Luminescent phosphor compounds, articles including such compounds, and methods for their production and use

• US 9,796,205 B2
• Filed: 05/20/2015
• Issued: 10/24/2017
• Est. Priority Date: 07/15/2011
• Status: Active Grant

• Current Assignee: Honeywell International Inc.
• Original Assignee: Honeywell International Inc.
• Inventors: Lau, Carsten, Kane, James, Rapoport, William Ross
• Primary Examiner(s): Koslow, Carol M
• Application Number:
  US14/717,855
• Publication Number:
  US 20150252256A1
• Time in Patent Office: 888 Days
• CPC Class Codes: B41M 3/144 using fluorescent, luminescent or iridescent effects
• CPC Class Codes: B42D 25/00 Information-bearing cards or sheet-like structures characterised by identification or security features; Manufacture thereof printing processes to produce identification or security features B41M3/14
• CPC Class Codes: B42D 25/29 Securities; Bank notes
• CPC Class Codes: B42D 25/36 comprising special materials
• CPC Class Codes: B42D 25/373 Metallic materials
• CPC Class Codes: B42D 25/382 absorbing or reflecting infrared light
• CPC Class Codes: B42D 25/387 absorbing or reflecting ultraviolet light
• CPC Class Codes: C09K 11/08 containing inorganic luminescent materials
• CPC Class Codes: C09K 11/77 containing rare earth metals
• CPC Class Codes: C09K 11/7774 Aluminates
• CPC Class Codes: Y10T 428/2958 Metal or metal compound in coating
• CPC Class Codes: Y10T 428/31993 Of paper
• CPC Class Codes: Y10T 442/20 Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer

Abstract

Embodiments include luminescent phosphor compounds that include one or more emitting ions and one or more disturbing ions, and methods for their production. An emitting ion in the compound may be characterized by a first decay time constant when the emitting ion is undisturbed. However, a corresponding disturbing ion in the compound, which is different from the emitting ion, causes the emitting ion to have a pre-defined, target disturbed decay time constant that is greater than zero and less than the first decay time constant. An embodiment of an authentication system is configured to measure the decay time constant of a phosphor compound applied to an article, and to determine whether the decay time constant corresponds to a phosphor compound that includes a particular disturbing ion (e.g., in order to determine whether or not the article is authentic).

Claims

1. Luminescent phosphor compositions for security applications, wherein the luminescent phosphor compositions are obtained from different lots of phosphor raw materials, wherein phosphor raw materials from which the respective luminescent phosphor compositions are synthesized have varying impurity amounts and wherein each luminescent phosphor composition comprises:

one or more emitting ions, one or more disturbing ions, optionally one or more sensitizing ions, and a quantity of rare earth impurities other than the one or more emitting ions and the one or more sensitizing ions;

wherein the one or more emitting ions have one or more first decay time constants when the one or more emitting ions are undisturbed, the one or more disturbing ions are different from the one or more emitting ions, and the one or more disturbing ions are included in the luminescent phosphor compositions in a quantity that will cause at least one of the one or more emitting ions to have a pre-defined, target disturbed decay time constant that is greater than zero and less than a corresponding one of the one or more first decay time constants;

wherein the first decay time constant and the target disturbed decay time constants can be distinguished by an authentication device,

wherein the luminescent phosphor compositions have substantially equal target disturbed decay time constants for the corresponding one or more first decay time constants despite the presence of a varying amount of impurity ions therein from the respective phosphor raw materials.

2. The luminescent phosphor compositions of claim 1, wherein the one or more emitting ions include one or more ions of one or more elements selected from a group consisting of chromium, cerium, praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium.

3. The luminescent phosphor compositions of claim 1, wherein the one or more disturbing ions include one or more ions of one or more elements selected from a group consisting of chromium, manganese, cerium, praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, iron, cobalt, and nickel.

4. The luminescent phosphor compositions of claim 1, wherein the one or more disturbing ions include one or more ions of one or more elements selected from a group consisting of praseodymium, samarium, europium, terbium, and dysprosium.

5. The luminescent phosphor compositions of claim 1, wherein one or more disturbing ions cause the at least one of the one or more emitting ions to have the target disturbed decay time constant by absorbing energy discharged by the at least one of the one or more emitting ions in transitioning from a storage level to a lower energy level, and by discharging the energy non-radiatively.

6. The luminescent phosphor compositions of claim 1, wherein the luminescent phosphor compositions further comprise:

one or more additional emitting ions, which have one or more additional first decay time constants when the one or more additional emitting ions are undisturbed, wherein the one or more disturbing ions or one or more additional disturbing ions cause at least one of the one or more additional emitting ions to have one or more additional, pre-defined target disturbed decay time constants that are greater than zero and less than corresponding ones of the one or more additional first decay time constants, and wherein the one or more additional, pre-defined target disturbed decay time constants for the corresponding one or more first decay time constants are substantially equal for all of the luminescent phosphor compositions.

