Hybrid particles and associated methods

التفاصيل البيبلوغرافية
العنوان: Hybrid particles and associated methods
Patent Number: 8,951,446
تاريخ النشر: February 10, 2015
Appl. No: 13/365800
Application Filed: February 03, 2012
مستخلص: Hybrid particles that comprise a coating surrounding a chalcopyrite material, the coating comprising a metal, a semiconductive material, or a polymer; a core comprising a chalcopyrite material and a shell comprising a functionalized chalcopyrite material, the shell enveloping the core; or a reaction product of a chalcopyrite material and at least one of a reagent, heat, and radiation. Methods of forming the hybrid particles are also disclosed.
Inventors: Fox, Robert V. (Idaho Falls, ID, US); Rodriguez, Rene (Pocatello, ID, US); Pak, Joshua J. (Pocatello, ID, US); Sun, Chivin (Staten Island, NY, US)
Assignees: Battelle Energy Alliance, LLC (Idaho Falls, ID, US)
Claim: 1. A hybrid particle, comprising: a chalcopyrite material having an empirical formula of NME 2 or NME 2 R, where N comprises at least one element in Group 11 of the periodic table, M comprises at least one element in Group 13 of the periodic table, each E is independently selected from the group consisting of oxygen, sulfur, selenium, tellurium, and polonium, and R is selected from the group consisting of an alkyl group, aryl group, vinyl group, (per)fluoro alkyl group, (per)fluoro aryl group, silane group, and carbamato group; and a functionalized chalcopyrite material on the chalcopyrite material, the functionalized chalcopyrite material having an empirical formula of NME 2 (RR), [NME 2 RE] m , or NME 2 RL, wherein N comprises at least one element in Group 11 of the periodic table, M comprises at least one element in Group 13 of the periodic table, each E is independently selected from the group consisting of oxygen, sulfur, selenium, tellurium, and polonium, each R is independently selected from the group consisting of an alkyl group, aryl group, vinyl group, (per)fluoro alkyl group, (per)fluoro aryl group, silane group, and carbamato group, L comprises a carboxylic acid group, a hydroxyl group, or an amine group, and m is an integer between 1 and 100.
Claim: 2. A hybrid particle, comprising: a reaction product of a chalcopyrite material and a reagent selected from the group consisting of hydrogen, hydrogen sulfide, oxygen, selenic acid, phenylselenol, ethaneselenol, N-acetyl-L-cysteine, thioacetic acid, thiobenzoic acid, dimethyldiselenide, diethyldiselenide, diphenyldiselenide, dibenzyldiselenide, seleno-L-cysteine, cystamine dihydrochloride, dimethylselenide, diphenylselenide, diethylselenide, p-terphenyl-4,4″-dithiol, 1,4-bis(4-mercaptophenyl)benzene, 4,4′-dimercaptostilbene, biphenyl-4,4′-dithiol, 1,4-benzenedimethanethiol, polyethylene glycol dithiol, 2-mercaptoethyl ether, 2,2′-(ethylenedioxy)diethanethiol, benzene-1,2-dithiol, benzene-1,3-dithiol, benzene-1,4-dithiol, 1,2,4-thiadiazole-3,5-dithiol, 1,3,4-thiadiazole-2,5-dithiol, 2,6-dithiopurine, M-carborane-1,7-dithiol, 4-phenyl-4H-(1,2,4)triazole-3,5-dithiol, DL-dithiothreitol, mercaptoacetic acid calcium salt, 1,2-ethanediselenol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, α, ω-dithiol, resorcinarene cavitand, thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptoethanol, thiolactic acid, 3-mercapto-1,2-propanediol, mercaptosuccinic acid, O-[2-(3-mercaptopropionylamino)ethyl]-O′-methylpolyethylene glycol, 4-mercaptophenol, 4-mercaptobenzoic acid, 4-aminothiophenol, cysteamine hydrochloride, 11-mercaptoundecanoic acid, cysteaminedimethylselenide, and combinations thereof, the chalcopyrite material formed from a single source precursor of the chalcopyrite material.
