Liquid chemical deposition apparatus and process and products therefrom

• US 8,354,294 B2
• Filed: 07/26/2010
• Issued: 01/15/2013
• Est. Priority Date: 01/24/2006
• Status: Active Grant

• Current Assignee: L Pierre Derochemont
• Original Assignee: L Pierre Derochemont
• Inventors: de Rochemont, L. Pierre, Kovacs, Alexander J.
• Primary Examiner(s): Nguyen, Dao H
• Application Number:
  US12/843,112
• Publication Number:
  US 20110021007A1
• Time in Patent Office: 904 Days
• Field of Search: 438/66, 438/80, 438/98, 257/290, 257/291, 257/434, 257/446, 257/461, 136/244, 136/251
• US Class Current: 438/66
• CPC Class Codes: B32B 15/00 Layered products comprising a layer of metal
• CPC Class Codes: B32B 18/00 Layered products essentially comprising ceramics, e.g. refractory products
• CPC Class Codes: B32B 5/00 Layered products characterised by the non- homogeneity or physical structure , i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
• CPC Class Codes: B32B 5/22 characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed layer formed of natural mineral fibres or particles next to a foam layer B32B19/047, next to a layer made of particles B32B19/048, or next to a fibrous or filamentary layer B32B19/06; paper layer or cardboard layer next to a paper layer or cardboard layer B32B29/005, next to a foam layer B32B29/007, next to a fibrous or filamentary layer B32B29/02, or next to a particulate layer B32B29/04
• CPC Class Codes: C23C 18/1204 inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
• CPC Class Codes: C23C 18/1212 Zeolites, glasses
• CPC Class Codes: C23C 18/1216 Metal oxides C23C18/1212 takes precedence
• CPC Class Codes: C23C 18/1291 by heating of the substrate
• CPC Class Codes: C23C 18/1295 with after-treatment of the deposited inorganic material
• CPC Class Codes: C23C 18/143 Radiation by light, e.g. photolysis or pyrolysis
• CPC Class Codes: Y10T 428/24942 including components having same physical characteristic in differing degree
• CPC Class Codes: Y10T 428/249921 Web or sheet containing structurally defined element or component
• CPC Class Codes: Y10T 428/25 Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
• CPC Class Codes: Y10T 428/258 Alkali metal or alkaline earth metal or compound thereof
• CPC Class Codes: Y10T 428/31504 Composite [nonstructural laminate]
• CPC Class Codes: Y10T 428/31678 Of metal

Abstract

A method, apparatus and material produced thereby in an amorphous or crystalline form having multiple elements with a uniform molecular distribution of elements at the molecular level.

Claims

1. A method for forming an amorphous material, comprising the steps of:

mixing liquid metalorganic precursors in solution;

projecting a liquid aerosol of the metalorganic precursor solution toward a surface in a deposition chamber having a controlled gas atmosphere;

exposing the projected aerosol to a plurality of internal process areas within the deposition chamber, prior to contact of the projected aerosol with the surface to phase separate and evaporate liquid solvents from the aerosolized metalorganic precursors;

heating the surface to a temperature higher than decomposition temperatures of the metalorganic precursors; and

decomposing the metalorganic precursors upon contact with the heated surface to form the amorphous material.

2. The method of claim 1, wherein the step of exposing comprises exposing the projected aerosol to a plurality of radiant energy or thermal sources located on a side of the deposition chamber to create the plurality internal process areas prior to contact with the surface.

3. The method of claim 2, wherein the step of exposing the projected aerosol forms a thermal gradient in a heating field located in the deposition chamber.

4. The method of claim 3, wherein the heating field thermal gradient raises the temperature of the projected liquid aerosol above the evaporation temperature of all liquid solvents in the aerosol.

5. The method of claim 2, wherein the step of exposing includes adjusting the plurality of radiant energy or thermal sources to delineate distinct phase boundaries of the projected aerosol within the deposition chamber.

6. The method of claim 1, wherein the step of projecting includes using a preheated gas or gas mixture to project the liquid aerosol and which determines the controlled gas atmosphere in the deposition chamber.

7. The method of claim 1, wherein the metalorganic precursors consist of carboxylate salts, alkoxides, or metal alkyls, or β

-ketonates.

8. The method of claim 1, wherein the surface is heated in the step of heating to a temperature above 250°

C. and below any crystallizing nucleation temperature of the amorphous material to be formed.

9. The method of claim 8, wherein the surface is heated to a temperature less than 400°

C.

10. The method of claim 9, further comprising removing any residual organic material from the amorphous material by the application of a heat treatment in a controlled gas atmosphere that raises the temperature of the formed amorphous material to ≦

450°

C.

11. The method of claim 10, wherein the heat treatment is performed with the simultaneous application of ultraviolet light.

12. The method of claim 1, further comprising forming a crystalline material from formed amorphous material with a subsequent heating step.

