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  • US8722205, An Issued Patent On OLED

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    A patent issued in US on OLED area.

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    A patent issued in US on OLED area.

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    © All Rights Reserved
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    Signaler comme contenu inapproprié
    10 vues90 pages

    US8722205, An Issued Patent On OLED

    Transféré par

    Suman Layek
    A patent issued in US on OLED area.

    Droits d'auteur :

    © All Rights Reserved
    Téléchargez comme PDF ou lisez en ligne sur Scribd
    Signaler comme contenu inapproprié
    sur 90
    1US008722205B2 «2 United States Patent (10) Patent No.: US 8,722,205 B2 Xia et al. (45) Date of Patent: May 13, 2014 (54) METEROLEPTIC IRIDIUM COMPLEX, ronson a1 Waters cta. Zevon AL tna (75) Inventors: Chuanjun Nia, Lawrenceville, NJ (US); 200640202194 AL Jeong eal Joooesioas Al inal Raymond Kwong, Plainsboro. NS (US, 20060251023 A Eogeeal Suman Taye, aweencevile. ICUS) Soneusaravs At Morais sta Sonics AL Noma (03) Assiance: Universal Display Corporation, Ewing, 2017019039 Al Raia NI(US) FOREIGN PATENT DOCUMENTS (4). Notice: Subject to an disclaimer, the erm of this pent is extended or aljusted under 35. GX clones A toss USC. 18400) by 300 das, ES "seuss | S95 Bp Syot 3008 21) Appl.Nos ramaT 61s ib Vest $3007 ” aoosiicio 12003 ‘lek Man ages tne (22) Fie: Mar 19,2010 ® moemes 72006 i dooresim? 103007 ) Prior Publication Data Epon wan US 201010244004 A1 Sep. 30, 2010 wo woo13024 S200 (Contino) Related US. Application Data ae (60) Provisional application No. 61/162.476 filed on Mar ir Bako ca, “Tighly Fiat Phosorescet Fison om Organic Hlectlumiaeacem Devices Nate, vol 395, 151-54 Gh mcr, 198 Bal. in Suse (200601) COOK 1106 (2006.01) (Continued) 2) US.c. USHC 42690; 429917 19506: 257SL 044 pny ier Nate Ranh papeoeee (94) storey, Agen, or Fem — Duane Moris LLP None Seo application efor complete serch istry. 6 ansTRACT 66) References Cled Novel compounds comprising heteolpic iridium com- USS. PATENT DOCUMENTS 470.292 § 91988 Tange Siao'se> A 104991 VanSiyke eta 911995 Friend et a 121997 Fomest tl T1908 Font et 11/1998 Bulow eal 31999 Tote "II3982 A 1/2000. ‘Thompson ea feus7i96 A 72000. Stanm eal 091198 A 72000 Fores etx "I 82000 Bald ea 200398 BL 92001 Kime {303.238 BI 10.2001 Thompson a O337 102 BL "12002 Fone eta 468819 BI 102002 Kime al 22004, Maet 122004. Kevong a “7005 Tabiauch $2006 Kwong etal 102007 Waters et 3002 ‘Thomnpeon eal 3002 tears {32003 Kamatai ea 4281690 20080178853 AL 9.2003 “Thompeon sa donsozw0980 AL 122003 Fomrestet 20040013908 AL “1/2008. Tsuboyam ea aoosorTaite AL 9.2008 Leta 20080025003 AL 2/3005 “Thompson eal doosoriadd AL 102005 Storset al nps0260441 AL 11/2005 ‘Thompson ea plexes are provided. The compounds have a particular com- bination of ligands which includes a single pyridyl dibeazo- substituted ligand as exemplified by Formula I, where X is NR.O, S, BR, or Se. The compounds may'be used in organic light emitting devices, particularly as emiting dopants, to provide devices having improved efficieney,Tifetime, and O Sx a 39 Claims, 3 Drawing Sheets Foals US 8,722,205 B2 Page 2 66) References Cited FOREIGN PATENT DOCUMENTS. wo wooorns 12002 Wo woos? = S008 WO WOO}0«I9s 7.2003 WO — wO2o407007 10-2004 Wo “Psppaitiiost 122004 WO — Wo .20ou107K22 12 2004 Wo — Wo2voso1dssi 2.2008 WO — Wo 2o0so30000 Anas WO — WO2g0sow02s 205 WO — WO200s123873 12.2005 WO Wo 20000002 ‘T2006 Wo WO2ossoselie 6 20a8 WO WO 200608742, ——$.2006 WO WO 20609K120 92008 Wo Woolas 102006 WO WO 2006119966 11 2006 WO Wo206132173 12.2006 WO — Wo2o0001380 ‘T2007 WO Wo2ooecvis = 62007 WO — WO200706379 6.2007 wo “Psnceored) 6 2008 WO wo2mmeati26 42% 22009 OTHER PUBLICATIONS Baldo et al, “Very high-clncy green organic lightemiting devicestasd onclecrophosporesenee” Appl Phys Lett vol 75, No, 146 (1999) (Baldo) ‘Kuwahara, Yoshiyuki ct al." Thenmally Stable Mutilayered Organic lectoluinescent Devices Using Novel Starburst Molecules. 4414 ci(W-crtao}yaiphenylamine (TCTA) and 44s :methyiphenyiphenl-aminoiphenylamine (mI DATA) soe ‘Transpo Material, Maer (9577-89 (1994), Pulse, Bey Masi lente St a, “Fast Examples of Alken Pyridine as Organic Ligands for Phosphorescem ndium Com plexes" Ad Mater, 1622) 2003-2007 (2008. Tong Yon iang etl, “Orpinic Ligh-Emiting Diodes Based on Charge-Neizal Ku" PHosphorescet Emirs” Ady. Mater, 118) 1089-1064 2009), Huang, Jinsong el al, “Highly Bfiient Re-Emisson Polymet Phospborescnt ight-Emiting Diodes Based on Two Novel Tis = henisoquaolaao-C2 Njidium(lt) Derivatives” ade Mater. 10,739-783 2007, ‘Wong, Wi-Yeung, “Multfinctiona Iidium Complexes Based on Carbrle Modsles a Highly Efficient Electophoxphors” Angew (Chem Ii Ed 85-7800-790 (2008. “Tang, CW. and VanSipke, SA. “Organic Hlecsoluminescen Diodes” pp Phys. Ltt 5(12}913-918 (1987) Adachi, Chihaya ctl, "Organic Hctouminescent Device Having a Hole Conductor as an Emiting Layer” ppl Plps. Let $5(18}: 1489-1491 (109 ‘Ma, Yuguang ol, “Triplet LoinescentDinicear-Goli() Com: Plex-Basot Ligh+Emiting Diodes with Low Tar-On voltage” ‘ppl. Phys: Let, 7410) 1361-1363 (1999), (Gao, Zhigang otal, “Brigh-Blue Elecsoluminescence From a Sil Substituted terdphenyiene-vinylene) dsl” ppl Pb Lest. 7H6)865-867 (1999) Tee, Chang-Lyoul eal, "Polym Phosphoresent Ligh-Emiting Devices Dope with Trs2-phenypyridine) leidium as a Triplet miter” ppl. Ph Lett, 7118): 2280-2282 (2000) ung. 8. al, "Anode Mesieaion in Organic Ligh-Emining Diodes by Low-frequency Plasma Polymerization of CHFy’4P0, Piys. Let, 78(5)673675 2001) Thal, Masinichi an Toit, Shizw, “Highly Elen Phosphores- ‘ence From Organic Light-Emiting Deviees witha Fxciton-Block Layer” Appl. Phys Lett, 792)156-58 (2001) Wang, Yt al, “Highly Eicon Elocuoluninesceat Materials Based on Flurialed Omzanomtallie Wiium Compounds” Appl Phys, Let, 744} 449.451 2001) Kovong, Raymond C. et al, “High Operations! Stailiy of Hletrophosphorescent Devices" Appl Phys. Leth, S1(1} 162-164 (e002, Holmes, Ru eta, “Bive Organic Festrophoaphorescence Using xothenie Hos-Guest Energy Transfer” pp. Phys Let 82(15}.2422-2424 009) Sotoyama, Wataru ca, “Efclnt Organic Liht-Emiting Diodes ‘with Phosphorescen Platinum Completes Containing NCN-Coord- ating Tidenate Ligand.” Appl Pips. Lett, 86153508. 