IP Library › Granted Patent US 12,522,621
Granted Patent B2
US 12,522,621 · App. 18/779,539 · Granted Jan 13, 2026

Tin dodecamers and radiation patternable coatings with strong euv absorption

Inventors: Brian J. Cardineau (Corvallis, OR); William Earley (Corvallis, OR); Stephen T. Meyers (Corvallis, OR); Kai Jiang (Corvallis, OR); Jeremy T. Anderson (Corvallis, OR)
Assignee: Inpria Corporation
C07F7/2224G03F7/0042G03F7/2004
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Quick Facts
Patent No.
US 12,522,621
App. No.
18/779,539
Granted
Jan 13, 2026
Kind
B2
Abstract

Patterning compositions are described based on organo tin dodecamers with hydrocarbyl ligands, oxo ligands, hydroxo ligands and carboxylato ligands. Alternative dodecamer embodiments have organo tin ligands in place of hydrocarbyl ligands. The organo tin ligands can be incorporated into the dodecamers from a monomer with the structure (RCC) 3 SnQ, where R is a hydrocarbyl group and Q is a alkyl tin moiety with a carbon bonded to the Sn atom of the monomer and with a Sn bonded as a replacement of a quaternary carbon atom with bonds to 4 carbon atoms. Some or all of the carboxylato and hydroxyl ligands can be replaced with fluoride ions. Good EUV patterning results are obtained with the dodecamer based patterning compositions.

Claims (27)

1 . A radiation-sensitive coating wherein the coating comprises a composition represented by the formula RSnO 3/2-1/2x-1/2y F x (OH) y , wherein (0<x+y≤3) and x>0, wherein R comprises an alkyl group with 1 to 16 carbon atoms.

2 . The radiation-sensitive coating of claim 1 wherein R comprises a methyl, an ethyl, an n-propyl, an n-pentyl, an isopropyl, a tert-butyl, a sec-butyl, an isobutyl, a t-amyl, a cyclo-propyl, a cyclo-butyl, a cyclo-pentyl group, or a combination thereof.

3 . The radiation-sensitive coating of claim 1 wherein R comprises a branched alkyl group or a cycloalkyl group.

4 . The radiation-sensitive coating of claim 1 wherein R comprises a tert-butyl group (—C(CH 3 ) 3 ).

5 . The radiation-sensitive coating of claim 1 wherein R comprises a blend of different alkyl groups.

6 . The radiation-sensitive coating of claim 1 wherein the coating can be patterned with EUV radiation at a dose from about 1 mJ/cm 2 to about 175 mJ/cm 2 .

7 . The radiation-sensitive coating of claim 1 wherein the coating, after EUV radiation, has a post-development contrast of at least about 3.

8 . A radiation-sensitive coating comprising a fluorinated organotin oxo composition comprising Sn—C bonds, Sn—O bonds, and Sn—F bonds.

9 . The radiation-sensitive coating of claim 8 further comprising Sn—OH bonds.

10 . A radiation-patternable coated substrate comprising the radiation-sensitive coating of claim 8 .

11 . The coated substrate of claim 10 wherein the substrate comprises a silicon wafer.

12 . The coated substrate of claim 10 wherein the radiation-sensitive coating comprises a tin oxo-hydroxo network with Sn—C bonds, Sn—O bonds, Sn—OH bonds, and Sn—F bonds.

13 . The coated substrate of claim 10 wherein the radiation-sensitive coating has an average thickness from about 1 nm to about 50 nm.

14 . The coated substrate of claim 10 wherein the radiation-sensitive coating has an average thickness from about 3 nm to about 35 nm.

15 . A method of forming a radiation-sensitive coating on a substrate, the method comprising

depositing a fluorinated organotin composition onto the substrate to form a radiation-sensitive coating having Sn—C bonds, Sn—O bonds, and Sn—F bonds.

16 . The method of claim 15 wherein the substrate comprises a silicon wafer.

17 . The method of claim 15 wherein the fluorinated organotin composition is represented by the formula (QSn) n O 3n/2-1/2x-1/2y F x (OH) y , wherein 1≤n≤12, (0<x+y≤8), and x>0, wherein Q is an alkyl group with 1 to 16 carbon atoms or an alkyltin group with a structure —CH 2 Sn(R 1 R 2 R 3 ) with 4 to 15 total carbon atoms, and R 1 , R 2 , and R 3 are independently alkyl groups with 1 to 5 carbon atoms.

