CA2388094A1 - Synthesis of nanoparticles - Google Patents

Synthesis of nanoparticles Download PDF

Info

Publication number
CA2388094A1
CA2388094A1 CA002388094A CA2388094A CA2388094A1 CA 2388094 A1 CA2388094 A1 CA 2388094A1 CA 002388094 A CA002388094 A CA 002388094A CA 2388094 A CA2388094 A CA 2388094A CA 2388094 A1 CA2388094 A1 CA 2388094A1
Authority
CA
Canada
Prior art keywords
nanoparticles
lanthanides
substance
zns
preferred
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CA002388094A
Other languages
French (fr)
Other versions
CA2388094C (en
Inventor
Stephan Haubold
Markus Haase
Carsten Riwotzky
Horst Weller
Heike Meysamy
Fernando Ibarra
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Centrum fuer Angewandte Nanotechnologie CAN GmbH
Original Assignee
Nanosolutions Gmbh
Stephan Haubold
Markus Haase
Carsten Riwotzky
Horst Weller
Heike Meysamy
Fernando Ibarra
Centrum Fuer Angewandte Nanotechnologie (Can) Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanosolutions Gmbh, Stephan Haubold, Markus Haase, Carsten Riwotzky, Horst Weller, Heike Meysamy, Fernando Ibarra, Centrum Fuer Angewandte Nanotechnologie (Can) Gmbh filed Critical Nanosolutions Gmbh
Publication of CA2388094A1 publication Critical patent/CA2388094A1/en
Application granted granted Critical
Publication of CA2388094C publication Critical patent/CA2388094C/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/77742—Silicates
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N21/643—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" non-biological material
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/50—Sympathetic, colour changing or similar inks
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/57—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing manganese or rhenium
    • C09K11/572—Chalcogenides
    • C09K11/574—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/59—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing silicon
    • C09K11/592—Chalcogenides
    • C09K11/595—Chalcogenides with zinc or cadmium
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/62—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing gallium, indium or thallium
    • C09K11/621—Chalcogenides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/66—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing germanium, tin or lead
    • C09K11/666—Aluminates; Silicates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/67—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals
    • C09K11/68—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing refractory metals containing chromium, molybdenum or tungsten
    • C09K11/681—Chalcogenides
    • C09K11/684—Chalcogenides with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7715—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing cerium
    • C09K11/7727—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7736—Vanadates; Chromates; Molybdates; Tungstates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7737—Phosphates
    • C09K11/7738—Phosphates with alkaline earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
    • C09K11/7741—Sulfates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
    • C09K11/7755—Borates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7767—Chalcogenides
    • C09K11/7769—Oxides
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7774—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7776—Vanadates; Chromates; Molybdates; Tungstates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
    • C09K11/7777—Phosphates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7792—Aluminates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7794—Vanadates; Chromates; Molybdates; Tungstates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7797—Borates
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
    • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
    • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
    • C09K11/7798—Antimonates; Arsenates
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
    • G01N21/64—Fluorescence; Phosphorescence
    • G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
    • G01N2021/6439—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes" with indicators, stains, dyes, tags, labels, marks

Abstract

The present invention relates to methods for the preparation of inorganic nanoparticles capable of fluorescence, wherein the nanoparticles consist of a host material that comprises at least one dopant. The synthesis of the invention in organic solvents allows to gain a considerably higher yield compared to the prior art synthesis in water. The nanoparticles obtained by the method of the present invention can be used to advantageously mark and reliably authenticate all kinds of objects by using an automated method on the basis of a characteristic emission.
Further, the size distribution of the prepared nanoparticles is narrower which renders a subsequent size-selected separation process superfluous.

Claims (58)

