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US6534395B2 Expired / Lapsed US ⏱️ 0.0 years remaining

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

Assignee: ASM International NV
•
Filing: 2001-03-06
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Granted: 2003-03-18
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Expires: 2021-03-06
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Abstract

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., ZrO2) 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.

Inventors

  • 👤 Christiaan J. Werkhoven
  • 👤 Ivo Raaijmakers
  • 👤 Suvi P. Haukka

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-09 01:21
CPC Classifications
H; H10; H10D; H10D64/00; H10D64/01; H10D64/013; H10D64/01302; H10D64/01332; H10D64/01336; H10D64/0134; C; C23; C23C; C23C16/00; C23C16/02; C23C16/0272; C23C16/029; C23C16/22; C23C16/30; C23C16/34; C23C16/40; C23C16/401; C23C16/403; C23C16/405; C23C16/44; C23C16/448; C23C16/452; C23C16/455; C23C16/45523; C23C16/45525; C23C16/45527; C23C16/45529; C23C16/45531; C23C16/45534; C30; C30B; C30B25/00; C30B25/02; C30B25/14; H10D30/00; H10D30/60; H10D30/67; H10D30/6729; H10D30/6737; H10D30/6739; H10D64/01342; H10D64/01344; H10D64/60; H10D64/66; H10D64/68; H10D64/681; H10D64/685; H10D64/691; H10D64/693; H10P; H10P14/00; H10P14/40; H10P14/42; H10P14/43; H10P14/432; H10P14/60; H10P14/63; H10P14/6326; H10P14/6328; H10P14/6334; H10P14/6336; H10P14/66; H10P14/668; H10P14/6681; H10P14/6682; H10P14/69; H10P14/692; H10P14/6921; H10P14/6922; H10P14/6927; H10P14/6928; H10P14/6938; H10P14/6939; H10P14/69395; H10P14/69397; H10W; H10W20/00; H10W20/01; H10W20/031; H10W20/032; H10W20/033; H10W20/035; H10W20/042; H10W20/043; H10W20/056; H10W20/057; H10P14/6339; H10P14/69391; H10P14/69392; H10W20/0425; Y; Y10; Y10T; Y10T428/00; Y10T428/24; Y10T428/24942; Y10T428/2495

Claims Analysis

Total Claims: 34
Claim 1
Independent Claim 64 words
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.
Claim 2
Independent Claim 64 words
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.
Claim 3
Dependent Claim 17 words
The method of claim 1 , wherein the first vapor phase reactant comprises a silicon source gas.
Claim 4
Dependent Claim 61 words
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.
Claim 5
Dependent Claim 40 words
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.
Claim 6
Dependent Claim 28 words
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.
Claim 7
Dependent Claim 21 words
The method of claim 5 , wherein the oxidant source gas comprises water vapor and the nitrogen source gas comprises ammonia.
Claim 8
Dependent Claim 18 words
The method of claim 1 , wherein the first vapor phase reactant comprises a first metal source gas.
Claim 9
Dependent Claim 34 words
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.
Claim 10
Dependent Claim 34 words
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.
Claim 11
Dependent Claim 13 words
The method of claim 9 , wherein the interface layer comprises aluminum oxide.
Claim 12
Dependent Claim 15 words
The method of claim 10 , wherein the higher dielectric constant material comprises zirconium oxide.
Claim 13
Dependent Claim 40 words
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.
Claim 14
Dependent Claim 26 words
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.
Claim 15
Dependent Claim 17 words
The method of claim 12 , wherein the third vapor phase reactant is a copper source gas.
Claim 16
Dependent Claim 29 words
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.
Claim 17
Dependent Claim 19 words
The method of claim 15 , wherein introducing comprises adding progressively more copper source gas to the deposition cycles.
Claim 18
Dependent Claim 33 words
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.
Claim 19
Dependent Claim 37 words
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.
Claim 20
Dependent Claim 22 words
The method of claim 18 , wherein the copper concentration is lowest at the lower surface and highest at the upper surface.
Claim 21
Dependent Claim 30 words
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.
Claim 22
Dependent Claim 32 words
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.
Claim 23
Dependent Claim 35 words
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.
Claim 24
Dependent Claim 19 words
The method of claim 19 , forming the graded transition layer with a thickness of less than 50 Å.
Claim 25
Dependent Claim 18 words
The method of claim 19 , forming the graded transition layer with a thickness of about 10 Å.
Claim 26
Dependent Claim 36 words
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.
Claim 27
Dependent Claim 36 words
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.
Claim 28
Dependent Claim 36 words
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.
Claim 29
Dependent Claim 36 words
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.
Claim 30
Dependent Claim 28 words
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.
Claim 31
Dependent Claim 24 words
The method of claim 28 , wherein the varying levels of the third vapor phase reactant are provided in separate pulses of varying duration.
Claim 32
Dependent Claim 29 words
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.
Claim 33
Dependent Claim 20 words
The method of claim 1 , forming a graded thin film with a thickness of less than about 50 Å.
Claim 34
Dependent Claim 31 words
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.

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3.5 Years (Year 4) 2006-03-17 2006-09-16 2007-03-18 $2000.00 Window Closed / Lapsed
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