IP Library › Granted Patent US 12,554,195
Granted Patent B2
US 12,554,195 · App. 18/428,593 · Granted Feb 17, 2026

Radiation based patterning methods

Inventors: Jason K. Stowers (Corvallis, OR); Alan J. Telecky (Albany, OR); Douglas A. Keszler (Corvallis, OR); Andrew Grenville (Corvallis, OR)
Assignee: Inpria Corporation
G03F7/0043G03F7/0042G03F7/20G03F7/327Y10T428/24355
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,554,195
App. No.
18/428,593
Granted
Feb 17, 2026
Kind
B2
Abstract

Stabilized precursor solutions can be used to form radiation inorganic coating materials. The precursor solutions generally comprise metal suboxide cations, peroxide-based ligands and polyatomic anions. Design of the precursor solutions can be performed to achieve a high level of stability of the precursor solutions. The resulting coating materials can be designed for patterning with a selected radiation, such as ultraviolet light, x-ray radiation or electron beam radiation. The radiation patterned coating material can have a high contrast with respect to material properties, such that development of a latent image can be successful to form lines with very low line-width roughness and adjacent structures with a very small pitch.

Claims (28)

1 . A method of forming a radiation patternable coating, the method comprising:

depositing a coating composition comprising metal ions with radiation sensitive ligands onto a substrate comprising a silicon wafer and one or more structures patterned along a surface of the silicon wafer to form the radiation patternable coating.

2 . The method of claim 1 wherein the metal of the metal ions comprises Cu, Al, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Zn, Y, Zr, Nb, Mo, In, Sn, Sb, Hf, Ta, W, Ir, Pt, La, Ce, Pr, Nb, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu or a combination thereof.

3 . The method of claim 1 wherein the metal of the metal ions comprises Sn.

4 . The method of claim 1 wherein the coating composition comprises a blend of metal ions.

5 . The method of claim 1 wherein the silicon wafer is a single crystal silicon wafer.

6 . The method of claim 1 wherein the depositing comprises spin coating.

7 . The method of claim 1 wherein the depositing is sequentially performed two to five times to form the radiation patternable coating.

8 . The method of claim 1 wherein the radiation patternable coating has a thickness from about 1 nm to about 40 nm.

9 . The method of claim 1 wherein the radiation patternable coating has a thickness from about 1 nm to about 25 nm.

10 . The method of claim 1 wherein the radiation patternable coating comprises a metal suboxide.

11 . The method of claim 1 wherein the one or more structures comprise a developed patterned coating material.

12 . The method of claim 1 wherein the one or more structures comprise ions, a dielectric, a semiconductor, a dopant, or a conductor.

13 . The method of claim 1 wherein the one or more structures comprise a step.

14 . The method of claim 1 wherein the substrate comprises an etched silicon wafer.

15 . The method of claim 1 , further comprising patterning the radiation patternable coating to integrate the one or more structures.

16 . The method of claim 1 , further comprising

irradiating the radiation patternable coating along pattern to form a coating material with a latent image having irradiated coating material and un-irradiated coating material according to the pattern;

developing the coating material with the latent image to remove the un-irradiated coating material to form a developed patterned coating material having openings to the substrate; and

depositing a deposited material through the openings to the substrate or etching the substrate through the openings.

17 . The method of claim 16 wherein the irradiating is performed with EUV radiation at a dose of no more than about 100 mJ/cm 2 .

18 . The method of claim 16 wherein the deposited material comprises ions, a dielectric, a semiconductor, a dopant, or a conductor.

19 . The method of claim 16 wherein depositing the deposited material comprises chemical vapor deposition (CVD), sputtering, or physical vapor deposition (PVD).

20 . A method of forming a radiation patternable coating, the method comprising:

depositing a coating composition comprising metal ions with radiation sensitive ligands onto a substrate comprising a silicon wafer and one or more structures to form the radiation patternable coating, wherein the one or more structures comprise a step.

21 . The method of claim 20 wherein the step comprises an increase in height of no more than about 150 nm.

22 . The method of claim 20 wherein the step comprises sharp edges.