7. The luminescent phosphor compositions of claim 1, wherein the luminescent phosphor compositions further comprise:

one or more additional disturbing ions, wherein the one or more disturbing ions or the one or more additional disturbing ions cause at least one of the one or more emitting ions or one or more additional emitting ions, which have one or more additional first decay time constants when the one or more additional emitting ions are undisturbed, to have one or more additional, pre-defined target disturbed decay time constants that are greater than zero and less than corresponding ones of the one or more additional first decay time constants.

8. The luminescent phosphor compositions of claim 1, further comprising a phosphor host crystal lattice material selected from a group consisting of an oxide, a fluoride, an oxysulfide, a halide, a borate, a silicate, a gallate, a phosphate, a vanadate, an oxyhalide, an aluminate, a molybdate, a tungstate, a garnet, or a niobate.

9. A method for producing luminescent phosphor compositions from different lots of phosphor raw materials, wherein the method comprises the steps of:

obtaining a phosphor raw material that includes a phosphor host crystal lattice material, one or more emitting ions, optionally one or more sensitizing ions, and a quantity of rare earth impurities other than the one or more emitting ions and the one or more sensitizing ions, wherein the phosphor raw material is characterized by one or more first decay time constants;

synthesizing a disturbed phosphor composition that includes the phosphor host crystal lattice material, the one or more emitting ions, the quantity of rare earth impurities, and a quantity of one or more disturbing ions;

measuring one or more second decay time constants of the disturbed phosphor composition;

determining whether the one or more second decay time constants are substantially equal to one or more target disturbed decay time constants that are greater than zero and less than corresponding ones of the one or more first decay time constants;

when at least one of the one or more second decay time constants is not substantially equal to the one or more target disturbed decay time constants, repeating the synthesizing, measuring, and determining steps for an additional candidate disturbed phosphor composition that has an adjusted quantity of the one or more disturbing ions that is different from the initial quantity; and

synthesizing another disturbed phosphor composition from a different lot of phosphor raw materials than the disturbed phosphor composition, wherein the different lot of phosphor raw materials has a varying impurity level from the impurity level of phosphor raw materials used to synthesize the disturbed phosphor composition, wherein the disturbed phosphor composition and the other disturbed phosphor composition have substantially equal target disturbed decay time constants for the corresponding one or more first decay time constants despite the presence of a varying amount of impurity ions therein from the respective phosphor raw materials.

10. The method of claim 9, wherein repeating the synthesizing step comprises:

increasing the quantity of the one or more disturbing ions when the one or more second decay time constants are greater than the one or more target disturbed decay time constants; and

decreasing the quantity of the one or more disturbing ions when the one or more second decay time constants are less than the one or more target disturbed decay time constants.

11. The method of claim 9, wherein the one or more emitting ions include one or more ions elements selected from a group consisting of chromium, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium.

12. The method of claim 9, wherein the one or more disturbing ions include one or more ions of elements selected from a group consisting of chromium, manganese, cerium, praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, iron, cobalt, and nickel.

13. Articles comprising:

a substrate; and

an authentication feature on a surface of the substrate or integrated within the substrate, wherein authentication features of different articles comprise different luminescent phosphor compositions obtained from different lots of phosphor raw materials, wherein the phosphor raw materials from which the luminescent phosphor compositions are synthesized have varying impurity levels, and wherein each luminescent phosphor composition comprises;

one or more emitting ions, one or more disturbing ions, optionally one or more sensitizing ions, and a quantity of rare earth impurities other than the one or more emitting ions and the one or more sensitizing ions;

wherein the one or more emitting ions have one or more first decay time constants when the one or more emitting ions are undisturbed, the one or more disturbing ions are different from the one or more emitting ions, and the one or more disturbing ions are included in the phosphor compositions in a quantity that will cause at least one of the one or more emitting ions to have a pre-defined, target disturbed decay time constant that is greater than zero and less than a corresponding one of the one or more first decay time constants;

wherein the first decay time constant and the target disturbed decay time constants can be distinguished by an authentication device, and

wherein the luminescent phosphor compositions all have substantially equal target disturbed decay time constants for the corresponding one or more first decay time constants despite the presence of a varying amount of impurity ions therein from the respective phosphor raw materials.

14. The articles of claim 13, wherein the articles are selected from a group consisting of an identification card, a driver'"'"'s license, a passport, identity papers, a banknote, a check, a document, a paper, a stock certificate, a packaging component, a credit card, a bank card, a label, a seal, a postage stamp, a liquid, an animal, and a biological sample.

15. The articles of claim 13, wherein the substrate includes one or more materials selected from a group consisting of paper, a polymer, glass, a metal, a textile, and a fiber.

16. The articles of claim 13, wherein the one or more emitting ions include one or more ions elements selected from a group consisting of chromium, cerium, praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, and ytterbium.

17. The articles of claim 13, wherein the one or more disturbing ions include one or more ions of elements selected from a group consisting of chromium, manganese, cerium, praseodymium, neodymium, samarium, europium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, iron, cobalt, and nickel.