1. A method for synthesizing metal salt nanoparticles, comprising a crystal lattice or host lattice of which the cation is capable of being produced from a cation source and of which the anion is capable of being produced from a class of substances that serves as an anion source, in which method the host material can include compounds particularly from the group consisting of phosphates, halophosphates, arsenates, sulphates, borates, aluminates, gallates, silicates, germanates, oxides, vanadates, niobates, tantalates, wolframates, molybdates, alkalihalogenates, other halides, nitrides, sulphides, selenides, sulphoselenides, as well as oxysulphides, the method being characterized by the following steps:
a) preparation of a synthesis mixture, at least from aa) an organic solvent which comprises at least one component controlling the crystal growth of the nanoparticles, in particular a component comprising a phosphororganic compound, or a monoalkylamine, particularly dodecylamine, or a dialkylamine, particularly bis(ethylhexyl)amine, bb) a cation starting material which serves as cation source and which is soluble or at least dispersible in the synthesis mixture, particularly a metal salt starting compound, preferred a metal chloride or an alkoxide, or a metal acetate, and cc) an anion starting material that serves as anion source, which is soluble or at least dispersible in the synthesis mixture and which is selected from said class of substances, said class of substances comprising:
aaa) free acids of the salts of the particular metal salt nanoparticles which are to be prepared, or bbb) salts that are soluble or at least dispersible in the synthesis mixture, in particular salts with an organic cation, or metal salts, the latter preferably being alkali metal salts, or ccc) organic compounds which release the anion beyond an increased synthesis minimum temperature, and a suitable, anion-donating substance is selected from the class of substances depending on a respective selection of the salt of the nanoparticles to be prepared , and b) keeping the mixture at a predetermined synthesis minimum temperature during a synthesis period appropriate for said temperature.
2. The method according to claim 1, wherein a) phosphoric acid is used as anion source for the preparation of nanoparticles with phosphorus-containing anions, wherein boric acid is used as anion source for the preparation of nanoparticles with boron-containing anions, wherein hydrofluoric acid is used as anion source for the preparation of nanoparticles with fluorine-containing anions, wherein b) in case of using a salt of the anion substance class that is sparingly soluble in the synthesis mixture, a complexing agent for the metal component of the metal salt is added to the synthesis mixture in order to improve the solubility of the salt, preferably a crown ether for alkali metal salts.
3. The method according to the preceding claim, wherein at least one of the following substances is comprised of the solvent as the phosphororganic compound for the growth controlling component:
a) esters of phosphinic acid, ((R1-)(R2-)(R3-O-)P=O), b) diesters of phosphoric acid, ((R1-)(R2-O-)(R3-O-)P=O), c) triesters of phosphoric acid (trialkyl-phosphates), ( (R1-O-)(R2-O-)(R3-O-)P=O), d) trialkyl phosphines, ((R1-)(R2-)(R3-)P), particularly trioctylphosphine (TOP), e) trialkyl phosphine oxides, ((R1-)(R2-)(R3-)P=O), particularly trioctylphosphine oxide (TOPO), wherein R1, R2, R3 are branched or unbranched alkane chains comprising at least one carbon atom, or phenyl, tolyl, xylyl, or benzyl groups, or f) a phosphoric amide, preferred tris-(dimethylamino)-phosphine, or g) a phosphoric amide oxide, preferred tris-(dimethylamino)-phosphine oxide.
4. The method according to the preceding claim, wherein a trialkyl phosphate or a trialkyl phosphine is used as a controlling component for the preparation of nanoparticles, and wherein per mol metal ions less than 10 mol, preferred 0.9 to 5 mol, and more preferred 0.95 to 2 mol of the controlling component is used.
5. The method according to one of the preceding claims, wherein at least one further component with preferably metal-chelating properties is added to the synthesis mixture, preferably in order to displace any water of crystallization present in the metal salt starting compounds,, in particular a) an ether compound, preferred dipentyl ether, dihexyl ether, diheptyl ether, dioctyl ether, dibenzyl ether, diisoamyl ether, ethylene glycol dibutyl ether, diethylene glycol dibutyl ether, or diphenyl ether, or / and b) an alkane compound that boils above the synthesis minimum temperature, preferred dodecane or hexadecane, or / and c) an amine compound, preferred dihexylamine, bis(2-ethylhexyl)amine, trioctylamine, tris(2-ethylhexyl)amine.
6. The method according to claim 3, wherein R1, R2, or R3 are branched or unbranched alkane chains which carry at least one of the following groups:
carboxyl group (-COOH), carboxylic acid ester group (-COOR), amino groups (-NH2) and (NHR), hydroxyl group (-OH), cyano group (-CN), mercapto group (-SH), bromine (-Br) and chlorine (-Cl), or combinations of these groups.
7. The method according to claim 3, wherein mixtures of the phosphororganic compounds are used.
8. The method according to one of the preceding claims, wherein at least one of the group consisting of chlorides, bromides, iodides, alkoxides, metal acetates, or acetylacetonate is used as a starting material for the cation source.
9. The method according to one of the preceding claims , further comprising the following steps:
a) preparation of a first solution of the cation starting material in a - preferably lower - alcohol, particularly methanol, wherein preferably a metal salt is used which is non-oxidative and soluble in the synthesis mixture, and b) mixing of the first solution with the solvent according to claim 1 or 2 in order to prepare the metal-chelating synthesis mixture, c) keeping the synthesis mixture heated under inert gas, in particular under nitrogen.
10. The method according to the preceding claim further compising the step of removing the preferably lower alcohol by distillation.from the synthesis mixture during the synthesis
11. The method according to one of the preceding claims further comprising the step of:
Removing of one or more of the solvent components by distillation from the synthesis mixture, preferred under vacuum, preferred after the end of the synthesis period.
12. The method according to one of the preceding claims further comprising the step of :
Purifying the nanoparticles by washing with an alcohol, preferred with ethanol, or by diafiltration to get rid of attached by-products.
13. The method according to one of the preceding claims further comprising the step of:
Neutralizing the synthesis mixture using a base that is soluble in the synthesis mixture, preferred trihexylamine, triheptylamine, trioctylamine, tris(2-ethylhexyl)amine.
14. The method according to one of the preceding claims, wherein a hydrated metal salt is used as starting material.
15. The method according to one of the preceding claims which is used for synthesizing nanoparticles capable of fluorescence.