1538053 (205, Okumoto, Kenji et al, “Green Florescent Organic Light Device with External Quaatum Efficiency of Nearly 10%" 4pp Phys. Lert $9.06 04-1 0635043 (2006) ‘Kanno, Hitoshi et al, “Highly Eien and Stable Red Phosphores- cat Organic. ight-Emiting Device Using isl2.0- tenzothiazoy phenoatofzne I) ashost material" App Phys Let 90:123809-1 12380032007) Aonuma Masikit "Matera Design of Hole Transport Materials Capable of Thick-Flm Formation in Onganie Light Emiting Diodes" ppl Pip. Ler, 90:183503-l183803-8 2007 ‘Sun, Viu and Forest, Stephen R., "High Eciency White Oxganic ight Emiting Devices with Thrce Separite Phorphorescent Ei sion Layers” Appt Pye Let 91:26350%+I — 2635033 (2007). Adachi Chaya “HighEficieney Red Flectrophosphoresence Devies” Appl. Ply. Lett, 7(11)!1622- 1624 2001) ‘Wong, Keith Man-Chung etl. “A Novel Clas of Phosphorescent Gold} Atk Based Organic Ligh-Emiting Devices with Tun able Colour” Chem. Commun, 2906-2908 (200). “Hamada, Yujeta.“High Luminance in OganicElestroluminescent Devices with Bis 10-hydroxsherzohauinolinaberyliam as an miter” Chem. Le, 998.906 (1993). Nishida Junichi et al, “Propsration, Charsterization, and HetohuninscenceCharacteriis of -Dlimine type Pai) ‘Complexes with Peforinated Phenyl Groups as Ligands" Chem Let, 344}592-593 (2005). ‘Mi, Bao-Xin eta, “Theomally Stable Hole‘Transporing Material for Organic Light-Emiting Dre: an Isoindle Deratve” Chem Mare 1516) 31483151 (2003), Huang) Weisheag ct al, “Highly Phosphoresceat Bis Cyeometlted riium Complexes Containing Benzoimidazol- Based Ligands" Cho: Mater 16(12)2480-2488 200), ‘iu, Yuen al," Hhly ficient Eectrophosphoresceat Devices ‘wth Saturated Rot Emission fom a Nettal Osmium Complex (Chem ater, 1113}3832-3836 (2008) Lo, Shit-Chn etal, "Blue Phosporescence from ium) Com- plexes at Room Temperature” Chem. Mater. 1821)SU19-S120 (Gone), ‘Takioaws, Shins etal Phosphorescent idm Complexes Based ‘on 2-Phenyimazo|1.3- pyridine Ligands: Tuning of Emision {Coortoward the ve Region and Application to Patynse Ligh. Eniting Deviews,” nary. Com. 46(10)4308-4319 2007), Lamas. Seige ot al, “Synthesis and Chataetrztion of Phos phorescent Cyslometalated Iridium Complexes” org Chem #00) 1708-1711 G01), ‘Ranjan. Suir eta, "Resizing Green Phosphoresceat Light-Emit- ting Materials fiom Rheniun Pyracoato Diimine Complexes” Inorg Chem. AX) 12481255 (200%). Noda, Tetstya and Shirta Yasuhiko, "S.8-Bis(dimesiybon)-22 bithiophene and 5.5-Bis(dinesigibort}-22-5.2"enhiophene 2 Novel Family of HectoaTeansporting Amoyphous Molecular Material". Am. Cher, Soe 120(37) 971439715 (1998). Sakamoto, Youiehi etal “Sjbess, Characterization and Eleton- “Transport PrperyofPerfhoriatedPhenylene Derimers.”J Chem Soe. 12208) 1832-1833 (200). ‘Adachi, Chihaya etal, “Nearly 100% Intra Phosphoreacence [Eieieney in an Organic Light Emiting Device” J App. Pps '99(10):5088:50S1 2001), ‘Shiro, Yasuhiko ca, "Staurst Molsculs Bas on 2-Eetron Systems as Mattias for Oxganic Flecuoluninescent Devices” Toumnal of Luminescence, 1149%8-991 (1997) US 8,722,205 B2 Page 3 66) References Cited OTHER PUBLICATIONS Inada, Hiroshi and Shiota, Yasuhiko, “15 $-tris- ipbenylanino)phen)Ibeazene and its Metiyleattiuied Dera livesas aNovel Clas of Amorphous Molecula Material” Maer Chem, 3)319-320 1993). ‘Kio, niet al,"1.24-Triazole Deivaveas an Hleton Tanspot Layer in Organic Electoluminescem Devices" Jon pt Ph SL91T.1920 0999. Van Siyks, S.A. et al, “Organi Hlectrluminesont Devices with proved Sabils.” Appl Phys Ler 69(18)2160-2162 (1996) Guo, TaingFang ota. “Highly Picea Flectrophosphorescent Polymer Lighting Devices” Organle Hletanis, Ul 2000), Palilis, Leonidas C, “High Eficiensy Molecular Organic Light Emiting Dns Basi on Sle Derivatives and Their Excplexes” Organi Ferries. 4113121 2003) ‘Wea Hisao etl "P-185-Low-Drive. Voltage OLEDs with Baler Layertfaving Molytleaum Oxide’ SID Symposium Digest, 37923 926 2006). 1. Osrphd ot al, “LangnuirBlodgot Light-Emiting Diodes of Poly@-enytiophene: Hectro-Optieal Charteris Related to Stroctne Shei Metals, 87171177 (1997). ‘Hu, Nan-Xing otal, “Novel High 1, Hole-Trnspomt Molecules Tiased on Infolo(3.2-barazoles for Organic Tight-Emiting Davies” Sythetie Metal, 11-112:421-424 (200), Satbeck, 1 et al, “Low Molecular Organic Gates for Blue Fletoluminesconc.” Shee Metals, 91:200-215 (1997) CMing etal, “Tuning the eaezy level and photophysical and losroluninescent properties of eat metal complexes by conto ling the ligation of the metal with he carbon ofthe earbazole uni “Ads Funct Mater. 2007.17, pp 65-861 §.Betington et ~Triesyctometlate rd (if) complexes of cavtncole (Uioresl) pyridine ligands synthesis redox and hotoplysical propertcn, ad electeophomhorescentLigh-eiing Minds”, Chem Bur 1 2007.13, pp- 23-143 IK. Zhang ota, “Improving the performance of phosphorescent polymer lightemiting odes usiag momphology-sable cabazole- thse iridium compleses”). Mater Chom. 2007. 