Claim: 3. The hybrid particle of claim 2 , wherein the hybrid particle comprises a reaction product of CuInS 2 , CuInSe 2 , Cu(In,Ga)Se 2 , CuGaSe 2 , or AgInS 2 and a functional group comprising an alkyl group, aryl group, vinyl group, (per)fluoro alkyl group, (per)fluoro aryl group, silane group, or carbamato group of the reagent.
Claim: 4. A method of forming hybrid particles, comprising: forming chalcopyrite particles from a single source precursor of a chalcopyrite material, the chalcopyrite particles having an empirical formula of NME 2 or NME 2 R, where N comprises at least one element in Group 11 of the periodic table, M comprises at least one element in Group 13 of the periodic table, each E is independently selected from the group consisting of oxygen, sulfur, selenium, tellurium, and polonium, and R comprises an alkyl group, aryl group, vinyl group, (per)fluoro alkyl group, (per)fluoro aryl group, silane group, or carbamato group; and functionalizing the chalcopyrite particles to form hybrid particles having an empirical formula of NME 2 (RR), [NME 2 RE] m , or NME 2 RL, where N comprises at least one element in Group 11 of the periodic table, M comprises at least one element in Group 13 of the periodic table, each E is independently selected from the group consisting of oxygen, sulfur, selenium, tellurium, and polonium, R comprises an alkyl group, aryl group, vinyl group, (per)fluoro alkyl group, (per)fluoro aryl group, silane group, or carbamato group, m comprises an integer greater than or equal to 1, and L comprises a carboxylic acid group, a hydroxyl group, or an amine group.
Claim: 5. The method of claim 4 , wherein functionalizing the chalcopyrite particles comprises subjecting at least a surface of the chalcopyrite particles to at least one reagent selected from the group consisting of hydrogen (H 2), hydrogen sulfide (H 2 S), oxygen (O 2), an acidic selenium compound, phenylselenol, ethaneselenol, N-acetyl-L-cysteine, thioacetic acid, thiobenzoic acid, dimethyldiselenide, diethyldiselenide, diphenyldiselenide, dibenzyldiselenide, seleno-L-cysteine, cystamine dihydrochloride, dimethylselenide, diphenylselenide, diethylselenide, p-terphenyl-4,4″-dithiol, 1,4-bis(4-mercaptophenyl)benzene, 4,4′-dimercaptostilbene, biphenyl-4,4′-dithiol, 1,4-benzenedimethanethiol, polyethylene glycol dithiol, 2-mercaptoethyl ether, 2,2′-(ethylenedioxy)diethanethiol, benzene-1,2-dithiol, benzene-1,3-dithiol, benzene-1,4-dithiol, 1,2,4-thiadiazole-3,5-dithiol, 1,3,4-thiadiazole-2,5-dithiol, 2,6-dithiopurine, M-carborane-1,7-dithiol, 4-phenyl-4H-(1,2,4)triazole-3,5-dithiol, DL-dithiothreitol, mercaptoacetic acid calcium salt, 1,2-ethanediselenol, 1,2-ethanedithiol, 1,3-propanedithiol, 1,4-butanedithiol, 1,5-pentanedithiol, 1,6-hexanedithiol, 1,8-octanedithiol, 1,9-nonanedithiol, α,ω-dithiol, resorcinarene cavitand, thioglycolic acid, 3-mercaptopropionic acid, 2-mercaptoethanol, thiolactic acid, 3-mercapto-1,2-propanediol, mercaptosuccinic acid, O-[2-(3-mercaptopropionylamino)ethyl]-O′-methylpolyethylene glycol, 4-mercaptophenol, 4-mercaptobenzoic acid, 4-aminothiophenol, cysteamine hydrochloride, 11-mercaptoundecanoic acid, and cysteaminedimethylselenide.
Claim: 6. The method of claim 4 , wherein functionalizing the chalcopyrite particles comprises forming hybrid particles comprising a functionalized chalcopyrite material on the chalcopyrite material.
Claim: 7. The method of claim 4 , wherein functionalizing the chalcopyrite particles comprises forming hybrid particles consisting essentially of a functionalized chalcopyrite material.
