US20040214501A1 - Electroluminescent phosphor with plural moisture resistant coatings thereon - Google Patents

Electroluminescent phosphor with plural moisture resistant coatings thereon Download PDF

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Publication number
US20040214501A1
US20040214501A1 US10/851,298 US85129804A US2004214501A1 US 20040214501 A1 US20040214501 A1 US 20040214501A1 US 85129804 A US85129804 A US 85129804A US 2004214501 A1 US2004214501 A1 US 2004214501A1
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moisture
phosphor
layer
coating
resistant
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US10/851,298
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Keith Klinedinst
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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
    • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
    • 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
    • C09K11/58—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing copper, silver or gold
    • C09K11/582—Chalcogenides
    • C09K11/584—Chalcogenides with zinc or cadmium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y10T428/2991—Coated
    • Y10T428/2998—Coated including synthetic resin or polymer

Definitions

  • This invention relates to electroluminescent phosphors and more particularly to electroluminescent phosphors that have been treated to be moisture resistant. More particularly, this invention relates to electroluminescent phosphors having greatly reduced moisture absorption, greatly increased life and efficacy, and an economical manufacturing cost.
  • Treated phosphors are known from U.S. Pat. Nos. 4,585,673; 4,825,124; 5,080,928; 5,118,529; 5,156,885; 5,220,243; 5,244,750; and 5,418,062. It is known from some of the just-mentioned patents that a coating precursor and oxygen can be used to apply a protective coating. See, for example, U.S. Pat. Nos. 5,244,750 and 4,585,673. The treatment processes in several of the others of these patents employ chemical vapor deposition to apply a protective coating by hydrolysis.
  • U.S. Pat. No. 5,856,009 discloses a high temperature process (i.e., 300 to 700° C.) for applying a silicon nitride coating over a previously applied heat resistant coating on phosphor particles.
  • U.S. Pat. No. 6,064,150 discloses an aluminum nitride coating process using a highly reactive hexakis(dimethylamido)dialuminum. The freshly applied nitride coating is susceptible to absorbing, or reacting with, atmospheric oxygen and moisture upon removal from the coating reactor.
  • a process for providing a moisture-resistant electroluminescent phosphor that comprises the steps of providing individual particles of the phosphor with a first layer of an inorganic moisture-resistant coating to form a first-coated phosphor, substantially isolating the first-coated phosphor from contact with atmospheric oxygen and moisture, and providing the first-coated phosphor with a second layer of an organic moisture-resistant coating to form a second-coated phosphor.
  • the second layer inhibiting the first layer from absorbing, or reacting with, atmospheric oxygen or moisture.
  • a process for providing a moisture-resistant electroluminescent phosphor comprises the steps of providing individual particles of the phosphor with a first layer of an inorganic moisture-resistant coating to form a first-coated phosphor.
  • the electroluminescent phosphor can be copper-activated zinc sulfide (ZnS:Cu) and the first coating can be an aluminum nitride such as that disclosed in the above-mentioned U.S. Pat. No. 6,064,150.
  • This material is an excellent moisture inhibitor but is susceptible to absorbing, or reacting with, atmospheric oxygen and water vapor following removal from the coating processing chamber and exposure to ambient conditions. Thus, additional handling procedures must be put into place to protect the phosphor until its incorporation into a lamp.
  • the organic layer must be substantially transmissive of visible light, a good electrical insulator (electroluminescent lamps operate on a capacitive principle, emitting light when placed in an alternating electric field) and must have low moisture permeability.
  • a good electrical insulator electrospray lamps operate on a capacitive principle, emitting light when placed in an alternating electric field
  • Such materials can be selected from polyesters, polyalkylacrylates, or vinyl-epoxy resins. These materials have been used in the past to reduce the moisture sensitivity of metal halide radiographic phosphors.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electroluminescent Light Sources (AREA)
  • Luminescent Compositions (AREA)

Abstract

A moisture-resistant electroluminescent phosphor is provided wherein the individual phosphor particles have a first coating of an inorganic moisture-resistant coating and a second coating of an organic moisture-resistant coating. The process for making the moisture-resistant phosphor comprises applying a first layer of an inorganic moisture-resistant coating to individual particles of an electroluminescent phosphor to form a first-coated phosphor, substantially isolating said first-coated phosphor from contact with atmospheric oxygen and moisture, and applying a second layer of an organic moisture-resistant coating to the first-coated phosphor to form a second-coated phosphor.

