# US 12,760,416 B2 · Methods for depositing germanium films by atomic layer deposition

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

- Number: US 12,760,416 B2
- Document ID: US12760416B2
- Status: Granted
- Kind: B2
- Application number: 18/784,827
- Filed: 2024-07-25
- Published: 2025-02-20
- Granted: 2026-10-13
- Earliest claimed: 2023-08-15
- Assignees: Micron Technology, Inc.
- Applicants: Micron Technology, Inc.
- Inventors: Jean-Sebastien Materne Lehn; Francois H. Fabreguette; Timothy A. Quick
- Web page: https://patentgrep.com/patent/US12760416B2

## CPC

- C23C 16/45553: {characterized by the use of precursors specially adapted for ALD}
- C23C 16/45527: {characterized by the ALD cycle, e.g. different flows or temperatures during half-reactions, unusual pulsing sequence, use of precursor mixtures or auxiliary reactants or activations}
- H10P 14/24: using chemical vapour deposition [CVD]
- H10P 14/3411: {Silicon, silicon germanium or germanium}
- 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

Methods, systems, and devices for methods for depositing germanium films by atomic layer deposition are described. For instance, a device may expose a base material (e.g., multiple stacks of materials) to a first precursor to form a germanium compound on the base material, the first precursor including a germanium amidinate. In some examples, the germanium compound may include germanium and at least one leaving group. The device may react a second precursor with the germanium compound and may form a layer of germanium on the base material based on exposing the base material to the first precursor and reacting the second precursor with the germanium compound. In some examples, the device may remove the at least one leaving group from the germanium compound based on reacting the second precursor with the germanium compound.

## Claims

### Claim 1

A method, comprising:
reacting a first precursor with a base material to form a germanium compound on the base material, wherein the first precursor comprises germanium in a (+2) oxidation state and wherein the germanium compound comprises germanium and at least one leaving group;
reacting a second precursor with the germanium compound at a temperature below 300 degrees Celsius; and
removing the at least one leaving group from the germanium compound based at least in part on reacting the second precursor with the germanium compound, wherein removing at least one leaving group leads to a disproportionation reaction in which a first portion of germanium atoms in the germanium compound is reduced to a zero oxidation state and deposited on the base material and a second portion of the germanium atoms in the germanium compound is oxidized to a (+4) oxidation state and removed as a byproduct.

### Claim 2 (depends on 1)

The method of claim 1, wherein the first precursor comprises the chemical formula:
wherein R1, R3, R11, and R13 each comprise at least one of methyl, ethyl, propyl, butyl, secondary butyl, tertiary butyl, iso-propyl, linear alkyl, branched alkyl, or hexyl alkyl, wherein R2 and R12 each comprise at least one of hydrogen, deuterium, methyl, ethyl, propyl, butyl, secondary butyl, tertiary butyl, iso-propyl, linear alkyl, branched alkyl, hexyl alkyl, octyl alkyl, or a dialkylamino, wherein C corresponds to carbon, and wherein N corresponds to nitrogen.

### Claim 3 (depends on 2)

The method of claim 2, wherein dialkylamino comprises a dimethylamino, a diethylamino, or a methylethylamino.

### Claim 4 (depends on 2)

The method of claim 2, wherein:
each of R1, R3, R11, and R13 are ethyl; and
each of R2 and R12 are hydrogen.

### Claim 5 (depends on 2)

The method of claim 2, wherein:
each of R1, R3, R11, and R13 are ethyl; and
each of R2 and R12 are methyl.

### Claim 6 (depends on 1)

The method of claim 1, wherein:
the first precursor comprises the chemical formula X—Ge(AMD);
Ge corresponds to germanium;
AMD corresponds to amidinate; and
X comprises an alkoxide, an alkylsulfide, an alkylselenide, an alkyltelluride, an amide comprising two substituents, a hydrazide comprising three substituents, a cyanide, an isocyanide, a cyanate, an isocyanate, a thiocyanate, an isothiocyanate, a selenocyanate, an isoselenocyanate, a tellurocyanate, an isotellurocyanate, an azide, a fulminate, an isofulminate, a halide, or any combination thereof,
wherein the two substituents of the amide or the three substituents of the hydrazide are selected among an alkyl substituent, a silyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents, and a germyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents.