16. The method according to one of the preceding claims, wherein several different cation sources are used, particularly metal salt starting compounds, of which at least one metal is used as doping agent for the nanoparticles to be produced.
17. The method according to claim 1, wherein the crystal lattice or, in case of a doping, the host lattice comprises compounds of the type XY, wherein X is a cation of one or more elements of the main groups 1a, 2a, 3a, 4a, the subgroups 2b, 3b, 4b, 5b, 6b, 7b, or of the lanthanides of the periodical system, and wherein Y is either a polyatomic anion of one or more of the elements of the main groups 3a, 4a, 5a, of the subgroups 3b, 4b, 5b, 6b, 7b, and/or 8b as well as of elements of the main groups 6a, and/or 7, or a monoatomic anion of the main groups 5a, 6a, or 7a of the periodical system.
18. The method according to one of the preceding claims, wherein a phosphate ester, in particular a trialkyl phosphate, and preferred tributyl phosphate, is used as growth controlling component of the solvent for the preparation of LaPO4 nanoparticles.
19. The method according to one of the preceding claims, wherein one ore more elements selected from a group comprising elements of the main groups 1a, 2a, or Al, Cr, Tl, Mn, Ag, Cu, As, Nb, Ni, Ti, In, Sb, Ga, Si, Pb, Bi, Zn, Co, and/ or elements of the lanthanides are used for the doping.
20. The method according to one of the preceding claims, wherein two elements are used for the doping in different relative concentrations to each other, wherein one of the doping elements has a local maximum in the absorption spectrum for light, preferred for UV-light, and the other doping element has a fluorescence emission spectrum with at least one local maximum that has a distance ~/ .dottedcircle.
from the absorption maximum of the first doping element of at least 4 %, preferred of more than 20 %.
21. The method according to the preceding claim, wherein cerium and terbium are used for the doping and LaPO4 as host material.
22. The method according to one of the preceding claims 1 to 19, wherein nanoparticles are synthesized using one of the following founds:
LiI:Eu; NaI:T1; CsI:Tl; CsI:Na; LiF:Mg; LiF:Mg,Ti, LiF:Mg,Na;
KMgF3:Mn; A12O3:Eu; BaFCI:Eu; BaFCI:Sm; BaFBr:Eu; BaFCl0.5Br0.5=sm;
BaY2F8:A (A=Pr, Tm, Er, Ce); BaSi2O5:Pb; BaMg2Al16O27:Eu;
BaMgAl14O23:Eu; BaMgAl10O17:Eu; (Ba, Mg)Al2O4:Eu; Ba2P2O7:Ti: (Ba, Zn, Mg)3Si2O7:Pb; Ce(Mg, Ba)Al11O19; Ce0.65Tb0.35MgAl11O19;
MgAl11O19:Ce,Tb; MgF2:Mn; MgS:Eu; MgS:Ce; MgS:Sm; MgS(Sm, Ce); (Mg, Ca)S:Eu; MgSiO3:Mn; 3.5Mg0Ø5MgF2.GeO2:Mn; MgWO4:Sm; MgWO4:Pb;
6MgO.As2O5:Mn; (Zn, Mg)F2:Mn; (Zn, Be)SO4:Mn; Zn2SiO4:Mn;
Zn2SiO4:Mn,As; ZnO:Zn; ZnO:Zn,Si,Ga; Zn3(PO4)2:Mn; ZnS:A (A-Ag, A1, Cu); (Zn, Cd)S:A (A=Cu, A1, Ag, Ni); CdBO4:Mn; CaF2:Dy; CaS:A
(A=lanthanides, Bi); (Ca, Sr)S:Bi; CaWO4:Pb; CaWO4:Sm; CaSO4:A (A=Mn, lanthanides); 3Ca3(PO4)2.Ca(F, C1)2:Sb, Mn; CaSiO3:Mn, Pb;
Ca2A12Si2O7:Ce; (Ca, Mg)SiO3:Ce; (Ca, Mg)SiO3:Ti; 2Sr0.6(B2O3).SrF2:Eu;
3Sr3(PO4)2.CaC12:Eu; A3(P04)2.AC12:Eu (A=Sr, Ca, Ba); (Sr,Mg)2P2O7:Eu;
(Sr, Mg)3(PO4)2:Sn; SrS:Ce; SrS:Sm,Ce; SrS:Sm; SrS:Eu; SrS:Eu,Sm;
SrS:Cu,Ag; Sr2P2O7:Sn; Sr2P2O7:Eu; Sr4Al14O25:Eu; SrGa2S4:A
(A=lanthanides, Pb); SrGa2S4:Pb; Sr3Gd2Si6O18:Pb,Mn; YF3:Yb,Er; YF3:Ln (Ln=lanthanides); YLiF4:Ln (Ln=lanthanides); Y3A15O12:Ln (Ln=lanthanides); YA13(BO4)3:Nd,Yb; (Y,Ga)BO3:Eu; (Y,Gd)BO3:Eu;
Y2A13Ga2O12:Tb: Y2SiO5:Ln (Ln=lanthanides); Y2O3:Ln (Ln=lanthanides);
Y2O2S:Ln (Ln=lanthanides); YVO4:A (A=lanthanides, In); Y(P,V)O4:Eu;
YTaO4:Nb; YAlO3:A (A= Pr, Tm, Er, Ce); YOCl:Yb,Er; LnPO4:Ce,Tb (Ln=lanthanides or mixtures of lanthanides); LuVO4:Eu; GdVO4:Eu;
Gd2O2S:Tb; GdMgB5O10:Ce,Tb: LaOBrTb; La2O2S:Tb: LaF3:Nd,Ce: BaYb2F8:Eu;
NaYF4:Yb,Er; NaGdF4:Yb,Er; NaLaF4:Yb,Er; LaF3:Yb,Er,Tm; BaYF5:Yb,Er;
Ga2O3:Dy; GaN:A (A= Pr, Eu, Er, Tm); Bi4Ge3O12; LiNbO3:Nd,Yb;
LiNbO3:Er; LiCaAlF6:Ce; LiSrAlF6:Ce; LiLuF4:A (A= Pr, Tm, Er, Ce);
Gd3Ga5O12:Tb; Gd3Ga5O12:Eu; Li2B4O7:Mn,SiOx:Er,A1 (0<x<2).
23. The method according to one of the preceding claims 1 to 19, wherein nanoparticles are synthesized using one of the following compounds:
YVO4:Eu; YVO4:Sm; YVO4:Dy; LaPO4:Eu; LaPO4:Ce; LaPO4:Ce,Tb;
ZnS:Tb; ZnS:TbF3; ZnS:Eu; ZnS:EuF3; Y2O3:Eu; Y2O2S:Eu; Y2SiO5:Eu;
SiO2:Dy; SiO2:A1; Y2O3:Tb; CdS:Mn; ZnS:Tb; ZnS:Ag; ZnS:Cu;
Ca3(PO4)2:Eu2+; Ca3(PO4)2:Eu2+, Mn2+; Sr2SiO4:Eu2+; or BaA12O4:Eu2+.
24. The method according to one of the preceding claims 1 to 19, wherein nanoparticles are synthesized using one of the following compounds: MgF2:Mn; ZnS:Mn; ZnS:Ag; ZnS:Cu; CaSiO3:A; CaS:A; CaO:A;
ZnS:A; Y2O3:A, or MgF2:A (A = lanthanides).
25. The method according to one of the preceding claims, in particular according to claim 21, wherein a doping with terbium is achieved in the range from 0.5 to 30 mol percent, preferred from 5 to 25 mol percent and most preferred from 13 to 17 mol percent, wherein the respective molar ratio between lanthanum and cerium is a ratio ranging from 0.13 to 7.5, preferred from 0.25 to 4, and most preferred from 0.9 to 1.1, and metal chloride salts serve as metal source.
26. The method according to claim 1 for synthesizing semiconductor (sc) nanoparticles, in particular of III V- or of II-VI-semiconductors.
27. Nanoparticles prepared by using the method according to one of the preceding claims.
28. A substance, comprising nanoparticles according to the preceding claim.
29. A substance, comprising nanoparticles, comprising a crystal lattice or, in case of a doping, a host lattice, wherein the host lattice comprises compounds of the type XY, wherein X is a cation of one or more elements of the main groups 1a, 2a, 3a, 4a, the subgroups 2b, 3b, 4b, 5b, 6b, 7b, or of the lanthanides of the periodical system, and wherein Y is either a polyatomic anion of one or more of the elements of the main groups 3a, 4a, 5a, of the subgroups 3b, 4b, 5b, 6b, 7b, and/or 8b as well as of elements of the main groups 6a, and/or 7, or a monoatomic anion of the main groups 5a, 6a, or 7a of the periodical system, and wherein one ore more elements selected from a group comprising elements of the main groups 1a, 2a, or A1, Cr, T1, Mn, Ag, Cu, As, Nb, Ni, Ti, In, Sb, Ga, Si, Pb, Bi, Zn, Co, and/ or elements of the lanthanides are contained as a doping.
30. The substance according to the preceding claim, wherein the lattice comprises compounds particularly from one of the following groups: phosphates, halaphosphates, arsenates, sulphates, borates, aluminates, gallates, silicates, germanates, oxides, vanadates, niobates, tantalates, wolframates, molybdates, alkalihalogenates, other halides, nitrides, sulphides, selenides, sulphoselenides, or oxysulphides.
31. The substance according to one of the two preceding claims, comprising two elements used for the doping in predetermined relative concentrations to each other, wherein one of the doping elements has a local maximum in the absorption spectrum for light, in particular for UV-light, and the other doping element has a fluorescence emission spectrum with at least one local maximum that has a distance from the absorption maximum of the first doping element of at least 4 %.
32. The substance according to claim 29, which comprises one or more of LiI:Eu: NaI:Tl; CsI:Tl; CsI:Na; LiF:Mg; LiF:Mg,Ti, LiF:Mg,Na;
KMgF3:Mn; A12O3:Eu; BaFCl:Eu; BaFCl:Sm; BafBr:Eu; BaFCl0.5Br0,5:Sm;

