# US 2026/0096367 A1 · Methods for wet atomic layer etching of titanium nitride using halogenation

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- Number: US 2026/0096367 A1
- Document ID: US20260096367A1
- Status: Published application
- Kind: A1
- Application number: 19/042,196
- Filed: 2025-01-31
- Published: 2026-04-02
- Earliest claimed: 2024-09-29
- Assignees: Tokyo Electron Limited
- Applicants: Tokyo Electron Limited
- Inventors: Tulashi Dahal; Kate Abel
- Web page: https://patentgrep.com/patent/US20260096367A1

## CPC

- C23F 1/10: Etching compositions (C23F1/44 takes precedence)
- H10P 50/667: {by liquid etching only}
- C09K 13/06: with organic material
- C09K 13/08: containing a fluorine compound
- C23F 1/26: for etching refractory metals
- C23F 1/30: for etching other metallic material
- H10P 70/27: {during, before or after processing of conductive materials, e.g. polysilicon or amorphous silicon layers}
- H10P 72/0424: {using mainly spraying means, e.g. nozzles}
- C23F: NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE (working metal by laser beams B23K26/00; desurfacing by applying flames B23K7/00; working of metal by electro-erosion B23H; producing decorative effects by removing surface material, e.g. by engraving, by etching, B44C1/22; electrolytic etching or polishing C25F); INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

Various embodiments of methods are provided for etching titanium nitride (TiN) and other transition metal nitride materials in a wet ALE process. The methods disclosed herein use a wide variety of wet etch chemistries to: (a) halogenate a TiN surface and form a self-limiting, titanium halide or titanium oxyhalide passivation layer in a surface modification step of the wet ALE process, and (b) selectively remove the titanium halide or titanium oxyhalide passivation layer in a dissolution step of the wet ALE process. In the embodiments disclosed herein, a surface modification solution containing a halogenation agent dissolved in non-aqueous solvent is used to form a self-limiting, titanium halide or titanium oxyhalide passivation layer, which is selectively removed in an acidic dissolution solution via reactive dissolution.

## Claims

### Claim 1

A method of etching, the method comprising:
receiving a substrate having a titanium nitride (TiN) layer, wherein a TiN surface is exposed on a surface of the substrate;
exposing the surface of the substrate to a surface modification solution comprising an electrophilic halogenation agent dissolved in a non-aqueous solvent, wherein the electrophilic halogenation agent reacts with the TiN surface to form a titanium halide or titanium oxyhalide passivation layer, which is self-limiting and insoluble in the surface modification solution;
removing the surface modification solution from the surface of the substrate subsequent to forming the titanium halide or titanium oxyhalide passivation layer;
exposing the surface of the substrate to a dissolution solution to selectively remove the titanium halide or titanium oxyhalide passivation layer, wherein the dissolution solution reacts with the titanium halide or titanium oxyhalide passivation layer to form soluble species, which are dissolved by the dissolution solution to expose an unmodified TiN surface underlying the titanium halide or titanium oxyhalide passivation layer; and
removing the dissolution solution and the soluble species from the surface of the substrate to etch the TiN layer.

### Claim 2 (depends on 1)

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 TiN layer is removed from the substrate.

### Claim 3 (depends on 1)

The method of claim 1, wherein the electrophilic halogenation agent is an electrophilic chlorinating agent, an electrophilic fluorinating agent or an electrophilic brominating agent.

### Claim 4 (depends on 3)

The method of claim 3, wherein the electrophilic chlorinating agent is trichloroisocyanuric acid (TCCA), thionyl chloride, sulfuryl chloride, N-chlorosuccinimide, 1-chlorobenzotriazole, Chloramine-T and tert-butyl-N-chlorocyanamide.

### Claim 5 (depends on 3)

The method of claim 3, wherein the non-aqueous solvent is an ether, a ketone, a halocarbon, a heterocyclic, an alcohol or another polar organic solvent or chlorocarbon solvent.

### Claim 6 (depends on 1)

The method of claim 1, wherein the surface modification solution is a non-aqueous solution comprising an electrophilic chlorinating agent dissolved in the non-aqueous solvent, wherein the electrophilic chlorinating agent reacts with the TiN surface to form a titanium chloride or titanium oxychloride passivation layer, which is self-limiting and insoluble in the surface modification solution.

### Claim 7 (depends on 6)

The method of claim 6, wherein prior to exposing the surface of the substrate to the surface modification solution, the method further comprises selecting a concentration of the electrophilic chlorinating agent in the surface modification solution to adjust an etch rate of the TiN layer without increasing a post-etch surface roughness of the TiN layer compared to an initial surface roughness of the TiN layer before etching.

### Claim 8 (depends on 6)

The method of claim 6, wherein the surface modification solution comprises trichloroisocyanuric acid (TCCA) dissolved in a polar organic solvent, and wherein a concentration of the TCCA in the surface modification solution ranges between 0.1% and 10%.