### Claim 7 (depends on 6)

The method of claim 6, wherein the first precursor comprises the chemical formula:
wherein R1 and R3 each comprise at least one of methyl, ethyl, propyl, butyl, secondary butyl, tertiary butyl, iso-propyl, linear alkyl, branched alkyl, or hexyl alkyl, wherein R2 comprise at least one of hydrogen, deuterium, methyl, ethyl, propyl, butyl, secondary butyl, tertiary butyl, iso-propyl, linear alkyl, branched alkyl, hexyl alkyl, octyl alkyl, wherein C corresponds to carbon, and wherein N corresponds to nitrogen.

### Claim 8 (depends on 1)

The method of claim 1, wherein:
the second precursor has the chemical formula YH;
H is a hydrogen; and
Y is an amide comprising two substituents, a hydrazide comprising three substituents, an alkoxy, a silyloxy, a trimethylsiyloxy, a germyloxy, a trimethylgermyloxy, a cyanide, an isocyanide, a cyanate, an isocyanate, a thiocyanate, an isothiocyanate, a selenocyanate, an isoselenocyanate, a tellurocyanate, an isotellurocyanate, an azide, a fulminate, an isofulminate, or a halide,
wherein the two substituents of the amide or the three substituents of the hydrazide are selected among an alkyl substituent, a silyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents, and a germyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents.

### Claim 9 (depends on 1)

The method of claim 1, wherein:
the second precursor has the chemical formula Y—ZR1R2R3;
Y is an amide comprising two substituents, a hydrazide comprising three substituents, an alkoxy, a silyloxy, a trimethylsiyloxy, a germyloxy, a trimethylgermyloxy, a cyanide, an isocyanide, a cyanate, an isocyanate, a thiocyanate, an isothiocyanate, a selenocyanate, an isoselenocyanate, a tellurocyanate, an isotellurocyanate, an azide, a fulminate, an isofulminate, or a halide;
the two substituents of the amide or the three substituents of the hydrazide are selected among an alkyl substituent, a silyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents, and a germyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents;
Z is independently selected from silicon, germanium, or tin; and
each of R1, R2, and R3 are independently selected from hydrogen, deuterium, an alkyl group, an aryl group, a —SiRaRbRc moiety, a —GeRaRbRc moiety, a —SnRaRbRc moiety, a —SiRaRbCRcRdRe moiety, a —CRaRbSiRcRdRe moiety, a —SiRaRbGeRcRdRe moiety, or a moiety comprising carbon atoms, silicon atoms, germanium atoms, or tin atoms, or any combination thereof,
wherein each atom of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof is fully saturated by having 4 bonds with respective substituents Ra through Rx or at least one other of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof,
wherein up to 10 atoms of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof are distinct from any carbon atoms, silicon atoms, germanium atoms, or tin atoms of Ra through Rx,
wherein Ra through Rx are independently selected from hydrogen, deuterium, an alkyl group, or an aryl group, and
wherein x of Rx is an index distinct from a of Ra.

### Claim 10 (depends on 1)

The method of claim 1, wherein the reacting occurs at a temperature below 250 degrees Celsius.

### Claim 11 (depends on 10)

The method of claim 10, wherein the reacting occurs at a temperature below 150 degrees Celsius.

### Claim 12

A method, comprising:
exposing a base material to a first precursor to form a germanium compound on the base material, wherein the first precursor comprises germanium bis(trimethylsilyl)amide or a germanium bis(amide) having the chemical formula (R1R2R3Z1)(R4R5R6Z2)N—Ge—N(Z3R7R8R9)(Z4R10R11R12) and comprises germanium in a (+2) oxidation state, wherein Z1, Z2, Z3, and Z4 are independently selected from germanium, tin, or silicon, and wherein R1, R2, R3, R4, R5, R6, R7, R8, R9, R10, R11, and R12 are independently selected from hydrogen, deuterium, an alkyl group, an aryl group, a —SiRaRbRc moiety, a —GeRaRbRc moiety, a —SnRaRbRc moiety, a —SiRaRbCRcRdRe moiety, a —CRaRbSiRcRdRe moiety, a —SiRaRbGeRcRdRe moiety, or a moiety comprising carbon atoms, silicon atoms, germanium atoms, or tin atoms, or any combination thereof, wherein each atom of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof is fully saturated by having 4 bonds with respective substituents Ra through Rx or at least one other of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof, wherein up to 6 atoms of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof are distinct from any carbon atoms, silicon atoms, germanium atoms, or tin atoms of Ra through Rx, wherein Ra through Rx are independently selected from hydrogen, deuterium, an alkyl group, or an aryl group, and wherein x of Rx is an index distinct from a of Ra;
reacting a second precursor with the germanium compound; and
forming a layer of germanium on the base material based at least in part on exposing the base material to the first precursor and reacting the second precursor with the germanium compound, wherein forming the layer of germanium removes at least one leaving group and leads to a disproportionation reaction in which a first portion of germanium atoms in the germanium compound is reduced to a zero oxidation state and deposited on the base material and a second portion of the germanium atoms in the germanium compound is oxidized to a (+4) oxidation state and removed as a byproduct.

