Methods for charge-titrating particle assembly, and structures produced therefrom

Patent metadata

Field	Value
Publication number	US-10189718-B1
Application number	US-201615241536-A
Country	US
Kind code	B1
Filing date	Aug 19, 2016
Priority date	Sep 1, 2015
Publication date	Jan 29, 2019
Grant date	Jan 29, 2019

Abstract

Methods to fabricate tightly packed arrays of nanoparticles are disclosed, without relying on organic ligands or a substrate. In some variations, a method of assembling particles into an array comprises dispersing particles in a liquid solution; introducing a triggerable pH-control substance capable of generating an acid or a base; and triggering the pH-control substance to generate an acid or a base within the liquid solution, thereby titrating the pH. During pH titration, the particle-surface charge magnitude is reduced, causing the particles to assemble into a particle array. Other variations provide a device for assembling particles into particle arrays, comprising a droplet-generating microfluidic region; a first-fluid inlet port; a second-fluid inlet port; a reaction microfluidic region, disposed in fluid communication with the droplet-generating microfluidic region; and a trigger source configured to trigger generation of an acid or a base from at least one pH-control substance contained within the reaction microfluidic region.

First claim

What is claimed is:

1. A method of assembling a plurality of particles into a particle array, said method comprising:
dispersing a plurality of first particles in a volume of liquid solution, wherein said first particles are characterized by an average zeta potential, and wherein said liquid solution is characterized by a starting pH;
introducing to said liquid solution before, during, or after said first particles are dispersed in said liquid solution, a triggerable pH-control substance capable of generating an acid or a base when triggered; and
triggering said pH-control substance to generate an acid or a base within said volume of liquid solution, thereby adjusting solution pH from said starting pH to a titrated pH, wherein said average zeta potential is closer to zero at said titrated pH compared to said starting pH, causing said first particles to assemble into a particle array.

2. The method of claim 1 , wherein said first particles are characterized by an average particle size from about 1 nanometer to about 100 microns.

3. The method of claim 2 , wherein said first particles are characterized by an average particle size from about 5 nanometers to about 1 micron.

4. The method of claim 1 , wherein said first particles contain a core and a shell, wherein said core comprises a metal, a ceramic, or a combination thereof, and wherein said shell comprises a fluoride, an oxide, a sulfide, or a combination thereof.

5. The method of claim 1 , wherein said liquid solution comprises one or more compounds selected from the group consisting of water, dimethyl formamide, dimethylsulfoxide, isopropanol, acetone, tetrahydrofuran, and combinations thereof.

6. The method of claim 1 , wherein said pH-control substance is triggered with electromagnetic radiation to generate said acid or said base.

7. The method of claim 6 , wherein said pH-control substance is a photoacid generator or a photobase generator.

8. The method of claim 7 , wherein said pH-control substance is sodium tetraphenylborate, (4-fluorophenyl)diphenylsulfonium triflate, 2-(9-oxoxanthen-2-yl)propionic acid 1,5,7-triazabicyclo[4.4.0]dec-5-ene, or a combination thereof.

9. The method of claim 1 , wherein said pH-control substance is triggered with a change in temperature to generate said acid or said base.

10. The method of claim 9 , wherein said pH-control substance is urea, carbon dioxide, or a combination thereof.

11. The method of claim 1 , wherein said titrated pH is within 1.5 pH units of the average isoelectric point of said first particles.

12. The method of claim 11 , wherein said titrated pH is within 0.5 pH units of said average isoelectric point of said first particles.

13. The method of claim 1 , wherein the magnitude of rate of change of said solution pH, measured at said titrated pH, is about 0.05 pH units per minute, or less.

14. The method of claim 13 , wherein said magnitude of rate of change of said solution pH, measured at said titrated pH, is about 0.01 pH units per minute, or less.

15. The method of claim 1 , wherein the magnitude of said average zeta potential, prior to said triggering said pH-control substance, is at least 20 mV.

16. The method of claim 1 , wherein the magnitude of said average zeta potential is reduced to 10 mV, or less, at said titrated pH compared to said starting pH.

17. The method of claim 16 , wherein said magnitude of said average zeta potential is reduced to 5 mV, or less, at said titrated pH compared to said starting pH.

18. The method of claim 17 , wherein said magnitude of said average zeta potential is reduced to 2 mV, or less, at said titrated pH compared to said starting pH.

19. The method of claim 1 , wherein the magnitude of said average zeta potential changes at a rate from about 1 mV/hr to about 50 mV/hr during said adjusting solution pH from said starting pH to a titrated pH.

20. The method of claim 15 , wherein said magnitude of said average zeta potential changes at a rate from about 5 mV/hr to about 30 mV/hr.

21. The method of claim 1 , wherein said pH-control substance is triggered uniformly in space within said volume of liquid solution.

22. The method of claim 1 , wherein said pH-control substance is triggered in a spatial pattern within said volume of liquid solution.

23. The method of claim 1 , wherein said pH-control substance is triggered at constant trigger intensity in time.

24. The method of claim 1 , wherein said pH-control substance is triggered at temporally varying trigger intensity.

25. The method of claim 1 , wherein at least two different pH-control substances are introduced to said volume of liquid solution.

26. The method of claim 25 , wherein one of said two different pH-control substances generates an acid when triggered and the other of said two different pH-control substances generates a base when triggered.

27. The method of claim 1 , said method further comprising oscillating said solution pH to enhance said assembly of said first particles.

28. The method of claim 1 , wherein said method is performed as a batch process.

29. The method of claim 1 , wherein said method is performed as a continuous process.

30. The method of claim 1 , said method further comprising dispersing a plurality of second particles in said volume of liquid solution;
wherein said second particles are distinct chemically and/or physically from said first particles;
wherein said second particles are characterized by an second average zeta potential; and
wherein said second zeta potential is closer to zero at said titrated pH compared to said starting pH, causing said second particles to assemble.

31. The method of claim 1 , said method further comprising introducing a crystallized assembly containing said first particles as a seed material in said volume of liquid solution.

Assignees

• Hrl Lab Llc

Inventors

• Gross Adam F
• Cui Shanying
• Vajo John J
• Roper Christopher S

Classifications

• C01F17/36

  halogen being the only anion, e.g. NaYF4 · CPC title

• B01L3/502784

  specially adapted for droplet or plug flow, e.g. digital microfluidics · CPC title

• C01P2004/62

  Submicrometer sized, i.e. from 0.1-1 micrometer · CPC title

• C30B29/60

  characterised by shape · CPC title

• B01J2219/00754

  Metal oxides · CPC title