Patent · US6534395B2 · B2 · US

Method of forming graded thin films using alternating pulses of vapor phase reactants

(11) Publication number

US6534395B2

(21) Application number

US-80075701-A

(22) Filing date

2001-03-06

(30) Priority date

2000-03-07

(43) Publication date

2003-03-18

(45) Date of grant

2003-03-18

(52) CPC

H10D Inorganic electric semiconductor devices: 64/0134, 30/6739, 64/01342, 64/01344, 64/685, 64/691, 64/693
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: 16/029, 16/34, 16/401, 16/403, 16/405, 16/452, 16/45529, 16/45531, 16/45534
C30B Single-crystal growth; unidirectional solidification of eutectic material or unidirectional demixing of eutectoid material; refining by zone-melting of material; production of a homogeneous polycrystalline material with defined structure; single crystals or homogeneous polycrystalline material with defined structure; after-treatment of single crystals or a homogeneous polycrystalline material with defined structure; apparatus therefor: 25/14
H10P Generic processes or apparatus for the manufacture or treatment of devices covered by class H10: 14/432, 14/6336, 14/6339, 14/6682, 14/6927, 14/6928, 14/69391, 14/69392, 14/69395, 14/69397
H10W Generic packages, interconnections, connectors or other constructional details of devices covered by class H10: 20/035, 20/0425, 20/043, 20/057
Y10T Technical subjects covered by former us classification: 428/24942, 428/2495

(73) Assignee

ASM MICROCHEMISTRY OY

(54) Title

Method of forming graded thin films using alternating pulses of vapor phase reactants

(57) Abstract

Thin films are formed by atomic layer deposition, whereby the composition of the film can be varied from monolayer to monolayer during cycles including alternating pulses of self-limiting chemistries. In the illustrated embodiments, varying amounts of impurity sources are introduced during the cyclical process. A graded gate dielectric is thereby provided, even for extremely thin layers. The gate dielectric as thin as 2 nm can be varied from pure silicon oxide to oxynitride to silicon nitride. Similarly, the gate dielectric can be varied from aluminum oxide to mixtures of aluminum oxide and a higher dielectric material (e.g., ZrO 2) to pure high k material and back to aluminum oxide. In another embodiment, metal nitride (e.g., WN) is first formed as a barrier for lining dual damascene trenches and vias. During the alternating deposition process, copper can be introduced, e.g., in separate pulses, and the copper source pulses can gradually increase in frequency, forming a graded transition region, until pure copper is formed at the upper surface. Advantageously, graded compositions in these and a variety of other contexts help to avoid such problems as etch rate control, electromigration and non-ohmic electrical contact that can occur at sharp material interfaces.

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Claims (33)

