# US 8,541,276 B2 · Methods of forming an insulating metal oxide

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- Number: US 8,541,276 B2
- Document ID: US8541276B2
- Status: Granted
- Kind: B2
- Application number: 13/442,140
- Filed: 2012-04-09
- Published: 2012-08-02
- Granted: 2013-09-24
- Earliest claimed: 2004-08-31
- Assignees: Micron Technology, Inc.
- Applicants: Kie Y. Ahn; Leonard Forbes
- Inventors: Kie Y. Ahn; Leonard Forbes
- Web page: https://patentgrep.com/patent/US8541276B2

## CPC

- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- C23C 16/0281: {of metallic sub-layers (C23C16/029 takes precedence)}
- C23C 16/40: Oxides
- C23C 16/45531: {specially adapted for making ternary or higher compositions}
- H10D 64/0135: {by deposition of a layer, e.g. metal, metal compound or polysilicon, followed by transformation thereof into the insulator}
- 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)}
- H10P 14/6529: {by exposure to a gas or vapour}
- H10P 14/6314: {of a metallic layer}
- H10P 14/662: {Laminate layers, e.g. stacks of alternating high-k metal oxides (adhesion layers or buffer layers H10P14/6508, H10P14/6548)}
- H10P 14/69391: {the material containing aluminium, e.g. Al2O3}
- H10P 14/69394: {the material containing titanium, e.g. TiO2}
- H10P 14/69397: {the material containing two or more metal elements}
- 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)
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES

## Abstract

A dielectric containing an insulating metal oxide film having multiple metal components and a method of fabricating such a dielectric produce a reliable dielectric for use in a variety of electronic devices. Embodiments include a titanium aluminum oxide film structured as one or more monolayers. Embodiments also include structures for capacitors, transistors, memory devices, and electronic systems with dielectrics containing a titanium aluminum oxide film.

## Claims

### Claim 1

A method comprising:
forming a dielectric containing an insulating metal oxide using a reaction sequence ALD process, the insulating metal oxide being an oxide compound containing multiple different metals and containing titanium, aluminum, and oxide, including forming the insulating metal oxide by conducting cycles of a monolayer or partial monolayer sequencing process in a multiple layer process with one or more oxygen annealings performed between the cycles of the monolayer or partial monolayer sequencing process such that a first titanium aluminum oxide layer in the multiple layer process is titanium rich and is converted to an oxide layer by one of the oxygen annealings, the annealings being different from the monolayer or partial monolayer sequencing process, a second titanium aluminum oxide layer having a stoichiometry different from being titanium rich, and a nitride layer.

### Claim 2 (depends on 1)

The method of claim 1, wherein conducting cycles of the monolayer or partial monolayer sequencing process comprises conducting cycles of a self-limiting monolayer or partial monolayer sequencing process.

### Claim 3 (depends on 1)

The method of claim 1, wherein the one or more oxygen annealings performed includes using atomic oxygen.

### Claim 4 (depends on 1)

The method of claim 1, wherein the one or more oxygen annealings performed includes using molecular oxygen.

### Claim 5 (depends on 1)

The method of claim 1, wherein forming the insulating metal oxide includes forming a bimetal oxide.

### Claim 6 (depends on 1)

The method of claim 1, wherein conducting cycles of the monolayer or partial monolayer sequencing process in the multiple layer process includes first forming a layer of only one metal species of the multiple different metals, converting the layer of the only one metal species to a layer of an oxide of the metal species by one of the oxygen annealings, and further processing with the multiple different metals to form a composition of the insulating metal oxide containing multiple different metals.

### Claim 7 (depends on 1)

The method of claim 1, wherein the method includes forming silicon oxide having a thickness of at most four monolayers as an interface between the dielectric and a structure on which the dielectric is disposed.

### Claim 8 (depends on 1)

The method of claim 1, wherein forming the dielectric includes forming the dielectric structured substantially as the insulating metal oxide.

### Claim 9 (depends on 1)

The method of claim 1, wherein forming the dielectric includes forming the dielectric structured as a nanolaminate.