BaY2Fg:A (A=Pr, Tm, Er, Ce); BaSi2O5:Pb; BaMg2Al16O27:Eu;
BaMgAl14O23:Eu; BaMgAl10O17:Eu; (Ba, Mg)Al2O4:Eu; Ba2P2O7:Ti; (Ba, Zn, Mg)3Si2O7:Pb; Ce(Mg, Ba)Al11O19% Ce0.65Tb0.35MgAl11O19;
MgAl11O19:Ce,Tb; MgF2:Mn; MgS:Eu; MgS:Ce; MgS:Sm; MgS(Sm, Ce); (Mg, Ca)S:Eu; MgSiO3:Mn; 3.5MgOØ5MgF2.GeO2:Mn; MgWO4:Sm; MgWO4:Pb;
6MgO.As2O5:Mn; (Zn, Mg)F2:Mn; (Zn, Be)SO4:Mn; Zn2SiO4:Mn;
Zn2SiO4:Mn,As; ZnO:Zn; ZnO:Zn,Si,Ga; Zn3(PO4)2:Mn; ZnS:A (A Ag, A1, Cu); (Zn, Cd)S:A (A=Cu, A1, Ag, Ni); CdBO4:Mn; CaF2:Dy; CaS:A
(A=lanthanides, Bi); (Ca, Sr)S:Bi; CaWO4:Pb; CaWO4:Sm; CaSO4:A (A~Mn, lanthanides); 3Ca3(PO4)2.Ca(F, C1)2:Sb, Mn; CaSiO3:Mn, Pb;
Ca2Al2Si2O7:Ce; (Ca, Mg)SiO3:Ce; (Ca, Mg)SiO3:Ti; 2Sr0.6(B2O3).SrF2:Eu;
3Sr3(PO4)2.CaCl2:Eu; A3(PO4)2.ACl2:Eu (A=Sr, Ca, Ba); (Sr,Mg)2P2O7:Eu;
(Sr, Mg)3(PO4)2:Sn; SrS:Ce; SrS:Sm,Ce; SrS:Sm; SrS:Eu; SrS:Eu,Sm;
SrS:Cu,Ag; Sr2P2O7:Sn; Sr2P2O7:Eu; Sr4A114O25:Eu; SrGa2S4:A
(A=lanthanides, Pb); SrGa2S4:Pb; Sr3Gd2Si6O1g:Pb,Mn; YF3:Yb,Er; YF3:Ln (Ln=lanthanides); YLiF4:Ln (Ln=lanthanides); Y3Al5O12:Ln (Ln=lanthanides); YAl3(BO4)3:Nd,Yb; (Y,Ga)BO3:Eu; (Y,Gd)BO3:Eu;
Y2Al3Ga2O12:Tb; Y2SiO5:Ln (Ln=lanthanides); Y2O3:Ln (Ln=lanthanides);
Y202S:Ln (Ln=lanthanides); YV04:A (A=lanthanides, In); Y(P,V)04:Eu;
YTa04:Nb; YA103:A (A= Pr, Tm, Er, Ce); YOCl:Yb,Er; LnP04:Ce,Tb (Ln=lanthanides or mixtures of lanthanides); LuVO4:Eu; GdVO4:Eu;
Gd2O2S:Tb; GdMgB5O10:Ce,Tb; LaOBrTb; La2O2S:Tb; LaF3:Nd,Ce; BaYb2F8:Eu;
NaYF4:Yb,Er; NaGdF4:Yb,Er; NaLaF4:Yb,Er; LaF3:Yb,Er,Tm; BaYF5:Yb,Er;
Ga2O3:Dy; GaN:A (A= Pr, Eu, Er, Tm); Bi4Ge3O12; LiNbO3:Nd,Yb;
LiNbO3:Er; LiCaAlF6:Ce; LiSrAlF6:Ce; LiLuF4:A (A= Pr, Tm, Er, Ce);
Gd3Ga5O12:Tb; Gd3Ga5O12:Eu; Li2B4O7:Mn,SiOx:Er,Al (0<x<2) as a material for the doped nanoparticles.
33. The substance according to claim 29, wherein the material for the doped nanoparticles comprises one or more of YVO4:Eu; YVO4:Sm;
YVO4:Dy; LaPO4:Eu; LaPO4:Ce; LaPO4:Ce,Tb; ZnS:Tb; ZnS:TbF3; ZnS:Eu;
ZnS:EuF3; Y203:Eu; Y202S:Eu: Y2SiO5:Eu; SiO2:Dy; SiO2:A1; Y2O3:Tb;

