IP Library Granted Patent US 12663709
Granted Patent B2
US 12663709 · App. 18/133,937 · Granted Jun 23, 2026

Pellicle and method of manufacturing thereof

Inventors: Pei-Cheng Hsu (Hsinchu, TW); Hsin-Chang Lee (Hsinchu, TW); Huan-Ling Lee (Hsinchu, TW); Chin-Hsiang Lin (Hsinchu, TW)
Assignee: TAIWAN SEMICONDUCTOR MANUFACTURING COMPANY, LTD.
G03F1/64
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Quick Facts
Patent No.
US 12663709
App. No.
18/133,937
Granted
Jun 23, 2026
Kind
B2
Abstract

A pellicle for an EUV photo mask includes a membrane attached to a frame. The membrane includes nanotubes, Ru—O—X catalyst structures partially covering a surface of each nanotube, and a protection layer to cover the Ru—O—X catalyst structures and the surface of each nanotube. X is a metal element of Mo, Ti, Zr or Nb. The Ru—O—X catalyst structures include first nano-particles of a X-containing material formed on the surface of each nanotube, and second nano-particles of a Ru-containing material formed on the first nano-particles, thereby forming catalysts or catalyst bridges. The pellicle advantageously has high EUV light transmittance and improved endurance against attacking particles (such as hydrogen particles), thereby having prolonged lifetime.

Claims (41)

1 . A method of manufacturing a pellicle for an extreme ultraviolet (EUV) photo mask, comprising:

forming a plurality of nanotubes made of a nanotube material to form a membrane;

forming functional groups to at least partially cover a surface of each nanotube of the plurality of nanotubes;

forming a plurality of first nano-particles made of a first material over the plurality of nanotubes;

forming a plurality of second nano-particles made of a second material in contact with the plurality of first nano-particles;

forming a first protection layer made of a first capping material to cover the plurality of first nano-particles, the plurality of second nano-particles, and the surface of each nanotube; and

attaching the membrane to a pellicle frame.

2 . The method of claim 1 , wherein the first material is selected from the group consisting of Mo, MoO 2 , and MoO 3 , and wherein the second material is selected from the group consisting of Ru, RuO 2 , RuSi 2 , RuSi, and Ru 2 Si 3 .

3 . The method of claim 1 , wherein the first material is selected from the group consisting of Ti, TiO 2 , TiN, and TION, and wherein the second material is selected from the group consisting of Ru, RuO 2 , RuSi 2 , RuSi, and Ru 2 Si 3 .

4 . The method of claim 1 , wherein the first material is selected from the group consisting of Zr, ZrO 2 , and ZrO 3 , and wherein the second material is selected from the group consisting of Ru, RuO 2 , RuSi 2 , RuSi, and Ru 2 Si 3 .

5 . The method of claim 1 , wherein the first material is selected from the group consisting of Nb, NbO, NbO 2 , Nb 2 O 5 , and wherein the second material is selected from the group consisting of Ru, RuO 2 , RuSi 2 , RuSi, and Ru 2 Si 3 .

6 . The method of claim 1 , further comprising:

forming a second protection layer made of a second capping material different from the first capping material on the first protection layer.

7 . The method according to claim 1 , wherein the first capping material is selected from the group consisting of SiN, SiON, AlN, Y 2 O 3 , Al 2 O 3 , YSiO, and SiC.

8 . A method of manufacturing a pellicle for an extreme ultraviolet (EUV) photo mask, comprising:

forming a plurality of bundles of nanotubes made of a nanotube material to form a membrane;

forming a plurality of Ru—O—X catalyst structures to at least partially cover a surface of each bundle of the plurality of bundles, X being a metal element selected from the group consisting of Ru, Ti and Zr;

forming a protection layer of a capping material to cover the plurality of Ru—O—X structures and the surface of each bundle; and

attaching the membrane to a pellicle frame.

9 . The method of claim 8 , wherein forming the plurality of Ru—O—X structures comprising:

forming a plurality of first nano-particles made of a X-containing material to partially cover the surface of each bundle; and

forming a plurality of second nano-particles made of a Ru-containing material on the plurality of first nano-particles.

10 . The method of claim 9 , wherein the plurality of first nano-particles and the plurality of second nano-particles are nano-grains or nano-islands.

11 . The method of claim 8 , further comprising:

forming functional groups on the surface of each bundle before forming the plurality of Ru—O—X structures, wherein the plurality of Ru—O—X structures are formed at sites of the functional groups on the surface of each bundle.

12 . The method of claim 8 , further comprising:

after forming the plurality of Ru—O—X structures, annealing the membrane at a temperature from about 500° C. to about 1000° C. to form interdiffusions at interfaces between the plurality of first nano-particles and the plurality of second nano-particles.

13 . The method of claim 8 , further comprising:

densifying the protection layer by applying an Ar plasma thereto.

14 . A pellicle for an extreme ultraviolet (EUV) photo mask, comprising:

a frame; and

a membrane attached to the frame, wherein the membrane comprises:

a plurality of nanotubes made of a nanotube material;

a plurality of Ru—O—X catalyst structures at least partially covering a surface of each nanotube of the plurality of nanotubes, wherein X is a metal element selected from the group consisting of Mo, Ti, Nb, and Zr; and

a protection layer made of a capping material to cover the plurality of Ru—O—X structures and the surface of each nanotube.

15 . The pellicle of claim 14 , wherein the plurality of Ru—O—X catalyst structures comprise a plurality of first nano-particles made of a X-containing material to partially cover the surface of each nanotube, and a plurality of second nano-particles made of a Ru-containing material formed on the plurality of first nano-particles.

16 . The pellicle of claim 15 , wherein the membrane comprises first interdiffusions at first interfaces of the plurality of first nano-particles and the plurality of second nano-particles.

17 . The pellicle of claim 15 , wherein the membrane comprises second interdiffusions at second interfaces of the plurality of first nano-particles and the protection layer and third interdiffusions at third interfaces of the plurality of second nano-particles and the protection layer.

18 . The pellicle of claim 14 , wherein at least one of the plurality of Ru—O—X catalyst structures protrudes from the protection layer, and wherein the plurality of nanotubes are dispersed in a specific orientation or randomly dispersed.

19 . The pellicle of claim 14 , wherein the capping material is selected from the group consisting of SiN, SiON, AlN, Y 2 O 3 , Al 2 O 3 , YSiO, and SiC.

20 . The pellicle of claim 14 , wherein the protection layer comprises two or more sub-protection layers of different capping materials respectively selected from the group consisting of SiN, SiON, AlN, Y 2 O 3 , Al 2 O 3 , YSiO, and SiC.