WO1999046204A1 - Self activated rare earth oxide nanoparticles - Google Patents
Self activated rare earth oxide nanoparticles Download PDFInfo
- Publication number
- WO1999046204A1 WO1999046204A1 PCT/GB1999/000408 GB9900408W WO9946204A1 WO 1999046204 A1 WO1999046204 A1 WO 1999046204A1 GB 9900408 W GB9900408 W GB 9900408W WO 9946204 A1 WO9946204 A1 WO 9946204A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- rare earth
- particles
- earth metal
- surface active
- compound
- Prior art date
Links
Classifications
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- 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
- C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
-
- 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
-
- 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
- C09K11/7784—Chalcogenides
Definitions
- the present invention relates to rare earth activated phosphors.
- Such phosphors are known to possess excellent light output and colour rendering properties and have been utilised successfully in many display technologies.
- One particularly successful material europium activated yttrium oxide (Y 2 0 3 :Eu 3+ ) has shown particular promise in the field of field emission displays.
- the present invention provides a compound of the formula Z 2 0 3 :Z x+ where Z represents a rare earth element and x is 2 to 4, generally 3.
- Preferred rare earth elements/metals include terbium, europium and cerium.
- the phosphors are in the form of nanoparticles, especially ones having a particle size from 2 to 10 nm, especially not exceeding 5 nm, for example about 4 nm.
- the phosphors of the present invention can readily be produced by a simple precipitation method.
- alkali is added to a solution of a rare earth metal salt, typically a chloride, in the presence of a metal complexing surface active molecule.
- the preferred salts are chlorides and it is believed that the presence of chlorine enhances the display technology but it is also possible to produce luminescent nanoparticles in the complete absence of chlorine from any soluble salt, for example from nitrates .
- the surface active molecule binds to the rare earth ions and acts to passivate any surface state which may allow for nonradiative recombination; it thus has a surface capping effect. This binding action is also beneficial to the optical properties as it reduces the likelihood of recombination via surface dangling bond states.
- Suitable surface active molecules which may be used include trioctyl phosphine oxide (TOPO) , which is preferred, sodium hexametaphosphate, crown ethers and amines. It is generally better to use a purely organic molecule not containing any metal.
- alkali used is not particularly critical provided it dissolves in the solvent employed.
- Typical alkalis include ammonium hydroxide and sodium hydroxide .
- the process is carried out by mixing the salt and surface active molecule in a mutual solvent, for example for about 15 minutes, and then adding the alkali in a solvent thereto to cause colloidal precipitation over a period of a few minutes.
- solvents which must, of course, be capable of dissolving the salt
- solvents which are slightly reducing or dehydrating such as thiols and alcohols, including glycols such as ethylene glycol, as well as aliphatic alcohols such as ethanol, propanol and methanol which is strongly preferred.
- the process is carried out with little or no water since this has a tendency to promote the formation of hydroxide.
- the pH should generally be from 5 to 9 (measured in methanol; 5.7 is equivalent to about 8 in water) .
- the reaction is conveniently carried out at room temperature. By increasing the temperature there is a tendency to increase particle size or vice versa. Thus a typical temperature range is from 20° to 40°C.
- the relative molar amounts of the rare earth salt and surface active molecule generally range from a minimum of 0.3 up to 2.0 although a significant excess is generally unnecessary.
- the molar ratio of surface active molecule to rare earth salt is from about 1:1 to 2:1.
- Particle size in the sub 50 nm range may be varied by varying this ratio; the preferred ratio can provide particles in the sub 5 nm range.
- Figure 3 of the accompanying drawings shows how the luminescence efficiency varies with particle size for Eu 2 0 3 nanoparticles, the figures in parenthesis being the ratio of rare earth salt to surface active molecule, (TOPO) .
- the concentration of rare earth metal salt in the solution will be from 0.0001 to 0.5 moles, for example from 0.0005 to 0.1 moles. There is a tendency for flocculation to occur at higher concentrations.
- the resulting precipitate and solvent can be concentrated by evaporation and the particles separated and dried. If desired or necessary, specific particle sizes can be selected using various methods known in the art .
- Preferred compounds of the present invention include Tb 2 0 3 :Tb 3+ , Ce 2 0 3 :Ce 3+ and Eu 2 0 3 :Eu 3+ .
- the properties of the various rare earth oxides obtained are similar.
- Dy dysprosium
- S samarium
- Ho holmium
- Er erbium
- Nd neodymium
- the nanoparticles of the present invention are suitable for use in FED type displays.
- the particles can be embedded in a suitable plastics material by a variety of methods including dip coating, spin coating and meniscus coating or by using an air gun spray.
- the present invention also provides a plastics material which incorporates nanoparticles of the present invention.
- Suitable polymers which can be employed include polyacrylic acid, polystyrene and polymethyl methacrylate .
- Such plastics materials can be used for photoluminescence applications and also in electroluminescence applications where an AC current is to be employed. If a DC current is employed then conducting polymers such as polyvinylcarbazole, polyphenylenevinylidene and polymethylphenylsilane can be employed.