Claim: 8. The method of claim 4 , further comprising forming a combination of chalcopyrite phase hybrid particles and wurtzite phase hybrid particles.
Claim: 9. The method of claim 4 , wherein functionalizing the chalcopyrite particles to form hybrid particles having an empirical formula of NME 2 (RR), [NME 2 RE] m , or NME 2 RL comprises reacting the chalcopyrite particles with a reagent having the empirical formula REH to form the hybrid particles having the empirical formula NME 2 (RR).
Claim: 10. The method of claim 4 , wherein functionalizing the chalcopyrite particles to form hybrid particles having an empirical formula of NME 2 (RR), [NME 2 RE] m , or NME 2 RL comprises reacting the chalcopyrite particles with a reagent having the empirical formula REER to form hybrid particles having the empirical formula NME 2 (RR).
Claim: 11. The method of claim 4 , wherein functionalizing the chalcopyrite particles to form hybrid particles having an empirical formula of NME 2 (RR), [NME 2 RE] m , or NME 2 RL comprises reacting the chalcopyrite particles with a reagent having the empirical formula RER to form hybrid particles having the empirical formula NME 2 (RR).
Claim: 12. The method of claim 4 , wherein functionalizing the chalcopyrite particles to form hybrid particles having an empirical formula of NME 2 (RR), [NME 2 RE] m , or NME 2 RL comprises reacting the chalcopyrite particles with a reagent having the empirical formula HEREH to form hybrid particles having the empirical formula [NME 2 RE] m .
Claim: 13. The method of claim 4 , wherein functionalizing the chalcopyrite particles to form hybrid particles having an empirical formula of NME 2 (RR), [NME 2 RE] m , or NME 2 RL comprises reacting the chalcopyrite particles with a reagent having the empirical formula HERL to form hybrid particles having the empirical formula NME 2 RL.
Claim: 14. A method of forming hybrid particles, comprising: forming chalcopyrite particles from a single source precursor of a chalcopyrite material, the chalcopyrite particles having an empirical formula of NME 2 , where N comprises copper, M comprises at least one of indium and gallium, and each E is independently selected from the group consisting of sulfur and selenium; and functionalizing the chalcopyrite particles to form CuIn(S,Se) 2 hybrid particles, CuIn 0.7 Ga 0.3 (S,Se) 2 hybrid particles, CuGa(S,Se) 2 hybrid particles, or CuInS 2 (SR/SCH 2 CH 2 COOH) m hybrid particles, where R is an alkyl group, aryl group, vinyl group, (per)fluoro alkyl group, (per)fluoro aryl group, silane group, or carbamato group and m is an integer greater than or equal to 1.
Claim: 15. The method of claim 14 , wherein forming chalcopyrite particles from a single source precursor of a chalcopyrite material comprises forming the chalcopyrite particles from CuInS 2 , CuInSe 2 , CuIn 0.7 Ga 0.3 S 2 , Cu(In,Ga)Se 2 , CuGaSe 2 , or AgInS 2 .
Claim: 16. The method of claim 14 , wherein functionalizing the chalcopyrite particles to form CuIn(S,Se) 2 hybrid particles, CuIn 0.7 Ga 0.3 (S,Se) 2 hybrid particles, CuGa(S,Se) 2 hybrid particles, or CuInS 2 (SR/SCH 2 CH 2 COOH) m hybrid particles comprises reacting CuInS 2 particles with phenylselenol to form the CuIn(S,Se) 2 hybrid particles.
Claim: 17. The method of claim 14 , wherein functionalizing the chalcopyrite particles to form CuIn(S,Se) 2 hybrid particles, CuIn 0.7 Ga 0.3 (S,Se) 2 hybrid particles, CuGa(S,Se) 2 hybrid particles, or CuInS 2 (SR/SCH 2 CH 2 COOH) m hybrid particles comprises reacting CuIn 0.7 Ga 0.3 S 2 particles with diethyldiselenide to form the CuIn 0.7 Ga 0.3 (S,Se) 2 hybrid particles.
