# US 12,000,062 B1 · Method for the deposition of monocrystalline or polycrystalline tin alloys on crystallographcially mis-matched or amorphous substrates

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- Number: US 12,000,062 B1
- Document ID: US12000062B1
- Status: Granted
- Kind: B1
- Application number: 16/526,015
- Filed: 2019-07-30
- Granted: 2024-06-04
- Earliest claimed: 2019-07-30
- Assignees: The United States of America as represented by the Secretary of the Air Force
- Applicants: Government of the United States, as represented by the Secretary of the Air Force
- Inventors: Bruce B. Claflin; Gordon J. Grzybowski; Arnold M. Kiefer
- Web page: https://patentgrep.com/patent/US12000062B1

## CPC

- C30B 25/105: {by irradiation or electric discharge}
- C23C 16/06: characterised by the deposition of metallic material
- C23C 16/08: from metal halides
- C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)}
- C23C 16/505: using radio frequency discharges
- C30B 25/165: {the flow of the reactive gases}
- C30B 25/18: characterised by the substrate
- C30B 29/52: Alloys
- H10P 14/24: using chemical vapour deposition [CVD]
- H10P 14/2901: {Materials}
- H10P 14/3412: {including tin}
- H10P 14/3456: {Polycrystalline}
- H10P 14/3458: {Monocrystalline}
- H10P 14/3411: {Silicon, silicon germanium or germanium}
- C30B: SINGLE-CRYSTAL GROWTH (by using ultra-high pressure, e.g. for the formation of diamonds, B01J3/06); UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL (zone-refining of metals or alloys C22B); PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (casting of metals, casting of other substances by the same processes or devices B22D; working of plastics B29; modifying the physical structure of metals or alloys C21D, C22F); SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE (for producing semiconductor devices or parts thereof H10); APPARATUS THEREFOR
- 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 depositing a monocrystalline or polycrystalline tin alloy layer on an amorphous or crystallographically mis-matched substrate. The method includes selecting tin halide as the tin source; selecting an alloying metal precursor from germanium precursors, silicon precursors, and mixtures of germanium and silicon precursors; selecting a substrate from amorphous substrates and crystallographically mis-matched substrates; generating an inert gas plasma in a remote plasma generation reactor; contacting the inert gas plasma with the tin halide to provide an activated tin halide flow stream; contacting the inert gas plasma with the alloying metal precursor to provide an activated alloying metal flow stream; directing the activated tin halide flow stream and activated alloying metal flow stream to an alloy deposition chamber physically remote from the plasma chamber; and depositing the monocrystalline or polycrystalline tin alloy layer on the substrate in the deposition chamber.

## Claims

### Claim 1

A method for depositing a monocrystalline or polycrystalline tin alloy layer on a substrate, comprising the steps of:
selecting tin halide as a tin source;
selecting an alloying metal precursor from the group consisting of disilane, trisilane, digermane, trigermane, and a mixture of two or more of the foregoing;
selecting a substrate from the group consisting of amorphous substrates and crystallographically mis-matched substrates, wherein the substrate is selected from the group consisting of TiN, and TiW;
generating an inert gas plasma in a remote plasma generation reactor, wherein the inert gas is xenon;
contacting the inert gas plasma with the tin halide to provide an activated tin halide flow stream;
contacting the inert gas plasma with the alloying metal precursor to provide an activated alloying metal flow stream;
directing the activated tin halide flow stream and activated alloying metal flow stream to an alloy deposition chamber physically remote from a plasma chamber; and
depositing the monocrystalline or polycrystalline tin alloy layer on the substrate in the alloy deposition chamber.

### Claim 2 (depends on 1)

The method of claim 1, wherein the substrate is maintained at a temperature ranging from about 250° to about 450° during the deposition process.

### Claim 3 (depends on 1)

The method of claim 1, wherein the deposition chamber is maintained at a pressure ranging from about 100 mTorr to about 10 Torr during the deposition process.

### Claim 4 (depends on 1)

The method of claim 1, wherein the tin alloy is selected from the group consisting of Si1−xSnx, Ge1−xSnx, and Si1−x−yGexSny, wherein x and y are greater than 0 and less than 1.

### Claim 5 (depends on 1)

The method of claim 1, wherein the tin halide is SnCl2.

### Claim 6 (depends on 1)

The method of claim 1, wherein a weight ratio of activated alloying metal precursor to activated tin halide flow ranges from about 0.5:1 to about 20:1.

### Claim 7

A method for depositing a monocrystalline or polycrystalline tin alloy layer on a substrate, comprising the steps of:
selecting SnCl4 as a tin source;
selecting an alloying metal precursor from the group consisting of disilane, trisilane, digermane, trigermane, and a mixture of two or more of the foregoing;
selecting a substrate from the group consisting of TiN, and TiW;
generating a helium plasma in a remote plasma generation reactor;
contacting the helium plasma with the SnCl4 to provide an activated SnCl4 flow stream;
contacting the helium plasma with the alloying metal precursor to provide an activated alloying metal flow stream;
directing the activated SnCl4 flow stream and activated alloying metal flow stream to an alloy deposition chamber physically remote from a plasma chamber; and
depositing the monocrystalline or polycrystalline tin alloy layer on the substrate in the alloy deposition chamber,
wherein a weight ratio of activated alloying metal precursor to activated SnCl4 flow ranges from about 0.5:1 to about 20:1.

### Claim 8 (depends on 7)

The method of claim 7, wherein the substrate is maintained at a temperature ranging from about 250° to about 450° during the deposition process.

### Claim 9 (depends on 7)

The method of claim 7, wherein the deposition chamber is maintained at a pressure ranging from about 100 mTorr to about 10 Torr during the deposition process.

### Claim 10 (depends on 7)

The method of claim 7, wherein the tin alloy is selected from the group consisting of Si1−xSnx, Ge1−xSnx, and Si1−x−yGexSny, wherein x and y are greater than 0 and less than 1.