# US 7,608,237 B2 · Synthesis of nanostructured materials using liquid crystalline templates > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 7,608,237 B2 - Document ID: US7608237B2 - Status: Granted - Kind: B2 - Application number: 11/391,022 - Filed: 2006-03-28 - Published: 2006-12-07 - Granted: 2009-10-27 - Earliest claimed: 2005-03-28 - Assignees: The Research Foundation of State University of New York - Inventors: Paschalis Alexandridis; Georgios N. Karanikolos; Triantafillos J. Mountziaris - Web page: https://patentgrep.com/patent/US7608237B2 ## CPC - C01B 19/007: {Tellurides or selenides of metals (C01B19/002 takes precedence)} - B82Y 10/00: Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic - B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites - C01B 13/328: {by processes making use of emulsions, e.g. the kerosine process} - C01B 17/20: Methods for preparing sulfides or polysulfides, in general (ammonium sulfides or polysulfides C01C; sulfides or polysulfides of metals, other than alkali metals, magnesium, calcium, strontium and barium, see the relevant groups of subclasses C01F or C01G, according to the metal) - C01G 1/00: Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general (electrolytic production of inorganic compounds C25B1/00) - C01G 1/02: Oxides - C01G 1/12: Sulfides - C01G 9/00: Compounds of zinc - C01G 9/08: Sulfides - C01G 11/00: Compounds of cadmium - C01G 11/02: Sulfides - C01G 21/00: Compounds of lead - C01G 21/21: Sulfides - C09K 11/02: Use of particular materials as binders, particle coatings or suspension media therefor - C09K 11/883: {with zinc or cadmium} - H10D 62/814: {Quantum box structures} - H10D 62/86: being Group II-VI materials, e.g. ZnO - C01P 2002/72: by d-values or two theta-values, e.g. as X-ray diagram - C01P 2002/84: by UV- or VIS- data - C01P 2002/85: by XPS, EDX or EDAX data - C01P 2004/04: obtained by TEM, STEM, STM or AFM - C01P 2004/13: Nanotubes - C01P 2004/17: Nanostrips, nanoribbons or nanobelts, i.e. solid nanofibres with two significantly differing dimensions between 1-100 nanometer - C01P 2004/20: extending in two dimensions, e.g. plate-like - C01P 2004/34: hollow - C01P 2004/64: Nanometer sized, i.e. from 1-100 nanometer - C01P 2006/40: Electric properties - C01P 2006/60: Optical properties, e.g. expressed in CIELAB-values - Y10S 977/70: Nanostructure - Y10S 977/773: Nanoparticle, i.e. structure having three dimensions of 100 nm or less - Y10S 977/811: Of specified metal oxide composition, e.g. conducting or semiconducting compositions such as ITO, ZnOx - C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C} - B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES - C01G: COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F (metal hydrides {monoborane, diborane or addition complexes thereof} C01B6/00; salts of oxyacids of halogens C01B11/00; peroxides, salts or peroxyacids C01B15/00; thiosulfates, dithionites, polythionates C01B17/64; compounds containing selenium, or tellurium C01B19/00; binary compounds of nitrogen with metals C01B21/06; azides C01B21/08; {compounds containing nitrogen, other non-metals and metal C01B21/082}; metal amides C01B21/092; nitrites C01B21/50; {compounds of noble gases C01B23/0005}; phosphides C01B25/08; salts of oxyacids of phosphorus C01B25/16; carbides C01B32/90; compounds containing silicon C01B33/00; compounds containing boron C01B35/00; compounds having molecular sieve properties but not having base-exchange properties C01B37/00; compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites, C01B39/00; cyanides C01C3/08; salts of cyanamide C01C3/16; thiocyanates C01C3/20) - C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE - H10D: INORGANIC ELECTRIC SEMICONDUCTOR DEVICES - C01P: INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS - Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS ## Abstract A process for synthesizing nanostructures is disclosed. The process involves forming a liquid crystalline template by combining a block copolymer, a first reactant in a polar phase, and a nonpolar phase, then contacting the template with a gas phase composed of a second reactant, under conditions effective to form nanostructures. ## Claims ### Claim 1 A process for synthesizing nanostructures, said process comprising: providing a first reactant in a polar phase; forming a liquid crystalline template containing the first reactant; contacting the liquid crystalline template with a gas phase comprising a second reactant diluted in a carrier gas; and allowing the second reactant to react with the first reactant; under conditions effective to form nanostructures. ### Claim 