CdS:Mn; ZnS:Tb; ZnS:Ag; ZnS:Cu; Ca3(PO4)2:Eu2+; Ca3(PO4)2:Eu2+, Mn2+;
Sr2SiO4:Eu2+; or BaAl2O4:Eu2+.
34. The substance according to claim 29, wherein the material for the doped nanoparticles comprises one or more of MgF2:Mn; ZnS:Mn;
ZnS:Ag; ZnS:Cu; CaSiO3:A; CaS:A; CaO:A; ZnS:A; Y2O3:A, or MgF2:A (A =
lanthanides).
35. The substance according to claim 29, wherein the host lattice comprises a lanthanum or lanthanide compound, in particular LaPO4, and wherein dopants of the group of lanthanides are contained.
36. The substance according to the preceding claim, comprising two dopants, in particular cerium and terbiLUn, wherein one of the two is characterized as an energy absorber, in particular as a W-light absorber, and the other as a fluorescence light emitter.
37. The substance according to one of the preceding claims 29 to 36, preferably comprising nanoparticles which are selected from the substance group consisting of rare earth metal phosphates, or IIIrd main group phosphates, or phosphates of calcium (Ca), strontium (Sr), or barium (Ba), wherein the nanoparticles have a size, measured along their longest axis, of maximally 15 nm, preferred of maximally l0 nm, and most preferred of 4 to 5 nm with a standard deviation of less than 30 %, preferred for each case of less than 10 %.
38. A nanoparticle carrier substance, in particular a carrier film, a carrier liquid, thereof in particular a carrier varnish or a carrier paint, or an aerosol, comprising doped nanoparticles according to claim 27, or a substance according to one of the claims 28 to 37.
39. The nanoparticle carrier substance according to the preceding claim, wherein the nanoparticles are embedded in a polymer, preferred a polymer film, in particular one made of polyethylene or polypropylene.
40. A polymer film, comprising doped nanoparticles according to claim 27 or a substance according to claim 28 to 37.
41. An object which is marked, into which the nanoparticles prepared by using the method according to one of the preceding claims 1 to 26 or into which a substance according to one of the claims 27 to 37 is/are incorporated such that the particles or the substance is/are excitable by a predetermined energy source, preferred by electromagnetic irradiation, in particular radiation with a wavelength below 300 nm, or by irradiation by particles or electrons, and that a fluorescence emission is caused, preferred in the visible range of light, in the UV-range, or in the near infra red-range (NIR), which is detectable externally to the object.
42. The object according to the preceding claim provided with a nanoparticle carrier substance according to one of the claims 38 or 39, or a polymer film according to claim 40.
43. The object according to the preceding claim, comprising a coating with a nanoparticle carrier substance.
44. A use of nanoparticles, comprising one or more substances selected from the family of phosphors, in particular a use of wolframates, tantalates, borates, vanadates, sulphoxides, silicates, gallates, aluminates, halide compounds for the marking of objects, in particular of banknotes, carriers for information, computer components, automobile components, motor elements, documents, locking devices, anti-burglary devices, objects transparent for visible light, jewellery, or of works of art, or for the making of finger-prints.
45. A use of doped nanoparticles for a marking according to the preceding claim.
46. The use of nanoparticles according to claim 27 or of a substance according to one of the claims 28 to 38 for the marking according to claim 44.
47. The use of nanoparticles according to claim 27 or of a substance according to one of the claims 28 to 38 for the marking of liquids or gases.
48. The use of a UV-light absorbing substance according to claim 36 for converting UV-light into another forth of energy.
49. The use of a UV-light absorbing substance according to claim 36 as a converter to visible light.
50. A use of nanoparticles, comprising one or more substances selected from the family of phosphors, in particular a way of use of wolframates, tantalates, borates, vanadates, sulphoxides, silicates, gallates, aluminates, halide compounds for producing light in devices or lighting bodies.
51. The use of doped nanoparticles according to claim 27 or of a substance according to one of the claims 28 to 39 for producing light in devices or lighting bodies.
52. The use of doped nanoparticles according to claim 27 or of a substance according to one of the claims 28 to 39 or of a polymer film according to claim 40 for the preparation of images which become visible only after an appropriate excitation.
53. A detection method to recognize the fluorescence of a test substance (28) as identical with the fluorescence of a reference substance of a predetermined nanoparticle type having a fluorescence emission main peak (40), comprising the steps:
exciting the test substance (28) using an excitation method that is known to be suitable for the predetermined nanoparticle type, filtering the spectral region of the main peak of the test substance (28), filtering at least one secondary spectral region next to the main peak (40), where relatively to the intensity of the main peak a low or not any intensity is expected for the predetermined nanoparticle type, quantifying the filtered emission intensities within the predetermined spectral regions, and determining one or several relations of the filtered emission intensities to each other, evaluating the correspondence of the test substance (28) with the reference substance on the basis of the relations.
54. The detection method according to the preceding claim, wherein apart from the main peak (90) two or more of the secondary spectral regions are filtered and evaluated.
55. The detection method according to one of the two preceding claims, comprising the steps of recording and analysing the image of the fluorescence radiation source.
56. A device to carry out the detection method according to claim 53, comprising a means (26) for exciting the test substance (28) with an excitation spectrum that is known to be suitable for the predetermined nanoparticle type, a means (12) for filtering the spectral region of the main peak of the test substance (28), a means (10, 14) for filtering at least one secondary spectral region next to the main peak (40) where relatively to the intensity of the main peak a low or not any intensity is expected for the predetermined nanoparticle type, a means (16, 18, 20) for quantifying the filtered emission intensities within the predetermined spectral regions, a means (22) for determining one or several relations of the filtered emission intensities to each other, a means (22, 24) for evaluating the correspondence of the test substance (28) with the reference substance on the basis of the relations.
57. The device according to the preceding claim, comprising a means (16, 20, 22, 24) for filtering and analysing two or more of the secondary spectral regions apart from the main peak (40).
58. The device according to one of the two preceding claims, comprising a means (30, 32, 34) for recording the image of the fluorescence source, and a means (22, 24) for analysing the image of the fluorescence radiation source.
CA2388094A 2000-09-08 2001-09-07 Synthesis of nanoparticles Expired - Fee Related CA2388094C (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DEPCT/DE00/03130 2000-09-08
PCT/DE2000/003130 WO2002020695A1 (en) 2000-09-08 2000-09-08 Doped nanoparticles
PCT/DE2001/003433 WO2002020696A1 (en) 2000-09-08 2001-09-07 Synthesis of nanoparticles