Claim: 18. The method of claim 14 , wherein functionalizing the chalcopyrite particles to form CuIn(S,Se) 2 hybrid particles, CuIn 0.7 Ga 0.3 (S,Se) 2 hybrid particles, CuGa(S,Se) 2 hybrid particles, or CuInS 2 (SR/SCH 2 CH 2 COOH) m hybrid particles comprises reacting CuGaS 2 particles with α,ω-dithiol and diethyldiselenide to form the CuGa(S,Se) 2 hybrid particles.
Claim: 19. The method of claim 14 , wherein functionalizing the chalcopyrite particles to form CuIn(S,Se) 2 hybrid particles, CuIn 0.7 Ga 0.3 (S,Se) 2 hybrid particles, CuGa(S,Se) 2 hybrid particles, or CuInS 2 (SR/SCH 2 CH 2 COOH) m hybrid particles comprises reacting CuInS 2 particles with 3-mercaptopropionic acid to form the CuInS 2 (SR/SCH 2 CH 2 COOH) m hybrid particles.
Current U.S. Class: 25251/914
Patent References Cited: 4155781 May 1979 Diepers
4687881 August 1987 Goslowsky et al.
4906290 March 1990 Worner
5445847 August 1995 Wada et al.
5501786 March 1996 Gremion et al.
5567469 October 1996 Wada et al.
5858120 January 1999 Nakagawa et al.
6127202 October 2000 Kapur et al.
6145342 November 2000 Bayya et al.
6284314 September 2001 Kato et al.
6307148 October 2001 Takeuchi et al.
6355874 March 2002 Yagi et al.
6429369 August 2002 Tober et al.
6592938 July 2003 Pessey et al.
6875661 April 2005 Mitzi
6992201 January 2006 Scholz et al.
6992202 January 2006 Banger et al.
7068898 June 2006 Buretea et al.
7265037 September 2007 Yang et al.
7351282 April 2008 Yamaguchi
7466376 December 2008 Galvin et al.
7545051 June 2009 Yang et al.
7575699 August 2009 Strouse et al.
7615169 November 2009 Strouse et al.
7883799 February 2011 Seo et al.
7892519 February 2011 Pak et al.
2002/0005145 January 2002 Sherman
2002/0071970 June 2002 Elder et al.
2003/0226498 December 2003 Alivisatos et al.
2004/0031519 February 2004 Andriessen
2004/0095658 May 2004 Buretea et al.
2004/0120884 June 2004 Sherman
2004/0126485 July 2004 Thompson et al.
2004/0131934 July 2004 Sugnaux et al.
2004/0256001 December 2004 Mitra et al.
2005/0016577 January 2005 Andriessen et al.
2005/0133087 June 2005 Alivisatos et al.
2005/0183767 August 2005 Yu et al.
2005/0267345 December 2005 Korgel et al.
2005/0271827 December 2005 Krunks et al.
2006/0110314 May 2006 Torardi
2006/0110315 May 2006 Torardi
2006/0110316 May 2006 Torardi
2006/0110317 May 2006 Torardi
2006/0110318 May 2006 Torardi
2006/0144793 July 2006 Dadachov
2006/0159611 July 2006 Hummelen et al.
2006/0216610 September 2006 Galvin et al.
2006/0249373 November 2006 Vanderstraeten
2006/0263291 November 2006 Torardi
2007/0000537 January 2007 Leidholm et al.
2007/0025139 February 2007 Parsons
2007/0102040 May 2007 Beckenbaugh et al.
2007/0128350 June 2007 Nakamura et al.
2007/0204904 September 2007 Brooks et al.
2007/0209700 September 2007 Yonezawa et al.
2007/0277871 December 2007 Lee et al.
2007/0295385 December 2007 Sheats et al.
2008/0006322 January 2008 Wang et al.
2008/0006324 January 2008 Berke et al.
2008/0012015 January 2008 Shim et al.
2008/0023677 January 2008 Frechet et al.
2008/0026929 January 2008 Jensen et al.
2008/0031832 February 2008 Wakefield et al.
2008/0041447 February 2008 Tseng et al.
2008/0110494 May 2008 Reddy
2008/0142075 June 2008 Reddy et al.
