# US 12,604,684 B2 · Method and system for mitigating underlayer damage during formation of patterned structures

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- Number: US 12,604,684 B2
- Document ID: US12604684B2
- Status: Granted
- Kind: B2
- Application number: 17/711,998
- Filed: 2022-04-01
- Published: 2022-10-06
- Granted: 2026-04-14
- Earliest claimed: 2021-04-06
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Eiichiro Shiba; Tomomi Takayama; Che Chen Hsu
- Web page: https://patentgrep.com/patent/US12604684B2

## CPC

- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- C23C 16/345: {Silicon nitride}
- C23C 16/45536: {Use of plasma, radiation or electromagnetic fields}
- C23C 16/4554: {Plasma being used non-continuously in between ALD reactions (C23C16/56 takes precedence)}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- H01J 37/32449: {Gas control, e.g. control of the gas flow}
- H10P 14/6336: {in the presence of a plasma [PECVD]}
- H10P 14/6682: {the compound being a silane, e.g. disilane, methylsilane or chlorosilane}
- H10P 14/69215: {the material being a silicon oxide, e.g. SiO2}
- H10P 14/69433: {the material being a silicon nitride not containing oxygen, e.g. SixNy or SixByNz}
- H10P 76/405: {characterised by their composition, e.g. multilayer masks}
- H10P 76/4085: {characterised by the processes involved to create the masks}
- H01J 2237/3321: CVD [Chemical Vapor Deposition]
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)

## Abstract

Methods of forming structures suitable for a multiple patterning process are disclosed. Exemplary methods include forming a material overlying the substrate by providing a silicon precursor to the reaction chamber for a silicon precursor pulse period providing one or more of a nitrogen reactant and an oxygen reactant to the reaction chamber for a reactant pulse period, providing an inert gas to the reaction chamber for an inert gas pulse period, and providing a plasma power to form a plasma within the reaction chamber for a plasma pulse period. The inert gas can be provided during the plasma period and/or the plasma power can be pulsed to mitigate any damage to an underlying layer, while providing desired properties of the material layer.

## Claims

### Claim 1

A method of forming a structure, the method comprising the steps of:
providing a substrate within a reaction chamber; and
forming a material layer, wherein the step of forming the material layer comprises:
providing a silicon precursor to the reaction chamber for a silicon precursor pulse period, wherein providing the silicon precursor to the reaction chamber is ceased at an end of the silicon precursor pulse period;
after the silicon pulse period, performing a first purge during a first purge period;
providing one or more of a nitrogen reactant and an oxygen reactant to the reaction chamber during a reactant pulse period;
after the silicon precursor pulse period, providing an inert gas to the reaction chamber for an inert gas pulse period, wherein providing the inert gas is ceased at the end of the inert gas pulse period;
after the purge period, forming a plasma for a plasma period using the inert gas to thereby deposit one or more of silicon nitride and silicon oxide on a surface of the substrate; and
after the inert gas pulse period, performing a second purge during a second purge period.

### Claim 2 (depends on 1)

The method of claim 1, wherein the inert gas pulse period and the plasma period overlap, and wherein the inert gas pulse period comprises a first period before the plasma period.

### Claim 3 (depends on 1)

The method of claim 1, wherein a power during the step of forming the plasma is less than 800 W.

### Claim 4 (depends on 1)

The method of claim 1, wherein a plasma power is pulsed during the plasma period, wherein a pulse period of the plasma power is less than 100 microseconds.

### Claim 5 (depends on 1)

The method of claim 1, further comprising removing at least a portion of the material layer through a dry etch process comprising providing activated fluorine, wherein the dry etch process comprises providing NF3, and wherein a temperature of the reaction chamber during the dry etch process is between about 50° C. and about 300° C.

### Claim 6 (depends on 1)

The method of claim 1, wherein the substrate comprises a plurality of carbon features, wherein the material layer is formed on the carbon features.

