# US 10,121,652 B1 · Formation of metal oxide layer

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 10,121,652 B1
- Document ID: US10121652B1
- Status: Granted
- Kind: B1
- Application number: 15/615,884
- Filed: 2017-06-07
- Granted: 2018-11-06
- Earliest claimed: 2017-06-07
- Assignees: NXP USA, Inc.
- Applicants: NXP USA, Inc.
- Inventors: Rama I. Hegde
- Web page: https://patentgrep.com/patent/US10121652B1

## CPC

- C23C 16/4404: {Coatings or surface treatment on the inside of the reaction chamber or on parts thereof}
- C23C 16/405: {of refractory metals or yttrium}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/6516: {of treatments performed after formation of the materials}
- H10P 14/6546: {to change the surface groups of the insulating materials}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/69392: {the material containing hafnium, e.g. HfO2}
- H10P 14/69395: {the material containing zirconium, e.g. ZrO2}
- H10P 14/69396: {the material containing at least one rare earth metal element, e.g. oxides of lanthanides, scandium or yttrium}
- H10P 14/69397: {the material containing two or more metal elements}
- 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)
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

A method for forming a metal oxide layer on a wafer. In some embodiments, the method includes forming a layer of a metal oxyhalide on a wafer followed by an anneal of the wafer which removes halogens from the layer to form a layer of metal oxide. A semiconductor device may be formed from the wafer.

## Claims

### Claim 1

A method comprising:
forming a layer of metal oxyhalide on a wafer;
after the forming, annealing the wafer to remove halogens from the layer;
forming a semiconductor device from the wafer.

### Claim 2 (depends on 1)

The method of claim 1 wherein the metal oxyhalide includes hafnium and the layer include hafnium.

### Claim 3 (depends on 1)

The method of claim 1 wherein the metal oxyhalide includes zirconium.

### Claim 4 (depends on 1)

The method of claim 1 wherein the metal oxyhalide includes lanthanum.

### Claim 5 (depends on 1)

The method of claim 1 wherein the metal oxyhalide includes chlorine and the annealing includes removing chlorine from the layer.

### Claim 6 (depends on 1)

The method of claim 1 wherein the metal oxyhalide s includes bromine and the annealing includes removing bromine form the layer.

### Claim 7 (depends on 1)

The method of claim 1 wherein the metal oxyhalide includes iodine and the annealing includes removing iodine form the layer.

### Claim 8 (depends on 1)

The method of claim 1 wherein the semiconductor device is characterized as a transistor and a portion of the layer is characterized as a gate dielectric layer of the transistor.

### Claim 9 (depends on 1)

The method of claim 1 wherein the layer includes hafnium zirconate after the annealing.

### Claim 10 (depends on 1)

The method of claim 1 wherein the forming the layer is includes flowing a metal oxyhalide material in a gaseous form into a wafer processing chamber for deposition on the wafer in the wafer processing chamber.

### Claim 11 (depends on 10)

The method of claim 10 wherein prior to the flowing the metal oxyhalide in a gaseous form, heating the metal oxyhalide material to a temperature in a range 35-250 C.

### Claim 12 (depends on 11)

The method of claim 11 further comprising heating the wafer to a temperature in a range of 250 C to 450 C during the forming the layer.

### Claim 13 (depends on 1)

The method of claim 1 wherein the layer is formed on a layer of semiconductor oxide material of the wafer.

### Claim 14 (depends on 1)

The method of claim 1 wherein the annealing includes heating the wafer to a temperature in a range of 350 C to 1100 C in the presence of an inert gas.

### Claim 15 (depends on 1)

The method of claim 1 wherein the forming the layer includes flowing a metal oxyhalide material in a gaseous form in a chamber, wherein the annealing is performed while the wafer is in the chamber, the method further comprising after the flowing and before the annealing, purging the chamber with an inert gas, wherein the wafer is in the chamber during the purging.

### Claim 16 (depends on 15)

The method of claim 15 wherein the forming the layer includes:
flowing a metal oxyhalide material in a gaseous form in the chamber for a second time after the purging;
purging the chamber for a second time after flowing the metal oxyhalide material in gaseous form for a second time, wherein the wafer is in the chamber during the purging for a second time.

### Claim 17 (depends on 16)

The method of claim 16 wherein the flowing the metal oxyhalide material in the chamber includes flowing a metal oxyhalide material with a first metal, wherein the flowing a metal oxyhalide material in the chamber for a second time includes a flowing a metal oxyhalide material with a second metal different than the first metal.

### Claim 18 (depends on 17)

The method of claim 17 wherein the first metal is one of zirconium and hafnium and the second metal is the other of zirconium and hafnium.

### Claim 19

A method comprising:
forming a layer of metal oxyhalide on a wafer in a chamber, the forming a layer comprising performing a sequence of operations a plurality of times, the sequence of operations comprising:
flowing a metal oxyhalide material in a gaseous form into the chamber with the wafer to deposit metal oxyhalide on the wafer;
after the flowing, purging the chamber with an inert gas;
after the forming the layer, annealing the wafer to remove halogens from the layer, wherein after the annealing, the layer includes a metal oxide;
forming a semiconductor device with the layer including the metal oxide.

### Claim 20 (depends on 19)

The method of claim 19 wherein the semiconductor device is characterized as a transistor and a portion of the layer is characterized as a gate dielectric layer of the transistor.