Insulating and functionalizing fine metal-containing particles with conformal ultra-thin films

• US 6,713,177 B2
• Filed: 07/16/2002
• Issued: 03/30/2004
• Est. Priority Date: 06/21/2000
• Status: Expired due to Term

• Current Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Original Assignee: The Board of Regents of the University of Colorado (University of Colorado System)
• Inventors: George, Steven M., Wank, Jeffrey R., Ferguson, John D., Weimer, Alan W.
• Primary Examiner(s): KILIMAN, LESZEK B
• Application Number:
  US10/196,934
• Publication Number:
  US 20030026989A1
• Time in Patent Office: 623 Days
• Field of Search: 428/402, 428/403, 428/404, 427/128, 427/215, 427/561, 427/255, 427/255.3, 427/126.1, 427/212, 427/214, 427/249.1, 427/249.5
• US Class Current: 428/402
• CPC Class Codes: B01J 2/006 Coating of the granules without description of the process or the device by which the granules are obtained to prevent the granules sticking together B01J2/30
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 23/755 Nickel
• CPC Class Codes: B01J 27/24 Nitrogen compounds
• CPC Class Codes: B01J 37/0207 Pretreatment of the support
• CPC Class Codes: B01J 37/0238 via the gaseous phase-sublimation
• CPC Class Codes: B01J 37/024 Multiple impregnation or coating
• CPC Class Codes: B01J 37/086 Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
• CPC Class Codes: B22F 1/16 Metallic particles coated with a non-metal coated with lubricating or binding agents or with organic material B22F1/10
• CPC Class Codes: B22F 1/17 Metallic particles coated with metal
• CPC Class Codes: B22F 1/18 Non-metallic particles coated with metal
• CPC Class Codes: C04B 14/322 Carbides
• CPC Class Codes: C04B 14/325 Nitrides
• CPC Class Codes: C04B 20/1066 Oxides, Hydroxides
• CPC Class Codes: C04B 2235/3225 Yttrium oxide or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3244 Zirconium oxides, zirconates, hafnium oxides, hafnates, or oxide-forming salts thereof
• CPC Class Codes: C04B 2235/3821 Boron carbides
• CPC Class Codes: C04B 2235/3839 Refractory metal carbides
• CPC Class Codes: C04B 2235/3843 Titanium carbides
• CPC Class Codes: C04B 2235/3847 Tungsten carbides
• CPC Class Codes: C04B 2235/386 : Boron nitrides
• CPC Class Codes: C04B 2235/3865 : Aluminium nitrides
• CPC Class Codes: C04B 2235/3873 : Silicon nitrides, e.g. silicon carbonitride, silicon oxynitride
• CPC Class Codes: C04B 2235/444 : Halide containing anions, e.g. bromide, iodate, chlorite
• CPC Class Codes: C04B 2235/446 : Sulfides, tellurides or selenides
• CPC Class Codes: C04B 35/581 : based on aluminium nitride
• CPC Class Codes: C04B 35/583 : based on boron nitride
• CPC Class Codes: C04B 35/584 : based on silicon nitride
• CPC Class Codes: C04B 35/628 : Coating the powders or the macroscopic reinforcing agents
• CPC Class Codes: C04B 35/62807 : Silica or silicates
• CPC Class Codes: C04B 35/62813 : Alumina or aluminates
• CPC Class Codes: C04B 35/62815 : Rare earth metal oxides
• CPC Class Codes: C04B 35/62821 : Titanium oxide
• CPC Class Codes: C04B 35/62828 : Non-oxide ceramics
• CPC Class Codes: C04B 35/62831 : Carbides
• CPC Class Codes: C04B 35/62836 : Nitrides
• CPC Class Codes: C04B 35/62842 : Metals
• CPC Class Codes: C04B 35/62884 : by gas phase techniques
• CPC Class Codes: C04B 35/62894 : with more than one coating layer
• CPC Class Codes: C04B 35/62897 : Coatings characterised by their thickness
• CPC Class Codes: C04B 41/009 : characterised by the material treated
• CPC Class Codes: C04B 41/4531 : by C.V.D.
• CPC Class Codes: C04B 41/4584 : Coating or impregnating of particulate or fibrous ceramic material C04B20/10, C04B35/628 take precedence
• CPC Class Codes: C04B 41/5027 : Oxide ceramics in general; Specific oxide ceramics not covered by C04B41/5029 - C04B41/5051
• CPC Class Codes: C04B 41/5031 : Alumina
• CPC Class Codes: C04B 41/5035 : Silica
• CPC Class Codes: C04B 41/52 : Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
• CPC Class Codes: C04B 41/81 : Coating or impregnation
• CPC Class Codes: C04B 41/89 : for obtaining at least two superposed coatings having different compositions
• CPC Class Codes: C23C 10/06 : using gases
• CPC Class Codes: C23C 16/402 : Silicon dioxide
• CPC Class Codes: C23C 16/403 : of aluminium, magnesium or beryllium
• CPC Class Codes: C23C 16/4417 : Methods specially adapted for coating powder
• CPC Class Codes: C23C 16/442 : using fluidised bed process
• CPC Class Codes: C23C 16/45525 : Atomic layer deposition [ALD]
• CPC Class Codes: C23C 16/45555 : applied in non-semiconductor technology
• CPC Class Codes: C23C 30/00 : Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process C23C26/00, C23C28/00 take precedence
• CPC Class Codes: C23C 8/02 : Pretreatment of the material to be coated C23C8/04 takes precedence
• CPC Class Codes: H01L 23/295 : containing a filler H01L23/296 takes precedence
• CPC Class Codes: H01L 23/3737 : Organic materials with or without a thermoconductive filler
• CPC Class Codes: H01L 2924/00 : Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
• CPC Class Codes: H01L 2924/0002 : Not covered by any one of groups H01L24/00, H01L24/00 and H01L2224/00
• CPC Class Codes: Y02T 50/60 : Efficient propulsion technologies, e.g. for aircraft
• CPC Class Codes: Y10T 428/2982 : Particulate matter [e.g., sphere, flake, etc.]
• CPC Class Codes: Y10T 428/2991 : Coated
• CPC Class Codes: Y10T 428/2993 : Silicic or refractory material containing [e.g., tungsten oxide, glass, cement, etc.]
• CPC Class Codes: Y10T 428/2998 : including synthetic resin or polymer