18 . The method of claim 17 wherein Q is a tert-butyl group (—C(CH 3 ) 3 ).

19 . The method of claim 17 wherein Q is —CH 2 Sn(CH 3 ) 3 .

20 . The method of claim 15 wherein the fluorinated organotin composition comprises a composition represented by the formula (RSn) 12 O 14 F x (OH) 8-x , wherein (0<x<8), wherein R is an alkyl group with 1 to 16 carbon atoms.

21 . The method of claim 15 wherein the fluorinated organotin composition comprises a composition represented by the formula (RSn) 12 O 14 F 8 , wherein R is an alkyl group with 1 to 16 carbon atoms.

22 . The method of claim 15 wherein the depositing comprises depositing a photoresist composition comprising an organic solvent and the fluorinated organotin composition onto the substrate.

23 . The method of claim 15 wherein the depositing comprises spin coating.

24 . The method of claim 15 wherein the radiation-sensitive coating has radiation sensitive Sn—C bonds.

25 . The method of claim 15 wherein the radiation-sensitive coating comprises a tin oxo-hydroxo network.

26 . The method of claim 15 wherein the radiation-sensitive coating can be patterned with EUV radiation at a dose from about 1 mJ/cm 2 to about 175 mJ/cm 2 .

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Jul 23, 2024
From: CARDINEAU, BRIAN J.; EARLEY, WILLIAM; MEYERS, STEPHEN T.; JIANG, KAI; ANDERSON, JEREMY T.
To: INPRIA CORPORATION
Reel/Frame 068050/0421 →
Continuity (4)
Continuation 17840844 · Jun 15, 2022
Division 16375032 · Apr 4, 2019
Provisional Application 62653043 · Apr 5, 2018
Related Publication 20240376135A1 · Nov 14, 2024
References Cited (42)
US 6071676A · Thomson · 2000 [cited by examiner]
US 9310684B2 · Meyers et al. · 2016 [cited by applicant]
US 10228618B2 · Meyers et al. · 2019 [cited by applicant]
US 10642153B2 · Meyers et al. · 2020 [cited by applicant]
US 10787466B2 · Edson et al. · 2020 [cited by applicant]
US 10975109B2 · Edson et al. · 2021 [cited by applicant]
US 11098070B2 · Cardineau et al. · 2021 [cited by applicant]
US 11392028B2 · Cardineau et al. · 2022 [cited by applicant]
US 20160116839A1 · Meyers et al. · 2016 [cited by applicant]
US 20170102612A1 · Meyers et al. · 2017 [cited by applicant]
US 20170146909A1 · Smith et al. · 2017 [cited by applicant]
US 20170256418A1 · Chang et al. · 2017 [cited by applicant]
US 20190137870A1 · Meyers et al. · 2019 [cited by applicant]
US 20190153001A1 · Cardineau et al. · 2019 [cited by applicant]
US 20190369489A1 · Meyers et al. · 2019 [cited by applicant]
US 20200064733A1 · Meyers et al. · 2020 [cited by applicant]
US 20220064192A1 · Edson et al. · 2022 [cited by applicant]
US 20220324886A1 · Cardineau et al. · 2022 [cited by applicant]
RU 2317933C1 · 2008 [cited by applicant]
TW 201734025A · 2017 [cited by applicant]
WO 20170063119A1 · 2017 [cited by applicant]
Cardineau et al., “Photolithographic properties of tin-oxo clusters using extreme ultraviolet light (13.5 nm)”, Microelectronic Engineering, Apr. 24, 2014 (E-pub.), vol. 127, pp. 44-50. [cited by applicant]
Chandrasekhar et al., “Organotin assemblies containing Sn—O bonds”, Coordination Chemistry Reviews, Dec. 1, 2002, vol. 235, pp. 1-5. [cited by applicant]
Chandrasekhar et al., “Organotin Cages, {[(n-BuSn)3(∥3-O)(OC6H4-4-X)3]2(HPO3]4}, X = H, Ci, Br, and I, in Double O-Capped Structures: Halogen-Bonding-Mediated Supramolecular Formation,” Organometallics 2005, vol. 24, 49… [cited by applicant]
