THATTHE TOUT UNTUK USU 20180134954A1ROMAW ATU TO NIKALI HINTHI ( 19) United States (12 ) Patent Application Publication ( 10) Pub . No. : US 2018 /0134954 A1 TSAI et al. (43 ) Pub . Date : May 17 , 2018 (54 ) ORGANIC ELECTROLUMINESCENT Related U . S . Application Data MATERIALS AND DEVICES (63 ) Continuation - in -part of application No. 15 /407 ,337 , (71 ) Applicant: Universal Display Corporation , filed on Jan . 17 , 2017 . Ewing , NJ (US ) (60 ) Provisional application No .62 / 293 ,100 , filed on Feb . 9 , 2016 , provisional application No. 62 / 338 ,616 , filed (72 ) Inventors : Jui- Yi TSAI, Newtown, PA (US ) ; on May 19, 2016 . Chuanjun XIA , Lawrenceville , NJ (US ) ; Chun LIN , Yardley, PA (US ) ; Publication Classification Adrian U . PALACIOS , Zaragoza (ES ) ; (51 ) Int. CI. Enrique OÑATE , Zaragoza (ES ); CO9K 11 /06 (2006 .01 ) Miguel A . Esteruelas , Zaragoza (ES ) ; CO7F 15 / 00 ( 2006 . 01 ) Pierre -Luc T. BOUDREAULT, HOIL 51/ 00 (2006 .01 ) Pennington , NJ (US ); Sonia BAJO , 2 ) U . S . CI. Zaragoza (ES ) ; Montserrat OLIVÁN , CPC .. . C09K 11 /06 ( 2013 . 01 ) ; HOIL 51 /5016 Zaragoza (ES ) (2013 . 01 ); HOIL 51/ 0085 ( 2013 .01 ); CO7F ( 73 ) Assignee : Universal Display Corporation , 15/ 0033 (2013 . 01 ) Ewing , NJ (US ) (57 ) ABSTRACT Novel Iridium complexes having three different bidentate (21 ) Appl. No .: 15 /866 , 561 ligands useful for phosphorescent emitters in OLEDs are disclosed . At least one of the three different bidentate ligands (22 ) Filed : Jan . 10 , 2018 is a carbene ligand .
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ORGANIC ELECTROLUMINESCENT MATERIALS AND DEVICES CROSS -REFERENCE TO RELATED APPLICATIONS [ 0001 ] This application is a continuation - in - part applica tion of U . S . patent application Ser. No . 15 / 407, 337 , filed Jan . 17 , 2017 , which claims priority under 35 U . S . C . $ 119 ( e ) ( 1 ) from U . S . Provisional Application Ser . No . 62 /293 , 100 , filed Feb . 9 , 2016 , and U . S . Provisional Application Ser. No . [ 0007 ] In this , and later figures herein , we depict the dative 62 /338 ,616 , filed May 19 , 2016 , the entire contents of which bond from nitrogen to metal (here , Ir ) as a straight line . are incorporated herein by reference . [0008 ] As used herein , the term " organic ” includes poly meric materials as well as small molecule organic materials FIELD that may be used to fabricate organic opto - electronic devices. “ Small molecule ” refers to any organic material that [ 0002 ] The present invention relates to compounds for use is not a polymer, and “ small molecules ” may actually be as phosphorescent emitters , and devices , such as organic quite large . Small molecules may include repeat units in light emitting diodes, including the same. some circumstances . For example , using a long chain alkyl group as a substituent does not remove a molecule from the " small molecule” class . Small molecules may also be incor BACKGROUND porated into polymers , for example as a pendent group on a polymer backbone or as a part of the backbone . Small [ 0003] Opto -electronic devices that make use of organic molecules may also serve as the core moiety of a dendrimer, materials are becoming increasingly desirable for a number which consists of a series of chemical shells built on the core of reasons .Many of the materials used to make such devices moiety . The core moiety of a dendrimer may be a fluorescent are relatively inexpensive , so organic opto - electronic or phosphorescent small molecule emitter. A dendrimer may devices have the potential for cost advantages over inorganic be a “ small molecule, " and it is believed that all dendrimers devices. In addition , the inherent properties of organic currently used in the field of OLEDs are small molecules . materials , such as their flexibility , may make them well [0009 ] As used herein , “ top ” means furthest away from suited for particular applications such as fabrication on a the substrate , while “ bottom ” means closest to the substrate. flexible substrate . Examples of organic opto - electronic Where a first layer is described as “ disposed over” a second devices include organic light emitting diodes/ devices layer, the first layer is disposed further away from substrate . (OLEDs ) , organic phototransistors , organic photovoltaic There may be other layers between the first and second layer, cells , and organic photodetectors . For OLEDs, the organic unless it is specified that the first layer is “ in contact with " materials may have performance advantages over conven the second layer . For example , a cathode may be described tional materials. For example, the wavelength at which an as “ disposed over ” an anode, even though there are various organic emissive layer emits light may generally be readily organic layers in between . tuned with appropriate dopants . [0010 ] As used herein , “ solution processible ” means [ 0004 ] OLEDs make use of thin organic films that emit capable of being dissolved , dispersed , or transported in light when voltage is applied across the device . OLEDs are and /or deposited from a liquid medium , either in solution or becoming an increasingly interesting technology for use in suspension form . applications such as flat panel displays , illumination , and [0011 ] A ligand may be referred to as “ photoactive ” when backlighting . Several OLED materials and configurations it is believed that the ligand directly contributes to the are described in U . S . Pat . Nos . 