23 . The method of claim 20 wherein the step comprises a thin film transistor gate dielectric structure.

Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 1, 2024
From: STOWERS, JASON K.; TELECKY, ALAN J.; KESZLER, DOUGLAS A.; GRENVILLE, ANDREW
To: INPRIA CORPORATION
Reel/Frame 066323/0042 →
Continuity (9)
Continuation 18200125 · May 22, 2023
Continuation 17895657 · Aug 25, 2022
Continuation 17839784 · Jun 14, 2022
Continuation 16885581 · May 28, 2020
Continuation 15784258 · Oct 16, 2017
Division 14858612 · Sep 18, 2015
Continuation 12850867 · Aug 5, 2010
Provisional Application 61350103 · Jun 1, 2010
Related Publication 20250004365A1 · Jan 2, 2025
References Cited (165)
US 3385915A · Hamling · 1968 [cited by applicant]
US 3944684A · Kane et al. · 1976 [cited by applicant]
US 4014858A · Chipman et al. · 1977 [cited by applicant]
US 4102683A · DiPiazza · 1978 [cited by applicant]
US 4104292A · Dworkin et al. · 1978 [cited by applicant]
US 4144222A · Shinmi et al. · 1979 [cited by applicant]
US 4174346A · Collins et al. · 1979 [cited by applicant]
US 4370405A · O'Toole et al. · 1983 [cited by applicant]
US 4380559A · Mandai et al. · 1983 [cited by applicant]
US 4601917A · Russo et al. · 1986 [cited by applicant]
US 4639208A · Inui et al. · 1987 [cited by applicant]
US 4732841A · Radigan · 1988 [cited by applicant]
US 4851481A · Kuriyama et al. · 1989 [cited by applicant]
US 4891303A · Garza et al. · 1990 [cited by applicant]
US 4910122A · Arnold et al. · 1990 [cited by applicant]
US 5025094A · King · 1991 [cited by applicant]
US 5302198A · Allman · 1994 [cited by applicant]
US 5440138A · Nishi · 1995 [cited by applicant]
US 5672243A · Hsia et al. · 1997 [cited by applicant]
US 6020269A · Wang et al. · 2000 [cited by applicant]
US 6060380A · Subramanian et al. · 2000 [cited by applicant]
US 6183716B1 · Sleight et al. · 2001 [cited by applicant]
US 6194323B1 · Downey et al. · 2001 [cited by applicant]
US 6197896B1 · Aviram et al. · 2001 [cited by applicant]
US 6268457B1 · Kennedy et al. · 2001 [cited by applicant]
US 6287951B1 · Lucas et al. · 2001 [cited by applicant]
US 6387012B1 · Mitamura · 2002 [cited by applicant]
US 6420088B1 · Angelopoulos et al. · 2002 [cited by applicant]
US 6566276B2 · Maloney et al. · 2003 [cited by applicant]
US 6583071B1 · Weidman et al. · 2003 [cited by applicant]
US 6730454B2 · Pfeiffer et al. · 2004 [cited by applicant]
US 6825131B2 · Nishida et al. · 2004 [cited by applicant]
US 6844604B2 · Lee et al. · 2005 [cited by applicant]
US 6927108B2 · Weng et al. · 2005 [cited by applicant]
US 6946677B2 · Ostergard · 2005 [cited by applicant]
US 7001821B2 · Aggarwal et al. · 2006 [cited by applicant]
US 7208341B2 · Lee et al. · 2007 [cited by applicant]
US 7256129B2 · Nam et al. · 2007 [cited by applicant]
US 7270886B2 · Lee et al. · 2007 [cited by applicant]
US 8053370B2 · Yang et al. · 2011 [cited by applicant]
US 8092703B2 · Ishibashi et al. · 2012 [cited by applicant]
US 8158338B2 · Fednyshyn · 2012 [cited by applicant]
US 8257910B1 · Guerrero et al. · 2012 [cited by applicant]
US 8415000B2 · Stowers et al. · 2013 [cited by applicant]
US 8426107B2 · Takashi et al. · 2013 [cited by applicant]
US 8703386B2 · Bass et al. · 2014 [cited by applicant]
US 8828493B2 · Cheng et al. · 2014 [cited by applicant]
