# US 10,872,763 B2 · Treatments to enhance material structures

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- Number: US 10,872,763 B2
- Document ID: US10872763B2
- Status: Granted
- Kind: B2
- Application number: 16/403,312
- Filed: 2019-05-03
- Published: 2020-11-05
- Granted: 2020-12-22
- Earliest claimed: 2019-05-03
- Assignees: Applied Materials, Inc.
- Applicants: Applied Materials, Inc.
- Inventors: David Chu; Steven C. Hung; Malcolm J. Bevan; Charles Chu; Tatsuya E. Sato; Shih-Chung Chen; Patricia M. Liu; Johanes Swenberg
- Web page: https://patentgrep.com/patent/US10872763B2

## CPC

- H10D 64/01344: {in a nitrogen-containing ambient, e.g. N2O oxidation}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10D 64/01332: {Making the insulator}
- H10D 64/0134: {with a treatment, e.g. annealing, after the formation of the insulator and before the formation of the conductor}
- H10D 64/01342: {by deposition, e.g. evaporation, ALD or laser deposition (H10D64/01344 takes precedence)}
- H10D 64/685: {being perpendicular to the channel plane}
- H10D 64/691: {comprising metallic compounds, e.g. metal oxides or metal silicates (insulators comprising nitrogen H10D64/693)}
- H10D 64/693: {the insulator comprising nitrogen, e.g. nitrides, oxynitrides or nitrogen-doped materials}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/6512: {by exposure to a gas or vapour}
- H10P 14/6519: {the substance being oxygen}
- H10P 14/6524: {the substance being nitrogen}
- H10P 14/6526: {introduced into an oxide material, e.g. changing SiO to SiON}
- H10P 14/6529: {by exposure to a gas or vapour}
- H10P 14/6532: {by exposure to a plasma}
- H10P 14/6938: {the material containing at least one metal element, e.g. metal oxides, metal oxynitrides or metal oxycarbides}
- H10P 14/69392: {the material containing hafnium, e.g. HfO2}
- H10P 14/6903: {containing silicon}
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

Processing methods may be performed to produce semiconductor structures that may include a high-k dielectric material. The methods may include delivering a nitrogen-containing precursor or an oxygen-containing precursor to a substrate contained in a semiconductor processing chamber. The methods may include forming reactive ligands on an exposed surface of the substrate with the nitrogen-containing precursor or the oxygen-containing precursor. The methods may also include forming a high-k dielectric material overlying the substrate.

## Claims

### Claim 1

A method of forming a semiconductor structure, the method comprising:
delivering a nitrogen-containing precursor or an oxygen-containing precursor to a substrate contained in a semiconductor processing chamber, wherein the nitrogen-containing precursor comprises a first nitrogen-containing precursor and the oxygen-containing precursor comprises a first oxygen-containing precursor;
introducing reactive ligands on an exposed surface of the substrate with the nitrogen-containing precursor or the oxygen-containing precursor;
forming a high-k dielectric material overlying the substrate; and
treating the high-k dielectric material with a second nitrogen-containing precursor or a second oxygen-containing precursor, and wherein the treating incorporates nitrogen into the high-k dielectric material in an amount that is less than or about 10 atomic %.

### Claim 2 (depends on 1)

The method of forming a semiconductor structure of claim 1, wherein the second nitrogen-containing precursor comprises a thermally-activated nitrogen-containing precursor or a plasma-enhanced nitrogen-containing precursor.

### Claim 3 (depends on 1)

The method of forming a semiconductor structure of claim 1, further comprising, subsequent forming the high-k dielectric material, performing a thermal anneal.

### Claim 4 (depends on 1)

The method of forming a semiconductor structure of claim 1, wherein the forming a high-k dielectric material comprises performing an atomic layer deposition process.

### Claim 5 (depends on 1)

The method of forming a semiconductor structure of claim 1, wherein the nitrogen-containing precursor comprises ammonia.

### Claim 6 (depends on 1)

The method of forming a semiconductor structure of claim 1, wherein the substrate comprises a silicon-containing material.

### Claim 7 (depends on 1)

The method of forming a semiconductor structure of claim 1, wherein the high-k dielectric material comprises at least one element selected from the group consisting of hafnium, zirconium, silicon, lanthanum, aluminum, titanium, and strontium.

### Claim 8 (depends on 5)

The method of forming a semiconductor structure of claim 5, wherein the substrate is maintained at a temperature above or about 300° C. while delivering the ammonia.

### Claim 9

A method of forming a semiconductor structure, the method comprising:
pre-treating a substrate by contacting the substrate with a nitrogen-containing precursor or an oxygen-containing precursor;
forming a high-k dielectric material overlying the pre-treated substrate in a first semiconductor processing chamber housing the pre-treated substrate;
transferring the substrate to a second semiconductor processing chamber; and
post-treating the high-k dielectric material, wherein the post-treating comprises exposing the substrate and high-k dielectric material to an oxygen-containing precursor or a nitrogen-containing precursor, and wherein the post-treating incorporates nitrogen into the high-k dielectric material in an amount that is less than or about 10 atomic %.

### Claim 10 (depends on 9)

The method of forming a semiconductor structure of claim 9, further comprising, subsequent the post-treating, annealing the high-k dielectric material.

### Claim 11 (depends on 9)

The method of forming a semiconductor structure of claim 9, wherein transferring the substrate to a second semiconductor processing chamber comprises transferring the substrate between two chambers on a multi-chamber processing system, and wherein the transferring is performed while maintaining vacuum conditions on the multi-chamber processing system.

### Claim 12 (depends on 9)

The method of forming a semiconductor structure of claim 9, wherein the nitrogen-containing precursor for the pre-treating comprises ammonia.

### Claim 13 (depends on 9)

The method of forming a semiconductor structure of claim 9, wherein the substrate comprises a silicon-containing material, and wherein an exposed surface layer of the silicon-containing material comprises silicon.

### Claim 14 (depends on 9)

The method of forming a semiconductor structure of claim 9, wherein the high-k dielectric material comprises at least one element selected from the group consisting of hafnium, zirconium, silicon, lanthanum, aluminum, titanium, and strontium.

### Claim 15 (depends on 12)

The method of forming a semiconductor structure of claim 12, wherein the substrate is maintained at a temperature below about 700° C. while the ammonia is delivered to the substrate, and wherein the pre-treating is performed for less than or about one minute.

### Claim 16 (depends on 13)

The method of forming a semiconductor structure of claim 13, wherein the silicon-containing material comprises silicon oxide.