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Hoto P QH PH US010211400B2 (12 ) United States Patent ( 10 ) Patent No. : US 10 ,211 , 400 B2 Hawker et al. ( 45 ) Date of Patent: Feb . 19 , 2019 (54 ) PHOTOPATTERNED GROWTH OF (51 ) Int . Ci. ELECTRONICALLY ACTIVE BRUSH HOIL 51/ 00 ( 2006 . 01 ) POLYMERS FOR LIGHT EMITTING DIODE C09K 11 / 06 (2006 . 01) DISPLAYS (Continued ) (71 ) Applicants : The Regents of the University of ( 52 ) U .S . CI. California , Oakland , CA (US ) ; Rohm CPC . .. .. HOIL 51 /0035 (2013 . 01 ) ; C09K 11/ 06 and Haas Electronic Materials LLC , ( 2013. 01 ) ; HOIL 51/ 0043 ( 2013 .01 ) ; Marlborough , MA (US ) ; Dow Global ( Continued ) Technologies LLC , Midland , MI (US ) (58 ) Field of Classification Search CPC .. .. .. HO1L 51 /0035 ; HO1L 51 /0043 ; HOIL ( 72 ) Inventors : Craig J . Hawker , Santa Barbara , CA (58 ) Fieldof c . 51. .HOZZ /5072 ; HOLLHOIL 551 / 5088 ; HO1L 51/ 5206 ; (US ) ; Zachariah Allen Page , Goleta , CA (US ) ; Peter Trefonas, III, Medway , (Continued ) MA (US ) ; Anatoliy N . Sokolov , Midland , MI (US ) ; John Kramer , ( 56 ) References Cited Midland , MI (US ) ; David S . Laitar, U . S . PATENT DOCUMENTS Midland , MI (US ) ; Sukrit Mukhopadhyay , Midland , MI (US ) ; 6 ,423 , 465 B1 7 /2002 Hawker et al . Benjaporn Narupai, Goleta , CA (US ) ; 6 , 447 , 879 B19 / 2002 Sakurai et al . Christian Wilhelm Pester , Goleta , CA ( Continued ) (US ) OTHER PUBLICATIONS (73 ) Assignees : DOW GLOBAL TECHNOLOGIES LLC , Midland , MI (US ) ; ROHM AND Choi et al. ; “ Simple Detachment Patterning of Organic Layers and HAAS ELECTRONIC MATERIALS Its Application to Organic Light- Emitting Diodes ” ; Adv. Mater. ; 17 , LLC , Marlborough , MA (US ) ; THE No . 2 ; Jan . 31 , 2005 , pp . 166 - 171 . REGENTS OF THE UNIVERSITY (Continued ) OF CALIFORNIA , Oakland, CA (US ) Primary Examiner — Su C Kim ( * ) Notice: Subject to any disclaimer, the term of this ( 74 ) Attorney , Agent , or Firm — Cantor Colburn LLP patent is extended or adjusted under 35 U . S . C . 154 ( b ) by 0 days . (57 ) ABSTRACT Disclosed herein is a device comprising a substrate ; where (21 ) Appl. No. : 15 /476 , 492 the substrate comprises a plurality of brush polymers that are covalently or ionically bonded to the substrate ; where at ( 22 ) Filed : Mar. 31, 2017 least a portion of the brush polymers comprise a covalently (65 ) Prior Publication Data bonded emitter moiety . US 2018 /0287065 A1 Oct . 4 , 2018 15 Claims, 10 Drawing Sheets Step 1 Step 2 P 106cm , 104 XMA MOMA temporal hotoP QH PH SW 112 108 110 US 10 ,211 ,400 B2 Page 2 (51 ) Int. Ci. OTHER PUBLICATIONS HOIL 51/ 50 ( 2006 .01 ) ( 2006 . 01 ) Derue et al. ; " All- Solution - Processed Organic Light- Emitting Diodes HOIL 51/ 52 Based on Photostable Photo - cross - linkable Fluorescent Small Mol ( 52 ) U . S . CI. ecules” ; ACS Appl. Mater. Interfaces ; 8 ; 2016 , pp . 16207 - 16217 . CPC .. .. .. .. COOK 2211 /1029 ( 2013 .01 ) ; COOK Gather et al. ; " Solution - Processed Full - Color Polymer Organic 2211/ 185 ( 2013 .01 ) ; HOIL 51 /0096 (2013 .01 ) ; Light- Emitting Diode Displays Fabricated by Direct Photolithog HOIL 51/ 5036 ( 2013 .01 ) ; HOIL 51 / 5056 raphy ” ; Adv. Funct . Mater .; 17 ; 2007 , pp . 