A method of forming a thin film with a varying composition in an integrated circuit comprising: placing a substrate in a reaction chamber; introducing first and second vapor phase reactants in alternate and temporally separated pulses to the substrate in a plurality of deposition cycles; and introducing varying amounts of a third vapor phase reactant to the substrate during said plurality of deposition cycles.
The method of claim 1, wherein the first vapor phase reactant comprises a silicon source gas.
The method of claim 2, wherein the silicon source gas is selected from the group consisting of silanes of the formula Si m L 2m+2, siloxanes of the formula Si y O y−1 L 2y+2, and silazanes of the formula Si y (NH) y−1 L 2y+2, where m and y are integers and L is a ligand.
The method of claim 3, wherein the ligands in the silicon source gas are selected from the group consisting of H, F, Cl, Br, I, alkyl, aryl, alkoxy, vinyl, cyano, isocyanato, amino, silyl, alkylsilyl, alkoxysilyl, silylene and alkylsiloxane groups.
The method of claim 3, wherein the second vapor phase reactant comprises an oxidant source gas and the third vapor phase reactant comprises a nitrogen source gas.
The method of claim 5, wherein the oxidant source gas comprises water vapor and the nitrogen source gas comprises ammonia.
The method of claim 1, wherein the first vapor phase reactant comprises a first metal source gas.
The method of claim 7, wherein the second vapor phase reactant is an oxidant and the third vapor phase reactant comprises a second metal source gas different from the first metal source gas.
The method of claim 8, wherein the first and second vapor phase reactants produce an interface layer for a gate dielectric, and the third vapor phase reactant produces a higher dielectric constant material.
The method of claim 9, wherein the interface layer comprises aluminum oxide.
The method of claim 10, wherein the higher dielectric constant material comprises zirconium oxide.
The method of claim 1, wherein the first vapor phase reactant is a first metal source gas, the second vapor phase reactant is a nitrogen source gas, and the third vapor phase reactant is a second metal source gas.
The method of claim 12, wherein the thin film comprises a graded transition layer between a metal nitride barrier layer and a more conductive material.
The method of claim 12, wherein the third vapor phase reactant is a copper source gas.
The method of claim 14, wherein the thin film forms a graded transition layer between a metal nitride barrier layer and a copper fill in a damascene trench.
The method of claim 15, wherein introducing comprises adding progressively more copper source gas to the deposition cycles.
The method of claim 16, wherein introducing varying amounts of the third vapor phase reactant comprises providing copper source gas pulses to the deposition cycles with greater frequency as the deposition proceeds.
The method of claim 14, wherein introducing varying amounts of the third vapor phase reactant comprises varying a copper concentration from a lower surface of the transition layer to an upper surface of the transition layer.
The method of claim 18, wherein the copper concentration is lowest at the lower surface and highest at the upper surface.
The method of claim 19, wherein introducing varying amounts of the third vapor phase reactant comprises linearly grading the copper concentration from the lower surface to the upper surface.
The method of claim 19, wherein introducing varying amounts of the third vapor phase reactant comprises providing 0% copper at the lower surface and about 50% copper at the upper surface.
The method of claim 19, wherein introducing varying amounts of the third vapor phase reactant comprises forming a pure metal nitride at the lower surface and a pure copper layer at the upper surface.
The method of claim 19, forming the graded transition layer with a thickness of less than 50 Å.
The method of claim 19, forming the graded transition layer with a thickness of about 10 Å.
The method of claim 1, wherein introducing varying amounts of the third vapor phase reactant comprises providing pulses of the third vapor phase reactant to the deposition cycles with varying frequency as the deposition proceeds.
The method of claim 25, wherein introducing varying amounts of the third vapor phase reactant comprises providing pulses of the third vapor phase reactant to the deposition cycles with greater frequency as the deposition proceeds.
The method of claim 25, wherein introducing varying amounts of the third vapor phase reactant comprises providing pulses of the third vapor phase reactant to the deposition cycles with lesser frequency as the deposition proceeds.
The method of claim 1, wherein introducing varying amounts of the third vapor phase reactant comprises providing varying levels of the third vapor phase reactant in each of the deposition cycles as the deposition proceeds.
The method of claim 28, wherein the varying levels of the third vapor phase reactant are provided simultaneously with the second vapor phase reactant in each cycle.
The method of claim 28, wherein the varying levels of the third vapor phase reactant are provided in separate pulses of varying duration.
The method of claim 28, wherein the varying levels of the third vapor phase reactant replace atoms at the surface of the thin film from a previous pulse.
The method of claim 1, forming a graded thin film with a thickness of less than about 50 Å.
The method of claim 32, wherein introducing varying amounts of the third vapor phase reactant comprises linearly varying an amount of an impurity incorporated into the layer during the deposition.

Citations (27)

GB2372042A
GB2372043A
GB2372044A
US2002006468A1
US2002102838A1
US4058430A
US4486487A
US4747367A
US4761269A
US5071670A
US5294286A
US5306666A
US5449314A
US5769950A
US5795495A
US5916365A
US6174799B1
US6174809B1
US6294836B1
US6329704B1
US6362526B1
US6365502B1
US6368954B1
US6368961B1
US6399522B1
WO0054320A1
WO0061833A1