2008/0149171 June 2008 Lu et al.
2008/0156371 July 2008 LoCascio et al.
2008/0207581 August 2008 Whiteford et al.
2008/0230120 September 2008 Reddy
2008/0289681 November 2008 Adriani et al.
2008/0289682 November 2008 Adriani et al.
2008/0308148 December 2008 Leidholm et al.
2009/0050207 February 2009 Galvin et al.
2009/0133751 May 2009 Sreenivasan et al.
2009/0173371 July 2009 Skoczenski et al.
2009/0233398 September 2009 Fox et al.
2011/0027572 February 2011 Wiesner
2011/0152554 June 2011 Fox et al.
2011/0204320 August 2011 Fox et al.
2012/0061627 March 2012 Reiss et al.
2012/0108418 May 2012 Nair et al.
2012/0192930 August 2012 Fox et al.
2472541 March 2011
WO 2010-052221 May 2010



































































Other References: Bahnemann, D. W., “Ultrasmall Metal Oxide Particles: Preparation, Photophysical Characterization, and Photocatalytic Properties”. Israel J. Chem., 1993, pp. 115-136, vol. 33. cited by applicant
Bamba et al., “TiO2—ZnO Porous Films Formed by ZnO Dissolution,” AZojomo, vol. 3, Dec. 2007, 7 pages. cited by applicant
Banger et al., “A review of single source precursors for the deposition of ternary chalcopyrite materials,” NASA Conference Publication (2002), 17th Space Photovoltaic Research and Technology Conference, 2001, pp. 115-125. cited by applicant
Banger et al., “Ternary single-source precursors for polycrystalline thin-film solar cells,” Appl. Organomet. Chem. (2002) 16:617-627. cited by applicant
Banger, K.K., et al., “A New Facile Route for the Preparation of Single-Source Precursors for Bulk, Thin-Film, and Nanocrystallite I-III-VI Semiconductors,” Inorg. Chem., 2003, pp. 7713-7715, vol. 42, No. 24. cited by applicant
Banger, K.K., et al., “Facile modulation of single source precursors: the synthesis and characterization of single source precursors for deposition of ternary chalcopyrite materials,” Thin Solid Films, 2002, pp. 390-395, vol. 403-404. cited by applicant
Banger, K.K., et al., “Synthesis and Characterization of the First Liquid Single-Source Precursors for the Deposition of Ternary Chalcopyrite (CuInS(2)) Thin Film Materials,” Chem. Mater., 2001, pp. 3827-3829, vol. 13. cited by applicant
Cardellicchio, N., et al., “Optimization of Microwave Digestion for Mercury Determination in Marine Biological Samples by Cold Vapour Atomic Absorption Spectrometry”, Annali di Chimica, 2006, pp. 159-165, vol. 96 (3-4). cited by applicant
Carro, N., et al., “Microwave-assisted solvent extraction and gas chromatography ion trap mass spectrometry procedure for the determination of persistent organochlorine pesticides (POPs) in marine sediment”, Anal. Bioanal. Chem., 2006, pp. 901-909, vol. 385. cited by applicant
Castro, S.L., et al., “Synthesis and Characterization of Colloidal CuInS(2) Nanoparticles from a Molecular Single-Source Precursor,” J Phys Chem B., 2004, pp. 12429-12435, vol. 108. cited by applicant
Castro, S.L., et al., “Nanocrystalline Chalcopyrite Materials (CuInS(2)), and CuInSe(2)) via Low-Temperature Pyrolysis of Molecular Single-Source Precursors”, Chem. Mater., 2003, pp. 3142-3147, vol. 15. cited by applicant
Choi, S.H., et al., “One-Pot Synthesis of Copper—Indium, Sulfide Nanocrystal Heterostructures with Acorn, Bottle, and Larva Shapes,” J. Am Chem Soc., 2006, pp. 2520-2521, vol. 128 (8). cited by applicant