Abstract

Particles have an ultrathin, conformal coating are made using atomic layer deposition methods. The base particles include ceramic and metallic materials. The coatings can also be ceramic or metal materials that can be deposited in a binary reaction sequence. The coated particles are useful as fillers for electronic packaging applications, for making ceramic or cermet parts, as supported catalysts, as well as other applications.

Claims

1. A material in the form of non-agglomerated particles having an average diameter of less than about 500 microns, comprising substrate particles having an ultrathin film of an inorganic material deposited on the surface thereof.

2. The material of claim 1 wherein the inorganic material has a thickness of from about 0.5 to about 35 nanometers.

3. The material of claim 1 wherein the inorganic material is a metal or an inorganic oxide, nitride, sulfide or phosphide.

4. The material of claim 3 wherein the substrate particles are of a Group 3, 13 or 14 nitride or a Group 4, 6, 13 or 14 carbide, and the ultrathin inorganic material is an inorganic oxide or a metal.

5. The material of claim 4 wherein the substrate particles are of a sinterable material and the inorganic material is a metal.

6. The material of claim 5 wherein the ultrathin inorganic material is a sintering aid.

7. The material of claim 2 wherein the substrate particles are metal particles and the ultrathin inorganic material is an inorganic oxide, nitride, sulfide or phosphide.

8. The material of claim 7 wherein the metal is iron and the ultrathin inorganic material is transparent to IR radiation.

21. A resin matrix filled with particles of claim 1.

22. An electronic component encapsulated with a resin matrix of claim 21.

23. A method of making a cermet part, comprising forming a shaped mass of particles of claim 5, and then exposing said shaped mass to conditions sufficient to sinter the particles to form a part.

24. The method of claim 23, wherein said ultrathin inorganic material is cobalt, aluminum, or nickel aluminide.

25. A method of making a ceramic material, comprising forming a shaped mass of particles of claim 6 and then exposing said shaped mass to conditions sufficient to sinter the particles to form a shaped part.

26. A method of catalyzing a chemical reaction, comprising conducting said chemical reaction in the presence of particles of claim 1, wherein the inorganic material is a metal that is a catalyst for said chemical reaction.

27. The resin matrix of claim 21, wherein the particles are BN particles coated with an ultrathin layer of alumina, which is in turn coated with an ultrathin layer of silica.

28. The resin matrix of claim 21, wherein the substrate particle is a metal and the inorganic material is a conformal coating of a non-conductive inorganic material.

29. The resin matrix of claim 21, wherein the substrate particle is a metal and the inorganic material is a conformal coating of an inorganic material having surface O—

H, N—

H or S—

H groups.