- Poly 2- (4-biphenylyl) -5- (4-tertiarybutyl phenyl) -1, 3, 4-oxidiazole (butyl-PBD) can also be used.
- the polymer should be compatible with the solvent employed, typically methanol, in coating the plastics material with the particles.
- the particles will be applied to a thin layer of the plastics material, typically having a thickness from 0.5 to 15 microns.
- the maximum concentration of particles is generally about 35% by weight with 65% by weight of polymer. There is a tendency for the polymer to crack if the concentration exceeds this value. A typical minimum concentration is about 2% by weight (98% by weight polymer) . If the concentration is reduced below this value then "holes" tend to form in the plastics material.
- Figure 4 gives the particle size distribution for a representative sample of 180 terbia nanoparticles; a drop of the particles in solution was placed on a lacey carbon film and the methanol evaporated. The size of the particles was determined using a high resolution transmission electron microscope.
- Figure 5 is a transmission electron microscope photograph of europia nanoparticles obtained in a similar manner.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Luminescent Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2000535587A JP2002507630A (en) | 1999-02-09 | 1999-02-09 | Self-activating rare earth oxide nanoparticles |
US09/601,918 US6596194B1 (en) | 1998-02-09 | 1999-02-09 | Self activated rare earth oxide nanoparticles |
EP99904997A EP1047637A1 (en) | 1998-02-09 | 1999-02-09 | Self activated rare earth oxide nanoparticles |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB9802760A GB2334033A (en) | 1998-02-09 | 1998-02-09 | Self activated rare earth oxide nanoparticles |
GB9802760.0 | 1998-03-09 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999046204A1 true WO1999046204A1 (en) | 1999-09-16 |
Family
ID=10826722
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB1999/000408 WO1999046204A1 (en) | 1998-02-09 | 1999-02-09 | Self activated rare earth oxide nanoparticles |
Country Status (4)
Country | Link |
---|---|
US (1) | US6596194B1 (en) |
EP (1) | EP1047637A1 (en) |
GB (1) | GB2334033A (en) |
WO (1) | WO1999046204A1 (en) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6177088B1 (en) * | 1999-01-07 | 2001-01-23 | Fayette Environmental Services, Inc. | Surface-functionalized, probe-containing nanospheres |
WO2002034842A1 (en) * | 2000-10-27 | 2002-05-02 | Oxonica Limited | Coated metal oxides and hydroxides |
US6692660B2 (en) | 2001-04-26 | 2004-02-17 | Nanogram Corporation | High luminescence phosphor particles and related particle compositions |
US6706210B1 (en) | 1998-12-17 | 2004-03-16 | Isis Innovation Limited | Ternary oxide phosphor particles |
US6783855B1 (en) | 1998-12-17 | 2004-08-31 | Isis Innovation Limited | Rare-earth-activated phosphors |
US6869596B1 (en) | 1998-05-27 | 2005-03-22 | Isis Innovation Limited | Ultraviolet light screening compositions |
US7306845B2 (en) | 2001-08-17 | 2007-12-11 | Neophotonics Corporation | Optical materials and optical devices |
Families Citing this family (9)
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---|---|---|---|---|
WO2002020695A1 (en) * | 2000-09-08 | 2002-03-14 | Nanosolutions Gmbh | Doped nanoparticles |
IL138471A0 (en) * | 2000-09-14 | 2001-10-31 | Yissum Res Dev Co | Novel semiconductor materials and their uses |
WO2002048432A2 (en) * | 2000-12-15 | 2002-06-20 | The Arizona Board Of Regents | Method for patterning metal using nanoparticle containing precursors |
US7160614B2 (en) | 2002-11-01 | 2007-01-09 | Sony Corporation | Crystalline superfine particles, complex material, method of manufacturing crystalline superfine particles, inverted micelles, inverted micelles enveloping precursor superfine particles, inverted micelles enveloping crystalline superfine particles, and precursor superfine particles |
US7405002B2 (en) * | 2004-08-04 | 2008-07-29 | Agency For Science, Technology And Research | Coated water-soluble nanoparticles comprising semiconductor core and silica coating |
US7534489B2 (en) * | 2004-09-24 | 2009-05-19 | Agency For Science, Technology And Research | Coated composites of magnetic material and quantum dots |
DE102006032590A1 (en) * | 2006-07-13 | 2008-01-17 | H.C. Starck Gmbh | Hydrothermal process for the production of nano- to microscale particles |
US8625428B2 (en) | 2008-06-05 | 2014-01-07 | Telefonaktiebolaget Lm Ericsson (Publ) | Method and apparatus for handling a switch using a preferred destination list |
JP6939741B2 (en) | 2018-08-31 | 2021-09-22 | 信越化学工業株式会社 | Method for producing rare earth compound particles |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0253552A2 (en) * | 1986-07-14 | 1988-01-20 | Corning Glass Works | Preparation of unagglomerated metal oxide particles with uniform particle size |
