Three-dimensional nanofabrication by patterning of hydrogels
The present invention enables three-dimensional nanofabrication by isotropic shrinking of patterned hydrogels. A hydrogel is first expanded, the rate of expansion being controlled by the concentration of the crosslinker. The hydrogel is then infused with a reactive group and patterned in three dimensions using a photon beam through a limited-diffraction microscope. Functional particles or materials are then deposited on the pattern. The hydrogel is then shrunk and cleaved from the pattern.
1. A method for three-dimensional fabrication of a nanostructure, the method comprising the steps of:
a. providing a polyelectrolyte gel;
b. infusing the polyelectrolyte gel with one or more reactive groups;
c. illuminating selected voxels within the polyelectrolyte gel to yield a three-dimensional pattern of reactive group sites on the polyelectrolyte gel;
d. anchoring the one or more reactive groups to the reactive group sites;
e. removing excess reactive groups from the polyelectrolyte gel;
f. depositing nanomaterials on the reactive group sites;
g. shrinking the polyelectrolyte gel by a factor of at least 10× to yield a three-dimensional pattern of reduced scale;
the three-dimensional pattern is maintained and wherein the three-dimensional pattern of reduced scale is a three-dimensional pattern of nano scale.
2. The method of claim 1 , wherein shrinking the polyelectrolyte gel is achieved by exposing the polyelectrolyte gel to salt or an acid.
3. The method of claim 2 , further comprising the step of desolvating the polyelectrolyte gel wherein a salt or an acid is used to shrink the gel.
4. The method of claim 1 , wherein the nanomaterials comprise metal, or semiconductors.
5. The method of claim 1 , further comprising the step of depositing metal on the nanomaterials to grow or enhance the nanomaterials in situ.
6. The method of claim 4 , further comprising the step of sintering the nanomaterials.
7. The method of claim 6 , wherein the nanomaterials are sintered using any of: application of electrical current across the nanomaterials; a laser; plasma etching, a pulsed light source, or infrared light.
8. The method of claim 1 , comprising the additional step of removing a portion of the polyelectrolyte gel.
9. The method of claim 1 , wherein the one or more reactive groups further comprise semiconductor nanocrystals.
10. The method of claim 9 , wherein the semiconductor nanocrystals comprise cadmium telluride nanoparticles.
11. The method of claim 9 , wherein the semiconductor nanocrystals comprise cadmium selenide nanoparticles.
12. The method of claim 1 , wherein steps b-e are repeated and the one or more reactive groups formed from one iteration to the next are distinct.
13. The method of claim 1 , wherein steps b-f are repeated and the nanomaterials deposited on the reactive group sites from one iteration to the next are distinct.
14. The method of claim 5 , wherein the metal is silver.
15. The method of claim 1 , wherein any or all of steps b-e are repeated one or more times.
16. The method of claim 1 , wherein the three-dimensional pattern of reduced scale also comprises increased resolution.
17. A method for three-dimensional fabrication of a nanostructure, the method comprising the steps of:
a. providing a polyelectrolyte gel;
b. infusing the polyelectrolyte gel with one or more reactive groups;
c. illuminating selected voxels within the polyelectrolyte gel to yield a three-dimensional pattern of reactive group sites anchored to the polyelectrolyte gel;
d. removing excess reactive groups from the polyelectrolyte gel;
e. depositing nanomaterials on the reactive group sites; and
f. shrinking the polyelectrolyte gel to yield a three-dimensional pattern of reduced scale the three-dimensional pattern is maintained and wherein the three-dimensional pattern of reduced scale is a three-dimensional pattern of nanoscale.
18. The method of claim 17 , wherein shrinking the polyelectrolyte gel is achieved by exposing the polyelectrolyte gel to a salt or an acid.
19. The method of claim 17 , wherein the three-dimensional pattern of reduced scale also comprises increased resolution.
20. The method of claim 17 , further comprising the step of desolvating the polyelectrolyte gel wherein a salt or an acid is used to shrink the gel.
