Method for delivering an involatile reagent in vapor form to a CVD reactor

• US 5,204,314 A
• Filed: 12/13/1991
• Issued: 04/20/1993
• Est. Priority Date: 07/06/1990
• Status: Expired due to Term

• Current Assignee: Entegris Incorporated
• Original Assignee: Advanced Technology Materials, Inc. (Entegris Incorporated)
• Inventors: Gardiner, Robin A., Kirlin, Peter S., Binder, Robin L.
• Primary Examiner(s): Beck, Shrive
• Assistant Examiner(s): King, Roy V.
• Application Number:
  US07/807,807
• Time in Patent Office: 494 Days
• Field of Search: 505/1, 505/734, 505/730, 427/62, 427/63, 427/255.3, 427/255.2, 427/255.1, 427/126.3, 427/248.1, 427/314, 427/419.1, 427/419.2, 118/726, 219/6.5, 219/10.41, 261/DIG. 65, 159/906
• US Class Current: 505/447
• CPC Class Codes: C23C 16/18 from metallo-organic compounds
• CPC Class Codes: C23C 16/40 Oxides
• CPC Class Codes: C23C 16/408 of copper or solid solutions thereof
• CPC Class Codes: C23C 16/409 of the type ABO3 with A representing alkali, alkaline earth metal or lead and B representing a refractory metal, nickel, scandium or a lanthanide
• CPC Class Codes: C23C 16/4481 by evaporation using carrier gas in contact with the source material C23C16/4486 takes precedence
• CPC Class Codes: C23C 16/4483 using a porous body
• CPC Class Codes: C23C 16/45561 Gas plumbing upstream of the reaction chamber
• CPC Class Codes: H10N 60/0464 by metalloorganic chemical vapour deposition [MOCVD]
• CPC Class Codes: Y10S 438/935 Gas flow control
• CPC Class Codes: Y10S 505/73 Vacuum treating or coating
• CPC Class Codes: Y10S 505/734 From organometallic precursors, e.g. acetylacetonates

Abstract

A process and apparatus for delivering an involatile reagent in gaseous form, wherein an involatile reagent source liquid is flash vaporized on a vaporization matrix structure at elevated temperature. A carrier gas may be flowed past the flash vaporization matrix structure to yield a carrier gas mixture containing the flash vaporized source reagent. The matrix structure preferably has a high surface-to-volume ratio, and may suitably com

GOVERNMENT RIGHTS IN INVENTION

This invention was made with Government support under Contract No. N00014 88-0531 awarded by the Defense Advanced Projects Research Administration (DARPA). The Government has certain rights in this invention.

Claims

1. A process for delivering an involatile solid source reagent material having a vapor pressure of less than about 0.1 torr at 25°

C. and 1 atmosphere conditions, and which is thermally unstable at its vaporization temperature, as a source regent material vapor into a CVD reactor, said process comprising;

providing a supply vessel containing a reagent source liquid formed by dissolving the involatile solid source reagent material in a non-azotropic organic solvent, wherein the reagent source liquid is contained in the supply vessel in a non-heated state, at or below room temperature;

arranging a flash vaporization structure comprising a foraminous element having a surface-to-volume ratio of at least 4, in liquid flow communication with the supply vessel containing the reagent source liquid;

heating the foraminous element to a flash vaporization temperature for the involatile solid source reagent material; and

flowing the reagent source liquid from the supply vessel to the heated foraminous element, with the reagent source liquid in a non-atomized state directly issuing a liquid stream of the reagent source liquid onto the heated foraminous element, and flash vaporizing the involatile solid source material from the reagent source liquid to form the source reagent material vapor.

2. A process according to claim 1, wherein the involatile solid source reagent material comprises inorganic and/or organometallic compound(s).

3. A process according to claim 1, wherein the solvent comprises a solvent selected from the group consisting of alcohols, ethers, and amines.

4. A process according to claim 1, wherein the solvent comprises an alkanolic solvent.

5. A process according to claim 1, comprising the further step of flowing a carrier gas past the flash vaporization structure to form a carrier gas mixture containing the source reagent material vapor.

6. A process according to claim 5, comprising the further step of flowing the carrier gas mixture into a CVD reaction zone, and depositing a constituent of the source reagent material vapor on a substrate therein.

7. A process according to claim 5, wherein the carrier gas comprises an inert gas.

8. A process according to claim 1, wherein the involatile solid source reagent material comprises a beta-diketonate source reagent.