DE4210153A1 (en) * | 1991-03-28 | 1992-10-01 | Taki Chemical | Stable cerium di:oxide solns. - contain phosphoric acid and/or phosphate, and pref. also quat. ammonium salt as cationic surfactant |
EP0684072A2 (en) * | 1994-05-27 | 1995-11-29 | Rhone-Poulenc Chimie | Rare earth-based dispersible compound, colloidal suspension obtained from it, processes for their preparation and their use for making catalysts |
EP0732356A2 (en) * | 1995-03-16 | 1996-09-18 | General Electric Company | Acrylic coatings containing inorganic UV screen |
US5637258A (en) * | 1996-03-18 | 1997-06-10 | Nanocrystals Technology L.P. | Method for producing rare earth activited metal oxide nanocrystals |
Family Cites Families (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3291747A (en) * | 1965-03-31 | 1966-12-13 | Gen Telephone And Electronic L | Method for making doped yttrium oxide phosphors |
JPS4631844B1 (en) * | 1969-03-10 | 1971-09-17 | ||
NL164697C (en) * | 1973-10-05 | 1981-01-15 | Philips Nv | LOW-PRESSURE MERCURY DISCHARGE LAMP. |
US4032471A (en) * | 1975-01-27 | 1977-06-28 | Eastman Kodak Company | Process for preparing yttrium oxide and rare earth metal oxide phosphors |
JPS5813688A (en) * | 1981-07-20 | 1983-01-26 | Mitsubishi Chem Ind Ltd | Production of fluorescent substance |
US5015452A (en) * | 1986-11-17 | 1991-05-14 | Clarkson University | Process for synthesis of uniform colloidal particles of rare earth oxides |
JPH08119631A (en) * | 1994-10-21 | 1996-05-14 | Shin Etsu Chem Co Ltd | Production of spherical oxide of rare earth element and its precursor |
US6251303B1 (en) * | 1998-09-18 | 2001-06-26 | Massachusetts Institute Of Technology | Water-soluble fluorescent nanocrystals |
-
1998
- 1998-02-09 GB GB9802760A patent/GB2334033A/en not_active Withdrawn
-
1999
- 1999-02-09 EP EP99904997A patent/EP1047637A1/en not_active Withdrawn
- 1999-02-09 WO PCT/GB1999/000408 patent/WO1999046204A1/en not_active Application Discontinuation
- 1999-02-09 US US09/601,918 patent/US6596194B1/en not_active Expired - Fee Related
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0253552A2 (en) * | 1986-07-14 | 1988-01-20 | Corning Glass Works | Preparation of unagglomerated metal oxide particles with uniform particle size |
DE4210153A1 (en) * | 1991-03-28 | 1992-10-01 | Taki Chemical | Stable cerium di:oxide solns. - contain phosphoric acid and/or phosphate, and pref. also quat. ammonium salt as cationic surfactant |
EP0684072A2 (en) * | 1994-05-27 | 1995-11-29 | Rhone-Poulenc Chimie | Rare earth-based dispersible compound, colloidal suspension obtained from it, processes for their preparation and their use for making catalysts |
EP0732356A2 (en) * | 1995-03-16 | 1996-09-18 | General Electric Company | Acrylic coatings containing inorganic UV screen |
US5637258A (en) * | 1996-03-18 | 1997-06-10 | Nanocrystals Technology L.P. | Method for producing rare earth activited metal oxide nanocrystals |
Non-Patent Citations (1)
Title |
---|
KOBAYASHI M: "PREPARATION OF ULTRAFINE PRECURSOR PARTICLES FOR Y2O3 FROM YCI3/ETHYLENEDIAMINETETRACETIC ACID/UREA AQUEOUS SOLUTION", JOURNAL OF MATERIALS SCIENCE LETTERS, vol. 11, no. 11, 1 June 1992 (1992-06-01), pages 767 - 768, XP000292249 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6869596B1 (en) | 1998-05-27 | 2005-03-22 | Isis Innovation Limited | Ultraviolet light screening compositions |
US8642019B2 (en) | 1998-05-27 | 2014-02-04 | Isis Innovation Limited | Ultraviolet light screening compositions |
US6706210B1 (en) | 1998-12-17 | 2004-03-16 | Isis Innovation Limited | Ternary oxide phosphor particles |
US6783855B1 (en) | 1998-12-17 | 2004-08-31 | Isis Innovation Limited | Rare-earth-activated phosphors |
US6177088B1 (en) * | 1999-01-07 | 2001-01-23 | Fayette Environmental Services, Inc. | Surface-functionalized, probe-containing nanospheres |
WO2002034842A1 (en) * | 2000-10-27 | 2002-05-02 | Oxonica Limited | Coated metal oxides and hydroxides |
US6692660B2 (en) | 2001-04-26 | 2004-02-17 | Nanogram Corporation | High luminescence phosphor particles and related particle compositions |
US7101520B2 (en) | 2001-04-26 | 2006-09-05 | Nanogram Corporation | High luminescence phosphor particles and methods for producing the particles |
US7306845B2 (en) | 2001-08-17 | 2007-12-11 | Neophotonics Corporation | Optical materials and optical devices |
Also Published As
Publication number | Publication date |
---|---|
EP1047637A1 (en) | 2000-11-02 |
GB9802760D0 (en) | 1998-04-08 |
GB2334033A (en) | 1999-08-11 |
US6596194B1 (en) | 2003-07-22 |
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