Methods for wet atomic layer etching of silicon dioxide
The present disclosure provides a new wet atomic layer etch (ALE) process for etching silicon dioxide (SiO 2 ) materials. More specifically, the present disclosure provides various embodiments of methods that utilize new etch chemistries for etching a SiO 2 layer in a cyclic wet ALE process. The new etch chemistries disclosed herein use an anhydrous basic surface modification solution to create self-limiting reactions on exposed surfaces of the SiO 2 layer and form a silicate passivation layer, which is insoluble in the surface modification solution, but readily soluble in a dissolution solution.
1 . A method of etching a silicon dioxide (SiO 2 ) layer, the method comprising:
receiving a substrate having the silicon dioxide (SiO 2 ) layer formed thereon, wherein a surface of the silicon dioxide (SiO 2 ) layer is exposed on a surface of the substrate;
exposing the surface of the substrate to a surface modification solution comprising a base dissolved in a non-aqueous solvent, wherein the base reacts with the surface of the silicon dioxide (SiO 2 ) layer to form a silicate passivation layer, which is self-limited and insoluble in the surface modification solution;
removing the surface modification solution from the surface of the substrate subsequent to forming the silicate passivation layer;
exposing the surface of the substrate to a dissolution solution that selectively dissolves the silicate passivation layer; and
removing the dissolution solution from the substrate to etch the silicon dioxide (SiO 2 ) 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 a number of cycles until an amount of the silicon dioxide (SiO 2 ) layer is removed from the substrate.
3 . The method of claim 1 , wherein the base included within the surface modification solution is a hydroxide or a carbonate salt.
4 . The method of claim 3 , wherein the base included within the surface modification solution is sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH) 2 ), calcium hydroxide (Ca(OH) 2 ), ammonium hydroxide (NH 4 OH), tetramethylammonium hydroxide (TMAH, N(CH 3 ) 4 OH), tetrabutylammonium hydroxide (C 16 H 37 NO) or choline hydroxide ([(CH 3 ) 3 NCH 2 CH 2 OH] + OH − ).
5 . The method of claim 3 , wherein the base is sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), magnesium carbonate (MgCO 3 ), calcium carbonate (CaCO 3 ), ammonium carbonate ((NH 4 ) 2 CO 3 ), tetramethylammonium carbonate ((N(CH 3 ) 4 CO 3 ), tetrabutylammonium carbonate (C 33 H 72 N 2 O 3 ), or choline carbonate (C 6 H 14 NO 3 + ).
6 . The method of claim 3 , wherein the base included within the surface modification solution is a hydroxide having R + cations and OH − anions, wherein the R + cations and the OH − anions in the surface modification solution react with the surface of the silicon dioxide (SiO 2 ) layer to form the silicate passivation layer in a self-limiting reaction, the silicate passivation layer having a chemical formula of R 2x Si y O 2y+x , where a ratio of x:y ranges between 0.25 and 2.
7 . The method of claim 6 , wherein the R + cations comprise alkali metal cations, alkali earth metal cations, ammonium cations or quaternary ammonium cations.
8 . The method of claim 3 , wherein the base included within the surface modification solution is a carbonate salt having R n+ cations and CO 3 2− anions, wherein the R n+ cations and the CO 3 2− anions in the surface modification solution react with the surface of the silicon dioxide (SiO 2 ) layer to form the silicate passivation layer in a self-limiting reaction, the silicate passivation layer having a chemical formula of R 2x Si y O 2y+x , where a ratio of x:y ranges between 0.25 and 2.
9 . The method of claim 8 , wherein the R n+ cations comprise alkali metal cations, alkali earth metal cations, ammonium cations or quaternary ammonium cations.
10 . The method of claim 1 , wherein the non-aqueous solvent included within the surface modification solution comprises an alcohol, an ether, a ketone, a halocarbon, a heterocyclic or another polar organic solvent.
11 . The method of claim 1 , wherein the non-aqueous solvent included within the surface modification solution comprises methanol, isopropyl alcohol, ethanol, dimethyl sulfoxide, acetonitrile, ethyl acetate, acetone, furans, dimethylformamide, or dioxane.