7.pp. 3451-3460, ‘Tao eal, *Solution-processable highly ecient yeHlow-and ra ‘miting phosphorescent organic iat miting devices froma small ‘molectle ipearhostanfindiumeomplenes™1 Mater Chem. 208, 18 pp. 4001-4000. ‘The Search Repor and Writen Opinion corresponding othe PCT '$2010002613 application, (ded Jum 21,2010), * cited by examiner U.S. Patent May 13, 2014 Sheet 1 of 3 US 8,722,205 B2 160 185 —- 150 — 145 —-J 100 \ 164 140 ——| 135 —-J 130 ——+ | 120 — 115 — 110 FIGURE 4 162 U.S. Patent May 13, 2014 Sheet 2 of 3 US 8,722,205 B2 200 230 —— 225 — 220 —— 215 — 210 FIGURE 2 U.S. Patent May 13, 2014 Sheet 3 of 3 US 8,722,205 B2 Re MS fey ea - a aa 2 x? A A = Rt 2 FIGURE 3 US 8,722,205 B2 1 HETEROLEPTIC IRIDIUM COMPLEX This application claims priority t U.S. Provisional Appli= ‘ation No, 61/162,476, led Mar. 23, 2008, the disclosure of ‘which is herein expressly incomporated by reference in its entirety, “Theclaimed invention was madeby, onbehalof and ‘connection with one or more the following parties oa joint university corporation research agreement: Regents of the University of Michigan, Princeton University, Tae University ‘of Southern California, andl the Universal Display Compora tion. The agreement was in effect on and before the date the ‘laimed invention was made, and the claimed invention Was made as a result of activites undertaken within the seope of the agreement FIELD OF THE INVENTION The present invention relates to novel organic complexes that may be advantageously used in organic light emitting devices. More particularh novel heteroleptic iridium complexes containing a pyridyl «libeno-substituted ligindand devices containing these com- pounds. BACKGROUND Opto-clectroni devies that make use of onganie materials are hecoming inereasngly desirable fr numberof reasons. Many of the materials used to make such devices are rela- Lively inexpensive, so organic opto-elecirnie devices have the potential for cost advantages over inorganic device. In addition, the inherent properties of organic materials, such as their Hesibiliy, may make them well suited for pareular applications such as fabrication on a flexible substeate amples of organic opto-electronie deviees include organic light emiting devices (OLEDs), organi phototransistors, ‘organic photovoltaic ells, and organie photodetectors. For ‘OLEDs, the organic materials may have performance advan- tages over conventional materials. For example, the wave- length at which an onganic emissve layer emits light may enerlly be readily tuned with appropriate dopants. COLEDs makewuse of thin organic films that emitlight when voltages applied aeoss the device. OLEDs are becoming aa increasingly interesting technology for use in applications suel as flat panel display, illumination, and backlighting. Several OLED materials and configurations are described in US. Pat, Nos, 5,844,363, 603,238, and 5,707,745, which ‘are incorporated herein by reference in ther entirety. One application for phosphorescent emissive molecules is fall color display. Industry standards for such a display call, for pixels adapted to emit particular colors, referred to as “saturated colors. In particular, these standards call fo satu rated red, green, and blue pixels. Color may be measured using CIE coordinates, which are well known to the at (One exainple ofa green emissive molecule is tris(2-phe- raylpyridine) iridium, denoted Irfppy)y, which hus the srwe- the present invention relates 10» o In this, and late figures herein, we depict the dive bond ‘rom nitrogen to metal (hee, If) as straight Line As used herein, the team “organic” includes polymeric materials as well as small molecule organic materials that ray be used to fabricate organie opto-electronie devices. “Small molecule” refers to any onganic material that is no a polymer, and “simall molecules” may actually be quite large. ‘Small molseules may inelide repeat units in some circum- stances. For example, using a Jong chain alkyl group as & substimeat doesnot removeia molecule from thesmall mol- cule” class, Small molecules may also be incorporated into polymers, for example as a pendent group on a polymer backbone oras apart ofthe backbone. Small molecules may also serveas the core moiety of dendrimer, which consistsof ‘series of chemical shells built on the core moiety. The core moiety of a dendrimer may be a fuorescent or phosphores- cent small molecule emitter. dendrimer may be a "small molecule” and it i believed that all dendrimers curently ‘ued inthe field of OLEDs are small molectles. "As used herein, “top” meaas furthest aviay from the sub- strat, while “bottom” means closes othe substrate, Where fist ayers deseribed as"disposed over” second layer, the fist layers disposed further away from substrate. There may be other layers between the first andl second layer, unless itis specified thatthe first layer is “in contact with” the second layer. For example, a cathode may be described a “disposed ver" an anode, eventhough there are various organic layers inbetween, As used herein, “solution processile” means capable of being dissolved, dispersed or transported inand/r deposited ‘roma liguid medium, either in solution or suspeasion form. A ligand may be refered to as ‘photoactive” when itis ‘elieveutha the ligand directly combust the photoactive sroperties of an emissive material, figand may be refered to as “ancillary” when its believed thatthe ligand does not contribute othe photoactive properties of an emissive mate- ‘al, although an ancillary igand may alter the properties ofa photosctive ligand "As used herein, and at would be generally understood by ‘one skilled in the ar, a fist “Highest Occupied Molecular Orbital” (HOMO) or “Lowest. Unoceupied Molecular Orbital” (LUMO) enorgy level is “greater than” or “higher than” second) HOMO or LUMO energy level i he fist tenergy level is close to the vacuum energy level. Since fon- ‘vation potentials (1P) are measured as a neyative enemy relative to a vacuum level, a higher HOMO energy level corresponds to an IP having a smaller absolute value (an IP that is less negative). Similarly, a higher LUMO energy level comesponds (0 an electron alfinty (FA) having a smaller absolute value an thatis