# US 10,119,190 B2 · Method of making a nanostructure and nanostructured articles

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- Number: US 10,119,190 B2
- Document ID: US10119190B2
- Status: Granted
- Kind: B2
- Application number: 15/354,086
- Filed: 2016-11-17
- Published: 2017-03-09
- Granted: 2018-11-06
- Earliest claimed: 2013-07-26
- Assignees: 3M Innovative Properties Company
- Applicants: 3M Innovative Properties Company
- Inventors: Moses M. David; Ta-Hua Yu; Daniel S. Bates; Jayshree Seth; Michael S. Berger; Carsten Franke; Sebastian F. Zehentmaier
- Web page: https://patentgrep.com/patent/US10119190B2

## CPC

- C23C 16/0245: {by etching with a plasma}
- B81C 1/00031: {Regular or irregular arrays of nanoscale structures, e.g. etch mask layer (photomechanical, e.g. photolithographic, production of textured or patterned surfaces G03F7/00; lithographic processes for making patterned surfaces using printing and stamping G03F7/0002)}
- C09J 7/22: Plastics; Metallised plastics
- C23C 16/50: using electric discharges {(generation and control of plasma in discharge tubes for surface treatment H01J37/32, H01J37/34)}
- H01J 37/32082: {Radio frequency generated discharge (H01J37/32357, H01J37/32366, H01J37/32394 and H01J37/32403 take precedence)}
- H01J 37/32541: {Shape}
- B81C 2201/0132: Dry etching, i.e. plasma etching, barrel etching, reactive ion etching [RIE], sputter etching or ion milling
- C09J 2301/302: the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
- F24S 70/60: characterised by the structure or construction (absorbing coatings or surface treatment for increasing absorption F24S70/20; auxiliary coatings F24S70/30)
- H01J 2237/3321: CVD [Chemical Vapor Deposition]
- H01J 2237/3341: Reactive etching
- 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)
- 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)
- C09J: ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES (preparation of glue or gelatine C09H)
- H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H)
- F24S: SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS (for producing mechanical power from solar energy F03G6/00)

## Abstract

A method of making a nanostructure and nanostructured articles by depositing a layer to a major surface of a substrate by plasma chemical vapor deposition from a gaseous mixture while substantially simultaneously etching the surface with a reactive species. The method includes providing a substrate; mixing a first gaseous species capable of depositing a layer onto the substrate when formed into a plasma, with a second gaseous species capable of etching the substrate when formed into a plasma, thereby forming a gaseous mixture; forming the gaseous mixture into a plasma; and exposing a surface of the substrate to the plasma, wherein the surface is etched and a layer is deposited on at least a portion of the etched surface substantially simultaneously, thereby forming the nanostructure. The substrate can be a (co)polymeric material, an inorganic material, an alloy, a solid solution, or a combination thereof. The deposited layer can include the reaction product of plasma chemical vapor deposition using a reactant gas comprising a compound selected from the group consisting of organosilicon compounds, metal alkyl compounds, metal isopropoxide compounds, metal acetylacetonate compounds, metal halide compounds, and combinations thereof. Nanostructures of high aspect ratio and optionally with random dimensions in at least one dimension and preferably in three orthogonal dimensions can be prepared.

## Claims

### Claim 1

An article comprising:
a flexible substrate comprising a nanostructured surface comprising a plurality of spaced apart nanostructures having random heights, at least one nanostructure having an aspect ratio greater than 1.5;
a species layer deposited on the nanostructured surface having a thickness that varies continuously according to a height of the nanostructures; and
a metal layer attached to the species layer.

### Claim 2 (depends on 1)

The article of claim 1, wherein the species layer is present over substantially the entire nanostructured surface.

### Claim 3 (depends on 1)

The article of claim 1, wherein the flexible substrate comprises a fluoropolymer.

### Claim 4 (depends on 1)

The article of claim 1, wherein at least one nanostructure has an aspect ratio greater than 2.

### Claim 5 (depends on 1)

The article of claim 1, wherein at least one nanostructure has an aspect ratio greater than 5.

### Claim 6 (depends on 1)

The article of claim 1, wherein at least one nanostructure has an aspect ratio greater than 15.

### Claim 7 (depends on 1)

The article of claim 1, wherein the nanostructures have heights between 1 nm and 1000 nm.

### Claim 8 (depends on 1)

The article of claim 1, wherein the nanostructures have lengths and widths between 1 nm and 1000 nm.

### Claim 9 (depends on 1)

The article of claim 1, wherein the nanostructured surface has a pattern that is random in three orthogonal dimensions.

### Claim 10 (depends on 1)

The article of claim 1, wherein an adhesive strength between the metal layer and the flexible substrate is greater than a cohesive strength of the metal layer.