Record as JSON

{
  "publication_number": "US6534395B2",
  "country": "US",
  "kind": "B2",
  "title": "Method of forming graded thin films using alternating pulses of vapor phase reactants",
  "abstract": "Thin films are formed by atomic layer deposition, whereby the composition of the film can be varied from monolayer to monolayer during cycles including alternating pulses of self-limiting chemistries. In the illustrated embodiments, varying amounts of impurity sources are introduced during the cyclical process. A graded gate dielectric is thereby provided, even for extremely thin layers. The gate dielectric as thin as 2 nm can be varied from pure silicon oxide to oxynitride to silicon nitride. Similarly, the gate dielectric can be varied from aluminum oxide to mixtures of aluminum oxide and a higher dielectric material (e.g., ZrO 2) to pure high k material and back to aluminum oxide. In another embodiment, metal nitride (e.g., WN) is first formed as a barrier for lining dual damascene trenches and vias. During the alternating deposition process, copper can be introduced, e.g., in separate pulses, and the copper source pulses can gradually increase in frequency, forming a graded transition region, until pure copper is formed at the upper surface. Advantageously, graded compositions in these and a variety of other contexts help to avoid such problems as etch rate control, electromigration and non-ohmic electrical contact that can occur at sharp material interfaces.",
  "claims": [
    "1. A method of forming a thin film with a varying composition in an integrated circuit comprising: placing a substrate in a reaction chamber; introducing first and second vapor phase reactants in alternate and temporally separated pulses to the substrate in a plurality of deposition cycles; and introducing varying amounts of a third vapor phase reactant to the substrate during said plurality of deposition cycles.",
    "2. The method of claim 1, wherein the first vapor phase reactant comprises a silicon source gas.",
    "3. The method of claim 2, wherein the silicon source gas is selected from the group consisting of silanes of the formula Si m L 2m+2, siloxanes of the formula Si y O y−1 L 2y+2, and silazanes of the formula Si y (NH) y−1 L 2y+2, where m and y are integers and L is a ligand.",
    "4. The method of claim 3, wherein the ligands in the silicon source gas are selected from the group consisting of H, F, Cl, Br, I, alkyl, aryl, alkoxy, vinyl, cyano, isocyanato, amino, silyl, alkylsilyl, alkoxysilyl, silylene and alkylsiloxane groups.",
    "5. The method of claim 3, wherein the second vapor phase reactant comprises an oxidant source gas and the third vapor phase reactant comprises a nitrogen source gas.",
    "6. The method of claim 5, wherein the oxidant source gas comprises water vapor and the nitrogen source gas comprises ammonia.",
    "7. The method of claim 1, wherein the first vapor phase reactant comprises a first metal source gas.",
    "8. The method of claim 7, wherein the second vapor phase reactant is an oxidant and the third vapor phase reactant comprises a second metal source gas different from the first metal source gas.",
    "9. The method of claim 8, wherein the first and second vapor phase reactants produce an interface layer for a gate dielectric, and the third vapor phase reactant produces a higher dielectric constant material.",
    "10. The method of claim 9, wherein the interface layer comprises aluminum oxide.",
    "11. The method of claim 10, wherein the higher dielectric constant material comprises zirconium oxide.",
    "12. The method of claim 1, wherein the first vapor phase reactant is a first metal source gas, the second vapor phase reactant is a nitrogen source gas, and the third vapor phase reactant is a second metal source gas.",
    "13. The method of claim 12, wherein the thin film comprises a graded transition layer between a metal nitride barrier layer and a more conductive material.",
    "14. The method of claim 12, wherein the third vapor phase reactant is a copper source gas.",
    "15. The method of claim 14, wherein the thin film forms a graded transition layer between a metal nitride barrier layer and a copper fill in a damascene trench.",
    "16. The method of claim 15, wherein introducing comprises adding progressively more copper source gas to the deposition cycles.",
    "17. The method of claim 16, wherein introducing varying amounts of the third vapor phase reactant comprises providing copper source gas pulses to the deposition cycles with greater frequency as the deposition proceeds.",