5 , 844 , 363 , 6 ,303 ,238 , and photoactive properties of an emissive material. A ligand may 5 ,707 ,745 , which are incorporated herein by reference in be referred to as “ ancillary ” when it is believed that the their entirety. ligand does not contribute to the photoactive properties of an emissive material, although an ancillary ligand may alter the [0005 ] One application for phosphorescent emissive mol properties of a photoactive ligand . ecules is a full color display . Industry standards for such a [0012 ] As used herein , and as would be generally under display call for pixels adapted to emit particular colors , stood by one skilled in the art, a first “ Highest Occupied referred to as “ saturated ” colors . In particular, these stan Molecular Orbital ” (HOMO ) or “ Lowest Unoccupied dards call for saturated red , green , and blue pixels . Alterna Molecular Orbital” ( LUMO ) energy level is “ greater than ” tively the OLED can be designed to emit white light . In or “ higher than ” a second HOMO or LUMO energy level if conventional liquid crystal displays emission from a white the first energy level is closer to the vacuum energy level. backlight is filtered using absorption filters to produce red , Since ionization potentials ( IP ) are measured as a negative green and blue emission . The same technique can also be energy relative to a vacuum level , a higher HOMO energy used with OLEDs. The white OLED can be either a single level corresponds to an IP having a smaller absolute value EML device or a stack structure . Color may be measured (an IP that is less negative ). Similarly , a higher LUMO using CIE coordinates , which are well known to the art . energy level corresponds to an electron affinity (EA ) having [ 0006 ] One example of a green emissive molecule is a smaller absolute value (an EA that is less negative ) . On a tris ( 2 - phenylpyridine ) iridium , denoted Ir (ppy ) 3 , which has conventional energy level diagram , with the vacuum level at the following structure : the top , the LUMO energy level of a material is higher than US 2018 /0134954 A1 May 17 , 2018 the HOMO energy level of the same material . A " higher ” and the ligand Lc is HOMO or LUMO energy level appears closer to the top of such a diagram than a “ lower ” HOMO or LUMO energy level. RY [0013 ] As used herein , and as would be generally under stood by one skilled in the art , a first work function is " greater than ” or “ higher than ” a second work function if the first work function has a higher absolute value . Because work functions are generally measured as negative numbers relative to vacuum level, this means that a “ higher” work function is more negative . On a conventional energy level wherein M is a metal having an atomic number greater than diagram , with the vacuum level at the top , a “ higher ” work 40 ; wherein x is 0 , 1 , or 2 ; wherein y is 1 , 2 , or 3 ; wherein function is illustrated as further away from the vacuum level z is 0 , 1 , or 2 ; wherein x + y + z is the oxidation state of the in the downward direction . Thus , the definitions of HOMO metal M ; wherein L , is different from L , and when x , y, or and LUMO energy levels follow a different convention than z is larger than 1 , each plurality of L?, LB , or Lc are also work functions . different ; wherein rings A , B , C , and D are each indepen [0014 ] More details on OLEDs, and the definitions dently a 5 or 6 -membered carbocyclic or heterocyclic ring ; described above , can be found in U .S . Pat. No . 7 ,279 ,704 , wherein R4, RB , RC, and RD each independently represent which is incorporated herein by reference in its entirety . mono substitution up to the maximum possible number of substitutions, or no substitution ; wherein Z ' and Z are each independently selected from the group consisting of carbon SUMMARY or nitrogen ; wherein C ) is an anionic donor carbon atom , C2 [0015 ] Disclosed herein are Iridium complexes compris is a neutral carbene carbon atom ; wherein each of R4, RP , ing three different bidenate ligands, wherein at least one of RC, R , R , R ' , and R2 are independently selected from the them is a carbene ligand . They are useful compounds for group consisting of hydrogen , deuterium , halide, alkyl, phosphorescent emitters . The inventors believe that incor cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy , amino , porating three different bidenate ligands to Ir ( III ) metal to silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, form a heterlopetic complex with three different bidenate heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile , ligands would be benefial for OLED performance . For isonitrile , sulfanyl, sulfinyl, sulfonyl , phosphino , and com example , the thermal properties, electrochemical properties , binations thereof; and wherein any adjacent substitutents are and photophysical properties of the complex can be tuned by optionally joined or fused into a ring. selecting three proper ligands . It offers more flexibility for [0017 ] According to another aspect, an OLED is disclosed materials design than three identical ligands. wherein the OLED comprises: an anode ; a cathode ; and an [ 0016 ] According to an aspect of the present disclosure , a organic layer, disposed between the anode and the cathode , compound having a formula M ( L X ) x (LB ) , (LC ) , is disclosed , comprising A compound having a formula M ( L ) (LB ) , (LC ) wherein the ligand LA is wherein the ligand L4 is
R21
z . 4
ROB Rot B the ligand LB is the ligand LB is
CH. . . Poto US 2018 /0134954 A1 May 17 , 2018 and the ligand Lc is incorporated by reference in its entirety . Fluorescent emis sion generally occurs in a time frame of less than 10 nanoseconds. [0027 ] More recently , OLEDs having emissive materials that emit light from triplet states ( phosphorescence” ) have 0- - been demonstrated . Baldo et al . , “ Highly Efficient Phospho R ! rescent Emission from Organic Electroluminescent - - - - Devices, ” Nature , vol. 395 , 151 - 154 , 1998 ; ( “ Baldo - I” ) and Baldo et al. , “ Very high - efficiency green organic light emitting devices based on electrophosphorescence , ” Appl. Phys . Lett. , vol. 75 , No . 3 , 4 - 6 ( 1999 ) (“ Baldo - II ” ), are wherein M is a metal having an atomic number greater than incorporated by reference in their entireties . Phosphores 40 ; wherein x is 0 , 1 , or 2 ; wherein y is 1 , 2 , or 3 ; wherein cence is described in more detail in U . S . Pat. No . 