2 (depends on 1) The process according to claim 1, wherein the first reactant comprises a metal acetate compound. ### Claim 3 (depends on 2) The process according to claim 2, wherein the metal comprises Zn, Cd, Hg, Pb, Mn, or Fe. ### Claim 4 (depends on 2) The process according to claim 2, wherein the metal acetate compound comprises Zn acetate, Cd acetate, Hg acetate, Pb acetate, Mn acetate, or Fe acetate. ### Claim 5 (depends on 1) The process according to claim 1, wherein the first reactant comprises a metal acetate dihydrate compound. ### Claim 6 (depends on 5) The process according to claim 5, wherein the metal acetate dihydrate compound is Zinc acetate dihydrate. ### Claim 7 (depends on 1) The process according to claim 1, wherein said process is performed between about 5° C. and about 50° C. and between about 1.0 and about 2.0 atmospheres of pressure. ### Claim 8 (depends on 1) The process according to claim 1, wherein said forming of a liquid crystalline template comprises: providing a block copolymer; providing a nonpolar phase; and allowing the block copolymer, nonpolar phase, and said first reactant in a polar phase to come into contact with each other, such that said polar phase is continuous and said nonpolar phase is dispersed within the continuous phase, under conditions effective to form said liquid crystalline template. ### Claim 9 (depends on 8) The process according to claim 8, wherein the block copolymer is comprised of poly (ethylene oxide) and poly (propylene oxide). ### Claim 10 (depends on 8) The process according the claim 8, wherein the polar continuous phase is a non-reactive polar solvent. ### Claim 11 (depends on 8) The process according the claim 8, wherein the polar continuous phase is water. ### Claim 12 (depends on 8) The process according to claim 8, wherein the nonpolar dispersed phase is an organic solvent. ### Claim 13 (depends on 12) The process according to claim 12, wherein said organic solvent is an alkene. ### Claim 14 (depends on 13) The process according to claim 13, wherein said alkene is p-xylene. ### Claim 15 (depends on 8) The process according to claim 8, wherein said process is performed between about 5° C. and about 50° C. and between about 1.0 and about 2.0 atmospheres of pressure. ### Claim 16 (depends on 1) The process according to claim 1, wherein said forming of a liquid crystalline template comprises: providing a block copolymer; providing a nonpolar phase; and allowing the block copolymer, nonpolar phase, and said first reactant in a polar phase to come into contact with each other, such that said nonpolar phase is continuous and said polar phase is dispersed within the continuous phase, under conditions effective to form said liquid crystalline template. ### Claim 17 (depends on 16) The process according to claim 16, wherein the block copolymer is comprised of poly (ethylene oxide) and poly (propylene oxide). ### Claim 18 (depends on 16) The process according the claim 16, wherein the polar dispersed phase is a non-reactive polar solvent. ### Claim 19 (depends on 16) The process according the claim 16, wherein the polar dispersed phase is water. ### Claim 20 (depends on 16) The process according to claim 16, wherein the nonpolar continuous phase is an organic solvent. ### Claim 21 (depends on 20) The process according to claim 20, wherein said organic solvent is an alkene. ### Claim 22 (depends on 21) The process according to claim 21, wherein said alkene is p-xylene. ### Claim 23 (depends on 16) The process according to claim 16, wherein the process is performed between about 5° C. and about 50° C. and between about 1.0 and about 2.0 atmospheres of pressure. ### Claim 24 (depends on 1) The process according to claim 1, wherein said second reactant is in the form of a gas or vapor. ### Claim 25 (depends on 1) The process according to claim 1, wherein said second reactant comprises a Group VI element-containing compound. ### Claim 26 (depends on 25) The process according to claim 25, wherein said Group VI element comprises Se, S, Te, or O. ### Claim 27 (depends on 25) The process according to claim 25, wherein said Group VI element-containing compound is in the form of a hydride. ### Claim 28 (depends on 27) The process according to claim 27, wherein said hydride is a hydride of Se, S, or Te. ### Claim 29 (depends on 28) The process according to claim 28, wherein said hydride of Se is H2Se gas. ### Claim 30 (depends on 26) The process according to claim 26, wherein said Group VI element is oxygen. ### Claim 31 (depends on 30) The process according to claim 30, wherein the oxygen-containing compound is in the form of