### Claim 13 (depends on 12)

The method of claim 12, wherein:
the second precursor has the chemical formula YH;
H is a hydrogen; and
Y is an amide comprising two substituents, a hydrazide comprising three substituents, an alkoxy, a silyloxy, a trimethylsiyloxy, a germyloxy, a trimethylgermyloxy, a cyanide, an isocyanide, a cyanate, an isocyanate, a thiocyanate, an isothiocyanate, a selenocyanate, an isoselenocyanate, a tellurocyanate, an isotellurocyanate, an azide, a fulminate, an isofulminate, or a halide,
wherein the two substituents of the amide or the three substituents of the hydrazide are selected among an alkyl substituent, a silyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents, and a germyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents.

### Claim 14 (depends on 12)

The method of claim 12, wherein:
the second precursor has the chemical formula Y—ZR1R2R3;
Y is an amide comprising two substituents, a hydrazide comprising three substituents, an alkoxy, a silyloxy, a trimethylsiyloxy, a germyloxy, a trimethylgermyloxy, a cyanide, an isocyanide, a cyanate, an isocyanate, a thiocyanate, an isothiocyanate, a selenocyanate, an isoselenocyanate, a tellurocyanate, an isotellurocyanate, an azide, a fulminate, an isofulminate, or a halide;
the two substituents of the amide or the three substituents of the hydrazide are selected among an alkyl substituent, a silyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents, and a germyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents;
Z is independently selected from silicon, germanium, or tin; and
each of R1, R2, and R3 are independently selected from hydrogen, deuterium, an alkyl group, an aryl group, a —SiRaRbRc moiety, a —GeRaRbRc moiety, a —SnRaRbRc moiety, a —SiRaRbCRcRdRe moiety, a —CRaRbSiRcRdRe moiety, a —SiRaRbGeRcRdRe moiety, or a moiety comprising carbon atoms, silicon atoms, germanium atoms, or tin atoms, or any combination thereof,
wherein each atom of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof is fully saturated by having 4 bonds with respective substituents Ra through Rx or at least one other of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof,
wherein up to 10 atoms of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof are distinct from any carbon atoms, silicon atoms, germanium atoms, or tin atoms of Ra through Rx,
wherein Ra through Rx are independently selected from hydrogen, deuterium, an alkyl group, or an aryl group, and
wherein x of Rx is an index distinct from a of Ra.

### Claim 15

A method, comprising:
forming a plurality of stacks of materials on a substrate;
exposing the plurality of stacks of materials to a first precursor to form a germanium compound on the plurality of stacks of materials, wherein the first precursor comprises germanium in a (+2) oxidation state and wherein the germanium compound comprises a germanium and at least one leaving group;
exposing the plurality of stacks of materials to a second precursor at a temperature below 300 degrees Celsius; and
forming a layer of germanium on the plurality of stacks of materials based at least in part on exposing the plurality of stacks of materials to the first precursor and reacting the second precursor with the germanium compound at the temperature below 300 degrees Celsius, wherein forming the layer of germanium removes the at least one leaving group and leads to a disproportionation reaction in which a first portion of germanium atoms in the germanium compound is reduced to a zero oxidation state and deposited on the plurality of stacks of materials and a second portion of the germanium atoms in the germanium compound is oxidized to a (+4) oxidation state and removed as a byproduct.

### Claim 16 (depends on 15)

The method of claim 15, wherein the first precursor comprises the chemical formula:
wherein R1, R3, R11, and R13 each comprise at least one of methyl, ethyl, propyl, butyl, secondary butyl, tertiary butyl, iso-propyl, linear alkyl, branched alkyl, or hexyl alkyl, wherein R2 and R12 each comprise at least one of hydrogen, deuterium, methyl, ethyl, propyl, butyl, secondary butyl, tertiary butyl, iso-propyl, linear alkyl, branched alkyl, hexyl alkyl, octyl alkyl, or a dialkylamino, wherein C corresponds to carbon, and wherein N corresponds to nitrogen.

### Claim 17 (depends on 16)

The method of claim 16, wherein dialkylamino comprises a dimethylamino, a diethylamino, or a methylethylamino.