les negative). Ona conventional energy level diagram, with the vacuum level atthe to, the TLUMO energy level ofa material i higher than the HOMO energy level of the same material, A “higher” HOMO or TLLUMO energy level appears closer tothe top of such a dine ‘ram than a “lower” HOMO or LUMO energy level US 8,722,205 B2 3 As used herein, and as would be zenerlly understood by ‘one sill in ther, fist work fnetion is greater than” oF “higher than” second work function if the frst work fune- tion has higher absolute value, Because work functions are enerlly measured as neyative numbers relative to vacuum level, this means that higher” work function is more nega- tive, On a conventional energy level diagram, with the vacuum evel atthe op, a “higher” work function is ilustrated as furher away from the vacuum level in the downward ‘direction, Thus, the definitions of HOMO and LUMO energy Jevels follow a different convention than work functions. ‘More details on OLEDs, and the definitions described hove, can be found in US. Pat, No. 7.279.704, which is Incomporated herein by reference in its entirety. SUMMARY OF THE INVENTION [Novel phosphorescent emissive compounds are provided The compounds comprise heteroleptic iridium complexes having the font Re “The compound comprises ligand having the steuere X is solocted from the group consisting of NRO, S, BR, and Se. R is selected from hydrogen and alkyl, Preferably, R has 4 or fewer carbon atoms. Ry, Roy Ry. and Ry may represent ‘mono, di, te, or fetta substitutions Bach of Ryy Ry Ry. td Re are independently selected from the gvoup consisting of hydrogen, alkyl, and ary. Preterably,alkyls inthe RR, and/or R, positions of Formula Ihave four or fewer earbon ‘atoms (e, methyl, ely, propyl, butyl, and isobutyl), Pre ‘erably, R, and R, ar independently hydrogen oralky having, ‘our o fewer carbon atoms; more preferably, Ry and Ry are independently hydrogen or methyl Preterably, Re and Ry are independently hydrogen or alky! having four fewer earbon 0 o 4 atoms; more preferably, Ry and R, are independently hydro- zen or methyl: most preferably, Ry and R, are hydrogen. Preferably, R, and R, are independently hydrogen, alkyl having four or fewer carbon atoms or aryl with 6 or fewer ‘toms inthe ring; more preferably, R, and R, are indepen- ently hydrogen, methyl or phenyl Preferably, Rand Ry are ndependently hydrogen, alkyl having four or fewer carbon atoms or aryl with 6.0 fewer atoms in the ring; more prefer ably, Rad R, are independently hydrogen, methyl or phe- yl: most preferably, and R, are hydrogen. Inone aspect, compounds are provided wherein RR. Ry, and are independently selocte from the group consisting ‘of hydrogen and alkyl having four or fewer carbon atoms, In nother aspeet, compounds are provided wherein R,, RR ‘and R, are independently selected from the group consisting fof bydiagen and methyl. In yet another aspoct, compennds are provided wherein RR, Ry, and R, are hydrogen Inanother aspect, compounds are provided wherein RR. R,, and R, are independently selected from the group cou sisting of hydrogen, alkyl having four or fewer earbon atoms And aryl with 6 oF fewer atoms in the ring, Inanotber aspect, compounds are provided whercin Ry, R, Ry, and Ry are independently selected from the group consisting of hydro- ‘gen, methyl and phenyl In yet another aspect, compounds are provided wherein Ry. Ra, Ry, and R, are hydrogen. Particular hetoroletic iridium complexes are also pro- vided. In one aspect, heteroleptic iridium complexes are pro- vided having the formula eal a In another aspect, beter Vided having the formula iridium complexes are pro FORMULAIV In yot another aspect, heteroleptic iridium complexes are provided having the Form US 8,722,205 B2 = ~ 1 LI : ™ % ‘compound are provided wherein X is O Ge, pyridyl diben- zofuran), for example, Compounds 1-12. Additionally, het ‘eroleptic compounds are provided wherein X is 8 (ie. pyridyl dibenzothiophene), or example, Compounds 13-24 Moreover, oterleptic compounds are provided wierein Xis IR (ie. pyridyl carbazole), for example, Compounds 25-36. ‘Additional spocitie examples of heteroleptie iridium com- plexes are provided, including Compounds 37-108. In par- ‘cular, heteroleptic compounds are provided wherein X isO, Jor example, Compounds 37-60. Further, heteroleptic com. pounds are provided wherein X is, for example, Com- Pounds 61-84. Moreover, heteroleptic compounds are pro- vided wherein X is NR, for example, Compounds 85-108, ‘Additionally. an organic light emitting device is also pro- vided. The device has an anole, a cathode, and an organic layer disposed between the ade and the eathode, where the ‘organie layer comprises a compound having FORMULA T In particular, the onzanic layer of the deviee may comprise 2 ‘compound selected from Compounals 1-36. The organic layer may further comprise a host. Preferably, the host contains @ teiphenylene moiety and a dibenzothiophene moiety. More preferably, the host has the formu Ri, Rly R's Ry Ry and Ri may represent mono di, ri, oF tetra substitutions. RR’, Ry, Ry, Rly and R’y are indepen- ‘dently selected from the group consisting of hydrogen, alkyl, and aryl “The organic layer of the device may comprise a compound sleted fom the group consisting of Compounds 1-108, Ta particular, the organi layer ofthe device may also comprise ‘ compouind selected from Compounds 37-108, "A constmer product comprising a device is also provided. The device coatains an anode, a cathode, and an onzanie ayer 0 o 6 isposed between the anode and the cathode, where the ‘ganic Layer further comprises a compound having FOR- MULALL BRIEF DESCRIPTION OP THE DRAWINGS. FIG. 1 shows an onganie light emitting deview. FIG. 2 shows an inverted organic light emitting device tht does ot have a separate electron transport layer, FIG. 3 shows a