Method of forming a germanium oxynitride film

{
  "publication_number": "US10367080B2",
  "country": "US",
  "kind": "B2",
  "title": "Method of forming a germanium oxynitride film",
  "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 (GeCl 4), or variants of above.",
    "6. The method of claim 1, wherein the oxygen precursor comprises at least one of: water (H 2 O), hydrogen peroxide (H 2 O 2), ozone (O 3), 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 (GeCl 4), or variants of above.",
    "11. The method of claim 1, wherein the nitrogen precursor comprises at least one of: hydrazine (N 2 H 4), dimethyl hydrazine, tertbutyl hydrazine, ammonia (NH 3), 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 (GeCl 4), or variants of above.",
    "16. The method of claim 14, wherein the oxygen precursor comprises at least one of: water (H 2 O), hydrogen peroxide (H 2 O 2), ozone (O 3), 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 (GeCl 4), or variants of above.",
    "18. The method of claim 14, wherein the nitrogen precursor comprises at least one of: hydrazine (N 2 H 4), dimethyl hydrazine, tertbutyl hydrazine, ammonia (NH 3), 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."
  ],
  "description_excerpt": "The present disclosure generally relates to processes for manufacturing electronic devices. More particularly, the disclosure relates to forming films through atomic layer deposition (ALD). Specifically, the disclosure discloses methods to form a charge trapping layer, such as a layer comprising germanium oxynitride, for example.\n\nV-NAND has been identified for use in flash memory applications. Different materials have been identified for use in the V-NAND space, such as poly silicon (as a channel layer), silicon oxide (as a tunneling oxide and blocking oxide), silicon nitride (as a charge trapping layer), and aluminum oxide (as a blocking oxide). For a material to be effective for V-NAND charge trapping layer (CTL), it should have a proper conduction band offset (CBO), as well as the ability to generate traps with deep energy level and reduce thermal emission. The CTL material should also comply with integration flow by having the following characteristics: compatibility with the blocking oxide (BO); high temperature stability; and high step coverage for an aspect ratio greater than 1:50.\n\nAs a result, a method for forming a V-NAND device with reliable operating capabilities is desired.\n\nIn accordance with at least one embodiment of the invention, a method for forming a V-NAND device is disclosed.",
  "cpc": [
    "H10P 14/68",
    "C23C 16/308",
    "C23C 16/45525",
    "H01L 21/02112",
    "H01L 21/02205",
    "H01L 21/0228",
    "H01L 21/28282",
    "H01L 29/66833",
    "H10B 41/35",
    "H10B 43/27",
    "H10D 30/0413",
    "H10D 64/037",
    "H10P 14/24",
    "H10P 14/3211",
    "H10P 14/3411",
    "H10P 14/42",
    "H10P 14/6339",
    "H10P 14/668",
    "H10P 95/90"
  ],
  "ipc": [
    "H01L 21/02",
    "H01L 29/66",
    "H10B 41/35",
    "H10B 43/27",
    "H01L 21/28"
  ],
  "assignees": [
    "ASM IP Holding BV"
  ],
  "inventors": [
    "Fu Tang",
    "Qi Xie",
    "Jan Willem Maes",
    "Xiaoqiang Jiang",
    "Michael Eugene Givens"
  ],
  "filing_date": "2016-05-02",
  "publication_date": "2019-07-30",
  "grant_date": "2019-07-30",
  "priority_date": "2016-05-02",
  "application_number": "US-201615144506-A",
  "family_id": "60157517",
  "cited_by_count": 378,
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