US6492283B2
Expired / Lapsed
US
⏱️ 0.0 years remaining
Method of forming ultrathin oxide layer
Assignee: ASM International NV
•
Filing: 2001-02-22
•
Granted: 2002-12-10
•
Expires: 2021-02-22
Abstract
Abstract A method is disclosed for forming an ultrathin oxide layer of uniform thickness. The method is particularly advantageous for producing uniformly thin interfacial oxides beneath materials of high dielectric permittivity, or uniformly thin passivation oxides. Hydrofluoric (HF) etching of a silicon surface, for example, is followed by termination of the silicon surface with ligands larger than H or F, particularly hydroxyl, alkoxy or carboxylic tails. The substrate is oxidized with the surface termination in place. The surface termination and relatively low temperatures moderate the rate of oxidation, such that a controllable thickness of oxide is formed. In some embodiments, the ligand termination is replaced with OH prior to further deposition. The deposition preferably includes alternating, self-limiting chemistries in an atomic layer deposition process, though any other suitable deposition process can be used. Two or more of the HF etching, surface termination, oxidation, hydroxyl replacement of the surface termination and deposition on the oxide can be conducted in situ.
Inventors
- 👤 Ivo Raaijmakers
- 👤 Yong-Bae Kim
- 👤 Marko Tuominen
- 👤 Suvi P. Haukka
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-09 02:18
CPC Classifications
H; H10; H10D; H10D64/00; H10D64/01; H10D64/013; H10D64/01302; H10D64/01332; H10D64/01336; H10D64/01342; H10D64/01346; H10D64/60; H10D64/66; H10D64/68; H10D64/691; H10P; H10P14/00; H10P14/60; H10P14/65; H10P14/6516; H10P14/6546; H10P14/63; H10P14/6302; H10P14/6304; H10P14/6306; H10P14/6308; H10P14/6309; H10P14/6322; H10P14/6326; H10P14/6328; H10P14/6334; H10P14/6339; H10P14/6502; H10P14/69; H10P14/692; H10P14/6938; H10P14/6939; H10P14/69392; H10P70/00; H10P70/10; H10P70/12; H10P70/125; H10P70/15; Y; Y10; Y10S; Y10S438/00; Y10S438/906
Claims Analysis
Total Claims: 39
Claim 1
Independent Claim
65 words
A method for growing an oxide layer from a substrate, the method comprising: exposing the substrate to an etchant, wherein the etchant is capable of etching a native oxide from the substrate; forming a surface termination on the substrate after etching, the surface termination comprising ligands larger than hydrogen or fluorine atoms; and oxidizing the substrate through the surface termination to grow the oxide layer.
Claim 2
Independent Claim
65 words
A method for growing an oxide layer from a substrate, the method comprising: exposing the substrate to an etchant, wherein the etchant is capable of etching a native oxide from the substrate; forming a surface termination on the substrate after etching, the surface termination comprising ligands larger than hydrogen or fluorine atoms; and oxidizing the substrate through the surface termination to grow the oxide layer.
Claim 3
Dependent Claim
13 words
The method of claim 1 , wherein the substrate comprises a silicon surface.
Claim 4
Dependent Claim
13 words
The method of claim 1 , wherein oxidizing comprises employing a strong oxidizer.
Claim 5
Dependent Claim
19 words
The method of claim 1 , wherein oxidizing comprises wet oxidation at between about 300° C. and 400° C.
Claim 6
Dependent Claim
23 words
The method of claim 1 , wherein the oxide layer comprises silicon oxide with a thickness between about 0.1 nm and 1.2 nm.
Claim 7
Dependent Claim
20 words
The method of claim 2 , wherein etching oxide from the substrate comprises exposing the substrate to hydrofluoric acid (HF).
Claim 8
Dependent Claim
17 words
The method of claim 6 , wherein etching oxide from the substrate comprises an HF vapor etch.
Claim 9
Dependent Claim
23 words
The method of claim 6 , wherein etching oxide from the substrate comprises wet etching the substrate with an aqueous solution of HF.
Claim 10
Dependent Claim
19 words
The method of claim 6 , wherein forming the surface termination comprises replacing a hydrogen termination with hydroxyl groups.
Claim 11
Dependent Claim
22 words
The method of claim 6 , wherein forming the surface termination comprises replacing a hydrogen termination with ligands larger than hydroxyl groups.
Claim 12
Dependent Claim
19 words
The method of claim 10 , wherein forming the surface termination comprises exposing the substrate to a carboxylic acid.
Claim 13
Dependent Claim
23 words
The method of claim 10 , wherein forming the surface termination comprises exposing the substrate to a compound capable of forming an alkoxide.
Claim 14
Dependent Claim
22 words
The method of claim 12 , wherein the carboxylic acid is selected from the group consisting of formic acid and acetic acid.
Claim 15
Dependent Claim
27 words
The method of claim 10 , further comprising continuing to supply the substrate with a source of the ligands while oxidizing the substrate through the surface termination.