### Claim 10 (depends on 1)

The method of claim 1, wherein forming the dielectric structured as a nanolaminate dielectric includes forming the dielectric structured as a nanolaminate having an insulating metal oxide different from the insulating metal oxide containing the multiple different metals.

### Claim 11 (depends on 1)

The method of claim 1, wherein forming the insulating metal oxide includes forming the insulating metal oxide rich in one species of the multiple different metals.

### Claim 12 (depends on 1)

The method of claim 1, wherein forming the dielectric includes forming the dielectric structured in a memory device.

### Claim 13

A method comprising:
forming a dielectric containing titanium aluminum oxide (TiAlOx) with a reaction sequence ALD process, including forming the titanium aluminum oxide by conducting cycles of a monolayer or partial monolayer sequencing process in a multiple layer process with one or more oxygen annealings performed between the cycles of the monolayer or partial monolayer sequencing process such that a first layer in the multiple layer process is formed of one or more of titanium or aluminum, a second layer is formed of one or more of titanium or aluminum, and a third layer is formed of nitride wherein the first layer is titanium rich and the second layer has as stoichiometry that is different from being titanium rich, at least the first and second layers converted to an oxide layer by one of the oxygen annealings, the annealings being different from the monolayer or partial monolayer sequencing process.

### Claim 14 (depends on 13)

The method of claim 13, wherein conducting cycles of the monolayer or partial monolayer sequencing process in the multiple layer process includes first forming a layer of titanium without aluminum, converting the layer of the titanium to a layer of an oxide of titanium by one of the oxygen annealings, and further processing with aluminum to form a composition of the titanium aluminum oxide.

### Claim 15 (depends on 13)

The method of claim 13, wherein conducting cycles of the monolayer or partial monolayer sequencing process in the multiple layer process includes first forming a first layer having only titanium and aluminum as metals in the first layer, converting the first layer to a layer of an oxide of titanium and aluminum by one or more of the oxygen annealings, and further processing with aluminum and titanium using the monolayer or partial monolayer sequencing process to form a composition of the titanium aluminum oxide.

### Claim 16 (depends on 13)

The method of claim 13, wherein forming the dielectric includes forming an insulating metal oxide different from the titanium aluminum oxide.

### Claim 17 (depends on 16)

The method of claim 16, wherein forming the insulating metal oxide different from the titanium aluminum oxide includes forming titanium oxide (TiOx).

### Claim 18

A method comprising:
forming a memory array having a dielectric containing titanium aluminum oxide (TiAlOx) with a reaction sequence ALD process, including forming the titanium aluminum oxide by conducting cycles of a monolayer or partial monolayer sequencing process in a multiple layer process with one or more oxygen annealings performed between the cycles of the monolayer or partial monolayer sequencing process such that a first layer in the multiple layer process is formed of one or more of titanium or aluminum, a second layer formed of one or more of titanium or aluminum, and a third layer formed of nitride wherein the first layer is titanium rich and the second layer has as stoichiometry that is different from being titanium rich, at least the first and second layers converted to an oxide layer by one of the oxygen annealings, the annealings being different from the monolayer or partial monolayer sequencing process.

### Claim 19 (depends on 18)

The method of claim 18, wherein forming the memory array structured as part of a flash memory device including forming the dielectric as nanolaminate having a titanium oxide film and a titanium aluminum oxide film.

### Claim 20 (depends on 18)

The method of claim 18, wherein the method includes forming the dielectric as a gate insulator of a transistor in the memory array.

### Claim 21 (depends on 18)

The method of claim 18, wherein the method includes forming the dielectric as an inter-gate insulator between and contacting a floating gate and a control gate of a transistor in the memory array.

### Claim 22 (depends on 18)

The method of claim 18, wherein the method includes forming the dielectric as a capacitor dielectric of a capacitor in the memory array.

### Claim 23 (depends on 18)

The method of claim 18, wherein forming the dielectric includes forming one or more of a nitride or insulating metal oxide, the insulating metal oxide different from the titanium aluminum oxide.