Description

  • This application claims priority from Provisional Application No. 60/282,391, filed Apr. 6, 2001.[0001]
    • TECHNICAL FIELD
  • This invention relates to electroluminescent phosphors and more particularly to electroluminescent phosphors that have been treated to be moisture resistant. More particularly, this invention relates to electroluminescent phosphors having greatly reduced moisture absorption, greatly increased life and efficacy, and an economical manufacturing cost. [0002]
    • BACKGROUND ART
  • Treated phosphors are known from U.S. Pat. Nos. 4,585,673; 4,825,124; 5,080,928; 5,118,529; 5,156,885; 5,220,243; 5,244,750; and 5,418,062. It is known from some of the just-mentioned patents that a coating precursor and oxygen can be used to apply a protective coating. See, for example, U.S. Pat. Nos. 5,244,750 and 4,585,673. The treatment processes in several of the others of these patents employ chemical vapor deposition to apply a protective coating by hydrolysis. It also has been reported that chemical vapor deposition, at atmospheric pressure, can be used to deposit thin films of aluminum nitride coatings from hexakis(dimethylamido)dialuminum and anhydrous ammonia precursors upon silicon, vitreous carbon and glass substrates. See, for example, “Atmospheric pressure chemical vapor deposition of aluminum nitride films at 200-250° C.”, Gordon, et al., Journal Material Resources, Vol. 6, No. 1, January 1991; and “Chemical vapor deposition of aluminum nitride thin films”, Gordon, et al., Journal Material Resources, Vol. 7, No. 7, July 1992. See, also, U.S. Pat. Nos. 5,139,825 and 5,178,911, Gordon, which also disclose transition metal nitrides and other metallic nitrides such as gallium and tin, respectively. U.S. Pat. No. 5,856,009 discloses a high temperature process (i.e., 300 to 700° C.) for applying a silicon nitride coating over a previously applied heat resistant coating on phosphor particles. U.S. Pat. No. 6,064,150 (incorporated herein by reference) discloses an aluminum nitride coating process using a highly reactive hexakis(dimethylamido)dialuminum. The freshly applied nitride coating is susceptible to absorbing, or reacting with, atmospheric oxygen and moisture upon removal from the coating reactor. [0003]
    • SUMMARY OF THE INVENTION
  • It is, therefore, an object of the present invention to obviate the disadvantages of the prior art. [0004]
  • It is another object of the invention to enhance electroluminescent phosphors. [0005]
  • These objects are accomplished, in one aspect of the invention, by a process for providing a moisture-resistant electroluminescent phosphor that comprises the steps of providing individual particles of the phosphor with a first layer of an inorganic moisture-resistant coating to form a first-coated phosphor, substantially isolating the first-coated phosphor from contact with atmospheric oxygen and moisture, and providing the first-coated phosphor with a second layer of an organic moisture-resistant coating to form a second-coated phosphor. The second layer inhibiting the first layer from absorbing, or reacting with, atmospheric oxygen or moisture.[0006]
    • DETAILED DESCRIPTION OF THE INVENTION
  • For a better understanding of the present invention, together with other and further objects, advantages and capabilities thereof, reference is made to the following disclosure and appended claims. [0007]
  • Referring now to the invention with greater particularity, a process for providing a moisture-resistant electroluminescent phosphor comprises the steps of providing individual particles of the phosphor with a first layer of an inorganic moisture-resistant coating to form a first-coated phosphor. In a preferred embodiment of the invention, the electroluminescent phosphor can be copper-activated zinc sulfide (ZnS:Cu) and the first coating can be an aluminum nitride such as that disclosed in the above-mentioned U.S. Pat. No. 6,064,150. This material is an excellent moisture inhibitor but is susceptible to absorbing, or reacting with, atmospheric oxygen and water vapor following removal from the coating processing chamber and exposure to ambient conditions. Thus, additional handling procedures must be put into place to protect the phosphor until its incorporation into a lamp. [0008]
  • This problem is solved by substantially isolating the first-coated phosphor from contact with atmospheric oxygen and moisture after its initial coating and providing the first-coated phosphor with a second layer of an organic moisture-resistant coating to form a second-coated phosphor. Ideally, the second operation is performed in the same apparatus as the first, without removing the first-coated phosphor. Suitable apparatus for coating the phosphors is shown in the above-cited U.S. Pat. No. 6,064,150 [0009]
  • The organic layer must be substantially transmissive of visible light, a good electrical insulator (electroluminescent lamps operate on a capacitive principle, emitting light when placed in an alternating electric field) and must have low moisture permeability. Such materials can be selected from polyesters, polyalkylacrylates, or vinyl-epoxy resins. These materials have been used in the past to reduce the moisture sensitivity of metal halide radiographic phosphors. [0010]
  • Similarly, organic coatings have been suggested for use singly to reduce the moisture sensitivity of electroluminescent phosphors. In the latter case, parylenes, including poly(p-xylylene), and poly(p-α-xylylene) with α=H, Cl, Br, F, alkyl or amino, have been suggested. [0011]
  • The use of two layers of different moisture-resistant coatings provides an electroluminescent phosphor with excellent lamp properties and long life. Additionally, the coatings are applied at low temperatures, that is, below 300° C., thus avoiding the potential elimination of sulfur that occurs if a high temperature coating process is employed. [0012]
  • While there have been shown and described what are at present considered to be the preferred embodiments of the invention, it will be apparent to those skilled in the art that various changes and modification can be made herein without departing from the scope of the invention as defined by the appended claims. [0013]