7 ,279 ,704 z is 0 , 1 , or 2 ; wherein x + y + z is the oxidation state of the at cols . 5 - 6 , which are incorporated by reference . metal M ; wherein L , is different from LR, and when x , y , or [0028 ] FIG . 1 shows an organic light emitting device 100 . z is larger than 1 , each plurality of LA , LB , or Lc are also The figures are not necessarily drawn to scale . Device 100 different; wherein rings A , B , C , and D are each indepen may include a substrate 110 , an anode 115 , a hole injection dently a 5 or 6 -membered carbocyclic or heterocyclic ring ; layer 120 , a hole transport layer 125 , an electron blocking wherein R4 , RB , RC, and RD each independently represent layer 130 , an emissive layer 135 , a hole blocking layer 140 , mono substitution up to the maximum possible number of an electron transport layer 145 , an electron injection layer substitutions , or no substitution ; wherein Z ' and Z are each 150 , a protective layer 155 , a cathode 160 , and a barrier layer independently selected from the group consisting of carbon 170 . Cathode 160 is a compound cathode having a first or nitrogen ; wherein C is an anionic donor carbon atom , C2 conductive layer 162 and a second conductive layer 164 . is a neutral carbene carbon atom ; wherein each of R4, RP , Device 100 may be fabricated by depositing the layers RC, RP, RY , RY, and R2 are independently selected from the described , in order. The properties and functions of these group consisting of hydrogen , deuterium , halide , alkyl, various layers, as well as example materials , are described in cycloalkyl, heteroalkyl, arylalkyl, alkoxy , aryloxy , amino , more detail in U . S . Pat . No. 7 , 279 , 704 at cols . 6 - 10 , which silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, are incorporated by reference . heteroaryl, acyl, carbonyl, carboxylic acids, ester, nitrile , [0029 ] More examples for each of these layers are avail isonitrile , sulfanyl, sulfinyl , sulfonyl, phosphino , and com able . For example , a flexible and transparent substrate - anode binations thereof; and wherein any adjacent substitutents are combination is disclosed in U . S . Pat. No . 5 , 844 , 363 , which optionally joined or fused into a ring . is incorporated by reference in its entirety. An example of a p - doped hole transport layer is m -MTDATA doped with BRIEF DESCRIPTION OF THE DRAWINGS FX - TCNQ at a molar ratio of 50 : 1 , as disclosed in U . S . Patent [0018 ] FIG . 1 shows an organic light emitting device . Application Publication No . 2003 /0230980 , which is incor [ 0019 ] FIG . 2 shows an inverted organic light emitting porated by reference in its entirety . Examples of emissive device that does not have a separate electron transport layer. and host materials are disclosed in U . S . Pat. No . 6 , 303 , 238 to Thompson et al ., which is incorporated by reference in its 10020 ] FIG . 3 shows Oak Ridge Thermal Ellipsoid Plot entirety . An example of an n - doped electron transport layer Program (ORTEP ) diagram of complex 5a . is BPhen doped with Li at a molar ratio of 1 : 1 , as disclosed [0021 ] FIG . 4 shows ORTEP diagram of complex 5b . in U . S . Patent Application Publication No . 2003 /0230980 , [0022 ] FIG . 5 shows ORTEP diagram of complex 7a . which is incorporated by reference in its entirety . U . S . Pat. [0023 ] FIG . 6 shows ORTEP diagram of complex 9 . Nos . 5 , 703 , 436 and 5 ,707 , 745 , which are incorporated by [0024 ] FIG . 7 shows ORTEP diagram of complex 10a . reference in their entireties , disclose examples of cathodes including compound cathodes having a thin layer of metal such as Mg: Ag with an overlying transparent, electrically DETAILED DESCRIPTION conductive , sputter - deposited ITO layer. The theory and use [ 0025 ] Generally , an OLED comprises at least one organic of blocking layers is described in more detail in U . S . Pat . layer disposed between and electrically connected to an No . 6 ,097 , 147 and U . S . Patent Application Publication No . anode and a cathode . When a current is applied , the anode 2003 /0230980 , which are incorporated by reference in their injects holes and the cathode injects electrons into the entireties . Examples of injection layers are provided in U . S . organic layer( s ) . The injected holes and electrons each Patent Application Publication No. 2004 /0174116 , which is migrate toward the oppositely charged electrode. When an incorporated by reference in its entirety . A description of electron and hole localize on the same molecule , an “ exci protective layers may be found in U . S . Patent Application ton , ” which is a localized electron -hole pair having an Publication No. 2004 /0174116 , which is incorporated by excited energy state , is formed . Light is emitted when the reference in its entirety . exciton relaxes via a photoemissive mechanism . In some [0030 ] FIG . 2 shows an inverted OLED 200 . The device cases , the exciton may be localized on an excimer or an includes a substrate 210 , a cathode 215 , an emissive layer exciplex . Non - radiative mechanisms, such as thermal relax 220 , a hole transport layer 225 , and an anode 230 . Device ation , may also occur, but are generally considered undesir 200 may be fabricated by depositing the layers described , in able . order . Because the most common OLED configuration has a [0026 ] The initial OLEDs used emissive molecules that cathode disposed over the anode , and device 200 has cath emitted light from their singlet states (“ fluorescence” ) as ode 215 disposed under anode 230 , device 200 may be disclosed , for example , in U .S . Pat. No . 4 ,769 , 292 , which is referred to as an “ inverted ” OLED . Materials similar to US 2018 /0134954 A1 May 17 , 2018 those described with respect to device 100 may be used in of the deposition methods such as ink - jet and OVJP . Other the corresponding layers of device 200 . FIG . 