# US 11,908,960 B2 · Plasmonic metal/graphene heterostructures and related methods

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- Number: US 11,908,960 B2
- Document ID: US11908960B2
- Status: Granted
- Kind: B2
- Application number: 17/255,817
- Filed: 2019-07-03
- Published: 2021-10-21
- Granted: 2024-02-20
- Earliest claimed: 2018-07-06
- Assignees: University of Kansas
- Applicants: University of Kansas
- Inventors: Judy Z. Wu; Qingfeng Liu
- Web page: https://patentgrep.com/patent/US11908960B2

## CPC

- H10F 77/306: {for devices having potential barriers}
- C23C 16/18: from metallo-organic compounds
- C23C 16/26: Deposition of carbon only
- C23C 16/30: Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C 16/448: characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
- C23C 16/52: Controlling or regulating the coating process {(C23C16/45557, C23C16/279 take precedence)}
- G01N 21/658: {enhancement Raman, e.g. surface plasmons}
- H10F 71/128: {Annealing}
- H10F 77/122: comprising only Group IV materials
- H10F 77/40: Optical elements or arrangements (surface textures H10F77/70)
- H10F 77/703: {of the semiconductor bodies, e.g. textured active layers}
- B82Y 20/00: Nanooptics, e.g. quantum optics or photonic crystals
- B82Y 30/00: Nanotechnology for materials or surface science, e.g. nanocomposites
- B82Y 40/00: Manufacture or treatment of nanostructures
- H10F: INORGANIC SEMICONDUCTOR DEVICES SENSITIVE TO INFRARED RADIATION, LIGHT, ELECTROMAGNETIC RADIATION OF SHORTER WAVELENGTH OR CORPUSCULAR RADIATION
- C23C: COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL (making metal-coated products by extrusion B21C23/22; covering with metal by connecting pre-existing layers to articles, see the relevant places, e.g. B21D39/00, B23K; metallising of glass C03C; metallising mortars, concrete, artificial stone, ceramics or natural stone C04B41/00; enamelling of, or applying a vitreous layer to, metals C23D; treating metal surfaces or coating of metals by electrolysis or electrophoresis C25D; single-crystal film growth C30B; by metallising textiles D06M11/83; decorating textiles by locally metallising D06Q1/04)
- 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)
- B82Y: SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES

## Abstract

A method of making a plasmonic metal/graphene heterostructure comprises heating an organometallic complex precursor comprising a metal at a first temperature T1 for a first period of time t1 to deposit a layer of the metal on a surface of a heated substrate, the heated substrate in fluid communication with the precursor; and heating, in situ, the precursor at a second temperature T2 for a second period of time t2 to simultaneously form on the layer of the metal, a monolayer of graphene and a plurality of carbon-encapsulated metal nanostructures comprising the metal, thereby providing the plasmonic metal/graphene heterostructure. The heated substrate is characterized by a third temperature T3. The plasmonic metal/graphene heterostructures, devices incorporating the heterostructures, and methods of using the heterostructures are also provided.

## Claims

### Claim 1

A method of making a plasmonic metal/graphene heterostructure, the method comprising:
heating an organometallic complex precursor comprising a metal at a first temperature T1 for a first period of time t1 to deposit a layer of the metal on a surface of a heated substrate, the heated substrate in fluid communication with the precursor; and
heating, in situ, the precursor at a second temperature T2 for a second period of time t2 to simultaneously form on the layer of the metal, a monolayer of graphene and a plurality of carbon-encapsulated metal nanostructures comprising the metal, thereby providing the plasmonic metal/graphene heterostructure,
wherein the heated substrate is characterized by a third temperature T3.

### Claim 2 (depends on 1)

The method of claim 1, wherein T1<T2<T3.

### Claim 3 (depends on 2)

The method of claim 2, wherein the organometallic complex precursor is characterized by a vaporization temperature and a decomposition temperature and T1 is greater than the vaporization temperature, T2 is less than the decomposition temperature and T3 is greater than the decomposition temperature.

### Claim 4 (depends on 1)

The method of claim 1, wherein t1<t2 and t1.

### Claim 5 (depends on 1)

The method of claim 1, wherein the heating steps are carried out in the presence of a flowing gas.

### Claim 6 (depends on 1)

The method of claim 1, wherein the metal of the organometallic complex precursor is selected from Cu, Ag, Au, Ti, Zn, Co, Fe, and combinations thereof.

### Claim 7 (depends on 1)

The method of claim 1, wherein the carbon of the carbon-encapsulated metal nanostructures has a thickness consistent with that of a graphene monolayer.

### Claim 8 (depends on 1)

The method of claim 1, wherein the substrate is a silicon-containing substrate.

### Claim 9 (depends on 1)

The method of claim 1, wherein the deposited layer of metal is ultrathin having an average thickness of no more than 2 nm.

### Claim 10 (depends on 9)

The method of claim 9, wherein the deposited layer of metal is continuous.

### Claim 11 (depends on 1)

The method of claim 1, wherein the monolayer of graphene and the carbon of the plurality of carbon-encapsulated metal nanostructures provide a continuous carbon layer forming a continuous interface with each metal nanostructure of the plurality of carbon-encapsulated metal nanostructures and with the layer of the metal between neighboring metal nanostructures of the plurality of carbon-encapsulated metal nanostructures.

### Claim 12 (depends on 1)

The method of claim 1, wherein the formed monolayer of graphene is characterized by an ID/IG value of less than 0.2.

### Claim 13 (depends on 1)

The method of claim 1, wherein the carbon-encapsulated metal nanostructures of the plurality of carbon-encapsulated metal nanostructures have an average size in the range of 10 nm to 100 nm.

### Claim 14 (depends on 13)

The method of claim 13, wherein a deviation of sizes of the carbon-encapsulated metal nanostructures from the average size is no more than ±1%.

### Claim 15

A plasmonic metal/graphene heterostructure comprising:
a substrate having a surface;
a layer of a metal on the surface of the substrate; and
a monolayer of graphene and a plurality of carbon-encapsulated metal nanostructures comprising the metal on a surface of the layer of the metal.

### Claim 16 (depends on 15)

The heterostructure of claim 15, wherein the carbon of the carbon-encapsulated metal nanostructures has a thickness consistent with that of a graphene monolayer.

### Claim 17 (depends on 15)

The heterostructure of claim 15, wherein the substrate is a silicon-containing substrate.

### Claim 18 (depends on 15)

The heterostructure of claim 15, wherein the monolayer of graphene and the carbon of the plurality of carbon-encapsulated metal nanostructures provide a continuous carbon layer forming a continuous interface with each metal nanostructure of the plurality of carbon-encapsulated metal nanostructures and with the layer of the metal between neighboring metal nanostructures of the plurality of carbon-encapsulated metal nanostructures.

### Claim 19 (depends on 15)

An optoelectronic device comprising the plasmonic metal/graphene heterostructure of claim 15, a source configured to illuminate the heterostructure with electromagnetic radiation, and a detector configured to detect scattered light from the heterostructure.

### Claim 20 (depends on 15)

A method of using a plasmonic metal/graphene heterostructure, the method comprising illuminating the plasmonic metal/graphene heterostructure of claim 15 with electromagnetic radiation to excite surface plasmons at a carbon-metal interface therein.