# US 10,308,673 B2 · Synthesis and use of precursors for ALD of tellurium and selenium thin films

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- Number: US 10,308,673 B2
- Document ID: US10308673B2
- Status: Granted
- Kind: B2
- Application number: 15/711,690
- Filed: 2017-09-21
- Published: 2018-03-15
- Granted: 2019-06-04
- Earliest claimed: 2008-04-25
- Assignees: ASM International N.V.
- Applicants: Asm International N.V.
- Inventors: Viljami Pore; Timo Hatanpaa; Mikko Ritala; Markku Leskelä
- Web page: https://patentgrep.com/patent/US10308673B2

## CPC

- C07F 11/005: {compounds without a metal-carbon linkage}
- C23C 16/306: {AII BVI compounds, where A is Zn, Cd or Hg and B is S, Se or Te}
- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- H10N 70/023: {by chemical vapor deposition, e.g. MOCVD, ALD}
- H10N 70/231: {based on solid-state phase change, e.g. between amorphous and crystalline phases, Ovshinsky effect}
- H10N 70/826: {adapted for essentially vertical current flow, e.g. sandwich or pillar type devices}
- H10N 70/8825: {Selenides, e.g. GeSe}
- H10N 70/8828: {Tellurides, e.g. GeSbTe}
- H10P 14/24: using chemical vapour deposition [CVD]
- H10P 14/3431: {Selenides}
- H10P 14/3432: {Tellurides}
- Y02P 20/582: Recycling of unreacted starting or intermediate materials
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)
- 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)
- H10N: ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- Y02P: CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS

## Abstract

Atomic layer deposition (ALD) processes for forming Te-containing thin films, such as Sb—Te, Ge—Te, Ge—Sb—Te, Bi—Te, and Zn—Te thin films are provided. ALD processes are also provided for forming Se-containing thin films, such as Sb—Se, Ge—Se, Ge—Sb—Se, Bi—Se, and Zn—Se thin films are also provided. Te and Se precursors of the formula (Te,Se)(SiR1R2R3)2 are preferably used, wherein R1, R2, and R3 are alkyl groups. Methods are also provided for synthesizing these Te and Se precursors. Methods are also provided for using the Te and Se thin films in phase change memory devices.

## Claims

### Claim 1

A process for forming a Te and/or Se containing thin film on a substrate in a reaction chamber comprising a plurality of deposition cycles, each cycle comprising in order:
contacting the substrate with a first vapor phase reactant comprising a metal halide, wherein the metal in the metal halide is selected from the group consisting of Sb, Ge, Bi, Zn, Cu, In, Ag, Au, Pb, Cd, and Hg;
removing excess first reactant with the aid of a purge gas;
contacting the substrate with a second vapor phase reactant, wherein the second reactant comprises Te(SiR1R2R3)2 or Se(SiR1R2R3), wherein R1, R2, and R3 are alkyl groups with one or more carbon atoms; and
removing excess second reactant with the aid of a purge gas.

### Claim 2 (depends on 1)

The method of claim 1, wherein the first reactant comprises SbCl3.

### Claim 3 (depends on 1)

The method of claim 1, wherein the first reactant comprises GeBr2 or GeCl2—C4H8O2.

### Claim 4 (depends on 1)

The method of claim 1, wherein the first reactant comprises GeX2, wherein X is a halogen.

### Claim 5 (depends on 1)

The method of claim 1, wherein the second reactant is Te(SiEt3)2, Te(SiMe3)2, Se(SiEt3)2, or Se(SiMe3)2.

### Claim 6 (depends on 1)

The method of claim 1, wherein the Te or Se in the second reactant has an oxidation state of −2.

### Claim 7 (depends on 1)

The method of claim 1, wherein the thin film comprises one or more of Sb—Te, Ge—Te, Ge—Sb—Te, Bi—Te, or Zn—Te doped with one or more dopants comprising O, N, Si, S, In, Ag, Sn, Au, As, Bi, Zn, Se, Te, Ge, Sb, and Mn.

### Claim 8 (depends on 1)

The method of claim 1, wherein the thin film comprises Sb—Te.

### Claim 9 (depends on 8)

The method of claim 8, wherein the plurality of deposition cycles comprises a plurality of Sb—Te deposition cycles in which the first reactant comprises Sb and the second reactant comprises Te.

### Claim 10 (depends on 1)

The method of claim 1, wherein the thin film comprises Ge—Te.

### Claim 11 (depends on 1)

The method of claim 1, wherein the plurality of deposition cycles comprises a plurality of Ge—Te deposition cycles in which the first reactant comprises Ge and the second reactant comprises Te.

### Claim 12 (depends on 1)

The method of claim 1, wherein the thin film comprises Ge—Sb—Te.

### Claim 13 (depends on 12)

The method of claim 12, wherein the plurality of deposition cycles comprises a plurality of Sb—Te deposition cycles in which the first reactant comprises Sb and the second reactant comprises Te and a plurality of Ge—Te deposition cycles in which the first reactant comprises Ge and the second reactant comprises Te.

### Claim 14 (depends on 13)

The method of claim 13, wherein the Ge—Te deposition cycles and Sb—Te deposition cycles are performed at a 1:1 ratio.

### Claim 15 (depends on 1)

The method of claim 1, wherein the first reactant comprises Bi and the deposited film comprises Bi—Te.

### Claim 16 (depends on 1)

The method of claim 1, wherein the first reactant comprises Zn and the deposited film comprises Zn—Te.

### Claim 17 (depends on 1)

The method of claim 1, wherein the first reactant comprises Bi and the deposited film comprises Bi—Se.

### Claim 18 (depends on 1)

The method of claim 1, wherein the first reactant comprises Cu and the deposited film comprises Cu—Se.

### Claim 19 (depends on 1)

The method of claim 1, wherein the thin film is part of a phase change memory device.

### Claim 20 (depends on 1)

The method of claim 1, wherein the thin film forms part of a solar cell absorber.