2 provides one methods may also be used . The materials to be deposited example of how some layers may be omitted from the may be modified to make them compatible with a particular structure of device 100 . deposition method . For example , substituents such as alkyl [0031 ] The simple layered structure illustrated in FIGS. 1 and aryl groups, branched or unbranched , and preferably and 2 is provided by way of non - limiting example , and it is containing at least 3 carbons , may be used in small mol understood that embodiments of the invention may be used ecules to enhance their ability to undergo solution process in connection with a wide variety of other structures . The ing . Substituents having 20 carbons or more may be used , specific materials and structures described are exemplary in and 3 -20 carbons is a preferred range . Materials with asym nature , and other materials and structures may be used . metric structures may have better solution processibility Functional OLEDs may be achieved by combining the than those having symmetric structures , because asymmetric various layers described in different ways , or layers may be materials may have a lower tendency to recrystallize . Den omitted entirely, based on design , performance , and cost drimer substituents may be used to enhance the ability of factors . Other layers not specifically described may also be small molecules to undergo solution processing . included . Materials other than those specifically described [ 0034 ] Devices fabricated in accordance with embodi may be used . Although many of the examples provided ments of the present invention may further optionally com herein describe various layers as comprising a single mate prise a barrier layer. One purpose of the barrier layer is to rial, it is understood that combinations of materials , such as protect the electrodes and organic layers from damaging a mixture of host and dopant, or more generally a mixture , exposure to harmful species in the environment including may be used . Also , the layers may have various sublayers . moisture , vapor and / or gases , etc . The barrier layer may be The names given to the various layers herein are not deposited over , under or next to a substrate, an electrode , or intended to be strictly limiting . For example , in device 200 , over any other parts of a device including an edge . The hole transport layer 225 transports holes and injects holes barrier layer may comprise a single layer, or multiple layers . into emissive layer 220 , and may be described as a hole The barrier layer may be formed by various known chemical transport layer or a hole injection layer. In one embodiment, vapor deposition techniques and may include compositions an OLED may be described as having an " organic layer " having a single phase as well as compositions having disposed between a cathode and an anode . This organic layer multiple phases . Any suitable material or combination of may comprise a single layer, or may further comprise materials may be used for the barrier layer . The barrier layer multiple layers of different organic materials as described , may incorporate an inorganic or an organic compound or for example , with respect to FIGS. 1 and 2 . both . The preferred barrier layer comprises a mixture of a [0032 ] Structures and materials not specifically described polymeric material and a non -polymeric material as may also be used , such as OLEDs comprised of polymeric described in U . S . Pat . No . 7 , 968, 146 , PCT Pat. Application materials (PLEDs ) such as disclosed in U . S . Pat. No . 5 , 247 , Nos . PCT /US2007 / 023098 and PCT /US2009 / 042829 , 190 to Friend et al. , which is incorporated by reference in its which are herein incorporated by reference in their entire entirety . By way of further example , OLEDs having a single ties. To be considered a “ mixture ” , the aforesaid polymeric organic layer may be used . OLEDs may be stacked , for and non -polymeric materials comprising the barrier layer example as described in U .S . Pat. No . 5 ,707 ,745 to Forrest should be deposited under the same reaction conditions et al, which is incorporated by reference in its entirety . The and / or at the same time. The weight ratio of polymeric to OLED structure may deviate from the simple layered struc non -polymeric materialmay be in the range of 95 : 5 to 5 :95 . ture illustrated in FIGS. 1 and 2 . For example , the substrate The polymeric material and the non - polymeric material may may include an angled reflective surface to improve out be created from the same precursor material. In one coupling , such as a mesa structure as described in U . S . Pat. example , the mixture of a polymeric material and a non No . 6 ,091 , 195 to Forrest et al. , and / or a pit structure as polymeric material consists essentially of polymeric silicon described in U . S . Pat. No . 5 ,834 , 893 to Bulovic et al. , which and inorganic silicon . are incorporated by reference in their entireties . [ 0035 ] Devices fabricated in accordance with embodi [0033 ] Unless otherwise specified , any of the layers of the ments of the invention can be incorporated into a wide various embodiments may be deposited by any suitable variety of electronic component modules ( or units ) that can method . For the organic layers , preferred methods include be incorporated into a variety of electronic products or thermal evaporation , ink -jet , such as described in U . S . Pat . intermediate components. Examples of such electronic prod Nos. 6 ,013 , 982 and 6 ,087 , 196 , which are incorporated by ucts or intermediate components include display screens , reference in their entireties , organic vapor phase deposition lighting devices such as discrete light source devices or (OVPD ), such as described in U . S . Pat. No. 6 , 337 , 102 to lighting panels , etc . that can be utilized by the end - user Forrest et al. , which is incorporated by reference in its product manufacturers . Such electronic component modules