OPTICAL PRINTING SYSTEMS AND METHODS

• US 20190264327A1
• Filed: 12/20/2018
• Published: 08/29/2019
• Est. Priority Date: 02/27/2018
• Status: Active Grant

• Current Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Original Assignee: Board of Regents of the University of Texas System (University of Texas System)
• Inventors: Zheng, Yuebing, Rajeeva, Bharath Bangalore
• Granted Patent: US 10,640,873 B2
• Time in Patent Office: Days
• CPC Class Codes: C23C 18/08 characterised by the deposition of metallic material
• CPC Class Codes: C23C 18/14 Decomposition by irradiation, e.g. photolysis, particle radiation or by mixed irradiation sources
• CPC Class Codes: C23C 18/1612 through irradiation means
• CPC Class Codes: C23C 18/1667 Radiant energy, e.g. laser
• CPC Class Codes: C23C 18/1817 Heat
• CPC Class Codes: C23C 18/182 Radiation, e.g. UV, laser
• CPC Class Codes: C23C 18/1865 Heat
• CPC Class Codes: C23C 18/1868 Radiation, e.g. UV, laser
• CPC Class Codes: G01N 2021/651 Cuvettes therefore
• CPC Class Codes: G01N 21/658 enhancement Raman, e.g. surface plasmons

Abstract

Disclosed herein are methods comprising: illuminating a first location of an optothermal substrate with electromagnetic radiation; wherein the optothermal substrate converts at least a portion of the electromagnetic radiation into thermal energy; and wherein the optothermal substrate is in thermal contact with a liquid sample comprising a plurality of thermally reducible metal ions; thereby: generating a confinement region at a location in the liquid sample proximate to the first location of the optothermal substrate; trapping at least a portion of the plurality of thermally reducible metal ions within the confinement region; and thermally reducing the trapped portion of the plurality of thermally reducible metal ions; thereby: depositing a metal particle on the optothermal substrate at the first location. Also disclosed herein are systems for performing the methods described herein. Also disclosed herein are patterned substrates made by the methods described herein, and methods of use thereof.

Claims

1. A method comprising:

illuminating a first location of an optothermal substrate with electromagnetic radiation;

wherein the optothermal substrate converts at least a portion of the electromagnetic radiation into thermal energy; and

wherein the optothermal substrate is in thermal contact with a liquid sample comprising a plurality of thermally reducible metal ions, the liquid sample having a first temperature;

thereby;

generating a confinement region at a location in the liquid sample proximate to the first location of the optothermal substrate,

wherein at least a portion of the confinement region has a second temperature that is greater than the first temperature such that the confinement region is bound by a temperature gradient;

trapping at least a portion of the plurality of thermally reducible metal ions within the confinement region; and

thermally reducing the trapped portion of the plurality of thermally reducible metal ions;

thereby;

depositing a metal particle comprising the reduced metal ions on the optothermal substrate at the first location.

2. The method of claim 1, wherein the electromagnetic radiation has a power density of from 0.2 mW/μ

m² to 1.2 mW/μ

m².

3. The method of claim 1, wherein the electromagnetic radiation is provided by a light source and the light source is a laser.

4. The method of claim 3, wherein the light source is configured to illuminate a mirror and the mirror is configured to reflect the electromagnetic radiation from the light source to illuminate the first location of the optothermal substrate.

5. The method of claim 1, wherein the optothermal substrate comprises a plasmonic substrate, a metal film, a metal oxide film, or a combination thereof.

6. The method of claim 1, wherein the optothermal substrate comprises a plasmonic substrate, wherein the plasmonic substrate comprises a plurality of plasmonic particles, and wherein the plurality of plasmonic particles comprise a metal selected from the group consisting of Au, Ag, Pd, Cu, Cr, Al, and combinations thereof.

7. The method of claim 6, wherein the electromagnetic radiation comprises a wavelength that overlaps with at least a portion of the plasmon resonance energy of the plasmonic substrate and the confinement region is generated by plasmon-enhanced photothermal effects.

8. The method of claim 1, wherein the optothermal substrate comprises a metal film comprising a metal selected from the group consisting of Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, Pd, Ag, Cd, Pt, Au, and combinations thereof;

or wherein the optothermal substrate comprises a metal oxide film comprising an oxide of a metal selected from the group consisting of Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, Pd, Ag, Cd, Pt, Au, In, Sn, Zn, and combinations thereof.

9. The method of claim 1, wherein the concentration of the plurality of thermally reducible metal ions in the liquid sample is from 10 wt % to 60 wt %.

10. The method of claim 1, wherein the plurality of thermally reducible metal ions comprise ions of a metal selected from the group consisting of Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, Pd, Ag, Cd, Pt, Au, Rh, Ir, and combinations thereof such that the deposited metal particle comprises a metal selected from the group consisting of Al, Ti, Cr, Mn, Fe, Co, Ni, Cu, Mo, Pd, Ag, Cd, Pt, Au, Rh, Ir, and combinations thereof.

11. The method of claim 1, wherein the deposited metal particle has a shape that is substantially linear, gammadion, U-shaped, or a combination thereof;

wherein the deposited metal particle is formed from one or more linear segments and each of the one or more linear segments has an average line thickness of from 200 nm to 2 μ

m;

wherein the deposited metal particle has an average height of from 100 nm to 250 nm;

or a combination thereof.

