# US 7,611,619 B2 · Electrochemical miniaturization of organic micro-and nanostructures

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 7,611,619 B2
- Document ID: US7611619B2
- Status: Granted
- Kind: B2
- Application number: 10/520,554
- Filed: 2003-07-07
- Published: 2006-04-20
- Granted: 2009-11-03
- Earliest claimed: 2002-07-05
- Assignees: Northwestern University
- Inventors: Chad A. Mirkin; Yi Zhang; Khalid Salaita
- Web page: https://patentgrep.com/patent/US7611619B2

## CPC

- C40B 60/14: for creating libraries
- B81C 1/00111: {Tips, pillars, i.e. raised structures (microneedles A61M37/0015)}
- B81C 1/00714: {Treatment for improving the physical properties not provided for in groups B81C1/0065 - B81C1/00706}
- B82Y 10/00: Nanotechnology for information processing, storage or transmission, e.g. quantum computing or single electron logic
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- C25F 1/00: Electrolytic cleaning, degreasing, pickling or descaling
- C40B 40/04: Libraries containing only organic compounds
- G03F 7/0002: {Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping}
- H10K 71/231: {by etching of existing layers}
- B01J 2219/00387: Applications using probes
- B01J 2219/00436: Maskless processes
- B01J 2219/00605: the compounds being directly bound or immobilised to solid supports
- B01J 2219/00612: the surface being inorganic
- B01J 2219/0063: Other, e.g. van der Waals forces, hydrogen bonding
- B01J 2219/00637: by coating it with another layer
- B01L 3/5027: {by integrated microfluidic structures, i.e. dimensions of channels and chambers are such that surface tension forces are important, e.g. lab-on-a-chip}
- H10K 71/125: {using electrolytic deposition e.g. in-situ electropolymerisation}
- C40B: COMBINATORIAL CHEMISTRY; LIBRARIES, e.g. CHEMICAL LIBRARIES (in silico combinatorial libraries of nucleic acids, proteins or peptides G16B35/00; in silico combinatorial chemistry G16C20/60)
- B81C: PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS (making microcapsules or microballoons B01J13/02; processes or apparatus specially adapted for the manufacture or treatment of piezoelectric, electrostrictive or magnetostrictive elements per se H10N30/01)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- C25F: PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01L: CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE

## Abstract

The invention provides a simple and convenient strategy for reducing the dimensions of organic micro- and nanostructures on metal surfaces. By varying electrochemical desorption conditions, organic structures patterned by Dip-Pen Nanolithography or any of the micro-contact printing procedures can be gradually desorbed in a controlled fashion. The electrochemical desorption is initiated at the exterior of the feature and moves inward as a function of time. The desorption process and adsorbate desorption are modified and controlled as a function of substrate morphology, adsorbate head and tail groups, and electrolyte solvent and salt. Different nanostructures made of different adsorbates can be miniaturized based upon judicious selection of adsorbate and supporting electrolyte.

## Claims

### Claim 1

A method of miniaturizing the size of an organic structure on a substrate comprising applying an electrical potential to the substrate whereby the organic structure is electrochemically desorbed from the outside of the organic structure.

### Claim 2 (depends on 1)

The method of claim 1, wherein the electrical potential is less than about −400 mV.

### Claim 3 (depends on 1)

The method of claim 1, wherein the electrical potential is between about −400 mV and about −1500 mV.

### Claim 4 (depends on 1)

The method of claim 1, wherein the electrical potential is applied in the presence of a solution.

### Claim 5 (depends on 1)

The method of claim 1, wherein the electrical potential is applied in the presence of an electrolyte.

### Claim 6 (depends on 5)

The method of claim 5, wherein the electrolyte is an inorganic molecule.

### Claim 7 (depends on 6)

The method of claim 6, wherein the electrolyte is selected from the group consisting of Li+, Cs+, Na+ and K+ cations.

### Claim 8 (depends on 5)

The method of claim 5, wherein the electrolyte is an organic molecule.

### Claim 9 (depends on 8)

The method of claim 8, wherein the electrolyte is a tetraalkylammonium cation.

### Claim 10 (depends on 9)

The method of claim 9, wherein the tetraalkylammonium cation is at least one of (CH3CH2)4N+ and [CH3(CH2)3]4N+.

### Claim 11 (depends on 1)

The method of claim 1, wherein the organic structure makes contact with the substrate through a sulfur atom.

### Claim 12 (depends on 1)

The method of claim 1, wherein the organic structure makes contact with the substrate through a selenium atom.