US 8951917B2 · Ogihara et al. · 2015 [cited by applicant]
US 9005875B2 · Bristol et al. · 2015 [cited by applicant]
US 9310684B2 · Meyers et al. · 2016 [cited by applicant]
US 9372402B2 · Freedman et al. · 2016 [cited by applicant]
US 9679095B1 · Li · 2017 [cited by applicant]
US 10228618B2 · Meyers et al. · 2019 [cited by applicant]
US 10627719B2 · Waller et al. · 2020 [cited by applicant]
US 10642153B2 · Meyers et al. · 2020 [cited by applicant]
US 10649328B2 · Stowers et al. · 2020 [cited by applicant]
US 20020076495A1 · Maloney et al. · 2002 [cited by applicant]
US 20020157418A1 · Ganguli et al. · 2002 [cited by applicant]
US 20020160298A1 · Minami et al. · 2002 [cited by applicant]
US 20040067444A1 · Wakabayashi et al. · 2004 [cited by applicant]
US 20050242330A1 · Herman et al. · 2005 [cited by applicant]
US 20050266700A1 · Jurisich et al. · 2005 [cited by applicant]
US 20060088962A1 · Herman et al. · 2006 [cited by applicant]
US 20060234138A1 · Fehlhaber et al. · 2006 [cited by applicant]
US 20080055597A1 · Sun et al. · 2008 [cited by applicant]
US 20080286683A1 · Brodsky et al. · 2008 [cited by applicant]
US 20090174036A1 · Fuller et al. · 2009 [cited by applicant]
US 20090214823A1 · Cheng et al. · 2009 [cited by applicant]
US 20100044698A1 · Herman et al. · 2010 [cited by applicant]
US 20100099908A1 · Yoshitomo et al. · 2010 [cited by applicant]
US 20100119939A1 · Misumi et al. · 2010 [cited by applicant]
US 20100167217A1 · Ando · 2010 [cited by applicant]
US 20100184259A1 · Radigan et al. · 2010 [cited by applicant]
US 20100279228A1 · Davis et al. · 2010 [cited by applicant]
US 20110045406A1 · Keszler et al. · 2011 [cited by applicant]
US 20110135823A1 · Lee et al. · 2011 [cited by applicant]
US 20110166268A1 · Deelman et al. · 2011 [cited by applicant]
US 20110206599A1 · Keszler et al. · 2011 [cited by applicant]
US 20110244403A1 · Carcasi et al. · 2011 [cited by applicant]
US 20110293888A1 · Stowers et al. · 2011 [cited by applicant]
US 20120202349A1 · Sun · 2012 [cited by applicant]
US 20120223418A1 · Stowers et al. · 2012 [cited by applicant]
US 20120315451A1 · Malik et al. · 2012 [cited by applicant]
US 20130078796A1 · Ganesan et al. · 2013 [cited by applicant]
US 20130224652A1 · Bass et al. · 2013 [cited by applicant]
US 20130253161A1 · Amako et al. · 2013 [cited by applicant]
US 20140303283A1 · Ding et al. · 2014 [cited by applicant]
US 20150040083A1 · Cheng et al. · 2015 [cited by applicant]
US 20150160557A1 · deVillers · 2015 [cited by applicant]
US 20150221519A1 · Marks et al. · 2015 [cited by applicant]
US 20150234272A1 · Sarma et al. · 2015 [cited by applicant]
US 20160116839A1 · Meyers et al. · 2016 [cited by applicant]
US 20170343896A1 · Darling et al. · 2017 [cited by applicant]
CN 1457504A · 2003 [cited by applicant]
CN 1821879A · 2006 [cited by applicant]
CN 101713923A · 2010 [cited by applicant]
CN 102027603A · 2011 [cited by applicant]
CN 108780739A · 2018 [cited by applicant]
EP 0094914A2 · 1983 [cited by applicant]
EP 1326136A · 2003 [cited by applicant]
EP 1992665A1 · 2008 [cited by applicant]
JP S63241061A · 1988 [cited by applicant]
JP H03148659A · 1991 [cited by applicant]
JP H7056354A · 1995 [cited by applicant]
JP 200181560A · 2001 [cited by applicant]
JP 2001154366A · 2001 [cited by applicant]
JP 2003218118A · 2003 [cited by applicant]
