Technique for three-dimensional nanoprinting

Patent metadata

Field	Value
Publication number	US-10751933-B2
Application number	US-201615767967-A
Country	US
Kind code	B2
Filing date	Dec 13, 2016
Priority date	Dec 16, 2015
Publication date	Aug 25, 2020
Grant date	Aug 25, 2020

Abstract

The disclosed embodiments provide a system that forms a three-dimensional (3D) nanostructure through 3D printing. During operation, the system performs a 3D printing operation that uses multiple passes of a scanning probe microscope (SPM) tip to deliver an ink to form the 3D nanostructure, wherein the ink includes both a positively charged polyelectrolyte (PE) and a negatively charged PE. While delivering the ink, the SPM tip is loaded with the ink and moved to a target location to deposit the ink. Finally, after the multiple passes are complete, the system cures the 3D nanostructure to remove excess positive or negative charges from the 3D nanostructure.

First claim

What is claimed is:

1. A method for forming a three-dimensional (3D) nanostructure through 3D printing, comprising:
performing a 3D printing operation that uses multiple passes of a scanning probe microscope (SPM) tip to deliver an ink to form the 3D nanostructure;
wherein the ink includes both a positively charged polyelectrolyte (PE) and a negatively charged PE;
wherein while delivering the ink, the SPM tip is loaded with the ink and moved to a target location to deposit the ink; and
after the multiple passes are complete, curing the 3D nanostructure to remove excess positive or negative charges from the 3D nanostructure.

2. The method of claim 1 , wherein loading the SPM tip with the ink involves loading a single ink containing both positively charged and negatively charged PEs onto the SPM tip.

3. The method of claim 1 , wherein loading the SPM tip with the ink involves:
loading a first ink containing a positively or negatively charged PE onto the SPM tip; and
loading a second ink containing an oppositely charged PE on the same SPM tip.

4. The method of claim 1 , wherein the ink is delivered layer-by-layer to form the 3D nanostructure, and wherein each layer is two-dimensional (2D) and comprises one or more of the following:
a plurality of dots;
a plurality of lines; and
a plurality of 2D geometries.

5. The method of claim 1 , wherein the ink is delivered line-by-line to form the 3D nanostructure.

6. The method of claim 1 , wherein curing the 3D nanostructure involves washing the 3D nanostructure with one or more of the following: water, methanol, ethanol, isopropanol, n-propanol, butanol, acetone, tetrahydrofuran, dimethylformamide, acetonitrile, ether, 1,4-dioxane, chloroform, diethyl ether, ethyl acetate, dimethyl sulfoxide, acetic acid, formic acid, and ammonium hydroxide.

7. The method of claim 1 , wherein curing the 3D nanostructure involves aging the 3D nanostructure in air.

8. The method of claim 1 , wherein the ink comprises:
the positively charged PE;
the negatively charged PE; and
a solvent.

9. The method of claim 8 , where the solvent is selected from: water, methanol, ethanol, isopropanol, n-propanol, butanol, acetone, tetrahydrofuran, dimethylformamide, acetonitrile, ether, 1,4-dioxane, chloroform, diethyl ether, ethyl acetate, dimethyl sulfoxide, acetic acid, formic acid, and ammonium hydroxide.

10. The method of claim 8 , wherein the ink includes a salt, which comprises ions selected from:
a group of positive ions comprising Li + , Na + , K + , Ca 2+ , Mg 2+ , Fe 2+ , Fe 3+ , Cu 2+ , Zn 2+ , Ag + , Ba 2+ ; and
a group of negative ions comprising F − , Cl − , Br − , CO 3 2− , ClO 4 − , PO 4 3− , NO 3 − ; NO 2 − , S 2 O 3 2− , SO 3 2− , SO 4 2− .

11. The method of claim 1 , wherein the positively charged PE is selected from a group comprising: poly(diallyldimethyl ammonium chloride), poly(allylamine) hydrochloride, poly(ethylenimine), poly(4-vinyl pyridine), polyaniline, polypyrrole, phenylbenzenamine, enzymes, basic polysaccharides, poly-(1,4)N-acetyl-D-glucosamine, cationic lipids, and polycarboxybetaine.

12. The method of claim 1 , wherein the negatively charged PE is selected from a group comprising: poly(styrene sulfonate), poly(acrylic acid), sulfonated poly-p-phenylene azobenzene, acidic polysaccharides, polyuronides, alginic acid, carrageenans, hyaluronic acid, polylactic acid, polyglycolic acid, copolymers of organic acids.

13. The method of claim 1 , wherein the ink includes a zwittorionic PE, which is selected from a group comprising: polynucleotides, peptides, proteins, peptide nucleic acids, enzymes, collagen, fibrin, proteoglycans.

14. The method of claim 1 , wherein the ink includes a neutral PE, which is selected from a group comprising: polyacetylene, polythiophene, poly(3,4 ethylenedioxythiophene), poly(tetrafluoroethylene) carboxylate, poly(tetrafluoroethylene) phosphonate, polyphenylene vinylene, enzymes, polysaccharides, starch, cellulose, hemicelluloses, arabinoglucuronoxylan, galactans, agarose.

15. The method of claim 1 , wherein after the 3D nanostructure is formed, the method further comprises performing an imaging operation to obtain an image of the 3D nanostructure.

Assignees

• Univ California

Inventors

• Liu Gang-Yu
• Zhao Jianli
• Swartz Logan A

Classifications

• B33Y70/00

  Materials specially adapted for additive manufacturing · CPC title

• B33Y40/20

  Post-treatment, e.g. curing, coating or polishing · CPC title

• C09D11/38

  characterised by non-macromolecular additives other than solvents, pigments or dyes · CPC title

• C09D11/106

  containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds · CPC title

• B29C64/188

  involving additional operations performed on the added layers, e.g. smoothing, grinding or thickness control (surface shaping B29C59/00; after-treatment of articles without altering their shape B29C71/00) · CPC title