heteroleptic iridium complex DETAILED DESCRIPTION Generally, an OLED comprises atleast one organic layer sisposed between and eletrically connected to an anode and ‘cathode. When a curent is applied, the anode injeets holes And the cathode injects electrons into the organic layer(s). The injected holes and electrons each migrate toward the oppo- sitely charged electrode. When an electron and hoe localize fon the same molecule, an “exciton.” which is a localized tlectronrhole pai having an excited energy state, i formed. Light is emited when the exciton relaxes viaa photoemissive ‘mechanism. Insome cases, theexciton may belocalized on an excimer or an exciplex. Non-radiative mechanisms, such as ‘thermal relaxation, may aso aceur, but are generally consid- cred undesirable, ‘The intial OLEDs used emisive molecules that emitted light from ther singlet states (“uorescence”) as disclosed, for example, in US. Pat. No. 4,769,292, which is incorpo” rated by melerence in its entirety. Fluorescent emission gen- cmlly occurs in atime frame of less than 10 nanoseconds ‘More recently, OLEDs having emissive materials that emit light from triplet sates ( phosphorescence”) have been dem- cnstrated. Baldo et al, “Highly Bificient Phosphoresce Emission from Organic Electroluminescent "Devices, Nature, vol.395, 151-154, 1998; (‘Baldo-I”) and Baldo etal. “Nery high-effcieney green omganic light-emitting devices based on electrophosphorescence," App. Phys. Let, vol. 75, No. 3, 46 (1999) (*Baldo-I"), which are incorporated by reference in their entireties, Phosphorescence is described in ‘mone detail in US. Pat. No. 7.279.704 at cols. $6, which are incorporated by reference FIG. 1 shows an omganic light emitting device 100, The figures are not necessarily drawn to seale. Device 100 may include a substrate 110, an anode 113, a hole injection layer 120, a hole transport layer 128, an electron blocking layer 130, an emissive layer 138, « hole blocking layer 140, an electron transport layer 148, an electron injection layer 180, 3 protective layer 188, and 2 cathode 160. Cathode 160 is 2 ‘compound eathode having a frst conductive layer 162 and 2 second conductive layer 164. Device 100 may be fabricated bby depositing the layers described, in onder. The properties tnd funetions of these various layers, as well as example ‘materials are described in more dota in US. Pat. No. 7,279, “os at cols. 610, which ae incorporated by reference ‘More examples for each of these layers are avilable. For ‘example, a flexible and transparent substrate-anode combi- nation js disclosedin U.S. Pat. No. 5,844,363, whic is incor porated by eferenceinits entirety. An example ofa p-doped hole transport layer is m-MIDATA doped with Fsub- TCNQ at a molar ratio of 50:1, as disclosed in U.S, Patent Application Publication No, 2003810230980, which is ineor- porated by reference in its entirety. Examples of emissive and host materials are disclosed in U.S. Pat. No. 6,303,238 10 ‘Thompson eta, which is incorporated by reference in its ctirety. An example of an n-dopesl elect transport layer is [BPhen doped with Liat a molar rato of I: a disclosed US 8,722,205 B2 1 US. Patent Application Publication No, 20030230980, which is incomporated by reference in its entirety. U.S. Pat. Nos, 5,703,436 and 5,707,745, which are incorporated by reference in their entities, disclose examples of eathodes ‘including compound cathodes having a thin layee of metal such as Mg:Ag with an overlying transparent, elctially- ‘conductive, sputte-deposited ITO layer. The theory and use ‘of blocking layers described in more detail in U.S. Pat. No. 6097. 147 and US. Patent Application Publication No. 2008) (0230980, which are incorporated by reference in their enti ties, Examples of injection layers are provided in US, Patent Application Publication No, 20040174116, which is incor- porated by reference inits etre. A description of protective layers may be found in U.S, Patent Application Publication No, 200410174116, which is incorporated by reference in its entirety, FIG. 2 shows an inverted OLED 200. The device includes a substrate 210, a cathode 218, an emissve layer 220, a hole transport layer 225, and an anode 230. Device 200 may be Tabrcated by depositing the layers described, in onder [Because the most common OLED configuration has a cath- ‘xe disposed over the anode, and device 200 has cathode 215, disposed under anode 230, device 200 may be relerred 10 a5 ‘an “inverted” OLED, Materials similar to those described ‘with respect to deviee 100 may be used inthe eomesponding layers of device 200. FIG. 2 provides one example of how some layers may be omitted from the structure of device 100. ‘The simple layered structure ilustrated in FIGS. Land is provided by way of non-limiting example, and itis under ‘ood that embodiments of the iavention may be used ia ‘connection with a wide vatiety of other strictures. The spe= tif materials and structures deseribed are exemplary in nature and other materials and structures may beused Fun tional OLEDs may be achieved by combining the various layers described in different ways, or layers may be omitted ‘entirely, based on design, perfomance, and cost factors ‘Other layers not specifically described may also be included Materials other than those specifically described may be used. Although many of the extmples provided herein describe various layers as comprising a single materia, itis under- stood that combinations of materials, such as a mixture of host and dopant, or more generally mixture, may be used. Also the ayers may have various sublayers. The names given (o the various layers herein are not intended to be steitly Timiting, For example, in device 200, hole transport layer 225 transports holes and injects holes into emissive layer 220, and may be described as.a hole ranspo layer or a hole