Publications (2)

Publication Number Publication Date
CA2388094A1 true CA2388094A1 (en) 2002-03-14
CA2388094C CA2388094C (en) 2011-11-15

Family

ID=5647917

Family Applications (1)

Application Number Title Priority Date Filing Date
CA2388094A Expired - Fee Related CA2388094C (en) 2000-09-08 2001-09-07 Synthesis of nanoparticles

Country Status (10)

Country Link
EP (2) EP1232226B1 (en)
JP (1) JP5241987B2 (en)
CN (1) CN100489058C (en)
AT (1) ATE331010T1 (en)
AU (1) AU782482B2 (en)
CA (1) CA2388094C (en)
DE (1) DE50110243D1 (en)
ES (1) ES2269466T3 (en)
IL (1) IL149172A0 (en)
WO (2) WO2002020695A1 (en)

Families Citing this family (78)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2439381C (en) 2001-03-08 2010-10-05 Nanosolutions Gmbh Paramagnetic nanoparticles
EP1458836A1 (en) 2001-12-18 2004-09-22 Nanosolutions GmbH Security printing liquid and method using nanoparticles
CN1157462C (en) 2002-04-15 2004-07-14 清华大学 Nano-class conversion fluorescence material on fluoride matrix and its preparing process
DE10254567A1 (en) 2002-11-21 2004-06-09 Nanosolutions Gmbh Process for the production of alkaline earth metal sulfate nanoparticles
ATE333701T1 (en) * 2002-12-17 2006-08-15 Lanxess Deutschland Gmbh LEAD-FREE MIXTURE AS A RADIATION PROTECTION ADDITIVE
DE10259937A1 (en) * 2002-12-20 2004-07-01 Bayer Ag New iminobis (methylenephosphono) carboxylic acid pentaalkyl esters
EP1431352B1 (en) * 2002-12-20 2008-04-23 Centrum für Angewandte Nanotechnologie (CAN) GmbH In fluorine-containing media homogeneously dispersible nanoparticles and media containing the same
DE10259935A1 (en) * 2002-12-20 2004-07-01 Bayer Ag Production and use of in-situ modified nanoparticles
US8337804B2 (en) * 2003-04-28 2012-12-25 Centrum Fur Angewandte Nanotechnologie (Can) Gmbh Synthesis of nanoparticles comprising metal (III) vanadate
ATE346898T1 (en) * 2003-04-30 2006-12-15 Nanosolutions Gmbh CORE-COAT NANOPARTICLES FOR (F) RESCUE TEST PROCEDURE
DE60312648T2 (en) * 2003-04-30 2007-11-22 Centrum Für Angewandte Nanotechnologie (Can) Gmbh Luminescent core-shell nanoparticles
US6982046B2 (en) 2003-10-01 2006-01-03 General Electric Company Light sources with nanometer-sized VUV radiation-absorbing phosphors
JP4625905B2 (en) * 2003-12-05 2011-02-02 独立行政法人産業技術総合研究所 Low temperature synthesis of low size distribution and fluorescent semiconductor nanoparticles using heterogeneous reaction
DE10357116A1 (en) * 2003-12-06 2005-07-07 Solvay Barium Strontium Gmbh Deagglomerated barium sulfate
US6979415B1 (en) * 2004-03-31 2005-12-27 General Electric Company Luminescent nanomaterials powders having predetermined morphology and method of making
US7575734B2 (en) * 2004-05-04 2009-08-18 Centrum Fur Angewandte Nanotechnologie (Can) Gmbh Process for preparing dispersible sulfate, preferably barium sulfate nanoparticles
DE102004033715B4 (en) * 2004-07-13 2017-08-10 Schott Ag Use of a glass or glass ceramic plate
JP2006028354A (en) * 2004-07-16 2006-02-02 Keio Gijuku Phosphor and manufacturing method of phosphor
US20080277625A1 (en) * 2004-07-16 2008-11-13 Nat'l Institute Of Advanced Industrial Science And Technology Phosphor And Production Process Of Same
JP2006096636A (en) * 2004-09-30 2006-04-13 Fuji Photo Film Co Ltd Crystalline metal oxide minute particle, its dispersion liquid, and their manufacturing method
DE102004050480A1 (en) * 2004-10-15 2006-04-27 Chemische Fabrik Budenheim Kg Pigment for laser-writable plastics and its use
JP2006117786A (en) * 2004-10-21 2006-05-11 Nec Tokin Corp Color-changing coating composition or ink composition and method for using color-changing coating or ink
JP2006213822A (en) * 2005-02-03 2006-08-17 Keio Gijuku Method for manufacturing fine-grain phosphor
DE102005026485A1 (en) 2005-06-09 2006-12-14 Bayer Technology Services Gmbh Hydrophilic nanoparticles with functional surface groups, their preparation and use
JP4534042B2 (en) * 2005-08-12 2010-09-01 独立行政法人産業技術総合研究所 Phosphor nanoparticles and method for producing the same
US7780913B2 (en) * 2005-08-26 2010-08-24 Lawrence Livermore National Security, Llc Paint for detection of corrosion and warning of chemical and radiological attack
US20080274028A1 (en) * 2005-10-03 2008-11-06 Hai Hui Lin Security pigments and the process of making thereof
ATE553371T1 (en) 2005-12-16 2012-04-15 Automation W & R Gmbh METHOD AND ARRANGEMENT FOR DETECTING MATERIAL DEFECTS IN WORKPIECES
WO2007086606A1 (en) * 2006-01-27 2007-08-02 Showa Denko K.K. Fluorescent substance and process for producing the same
JP2007197608A (en) * 2006-01-27 2007-08-09 Showa Denko Kk Phosphor and process for producing the same, and lamp
RU2434925C2 (en) 2006-03-06 2011-11-27 Конинклейке Филипс Электроникс Н.В. LUMINESCENT MATERIAL USING (Y, Gd)-CONTAINING NANOPARTICLES AND SURFACE-BOUND ORGANIC LIGANDS
JP4919223B2 (en) * 2006-08-03 2012-04-18 独立行政法人産業技術総合研究所 Sheet-like fluorescent particles and method for producing the same
KR100913610B1 (en) 2007-02-21 2009-08-26 제일모직주식회사 Multicomponent emitting nanoparticles?for organic photoelectric device comprising metal complex and organic photoelectric device thereby
WO2008126446A1 (en) * 2007-03-19 2008-10-23 Konica Minolta Medical & Graphic, Inc. Label for detecting biomolecule, method of producing the same and detection method using the same
DE102007014177B4 (en) * 2007-03-24 2008-12-04 Wincor Nixdorf International Gmbh Modular feature for surfaces of self-service systems
US8257612B2 (en) 2007-07-05 2012-09-04 Cabot Corporation Compositions having multiple responses to excitation radiation and methods for making same
US8404876B2 (en) * 2008-05-08 2013-03-26 3M Innovative Properties Company Process for producing nanoparticles
EP2120187A1 (en) 2008-05-14 2009-11-18 ADP International B.V. Multi-level markers
JP5388504B2 (en) * 2008-08-18 2014-01-15 株式会社トクヤマデンタル Method for producing wollastonite fine particles