Claims (9)

1. A process for providing a moisture-resistant electroluminescent phosphor comprising the steps of:
applying a first layer of an inorganic moisture-resistant coating to individual particles of a phosphor to form a first-coated phosphor,
substantially isolating said first-coated phosphor from contact with atmospheric oxygen and moisture; and
applying a second layer of an organic moisture-resistant coating to form a second-coated phosphor.
2. The process of claim 1 wherein said first layer is an aluminum nitride.
3. The process of claim 1 wherein said electroluminescent phosphor comprises zinc sulfide activated with one or more activators.
4. The process of claim 1 wherein said organic coating is substantially transmissive of visible light, electrically insulating, and has low moisture permeability.
5. The process of claim 1 wherein the second layer is a parylene, polyester, polyalkylacrylate, or vinyl-epoxy resin.
6. The process of claim 5 wherein the first layer is an aluminum nitride.
7. The process of claim 2 wherein the second layer is a parylene.
8. The process of claim 2 wherein the second layer is poly(p-xylylene) or poly(p-α-xylylene) with α=H, Cl, Br, F, alkyl or amino.
9-16. (canceled).
US10/851,298 2001-04-06 2004-05-21 Electroluminescent phosphor with plural moisture resistant coatings thereon Abandoned US20040214501A1 (en)

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US28239101P 2001-04-06 2001-04-06
US10/115,645 US7001665B2 (en) 2001-04-06 2002-04-03 Electroluminescent phosphor with plural moisture resistant coatings thereon
US10/851,298 US20040214501A1 (en) 2001-04-06 2004-05-21 Electroluminescent phosphor with plural moisture resistant coatings thereon

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Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6734466B2 (en) * 2002-03-05 2004-05-11 Agilent Technologies, Inc. Coated phosphor filler and a method of forming the coated phosphor filler
JP4725008B2 (en) * 2003-09-11 2011-07-13 日亜化学工業株式会社 Light emitting device, phosphor for light emitting element, and method for manufacturing phosphor for light emitting element
DE60330892D1 (en) 2002-11-08 2010-02-25 Nichia Corp LIGHT EMISSION ELEMENT, FLUORESIDE AND METHOD FOR PRODUCING A FLUOR
KR100700000B1 (en) * 2004-10-19 2007-03-26 삼성에스디아이 주식회사 Display device and fabricating method of the same
US8298666B2 (en) * 2006-01-26 2012-10-30 Global Tungsten & Powders Corp. Moisture resistant electroluminescent phosphor with high initial brightness and method of making
US7833437B2 (en) * 2006-01-26 2010-11-16 Global Tungsten & Powders Corp. Moisture-resistant electroluminescent phosphor with high initial brightness and method of making
US8816371B2 (en) 2011-11-30 2014-08-26 Micron Technology, Inc. Coated color-converting particles and associated devices, systems, and methods
US10875005B2 (en) 2013-02-25 2020-12-29 Lumileds Llc Coated luminescent particle, a luminescent converter element, a light source, a luminaire and a method of manufacturing a coated luminescent particle
TWI632705B (en) * 2013-12-03 2018-08-11 皇家飛利浦有限公司 A method of manufacturing a ceramic light transmitting barrier cell, a barrier cell, a light source and a luminaire
KR102397910B1 (en) 2015-07-06 2022-05-16 삼성전자주식회사 Fluoride phosphor, manufacturing method of the same, and light emitting device
DE102018125754A1 (en) 2018-10-17 2020-04-23 Leuchtstoffwerk Breitungen Gmbh Alkaline earth metal silicate phosphor and method for improving the long-term stability of an alkaline earth metal silicate phosphor
CN111171815B (en) * 2018-11-13 2021-12-17 厦门稀土材料研究所 Surface modification method of fluoride luminescent material and fluoride luminescent material prepared by same