injection layer. In one embodimeat, an OLED may bo described as havingan “organic layer” disposed between cathode and un node. This ganic layer may comprisea single layer, or may Turk comprise multiple layers of different organic materi als as described, for example, with respect o FIGS. Land 2 ‘Sirictures and materials not specifically described may also be used, such as OLEDs comprised of polymeric mate- rials (PLEDs) suchas disclosed in US. Pat. No. 5.247.190 10 Friend etal which is incorporatedby reference ints entirety. By way of further example, OLEDs having a single organic Jayer may be used. OLEDs may be stacked, for example as described in U.S, Pat, No, 5,707,745 o Forrest etal, which is ‘ncomporated by reference in it entirety. The OLED structure may deviate {rom the simple layered strcture illustrated in FIGS. 1 and 2, For example, the substrate may inelde an angled reflective suriee © improve out-coupling, such as a mesa structure as described in US. Pat. No. 6,091,195 to Forrest et al. andor a pt structure as described in US, Pat. No, 5.834.803 to Bulovie et al, which are incomporated by reference in thee entireties, 0 o 8 ‘Unless otherwise specified, any ofthe layers ofthe various embodiments may be deposited by any suitable metho. For the onznie layers, preferred methods include thermal evapo ration ink-jet, such as described in US. Pat. Nos. 6,013,982 and 6,087,196, which are incorporsted by reference in their entireties, organic vapor phase deposition (OVPD), such as described in US. Pat. No. 6,337,102 to Forrest etal, which is incorporated by reference in its entirety, and deposition by ‘organic vapor jet printing (OVP), such as described in US. patent application Ser. No, 10/233,470, now USS. Pat. No. 7,431,968, which is incomporated by relerence in is entity. Other suitable deposition methods include spin coating and cer solution based processes. Solution based processes are preferably carried out in nitrogen or an inet atmosphere. For the other layers, prefered methods include thermal evapor- ‘ion. Preferred patterning methods include deposition through a mask, cold welding such as described in U.S. Pt. Nos. 6,294,398 and 6,468,819, which are incorporated by reference in ther entireties, and patering associated with some ofthe deposition methods such as ink jet and OVID, Other methods may also be used. The mateils to be depos- ited may be modified to make them compatible with a par- ticular deposition method, For example, substituents sch as and aryl groups, branched or unbranched, and prefer- fhly containing at least 3 carbons, may he used in small ‘molecules to enhance their ability to undergo solution pro- cessing, Substituents having 20carbons ormore may be used, and 3-20 carbons isa preferred range. Materials with asym metre structures may have better solution processbiity than those having symmetric structures, because asymmetic materials may bave a lower tendency to reerystllize. Den- Grimer substituents may be used to enhance the ability of small molecules to undergo solution processing Devices fabricated in accordance with embodiments ofthe ‘invention may be incorporated into a wide variety of con- sumer products, inchuding flat panel displays, computer ‘monitors televisions, billboard, lights forinterioror exterior illumination andor signaling, heads up displays, fully trans- parent displays, flexible displays, laser printers, telephones, cel phones, personal digital assistants (PDAS), laptap com- puters, digital cameras, camcorders, viewfinders, micro“ plays, vehicles lane area wall, theater or stadium sereen, oF 4 siga, Various contol mechanisms may be used 9 control ‘devices fabricated in accordance withthe present inveation, ‘including passive matrix and active matrix. Many of the devices are intended for use in a temperature range comfort- able to humans, sue 3s 18 degrees C19 30 degrees C., and more preferably at room temperature (20-25 degrees C). ‘The materials and structures deseribod herein may have applications in devices other than OLEDS, For example, other ‘optoelectronie devices such as organic soar cells and organic photodetectors may employ the amatrials and structures More generily, onznie devies, such as onzanie transistors, ‘may employ the materials and structures ‘The terms halo, halogen, alkyl, eyeloalky, alkenyl, alky- yl, arylkyl, heteroeyelic group, aryl, aromatic group, and Ibeteroaryl are known to the art, and are defined in U.S. Pat. No. 7.299,704 at cols. 31-32, which are ineomporated herein by reference [Novel compounds are provided, the eompounds compris ing @heteroleptic iridium complex (lustrated in FIG. 3). In particular, the complex has two phenylpyridine ligands and ‘one ligand having te structure US 8,722,205 B2 ‘The ligand having the structure FORMULA II consists ofa pyridine joined to a dibenzofuran, dibenzothiophene, carha- ole, dibeazaborole, or dibenzosclenophene (herein also referred to as “pyridyl dibenzo-substiuted”). These com- pounds may be advantageously used in organic ight emitting ‘devices as an emiting dopant in an emissive layer Tidinm complexes containing two or three pyridyl diben- zofuran, dibenzothiophene, carbazole, and fluorene ligands have been reported. By replacing the phenyl group in teis(2- pheaylpyridineridium with dibenzofuran, —_diben- zothiophene, carbazole, and Auorene groups, the HOMO- LUMO eneray levels, photophysical properties, and ‘electronic properies of the resulting complex ean be signfi- ‘cantly aeeted. A variety of emission color, ranging rom laeen to red, have hoon achieved by sing complexes with ‘different combinations of pyridyl diben7o-substituted ligands (Ge, bis and tis complexes). However, the existing com- plexes may have practical limitations. For example, iidivm ‘Complexes having two or tee ofthese types of ligands (e. pyridyl