191- 200 . ( 2013 .01 ) ; HOIL 51 /5072 ( 2013 .01 ) ; HOIL Jou et al. ; “ Approaches for fabricating high efficiency organic light emitting diodes” ; J . Mater . Chem . C ; 3 ; 2015 ; pp . 2974 - 3002 . 51 /5088 ( 2013 .01 ) ; HOIL 51 /5206 ( 2013 .01 ) Jung et al .; " High performance inkjet printed phosphorescent organic (58 ) Field of Classification Search light emitting diodes based on small molecules commonly used in CPC . .. .. HO1L 51 /0096 ; HO1L 51/ 5036 ; HOIL vacuum processes” ; Thin Solid Films; 520 ; 2012 , pp . 6954 -6958 . 51 /5056 ; CO9K 11 / 06 ; CO9K 2211 / 1029 ; Muller et al . ; “Multi - colour organic light - emitting displays by COOK 2211 / 185 solution processing” ; Nature; vol . 421; Feb . 20 , 2003 , pp . 829 -833 . See application file for complete search history. Niu et al ., “ Full color and monochrome passive -matrix polymer light- emitting diodes flat panel displays made with solution pro ( 56 ) References Cited cesses” ; Organic Electronics ; 9 ; 2008 , pp . 95 - 100 . Oh et al . ; “ Patterned Taping : A High - Efficiency Soft Lithographic U . S . PATENT DOCUMENTS Method for Universal Thin Film Patterning ” ; ACS Nano ; 10 ; 2016 , pp . 3478 - 3485 . 2001/ 0024738 A1 9 / 2001 Hawker et al . Qiang et al. ; “ Novel Photo -Crosslinkable Light- Emitting Rod / Coil 2003 /0205696 AL 11/ 2003 Thoms et al . Copolymers : Underlying Facile Material for Fabricating Pixelated 2004 / 0260047 AL 12 / 2004 Chen et al. 2006 / 0099451 A1 * 5 / 2006 Igarashi .. .. .. COOK 11 /06 Displays ” ; Macromol. Rapid Commun .; 27 ; 2006 , pp . 1779 - 1786 . 428 /690 Shimoda et al. , “ Inkjet Printing of Light - Emitting Polymer 2007 /0169814 A1 7 / 2007 Huck et al. Displays” ;MRS Bulletin ; Nov . 2003 ; pp . 821 -827 . 2014 / 0099580 A14 / 2014 Hawker et al . Tao et al. , “ Organic host materials for phosphorescent organic 2014 /0134454 A1 * 5 / 2014 Fuchs .. H01B 5200 light - emitting diodes” ; Chem . Soc . Rev ; 40 ; 2011, pp . 2943 - 2970 . 428 /620 Zheng et al. ; “ All- solution processed polymer light - emitting diode 2014 /0205818 A1 * 7 / 2014 Schwartz .. .. GO3F 7 / 16 displays” ; Nature Communications; 4 ; 2013 , pp . 1 - 7 . 428 / 201 2015 / 0184024 A1 7 / 2015 Chang et al . * cited by examiner U . S . Patent Feb . 19, 2019 Sheet 1 of 10 US 10 ,211 , 400 B2 Dopane US Farr ca.pww 110 o 108 106 control spatial- control Step2 M6MA FIG.1 104 spatial UV Step1 102 Extra U . S . Patent Feb . 19 , 2019 Sheet 2 of 10 US 10 ,211 , 400 B2 co-bipMA) co-frpaM4.) Wavelength(nm) Poly(MAMA.co-rppyMA) FIG.2 ?????????? Poly(MOMA.co-IrdfppyMA) whilanlananinns Poly(M6MA) ). au( Intensity U . S . Patent Feb . 19 , 2019 Sheet 3 of 10 US 10 ,211 , 400 B2 - - - - - - - - - L )moi%Ir( 60 BindingEnergy(eV) Irloaded(mol%) Ir(41) 62 64 12-Theoretical ????????????????????????? ( % ow ) ). u. a ( CPS detected Ir FIG.3B U . S . Patent Feb . 19 , 2019 Sheet 4 of 10 US 10 ,211 , 400 B2 FIG.4A FIG.4B photomask photomask Step1 Step2Step2 Www ont * 9 . promesse * . |prorsmask U . S . Patent Feb . 19 , 2019 Sheet 5 of 10 US 10 ,211 , 400 B2 100110120 HAHA.90 FIG.5B Thickness(nm) SM RWARM 4050607080 30 * * * 20 10 Mny 0 * U . S . Patent Feb . 