21. The method of claim 17 , wherein the nanomaterials comprise metal, and/or a semiconductors.
22. The method of claim 21 , further comprising the step of depositing metal on the nanomaterials to grow or enhance the nanomaterials in situ.
23. The method of claim 21 , further comprising the step of sintering the nanomaterials.
24. The method of claim 23 , wherein the nanomaterials are sintered using any of: application of electrical current across the nanomaterials, a laser, a pulsed light source, infrared light or plasma etching.
25. The method of claim 17 , comprising the additional step of removing a portion of the polyelectrolyte gel.
26. The method of claim 17 , wherein the one or more reactive groups further comprise semiconductor nanocrystals.
27. The method of claim 26 , wherein the semiconductor nanocrystals comprise cadmium telluride nanoparticles.
28. The method of claim 26 , wherein the semiconductor nanocrystals comprise cadmium selenide nanoparticles.
29. The method of claim 17 , wherein steps b-e are repeated and the one or more reactive groups formed from one iteration to the next are distinct.
30. The method of claim 17 , wherein steps b-f are repeated and the nanoparticles deposited on the reactive group sites from one iteration to the next are distinct.
31. The method of claim 22 , wherein the metal is silver.
32. The method of claim 17 , wherein any or all of steps b-e are repeated one or more times.
33. A method for three-dimensional fabrication of a nanostructure, the method comprising the steps of:
a. providing a polyelectrolyte gel containing nanomaterials in one or more patterns; and
b. depositing metal on the patterned nanomaterials to grow or enhance the nanomaterials in situ; and
c. shrinking the polyelectrolyte gel to yield a three-dimensional pattern of reduced scale the three-dimensional pattern is maintained and wherein the three-dimensional pattern of reduced scale is a three-dimensional pattern of nano scale.
34. The method of claim 33 , wherein the three-dimensional pattern of reduced scale also comprises increased resolution.
35. The method of claim 33 , wherein shrinking the polyelectrolyte gel is achieved by exposing the polyelectrolyte gel to a salt or an acid.
36. The method of claim 33 , further comprising the optional step of desolvating the polyelectrolyte gel wherein a salt or an acid is used to shrink the gel.
37. The method of claim 33 , comprising the additional step of removing a portion of the polyelectrolyte gel.
38. A method for three-dimensional fabrication of nanostructures, the method comprising the steps of:
a. providing a polyelectrolyte gel;
b. infusing the polyelectrolyte gel with one or more reactive groups;
c. illuminating selected voxels within the polyelectrolyte gel to yield a three-dimensional pattern of reactive group sites anchored to the polyelectrolyte gel;
d. removing excess reactive groups from the polyelectrolyte gel;
e. depositing functional molecules on the reactive group sites;
f. shrinking the polyelectrolyte gel to yield a three-dimensional pattern of reduced scale and increased resolution the three-dimensional pattern is maintained and wherein the three-dimensional pattern of reduced scale is a three-dimensional pattern of nano scale.
39. The method of claim 38 , optionally further comprising the step of expanding the polyelectrolyte gel to yield an expanded gel at any point prior to step f.
40. The method of claim 38 , wherein shrinking the polyelectrolyte gel is achieved by exposing the polyelectrolyte gel to a salt or an acid.
41. The method of claim 38 , further comprising the optional step of desolvating the polyelectrolyte gel wherein a salt or an acid is used to shrink the gel.
42. The method of claim 38 , comprising the additional step of removing a portion of the polyelectrolyte gel.
43. The method of claim 38 , wherein steps b-e are repeated and the one or more reactive groups formed from one iteration to the next are distinct.
44. The method of claim 38 , wherein steps b-f are repeated and the functional molecules deposited on the reactive group sites from one iteration to the next are distinct.
45. The method of claim 38 , wherein any or all of steps b-e are repeated one or more times.