dibenzofuran, dibenzothiophene, or earbazole) have high molecular weights, which offen results ina high subli- ‘mation temperature, In some instances, these complexes can become non-mblimable due to the increased molecular ‘weight, For example, tris(2-(dibenzo[b.djuran-4-yl)pyei- dine)Iridium(l}) decomposed during sublimation attempts Additionally, known compounds comprising a pyridy! fhio- ‘enc ligand may have reduced stability. Fhuorenc groups. ‘C=O and CRR) dissupt conjugation within the ligand ste ture resulting in a diminished ability to stabilize electrons ‘Therefore, compounds with the beneficial properties of pyridyl dibenzo-substinted ligands (eg. dibenzofuran ‘libenzothiophene,carbazole dibencoborole, and dibenzose~ Jenophene) and a relatively low sublimation temperature are desirable, Additionally iridium complexes having two or tree the Jigands having FORMULA II have high molecular weights ‘and stonger intermolecular intervetions, which often results jn high sublimation temperature. In some instances, these ‘complexes can become non-sublimable due othe increased ‘molecular weight and sttong intermolecular interactions. ‘Novel heterleptc iridium complexes are provided herein, The complexes contain pyridyl dibenzo-substituted ligands having the structure FORMULA I. In particular, the novel heteroleptie complexes include single pyridyl dibenzo-sub- stituted ligand wherein the ligand contains O, S, N, Se, or B (is. the ligand is pyridyl dibenzofuran, pyridyl diben- zothiophene, pyridyl earbazole, pyridyl dibenzoselenophene, ibenzoborole)and two phenylpyrdine ligands. As ‘aresultof the particular combination of ligands i the hetero leptic compotnds disclosed herein, these compounds can provide both improved photochemical and electrical proper- 0 o 10 ties a5 well as improved device manufeeturing. li by containing only one of the dibenzo-substiuted pyridine ligands having FORMULA the complexes provided herein will likely have lower sublimation temperatures (correlated With educed molecular weight and/or weaker intermolecular interactions) Additionally, these compounds maintain all of the benefits associated with the pyridyl dibenzo-substtuted Jigand, suchas improved stability eflcieney, and narrow line width, Therefore, these compounds may be used to provide rover organic light emiting devices and improved com- mercial products comprising sueh devices. In particular, these ‘compounds may be particularly useful in ed and green phos- phorescent organic light emitting devices (PHOLEDs). ‘As mealioned previously, bis oF tris iridium complexes containing ligands having FORMULA Il may be limited ia practical use due tothe high sublimation temperature ofthe Complex. The invention compounds, however, havea lower sublinsation temperature which eaa improve device manufac turing. Table I provides the sublimation temperature for sev- eral compounds provided herein ad th corresponding bis oF ‘eis complex. For example, Compound 1 has a sublimation temperature of 243° C, while the corresponding tris complex {ails to sublime, Adaitionally, ther tris complexes eompris- ing three pyridyl dibenzo-substinned ligands (i.e, tis com- plex comprising pyridyl dibenzmthiophene) fil sublime Therefore, the compounds provided herein may allow for improved device manufacturing ae compared to previowsly reported bis and tris compounds. TABLE iT AY F h ~ ofp a US 8,722,205 B2 13 TABLE Lcontinved Compaants vey ompoind 37 Generally, the dibenz-substituted pyridine ligand would be expected to have lower triplet energy than the pheaylpyri- ‘ine ligand, and consequently the dibenzo-substituted pyri dine ligand would be expected to control the emission prop- ‘erties of the compound. Therefore, moxifiestions 10 the ibenzo-substituted pyridine ligand may be used to tune the ‘emission properties of the compound. The compounds dis ‘closed herein contain dibenao-substituted pyridine ligand containing a heteroatom (e.., O, S, or NR) and optionally, Jurter substituted by chemical groups al the R, and R, posie tions. Thus, the emission properties ofthe compoundsmay be tuned by selection of a particular heteroatom and/or varying the substituents present on the dibenzo-substituted pyridine Tigand The compounds described herein comprise heteroleptic iridium complexes having the formule a, Features ofthe compounds having FORMULA 1 inelude ‘comprising one ligand having the streture [ as 0 FORMULA and two phenylpyridine ligands that may have further subst ‘ution, wherein all igands are coordinated to Te X is selected from the group consisting of NR, O, 8, BR, and Se. Ris selected from hydrogen and alkyl R,-R,,Ry and Ray represent mono, dit, tetrasubsittions;and each of R,. Ry, Ry and Ry are independently selected fom the ‘up consisting of hydrogen, alkyl having four or fewer farbon atoms, ad aryl In another aspect, R,, Roy Ry and Ry are independently selected fom the group consisting oFhydropen,alky] having our or fewer carbon atoms, and aryl with 60 fewer atoms in the ring "The term “aryl” as used herein refers ton aryl comprising cither earbon atoms or heteroatoms, that is not fused to the phenyl ving ofthe phenylpyridine ligand (Le. aryl is a non- {used aryl). The term “ary?” as used herein contemplates single-ring groups and polycyclic ring systems. The palyey~ lie ings may have two or more rings in which two earboas fare common by two adjoining rings (the rings are “used” wherein a Jeast one ofthe rings is aromatic, eg, the other rings can be cycloalkyl, eycloalkenyls, ary, heterocycles andor heteroaryls. Additionally, the aryl group may be ‘optionally substituted with one or more subsitents selected {rom halo, CN, COR, C(O)R, NR, eyelie-amino, NO,, and (OR. “Ary” also escompasses a heteroaryl, such as single- ring heteroaromatic groups that may inclode from one to thre heteroatoms, for