entirety, and deposition by organic vapor jet printing can optionally include the driving electronics and /or power (OVJP ) , such as described in U . S . Pat. No. 7 ,431 , 968, which source ( s ) . Devices fabricated in accordance with embodi is incorporated by reference in its entirety . Other suitable ments of the invention can be incorporated into a wide deposition methods include spin coating and other solution variety of consumer products that have one or more of the based processes. Solution based processes are preferably electronic component modules ( or units ) incorporated carried out in nitrogen or an inert atmosphere . For the other therein . Such consumer products would include any kind of layers, preferred methods include thermal evaporation . Pre products that include one or more light source ( s ) and / or one ferred patterning methods include deposition through a or more of some type of visual displays . Some examples of mask , cold welding such as described in U . S . Pat . Nos. such consumer products include flat panel displays , com 6 ,294 ,398 and 6 , 468 ,819 , which are incorporated by refer puter monitors , medical monitors , televisions , billboards, ence in their entireties , and patterning associated with some lights for interior or exterior illumination and /or signaling , US 2018 /0134954 A1 May 17 , 2018 heads- up displays, fully or partially transparent displays , aromatic , e .g . , the other rings can be cycloalkyls , cycloalk flexible displays , laser printers , telephones, cell phones , enyls , aryl, heterocycles, and /or heteroaryls . Preferred aryl tablets , phablets , personal digital assistants ( PDAs) , wear groups are those containing six to thirty carbon atoms, able device , laptop computers , digital cameras, camcorders , preferably six to twenty carbon atoms, more preferably six viewfinders , micro - displays, 3 - D displays, vehicles, a large to twelve carbon atoms. Especially preferred is an aryl group area wall , theater or stadium screen , or a sign . Various having six carbons, ten carbons or twelve carbons . Suitable control mechanisms may be used to control devices fabri aryl groups include phenyl, biphenyl, triphenyl , triph cated in accordance with the present invention , including enylene , tetraphenylene , naphthalene , anthracene, phe passive matrix and active matrix . Many of the devices are nalene , phenanthrene , fluorene , pyrene , chrysene, perylene , intended for use in a temperature range comfortable to and azulene , preferably phenyl, biphenyl, triphenyl, triph humans , such as 18 degrees C . to 30 degrees C ., and more enylene, fluorene , and naphthalene. Additionally , the aryl preferably at room temperature ( 20 - 25 degrees C . ) , but group may be optionally substituted . could be used outside this temperature range , for example , [0045 ] The term " heteroaryl” as used herein contemplates from - 40 degree C . to + 80 degree C . single - ring hetero - aromatic groups that may include from [0036 ] The materials and structures described herein may one to five heteroatoms. The term heteroaryl also includes have applications in devices other than OLEDs . For polycyclic hetero - aromatic systems having two or more example , other optoelectronic devices such as organic solar rings in which two atoms are common to two adjoining rings cells and organic photodetectors may employ the materials ( the rings are “ fused ” ) wherein at least one of the rings is a and structures . More generally , organic devices, such as heteroaryl, e . g ., the other rings can be cycloalkyls , cycloalk organic transistors , may employ the materials and structures . enyls , aryl, heterocycles, and /or heteroaryls . Preferred het [0037 ] The term “ halo , " " halogen , ” or “ halide ” as used eroaryl groups are those containing three to thirty carbon herein includes fluorine, chlorine , bromine, and iodine . atoms, preferably three to twenty carbon atoms, more pref [ 0038 ]. The term “ alkyl” as used herein contemplates both erably three to twelve carbon atoms. Suitable heteroaryl straight and branched chain alkyl radicals . Preferred alkyl groups include dibenzothiophene , dibenzofuran , dibenzo groups are those containing from one to fifteen carbon atoms selenophene , furan , thiophene , benzofuran , benzothiophene, and includes methyl, ethyl, propyl, 1 -methylethyl , butyl, benzoselenophene , carbazole, indolocarbazole , pyridylin 1 - methylpropyl, 2 -methylpropyl , pentyl, 1 -methylbutyl , dole , pyrrolodipyridine, pyrazole , imidazole , triazole , 2 -methylbutyl , 3 -methylbutyl , 1 , 1 -dimethylpropyl , 1 , 2 - dim oxazole, thiazole , oxadiazole , oxatriazole , dioxazole , thia ethylpropyl, 2 , 2- dimethylpropyl , and the like. Additionally , diazole , pyridine, pyridazine , pyrimidine, pyrazine , triazine , the alkyl group may be optionally substituted . oxazine, oxathiazine , oxadiazine , indole , benzimidazole , [0039 ] The term “ cycloalkyl ” as used herein contemplates indazole, indoxazine, benzoxazole, benzisoxazole , benzo cyclic alkyl radicals . Preferred cycloalkyl groups are those thiazole , quinoline, isoquinoline, cinnoline , quinazoline , containing 3 to 10 ring carbon atoms and includes cyclo quinoxaline, naphthyridine , phthalazine, pteridine, xan propyl, cyclopentyl, cyclohexyl , adamantyl, and the like. thene , acridine , phenazine , phenothiazine , phenoxazine , Additionally , the cycloalkyl group may be optionally sub benzofuropyridine, furodipyridine, benzothienopyridine , stituted. thienodipyridine , benzoselenophenopyridine , and seleno 10040 ] The term “ alkenyl” as used herein contemplates phenodipyridine , preferably dibenzothiophene, dibenzo both straight and branched chain alkene radicals . Preferred furan , dibenzoselenophene, carbazole, indolocarbazole , imi alkenyl groups are those containing two to fifteen carbon dazole , pyridine, triazine, benzimidazole , 1 , 2 -azaborine , atoms. Additionally , the alkenyl group