Method of forming a germanium oxynitride film

• US 10,367,080 B2
• Filed: 05/02/2016
• Issued: 07/30/2019
• Est. Priority Date: 05/02/2016
• Status: Active Grant

• Current Assignee: ASM IP Holding B.V. (ASM International NV)
• Original Assignee: ASM IP Holding B.V. (ASM International NV)
• Inventors: Tang, Fu, Xie, Qi, Maes, Jan Willem, Jiang, Xiaoqiang, Givens, Michael Eugene
• Primary Examiner(s): Nguyen, Duy T
• Application Number:
  US15/144,506
• Publication Number:
  US 20170317194A1
• Time in Patent Office: 1,184 Days
• Field of Search: 438763
• CPC Class Codes: H01L 21/02112 characterised by the material of the layer
• CPC Class Codes: H01L 21/02205 the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/0228 deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 29/40117 the electrodes comprising a charge-trapping insulator
• CPC Class Codes: H01L 29/66833 with a charge trapping gate insulator, e.g. MNOS transistors

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

1. 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 atomic layer deposition cycle of an oxide comprising germanium onto the substrate; and

before or after performing the atomic layer deposition cycle of the oxide, using a germanium precursor and a nitrogen precursor, performing an atomic layer deposition cycle of a nitride comprising germanium onto the substrate;

wherein the atomic layer deposition cycle of the oxide and the atomic layer deposition cycle of the nitride 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.

2. The method of claim 1, wherein the atomic layer deposition cycle of the oxide takes place at a temperature ranging between 100°

C. and 500°

C. or between 100°

C. and 300°

C.

3. The method of claim 1, wherein the atomic layer deposition cycle of the oxide has a duration ranging between 0.1 s and 100 s or between 1 s and 60 s.

4. The method of claim 1, wherein the atomic layer deposition cycle of the oxide comprises:

pulsing the germanium precursor;

purging an excess of the germanium precursor;

pulsing the oxygen precursor; and

purging an excess of the oxygen precursor.

5. The method of claim 1 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.

6. The method of claim 1, wherein the oxygen precursor comprises at least one of:

water (H₂O), hydrogen peroxide (H₂O₂), ozone (O₃), oxygen plasma, or oxygen radicals.

7. The method of claim 1, wherein the atomic layer deposition cycle of the nitride takes place at a temperature ranging between 100°

C. and 500°

C. or between 100°

C. and 300°

C.

8. The method of claim 1, wherein the atomic layer deposition cycle of the nitride has a duration ranging between 0.1 s and 100 s or between 1 s and 60 s.

9. The method of claim 1, wherein the atomic layer deposition cycle of the nitride comprises:

pulsing the germanium precursor;

purging an excess of the germanium precursor;

pulsing the nitrogen precursor; and

purging an excess of the nitrogen precursor.

10. The method of claim 9, 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.

11. The method of claim 1, 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.

12. The method of claim 1, wherein the germanium oxynitride film is used for a VNAND application or as a sacrificial layer for patterning.

13. The method of claim 1, wherein the step of performing the atomic layer deposition cycle of the nitride is performed before performing the atomic layer deposition cycle of the oxide.

14. 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 atomic layer deposition cycle of an oxide onto the substrate, the atomic layer deposition cycle of the oxide comprising;

pulsing a germanium precursor; and

pulsing an oxygen precursor; and

before or after performing the atomic layer deposition cycle of the oxide, performing an atomic layer deposition cycle of a nitride onto the substrate, the atomic layer deposition cycle of the nitride comprising;

pulsing a germanium precursor; and

pulsing a nitrogen precursor;

wherein the atomic layer deposition cycle of the oxide and the atomic layer deposition cycle of the nitride 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.

15. The method of claim 14, 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.

16. The method of claim 14, wherein the oxygen precursor comprises at least one of:

water (H₂O), hydrogen peroxide (H₂O₂), ozone (O₃), oxygen plasma, oxygen radicals, or variants of above.

17. The method of claim 16, 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.

18. The method of claim 14, 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.

19. The method of claim 14, wherein the step of performing the atomic layer deposition cycle of the nitride is performed before performing the atomic layer deposition cycle of the oxide.

20. The method of claim 14, wherein the step of performing the atomic layer deposition cycle of the nitride is performed after performing the atomic layer deposition cycle of the oxide.