# US 12,604,690 B2 · Systems and methods for selective metal-containing hardmask removal

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- Number: US 12,604,690 B2
- Document ID: US12604690B2
- Status: Granted
- Kind: B2
- Application number: 18/244,583
- Filed: 2023-09-11
- Published: 2025-03-13
- Granted: 2026-04-14
- Earliest claimed: 2023-09-11
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: Baiwei Wang; Rohan Puligoru Reddy; Xiaolin C. Chen; Wanxing Xu; Zhenjiang Cui; Anchuan Wang
- Web page: https://patentgrep.com/patent/US12604690B2

## CPC

- H10P 50/285: {of materials not containing Si, e.g. PZT or Al2O3}
- H10P 50/267: {using plasmas}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

Exemplary semiconductor processing methods may include flowing an etchant precursor into a processing region of a semiconductor processing chamber. A substrate may be housed within the processing region. The substrate may define an exposed region of a metal-containing hardmask material and an exposed region of a material characterized by a dielectric constant of less than or about 4.0. The methods may include contacting the substrate with the etchant precursor. The methods may include removing at least a portion of the metal-containing hardmask material.

## Claims

### Claim 1

A semiconductor processing method comprising:
flowing an etchant precursor into a processing region of a semiconductor processing chamber, wherein a substrate is housed within the processing region, and wherein the substrate defines an exposed region of a metal-containing hardmask material, an exposed region of a metal material, and an exposed region of a material characterized by a dielectric constant of less than or about 4.0;
contacting the substrate with the etchant precursor; and
removing at least a portion of the metal-containing hardmask material.

### Claim 2 (depends on 1)

The semiconductor processing method of claim 1, wherein the etchant precursor comprises a halogen-containing precursor.

### Claim 3 (depends on 1)

The semiconductor processing method of claim 1, wherein the etchant precursor comprises nitrogen trifluoride (NF3), diatomic fluorine (F2), diatomic chlorine (Cl2), thionyl chloride (SOCl2), carbon tetrafluoride (CF4), hexafluoroethane (C2F6), sulfur hexafluoride (SF6), carbon tetrachloride (CCl4), dichloromethane (CH2Cl2), chloroform (CHCl3), or a combination thereof.

### Claim 4 (depends on 1)

The semiconductor processing method of claim 1, wherein the etchant precursor comprises nitrogen trifluoride (NF3).

### Claim 5 (depends on 1)

The semiconductor processing method of claim 1, further comprising:
flowing a hydrogen-containing precursor or an oxygen-containing precursor to the processing region of the semiconductor processing chamber with the etchant precursor.

### Claim 6 (depends on 1)

The semiconductor processing method of claim 1, wherein removing the portion of the metal-containing hardmask material is performed plasma-free.

### Claim 7 (depends on 1)

The semiconductor processing method of claim 1, wherein removing the portion of the metal-containing hardmask material is performed at a temperature greater than or about 350° C.

### Claim 8 (depends on 1)

The semiconductor processing method of claim 1, wherein removing the portion of the metal-containing hardmask material is performed at a pressure greater than or about 2 Torr.

### Claim 9 (depends on 1)

The semiconductor processing method of claim 1, further comprising:
prior to flowing the etchant precursor into the processing region of the semiconductor processing chamber, removing an oxidized portion of the metal-containing hardmask material.

### Claim 10 (depends on 1)

The semiconductor processing method of claim 1, further comprising:
subsequent to removing the portion of the metal-containing hardmask material, contacting the substrate with a second etchant precursor to remove fluorine-containing residue from the substrate or an oxidized portion of the metal-containing hardmask material.

### Claim 11 (depends on 1)

The semiconductor processing method of claim 1, wherein the metal-containing hardmask material is a titanium-containing hardmask material.

### Claim 12 (depends on 1)

The semiconductor processing method of claim 1, wherein the metal-containing hardmask material includes doped carbide.

### Claim 13

A semiconductor processing method comprising:
flowing a pre-etching precursor into a processing region of a semiconductor processing chamber, wherein a substrate is housed within the processing region, and wherein the substrate defines an exposed region of a metal-and-nitrogen-containing hardmask material, an exposed region of a metal-containing material, and an exposed region of a material characterized by a dielectric constant of less than or about 4.0;
contacting the substrate with the pre-etching precursor to at least partially oxidize the exposed region of the metal-containing material;
halting delivery of the pre-etching precursor;
flowing an etchant precursor into the processing region of the semiconductor processing chamber;
contacting the substrate with the etchant precursor; and
selectively removing at least a portion of the metal-and-nitrogen-containing hardmask material relative to the material characterized by the dielectric constant of less than or about 4.0.

### Claim 14 (depends on 13)

The semiconductor processing method of claim 13, wherein the pre-etching precursor comprises nitrogen trifluoride (NF3), tungsten hexafluoride (WF6), or boron trichloride (BCl3).

### Claim 15 (depends on 13)

The semiconductor processing method of claim 13, further comprising:
forming plasma effluents of the pre-etching precursor.

### Claim 16 (depends on 13)

The semiconductor processing method of claim 13, wherein the etchant precursor comprises nitrogen trifluoride (NF3), diatomic fluorine (F2), diatomic chlorine (Cl2), thionyl chloride (SOCl2), carbon tetrafluoride (CF4), hexafluoroethane (C2F6), sulfur hexafluoride (SF6), carbon tetrachloride (CCl4), dichloromethane (CH2Cl2), chloroform (CHCl3), or a combination thereof.

### Claim 17 (depends on 13)

The semiconductor processing method of claim 13, wherein removing the portion of the metal-and-nitrogen-containing hardmask material is performed plasma-free.

### Claim 18 (depends on 13)

The semiconductor processing method of claim 13, wherein the metal-containing material is a metal material.

### Claim 19

A semiconductor processing method comprising:
flowing an etchant precursor into a processing region of a semiconductor processing chamber, wherein a substrate is housed within the processing region, and wherein the substrate defines an exposed region of a metal-containing hardmask material;
contacting the substrate with the etchant precursor;
removing at least a portion of the metal-containing hardmask material relative to one or more other materials on the substrate;
halting delivery of the etchant precursor;
flowing a post-etching precursor into the processing region of the semiconductor processing chamber;
contacting the substrate with the post-etching precursor; and
removing a fluorine-containing residue from the substrate.

### Claim 20 (depends on 19)

The semiconductor processing method of claim 19, wherein the etchant precursor comprises a halogen-containing precursor.

### Claim 21 (depends on 20)

The semiconductor processing method of claim 20, wherein the one or more other materials on the substrate comprise a dielectric constant of less than or about 4.0, a metal material, a silicon-containing material, or a metal-and-oxygen-containing material.

### Claim 22 (depends on 19)

The semiconductor processing method of claim 19, wherein removing the portion of the metal-containing hardmask material is performed at a temperature greater than or about 350° C. and at a pressure greater than or about 2 Torr.