Claim 16
Dependent Claim
18 words
The method of claim 12 , wherein forming the surface termination comprises exposing the substrate to an alcohol.
Claim 17
Dependent Claim
20 words
The method of claim 15 , wherein the alcohol is selected from the group consisting of methanol, ethanol and propanol.
Claim 18
Dependent Claim
15 words
The method of claim 3 , wherein the strong oxidizer comprises an ozone containing gas.
Claim 19
Dependent Claim
15 words
The method of claim 3 , wherein the strong oxidizer comprises a peroxide containing gas.
Claim 20
Dependent Claim
17 words
The method of claim 3 , wherein oxidizing comprises maintaining a substrate temperature below about 300° C.
Claim 21
Dependent Claim
17 words
The method of claim 19 , wherein oxidizing comprises maintaining a substrate temperature below about 200° C.
Claim 22
Dependent Claim
14 words
The method of claim 4 , wherein oxidizing further comprises flowing O 2 .
Claim 23
Dependent Claim
25 words
The method of claim 5 , further comprising depositing a second dielectric material having a dielectric constant greater than about 5 over the silicon oxide.
Claim 24
Dependent Claim
16 words
The method of claim 22 , wherein depositing the second dielectric material comprises atomic layer deposition.
Claim 25
Dependent Claim
85 words
A process for forming a transistor gate dielectric material on a silicon substrate, comprising: providing a substrate with a native oxide; etching the native oxide from the silicon substrate with hydrofluoric acid; forming a surface termination over the silicon substrate with ligands larger than hydrogen and fluorine; growing an interfacial oxide by oxidizing the silicon substrate after forming the surface termination, the interfacial oxide having a thickness between about 0.1 nm and 1.2 nm; and depositing a high k dielectric material over the interfacial oxide.
Claim 26
Dependent Claim
85 words
A process for forming a transistor gate dielectric material on a silicon substrate, comprising: providing a substrate with a native oxide; etching the native oxide from the silicon substrate with hydrofluoric acid; forming a surface termination over the silicon substrate with ligands larger than hydrogen and fluorine; growing an interfacial oxide by oxidizing the silicon substrate after forming the surface termination, the interfacial oxide having a thickness between about 0.1 nm and 1.2 nm; and depositing a high k dielectric material over the interfacial oxide.
Claim 27
Dependent Claim
31 words
The method of claim 24 , wherein etching oxide comprises HF vapor etching and forming the surface termination is conducted in situ following the HF vapor etching within one reaction chamber.
Claim 28
Dependent Claim
23 words
The method of claim 24 , further comprising cleaning the silicon substrate prior to etching oxide, wherein cleaning includes growing a chemical oxide.
Claim 29
Dependent Claim
24 words
The method of claim 24 , further comprising replacing the surface termination with a hydroxyl tail termination before depositing the high k dielectric material.
Claim 30
Dependent Claim
19 words
The method of claim 27 , wherein depositing the high k dielectric material comprises an atomic layer deposition process.
Claim 31
Dependent Claim
28 words
The method of claim 27 , wherein growing the interfacial oxide and replacing the surface termination with hydroxyl tail termination are conducted in situ within one reaction chamber.
Claim 32
Dependent Claim
28 words
The method of claim 28 , wherein the high k dielectric material includes a material selected from the group consisting of aluminum oxide, zirconium oxide and lanthanide oxides.
Claim 33
Dependent Claim
22 words
The method of claim 29 , wherein depositing the high k material is also conducted in situ within the one reaction chamber.
Claim 34
Dependent Claim
28 words
The method of claim 29 , wherein forming the surface termination with ligands larger than hydrogen and fluorine is also conducted in situ within the one reaction chamber.
Claim 35
Dependent Claim
21 words
The method of claim 32 , wherein etching oxide comprises HF vapor etching conducted in situ within the one reaction chamber.
Claim 36
Dependent Claim
22 words
The method claim 32 , wherein depositing the high k dielectric material is also conducted in situ within the one reaction chamber.
Claim 37
Dependent Claim
19 words
The method of claim 26 , wherein cleaning comprises exposing the substrate to an aqueous mixture comprising hydrogen peroxide.
Claim 38
Dependent Claim
18 words
The method of claim 35 , wherein the aqueous mixture comprises an ammonium hydroxide and hydrogen peroxide mixture.
Claim 39
Dependent Claim
18 words
The method of claim 36 , wherein the aqueous mixture comprises a sulfuric acid and hydrogen peroxide mixture.
References Cited (Backward Citations)
US4058430A
Cited
US5769950A
Cited
US4747367A
Cited
US4761269A
Cited
US5071670A
Cited
US5476816A
Cited
US5916365A
Cited
US6124214A
Cited
WO2000054320A1
Cited
US6200893B1
Cited
US6124158A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 2005-12-09 | 2006-06-10 | 2006-12-10 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 2009-12-09 | 2010-06-10 | 2010-12-10 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 2013-12-09 | 2014-06-10 | 2014-12-10 | $7700.00 | Window Closed / Lapsed |