molecular oxygen (O2) gas, ozone (O3) gas, or water (H2O) vapor. ### Claim 32 (depends on 26) The process according to claim 26, wherein said Group VI element is Te. ### Claim 33 (depends on 32) The process according to claim 32, wherein the Te-containing compound is in the form of a vapor of dimethyl-Te, diethyl-Te, or diisopropyl-Te. ### Claim 34 (depends on 1) The process according to claim 1, wherein said carrier gas comprises hydrogen, nitrogen, helium, or argon. ### Claim 35 (depends on 1) The process according to claim 1, wherein said contacting comprises diffusing the gas phase over the liquid crystalline template under conditions effective to allow the second reactant to diffuse into the template and to react with the first reactant to form the nanostructures. ### Claim 36 (depends on 1) The process according to claim 1, wherein said contacting is performed at a temperature at which the liquid crystalline template remains stable at atmospheric pressure or at a pressure higher than atmospheric pressure. ### Claim 37 (depends on 1) The process according to claim 1, wherein said nanostructures have a diameter or thickness of between about 1 and about 100 nanometers. ### Claim 38 (depends on 1) The process according to claim 1, wherein said nanostructures are in crystalline form, polycrystalline form or amorphous form. ### Claim 39 (depends on 1) The process according to claim 1, wherein said nanostructures are nanocrystals. ### Claim 40 (depends on 39) The process according to claim 39, wherein said nanocrystals exhibit size-dependent luminescence or fluorescence. ### Claim 41 (depends on 39) The process according to claim 39, wherein said nanocrystals are PbSe or PbS nanocrystals. ### Claim 42 (depends on 39) The process according to claim 39, wherein said nanocrystals are luminescent Group II-Group VI nanocrystals of the form MX, wherein M is Zn, Cd, Hg, or Pb and wherein X is Se, S, Te, or O. ### Claim 43 (depends on 42) The process according to claim 42, wherein said nanocrystals are ZnSe nanocrystals. ### Claim 44 (depends on 43) The process according to claim 43, wherein said ZnSe nanocrystals have a diameter of between about 1 and about 200 nanometers. ### Claim 45 (depends on 42) The process according to claim 42, wherein said nanocrystals are CdSe nanocrystals. ### Claim 46 (depends on 45) The process according to claim 45, wherein said CdSe nanoerystals have a diameter of between about 1 and about 200 nanometers. ### Claim 47 (depends on 1) The process according to claim 1, further comprising incorporating a functional material onto the surface of said nanostructures. ### Claim 48 (depends on 47) The process according to claim 47, wherein said functional material is dissolved in an aliphatic hydrocarbon. ### Claim 49 (depends on 48) The process according to claim 48, wherein said aliphatic hydrocarbon is heptane. ### Claim 50 (depends on 48) The process according to claim 48, wherein said aliphatic hydrocarbon is octane. ### Claim 51 (depends on 47) The process according to claim 47, wherein said functional material is dissolved in an aromatic hydrocarbon. ### Claim 52 (depends on 51) The process according to claim 51, wherein said aromatic hydrocarbon is p-xylene. ### Claim 53 (depends on 51) The process according to claim 51, wherein said aromatic hydrocarbon is toluene. ### Claim 54 (depends on 47) The process according to claim 47, wherein said functional material is dissolved in heptane. ### Claim 55 (depends on 47) The process according to claim 47, wherein said functional material is added to the inner or outer surface of said nanostructure. ### Claim 56 (depends on 47) The process according to claim 47, wherein said functional material comprises either a thiol-based compound or an amine-based compound. ### Claim 57 (depends on 1) The process according to claim 1, further comprising isolating said nanostructures. ### Claim 58 (depends on 1) The process according to claim 1, wherein said nanostructures are of substantially the same size. ### Claim 59 (depends on 58) The process according to claim 58, wherein the size of said nanostructures is dependent on the initial concentration of the first reactant prior to said contacting. ### Claim 60 A process for synthesizing hollow nanostructures, said process comprising: combining together 67 wt % zinc acetate dihydrate, 31 wt % poly (ethylene oxide) and poly (propylene oxide), and 2 wt % p-xylene, thereby forming a liquid crystalline template; and diffusing H2Se gas into said liquid crystalline template; wherein zinc acetate dihydrate reacts with H2Se to form hollow ZnSe nanostructures. ### Claim 61 A process for