12. The method of claim 1, wherein illuminating the first location of the optothermal substrate further:

generates a bubble at a location in the liquid sample proximate to the first location of the optothermal substrate, the bubble having a gas-liquid interface with the liquid sample, and the bubble being within the confinement region;

such that;

trapping at least a portion of the plurality thermally reducible metal ions within the confinement region comprises trapping at least a portion of the plurality of thermally reducible metal ions at the gas-liquid interface of the bubble and the liquid sample; and

the deposited metal particle comprises a substantially ring shaped particle having an average inner diameter, an average outer diameter, an average wall thickness defined by the difference between the average outer diameter and the average inner diameter, and an average height.

13. The method of claim 12, wherein the substantially ring shaped particle has an average inner diameter of from 250 nm to 3 μ

m;

an average outer diameter of from 700 nm to 4 μ

m;

an average a wall thickness of from 150 nm to 800 nm;

an average height of from 100 nm to 250 nm;

or a combination thereof.

14. The method of claim 1, further comprising illuminating a second location of the optothermal substrate thereby:

generating a second confinement region at a location in the liquid sample proximate to the second location of the optothermal substrate, wherein at least a portion of the second confinement region has a third temperature that is greater than the first temperature such that the second confinement region is bound by a temperature gradient;

trapping at least a second portion of the plurality of thermally reducible metal ions within the second confinement region; and

thermally reducing the trapped second portion of the plurality of thermally reducible metal ions to thereby deposit a second metal particle comprising the reduced metal ions on the optothermal substrate at the second location.

15. The method of claim 14, wherein illuminating the second location of the optothermal substrate further:

generates a second bubble at a location in the liquid sample proximate to the second location of the optothermal substrate, the second bubble having a gas-liquid interface within the sample, and the second bubble being within the second confinement region;

such that;

trapping at least a second portion of the plurality thermally reducible metal ions within the second confinement region comprises trapping at least a second portion of the plurality of thermally reducible metal ions at the gas-liquid interface of the second bubble and the liquid sample; and

the second deposited metal particle comprises a second substantially ring shaped particle.

16. The method of claim 14, wherein the optothermal substrate is translocated to illuminate the second location;

wherein the electromagnetic radiation is provided by a light source, and the light source is translocated to illuminate the second location;

wherein the electromagnetic radiation is provided by a light source, the light source being configured to illuminate a mirror and the mirror is configured to reflect the electromagnetic radiation from the artificial light source to illuminate the optothermal substrate, and the mirror is translocated to illuminate the second location;

or a combination thereof.

17. The method of claim 1, further comprising annealing the deposited metal particle.

18. A patterned substrate made using the method of claim 1.

19. A method of use of the patterned substrate of claim 18, wherein the patterned substrate is used for single-particle sensing, functional optical devices, surface-enhanced Raman spectroscopy (SERS), surface-enhanced infrared Raman spectroscopy (SEIRS), catalysis, sensing in a microfluidic device, or a combination thereof.

20. A microfluidic device comprising a channel defining a path for fluid flow from a fluid inlet to a fluid outlet, and the patterned substrate of claim 18 disposed within the channel.

21. A method of detecting an analyte comprising flowing fluid along the channel of the microfluidic device of claim 20, thereby contacting the analyte with the patterned sample, and spectroscopically detecting the analyte in contact with the patterned sample.

22. The method of claim 21, wherein the analyte comprises Rhodamine 6G, Crystal Violet, 2,4,6-trinitrotoluene, or a combination thereof;

wherein spectroscopically detecting the analyte comprises surface-enhanced Raman spectroscopy (SERS), surface-enhanced infrared Raman spectroscopy (SEIRS), or a combination thereof;

or a combination thereof.

23. A microfluidic device comprising a channel defining a path for fluid flow from a fluid inlet to a fluid outlet and a patterned substrate disposed within the channel, wherein the patterned substrate is made in situ within the channel by the method of claim 1.

24. A method of detecting an analyte comprising flowing fluid along the channel of the microfluidic device of claim 23, thereby contacting the analyte with the patterned sample, and spectroscopically detecting the analyte in contact with the patterned sample.

25. The method of claim 24, wherein the analyte comprises Rhodamine 6G, Crystal Violet, 2,4,6-trinitrotoluene, or a combination thereof;

wherein spectroscopically detecting the analyte comprises surface-enhanced Raman spectroscopy (SERS), surface-enhanced infrared Raman spectroscopy (SEIRS), or a combination thereof;

or a combination thereof.

26. A method of use of the patterned substrate of claim 18, wherein the patterned substrate has an inverse-opal configuration and the patterned sample is used for catalysis.

27. A system comprising:

an optothermal substrate in thermal contact with a liquid sample comprising a plurality of thermally reducible metal ions, the liquid sample having a first temperature; and

a light source configured to illuminate the optothermal substrate at a first location, wherein the optothermal substrate converts at least a portion of the electromagnetic radiation into thermal energy;

thereby;

generating a confinement region at a location in the liquid sample proximate the first location of the optothermal substrate, wherein at least a portion of the confinement region has a second temperature that is greater than the first temperature such that the confinement region is bound by a temperature gradient;

trapping at least a portion of the plurality of thermally reducible metal ions within the confinement region; and

thermally reducing the trapped portion of the plurality of thermally reducible metal ions;

thereby;

depositing a metal particle comprising the reduced meal ions on the optothermal substrate at the first location.