JP 2006284947A · 2006 [cited by applicant]
JP 2007178452A · 2007 [cited by applicant]
JP 2008091215A · 2008 [cited by applicant]
JP 2007514182 · 2008 [cited by applicant]
JP 2009533521A · 2009 [cited by applicant]
JP 2010094583A · 2010 [cited by applicant]
JP 2016530565A · 2016 [cited by applicant]
JP 2018502173A · 2018 [cited by applicant]
KR 1020030007904 · 2003 [cited by applicant]
KR 1020110132288 · 2011 [cited by applicant]
KR 1020120092950A · 2012 [cited by applicant]
KR 101839255B1 · 2018 [cited by applicant]
TW 513745 · 2002 [cited by applicant]
TW 200831695A · 2008 [cited by applicant]
TW 201222144A · 2012 [cited by applicant]
WO 2005043246 · 2005 [cited by applicant]
WO 2008082448 · 2008 [cited by applicant]
WO WO2008082448A1 · 2008 [cited by examiner]
WO 2009120169 · 2009 [cited by applicant]
WO 2009138474A1 · 2009 [cited by applicant]
WO 2009139421A1 · 2009 [cited by applicant]
WO 2010000504A1 · 2010 [cited by applicant]
WO 2014150411A1 · 2014 [cited by applicant]
WO 2016065120A1 · 2016 [cited by applicant]
Stowers 2008 pp. 1-50 (Year: 2008). [cited by examiner]
Anonymous: “International Technology Roadmap for Semiconductors 2009 Edition Executive Summary”, Jan. 1, 2009, XP055464243, Retrived from the Internet: URL:https://www.semiconductors.prg/clientuploads/Research_Technolog… [cited by applicant]
Ahmed et al., “Synthesis And Characterization Of Zirconium And Hafnium Sulfates, Hydroxide Sulfates And Oxide Sulfates”, Acta Chemica Scandinavica, 53:24-33 (1999). [cited by applicant]
Anderson et al., “Solution-Processed HafSOx and ZircSOx Inorganic Thin-Film Dielectrics and Nanolaminates”, Advanced Functional Materials, vol. 17, p. 2117-2124, (2007). [cited by applicant]
Chandrasekhar et al., “Organotin Assemblies Containing SN—O Bonds,” Coordination Chemistry Reviews 235:1-52 (2002). [cited by applicant]
Eychenne-Baron et al., “New Synthesis Of The Nanobuilding Block {(BuSn) 12O14(OH)6 }2+ And Exchange Properties Of {(BuSn)12O14(OH)6}(O3SC6H4CH3)2,” Journal Of Organometallic Chemistry, 567:137-142 (1998). [cited by applicant]
Eychenne-Baron et al., “Reaction Of Butyltin Hydroxide Oxide With ρ-Toluenesulfonic Acid: Synthesis, X-ray Crystal Analysis, And Multinuclear NMR Characterization Of {(BuSn)12O14(OH)6}(4-CH3C6H4SO3)2,” Organometallics, … [cited by applicant]
Han et al., “Capacity Collaboration in Semiconductor Supply Chain with Failure Risk and Long-term Profit”, Supply Chain Management, p. 185-200, (Apr. 26, 2011). [cited by applicant]
Jouve et al., “Overcoming pattern collapse of ultra high resolution dense lines obtained with EUV resists”, Proceedings of SPIE 5753, p. 720-731, (May 2005). [cited by applicant]
Lee et al., “Effect of line-edge roughness (LER) and line-width roughness (LWR) on sub-100-nm device performance”, Microlithography 2004, vol. 5376, May 14, 2004, p. 426, XP055464997, DOI: 10.1117/12.534926. [cited by applicant]
Matsuzawa et al., “Theoretical Estimation of Absorption Coefficients of Various Polymers at 13 nm”, Journal of Photopolymer Science and Technology, vol. 12 No. 4, p. 571-576, (1999). [cited by applicant]
Meyers et al., “Solution-Processed Aluminum Oxide Phosphate Thin-Film Dielectrics” Chem. Mater., 2007, 19, 4023-4029. Abstract Only. [cited by applicant]
