the oxidizer reacts with the tungsten surface to oxidize the tungsten surface and form a tungsten trioxide (WO 3 ) passivation layer, which is self-limiting and insoluble in the non-aqueous solvent, and wherein a concentration of the oxidizer in the first etch solution is selected to avoid substantially increasing a post-etch surface roughness of the tungsten layer compared to an initial surface roughness of the tungsten layer before etching.
18 . The method of claim 17 , wherein the oxidizer comprises ammonium persulfate (APS), wherein the non-aqueous solvent comprises methanol (CH 3 OH), and wherein a concentration of the ammonium persulfate in the first etch solution ranges between 0.005% and 0.1%.
19 . The method of claim 17 , wherein the oxidizer comprises hydrogen peroxide (H 2 O 2 ), wherein the non-aqueous solvent comprises isopropyl alcohol (IPA), and wherein a concentration of the hydrogen peroxide in the first etch solution ranges between 0.05% and 1%.
20 . The method of claim 17 , wherein said exposing the tungsten surface to the first etch solution comprises:
exposing the tungsten surface to the first etch solution at a temperature ranging between 25° C. and 65° C. to increase an etch rate of the tungsten layer.
21 . The method of claim 16 , wherein the second etch solution is an aqueous basic solution comprising the ligand and a base, wherein the base removes the chemically modified W surface layer to expose the unmodified tungsten surface underlying the chemically modified W surface layer, and wherein the ligand prevents the base from removing the unmodified tungsten surface and increasing a post-etch surface roughness of the tungsten layer compared to an initial surface roughness of the tungsten layer before etching.
22 . The method of claim 21 , wherein the ligand is ascorbic acid, sodium ascorbate, calcium ascorbate, potassium ascorbate, oxalic acid, formic acid, acetic acid, ethylenediamine, ethylenediaminetetraacetic acid (EDTA) or iminodiacetic acid.
23 . The method of claim 21 , wherein the base is ammonium hydroxide (NH 4 OH), tetramethylammonium hydroxide (TMAH), potassium hydroxide (KOH) or calcium hydroxide (Ca(OH) 2 ).
24 . The method of claim 16 , wherein the second etch solution comprises 0 mM to 10 mM ascorbic acid dissolved in 0.05 mM to 1 M of ammonium hydroxide (NH 4 OH) and water.