30. The material of claim 1 wherein the inorganic material forms a conformal coating.

31. The material of claim 1 wherein the substrate particle is a metal fuel and the inorganic material is an oxidizer.

32. The material of claim 31 wherein the metal fuel is aluminum and the oxidizer is NiO, WO₃, Co₃O₄, MnO or SnO₂.

33. An explosive device comprising the material of claim 32.

34. A thermite rod comprising the material of claim 32.

35. The material of claim 1 wherein the substrate material is iron and the inorganic material is silica.

36. The material of claim 1 wherein the substrate particle is magnetic or paramagnetic.

37. A magnetically responsive composition comprising the material of claim 36, particles of activated carbon, the material and the activated carbon having a particle size of 1-1000 nm, and a therapeutic or diagnostic substance.

38. A magnetically responsive composition comprising the material of claim 36 having a particle size of 1-1000 nm, a biologically inert polymer and a therapeutic or diagnostic substance, wherein the therapeutic or diagnostic substance is sorbed onto the biologically inert polymer, the biologically inert polymer is present on a surface of the material, and the biologically inert polymer is biologically benign.

39. A method for delivering a pharmaceutical to a specific site in a patient, comprising:

(a) delivering the material of claim 37 into a blood vessel of the patient; and

(b) establishing a magnetic field exterior to the patient and adjacent to the specific site of sufficient field strength to guide a portion of said material through the blood vessel to a point at or near the site so that a therapeutic amount of the therapeutic or diagnostic substance concentrates at the specific site.

40. A method for delivering a pharmaceutical to a specific site in a patient, comprising:

(a) delivering the material of claim 38 into a blood vessel of the patient; and

(b) establishing a magnetic field exterior to the patient and adjacent to the specific site of sufficient field strength to guide a portion of said material through the blood vessel to a point at or near the site so that a therapeutic amount of the therapeutic or diagnostic substance concentrates at the specific site.

41. The method of claim 39 wherein the specific site is a disease site.

42. The method of claim 40 wherein the specific site is a disease site.

43. The material of claim 3 wherein the inorganic material is alumina and the substrate particles are Fe, Co, Ni, Zn, Mn, Mg, Ca, Ba, Sr, Cd, Hg, Al, B, Sc, Ga, V, Ti, or In.

44. The material of claim 3 wherein the inorganic material is alumina and wherein the substrate particles are Nd—

Fe—

B.

45. The material of claim 3 wherein the inorganic material is alumina and wherein the substrate particles are Fe₃O₄, Fe₂O₃, TiO₂, ZnO, or FeO.

46. The material of claim 3 wherein the inorganic material is alumina and the substrate material is nickel (Ni) and has a particle size of between 50 and 150 microns.

53. The material of claim 1 wherein the non-agglomerated particles have an average particle size not more than 5% greater than the substrate particles, apart from particle size increases attributable to the thickness of the coating.

54. The material of claim 1 wherein no more than 2 weight percent of the particles become agglomerated during the deposition of the ultrathin inorganic material.

9. A method for depositing an ultrathin inorganic material on substrate particles comprising conducting a sequence of two or more self-limiting reactions at the surface of said substrate particles to form coated particles having an ultrathin layer of an inorganic material bonded to the surface of said substrate particles.

10. The method of claim 9, wherein the sequence is a binary sequence of reactions represented as

11. The method of claim 10 wherein M¹ is silicon, titanium or aluminum.

12. The method of claim 9 wherein the sequence is a binary sequence of reactions represented as

13. The method of claim 9 wherein the sequence is a binary sequence of reactions represented as

14. The method of claim 9 wherein the substrate particles are an inorganic nitride or carbide.

15. The method of claim 9 wherein the sequence of reactions is continued until a coating of desired thickness is obtained.

16. The method of claim 15 wherein the ultrathin inorganic material has a thickness of about 0.5 to about 35 nanometers.

17. The method of claim 9 wherein a precursor reaction is conducted to impart functional groups on the surface of the substrate particle before conducting said sequence of reactions.

18. The method of claim 9 wherein said sequence of reactions is a sequence of catalyzed reactions.

19. The method of claim 9 wherein said sequence of reactions is a binary sequence of reactions comprising contacting said substrate particle alternately with a metal halide and a metal halide reducing agent.

20. The method of claim 19 wherein said metal halide is a fluoride or chloride of tungsten, rhenium, molybdenum, antimony, selenium, thallium, chromium, platinum, ruthenium, iridium, or germanium.

47. A non-agglomerated product made by the process of claim 9.

48. A non-agglomerated product made by the process of claim 13.

49. A non-agglomerated product made by the process of claim 16.

50. A non-agglomerated product made by the process of claim 18.

51. The process of claim 9 wherein the coated particles have an average particle size not more than 5% more than the substrate particles, apart froms particle size increases attributable to the thickness of the coating.