### Claim 18 (depends on 16)

The method of claim 16, wherein:
each of R1, R3, R11, and R13 are ethyl; and
each of R2 and R12 are hydrogen.

### Claim 19 (depends on 16)

The method of claim 16, wherein:
each of R1, R3, R11, and R13 are ethyl; and
each of R2 and R12 are methyl.

### Claim 20 (depends on 15)

The method of claim 15, wherein:
the first precursor comprises the chemical formula X—Ge(AMD);
Ge corresponds to germanium;
AMD corresponds to amidinate, and
X comprises an alkoxide, an alkylsulfide, an alkylselenide, an alkyltelluride, an amide comprising two substituents, a hydrazide comprising three substituents, a cyanide, an isocyanide, a cyanate, an isocyanate, a thiocyanate, an isothiocyanate, a selenocyanate, an isoselenocyanate, a tellurocyanate, an isotellurocyanate, an azide, a fulminate, an isofulminate, a halide, or any combination thereof,
wherein the two substituents of the amide or the three substituents of the hydrazide are selected among an alkyl substituent, a silyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents, and a germyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents.

### Claim 21 (depends on 20)

The method of claim 20, wherein the first precursor comprises the chemical formula:
wherein R1 and R3 each comprise at least one of methyl, ethyl, propyl, butyl, secondary butyl, tertiary butyl, iso-propyl, linear alkyl, branched alkyl, or hexyl alkyl, wherein R2 comprise at least one of hydrogen, deuterium, methyl, ethyl, propyl, butyl, secondary butyl, tertiary butyl, iso-propyl, linear alkyl, branched alkyl, hexyl alkyl, octyl alkyl, wherein C corresponds to carbon, and wherein N corresponds to nitrogen.

### Claim 22 (depends on 15)

The method of claim 15, wherein the second precursor has the chemical formula YH, wherein His a hydrogen, and wherein Y is an amide comprising two substituents, a hydrazide comprising three substituents, an alkoxy, a silyloxy, a trimethylsiyloxy, a germyloxy, a trimethylgermyloxy, a cyanide, an isocyanide, a cyanate, an isocyanate, a thiocyanate, an isothiocyanate, a selenocyanate, an isoselenocyanate, a tellurocyanate, an isotellurocyanate, an azide, a fulminate, an isofulminate, or a halide, wherein the two substituents of the amide or the three substituents of the hydrazide are selected among an alkyl substituent, a silyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents, and a germyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents.

### Claim 23 (depends on 15)

The method of claim 15, wherein the second precursor has the chemical formula Y—ZR1R2R3, wherein Y is an amide comprising two substituents, a hydrazide comprising three substituents, an alkoxy, a silyloxy, a trimethylsiyloxy, a germyloxy, a trimethylgermyloxy, a cyanide, an isocyanide, a cyanate, an isocyanate, a thiocyanate, an isothiocyanate, a selenocyanate, an isoselenocyanate, a tellurocyanate, an isotellurocyanate, an azide, a fulminate, an isofulminate, or a halide, wherein the two substituents of the amide or the three substituents of the hydrazide are selected among an alkyl substituent, a silyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents, and a germyl substituent comprising one or more hydrogen, deuterium, or alkyl substituents, wherein Z is independently selected from silicon, germanium, or tin, and wherein each of R1, R2, and R3 are independently selected from hydrogen, deuterium, an alkyl group, an aryl group, a —SiRaRbRc moiety, a —GeRaRbRc moiety, a —SnRaRbRc moiety, a —SiRaRbCRcRdRe moiety, a —CRaRbSiRcRdRe moiety, a —SiRaRbGeRcRdRe moiety, or a moiety comprising carbon atoms, silicon atoms, germanium atoms, or tin atoms, or any combination thereof, wherein each atom of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof is fully saturated by having 4 bonds with respective substituents Ra through Rx or at least one other of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof, wherein up to 10 atoms of the carbon atoms, silicon atoms, germanium atoms, tin atoms, or any combination thereof are distinct from any carbon atoms, silicon atoms, germanium atoms, or tin atoms of Ra through Rx, wherein Ra through Rx are independently selected from hydrogen, deuterium, an alkyl group, or an aryl group, and wherein x of Rx is an index distinct from a of Ra.

### Claim 24 (depends on 15)

The method of claim 15, wherein the reacting occurs at a temperature below 250 degrees Celsius.

### Claim 25 (depends on 24)

The method of claim 24, wherein the reacting occurs at a temperature below 150 degrees Celsius.