19 , 2019 Sheet 6 of 10 US 10 ,211 , 400 B2 FIG.6B 6C.FIG FIG.6D 8 & so 20pm * ** ** * ** ???????????????????????????? countso 12C14N 1151n160 tam 34973 . pube OOOOOOOR FIG.6A . Diblockcopolymer ??? Hote ? jual q? ' 61' 6107 t??US L JO OI SA 00??IIT?OI 78 EEEEE33333333333333 W .. 33321 2177 3 X TT T TTTTT . Wii :: : : : : : : : : : : : :24 : 33 2 33 33 : 57 : 3 3 : 22 :: : : : : : : : : : : : : : : : : : : : : : : : : : : : : : :: X CIE1934 : 23 229 333333333333 . WWW :: :: : :: : :: : : : : : :: : : : . M WEEEEEEE :: : : : :: X E27 W211 W . 12 :: : : : : : : : : : : : : : : :: :: : : : : : : : : : : : : : : :: * * : :: : : :: : : : : : : : : : : : : : :: * * 2 : :: : : : : : : :: * * : : :: Xt98 : :: : : : : : : : : : :: : :: X : : .7 X : : : : : : : 2000: : : : : :: : : : : : : : : : : : * * * * : 39 : 22 * 333333 : 37 : 22 : . * : : * * : : : : * : . * : . V : E VV : : : : : : : : . : . : . : . : . : . : . : . : . : : . * . KEYW Wavelength(nm) : :: : : : :: FIG.7A :: :: : :: : : :: : : : :: : : .' : : : : : :: * : 333333333 : :: : . : : : :. : : : :: : :: : W3594 : : : . : . : . : . : . : . : . : . : : : ¥Wide :: : : . : : :: :: : : :: :: : : :: : : : : : : : : : :: :: : : : : :: : : : CA ) . au( Intensity WW* 500um . FIG.7B UUCOD U . S . Patent Feb . 19 , 2019 Sheet 8 of 10 US 10 ,211 , 400 B2 : : : : : : : : : : : : : FIG.8B w Www TFDTL?QAL (ETL)EILcat. BOX80 ITO(an.) FIG.8A 88 PO-T2T U . S . Patent Feb . 19 , 2019 Sheet 9 of 10 US 10 ,211 , 400 B2 108 106106 201~ oors 112 OII 2104 FIG.9 * U . S . Patent Feb . 19 , 2019 Sheet 10 of 10 US 10 ,211 , 400 B2 co NE . e 2 photocatalystdopant-monomer FIG.10 90000 IrXMA ON Free (host/monomer)T,=28eV * MGMA 2 US 10 , 211 , 400 B2 PHOTOPATTERNED GROWTH OF solution , including, screen printing, contact lithography , jet ELECTRONICALLY ACTIVE BRUSH printing , and photocrosslinking , practical limitations such as POLYMERS FOR LIGHT EMITTING DIODE fabrication complexity , lack of triplet state emission , scal DISPLAYS ability issues , and the use of undesirable reagents have prevented commercialization . For example, printing and BACKGROUND contact lithography techniques require use either complex equipment or numerous iterative processing steps to achieve This disclosure relates to photopatterned growth of elec the desired pattern , while photocrosslinking has been used to tronically active brush polymers for light emitting diode more rapidly provide fluorescent semiconducting patterns displays. 10 Display devices have become an integral part of society as through step -wise spin -coating /irradiation cycles. However, a means of information transfer. In particular , organic light for photocrosslinking intense ultraviolet (UV ) radiation is emitting diode (OLED ) displays are among the most energy often used , along with the use of radical or cationic pho efficient 2D display technologies and can be found in toinitiators ( e . g ., cyclopentadienyl titanium or iodonium everyday appliances, including smartphones , laptops , and 15 hexafluoroantimonatehex derivatives ), that contaminate the televisions . Two aspects that have made efficient OLED emissive layer (EML ) in an OLED device . displays possible are the use of phosphorescent materials It is therefore
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