12 . The method of claim 1 , wherein the dissolution solution comprises an aqueous solvent, and wherein when exposed to the aqueous solvent, the silicate passivation layer is dissolved by the aqueous solvent.
13 . The method of claim 1 , wherein the dissolution solution comprises a non-aqueous solvent, and wherein when exposed to the non-aqueous solvent, the silicate passivation layer is dissolved by the non-aqueous solvent.
14 . The method of claim 13 , wherein the non-aqueous solvent included within the dissolution solution comprises ethylene glycol or glycerol.
15 . A method of etching a silicon dioxide (SiO 2 ) layer using a wet atomic layer etching (ALE) process, the method comprising:
a) receiving a substrate, the substrate having the silicon dioxide (SiO 2 ) layer formed thereon;
b) exposing the silicon dioxide (SiO 2 ) layer to a surface modification solution containing a base dissolved in a non-aqueous solvent, wherein the base reacts with an exposed surface of the silicon dioxide (SiO 2 ) layer to form a modified surface layer containing a silicate;
c) rinsing the substrate with a first purge solution to remove the surface modification solution from a surface of the substrate;
d) exposing the modified surface layer to a dissolution solution to dissolve the modified surface layer and uncover an unmodified surface of the silicon dioxide (SiO 2 ) layer underlying the modified surface layer;
e) rinsing the substrate with a second purge solution to remove the dissolution solution from the surface of the substrate; and
f) repeating steps b)-e) for one or more cycles until an amount of the silicon dioxide (SiO 2 ) layer is removed from the substrate.
16 . The method of claim 15 , wherein the base included within the surface modification solution is a hydroxide or a carbonate salt.
17 . The method of claim 15 , wherein the base included within the surface modification solution is a hydroxide having R + cations and OH-anions, wherein the R + cations and the OH anions in the surface modification solution react with the exposed surface of the silicon dioxide (SiO 2 ) layer to form a silicate passivation layer in a self-limiting reaction, the silicate passivation layer having a chemical formula of R 2x Si y O 2y+x , where a ratio of x:y ranges between 0.25 and 2.
18 . The method of claim 15 , wherein the base included within the surface modification solution is sodium hydroxide (NaOH), potassium hydroxide (KOH), magnesium hydroxide (Mg(OH) 2 ), calcium hydroxide (Ca(OH) 2 ), ammonium hydroxide (NH 4 OH), tetramethylammonium hydroxide (TMAH, N(CH 3 ) 4 OH), tetrabutylammonium hydroxide (C 16 H 37 NO) or choline hydroxide ([(CH 3 ) 3 NCH 2 CH 2 OH] + OH − ).
19 . The method of claim 15 , wherein the base included within the surface modification solution is a carbonate salt having R + cations CO 3 2− anions, wherein the R + cations and the CO 3 2− anions in the surface modification solution react with the exposed surface of the silicon dioxide (SiO 2 ) layer to form a silicate passivation layer in a self-limiting reaction, the silicate passivation layer having a chemical formula of R 2x Si y O 2y+x , where a ratio of x:y ranges between 0.25 and 2.
20 . The method of claim 15 , wherein the base included within the surface modification solution is sodium carbonate (Na 2 CO 3 ), potassium carbonate (K 2 CO 3 ), magnesium carbonate (MgCO 3 ), calcium carbonate (CaCO 3 ), ammonium carbonate ((NH 4 ) 2 CO 3 ), tetramethylammonium carbonate ((N(CH 3 ) 4 CO 3 ), tetrabutylammonium carbonate (C 33 H 72 N 2 O 3 ), or choline carbonate (C 6 H 14 NO 3 + ).
21 . The method of claim 15 , wherein the dissolution solution comprises an aqueous solvent or a non-aqueous solvent in which the silicate is soluble.
22 . The method of claim 15 , wherein the first purge solution and the second purge solution each comprise a non-aqueous organic solvent.