IP Library › Granted Patent US 12,557,609
Granted Patent B2
US 12,557,609 · App. 17/692,561 · Granted Feb 17, 2026

Methods for dry printing carbon nanotube membranes

Inventors: Hsin-Chang Lee (Zhubei, TW); Wei-Hao Lee (Taipei, TW); Pei-Cheng Hsu (Taipei, TW); Huan-Ling Lee (Hsinchu, TW)
Assignee: TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY, LTD.
H01L21/0276C01B32/16G03F1/64B82Y40/00C01P2004/13C01P2004/64
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Quick Facts
Patent No.
US 12,557,609
App. No.
17/692,561
Granted
Feb 17, 2026
Kind
B2
Abstract

Methods for preparing a nanotube membrane for use in a pellicle membrane using dry printing are disclosed. Nanotube fibers are produced in a reaction vessel and dry sprayed onto a filter to form the nanotube membrane. The thickness of the nanotube membrane can be controlled by moving the reaction vessel and the filter relative to each other, or by further processing to reduce the thickness of the layer deposited onto the filter. This method reduces the number of process steps, reducing overall production time, and can also be used to produce larger membranes. The pellicle membrane can be formed with multiple layers and has a combination of high transmittance, low deflection, and small pore size. A conformal coating may applied to an outer surface of the pellicle membrane to protect the pellicle membrane from damage that can occur due to heat and hydrogen plasma created during EUV exposure.

Claims (30)

1 . A method of forming a nanotube membrane, comprising:

producing nanotube fibers in a reaction vessel;

blowing carbon monoxide or carbon dioxide into the nanotube fibers downstream of the reaction vessel and upstream of a nozzle to promote the formation of nanotube bundles;

dry depositing the nanotube bundles through the nozzle downstream of the reaction vessel and onto a filter to form the nanotube membrane consisting of the nanotube fibers or bundles; and

reducing a thickness of the nanotube membrane deposited upon the filter by applying pressure uniaxially to the nanotube membrane.

2 . The method of claim 1 , wherein the filter moves relative to the nozzle.

3 . The method of claim 2 , wherein the filter moves uniaxially or biaxially relative to the nozzle.

4 . The method of claim 2 , wherein the filter rotates relative to the nozzle, with the nanotube bundles being deposited circumferentially onto the filter.

5 . The method of claim 1 , wherein the nanotube fibers comprise single-wall nanotubes, multi-wall nanotubes, and combination thereof.

6 . The method of claim 5 , wherein the nanotube fibers comprise less than 50% of multi-wall nanotubes by number.

7 . The method of claim 1 , further comprising flowing a carrier gas through the nanotube bundles upstream of the nozzle.

8 . The method of claim 1 , wherein the nanotube fibers or bundles are deposited at a rate of about 10 sccm to about 500 sccm.

9 . The method of claim 1 , further comprising applying suction to the filter.

10 . The method of claim 1 , wherein the nanotube fibers comprise carbon, boron nitride, silicon carbide, molybdenum disulfide, molybdenum diselenide, tungsten disulfide, or tungsten diselenide.

11 . A method of forming a nanotube membrane, comprising:

producing nanotube fibers in a reaction vessel;

blowing carbon monoxide or carbon dioxide into the nanotube fibers downstream of the reaction vessel to promote the formation of nanotube bundles; and

dry depositing the nanotube bundles through a nozzle downstream of the reaction vessel and onto a filter to form the nanotube membrane.

12 . The method of claim 11 , further comprising applying suction to the filter.

13 . The method of claim 11 , wherein a temperature inside the reaction vessel is maintained from about 500° C. to about 1000° C.

14 . The method of claim 11 , wherein the filter moves relative to the nozzle.

15 . The method of claim 14 , wherein the filter moves uniaxially or biaxially relative to the nozzle.

16 . The method of claim 14 , wherein the filter rotates relative to the nozzle, with the nanotube fibers or bundles being deposited circumferentially onto the filter.

17 . The method of claim 11 , further comprising flowing a carrier gas through the nanotube bundles upstream of the nozzle.

18 . The method of claim 11 , wherein the nanotube bundles are deposited at a rate of about 10 sccm to about 500 sccm.

19 . A method of forming a nanotube membrane, comprising:

producing nanotube fibers in a reaction vessel;

blowing carbon monoxide or carbon dioxide into the nanotube fibers downstream of the reaction vessel to promote the formation of nanotube bundles; and

dry depositing the nanotube bundles through a nozzle downstream of the reaction vessel and onto a filter to form the nanotube membrane, wherein the filter moves relative to the nozzle.

20 . The method of claim 19 , wherein the filter moves uniaxially or biaxially relative to the nozzle, or wherein the filter rotates relative to the nozzle.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Mar 29, 2022
From: LEE, HSIN-CHANG; LEE, WEI-HAO; HSU, PEI-CHENG; LEE, HUAN-LING
To: TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY, LTD
Reel/Frame 059420/0609 →
Continuity (2)
Provisional Application 63224892 · Jul 23, 2021
Related Publication 20230026114A1 · Jan 26, 2023
References Cited (3)
US 7763231B2 · Gardner · 2010 [cited by examiner]
US 20190036102A1 · Pierce · 2019 [cited by examiner]
US 20230227313A1 · Li · 2023 [cited by examiner]