Corey et al., “Preparation of trans-1,2-Bis (tri-n-butylstannyl) ethylene”, The Journal of Organic Chemistry, Dec. 1, 1975, vol. 40, No. 25, pp. 3788-3789. [cited by applicant]
Dakternieks et al., “Synthesis, structure and reactions of [(BuSn)12O14(OH)6]Cl2·2H2O: solution studies using 119Sn NMR and electrospray mass spectrometry”, Journal of Organometallic Chemistry, Aug. 9, 1994, vol. 476, N… [cited by applicant]
Day et al., “A New Structural Form of Tin in an Oxygen-Capped Cluster”, J. Am. Chem. Soc. 1987, vol. 109, 940-941. (First page). [cited by applicant]
Eyechenne-Baron et al., “New synthesis of the nanobuilding block {(BuSn)12O14(OH)6}2+and exchange properties of {(BuSn)12O14(OH)6} (O3SC6H4CH3)2,” J. Organometallic Chemistry 1998, 567, 137-142. [cited by applicant]
International Union of Pure and Applied Chemistry, “Copendium of Chemical Terminology (IUPAC)”, Gold Book, p. 694-695 of 1622, (2012). [cited by applicant]
Kuan et al., “Hexameric isopropyloxotin acetate chloroform tetrasolvate”, Acta Crystallographica, Section E: Structure Reports Online, vol. 58 No. 6, p. m301-m303, (2002). [cited by applicant]
Mack, “Fundamental Principles of Optical Lithography”, John Wiley & Sons, Chichester, U.K; pp. 271-272, 2007. (Abstract Only). [cited by applicant]
Nagabrahmanandachari et al., “Reaction of n-butyltin dihydroxy chloride with carboxylic and phosphinic acids: crystal structures of the ladder [{Sn(n-Bu)(O2CCHPh2)}3Cl2O2]2 and the unsolvated cluster [{Sn(n-Bu)(O2PPH2)C… [cited by applicant]
Prabusankar et al., “Sn3 and Sn10 sulfonate-oxide-hydroxide clusters with two different sulfonate binding modes”, Dalton Transactions, vol. 29, p. 3121-3123, (2007). [cited by applicant]
Puff et al., “Zur hydrolyse von monoorganylzinn-trihalogeniden (III. Isolierung und Röntgenstrukturanalyse von Verbindungen mit dem nueartigen Käfig-ion [(i-PrSn)12O14(OH)6+2]”, J. Organometallic Chemistry 1989, 373, 17… [cited by applicant]
Renaldo et al., “Palladium-Catalyzed Coupling of Acid Chlorides With Organotin Reagents: Ethyl (E)-4-(4-Nitrophenyl)-4-OXO-2-Butenoate”, Organic Syntheses, 1989, vol. 67, p. 86. internal pp. 1-8. [cited by applicant]
Reuter et al., “On the structural diversity anions coordinate to the butterfly-shaped [(R2Sn)3O(OH)2]2+ cations and vice versa”, Canadian Journal of Chemistry, vol. 92, pp. 496-507, (Jan. 2014). [cited by applicant]
Schmid et al., “Oxygen-and sulfur-capped organotin clusters”, Phosphorus, Sulfur and Silicon and the Related Elements, vol. 41 No. 1-2, p. 69-74, (1989). [cited by applicant]
Schumann et al., “Synthesis and characterization of some organo-all-tin dendrimers with different peripheral substituents”, Journal of Organometallic Chemistry 691, p. 1703-1712, (2006). [cited by applicant]
International Standard ISO 21348 (2007) (Abstract Only). [cited by applicant]
International Search Report And Written Opinion For International Application No. PCT/US2019/025739 dated Oct. 31, 2019. [cited by applicant]
Office Action from corresponding Taiwan Patent Application No. 111132226 dated Feb. 17, 2023. [cited by applicant]
Office Action from corresponding Korean Patent Application No. 10-2020-7028850 dated Feb. 20, 2023. [cited by applicant]