# US 2025/0085248 A1 · Resistive hydrogen sensor comprising sensing layer having semiconducting single-walled carbon nanotubes, and manufacturing method therefor

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- Number: US 2025/0085248 A1
- Document ID: US20250085248A1
- Status: Published application
- Kind: A1
- Application number: 18/291,633
- Filed: 2023-01-20
- Published: 2025-03-13
- Earliest claimed: 2022-01-25
- Assignees: Postech Research and Business Development Foundation
- Applicants: Postech Research and Business Development Foundation
- Inventors: Yong-Young NOH; Gi-Seong RYU
- Web page: https://patentgrep.com/patent/US20250085248A1

## CPC

- G01N 27/127: {comprising nanoparticles}
- C01B 32/158: Carbon nanotubes
- G01N 27/12: of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid {, for detecting components in the fluid}
- G01N 27/123: {for controlling the temperature (temperature control per se G05D23/00)}
- G01N 27/126: {comprising organic polymers}
- G01N 33/00: Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N 33/005: {H2}
- 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)
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}

## Abstract

A resistive hydrogen sensor comprising a sensing layer having semiconducting single-walled carbon nanotubes (SWCNTs), and a manufacturing method therefor are disclosed. The hydrogen sensor comprises: a substrate; a sensing layer, which is formed on the substrate and comprises semiconducting SWCNTs; and electrodes formed on the surface of the sensing layer in the direction opposite to the direction facing the substrate, or formed between the sensing layer and the substrate, and spaced from each other, and thus has a sensitivity of 5% or higher and a response time of two seconds or less with respect to a hydrogen gas having a hydrogen concentration of 4 vol % in comparison to when there is no hydrogen, and can be operated at a low temperature.

## Claims

### Claim 1

A hydrogen sensor for detecting hydrogen gas, the hydrogen sensor comprising:
a substrate;
a sensing layer formed on the substrate and containing semiconducting single-walled carbon nanotubes (SWCNTs); and
electrodes spaced from each other, the electrodes formed on a first surface of the sensing layer, the first surface being a surface opposite to and not facing the substrate, or formed between the sensing layer and the substrate.

### Claim 2 (depends on 1)

The hydrogen sensor of claim 1, wherein the sensing layer further comprises a conjugated polymer, and
the surface of the semiconducting single-walled carbon nanotubes is partially or entirely wrapped with the conjugated polymer.

### Claim 3 (depends on 2)

The hydrogen sensor of claim 2, wherein the conjugated polymer comprises one or more selected from the group consisting of polyfluorene, 1,4-diketopyrrolo [3,4-c]pyrrole (DPP), naphthalene diimide, naphthalene-bis(dicarboximide) (NDI), isoindigo, isothiophene indigo, benzodipyrrolidone (BPT), poly(9,9-di-n-dodecylfluorene) (PFDD), poly(3-dodecylthiophene-2,5-diyl) (P3DDT), and poly(3-hexylthiophene-2,5-diyl) (P3HT).

### Claim 4 (depends on 1)

The hydrogen sensor of claim 1, wherein the surface of the hydrogen sensor is treated with one or more selected from the group consisting of ozone, ultraviolet, a surfactant, a self-assembled monolayer (SAM), a polymer coating, and a plasma.

### Claim 5 (depends on 1)

The hydrogen sensor of claim 1, further comprising a catalyst layer positioned on the sensing layer and the electrodes, the catalyst layer comprising a catalyst.

### Claim 6 (depends on 1)

The hydrogen sensor of claim 1, further comprising a first insulating layer positioned on the sensing layer and the electrodes, the first insulating layer comprising a first insulator.

### Claim 7 (depends on 1)

The hydrogen sensor of claim 1, further comprising a second insulating layer and a microheater,
wherein the second insulating layer comprises a second insulator and is positioned on the substrate and under the sensing layer and the electrodes, and
the microheater is positioned between the substrate and the second insulating layer.