9. A process according to claim 1, wherein the involatile solid source reagent material comprises an element selected from the group consisting of barium, calcium, strontium, zirconium, and hafnium.

10. A process according to claim 1, wherein the involatile solid source reagent material comprises at least one material selected from the group consisting of Ba(fod)₂, Ca(fod)₂, and Sr(fod)₂.

11. A process according to claim 1, wherein the involatile solid source reagent material comprises at least one material selected from the group consisting of Ba(fod)₂ ;

barium hexafluoroacetylacetone;

barium hexafluoroacetylacetone/tetraglyme adduct;

1,1,3,4,5-pentamethyl-1,3-cyclopentadienyl barium; and

barium bis(2,2,6,6-tetramethyl-3,5-heptanedione).

12. A process according to claim 1, wherein the involatile solid source reagent material comprises at least one material selected from the group consisting of Ca(fod)₂ ;

calcium hexafluoroacetylacetone;

calcium hexafluoroacetylacetone/tetraglyme adduct;

1,1,3,4,5-pentamethyl-1,3-cyclopentadienyl calcium; and

calcium bis(2,2,6,6-tetramethyl-3,5-heptanedione).

13. A process according to claim 1, wherein the involatile solid source reagent material comprises at least one material selected from the group consisting of Sr(fod)₂ ;

strontium hexafluoroacetylacetone;

strontium hexafluoroacetylacetone/tetraglyme adduct;

1,1,3,4,5-pentamethyl-1,3-cyclopentadienyl strontium; and

strontium bis(2,2,6,6-tetramethyl-3,5-heptanedione).

14. A process according to claim 1, wherein the flash vaporization structure comprises a foraminous element selected from the group consisting of screen elements, porous sintered material elements, and grid elements.

15. A process according to claim 1, wherein the flash vaporization structure comprises a fine mesh screen.

16. A process according to claim 12, wherein the surface-to-volume ratio is at least 10.

17. A process according to claim 1, wherein the involatile solid source reagent material comprises a Group II beta-diketonate material, and the solvent comprises an alkanolic solvent.

18. A process according to claim 1, wherein the reagent source liquid comprises (i) the involatile solid source reagent material and (ii) a solvent which has sufficiently low volatility so that it is non-vaporized under conditions which are flash vaporizingly effective for the involatile solid source reagent material on the heated foraminous element, said process further comprising the step of recovering the solvent and recirculating same for make-up of the reagent source liquid.

19. A process according to claim 18, wherein the solvent is recovered at a locus in proximity to the flash vaporization structure.

20. A process according to claim 1, further comprising the steps of flowing the source reagent material vapor to a CVD reaction zone, and depositing a component of the source reagent material vapor on a substrate therein.

21. A process according to claim 18, wherein the solvent comprises a perfluorinated ether.

22. A process according to claim 20, wherein a tetraglyme adduct of the involatile solid source reagent material is dissolved in the perfluorinated ether, to form the reagent source liquid.

23. A method of forming a composite article comprising a silicon or gallium arsenide substrate comprising:

forming on the silicon or gallium arsenide substrate a graded epitaxial layer comprising at least two metal fluorides selected from the group consisting of barium fluoride, calcium fluoride, and strontium fluoride by CVD using metal involatile solid source reagent compounds therefor,

wherein the metal involatile solid source reagent compounds are supplied in a source reagent compounds vapor, by a process comprising;

dissolving each of the involatile solid source reagent compounds, which are thermally unstable at their vaporization temperatures, in a non-azeotropic organic solvent to form a reagent source liquid, wherein the reagent source liquid is maintained in a non-heated state, at or below room temperature;

providing a foraminous element having a surface-to-volume ratio of at least 4;

heating the foraminous element to a flash vaporization temperature for the involatile solid source reagent compounds; and

flowing reagent source liquid in a non-atomized state as a liquid stream onto the heated foraminous element, and flash vaporizing the involatile solid source reagent compounds from the reagent source liquid to form the source reagent compounds vapor; and

forming on the graded metal fluoride epitaxial layer an overlayer of a material selected from the group consisting of silicon, gallium arsenide, and copper oxide HTSC materials, with the proviso that the overlayer material is different from the material of the substrate.

24. A method according to claim 23, wherein the substrate comprises silicon, and the overlayer comprises an HTSC material.

25. A method according to claim 24, wherein the graded epitaxial layer is selected from layers of the group consisting of (BaF₂ /CaF₂), (SrF₂ /CaF₂), and (BaF₂ /CaF₂ /SrF₂).