Vapor deposition of metal oxides, silicates and phosphates, and silicon dioxide

• US 6,969,539 B2
• Filed: 09/28/2001
• Issued: 11/29/2005
• Est. Priority Date: 09/28/2000
• Status: Expired due to Term

• Current Assignee: President and Fellows of Harvard College (Harvard Corporation)
• Original Assignee: President and Fellows of Harvard College (Harvard Corporation)
• Inventors: Gordon, Roy G., Becker, Jill, Hausmann, Dennis, Suh, Seigi
• Primary Examiner(s): CHEN, BRET P
• Application Number:
  US10/381,628
• Publication Number:
  US 20040043149A1
• Time in Patent Office: 1,523 Days
• Field of Search: 427/255.29, 427/255.38
• US Class Current: 427/255.29
• CPC Class Codes: C01B 13/34 by oxidation or hydrolysis of sprayed or atomised solutions
• CPC Class Codes: C01B 25/30 Alkali metal phosphates
• CPC Class Codes: C01B 25/36 Aluminium phosphates
• CPC Class Codes: C01B 33/126 Preparation of silica of undetermined type
• CPC Class Codes: C01B 33/20 Silicates persilicates C01B15/14 ; containing aluminium C01B33/26
• CPC Class Codes: C01B 33/26 Aluminium-containing silicates , i.e. silico-aluminates
• CPC Class Codes: C01G 25/02 Oxides
• CPC Class Codes: C01G 27/02 Oxides
• CPC Class Codes: C01G 35/00 Compounds of tantalum
• CPC Class Codes: C07F 9/091 with hydroxyalkyl compounds with further substituents on alkyl
• CPC Class Codes: C07F 9/11 with hydroxyalkyl compounds without further substituents on alkyl
• CPC Class Codes: C23C 16/30 Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/401 containing silicon
• CPC Class Codes: C23C 16/402 Silicon dioxide
• CPC Class Codes: C23C 16/405 of refractory metals or yttrium
• CPC Class Codes: C23C 16/455 characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
• CPC Class Codes: C23C 16/45525 Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45531 specially adapted for making ternary or higher compositions
• CPC Class Codes: C23C 16/45553 characterized by the use of precursors specially adapted for ALD
• CPC Class Codes: H01L 21/02112 : characterised by the material of the layer
• CPC Class Codes: H01L 21/02148 : the material containing hafnium, e.g. HfSiOx or HfSiON
• CPC Class Codes: H01L 21/02156 : the material containing at least one rare earth element, e.g. silicate of lanthanides, scandium or yttrium
• CPC Class Codes: H01L 21/02159 : the material containing zirconium, e.g. ZrSiOx
• CPC Class Codes: H01L 21/02164 : the material being a silicon oxide, e.g. SiO2
• CPC Class Codes: H01L 21/02178 : the material containing aluminium, e.g. Al2O3
• CPC Class Codes: H01L 21/02205 : the layer being characterised by the precursor material for deposition
• CPC Class Codes: H01L 21/02271 : deposition by decomposition or reaction of gaseous or vapour phase compounds, i.e. chemical vapour deposition H01L21/02266 takes precedence
• CPC Class Codes: H01L 21/0228 : deposition by cyclic CVD, e.g. ALD, ALE, pulsed CVD
• CPC Class Codes: H01L 21/3141 : Deposition using atomic layer deposition techniques [ALD]
• CPC Class Codes: H01L 21/31612 : on a silicon body
• CPC Class Codes: H01L 28/40 : Capacitors
• CPC Class Codes: H01L 29/0684 : characterised by the shape, relative sizes or dispositions of the semiconductor regions or junctions between the regions
• CPC Class Codes: H01L 29/42364 : characterised by the insulating layer, e.g. thickness or uniformity H01L29/42324 and H01L29/4234 take precedence
• CPC Class Codes: H01L 29/517 : the insulating material comprising a metallic compound, e.g. metal oxide, metal silicate H01L29/518 takes precedence

Abstract

Metal silicates or phosphates are deposited on a heated substrate by the reaction of vapors of alkoxysilanols or alkylphosphates along with reactive metal amides, alkyls or alkoxides. For example, vapors of tris-(ter-butoxy)silanol react with vapors of tetrakis(ethylmethylamido)hafnium to deposit hafnium silicate on surfaces heated to 300° C. The product film has a very uniform stoichiometry throughout the reactor. Similarly, vapors of diisopropylphosphate react with vapors of lithium bis(ethyldimethylsilyl)amide to deposit lithium phosphate films on substrates heated to 250° C. supplying the vapors in alternating pulse produces these same compositions with a very uniform distribution of thickness and excellent step coverage.