example, pyrrole, fares, thiophene, imidazole, oxazole, thiazole, wizole, pyrazole, pyridine, pyraine and pyrimidine, aol the like, This includes polyey” clic hetero-aromatic systems having two or more rings in ‘hich two atoms are common to tWo adjoining rings (the rings are “fused”) wherein atleast one ofthe rings i a het- ceroaryl, et, the other rings ean be eyeloalkyls, eyeloalk- enyls, ary, heterocycles andor heteroaryl. Additionally, the Ibeeroary! group may be optionally substituied with one or ‘more substituents selected from halo, CN, COR, COR, NR, eyelicamino, NO. and OR. For example, Ry. Re. Ry andlor R, may be an aryl neluding an heteroaryl, that isnot used tothe phenyl ring of the phenylpyridine. “The tem “ally” as used herein contemplates both stright ‘nd branched chain alkyl radicals. Examples include methyl ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, and the like. Additionally, the alky! group may be optionally subst tuted with one oF more substituents selected from halo, CN, CO,R, C(O}R, NR,, eyelie-amino, NO,, and OR, wherein cach Ris independently solectod from H, alkyl, allen, alky- yl aralkyl, ary and heteroaryl. Preferably, in order io make the compounds sublimable andlor to reduce sublimation tem- perature, alkyl inthe R,.R,,., andor Ry positions of For ‘la [have four or fewer carbon atoms (eg. methyl, eth, propyl, butyl, and isobutyl) US 8,722,205 B2 15, In general, the compounds provided herein have relatively low tublimation temperatures “compared to. previously reported compounds, Thus, these novel compounds provide improved device fabrication among other beneficial proper ties, Moreover, itis believed that heteroleptic eomponnds having FORMULA I wherein RR, Ry and R, are sclected from smaller substituents may be particularly beneficial. A smaller substituents includes, fr example. hydogen orally. In particular, itis believed that compounds wherein the sub- stituents R,,B,, Ry and/or Ry are selected from smaller sub- ‘iments may have even lower sublimation temperatures thereby further improving manufacturing while maintaining the desirable properties (eg. improved stability and fite- times) provided by the ligand having the structure FOR- MULAIIL Generally the compounds provided having FORMULA 1 have substituents sue that Ry, Ro, Ry and Ry are indepen- ‘dently selected from the group consisting of hydrogen. alkyl and ary] Preferably any alky has fourar fewerearbon atoms. “To minimize molecular weight and thereby lower the subli ‘mation temperature, compounds having smaller substituents ‘on the ligand having the structure FORMULA Tl are pre= ‘ered, Preferably. Rand Rare independently selected rom the group consisting of hydrogen and alkyl having four or ewer carbon atoms; more preferably, Rand Rare indepen- ‘dently seleeted from the group consisting of ydrogen and methyl For similar reasons, compounds are preferred having smaller substituents present on the phenyipyridine ligang. Additionally, the phenylpyridine ligand is believed to con- trite less to the emission of the complex. Moreover, the ‘complex contains two ofthe phenylpyriine igand, thus sub- Stituents present on the phenyipyriine ligand contribute ‘more tothe overall molectlar weight ofthe complex, For at least these reasons, preferably R, and Ry are independently selected rom hydrogen andalkyThaving four or fewer earbon atoms more preferably Rand Rare independently solected from hydrogen and methy; most preferably, Rp andl Ry are hydrogen. ‘Compounels having alkyl and aryl substitutions that ean ‘decrease intermolecular interactions age also preferred. In another aspect, preferably R, and R, are independently selected from hydrogen, alky] having four or fewer carbon ‘atoms and aryl with 6 or fewer atoms in the ring: more preferably, R, and R,areinxdependently selected fom hydro- gen, methylandphenyl;most preferably, Rand Ry arehydro- en, ‘Compouncls are prefered wherein the overall molecolae weight of the comple is low to reduce the sublimation tem- perature and improve device manufacturing. Toward this end, ‘compounds wherein all substitute are relatively stall are prefered. In one aspect, prelerably Ry, Ra Ry and R, are independently selected from the group consisting of hydro- ‘gen and alkyl having four or fewer earbon atoms: more pref- ‘erably, RR, Ry and Ry are independently selected from the ‘group consisting of hydrogen and methyl; most preferably, R,.Ry,R, and R, are hydrogen. ‘in another aspect, preferably Ry, Re, Rs and Ry ae inde= pendently selected from the group consisting of hydrogen, alkyl having four or fewer carbon atoms and ary with 6 of eweralomsin hering: more preferably, R,,Ro.RyandR, are independently selected from the group consisting of hytro- gen, methyl and phenyl; most preferably, Ry, RyRy and Ry are hydrogen. As diseussed above, X can also be BR. Preferably, Ras 4 ‘oF fewer carbon atoms, For similar reasons as those previ- ‘uly discussed, smaller alkyl groups (i. alkyl having 4 oF 0 o 16 {ewer carbon atoms) on the carbazole portion of the subst ‘ted ligand will ike loser the sublimation temperature of the complex and thus improve device manufacturing Particular heteroleptic iridium complexes are also peo- vided. In one aspect, heteoleptic iridium complexes are pro- vided having the formal: In another aspect, heteolepic iridium complexes ate pro vided having the formula oor In yet another aspect, heteroleptic iridium complexes are provided having the forms R Specific examples of heterolepte iridium compleves are provided, snd include compounds selected from the group consisting of scontinved scontinved US 8,722,205 B2 Additional specific examples of heteroleptic iridium com- as Plexes a sd, and include compounds selected from the group consisting of Compouu 37 scontinved conpount 50

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