Connor et al., “Phase Transformation of Biphasic CuS#CuInS to Monophasic CuInS Nanorods,” J. Am. Chem. Soc, 2009, 131 (13), 4962-4966. cited by applicant
De Faria, et al., “Sol-Gel TiO2 Thin Films Sensitized with the Mulberry Pigment Cyanidin,” Materials Research, vol. 10, No. 4, 413-417, 2007. cited by applicant
Deivaraj et al., “Novel bimetallic thiocarboxylate compounds as single-source precursors to binary and ternary metal sulfide materials,” Chem. Mater. (2003) 15:2383-2391. cited by applicant
Deivaraj et al., “Single-source precursors to ternary silver indium sulfide materials,” Chem. Commun. (2001) 2304-2305. cited by applicant
Deniozou et al., “Surface structure of CuGASe2 (001)” Thin Solid Films 480-481 (2005) 382-387. cited by applicant
Domini, C.E., et al., “Comparison of three optimized digestion methods for rapid determination of chemical oxygen demand: Closed microwaves, open microwaves and ultrasound irradiation,” Analytica Chimica Acta., 2006, pp. 210-217, vol. 561. cited by applicant
Dutta, D.P., et al., “A facile route to the synthesis of CuInS(2) nanoparticles,” Materials Letters, 2006, pp. 2395-2398, vol. 60. cited by applicant
Gamallo-Lorenzo, D., et al., “Microwave-assisted alkaline digestion combined with microwave-assisted distillation for the determination of iodide and total iodine in edible seaweed by catalytic spectrophotometry,” Analytica Chimica Acta., 2005, pp. 287-295, vol. 542. cited by applicant
Garcia-Vidal, J.A., et al., “Green chemistry: Efficient epoxides ring-opening with I-butanol under microwave irradiation,” Applied Surface Science, 2006, pp. 6064-6066, vol. 252 (17). cited by applicant
Gardner et al., “Rapid synthesis and size control of CuInS2 semi-conductor nanoparticles using microwave irradiation,” J. Nanoparticle Research 2008, 10(4), pp. 633-641. cited by applicant
Gerbec, J.A., et al., “Microwave-Enhanced Reaction Rates for Nanoparticle Synthesis,” J. Am. Chem. Soc., 2005, pp. 15791-15800, vol. 127. cited by applicant
Gratzel, M., “Perspectives for Dye-sensitized Nanocrystalline Solar Cells,” Progress in Photovoltaics: Research and Applications, 2000, pp. 171-185, vol. 8. cited by applicant
Grisaru, H, et al., “Microwave-Assisted Polyol Synthesis of CuInTe(2) and CuInSe(2) Nanoparticles,” Inorg. Chem., 2003, pp. 7148-7155, vol. 42. cited by applicant
Halgand et al., “Physico-chemical characterisation of Cu(In,Al)Se2 thin film for solar cells obtained by a selenisation process,” Thin Solid Films 480-481 (2005) 443-446. cited by applicant
Hamid et al., “Preparation of Titanium Dioxide (TiO2) thin films by sol gel dip coating method,” Malaysian Journal of Chemistry, 2003, vol. 5, No. 1, pp. 086-091. cited by applicant
Hayes, B.L., “Recent Advances in Microwave-Assisted Synthesis,” Aldrichimica Acta., 2004, pp. 66-77, vol. 37 No. 2. cited by applicant
Hirashima et al., “Preparation of meso-porous TiO2 gels and their characterization,” Journal of Non-Crystalline Solids 285 (2001) pp. 96-100. cited by applicant
Hirpo, Wakgari, et al., Synthesis of Mixed Copper—Indium Chalcogenolates. Single-Source Precursors for The Photovoltaic Materials CuInQ(2) (Q=S, Se), J. Am. Chem. Soc., 1993, pp. 1597-1599, vol. 115, No. 4. cited by applicant
Huynh, W.U., et al., “Hybrid Nanorod-Polymer Solar Cells,” Science, 2002, pp. 2425-2427, vol. 295. cited by applicant
Huynh, W.U., et al., “CdSe Nanocrystal Rods/Poly (3-hexylthiophene) Composite Photovoltaic Devices,” Advanced Materials, 1999, pp. 923-927, vol. 11 No. 11. cited by applicant
