# US 2019/0378916 A1 · Method of forming a germanium oxynitride film

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- Number: US 2019/0378916 A1
- Document ID: US20190378916A1
- Status: Published application
- Kind: A1
- Application number: 16/453,249
- Filed: 2019-06-26
- Published: 2019-12-12
- Earliest claimed: 2016-05-02
- Assignees: ASM IP Holding B.V.
- Applicants: ASM IP Holding B.V.
- Inventors: Fu Tang; Qi Xie; Jan Willem Maes; Xiaoqiang Jiang; Michael Eugene Givens
- Web page: https://patentgrep.com/patent/US20190378916A1

## CPC

- H10D 30/0413: {of FETs having charge-trapping gate insulators, e.g. MNOS transistors}
- H10P 14/6339: {deposition by cyclic CVD, e.g. ALD, ALE or pulsed CVD}
- H10P 14/668: {the materials being characterised by the deposition precursor materials}
- H10P 14/68: Organic materials, e.g. photoresists
- H10D 64/037: {comprising charge-trapping insulators}
- H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10

## Abstract

A method for forming layers suitable for a V-NAND stack is disclosed. Specifically, the method may include multiple cycles for forming an oxide and a nitride in order to form an oxynitride layer.

## Claims

### Claim at position 1

1-17. (canceled)

### Claim 18

A method of forming a germanium oxynitride film comprising:
providing a substrate for processing in a reaction chamber;
using a germanium precursor and an oxygen precursor, performing an oxide cycle for deposing an oxide comprising germanium onto the substrate; and
before or after the performing the oxide cycle, using a germanium precursor and a nitrogen precursor, performing a nitride cycle for deposing a nitride comprising germanium onto the substrate;
wherein the performing the oxide cycle and the performing the nitride cycle are repeated as desired in order to form the germanium oxynitride film of a desired thickness and stoichiometry, and
wherein the oxygen precursor and the nitrogen precursor are different.

### Claim 19 (depends on 18)

The method of claim 18, wherein the performing the oxide cycle takes place at a temperature ranging between 100° C. and 500° C. or between 100° C. and 300° C.

### Claim 20 (depends on 18)

The method of claim 18, wherein the performing the oxide cycle has a duration ranging between 0.1 s and 100 s or between 1 s and 60 s.

### Claim 21 (depends on 18)

The method of claim 18, wherein the performing the oxide cycle comprises:
pulsing the germanium precursor;
purging an excess of the germanium precursor;
pulsing the oxygen precursor; and
purging an excess of the oxygen precursor.

### Claim 22 (depends on 18)

The method of claim 18, wherein the germanium precursor comprises at least one of:
tetrakis(dimethylamino)germanium (TDMAGe), tetrakis (diethylamino)germanium (TDEAGe), tetrakis(ethylmethylamino)germanium (TEMAGe), germanium ethoxide (Ge(OEt)4), germanium methoxide (Ge(OMe)4), tetrakis(trimethylsilyl)germane, germanium tetrachloride (GeCl4), or variants of above.

### Claim 23 (depends on 18)

The method of claim 18, wherein the oxygen precursor comprises at least one of: water (H2O), hydrogen peroxide (H2O2), ozone (O3), oxygen plasma, or oxygen radicals.

### Claim 24 (depends on 18)

The method of claim 18, wherein the performing the nitride cycle takes place at a temperature ranging between 100° C. and 500° C. or between 100° C. and 300° C.

### Claim 25 (depends on 18)

The method of claim 18, wherein the performing the nitride cycle has a duration ranging between 0.1 s and 100 s or between 1 s and 60 s.

### Claim 26 (depends on 18)

The method of claim 18, wherein the performing the nitride cycle comprises:
pulsing the germanium precursor;
purging an excess of the germanium precursor;
pulsing the nitrogen precursor; and
purging an excess of the nitrogen precursor.

### Claim 27 (depends on 26)

The method of claim 26, wherein the germanium precursor comprises at least one of:
tetrakis(dimethylamino)germanium (TDMAGe), tetrakis (diethylamino)germanium (TDEAGe), tetrakis(ethylmethylamino)germanium (TEMAGe), germanium ethoxide (Ge(OEt)4), germanium methoxide (Ge(OMe)4), tetrakis(trimethylsilyl)germane, germanium tetrachloride (GeCl4), or variants of above.

### Claim 28 (depends on 18)

The method of claim 18, wherein the nitrogen precursor comprises at least one of:
hydrazine (N2H4), dimethyl hydrazine, tertbutyl hydrazine, ammonia (NH3), nitrogen plasma, nitrogen radicals, or variants of above.

### Claim 29 (depends on 18)

The method of claim 18, wherein the germanium oxynitride film is used for a VNAND application or as a sacrificial layer for patterning.

### Claim 30 (depends on 18)

The method of claim 18, wherein the performing the nitride cycle is performed before the performing the oxide cycle.

### Claim 31

A method of forming a germanium oxynitride film layer for a V-NAND stack comprising:
providing a substrate for processing in a reaction chamber;
performing an oxide cycle for deposing an oxide onto the substrate, the performing the oxide cycle comprising:
pulsing a germanium precursor; and
pulsing an oxygen precursor; and
before or after the performing the oxide cycle, performing a nitride cycle for deposing a nitride onto the substrate, the performing the nitride cycle comprising:
pulsing a germanium precursor; and
pulsing a nitrogen precursor;
wherein the performing the oxide cycle and the performing the nitride cycle are repeated as desired in order to form the germanium oxynitride film of a desired thickness and stoichiometry, and
wherein the oxygen precursor and the nitrogen precursor are different.

### Claim 32 (depends on 31)

The method of claim 31, wherein the germanium precursor comprises at least one of:
tetrakis(dimethylamino)germanium (TDMAGe), tetrakis (diethylamino)germanium (TDEAGe), tetrakis(ethylmethylamino)germanium (TEMAGe), germanium ethoxide (Ge(OEt)4), germanium methoxide (Ge(OMe)4), tetrakis(trimethylsilyl)germane, germanium tetrachloride (GeCl4), or variants of above.

### Claim 33 (depends on 31)

The method of claim 31, wherein the oxygen precursor comprises at least one of: water (H2O), hydrogen peroxide (H2O2), ozone (O3), oxygen plasma, oxygen radicals, or variants of above.

### Claim 34 (depends on 33)

The method of claim 33, wherein the germanium precursor comprises at least one of:
tetrakis(dimethylamino)germanium (TDMAGe), tetrakis (diethylamino)germanium (TDEAGe), tetrakis(ethylmethylamino)germanium (TEMAGe), germanium ethoxide (Ge(OEt)4), germanium methoxide (Ge(OMe)4), tetrakis(trimethylsilyl)germane, germanium tetrachloride (GeCl4), or variants of above.

### Claim 35 (depends on 31)

The method of claim 31, wherein the nitrogen precursor comprises at least one of:
hydrazine (N2H4), dimethyl hydrazine, tertbutyl hydrazine, ammonia (NH3), nitrogen plasma, nitrogen radicals, or variants of above.

### Claim 36 (depends on 31)

The method of claim 31, wherein the performing the nitride cycle is performed before the performing the oxide cycle.

### Claim 37 (depends on 31)

The method of claim 31, wherein the performing the nitride cycle is performed after the performing the oxide cycle.