### Claim 7 (depends on 1)

The method of claim 1, wherein the silicon precursor comprises a silane.

### Claim 8 (depends on 7)

The method of claim 7, wherein the silicon precursor comprises one or more of hexachlorodisilane, octachlorotrisilane, and silicon tetrachloride (SiCl4).

### Claim 9 (depends on 5)

The method of claim 5, wherein the substrate comprises one or more features, wherein the material layer is formed on the one or more features, and wherein the method further comprises an ashing process comprising removing the one or more features while leaving a second portion of the material layer remaining.

### Claim 10 (depends on 1)

The method of claim 1, wherein the silicon precursor comprises one or more of di(sec-butylamino)silane, neopentasilane, (dimethylamino)silane (DMAS), bis(ethylmethylamino)silane (BEMAS), tetrakis(dimethylamino)silane (TKDMAS), tetra(ethoxy)silane (TEOS, Si(OC2H5)4), tris(tert-butoxy)silanol (TBOS), tris(tert-pentoxy)silanol (TPSOL), and dimethyldichlorosilane (Si(OC2H5)4, and Si(CH3)2(OCH3)2).

### Claim 11 (depends on 1)

The method of claim 1, wherein the inert gas pulse period overlaps with the purge period and the plasma period.

### Claim 12 (depends on 1)

The method of claim 1, wherein the one or more of the nitrogen reactant and the oxygen reactant comprises one or more of N2, and NO.

### Claim 13 (depends on 1)

The method of claim 1, wherein the reactant pulse period overlaps with the silicon precursor pulse period and the plasma period.

### Claim 14 (depends on 13)

The method of claim 13, wherein a flowrate of the one or more of the nitrogen reactant and the oxygen reactant is reduced during the step of forming the plasma for the plasma period, relative to a flowrate of the one or more of the nitrogen reactant and the oxygen reactant prior to the step of forming the plasma.

### Claim 15 (depends on 9)

The method of claim 9, wherein the substrate comprises a first layer overlying a bulk layer comprising a semiconductor material, wherein the one or more features are disposed on the first layer, wherein the second portion of the material layer is disposed on a first portion of the first layer, wherein the first layer comprises a second portion of the first layer with no second portion of the material layer disposed on it, and wherein the method further comprises removing the second portion of the material layer and the second portion of the first layer.

### Claim 16 (depends on 1)

The method of claim 1, wherein a temperature of a susceptor during the step of forming a plasma is between about 250° C. and about 300° C.

### Claim 17 (depends on 1)

The method of claim 1, wherein the inert gas comprises one or more of neon and xenon.

### Claim 18 (depends on 1)

The method of claim 1, wherein a pressure within the reaction chamber during the step of forming is between about 1500 Pa and about 3000 Pa.

### Claim 19 (depends on 15)

A device structure formed using the method of claim 15.

### Claim 20

A system comprising:
a reaction chamber;
a silicon precursor source;
one or more of an oxygen reactant source and a nitrogen reactant source;
an inert gas source;
a flow control system;
a plasma power source;
an exhaust source; and
a controller,
wherein the controller is configured to control gas flow of a silicon precursor for a silicon precursor pulse, a nitrogen and/or oxygen reactant for a reactant pulse, and an inert gas for an inert gas pulse into the reaction chamber to form one or more of a silicon nitride layer and a silicon oxide layer on a surface of a substrate, wherein the controller is configured to:
provide the silicon precursor,
provide the nitrogen and/or oxygen reactant,
cease providing the silicon precursor,
after ceasing providing the silicon precursor, provide the inert gas,
after ceasing providing the silicon precursor, providing a plasma power,
cease providing the inert gas,
cease providing a plasma power,
after ceasing providing the inert gas, performing a purge,
wherein a plasma power is pulsed during a plasma pulse period,
wherein the nitrogen and/or oxygen reactant and the inert gas are provided to the reaction chamber for the plasma pulse period.