may be optionally 1 , 3 - azaborine, 1 , 4 - azaborine , borazine , and aza - analogs substituted . thereof. Additionally, the heteroaryl group may be optionally [ 0041 ] The term " alkynyl” as used herein contemplates substituted . both straight and branched chain alkyne radicals . Preferred [0046 ] The alkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, alkynyl groups are those containing two to fifteen carbon heterocyclic group , aryl, and heteroaryl may be unsubsti atoms. Additionally , the alkynyl group may be optionally tuted or may be substituted with one or more substituents substituted . selected from the group consisting of deuterium , halogen , [0042 ] The terms " aralkyl” or “ arylalkyl” as used herein alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy , aryloxy , are used interchangeably and contemplate an alkyl group amino , cyclic amino , silyl, alkenyl, cycloalkenyl, heteroalk that has as a substituent an aromatic group . Additionally , the enyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic aralkyl group may be optionally substituted . acid , ether, ester , nitrile , isonitrile , sulfanyl, sulfinyl, sulfo [0043 ] The term " heterocyclic group ” as used herein con nyl, phosphino , and combinations thereof. templates aromatic and non -aromatic cyclic radicals . Het [ 0047 ] As used herein , “ substituted ” indicates that a sub ero - aromatic cyclic radicals also means heteroaryl. Preferred stituent other than His bonded to the relevant position , such hetero -non - aromatic cyclic groups are those containing 3 to as carbon . Thus , for example , where R ' is mono - substituted , 7 ring atoms which includes at least one hetero atom , and then one RI must be other than H . Similarly , where Rl is includes cyclic amines such as morpholino , piperdino , pyr di - substituted , then two of R1 must be other than H . Simi rolidino , and the like , and cyclic ethers, such as tetrahydro larly , where R is unsubstituted , R is hydrogen for all furan , tetrahydropyran , and the like . Additionally , the het available positions . erocyclic group may be optionally substituted . 10048 ]. The “ aza ” designation in the fragments described [ 0044 ] The term “ aryl” or “ aromatic group ” as used herein herein , i. e . aza -dibenzofuran , aza- dibenzothiophene , etc . contemplates single- ring groups and polycyclic ring sys means that one ormore of the C - H groups in the respective tems. The polycyclic rings may have two or more rings in fragment can be replaced by a nitrogen atom , for example , which two carbons are common to two adjoining rings (the and without any limitation , azatriphenylene encompasses rings are “ fused ” ) wherein at least one of the rings is both dibenzo [f ,h ] quinoxaline and dibenzo [f , h ]quinoline . US 2018 /0134954 A1 May 17 , 2018
One of ordinary skill in the art can readily envision other [0058 ] wherein R4 , RB , RC , and R each independently nitrogen analogs of the aza - derivatives described above, and represent mono substitution up to the maximum possible all such analogs are intended to be encompassed by the number of substitutions, or no substitution ; terms as set forth herein . [ 0059 ] wherein Z ' and Z2 are each independently selected from the group consisting of carbon or nitrogen ; [0049 ] It is to be understood that when a molecular [0060 ] wherein C is an anionic donor carbon atom , C2 is fragment is described as being a substituent or otherwise a neutral carbene carbon atom ; attached to another moiety , its name may be written as if it [0061 ] wherein each of R4, RP , RC, R ” , RY, R ', and R2 are were a fragment ( e .g . phenyl, phenylene, naphthyl, diben independently selected from the group consisting of hydro zofuryl) or as if it were the whole molecule ( e . g . benzene , gen , deuterium , halide , alkyl, cycloalkyl, heteroalkyl, aryl naphthalene , dibenzofuran ) . As used herein , these different alkyl, alkoxy, aryloxy, amino , silyl, alkenyl, cycloalkenyl, ways of designating a substituent or attached fragment are heteroalkenyl, alkynyl, aryl, heteroaryl , acyl, carbonyl , car considered to be equivalent. boxylic acids, ester, nitrile , isonitrile , sulfanyl, sulfinyl, [0050 ] According to an aspect , a compound having a sulfonyl, phosphino , and combinations thereof; and wherein formula M ( L ) (LR ) , (LC , is disclosed . In the formula , the any adjacent substitutents are optionally joined or fused into ligand L4 is a ring . 10062 ] In some embodiments of the compound , M is selected from the group consisting of Ir , Rh , Re , Ru , Os, Pt, Au , and Cu . In some embodiments , M is Ir or Pt . [ 0063 ] In some embodiments , Z ' is a neutral donor nitro gen atom , Z ? is an anionic donor carbon atom . [0064 ] In some embodiments , rings A , B , and Care 6 - membered aromatic rings , and ring D is a 5 - member 22- - - , aromatic rings . In some embodiments , rings B and C are benzene . [0065 ] In some embodiments , the compound is selected Pot from the group consisting of: Ir (LA ) (LB ) ( LC ) , Ir (LA ) ( LB ) 2, Ir (LA ) 2 (LB ) , Pt( LA ) (LB ), and Pt( LB ) 2 . [0066 ] In some embodiments of the compound , the ligand 4badothe ligand LB is LA is selected from the group consisting of:
= X1 Row 4- 13 poto - and the ligand Lc is
RE -
- - - - to= f
[0051 ] wherein M is a metal having an atomic number greater than 40 ; 7= p 72 [0052 ] wherein x is 0 , 1, or 2 ; [0053 ] wherein y is 1 , 2 , or 3 ; [ 0054 ] wherein z is 0 , 1, or 2 ; X6 [ 0055 ) wherein x + y + z is the oxidation state of the metal M ; Y 8 ore 9 [0056 ] wherein LA is different from LB , and when x , y , or z is larger than 1 , each plurality of L4, LB , or Lc are also different ; 17 [ 0057 ] wherein rings A , B , C , and D are each indepen 0+ dently a 5 or 6 -membered carbocyclic or heterocyclic ring ; ? US 2018/ 0134954 A1 May 17, 2018
7
- continued -continued ?? x3 . - x2 3-0 ? x3 " R ? - x! N|Y R xf
??? ? ? vs * o = ? ?? = y= R
R /? X11 - x10
X 4 ?m3 ??
