# US 8,465,803 B2 · Templated monolayer polymerization and replication

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- Number: US 8,465,803 B2
- Document ID: US8465803B2
- Status: Granted
- Kind: B2
- Application number: 13/556,148
- Filed: 2012-07-23
- Published: 2012-11-15
- Granted: 2013-06-18
- Earliest claimed: 2002-07-17
- Assignees: Massachusetts Institute of Technology
- Applicants: Joseph M. Jacobson; David W. Mosley
- Inventors: Joseph M. Jacobson; David W. Mosley
- Web page: https://patentgrep.com/patent/US8465803B2

## CPC

- H10P 14/68: Organic materials, e.g. photoresists
- B05D 1/185: {applying monomolecular layers (B05D1/204 takes precedence)}
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- G01N 31/22: using chemical indicators (G01N31/02 takes precedence)
- G03F 7/165: {Monolayers, e.g. Langmuir-Blodgett}
- H10P 14/40: of conductive or resistive materials
- Y10S 977/882: Assembling of separate components, e.g. by attaching
- Y10S 977/883: Fluidic self-assembly, FSA
- H10P: GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q)
- 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)
- Y10S: TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS

## Abstract

A self-replicating monolayer system employing polymerization of monomers or nanoparticle ensembles on a defined template provides synthesis of two-dimensional single molecule polymers. Systems of self-replicating monolayers are used as templates for growth of inorganic colloids. A preferred embodiment employs SAM-based replication, wherein an initial monolayer is patterned and used as a template for self-assembly of a second monolayer by molecular recognition. The second monolayer is polymerized in place and the monolayers are separated to form a replicate. Both may then function as templates for monolayer assemblies. A generic self-replicating monomer unit comprises a polymerizable moiety attached by methylene repeats to a recognition element and an ending unit that will not interfere with the chosen recognition chemistry. The recognition element is self-complementary, unless two replicating monomers with compatible cross-linking chemistry are employed. After replication, selective mineralization and/or electroless plating may produce a two-dimensional inorganic sheet having patterned domains within it.

## Claims

### Claim 1

A method for replicating a monolayer, comprising the steps of:
forming a first type of template from a subset of a first set of monomers having a first recognition chemistry;
binding a subset of a second set of monomers having a second recognition chemistry to the first type of template to form a monolayer replicant of a first replicant type, the second recognition chemistry being complementary to the first recognition chemistry;
polymerizing the monolayer replicant of a first replicant type;
disassociating the polymerized monolayer replicant of a first replicant type from the first type of template; and
forming at least one replicated monolayer by binding monomers from the first set of monomers to a second template type comprising the polymerized monolayer replicant of a first replicant type.

### Claim 2 (depends on 1)

The method of claim 1, wherein the monomers are nucleotides, oligonucleotides, or amino acids.

### Claim 3 (depends on 1)

The method of claim 1, wherein the monomers are nanoparticle ensembles.

### Claim 4 (depends on 1)

The method of claim 1, wherein the monomers contain at least two reactive functional groups.

### Claim 5 (depends on 1)

The method of claim 1, wherein the monomers contain a terminus bearing one or more molecular recognition elements.

### Claim 6 (depends on 1)

The method of claim 1, wherein the monomers are selected from the group consisting of Hentriaconta-11,13,20,22-tetraynoic acid, Hentriaconta-11,13,20,22-tetraynoic acid amide, Triaconta-10,12,19,21-tetraynoic acid amide, and Triaconta-10,12,19,21-tetraynoic acid.

### Claim 7 (depends on 1)

The method of claim 1, further including the step of disassociating the replicated monolayer from the template of a second template type.

### Claim 8 (depends on 1)

The method of claim 1, further including the step of growing an inorganic structure upon the replicated monolayer.

### Claim 9 (depends on 1)

The method of claim 1, further including the step of selective mineralization of the replicated monolayer.

### Claim 10 (depends on 1)

The method of claim 1, further including the step of electroless plating of the replicated monolayer.

### Claim 11 (depends on 1)

The method of claim 1, further including the steps of nanoparticle adhesion to, and sintering of, the replicated monolayer.

### Claim 12

A method for replicating a pattern, comprising the steps of:
providing a plurality of sets of monomers, each set of monomers having a recognition chemistry;
providing a template having a plurality of regions, the template being complementary to the pattern to be replicated and each region of the template being complementary to a different one of the sets of monomers;
binding a subset of one of the sets of monomers to each region according to said recognition chemistry, forming a replicate of the pattern;
polymerizing the replicate of the pattern; and
disassociating the polymerized replicate of the pattern from the template.

### Claim 13 (depends on 12)

The method of claim 12, further including the step of binding a plurality of inorganic materials to the replicate of the pattern.

### Claim 14 (depends on 13)

The method of claim 13, wherein at least one of the inorganic materials is metallic.

### Claim 15 (depends on 12)

The method of claim 12, further including the step of selective mineralization of the replicate of the pattern.

### Claim 16 (depends on 12)

The method of claim 12, further including the step of electroless plating of the replicate of the pattern.

### Claim 17 (depends on 12)

The method of claim 12, further including the step of growing a semiconductor upon the replicate of the pattern.

### Claim 18 (depends on 12)

The method of claim 12, wherein the monomers are nucleotides, oligonucleotides, amino acids, or nanoparticle ensembles.

### Claim 19 (depends on 12)

The method of claim 12, wherein the monomers contain at least two reactive functional groups.

### Claim 20 (depends on 12)

The method of claim 12, wherein the monomers contain a terminus bearing one or more molecular recognition elements.