    "18. The method of claim 14, wherein introducing varying amounts of the third vapor phase reactant comprises varying a copper concentration from a lower surface of the transition layer to an upper surface of the transition layer.",
    "19. The method of claim 18, wherein the copper concentration is lowest at the lower surface and highest at the upper surface.",
    "20. The method of claim 19, wherein introducing varying amounts of the third vapor phase reactant comprises linearly grading the copper concentration from the lower surface to the upper surface.",
    "21. The method of claim 19, wherein introducing varying amounts of the third vapor phase reactant comprises providing 0% copper at the lower surface and about 50% copper at the upper surface.",
    "22. The method of claim 19, wherein introducing varying amounts of the third vapor phase reactant comprises forming a pure metal nitride at the lower surface and a pure copper layer at the upper surface.",
    "23. The method of claim 19, forming the graded transition layer with a thickness of less than 50 Å.",
    "24. The method of claim 19, forming the graded transition layer with a thickness of about 10 Å.",
    "25. The method of claim 1, wherein introducing varying amounts of the third vapor phase reactant comprises providing pulses of the third vapor phase reactant to the deposition cycles with varying frequency as the deposition proceeds.",
    "26. The method of claim 25, wherein introducing varying amounts of the third vapor phase reactant comprises providing pulses of the third vapor phase reactant to the deposition cycles with greater frequency as the deposition proceeds.",
    "27. The method of claim 25, wherein introducing varying amounts of the third vapor phase reactant comprises providing pulses of the third vapor phase reactant to the deposition cycles with lesser frequency as the deposition proceeds.",
    "28. The method of claim 1, wherein introducing varying amounts of the third vapor phase reactant comprises providing varying levels of the third vapor phase reactant in each of the deposition cycles as the deposition proceeds.",
    "29. The method of claim 28, wherein the varying levels of the third vapor phase reactant are provided simultaneously with the second vapor phase reactant in each cycle.",
    "30. The method of claim 28, wherein the varying levels of the third vapor phase reactant are provided in separate pulses of varying duration.",
    "31. The method of claim 28, wherein the varying levels of the third vapor phase reactant replace atoms at the surface of the thin film from a previous pulse.",
    "32. The method of claim 1, forming a graded thin film with a thickness of less than about 50 Å.",
    "33. The method of claim 32, wherein introducing varying amounts of the third vapor phase reactant comprises linearly varying an amount of an impurity incorporated into the layer during the deposition."
  ],
  "cpc": [
    "H10D 64/0134",
    "C23C 16/029",
    "C23C 16/34",
    "C23C 16/401",
    "C23C 16/403",
    "C23C 16/405",
    "C23C 16/452",
    "C23C 16/45529",
    "C23C 16/45531",
    "C23C 16/45534",
    "C30B 25/14",
    "H10D 30/6739",
    "H10D 64/01342",
    "H10D 64/01344",
    "H10D 64/685",
    "H10D 64/691",
    "H10D 64/693",
    "H10P 14/432",
    "H10P 14/6336",
    "H10P 14/6339",
    "H10P 14/6682",
    "H10P 14/6927",
    "H10P 14/6928",
    "H10P 14/69391",
    "H10P 14/69392",
    "H10P 14/69395",
    "H10P 14/69397",
    "H10W 20/035",
    "H10W 20/0425",
    "H10W 20/043",
    "H10W 20/057",
    "Y10T 428/24942",
    "Y10T 428/2495"
  ],
  "assignees": [
    "ASM MICROCHEMISTRY OY"
  ],
  "filing_date": "2001-03-06",
  "publication_date": "2003-03-18",
  "grant_date": "2003-03-18",
  "priority_date": "2000-03-07",
  "application_number": "US-80075701-A",
  "family_id": "22688920",
  "citations": [
    "GB2372042A",
    "GB2372043A",
    "GB2372044A",
    "US2002006468A1",
    "US2002102838A1",
    "US4058430A",
    "US4486487A",
    "US4747367A",
    "US4761269A",
    "US5071670A",
    "US5294286A",
    "US5306666A",
    "US5449314A",
    "US5769950A",
    "US5795495A",
    "US5916365A",
    "US6174799B1",
    "US6174809B1",
    "US6294836B1",
    "US6329704B1",
    "US6362526B1",
    "US6365502B1",
    "US6368954B1",
    "US6368961B1",
    "US6399522B1",
    "WO0054320A1",
    "WO0061833A1"
  ]
}

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