= Ra X = x ???? ? ??? ?? ??? X|N? Rb ASY10 R . y3 _ y2 Ro, ? :8R and RS x = x Y3 ??? *
* XIN * ? Ra; 12 R?R ,
?x10
Rx = x ?? ?????? ? Bb ???? ?? ??? = ? =? ? ?N [ 0067] wherein each X ' to X '" are independently selected from the group consisting of carbon and nitrogen ; 10068 ] wherein X is selected from the group consisting of ry= 7o 2???? BRY, NRY, PR', 0 , S , Se, C - 0 , S - 0 , SO , CRR ", SiRR" , and GeRR" ; [0069 ] wherein R ' and R " are optionally fised or joined to form a ring; US 2018 /0134954 A1 May 17 , 2018
[0070 ] wherein each R?, Rb, Rc, and R , may represent [0080 ] In some embodiments , the ligand Lc has the for from mono substitution up to the maximum possible number mula : of substitutions, or no substitution ; [0071 ] wherein R ', R " , Ra, Ry, Rc, and Rg are each inde pendently selected from the group consisting of hydrogen , RA deuterium , halide , alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy , aryloxy , amino , silyl, alkenyl, cycloalkenyl, het eroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, carbox punt
ylic acids , ester, nitrile , isonitrile , sulfanyl, sulfinyl, sulfonyl, -- phosphino , and combinations thereof , and - - [ 0072 ] wherein any two adjacent substitutents of Ra, Rb, coma Re, and Ra are optionally fused or joined to form a ring or R22 form a multidentate ligand . [0073 ] In some embodiments of the compound , the ligand wherein R¥1 , R19 , R21 , and R22 are independently selected LB is selected from the group consisting of: from group consisting of alkyl, cycloalkyl, aryl, and het eroaryl; . x = x Ra [0081 ] wherein at least one of RX1, RX2 , R21, and R22 has RY= X at least two carbon atoms. = [0082 ] In some embodiments , the ligand L4 is selected from the group consisting of: and
= 48 Ra
AI= + 2 R Rb
+
[0074 ] wherein each X ! to X8 are independently selected from the group consisting of carbon and nitrogen ; 7 [0075 ] wherein X is selected from the group consisting of BR ', NR ', PR ', O , S , Se , C = O , SVO , SO2, CR 'R " , SIR ' R " , and GeR ' R " ; [0076 ] wherein R ' and R " are optionally fused or joined to form a ring ; [0077 ] wherein each R?, Rb, Rc, and Rd may represent from mono substitution up to the maximum possible number of substitutions, or no substitution ; ??????? [ 0078 ] wherein R ', R " , Ra, Rb , Rc, and R , are each inde pendently selected from the group consisting of hydrogen , deuterium , halide , alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy , aryloxy, amino , silyl, alkenyl, cycloalkenyl, het eroalkenyl, alkynyl, aryl, heteroaryl, acyl , carbonyl , carbox ylic acids, ester, nitrile , isonitrile , sulfanyl, sulfinyl, sulfonyl, phosphino , and combinations thereof; and [0079 ] wherein any two adjacent substitutents of Ra, Rb, Rc, and Rd are optionally fused or joined to form a ring or form a multidentate ligand . US 2018 / 0134954 ?1 May 17, 2018
- continued -continued
_ N N
S•- *
N
-/
z 40,20. =/ -/ Rb
_ Rb .
Rb.
Ro Rb. US 2018 / 0134954A1 May 17, 2018
-continued [ 0085 ] _ In some embodiments , lie ligaId I is selected from the group consisting of:
?? 4 ?
?? 42
? 43
and
L44
?? 45
[ 0083] _ wherein each RQ, RA , Re and Rd may represent from mono substitution up to the maximum possible number of substitutions , or no substitution ; LA6 [ 0084] _ whereinR , RA, Re, and Rare eachindependently selected from the group consisting of hydrogen , deuterium , lialide, alkyl, cycloalkyl, hetervalkyl ,aylalkyl , alkoxy, ay 10XV , armill0, Silyl , alkellyl , cycloalkenyl , hetervalkellyl , alkynyl , aryl, heteruaryl , acyl, carbonyl, carb0Xylic acids , ester, nitrile , is0nitrile, Sulfalyl , Sulfilyl, Sulfoilyl, phOS phino , and combinations thereof; and wherein any two adjacent substitutents of R?, R , R . , and R , are optionally fused or joined to form a ring or form a multidentate ligand . US 2018 / 0134954 A1 May 17, 2018
- continued -continued LAT L412
LA8
La13
LA9 LA14 CFT
LA15 F3C
LA10
LA16 CF
LAU L417 FC
•C3, * ( D US 2018 / 0134954 A1 May 17, 2018
- continued -continued LA18 L425
L419 >8| L426
LA20
LA27
L421
aofof LA28
LA23 F3C
DC CD32 LA29 LA24 >
DCN CD , US 2018 /0134954 A1 May 17 , 2018
- continued -continued LA30 LA36
D301 CD3 LA31 CH3ÇF3 LA37
N
?