Claims

1. A process for forming materials comprising silicon, oxygen and one or more metals or metalloids, comprising:

reacting the vapor of one of an alkoxysilanol and an alkoxysilanediol together with a vapor of one or more of a metal compound and a metalloid compound.

3. The process of claim 1, wherein compound is deposited as a film on a substrate.

4. The process as in claim 1 or 2, wherein the silanol has the formula

where the Rⁿ represents hydrogen, alkyl groups, fluoroalkyl groups or alkyl groups substituted by other atoms or groups, Rⁿ being any one of the groups R¹ through R⁹, and where Rⁿ are the same or different.

5. The process of claim 4, wherein the groups Rⁿ contain between one and four carbons and are the same or different.

6. The process of claim 5, wherein the groups Rⁿ are all methyl groups.

7. The process of claim 5, wherein R¹, R⁴ and R⁷ are ethyl groups and R², R³, R⁵, R⁶, R⁸ and R⁹ are methyl groups and the silanol has the formula

8. The process of claim 1 or 2, wherein a metal or metalloid compound contains metal-nitrogen or metalloid-nitrogen bonds.

9. The process of claim 8, wherein a metal or metalloid compound is selected from Table 1.

10. The process of claim 1 or 2, wherein a metal compound is selected from Table 2.

11. The process of claim 1 or 2, wherein a metal or metalloid compound is selected from Table 3.

2. A process for forming materials comprising silicon, oxygen and one or more metals or metalloids, comprising:

exposing a substrate alternately to the vapor of one or an alkoxysilanol and an alkoxysilanediol and the vapor of one or more of a metal compound or a metalloid compound to form a film on the substrate.

12. A process for forming materials comprising phosphorus, oxygen and one or more metals or metalloids, comprising:

reacting a vapor of a bis(alkyl)phosphate with a vapor of one or more of a metal compound and a metalloid compound.

14. The process of claim 12, wherein the material comprising phosphorus, oxygen and one or more metals or metalloids is deposited as a film on a substrate.

15. The process as in claim 12 or 13, wherein the bis(alkyl)phosphate has the formula

where the Rⁿ represents hydrogen, alkyl groups, fluoroalkyl groups or alkyl groups substituted by other atoms or groups, Rⁿ being any one of the groups R¹ through R6, and wherein Rⁿ are the same or different.

16. The process of claim 15, wherein the groups Rⁿ contain between one and four carbons and may be the same or different.

17. The process of claim 16, wherein the groups R¹, R³, R⁴ and R⁶ are methyl groups, the groups R² and R⁵ are hydrogen, and the compound has the formula

18. The process of claim 12 or 13, wherein a metal or metalloid compound contains metal-nitrogen or metalloid-nitrogen bonds.

19. The process of claim 18, wherein a metal or metalloid compound is chosen from Table 1.

20. The process of claim 12 or 13, wherein a metal compound is chosen from Table 2.

13. A process for forming materials comprising phosphorus, oxygen and one or more metals or metalloids, comprising:

exposing a substrate alternately to a vapor of a bis(alkyl)phosphate and a vapor of one or more of a metal compound and metalloid compound to form a film on the substrate.

21. The process of claim 13 or 14, wherein a metal or metalloid compound is selected from Table 3.

22. A process for forming a material comprising a metal and oxygen, comprising:

exposing a substrate to a vapor of one or more arene hydrates and a vapor of one or more metal compounds to form a metal oxide.

23. The process of claim 22, wherein the arene hydrate is benzene hydrate, a naphthalene hydrate, a substituted benzene hydrate or a substituted naphthalene hydrate.

24. A process for forming a metal oxide, comprising:

exposing a heated surface alternately to the vapor of one or more metal amides having an amido group selected from the group consisting of dialkylamido, disilylamido and (alkyl)(silyl) amido moieties, and then to the vapors of water or an alcohol.

25. A process as in claim 24, wherein the alcohol is an arene hydrate.

26. A process as in claim 24, wherein the metal amide or amides are chosen from Table 1.

29. A process as in claim 24, in which a metal amide compound is a liquid at room temperature.

30. A process as in claim 29, in which the liquid dialkylamido metal compound is tetrakis(ethylmethylamido)hafnium, Hf(NetMe)₄.

31. A process as in any one of claims 24, 26, 29 or 30, in which the metal oxide film covers an aspect ratio over 40.

27. A process for forming material comprising oxygen and one or more metals, comprising:

exposing a surface alternately to the vapor of one or more organometallic compounds and then to the vapors of an arene hydrate.

28. A process as in claim 27, wherein the organometallic compounds are chosen from Table 2.