Jin et al., “Solar cells fabricated with CuInS2 films deposited using single-source precursors,” Proceedings of the 19th European Photovoltaic Solar Energy Conference, 4AV.1.71, 2004. cited by applicant
Kim, K., et al., “Synthesis of CuInSe(2) and CuInGaSe(2) Nanoparticles by Solvothermal Route,” Materials Science Forum, 2004, pp. 273-276, vol. 449-452. cited by applicant
Liu et al., “Preparation and characterization of CuInS2 thin films completely converted from CuInSe2 by sulfurization,” Thin Solid Films 480-481 (2005) 50-54. cited by applicant
Luque, A., et al., “Increasing the Efficiency of Ideal Solar Cells by Photon Induced Transitions at Intermediate Levels,” Physical Review Letters, 1997, pp. 5014-5017, vol. 78 No. 26. cited by applicant
Malik et al., “A novel route for the preparation of CuSe and CuInSe2 nanoparticles,” Advanced Materials, (1999) 11:1441-1444. cited by applicant
Marcinkevicius, S., et al., “Changes in carrier dynamics induced by proton irradiation in quantum dots,” Physica. B, Condensed Matter, 2002, pp. 203-206, vol. 314. cited by applicant
Miki et al., “Influence of calcination temperature on the microstructure of pourous TiO2 film,” Materials Science Forum, vol. 569 (2008) pp. 17-20. cited by applicant
Murali, A., et al., Synthesis and Characterization of Indium Oxide Nanoparticles, Nano Letters, 2001, pp. 287-289, vol. 1, No. 6. cited by applicant
Nairn et al., “Preparation of Ultrafine Chalcopyrite Nanoparticles via the Photochemical Decomposition of Molecular Single-Source Precursors,” Nano Letters 2006, vol. 6(6), pp. 1218-1223. cited by applicant
Narako et al., “Synthesis of Metastable Wurtzite CuInSe2Nanocrystals,” Chem. Mater. 2010, 22, 1613-1615. cited by applicant
Navarro, P., et al., “Optimisation of microwave assisted digestion of sediments and determination of Sn and Hg,” Analytica Chimica Acta, 2006, pp. 37-44, vol. 566. cited by applicant
Nüchter, M., et al., “Microwave Assisted Synthesis—a critical technology overview,” Green Chem., 2004, pp. 128-141, vol. 6 (3). cited by applicant
Nüchter, M., et al., “Microwave-Assisted Chemical Reactions,” Chem. Eng. Technol., 2003, 1207-1216, vol. 26 (12). cited by applicant
Paez et al., “Properties of Sol-Gel TiO2 Layers on Glass Substrate,” Ceramics—Silikáty 48 (2) pp. 66-71 (2004). cited by applicant
Pak, J.J., et al., “An efficient synthesis of 4, 4′,5,5′-tetraiododibenzo-24-crown-8 and its highly conjugated derivatives,” Tetrahedron Letters, 2006, pp. 233-237, vol. 47. cited by applicant
Pan et al., “Synthesis of Cu-In-S Ternary Nanocrystals with Tunable Structure and Composition,” J. Am. Chem. Soc. Apr. 30, 2008; 130(17):5620-1, Epub Apr. 9, 2008. cited by applicant
PCT International Preliminary Report on Patentability for International Searching Authority for PCT/US09/36221, dated Sep. 14, 2010, 8 pages. cited by applicant
PCT International Search Report and Written Opinion of the International Searching Authority for PCT/US09/36221, dated Nov. 2, 2009, 11 pages. cited by applicant
PCT International Search Report and Written Opinion of the International Searching Authority for PCT/US10/60583, dated Mar. 21, 2011, 12 pages. cited by applicant
Perozo-Rondon, E., et al., “Microwave enhanced synthesis of N-propargyl derivatives of imidazole A green approach for the preparation of fungicidal compounds,” Applied Surface Science, 2006, pp. 6067-6070, vol. 252 (17). cited by applicant
