Quantum dot security inks

• US 9,382,432 B1
• Filed: 09/21/2015
• Issued: 07/05/2016
• Est. Priority Date: 09/21/2015
• Status: Active Grant

• Current Assignee: Ubiqd, LLC
• Original Assignee: Ubiqd, LLC
• Inventors: McDaniel, Hunter
• Primary Examiner(s): Gaworecki, Mark R
• Application Number:
  US14/860,676
• Time in Patent Office: 288 Days
• US Class Current: 1/1
• CPC Class Codes: B41M 3/144 using fluorescent, luminescent or iridescent effects
• CPC Class Codes: C09D 11/037 characterised by the pigment
• CPC Class Codes: C09D 11/322 Pigment inks
• CPC Class Codes: C09D 11/50 Sympathetic, colour changing or similar inks
• CPC Class Codes: C09D 5/22 Luminous paints luminescent compositions C09K11/00
• CPC Class Codes: G01N 21/6408 with measurement of decay time, time resolved fluorescence
• CPC Class Codes: G01N 21/643 non-biological material
• CPC Class Codes: G01N 21/6489 Photoluminescence of semiconductors
• CPC Class Codes: G01N 2201/061 Sources
• CPC Class Codes: G01N 2201/062 LED's
• CPC Class Codes: G07D 7/1205 Testing spectral properties

Abstract

A security ink is provided which includes a liquid medium having a plurality of quantum dots disposed therein. Upon excitation with a suitable light source, the ink exhibits a quantum yield greater than 30%, and a photoluminescence which has a lifetime of more than 40 nanoseconds and which varies by at least 5% across the emission spectrum of the quantum dots. Also disclosed are apparatuses for using the same for anti-counterfeit or authentication purposes, which uniquely identifying the presence of photoluminescent materials by spectrally resolving their photoluminescence lifetime.

Claims

1. A security ink, comprising:

a liquid medium; and

a plurality of quantum dots disposed in said medium which, upon excitation with a light source, exhibit a quantum yield greater than 30%, and a photoluminescence which has at least one lifetime of more than 40 nanoseconds but less than 1 millisecond and which varies by at least 5% across the emission spectrum of the quantum dots.

2. The security ink of claim 1, further comprising quantum dots composed of semiconductors that do not contain phosphorus, lead, cadmium, or mercury.

3. The security ink of claim 1, wherein said plurality of quantum dots comprises a first set of quantum dots having a first chemical composition and size, and a second set of quantum dots having a second chemical composition and size which are distinct from said first chemical composition and size.

4. The security ink of claim 1, wherein said plurality of quantum dots comprise a material selected from the group consisting of CuInS₂, CuInSe₂, AgInS₂, AgInSe₂, ZnS and ZnSe.

5. The security ink of claim 1, wherein said photoluminescence is characterized by light emission having wavelengths in the range of 450 nm to 1250 nm.

6. The security ink of claim 1, wherein said photoluminescence is characterized by a lifetime of more than 100 nanoseconds but less than 1 microsecond.

7. The security ink of claim 1, wherein said photoluminescence is characterized by a lifetime that varies by at least 10% across said emission spectrum.

8. The security ink of claim 1, wherein said photoluminescence is characterized by a lifetime that varies by at least 50 ns across said emission spectrum.

9. The security ink of claim 1, wherein said photoluminescence is characterized by a quantum yield that is greater than 50%.

10. The security ink of claim 1, wherein said photoluminescence is characterized by a quantum yield that is greater than 70%.

11. In combination with the security ink of claim 1, an optical apparatus for analyzing said security ink, comprising:

a time-varying light source which excites said security ink, thereby causing said security ink to emit an emission spectrum having first and second distinct regions which are characterized by first and second distinct lifetimes;

at least one photodetector;

a first optical element which allows only said first region of said emission spectrum from an optical signal to pass through it;

a second optical element which allows only said second region of said emission spectrum from an optical signal to pass through it; and

an electronics module which determines the photoluminescence lifetime of said security ink over said first and second regions by monitoring at least one time or frequency response of said at least one photodetector.

12. The combination of claim 11, wherein said light source is selected from the group consisting of UV LEDs, blue LEDs, green LEDs and red LEDs.

13. The combination of claim 11, wherein said at least one photodetector includes first and second photodetectors, wherein said first optical element is disposed in a first optical path which includes said first photodetector, and wherein said second optical element is disposed in a second optical path which includes said second photodetector.

14. The combination of claim 11, wherein said light source oscillates with a frequency of less than 100 MHz.

15. The combination of claim 11, wherein said light source oscillates with a frequency of less than 10 MHz.

16. The combination of claim 11, wherein said first plurality of quantum dots comprise a material selected from the group consisting of CuInS₂, CuInSe₂, AgInSe₂, AgInSe₂, ZnSe and ZnS.

17. The combination of claim 11, wherein said photodetector comprises a material selected from the group consisting of silicon, germanium, cadmium sulfide, indium phosphide, copper indium diselenide, indium gallium arsenide and gallium arsenide.

18. The combination of claim 11, wherein said first and second optical components are selected from the group consisting of light filters, quantum dot films and colored glasses.

19. The combination of claim 11, wherein the security ink contains a first of quantum dots, and further comprising at least one film containing a second plurality of quantum dots through which said photoluminescence passes through before reaching said at least one photodetector, wherein said second plurality of quantum dots comprise a material selected from the group consisting of CuInS₂, CuInSe₂, AgInSe₂, AgInSe₂, ZnSe and ZnS.

20. The combination of claim 11, further comprising a microcontroller in communication with said light source and said photodetector, wherein said microcontroller characterizes the time-varying photoluminescence from said security ink.

21. The combination of claim 11, further comprising a phase measuring device in communication with said light source and said at least one photodetector, wherein said phase measuring device measures a phase relationship between a time-varying excitation and a time-varying photoluminescence from said security ink.