synthesizing solid nanostructures, said process comprising: combining together 10 wt % zinc acetate dihydrate, 58 wt % poly (ethylene oxide) and poly (propylene oxide), and 32 wt % p-xylene, thereby forming a liquid crystalline template; and diffusing H2Se gas into said liquid crystalline template; wherein zinc acetate dihydrate reacts with H2Se to form solid ZnSe nanostructures. ### Claim 62 A liquid crystalline template produced by the process comprising: providing a block copolymer; providing a nonpolar phase; providing a first reactant in a polar phase; and allowing the block copolymer, non-polar phase, and first reactant in a polar phase to come into contact with each other, such that said polar phase is continuous and said nonpolar phase is dispersed within the continuous phase, under conditions effective to form said liquid crystalline template. ### Claim 63 (depends on 62) The process according to claim 62, wherein the block copolymer is comprised of poly (ethylene oxide) and poly (propylene oxide). ### Claim 64 (depends on 62) The process according to claim 62, wherein the polar continuous phase is a non-reactive polar solvent. ### Claim 65 (depends on 62) The process according the claim 62, wherein the polar continuous phase is water. ### Claim 66 (depends on 62) The process according to claim 62, wherein the nonpolar dispersed phase is an organic solvent. ### Claim 67 (depends on 66) The process according to claim 66, wherein said organic solvent is an alkene. ### Claim 68 (depends on 67) The process according to claim 67, wherein said alkene is p-xylene. ### Claim 69 (depends on 62) The process according to claim 62, wherein said process is performed between about 5° C. and about 50° C. and between about 1.0 and about 2.0 atmospheres of pressure. ### Claim 70 (depends on 62) The process according to claim 62, wherein the first reactant comprises a metal acetate compound. ### Claim 71 (depends on 70) The process according to claim 70, wherein the metal comprises Zn, Cd, Hg, Pb, Mn, or Fe. ### Claim 72 (depends on 62) The process according to claim 62, wherein the first reactant comprises a metal acetate dihydrate compound. ### Claim 73 (depends on 72) The process according to claim 72, wherein the metal acetate dihydrate compound comprises Zn acetate dihydrate, Cd acetate dihydrate, Hg acetate dihydrate, or Pb acetate dihydrate. ### Claim 74 (depends on 73) The process according to claim 73, wherein the metal acetate dihydrate compound is Zinc acetate dihydrate. ### Claim 75 A liquid crystalline template produced by the process comprising: providing a block copolymer; providing a nonpolar phase; providing a first reactant in a polar phase; and allowing the block copolymer, nonpolar phase, and first reactant in a polar phase to come into contact with each other, such that said nonpolar phase is continuous and said polar phase is dispersed within the continuous phase, under conditions effective to form said liquid crystalline template. ### Claim 76 (depends on 75) The process according to claim 75, wherein the block copolymer is comprised of poly (ethylene oxide) and poly (propylene oxide). ### Claim 77 (depends on 75) The process according to claim 75, wherein the polar dispersed phase material is a non-reactive polar solvent. ### Claim 78 (depends on 75) The process according the claim 75, wherein the polar dispersed phase material is water. ### Claim 79 (depends on 75) The process according to claim 75, wherein the nonpolar continuous phase material is an organic solvent. ### Claim 80 (depends on 79) The process according to claim 79, wherein said organic solvent is an alkene. ### Claim 81 (depends on 80) The process according to claim 80, wherein said alkene is p-xylene. ### Claim 82 (depends on 75) The process according to claim 75, wherein said process is performed between about 5° C .and about 50° C. and between about 1.0 and about 2.0 atmospheres of pressure. ### Claim 83 (depends on 75) The process according to claim 75, wherein the first reactant comprises a metal acetate compound. ### Claim 84 (depends on 83) The process according to claim 83, wherein the metal comprises Zn, Cd, Hg, Pb, Mn, or Fe. ### Claim 85 (depends on 75) The process according to claim 75, wherein the first reactant comprises a metal acetate dihydrate compound. ### Claim 86 (depends on 85) The process according to claim 85, wherein the metal acetate dihydrate compound comprises Zn acetate dihydrate, Cd acetate dihydrate, Hg acetate dihydrate, or Pb acetate dihydrate. ### Claim 87 (depends on 86) The process according to claim 86, wherein the metal acetate dihydrate compound is Zn acetate dihydrate.