### Claim 13 (depends on 1)

The method of claim 1, wherein the substrate is a polycrystalline metal.

### Claim 14 (depends on 1)

The method of claim 1, wherein the substrate is an ultra-flat single crystal metal.

### Claim 15 (depends on 1)

The method of claim 1, wherein the substrate is gold.

### Claim 16

A method of miniaturizing the size of an organic structure fabricated on a substrate by process selected from the group consisting of Dip Pen Nanolithography, printing, stamping, photolithography and combinations thereof, comprising applying an electrical potential to the substrate whereby the organic structure is electrochemically desorbed from the outside of the organic structure.

### Claim 17 (depends on 16)

The method of claim 16, wherein the electrical potential is less than about −400 mV.

### Claim 18 (depends on 16)

The method of claim 16, wherein the electrical potential is between about −400 mV and about −1500 mV.

### Claim 19 (depends on 16)

The method of claim 16, wherein the electrical potential is applied in the presence of a solution.

### Claim 20 (depends on 16)

The method of claim 16, wherein the electrical potential is applied in the presence of an electrolyte.

### Claim 21 (depends on 20)

The method of claim 20, wherein the electrolyte is an inorganic molecule.

### Claim 22 (depends on 21)

The method of claim 21, wherein the electrolyte is selected from the group consisting of Li+, Cs+, Na+ and K+ cations.

### Claim 23 (depends on 20)

The method of claim 20, wherein the electrolyte is an organic molecule.

### Claim 24 (depends on 23)

The method of claim 23, wherein the electrolyte is a tetraalkylammonium cation.

### Claim 25 (depends on 24)

The method of claim 24, wherein the tetraalkylammonium cation is at least one of (CH3CH2)4N+ and [CH3(CH2)3]4N+.

### Claim 26 (depends on 16)

The method of claim 16, wherein the organic structure makes contact with the substrate through a sulfur atom.

### Claim 27 (depends on 16)

The method of claim 16, wherein the organic structure makes contact with the substrate through a selenium atom.

### Claim 28 (depends on 16)

The method of claim 16, wherein the substrate is a polycrystalline metal.

### Claim 29 (depends on 16)

The method of claim 16, wherein the substrate is an ultra-flat single crystal metal.

### Claim 30 (depends on 16)

The method of claim 16, wherein the substrate is gold.

### Claim 31 (depends on 16)

The method of claim 16, wherein molecules forming the organic structures are selected from the group consisting of 16-mercaptohexadecanoic acid, 1-octadecanethiol, octadecaneselenol and combinations thereof.

### Claim 32

A method of miniaturizing the size of a first organic structure in the presence of a second organic structure on a substrate comprising applying an electrical potential to the substrate whereby the first organic structure is electrochemically desorbed from the outside of the organic structure without negatively affecting the second organic structure.

### Claim 33 (depends on 32)

The method of claim 32, wherein the first organic structure makes contact with the substrate through a selenium atom and the second organic molecule makes contact with the substrate through a sulfur atom.

### Claim 34 (depends on 32)

The method of claim 32, wherein the first organic structure comprises a hexadecanoic acid tail group and the second organic molecule comprises an octadecane tail group.

### Claim 35

A method of miniaturizing the size of organic structures on a substrate comprising:
a. applying a first electrical potential to the substrate whereby a first organic structure is electrochemically desorbed from the outside of the organic structure without negatively affecting a second organic structure; and,
b. applying a second electrical potential to the substrate whereby a second organic structure is electrochemically desorbed from the outside of the organic structure without negatively affecting the first organic structure.

### Claim 36 (depends on 35)

The method of claim 35, wherein the first applying step (a) is conducted in a first electrolyte solution and wherein the second applying step (b) is conducted in a second electrolyte solution.

### Claim 37

A method of forming organic structures on a conductive substrate comprising:
a. forming a first organic structure on a conductive substrate;
b. forming at least one additional organic structure on the conductive substrate; and,
c. applying an electrochemical potential to the substrate whereby the first organic structure is desorbed to form an organic structure comprising the at least one additional organic structure on the conductive substrate.

### Claim 38

A method of forming organic structures on a conductive substrate comprising:
a. forming a first organic structure on a conductive substrate in a first position;
b. forming at least one additional organic structure on the conductive substrate in at least one second position;
c. applying an electrochemical potential to the substrate whereby the first organic structure is desorbed;
d. contacting the conductive substrate with a molecule that will adhere to the surface of the substrate to form an organic structure comprising the at least one additional organic structure in the at least one second position and the molecule that will adhere to the surface of the substrate in the first position on the conductive substrate.