DE102009012698A1 (en) 2009-03-11 2010-09-16 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Particles with a luminescent inorganic shell, process for coating particles and their use
DE102009024685A1 (en) 2009-06-12 2010-12-16 Gmbu E.V., Fachsektion Dresden Luminescent composite particle, useful e.g. as marking agent in polymeric films and articles for forgery-proof product identification, comprises organic optical brightener, which is homogeneously embedded in microspherical inorganic oxide
JP5328725B2 (en) * 2009-07-31 2013-10-30 キヤノン株式会社 Method for producing ytterbium phosphate fine particles, method for producing optical component, method for adjusting crystallite diameter of ytterbium phosphate fine particles
DE102009029395A1 (en) 2009-09-11 2011-03-24 G.I.P.C. Holdings Ltd. Mixture, luminescent composition, method of preparation and use
ES2359411B1 (en) * 2009-10-19 2012-04-03 Universidad De Zaragoza METHOD OF AUTHENTICATION OF OBJECTS.
DE102010026627A1 (en) 2010-07-09 2012-01-12 Giesecke & Devrient Gmbh Alkali metal and alkaline earth metal niobates and tantalates as security feature substances
WO2012003854A1 (en) 2010-07-09 2012-01-12 Giesecke & Devrient Gmbh Security feature
CN102735659A (en) * 2011-03-31 2012-10-17 复旦大学 Nanoparticles used for biological detection with fluoride lutecium as main component
WO2012162858A1 (en) * 2011-06-03 2012-12-06 拜尔技术工程（上海）有限公司 Preparation methods for fluorescent nanoparticles doped with rare earth and their solution, and system thereof
EP2739772A1 (en) * 2011-08-02 2014-06-11 Fondazione Istituto Italiano Di Tecnologia Ordered superstructures of octapod - shaped nanocrystals, their process of fabrication and use thereof
EP2570468B1 (en) 2011-09-13 2013-11-27 Bundesdruckerei GmbH Anti-stokes luminescent substances and use thereof in security documents
CN102368508B (en) * 2011-11-01 2013-03-13 吉林大学 Sodium tantalate film ultraviolet light detector and preparation method thereof
CN102517018B (en) * 2011-11-10 2013-11-20 深圳大学 Preparation method of nanowires of lanthanum phosphate activated by cerium and terbium
JP6051776B2 (en) * 2012-10-31 2016-12-27 堺化学工業株式会社 Rare earth doped barium sulfate and cosmetics
CN102994085A (en) * 2013-01-08 2013-03-27 哈尔滨工业大学 Novel red light emitting nanometer fluorescent powder and manufacture method thereof
DE102013013108A1 (en) * 2013-08-06 2015-02-12 Jürgen Martens Lanthanide-containing marking composition for the counterfeit-proof marking of objects, their production and use
CN103394165B (en) * 2013-08-08 2015-08-19 赵同泉 The artificial lighting health-care physical therapy instrument of a kind of energy vitamin D and calcium
US10533996B2 (en) * 2013-08-19 2020-01-14 University Of Houston Phosphorescent reporters
CN103601242A (en) * 2013-11-18 2014-02-26 宁夏东方钽业股份有限公司 Preparation method of phosphorus-containing tantalum powder
CN104312583A (en) * 2014-09-28 2015-01-28 彩虹集团电子股份有限公司 Preparation method of near ultraviolet excited red fluorescent powder for LEDs (light emitting diodes)
DE102015205082B4 (en) 2015-03-20 2020-10-01 Volkswagen Aktiengesellschaft Method for controlling an external coating of a vehicle and corresponding control device
DE102015225457B4 (en) * 2015-12-16 2017-07-20 BSH Hausgeräte GmbH Sensor device for determining at least one property of a liquid, water-conducting household appliance with the sensor device and method for determining at least one property of a liquid
US9517723B1 (en) * 2016-01-21 2016-12-13 Ford Global Technologies, Llc Illuminated tie-down cleat
EP3220112B1 (en) * 2016-03-01 2023-05-24 Matrix Vision GmbH Bildverarbeitung Device with at least one optical sensor module and operating method for same
CN106006593B (en) * 2016-05-18 2018-08-17 西南交通大学 A kind of nano-calcium phosphate preparation method of simple and effective
FR3066501B1 (en) 2017-05-18 2020-10-09 Ecole Polytech LUMINESCENT PARTICLES BASED ON RARE EARTHS AND THEIR USE AS A DIAGNOSIS AGENT
CN109385139B (en) * 2017-08-03 2021-10-12 深圳Tcl工业研究院有限公司 Purification method of zinc oxide-based nanoparticle ink
PL3513777T3 (en) 2018-01-22 2024-02-26 Ivoclar Vivadent Ag Method for the remineralisation of teeth
CN108557836B (en) * 2018-04-28 2021-10-22 陕西师范大学 BaB8O11(OH)4 nano flame-retardant material and preparation method thereof
CN110054205B (en) * 2018-06-06 2021-11-09 南方科技大学 Cesium iodide nanocrystal and preparation method and application thereof
CN111496265B (en) * 2019-01-31 2022-09-27 中国科学院大连化学物理研究所 Reduced noble metal lone atom material stable in solution and preparation method thereof
CN112079335B (en) * 2019-06-12 2023-06-20 北京化工大学 Preparation method of nano elemental sulfur particles
DE102019122840B4 (en) * 2019-08-26 2023-01-26 Bundesrepublik Deutschland, vertreten durch den Bundesminister für Wirtschaft und Energie, dieser vertreten durch den Präsidenten der Bundesanstalt für Materialforschung und –prüfung (BAM) Application of cadmium-free quantum dots as fluorescence standards and for signal referencing and as an internal light source for sensor materials
CN112450917B (en) * 2019-09-09 2022-04-19 中国科学院上海有机化学研究所 Fingerprint fluorescent fuming reagent and fuming method thereof
CN111115620B (en) * 2020-01-16 2021-11-23 宁波石墨烯创新中心有限公司 Preparation method of graphene quantum dots
CN112062155B (en) * 2020-08-26 2022-03-25 广东工业大学 Ultra-thin two-dimensional material with limited growth and preparation method thereof
CN113388398A (en) * 2021-06-11 2021-09-14 厦门理工学院 Eu (Eu)3+Rare earth yttrium-based tungstate doped fluorescent powder and preparation method thereof
CN113789571A (en) * 2021-09-18 2021-12-14 福州大学 Lanthanum-terbium silicate magneto-optical crystal and preparation method thereof
CN116515486B (en) * 2023-05-05 2024-03-15 西华大学 Rare earth doped scandium barium tungstate up-conversion luminescent material and preparation method thereof

