# US 2022/0044922 A1 · Methods for forming dielectric materials with selected polarization for semiconductor devices

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- Number: US 2022/0044922 A1
- Document ID: US20220044922A1
- Status: Published application
- Kind: A1
- Application number: 17/390,399
- Filed: 2021-07-30
- Published: 2022-02-10
- Earliest claimed: 2020-08-10
- Assignees: Tokyo Electron Limited
- Applicants: Tokyo Electron Limited
- Inventors: Dina H. Triyoso; Robert D. Clark; Steven P. Consiglio; Kandabara N. Tapily
- Web page: https://patentgrep.com/patent/US20220044922A1

## CPC

- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10D 1/684: {the dielectrics comprising multiple layers, e.g. comprising buffer layers, seed layers or gradient layers}
- H10P 14/6544: {to change the morphology of the insulating materials, e.g. transformation of an amorphous layer into a crystalline 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 14/69392: {the material containing hafnium, e.g. HfO2}
- H10P 14/69395: {the material containing zirconium, e.g. ZrO2}
- 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
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES

## Abstract

Dielectric films for semiconductor devices and methods of forming. A processing method includes forming a first film of a first dielectric material on a substrate by performing a first plurality of cycles of atomic layer deposition and, thereafter, heat-treating the first film, where a thickness of the first film is below a threshold thickness needed for spontaneous polarization in the first dielectric material. The processing method further includes forming a second film of a second dielectric material on the substrate by performing a second plurality of cycles of atomic layer deposition and, thereafter, heat-treating the second film, where a thickness of the second film is greater than the thickness of the first film, and the second film is ferroelectric or antiferroelectric. The first and second dielectric materials can include at least one metal oxide, for example zirconium oxide, hafnium oxide, or a laminate or mixture thereof.

## Claims

### Claim 1

A substrate processing method, comprising:
forming a first film of a first dielectric material on a substrate by performing a first plurality of cycles of atomic layer deposition and, thereafter, heat-treating the first film, wherein a thickness of the first film is below a threshold thickness needed for spontaneous polarization in the first dielectric material; and
forming a second film of a second dielectric material on the substrate by performing a second plurality of cycles of atomic layer deposition and, thereafter, heat-treating the second film, wherein a thickness of the second film is greater than the thickness of the first film, and the second film is ferroelectric or antiferroelectric.

### Claim 2 (depends on 1)

The method of claim 1, wherein the second film is formed on the first film.

### Claim 3 (depends on 1)

The method of claim 1, wherein the first film is formed on the second film.

### Claim 4 (depends on 1)

The method of claim 1, wherein the first and second dielectric materials include at least one metal oxide.

### Claim 5 (depends on 4)

The method of claim 4, wherein the at least one metal oxide includes zirconium oxide, hafnium oxide, or a laminate or a mixture thereof

### Claim 6 (depends on 1)

The method of claim 1, wherein the thickness of the first film is about 1.5nm, or less.

### Claim 7 (depends on 1)

The method of claim 1, wherein the first film exhibits linear polarization in the presence of an external electric field.

### Claim 8 (depends on 1)

The method of claim 1, further comprising:
repeating the forming the first film to form an additional film on the first film, wherein the additional film lacks spontaneous polarization.

### Claim 9 (depends on 1)

The method of claim 1, further comprising:
depositing a cap layer on the second film prior to heat-treating the second dielectric material.

### Claim 10 (depends on 1)

The method of claim 1, wherein heat-treating the first film and heat-treating the second film are performed at a substrate temperature between about 650° C. and about 900° C. in the presence of an inert gas.

### Claim 11

A substrate processing method, comprising:
forming a first film of a first zirconium oxide material on a substrate by performing a first plurality of cycles of atomic layer deposition and, thereafter, heat-treating the first film, wherein a thickness of the first film is below a threshold thickness needed for spontaneous polarization in the first zirconium oxide material; and
forming a second film of a second zirconium oxide material on the substrate by performing a second plurality of cycles of atomic layer deposition and, thereafter, heat-treating the second film, wherein a thickness of the second film is greater than the thickness of the first film, and the second film is ferroelectric or antiferroelectric.

### Claim 12

A semiconductor device, comprising:
a first film containing a first dielectric material on a substrate, wherein a thickness of the first film is below a threshold thickness needed for spontaneous polarization in the first dielectric material; and
a second film containing a second dielectric material on the substrate, where a thickness of the second film is greater than the thickness of the first film, and the second film is ferroelectric or antiferroelectric.

### Claim 13 (depends on 12)

The device of claim 12, wherein the second film is formed on the first film.

### Claim 14 (depends on 12)

The device of claim 12, wherein the first film is formed on the second film. Docket no. 190810US02

### Claim 15 (depends on 12)

The device of claim 12, wherein the first and second dielectric materials include at least one metal oxide.

### Claim 16 (depends on 15)

The device of claim 15, wherein the at least one metal oxide includes zirconium oxide, hafnium oxide, or a laminate or a mixture thereof

### Claim 17 (depends on 12)

The device of claim 12, wherein the thickness of the first film is about 1.5 nm, or less.

### Claim 18 (depends on 12)

The device of claim 12, wherein the first film exhibits linear polarization in the presence of an external electric field.

### Claim 19 (depends on 12)

The device of claim 12, further comprising:
an additional film on the first film, wherein the additional film lacks spontaneous polarization.

### Claim 20 (depends on 12)

The device of claim 12, wherein the first film has tetragonal (111) crystallographic orientation.