### Claim 8 (depends on 1)

The hydrogen sensor of claim 1, wherein the substrate comprises one or more selected from the group consisting of a silicon (Si) substrate, a silicon/silicon dioxide (Si/SiO2) substrate, a silicon/silicon nitride (Si/SiNx) substrate, a glass substrate, polyethylene terephthalate (PET), polyimide (PI), polyethylene naphthalate (PEN), polyethersulfone (PES), polyacrylate, and polyetherimide.

### Claim 9 (depends on 1)

The hydrogen sensor of claim 1, wherein the electrodes comprise one or more selected from the group consisting of a metal, an oxide, a conductive polymer, and a carbon compound.

### Claim 10 (depends on 1)

The hydrogen sensor of claim 1, wherein the hydrogen sensor is a resistive hydrogen sensor in which a resistance value of the sensing layer changes in the presence of hydrogen gas.

### Claim 11

A method of manufacturing a hydrogen sensor for detecting hydrogen, the method comprising:
(a) providing a substrate;
(b) forming a sensing layer by coating the substrate with a solution comprising semiconducting single-walled carbon nanotubes; and
(c) manufacturing a hydrogen sensor by forming electrodes to be spaced from each other, the electrodes formed on a first surface of the sensing layer, the first surface being a surface opposite to and not facing the substrate, or formed between the sensing layer and the substrate.

### Claim 12 (depends on 11)

The method of claim 11, further comprising:
(b′-1) preparing a first mixture by mixing a conjugated polymer and unrefined single-walled carbon nanotubes comprising metallic and semiconducting single-walled carbon nanotubes;
(b′-2) preparing a second mixture comprising conjugated polymer-wrapped semiconducting single-walled carbon nanotubes by sonicating the first mixture such that the surface of the semiconducting single-walled carbon nanotubes selected from among the metallic and semiconducting single-walled carbon nanotubes is wrapped with the conjugated polymer; and
(b′-3) separating the conjugated polymer-wrapped semiconducting single-walled carbon nanotubes from the second mixture, before the (b) forming.

### Claim 13 (depends on 12)

The method of claim 12, further comprising (b′-4) obtaining the semiconducting single-walled carbon nanotubes by removing the conjugated polymer from the conjugated polymer-wrapped semiconducting single-walled carbon nanotubes, after the (b′-3) separating.

### Claim 14 (depends on 12)

The method of claim 12, wherein the unrefined single-walled carbon nanotubes are prepared by one selected from the group consisting of a plasma growth method, a high-pressure carbon monoxide (HiPco) method, an electric arc-discharge method, a laser vaporization method, a thermal chemical vapor deposition method, and a vapor-phase growth method.

### Claim 15 (depends on 11)

The method of claim 11, further comprising (d-1) treating the surface of the hydrogen sensor with one or more selected from the group consisting of ultraviolet, ozone, a surfactant, a self-assembled monolayer (SAM), a polymer coating, and a plasma, after the (c) manufacturing.

### Claim 16 (depends on 11)

The method of claim 11, further comprising (d-2) forming a catalyst layer positioned on the sensing layer and the electrodes, the catalyst layer comprising a catalyst, after the (c) manufacturing.

### Claim 17 (depends on 11)

The method of claim 11, further comprising (d-3) forming a first insulating layer positioned on the sensing layer electrodes, the first insulating layer comprising a first insulator, after the (c) manufacturing.

### Claim 18 (depends on 11)

The method of claim 11, further comprising (a′) positioning a microheater on the substrate and then forming a second insulating layer comprising a second insulator on the microheater, after the (a) providing.

### Claim 19 (depends on 1)

A method of detecting hydrogen, the method comprising:
(1) bringing a gas from which hydrogen is required to be detected into contact with a sensing layer of the hydrogen sensor of claim 1; and
(2) detecting hydrogen gas by confirming a change in resistance or current value of the hydrogen sensor.

### Claim 20 (depends on 19)

The method of claim 19, wherein the (1) bringing is performed in the air.