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3886083A (en) 1974-05-09 1975-05-27 American Bank Note Co Safety inks and documents
US4238524A (en) 1978-03-06 1980-12-09 American Optical Corporation Process for identification marking clear plastic articles
US4331871A (en) 1979-09-18 1982-05-25 The United States Of America As Represented By The Secretary Of The Air Force Fluorescent detection of flaws
US4558144A (en) * 1984-10-19 1985-12-10 Corning Glass Works Volatile metal complexes
US4700657A (en) 1985-07-10 1987-10-20 Print-Lock Corporation Fingerprinting system incorporating a spray container and a portable vapor tank
EP0508345A3 (en) * 1991-04-09 1994-06-01 Hoechst Ag Volatile alkaline earth complex and its application
JP3410777B2 (en) * 1993-09-13 2003-05-26 株式会社東芝 Ultrafine inorganic phosphor-labeled specific binding substance and detection method using the same
US5418855A (en) 1993-09-27 1995-05-23 Angstrom Technologies, Inc. Authentication system and method
JPH07228620A (en) * 1994-02-15 1995-08-29 Mitsubishi Rayon Co Ltd Production of methacrylic ester polymer
EP0686997A3 (en) * 1994-06-06 1996-06-26 Matsushita Electric Ind Co Ltd Discharge lamp and illumination instrument for general illumination
AU4767096A (en) * 1995-01-25 1996-08-14 Northern Engraving Corporation Improved fluorescent inks
US5811924A (en) * 1995-09-19 1998-09-22 Kabushiki Kaisha Toshiba Fluorescent lamp
US5637258A (en) * 1996-03-18 1997-06-10 Nanocrystals Technology L.P. Method for producing rare earth activited metal oxide nanocrystals
US5667724A (en) * 1996-05-13 1997-09-16 Motorola Phosphor and method of making same
US5988821A (en) * 1996-05-16 1999-11-23 Nippon Carbide Kogyo Kabushiki Kaisha Lens type functional retroreflective sheeting and method of producing same
AU5242998A (en) 1996-11-05 1998-05-29 Corrosion Consultants, Inc. Ultraviolet light illumination and viewing system and method for fluorescent dye leak detection
EP0856871A1 (en) * 1997-01-29 1998-08-05 Nec Corporation Fluorescent lamp
JP3468750B2 (en) 1998-01-22 2003-11-17 ルミネックス コーポレイション Microparticles with multiple fluorescent signals
GB2334033A (en) * 1998-02-09 1999-08-11 Isis Innovation Self activated rare earth oxide nanoparticles
CN1059690C (en) 1998-04-27 2000-12-20 杨江 Anti-faking ink for plastic gravure printing and method therefor
JP2000104058A (en) * 1998-09-28 2000-04-11 Sony Corp Production of luminescent material
JP2000256251A (en) * 1999-03-09 2000-09-19 New Japan Chem Co Ltd Rare-earth metal-carrying nano-size (host-guest) complex

Also Published As

Publication number Publication date
JP5241987B2 (en) 2013-07-17
CN100489058C (en) 2009-05-20
AU1003602A (en) 2002-03-22
EP1232226A1 (en) 2002-08-21
WO2002020696A1 (en) 2002-03-14
ATE331010T1 (en) 2006-07-15
DE50110243D1 (en) 2006-08-03
JP2004508215A (en) 2004-03-18
ES2269466T3 (en) 2007-04-01
WO2002020695A1 (en) 2002-03-14
AU782482B2 (en) 2005-08-04
EP1707611A2 (en) 2006-10-04
CA2388094C (en) 2011-11-15
IL149172A0 (en) 2002-11-10
CN1388827A (en) 2003-01-01
EP1707611A3 (en) 2008-05-28
EP1232226B1 (en) 2006-06-21

Similar Documents

Publication Publication Date Title
CA2388094A1 (en) Synthesis of nanoparticles
US7241399B2 (en) Synthesis of nanoparticles
US7651771B2 (en) Luminescent core/shell nanoparticles comprising a luminescent core and method of making thereof
JP2004508215A5 (en)
US6953536B2 (en) Long persistent phosphors and persistent energy transfer technique
US6596196B2 (en) Rare earth borate, its precursor, and luminophore made thereof
KR940002343A (en) Lanthanum Cerium Terbium Mixed Phosphate Based Green Light Emitting Material, Precursor And Synthesis Method Of The Compound
US7344895B2 (en) Production and use of in situ-modified nanoparticles
US20220177778A1 (en) Annealing method
WO2009134507A2 (en) Phosphorescent compositions, methods of making the compositions, and methods of using the compositions
US20230295498A1 (en) Y2o3:re nanoparticles
EP0415469B1 (en) Phosphor preparation
US3507804A (en) Method of coprecipitating mixed rare-earth orthophosphates suitable for making phosphor
EP1141170A1 (en) Rare earth-activated phosphors
WO2023126447A1 (en) A3b5o12:re garnet nanoparticles
KR930010745B1 (en) Phosphor and cathode-ray tube using the same
WO2023111247A1 (en) Microjet reactor based synthesis of nanophosphors
Haranath et al. Optimization of boric acid content in developing efficient blue emitting, long persistent phosphor
US20050013943A1 (en) Near uv excited phospors
Chaudhary SYNTHESIS AND CHARECTERIZATION OF REAR EARTH DOPED PHOSPHOR
Popovici et al. Photo-and cathodoluminescence investigation of CaWO4: Eu, Tb phosphors
BHONSULE et al. ENERGY TRANSFER AND PHOTOLUMINESCENCE STUDY OFLANTHANIDE IONS DOPEDMETAPHOSPHATE Ce (PO) 3 3

Legal Events

Date Code Title Description
EEER Examination request
MKLA Lapsed

Effective date: 20170907