52. The process of claim 9 wherein no more than 2 weight percent of the particles become agglomerated during the deposition of the ultrathin inorganic material.

55. A material in the form of particles having an average diameter of less than about 500 microns, comprising substrate particles having an ultrathin, conformal continuous or semicontinuous film of an inorganic material deposited on the surface thereof.

56. The material of claim 55 wherein the film has thickest regions that are no greater than 3 times the thickness of thinnest regions of the film, as determined by a method that has a resolution of 10 nm or below.

57. The material of claim 56 wherein the inorganic material has a thickness of from about 0.5 to about 35 nanometers.

58. The material of claim 57 wherein the inorganic material is a metal or an inorganic oxide, nitride, sulfide or phosphide.

59. The material of claim 58 wherein the substrate particles are of a Group 3, 13 or 14 nitride or a Group 4, 6, 13 or 14 carbide, and the ultrathin inorganic material is an inorganic oxide or a metal.

60. The material of claim 59 wherein the substrate particles are of a sinterable material and the inorganic material is a metal.

61. The material of claim 60 wherein the ultrathin inorganic material is a sintering aid.

62. The material of claim 57 wherein the substrate particles are metal particles and the ultrathin inorganic material is an inorganic oxide, nitride, sulfide or phosphide.

63. The material of claim 62 wherein the metal is iron and the ultrathin inorganic material is transparent to IR radiation.

64. The material of claim 55 wherein the substrate particle is a metal fuel and the inorganic material is an oxidizer.

65. The material of claim 64 wherein the metal fuel is aluminum and the oxidizer is NiO, WO₃, Co₃O₄, MnO or SnO₂ .

66. The material of claim 55 wherein the substrate material is iron and the inorganic material is silica.

67. The material of claim 55 wherein the substrate particle is magnetic or paramagnetic.

68. The material of claim 55 wherein the film is substantially free of pinholes and defects.

69. A resin matrix filled with particles of claim 55.

70. The resin matrix of claim 69, wherein the particles are BN particles coated with an ultrathin layer of alumina, which is in turn coated with an ultrathin layer of silica.

71. The resin matrix of claim 69, wherein the substrate particle is a metal and the inorganic material is a conformal coating of a non-conductive inorganic material.

72. A method of making a cermet part, comprising forming a shaped mass of particles of claim 60, and then exposing said shaped mass to conditions sufficient to sinter the particles to form a part.

73. The method of claim 72, wherein said ultrathin inorganic material is cobalt, aluminum, or nickel aluminide.

74. A method of making a ceramic material, comprising forming a shaped mass of particles of claim 61 and then exposing said shaped mass to conditions sufficient to sinter the particles to form a shaped part.

75. A method of catalyzing a chemical reaction, comprising conducting said chemical reaction in the presence of particles of claim 55, wherein the inorganic material is a metal that is a catalyst for said chemical reaction.

76. An explosive device comprising the material of claim 64.

77. A thermite rod comprising the material of claim 64.

78. A magnetically responsive composition comprising the material of claim 67, having particles of activated carbon, the material and the activated carbon each having a particle size of 1-1000 nm, and a therapeutic or diagnostic substance.

79. A magnetically responsive composition comprising the material of claim 67 having a particle size of 1-1000 nm, a biologically inert polymer and a therapeutic or diagnostic substance, wherein the therapeutic or diagnostic substance is sorbed onto the biologically inert polymer, the biologically inert polymer is present on a surface of the material and the biologically inert polymer is in biologically benign.

80. A method for delivering a pharmaceutical to a specific site in a patient, comprising:

(a) delivering the material of claim 78 into a blood vessel of the patient; and

(b) establishing a magnetic field exterior to the patient and adjacent to the specific site of sufficient field strength to guide a portion of said material through the blood vessel to a point at or near the site so that a therapeutic amount of the therapeutic or diagnostic substance concentrates at the specific site.

81. A method for delivering a pharmaceutical to a specific site in a patient, comprising:

(a) delivering the material of claim 79, into a blood vessel of the patient; and

(b) establishing a magnetic field exterior to the patient and adjacent to the specific site of sufficient field strength to guide a portion of said material through the blood vessel to a point at or near the site so that a therapeutic amount of the therapeutic or diagnostic substance concentrates at the specific site.

82. The method of claim 80 wherein the specific site is a disease site.

83. The method of claim 81 wherein the specific site is a disease site.