# US 10,501,851 B2 · Attachment of nano-objects to beam-deposited structures

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- Number: US 10,501,851 B2
- Document ID: US10501851B2
- Status: Granted
- Kind: B2
- Application number: 15/188,862
- Filed: 2016-06-21
- Published: 2017-11-16
- Granted: 2019-12-10
- Earliest claimed: 2016-05-12
- Assignees: FEI Company
- Applicants: FEI Company
- Inventors: Mehran Kianinia; Olga Shimoni; Igor Aharonovich; Charlene Lobo; Milos Toth; Steven Randolph; Clive D. Chandler
- Web page: https://patentgrep.com/patent/US10501851B2

## CPC

- C23C 16/487: {using electron radiation}
- C23C 16/56: After-treatment
- H01J 37/317: for changing properties of the objects or for applying thin layers thereon, e.g. for ion implantation (H01J37/36 takes precedence)
- B82Y 40/00: Manufacture or treatment of nanostructures
- G01N 33/54353: {with ligand attached to the carrier via a chemical coupling agent (coatings G01N33/54393)}
- H01J 2237/31732: Depositing thin layers on selected microareas
- 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)
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)
- 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)

## Abstract

Beam-induced deposition decomposes a precursor at precise positions on a surface. The surface is processed to provide linker groups on the surface of the deposit, and the sample is processed to attach nano-objects to the linker groups. The nano-objects are used in a variety of application. When a charged particle beam is used to decompose the precursor, the charged particle beam can be used to form an image of the surface with the nano-objects attached.

## Claims

### Claim 1

A method of attaching nano-objects to a sample substrate, comprising:
providing a deposition precursor at the surface of the substrate located within the vacuum chamber of a charged particle beam apparatus;
directing a beam towards the substrate, the beam decomposing the deposition precursor to form a deposit on the surface of the substrate at positions impacted by the beam;
processing the sample to provide linker groups on the surface of the deposit by exposing the surface of the sample to a plasma; and
processing the sample to chemically bond nano-objects to the linker groups.

### Claim 2 (depends on 1)

The method of claim 1, wherein directing a beam towards the substrate comprises directing a charged particle beam towards the surface.

### Claim 3 (depends on 1)

The method of claim 1, wherein the chemical bond comprises a covalent bond selected from the group consisting of an amide bond, a disulfide bond, a sulfonamide bond, and a phosphonamide bond.

### Claim 4 (depends on 1)

The method of claim 1, wherein the nano-objects comprise nanodiamonds or biomolecules.

### Claim 5 (depends on 1)

The method of claim 1, wherein the nano-objects comprise a critical dimension in the range of between 1 nm and 1000 nm.

### Claim 6 (depends on 5)

The method of claim 5, wherein the nano-objects comprise nano dots, crystals, wires, tubes, sheets or flakes.

### Claim 7 (depends on 1)

The method of claim 1, wherein the deposition precursor comprises a carbon-bearing precursor, and the deposit comprises carbon.

### Claim 8 (depends on 1)

The method of claim 1, wherein the deposition precursor comprises a sulfur-bearing precursor, and the deposit is substantially sulfur.

### Claim 9 (depends on 8)

The method of claim 8, wherein the deposit has an aspect ratio greater than 1.

### Claim 10 (depends on 9)

The method of claim 9, wherein the deposit is sufficiently tall to isolate bonded nano-objects from interaction with the sample substrate.

### Claim 11 (depends on 1)

The method of claim 1, wherein the deposition precursor comprises a phosphorus-bearing precursor, and the deposit is substantially phosphorus.

### Claim 12 (depends on 1)

The method of claim 1, wherein processing the sample to provide linker groups takes place within the vacuum chamber of the charged particle beam apparatus.

### Claim 13 (depends on 1)

The method of claim 1, wherein exposing the surface of the sample to a -plasma comprises exposing the surface of the sample to an ammonia plasma.

### Claim 14 (depends on 1)

The method of claim 1, wherein the processing is realized by using ammonia vapor as a linker precursor gas.

### Claim 15 (depends on 1)

The method of claim 1, in which the beam is a laser beam.

### Claim 16 (depends on 1)

The method of claim 1, wherein processing the sample to chemically bond nano-objects comprises processing the sample with a liquid containing nano-objects.

### Claim 17 (depends on 1)

The method of claim 1, wherein the nano-objects undergo surface processing before bonding to the linker groups.

### Claim 18 (depends on 17)

The method of claim 17, wherein the surface modification comprises functionalizing the surface of the nano-object with carboxylic acid groups.

### Claim 19

A method of attaching nano-objects to a sample substrate, comprising:
providing a deposition precursor at the surface of the substrate located within the vacuum chamber of a charged particle beam apparatus;
directing a beam towards the substrate, the beam decomposing the deposition precursor to form a deposit on the surface of the substrate at positions impacted by the beam;
processing the sample to provide linker groups on the surface of the deposit; and
processing the sample to chemically bond nano-objects to the linker groups, wherein the processing is performed using a charged particle beam and a precursor gas mixture comprised of a deposition precursor gas and a linker precursor gas.

### Claim 20 (depends on 19)

The method of claim 19 in which:
providing a deposition precursor at the surface of the substrate located within the vacuum chamber of a charged particle beam apparatus includes providing a carbon precursor; and
directing a beam towards the substrate, the beam decomposing the deposition precursor to form a deposit on the surface of the substrate at positions impacted by the beam includes forming a carbon deposit on the surface at positions impacted by the beam.