Morecroft et al., “Sub-15nm nanoimprint Molds and Pattern Transfer”, Journal of Vacuum Science and Technology: Part B, AVS / AIP, Melville, New York, NY, vol. 27, No. 6, Dec. 3, 2009, pp. 2837-2840, XP012129582, ISSN:10… [cited by applicant]
Nakatta et al., “Improvement Of InGaZnO4 Thin Film Transistors Characteristics Utilizing Excimer Laser Annealing” The Japan Society Of Applied Physics, 2009. [cited by applicant]
Neef et al., “Effects Of Carbon/Hardmask Interactions On Hardmask Performance”, Proceedings of SPIE, 7273, 727311-1-727311-7 (2009). [cited by applicant]
Owen et al., “1/8 μm Optical Lithography,” J. Vac. Sci. Technol. B 10, 3032 (1992). [cited by applicant]
Patel et al., “Comparative Study of Line Width Roughness (LWR) in Next-generation Lithography (NGL) Processes”, SPIE Advanced Lithography, vol. 7640, p. 76400T-1-76400T-13, (Mar. 3, 2010). [cited by applicant]
Puurunen et al., “Hafnium oxide films by atomic layer deposition for high- κ gate dielectric applications: Analysis of the density of nanometer-thin films”, applied Physics Letters, vol. 86 No. 073116, (2005). [cited by applicant]
Stowers, “Direct Patterning of Solution Deposited Metal Oxides”, A Dissertation to Oregon State University, Aug. 14, 2008 (149 pages). [cited by applicant]
Stowers et al., “High Resolution, High Sensitivity Inorganic Resists”, Microelectronic Engineering, 86:730-733 (2009). [cited by applicant]
Stowers et al., “Directly Patterned Inorganic Hardmask For EUV Lithography,” Proc. SPIE 7969, 796915 (2011); http://dx.doi.org/10.1117/12.879542. [cited by applicant]
Trikeriotis et al., “Development of an inorganic photoresist for DUV, EUV, and electron beam imaging,” Proceedings of SPIE 76390E, (Mar. 2010). [cited by applicant]
Wang et al., “TiO2 Micro-Devices Fabricated By Laser Direct Writing” Optics Express, 19(18):17390-17935 (Aug. 29, 2011). [cited by applicant]
Zhang et al., Stabilization Of Cubic ZrO2 With Rh(III) And/Or La(III), Journal Of Solid State Chemistry, 72:131-136 (1988). [cited by applicant]
Zimmerman, “Extension Options for 193nm Immersion Lithography”, Journal Of Photopolymer Science And Technology, 22(5):625-634 (2009) (Abstract), for full article please see http://www.jstage.jst.go.jp/article/photopolym… [cited by applicant]
International Standard ISO 21348 “Space Environment (Natural and Artificial)—Process For Determining Solar Irradiances”, First Edition 2007, Reference No. ISO 21348:2007(E) (20 pages). [cited by applicant]
Supplementary European Search Report From Corresponding European Patent Application No. 11168027.8 Dated Jan. 6, 2012 (8 pages). [cited by applicant]
Office Action From Co-pending Korean Application No. 10-2011-0052919 dated Mar. 14, 2013. [cited by applicant]
Office Action From Co-pending Japanese Application No. 2011-120402 dated Jun. 11, 2013. [cited by applicant]
Office Action From Co-pending Taiwan Application No. 100116897 dated Jul. 29, 2013 (14 pages with translation). [cited by applicant]
Office Action From Co-pending Japanese Application No. 2015-207978 dated Aug. 23, 2016. [cited by applicant]
Office Action from Co-pending European Application No. 15178638.1 dated Apr. 16, 2018. [cited by applicant]
Office Action from corresponding European Patent Application No. 15178638.1 dated Dec. 15, 2022. [cited by applicant]
Declaration by Karey Holland dated Oct. 16, 2023. [cited by applicant]