13. The method of claim 12, wherein the subsequent heating step is a rapid thermal annealing step.

14. The method of claim 12, wherein the formed crystalline material has a grain size less than 100 nm in length.

15. The method of claim 14, further comprising removing the surface upon which the amorphous material was formed.

16. The method of claim 12, wherein the formed crystalline material is semiconductor, metal, super-alloy or ceramic.

17. The method of claim 12, wherein the formed crystalline material is a semiconductor selected from the group consisting of gallium arsenide, cadmium telluride, silicon-germanium, germanium, or copper indium gallium selenide.

18. The method of claim 12, where the liquid metalorganic precursors are mixed at the molecular level, and further wherein the formed crystalline material has a chemical mixture of elements that are uniformly subdivided at the atomic scale.

19. The method of claim 1, wherein the amorphous material is a metal oxide ceramic and the controlled gas atmosphere comprises air, an inert gas mixture containing an oxygen partial pressure, or an inert gas mixture containing chemically oxidizing partial pressures of carbon dioxide and carbon monoxide.

20. The method of claim 1, wherein the amorphous material is a metal alloy, superalloy, a semi-metal or semiconductor and the controlled gas atmosphere comprises an inert gas mixture containing argon, nitrogen or hydrogen, or chemically reducing partial pressures of carbon dioxide and carbon monoxide.

21. The method of claim 1, wherein the formed amorphous material has an elemental composition which varies ≦

±

1.5 mol % at the atomic scale.

22. The method of claim 1, wherein the formed amorphous material is amorphous silica, indium-tin oxide, gallium arsenide, cadmium telluride, silicon-germanium, germanium or copper indium gallium selenide.

23. The method of claim 1, wherein the liquid metalorganic precursors are mixed at a molecular level, and further wherein the amorphous material has a chemically precise mixture of elements that are uniformly subdivided at an atomic scale.

24. An apparatus for forming an amorphous material comprising:

a deposition chamber;

a spraying device located for projecting a liquid aerosol of metalorganic precursors toward a surface located in the deposition chamber;

a plurality of radiant energy or thermal sources located on a side of the deposition chamber to create a plurality of internal process areas to phase separate and evaporate liquid solvents from aerosolized metalorganic precursors prior to contact with the surface; and

a heater adapted to heat the surface to a temperature higher than the decomposition temperature of the metalorganic precursors,

wherein the heater is effective to cause decomposition of the metalorganic precursors upon contact with the surface when heated to form the amorphous material.

25. The apparatus of claim 24, wherein the plurality of radiant energy or thermal sources form a thermal gradient to raise the temperature of the metalorganic precursors exposed thereto.

26. The apparatus of claim 25, wherein thermal gradient is adapted to raise the temperature of the projected liquid solution above the evaporation temperature of all liquid solvents in the liquid aerosol.

27. The apparatus of claim 24, further comprising a controlled gas atmosphere in the deposition chamber, wherein the controlled gas atmosphere and the heater are effective to cause decomposition of the metalorganic precursors upon contact with the surface to form the amorphous material.

28. The apparatus of claim 27, wherein the spraying device includes a gas source for use in projecting the liquid aerosol and for thereby providing the controlled gas atmosphere and further comprising a supplemental heater coupled for preheating gasses from the gas source prior to projecting the liquid aerosol.

29. The apparatus of claim 24, further comprising a secondary bake out station that provides a controlled gas atmosphere and is adapted to remove any residual organic matter by heat treating the formed amorphous material at temperatures between 400°

C. and 600°

C.

30. The apparatus of claim 29, wherein the secondary bake-out station includes an ultraviolet light source used to accelerate the removal of organic material from the formed amorphous matter.

31. The apparatus of claim 24, further comprising an annealing station having a controlled gas environment and a heating mechanism effective to crystallize the formed amorphous material.

32. The apparatus of claim 31, wherein the heating mechanism is a rapid thermal annealing mechanism.

33. The apparatus of claim 32, wherein the rapid thermal annealing mechanism is an atmosphere controlled ionizing plasma.

34. The apparatus of claim 24, further comprising a robotic handling system adapted to transfer formed amorphous material between one or more deposition chambers, one or more secondary bake-out stations, and one or more annealing stations.

35. The apparatus of claim 34, further comprising an overall control system for coordinated operation of the robotic handling system, one or more deposition chambers, one or more secondary bake-out stations, and one or more annealing stations.

36. The apparatus of claim 34, further comprising a device adapted to provide a localized gas environment for shielding the formed amorphous material or reactive elements located on the surface from hazardous atmosphere.

37. A material comprising four or more elements in a crystalline material of macroscopic dimensions and having an elemental composition which varies ≦

±

1.5 mol % at the atomic scale.

38. The material of claim 37 wherein the elements have a crystalline structure and a uniform grain size less than or equal to 100 nm.

39. The material of claim 37, including copper indium gallium selenide.