Qi et al., “Synthesis and Characterization of Nanostructured Wurtzite CuInS2: A New Cation Disordered Polymorph of CuInS2,” J. Phys. Chem. C 2009, 113, 3939-3944. cited by applicant
Rodrigues, et al., “Pulsed-Spray Radiofrequency Plasma Enhanced Chemical Vapor Deposition of CUInS2 Thin Films,” Plasma Chemistry and Plasma Processing, vol. 26, No. 2, Apr. 2006 , pp. 137-148. cited by applicant
Rodriguez et al., “The Formation of Copper Indium Disulfide Nano-Particles in Supercritical Carbon Dioxide,” NORM 2007, American Chemical Society, The 62nd Northwest Regional Meeting, Boise, Idaho, Jun. 17-20, 2007, 5 pages. cited by applicant
Sayilkan et al., “Characterization of TiO2 Synthesized in Alcohol by a Sol-Gel Process: The Effects of Annealing Temperature and Acid Catalyst,” Turk J Chem, 29 (2005) pp. 697-706. cited by applicant
Sobolev, N.A., et al., “Enhanced Radiation Hardness of InAs/GaAs quantum Dot Structures,” Phys. Stat. Sol. (B), 2001, pp. 93 -96, vol. 224, No. 1. cited by applicant
Sun et al., “A High-Yield Synthesis of Chalcopyrite CuInS2 Nanoparticles with Exceptional Size Control,” Journal of Nanomaterials, vol. 2009, Article ID 748567, 7 pages. cited by applicant
Tang, Z., et al., “Semiconductor Nanoparticles on Solid Substrates: Film Structure, Intermolecular Interactions, and Polyelectrolyte Effects,” Langmuir, 2002, pp. 7035-7740, vol. 18. cited by applicant
Tomalia, D.A., “Birth of a New Macromolecular Architecture: Dendrimers as Quantized Building Blocks for Nanoscale Synthetic Organic Chemistry,” Aldrichimica ACTA, 2004, pp. 39-57, vol. 27, No. 2. cited by applicant
Vittal et al., “Chemistry of metal thio- and selenocarboxylates: precursors for metal sulfide/selenide materials, thin films, and nanocrystals,” Acc. Chem. Res. (2006) 39:869-877. cited by applicant
Walters, R.J., et al., “Radiation Hard Multi-quantum Well InP/InAsP Solar Cells for Space Applications,” Progress in Photovoltaics: Research and Applications, 2000, pp. 349-354, vol. 8. cited by applicant
Wang et al., “Synthesis of Monodispersed Wurtzite Structure CuInSe2 Nanocrystals and Their Application in High-Performance Organic-Inorganic Hybrid Photodetectors,” J. Am. Chem. Soc., 2010, 132 (35), pp. 12218-12221. cited by applicant
Wang, Y., et al., “Nanometer-Sized Semiconductor Clusters: Materials Synthesis, Quantum Size Effects, and Photophysical Properties,” J. Phys. Chem., 1991, pp. 525-532, vol. 95. cited by applicant
Wei, Q., et al., “Synthesis of CuInS(2) Nanocubes by a Wet Chemical Process,” Journal of Dispersion Science and Technology, 2005, pp. 555-558, vol. 26. cited by applicant
Zhang, X., et al., “Applications of microwave dielectric heating in environment-related heterogeneous gas-phase catalytic systems,” Inorganica Chimica Acta, 2006, pp. 3421-3433, vol. 359. cited by applicant
Zhu, J., et al., “Microwave assisted preparation of CdSe, PbSe, andCU2-x Se nanoparticles,” J. Phys. Chem. B., 2000, 104 (31), 7344-7347. cited by applicant
Li et al., “Solution Synthesis of High-Quality CuInS2 Quantum Dots as Sensitizers for TiO2 Photoelectrodes”, Journal of Materials Chemistry, Mar. 2010, pp. 3656-3664. cited by applicant
Primary Examiner: Nguyen, Khanh Tuan
Attorney, Agent or Firm: TraskBritt
رقم الانضمام: edspgr.08951446
قاعدة البيانات: USPTO Patent Grants