### Claim 9 (depends on 6)

The method of claim 6, wherein the surface modification solution comprises 2% to 5% trichloroisocyanuric acid (TCCA) dissolved in ethyl acetate or acetone.

### Claim 10 (depends on 6)

The method of claim 6, 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 an elevated temperature ranging between 25° C. and 100° C., wherein the elevated temperature increases an etch rate of the TiN layer by increasing a chlorination rate of the TiN surface.

### Claim 11 (depends on 6)

The method of claim 6, wherein the dissolution solution comprises an acid, which reacts with the titanium chloride or titanium oxychloride passivation layer to form the soluble species, which are dissolved by the dissolution solution to expose the unmodified TiN surface underlying the titanium chloride or titanium oxychloride passivation layer.

### Claim 12 (depends on 11)

The method of claim 11, wherein said exposing the surface of the substrate to the dissolution solution comprises:
exposing the surface of the substrate to the dissolution solution at an elevated temperature ranging between 25° C. and 100° C., wherein the elevated temperature increases an etch rate of the TiN layer by increasing a dissolution rate of the titanium chloride or titanium oxychloride passivation layer.

### Claim 13 (depends on 11)

The method of claim 11, wherein the acid is sulfuric acid (H2SO4), hydrochloric acid (HCl), hydrofluoric acid (HF) or nitric acid (HNO3).

### Claim 14 (depends on 11)

The method of claim 11, wherein the dissolution solution further comprises a ligand, which assists in the selective removal of the titanium chloride or titanium oxychloride passivation layer and/or increases a dissolution rate of the titanium chloride or titanium oxychloride passivation layer.

### Claim 15 (depends on 14)

The method of claim 14, wherein the ligand is oxalic acid, formic acid, acetic acid, cupferron, ethylenediamine, ethylenediaminetetraacetic acid (EDTA), iminodiacetic acid, catechol, ascorbic acid, sodium ascorbate, calcium ascorbate or potassium ascorbate.

### Claim 16 (depends on 14)

The method of claim 14, wherein the dissolution solution comprises 0.05 mM to 5 M of sulfuric acid (H2SO4).

### Claim 17

A method of etching a substrate using a wet atomic layer etching (ALE) process, the method comprising:
receiving the substrate, the substrate having a titanium nitride (TiN) layer, wherein a TiN surface is exposed on a surface of the substrate; and
selectively etching the TiN layer by performing multiple cycles of the wet ALE process, wherein each cycle comprises:
exposing the TiN surface to a first etch solution comprising an electrophilic chlorinating agent dissolved in a non-aqueous solvent to form a chemically modified TiN 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 TiN surface layer to a second etch solution to selectively dissolve the chemically modified TiN surface layer and expose an unmodified TiN surface underlying the chemically modified TiN surface 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 TiN layer.

### Claim 18 (depends on 17)

The method of claim 17, wherein the electrophilic chlorinating agent reacts with the TiN surface to form a titanium chloride or titanium oxychloride passivation layer, which is self-limiting and insoluble in the non-aqueous solvent, and wherein a concentration of the electrophilic chlorination agent in the first etch solution is selected to adjust an etch rate of the TiN layer without increasing a post-etch surface roughness of the TiN layer compared to an initial surface roughness of the TiN layer before etching.

### Claim 19 (depends on 18)

The method of claim 18, wherein the first etch solution comprises trichloroisocyanuric acid (TCCA) dissolved in a polar organic solvent, and wherein a concentration of the TCCA in the first etch solution ranges between 0.1% and 10%.

### Claim 20 (depends on 18)

The method of claim 18, wherein the first etch solution comprises 2% to 5% trichloroisocyanuric acid (TCCA) dissolved in ethyl acetate or acetone.

### Claim 21 (depends on 18)

The method of claim 18, wherein the second etch solution comprises an acid, wherein the titanium chloride or titanium oxychloride passivation layer is selectively dissolved by the acid to expose the unmodified TiN surface underlying the titanium chloride or titanium oxychloride passivation layer.

### Claim 22 (depends on 21)

The method of claim 21, wherein the second etch solution further comprises a ligand, which assists in the selective dissolution of the titanium chloride or titanium oxychloride passivation layer and/or increases a dissolution rate of the titanium chloride or titanium oxychloride passivation layer.

### Claim 23 (depends on 21)

The method of claim 21, wherein the second etch solution comprises 0.05 mM to 5 M of sulfuric acid (H2SO4).

### Claim 24 (depends on 17)

The method of claim 17, wherein the substrate further comprises an oxide layer, wherein an oxide surface of the oxide layer is exposed on the surface of the substrate, and wherein said selectively etching the TiN layer is selective to the oxide layer.

### Claim 25 (depends on 24)

The method of claim 24, wherein the oxide layer comprises zirconium dioxide (ZrO2), hafnium dioxide (HfO2) or hafnium zirconium dioxide (HfxZr(1-x)O2).