# US 12,224,177 B2 · Method of running an etch process in higher selectivity to mask and polymer regime by using a cyclic etch process

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- Number: US 12,224,177 B2
- Document ID: US12224177B2
- Status: Granted
- Kind: B2
- Application number: 17/666,725
- Filed: 2022-02-08
- Published: 2023-08-10
- Granted: 2025-02-11
- Earliest claimed: 2022-02-08
- Assignees: American Air Liquide, Inc.
- Applicants: American Air Liquide, Inc.
- Inventors: Xiangyu Guo; Nathan Stafford
- Web page: https://patentgrep.com/patent/US12224177B2

## CPC

- H10P 50/283: {by chemical means}
- H10P 50/287: {by chemical means}
- H10P 50/73: {using masks for insulating materials}
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

This disclosure describes an improved etch selectivity of a-C mask during HAR etch processes by using a cyclic etch process. The process has two principle steps: 1) A partial etch using a polymerizing etching recipe with lower O2 and extra polymer generation where a-C mask selectivity to dielectric (e.g. for SiO2 or ONON layers) is high; and 2) A polymer cleaning step using Kr sputter, Xe sputter, NF3, SF6, IF7, IF5, CF4, or other F based etching process, with or without bias, to etch the polymer. The polymer cleaning step may include addition of O containing molecules such as O2, CO, CO2, NO, NO2, N2O, SO2, and/or COS. These steps are repeated between a partial etch process (polymer creating) and polymer cleaning step (cycle etching).

## Claims

### Claim 1

A method for selectively etching a patterned structure into a substrate, the method comprising the steps of:
a) in an etching chamber, performing a first partial etching by exposing the substrate to an etching gas or etching gas mixture and an oxidizing gas, under conditions and for a period of time sufficient to preferentially etch a first substrate material over a second substrate material, wherein a polymer of the etching gas is deposited on the substrate, and wherein the first partial etching produces an intermediate patterned structure on the substrate that can be further etched to yield a final intended patterned structure on the substrate,
b) performing a first polymer removal step by exposing the substrate to a polymer removal gas or polymer removal gas mixture under conditions and for a period of time sufficient to remove some or all of the polymer formed in step a), and
c) repeating steps a) and b) at least once,
wherein the polymer removal gas or polymer removal gas mixture comprises one or more of Kr, Xe, NF3, SF6, IF7, IF5, and CF4.

### Claim 2 (depends on 1)

The method of claim 1, wherein the final intended patterned structure on the substrate comprises an aspect ratio of 1:20 or higher.

### Claim 3 (depends on 2)

The method of claim 2, wherein the aspect ratio is 1:100 or higher.

### Claim 4 (depends on 1)

The method of claim 1, wherein the first substrate material is SiO2 or ONON and the second substrate material is a hard mask layer.

### Claim 5 (depends on 4)

The method of claim 4, wherein the hard mask layer is an amorphous carbon containing hard mask layer.

### Claim 6 (depends on 1)

The method of claim 1, further comprising a vacuum purge of the etching chamber between step a) and step b), and/or after step b) and before a subsequent step a).

### Claim 7 (depends on 6)

The method of claim 6, further comprising a purge gas step and a second vacuum purge, both between step a) and step b), and/or after step b) and before a subsequent step a), wherein the purge gas flushes out of the etching chamber a residual gas from the prior step a) or step b).

### Claim 8 (depends on 1)

The method of claim 1, wherein the polymer removal steps comprise forming a plasma of the polymer removal gas or polymer removal gas mixture.

### Claim 9 (depends on 1)

The method of claim 1, wherein the partial etching steps comprise forming a plasma of the etching gas or etching gas mixture.

### Claim 10 (depends on 1)

The method of claim 1, wherein the preferential etching comprising an etch rate selectivity of ≥15 for etching the first substrate material over a second substrate material.

### Claim 11 (depends on 1)

The method of claim 1, wherein the etching gas or etching gas mixture comprises one or more of C4H2F6, C4F6, C4F8, CH2F2, CHF3, and CH3F.

### Claim 12 (depends on 11)

The method of claim 11, wherein the etching gas or etching gas mixture further comprises one or more of CH3I, C2F5I, C2F3I, C3F7I, C4F9I, and C2HF3I.

### Claim 13 (depends on 1)

The method of claim 1, wherein the polymer removal gas or polymer removal gas mixture further comprises one or more of O2, CO, CO2, NO, NO2, N2O, SO2, and COS.

### Claim 14 (depends on 1)

The method of claim 1, wherein the oxidizing gas comprises one or more of O2, CO, CO2, NO, NO2, N2O, SO2, and COS.

### Claim 15 (depends on 1)

The method of claim 1, wherein steps a) and b) are repeated more than once.