# US 12,217,931 B2 · Graphene based substrates for imaging

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- Number: US 12,217,931 B2
- Document ID: US12217931B2
- Status: Granted
- Kind: B2
- Application number: 17/413,114
- Filed: 2019-12-11
- Published: 2022-03-03
- Granted: 2025-02-04
- Earliest claimed: 2018-12-11
- Assignees: University of Kansas; Kansas State University Research Foundation
- Applicants: The University of Kansas; Kansas State University Research Foundation
- Inventors: Eduardo Rosa-Molinar; Noraida Martinez-Rivera; Prem Singh Thapa-Chetri; WenJun Xiang; Suprem Ranjan Das
- Web page: https://patentgrep.com/patent/US12217931B2

## CPC

- G02B 21/34: Microscope slides, e.g. mounting specimens on microscope slides
- H01J 37/261: {Details}
- B05D 1/30: performed by gravity only, i.e. flow coating
- B05D 3/0254: {After-treatment}
- B05D 7/56: {Three layers or more}
- C09D 1/00: Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
- C09D 7/65: macromolecular (C09D7/41-C09D7/48 take precedence)
- G01N 1/06: providing a thin slice, e.g. microtome
- H01J 37/20: Means for supporting or positioning the object or the material; Means for adjusting diaphragms or lenses associated with the support
- H01J 37/28: with scanning beams {(H01J37/268, H01J37/292, H01J37/2955 take precedence)}
- H01J 37/285: Emission microscopes, e.g. field-emission microscopes
- B05D 2201/02: Polymeric substrate
- B05D 2202/40: based on other transition elements
- B05D 2203/35: Glass
- B05D 2601/20: used for non-pigmentation effect
- H01J 2237/2801: Details
- H01J 2237/2802: Transmission microscopes
- H01J 2237/2813: characterised by the application
- G02B: OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)
- B05D: PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL (conveying articles or workpieces through baths of liquid B65G, e.g. B65G49/02)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)
- 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)

## Abstract

Disclosed are articles comprising substrate and graphene coating that are configured to support a sample for electron or optical microscopy. Also disclosed are methods of making the same and methods of using the same in imaging technology.

## Claims

### Claim 1

An article comprising:
a) a substrate comprising a polymer film, a glass or a metal and having a first surface and an opposed second surface, wherein the polymer film has a thickness of from about 2 microns to about 300 microns; and
b) a graphene coating disposed on the first surface of the substrate, and
wherein the article is configured to support a sample for electron or optical microscopy.

### Claim 2 (depends on 1)

The article of claim 1, wherein the substrate comprises the polymer film, and wherein the polymer film comprises a polyimide.

### Claim 3 (depends on 2)

The article of claim 2, wherein the polyimide film comprises a poly(4,4′-oxydiphenylene-pyromellitimide).

### Claim 4 (depends on 1)

The article of claim 1, wherein the substrate comprises the glass, and wherein the glass substrate has a thickness from about 10 to about 60 mm.

### Claim 5 (depends on 1)

The article of claim 1, wherein the substrate comprises the metal, and wherein the metal substrate has a thickness from about 10 microns to about 50 microns and comprises gold, copper, or nickel grids.

### Claim 6 (depends on 1)

The article of claim 1, wherein the graphene coating has a thickness from about 1 nm to about 1 micron.

### Claim 7 (depends on 1)

The article of claim 1, wherein the graphene comprises a reduced graphene oxide.

### Claim 8 (depends on 7)

The article of claim 7, wherein the article exhibits a sheet resistance from about 25 Ohms/square to about 100 Ohms/square.

### Claim 9 (depends on 7)

The article of claim 7, wherein the reduced graphene oxide comprises from about 1% to about 30% of oxygen as measured by energy dispersive spectroscopy (EDS).

### Claim 10 (depends on 7)

The article of claim 7, wherein the reduced graphene oxide comprises a carbonyl group, a carboxyl group, an epoxy group, or a combination thereof.

### Claim 11 (depends on 10)

The article of claim 10, wherein the graphene coating is a substantially uniform film, and/or is substantially free of defects, and/or substantially mechanically flexible and/or substantially bendable.

### Claim 12 (depends on 1)

The article of claim 1, wherein the graphene coating substantially eliminates charging artifacts resulting from an electron beam in electron microscopy and/or wherein the graphene coating is effectively invisible in a resolution range for optical microscopy.

### Claim 13

A method of making an article, comprising:
a) providing a substrate comprising a polymer film, a glass, or a metal and having a first surface and an opposed second surface, wherein the polymer film has a thickness of from about 2 microns to about 300 microns; and
b) coating at least one layer comprising graphene on the first surface of the substrate;
wherein the article is configured to support a sample for electron microscopy.

### Claim 14 (depends on 13)

The method of claim 13, wherein the step of coating the at least one layer comprising graphene comprises a drop casting a composition comprising a reduced graphene oxide on the first surface of the substrate.

### Claim 15 (depends on 14)

The method of claim 14, wherein the composition comprising the reduced graphene oxide further comprises a solvent.

### Claim 16 (depends on 14)

The method of claim 14, wherein the composition further comprises a rheology modifier comprising ethyl cellulose.

### Claim 17 (depends on 13)

The method of claim 13, wherein prior to the step of forming the graphene coating, the substrate is substantially free of moisture.

### Claim 18 (depends on 13)

The method of claim 13, wherein the article is heated after the step of coating the at least one layer comprising graphene.

### Claim 19 (depends on 13)

The method of claim 13, wherein the step of coating the at least one layer comprising graphene is repeated at least twice to form a total number of three conductive carbon layers comprising graphene.

### Claim 20 (depends on 13)

The method of claim 13, further comprising annealing the article at a temperature about 250-300° C. for a time period from about 0.5 hours to about 4 hours.

### Claim 21 (depends on 1)

A method comprising:
a) mounting a ribbon of a specimen on the graphene coating of the article of claim 1; and
b) imaging the sample with an electron microscope.

### Claim 22 (depends on 21)

The method of claim 21, wherein prior to the mounting the specimen is formed by slicing a tissue sample.

### Claim 23 (depends on 22)

The method of claim 22, wherein the tissue sample comprises a resin impregnated with cells, wherein the resin has a substantially cylindrical form.

### Claim 24 (depends on 22)

The method of claim 22, wherein the slicing is performed in a slicing direction using a microtome knife to provide the at least one specimen section having a predetermined section thickness, wherein the section thickness is controlled by an advancement of the microtome knife into the tissue sample in a substantially perpendicular direction relative to the slicing direction.

### Claim 25 (depends on 24)

The method of claim 24, further comprising a feedback loop controlling the advancement of the microtome knife to provide the predetermined section thickness.

### Claim 26 (depends on 24)

The method of claim 24, wherein the ribbon of the specimen comprises from about 10 to about 20 specimen sections.
