# US 12,759,881 B2 · Fabrication of nanotube bundles and reactors for the same

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- Number: US 12,759,881 B2
- Document ID: US12759881B2
- Status: Granted
- Kind: B2
- Application number: 18/357,950
- Filed: 2023-07-24
- Published: 2024-10-24
- Granted: 2026-10-13
- Earliest claimed: 2023-04-24
- Assignees: Fabrication of Nanotube Bundles and Reactors for the Same
- Applicants: Taiwan Semiconductor Manufacturing Co., Ltd.
- Inventors: Dung-Yue Su; Pei-Cheng Hsu; Huan-Ling Lee; Hsin-Chang Lee
- Web page: https://patentgrep.com/patent/US12759881B2

## CPC

- C01B 32/168: After-treatment
- C01B 32/162: characterised by catalysts
- G03F 1/62: Pellicles, e.g. pellicle assemblies, e.g. having membrane on support frame; Preparation thereof
- C01B 2202/08: Aligned nanotubes
- C01B: NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; {METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C}
- G03F: PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR; (phototypographic composing devices B41B; photosensitive materials or processes for photographic purposes G03C; electrophotography, sensitive layers or processes therefor G03G)

## Abstract

A method for forming a pellicle for an extreme ultraviolet lithography mask is provided. The method includes forming a pellicle membrane over a filter membrane and transfer the pellicle membrane from the filter membrane to a membrane border. Forming the pellicle membrane includes growing carbon nanotubes (CNTs) from in-situ formed metal catalyst particles in a first reaction zone of a reactor, each of the CNTs including a metal catalyst particle at a growing tip thereof, promoting formation of bundles of nanotubes from the individual CNTs in a second zone of the reactor downstream of the first reaction zone. The bundled CNTs are then collected on the filter membrane.

## Claims

### Claim 1

A method for forming a pellicle for an extreme ultraviolet lithography mask, comprising:
forming a pellicle membrane over a filter membrane, wherein forming the pellicle membrane comprises:
growing carbon nanotubes (CNTs) from metal catalyst particles in a first reaction zone of a reactor, the reactor including an axial centerline, each of the CNTs including one of the metal catalyst particles at a growing tip of the CNTs;
flowing the CNTs in a direction substantially parallel to the axial centerline of the reactor;
altering the direction the CNTs are flowing to a direction that is different than the direction that is substantially parallel to the axial centerline of the reactor;
combining the CNTs into CNT bundles; and
collecting the CNT bundles on the filter membrane; and
transferring the pellicle membrane from the filter membrane to a membrane border.

### Claim 2 (depends on 1)

The method of claim 1, wherein the pellicle membrane comprises less than 0.01 atomic % of the metal catalyst particles.

### Claim 3 (depends on 1)

The method of claim 1, wherein the altering the direction the CNTs are flowing includes altering the direction the CNTs are flowing to a direction that is oblique to the substantially parallel direction.

### Claim 4 (depends on 1)

The method of claim 1, wherein growing the CNTs comprises:
supplying a feedstock comprising a carbon source, a catalyst precursor and a catalyst promoter carried by a carrier gas into the first reaction zone of the reactor;
heating the first reaction zone of the reactor to maintain a temperature gradient along a length of the first reaction zone;
decomposing the catalyst precursor to thereby form the metal catalyst particles; and
catalyzing, by the metal catalyst particles, decomposition of the carbon source to provide carbon atoms and growth of individual CNTs from the metal catalyst particles.

### Claim 5 (depends on 3)

The method of claim 3, wherein the altering the direction the CNTs are flowing includes directing an inert gas towards the axial centerline of the reactor.

### Claim 6 (depends on 5)

The method of claim 5, wherein directing an inert gas towards the axial centerline of the reactor includes flowing the inert gas through apertures formed in a liner of the reactor.

### Claim 7 (depends on 5)

The method of claim 5, wherein directing an inert gas towards the axial centerline of the reactor includes injecting the inert gas into the reactor through one or more nozzles.

### Claim 8 (depends on 1)

The method of claim 1, wherein the altering the direction the CNTs are flowing includes deflecting the flow of the CNTs by a portion of the reactor that has a conical shape.

### Claim 9 (depends on 1)

The method of claim 1, wherein the altering the direction the CNTs are flowing includes creating an electric field or magnetic field within the reactor.

### Claim 10

A method for forming a pellicle for an extreme ultraviolet lithography mask, comprising:
forming a pellicle membrane over a filter membrane, wherein forming the pellicle membrane comprises:
growing individual carbon nanotubes (CNTs) from in-situ formed metal catalyst particles in a first reaction zone of a reactor, the reactor including an axial centerline, each of the grown individual CNTs including a metal catalyst particle at a growing tip of the grown individual CNTs;
flowing the grown individual CNTs in a direction substantially parallel to the axial centerline of the reactor;
in a second zone of the reactor below the first reaction zone, altering a direction of the flow of the grown individual CNTs by exposing the grown individual CNTs to an electric or magnetic field;
combining the grown individual CNTs into CNT bundles; and
collecting the CNT bundles on the filter membrane; and
transferring the pellicle membrane from the filter membrane to a membrane border.

### Claim 11 (depends on 10)

The method of claim 10, wherein the altering a direction of the flow of the grown individual CNTs further includes energizing a conical electrode in the second zone of the reactor.

### Claim 12 (depends on 11)

The method of claim 11, wherein the energizing a conical electrode in the second zone of the reactor includes applying a pulsed voltage to the conical electrode.

### Claim 13 (depends on 12)

The method of claim 12, wherein the combining the grown individual CNTs into CNT bundles occurs during a period of applying the pulsed voltage to the conical electrode.

### Claim 14 (depends on 12)

The method of claim 12, wherein the combining the grown individual CNTs into CNT bundles includes attracting grown individual CNTs towards the conical electrode.

### Claim 15 (depends on 10)

The method of claim 10, wherein the altering the direction of the flow of the grown individual CNTs further includes generating a magnetic field in the reactor using an electromagnet.

### Claim 16 (depends on 15)

The method of claim 15, wherein the combining the grown individual CNTs into CNT bundles includes concentrating the grown individual CNTs by subjecting the metal catalyst particle of the grown individual CNTs to the magnetic field.

### Claim 17

A method for forming a pellicle for an extreme ultraviolet lithography mask, comprising:
forming a plurality of carbon nanotubes (CNTs) in a first reaction zone of a reactor;
flowing the plurality of CNTs from the first reaction zone to a second reaction zone of the reactor located downstream of the first reaction zone along a first direction;
flowing the plurality of CNTs through the second reaction zone along a second direction different from the first direction to exit the reactor, wherein, in the second reaction zone, the plurality of CNTs are initially separate and are caused to come together and bundle in response to the change in flow direction to form a plurality of CNT bundles; and
collecting the plurality of CNT bundles on a substrate to form a pellicle membrane.

### Claim 18 (depends on 17)

The method of claim 17, further comprising applying an electric field to the CNTs while the CNTs flow through the second reaction zone to promote bundling.

### Claim 19 (depends on 17)

The method of claim 17, further comprising applying an electromagnetic field to the CNTs while the CNTs flow through the second reaction zone to promote bundling.

### Claim 20 (depends on 17)

The method of claim 17, further comprising flowing an inert gas into the second reaction zone to promote bundling of the CNTs.