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Publication number Priority date Publication date Assignee Title
US4097776A (en) * 1977-03-25 1978-06-27 The United States Of America As Represented By The Secretary Of The Air Force Coated electroluminescent phosphors
US4508760A (en) * 1983-06-10 1985-04-02 Nova Tran Corporation Method and apparatus for microencapsulation
US4806389A (en) * 1987-03-02 1989-02-21 Gte Laboratories Incorporated Method of treating a coated phosphor
US4863826A (en) * 1985-10-08 1989-09-05 Fuji Photo Film Co., Ltd. Radiation image storage panel
US5049408A (en) * 1989-11-07 1991-09-17 Gte Laboratories Incorporated Method for coating phosphor particles using aluminum isopropoxide precursors and an isothermal fluidized bed
US5051277A (en) * 1990-01-22 1991-09-24 Gte Laboratories Incorporated Method of forming a protective bi-layer coating on phosphore particles
US5220243A (en) * 1990-10-05 1993-06-15 Gte Products Corporation Moisture insensitive zinc sulfide electroluminescent materials and an electroluminescent device made therefrom
US5454892A (en) * 1991-06-03 1995-10-03 Bkl, Inc. Method of making an improved electroluminescent device
US5646412A (en) * 1995-07-19 1997-07-08 Eastman Kodak Company Coated radiographic phosphors and radiographic phosphor panels
US5856009A (en) * 1995-10-12 1999-01-05 Nec Corporation Coating for phosphor particles
US5958591A (en) * 1997-06-30 1999-09-28 Minnesota Mining And Manufacturing Company Electroluminescent phosphor particles encapsulated with an aluminum oxide based multiple oxide coating
US6020067A (en) * 1997-09-09 2000-02-01 Kasei Optonix, Ltd. Phosphor having surface coated with a quaternary salt-containing compound
US6064150A (en) * 1998-01-12 2000-05-16 Osram Sylvania Inc. Nitride coated particle and composition of matter comprised of such particles
US6093492A (en) * 1996-12-06 2000-07-25 U.S. Philips Corporation Phosphor composition with a hydroxycarboxylic-acid coating
US6248261B1 (en) * 1998-08-26 2001-06-19 Kabushiki Kaisha Toshiba Electroluminescent phosphor and electroluminescent element using the same
US6562460B1 (en) * 2001-11-20 2003-05-13 Encap Technologies, Llc Microencapsulated particles and process for manufacturing same

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Publication number Priority date Publication date Assignee Title
US6734466B2 (en) * 2002-03-05 2004-05-11 Agilent Technologies, Inc. Coated phosphor filler and a method of forming the coated phosphor filler

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4097776A (en) * 1977-03-25 1978-06-27 The United States Of America As Represented By The Secretary Of The Air Force Coated electroluminescent phosphors
US4508760A (en) * 1983-06-10 1985-04-02 Nova Tran Corporation Method and apparatus for microencapsulation
US4863826A (en) * 1985-10-08 1989-09-05 Fuji Photo Film Co., Ltd. Radiation image storage panel
US4806389A (en) * 1987-03-02 1989-02-21 Gte Laboratories Incorporated Method of treating a coated phosphor
US5049408A (en) * 1989-11-07 1991-09-17 Gte Laboratories Incorporated Method for coating phosphor particles using aluminum isopropoxide precursors and an isothermal fluidized bed
US5051277A (en) * 1990-01-22 1991-09-24 Gte Laboratories Incorporated Method of forming a protective bi-layer coating on phosphore particles
US5220243A (en) * 1990-10-05 1993-06-15 Gte Products Corporation Moisture insensitive zinc sulfide electroluminescent materials and an electroluminescent device made therefrom
US5454892A (en) * 1991-06-03 1995-10-03 Bkl, Inc. Method of making an improved electroluminescent device
US5646412A (en) * 1995-07-19 1997-07-08 Eastman Kodak Company Coated radiographic phosphors and radiographic phosphor panels
US5856009A (en) * 1995-10-12 1999-01-05 Nec Corporation Coating for phosphor particles
US6093492A (en) * 1996-12-06 2000-07-25 U.S. Philips Corporation Phosphor composition with a hydroxycarboxylic-acid coating
US5958591A (en) * 1997-06-30 1999-09-28 Minnesota Mining And Manufacturing Company Electroluminescent phosphor particles encapsulated with an aluminum oxide based multiple oxide coating
US6020067A (en) * 1997-09-09 2000-02-01 Kasei Optonix, Ltd. Phosphor having surface coated with a quaternary salt-containing compound
US6064150A (en) * 1998-01-12 2000-05-16 Osram Sylvania Inc. Nitride coated particle and composition of matter comprised of such particles
US6456002B1 (en) * 1998-01-12 2002-09-24 Osram Sylvania Inc. Moisture insensitive electroluminescent phosphor
US6248261B1 (en) * 1998-08-26 2001-06-19 Kabushiki Kaisha Toshiba Electroluminescent phosphor and electroluminescent element using the same
US6562460B1 (en) * 2001-11-20 2003-05-13 Encap Technologies, Llc Microencapsulated particles and process for manufacturing same

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US20020150760A1 (en) 2002-10-17

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