L- A32 FC
1 LA38
LA33 CF3
-
1 L A39 D3C CD32 LA34 F3C
D3C ? CD LA40 LA35 F30
N - - .
F US 2018 / 0134954A1 May 17, 2018 14
- continued -continued L441 LA46
" ) ! ? 03. LA42 F L447
D3C L443 I448
? ? ? ?? ? ? ??
L444 LA49 E ,
L445 L450
D3CJ } , C CDD3? ] 030 ? 0 ?? ??? US 2018/ 0134954 A1 May 17 , 2018
- continued - continued LA51 1 L456
DC SCD ,
LA52 A57 ?
LA53 LA58
L54 0000 L59 ? 1_ A55 L460 US 2018 / 0134954 A1 May 17, 2018 16
- continued -continued LA61 LA66
L462 L467
F3C
L463 L468
DCDSC CD L464 LA69
| DCCITV L465 L470 XXXXX HAPPYDSC CD3 US 2018 / 0134954A1 May 17 , 2018
- continued -continued LA71 LA76
L77 L72
????
D , C L78 .??????? LA73 LA79
DC LA74 ??
D , C CD . LA75 LA80 ?? D , C CD3, US 2018 / 0134954A1 May 17 , 2018
- continued -continued LA86 LA81 CD D3C , ?
LA82 LA87
LA83
LA88 ?????? CD3 LA84
? ? ? LA89
LA85 CD D , C , US 2018 / 0134954 A1 May 17, 2018
- continued -continued L490 D L494 DSC | CD ,
L495
L491
> * * * * * LA96
LA92
, * * * *
N XXXand- * ** L497
493 US 2018 /0134954 A1 May 17 , 2018
- continued -continued L 498 LA102
L 299 LA103 D C
LA 100 LA104 anoeste LevelLA101 LA105 US 2018 /0134954 A1 May 17 , 2018 21
- continued - continued LA105 LA109
NO N
LA110
LA 106
LA111
LA107
L4112
LA108 LA113
- - - US 2018/ 0134954 A1 May 17 , 2018
-continued -continued LA114 LA118 CD ,
DC LA119
LA115
LA120 LA116
?? DC
LA121 LA117 CD ;
DC . US 2018 / 0134954 A1 May 17, 2018 23
- continued -continued LA122 LA126 | CD| D CD| Dscr
DSC LA123
Hd LA127 LA124 D | D
DSC
LA128 no LA125 HdHD DC US 2018 /0134954 A1 May 17 , 2018 24
- continued -continued LA 129 LA133
LA130 LA134
LA131 LA135
W
LA136
LA132 US 2018/ 0134954 A1 May 17 , 2018 25
- continued -continued LA137 FC LA141
LA142 LA138
LA143 LA139 TD
D3C
LA144 LA 140 US 2018/ 0134954 A1 May 17 , 2018 26
- continued - continued L4145 L4149
F3C
# * # #
L4146 14 LA150
, - a m * *
LA151 LA147
LA152 ???? L4148 ???? US 2018 /0134954 A1 May 17 , 2018 27
- continued - continued LA153 LA157 F3C
LA158 LA 154
CD32 CD3,
DzC LA159
LA155
LA160
F C LA156 US 2018 /0134954 A1 May 17 , 2018
- continued - continued LA161 LA165 CF3
CF3
LA162 PO L A166
-
LA163 CD39
LA167
- - - ?
LA 164 LA168 F C US 2018 /0134954 A1 May 17 , 2018
- continued -continued LA169 LA173
CD Dana
LA174 D3C CD3 LA170 D3C ww7
LA175 LA171 DzC CD3
LA172 LA176
7
w US 2018 / 0134954 A1 May 17, 2018 30
- continued - continued L4177 L4181 DSC, CD3
CD
D
L4178 L4182 DC, CD DSC
DC
DCr L4179 L4183 D; ICDD , ???????????198?? LA180 LA184
DC7 US 2018 / 0134954A1 May 17, 2018
- continued -continued ?? 4189 L4185 F F
1.
1
F F ?
Duc D3C LA190 L4186
L4191
L4187
L4192
? ? ?
193 ( US 2018/ 0134954 A1 May 17 , 2018 32
- continued -continued LA193 LA197
LA194 LA198
LA199
LA 195
* *
LA200
LA196 F F | F
|
| LA201 F F US 2018 / 0134954A1 May 17 , 2018 33
- continued -continued LA202 LA207
= = = =
LA203
LA208
Ph . I = ? ?
LA204 ???? LA209
L 205 LA210
??? LA206 LA211
? ? ? ? . = = .
Ph .
US 2018 / 0134954 A1 May 17, 2018 34
- continued - continued L4212 L4217
• .
• - - )
[ 0086 ] In some embodiments , the ligand Lg is selected LA213 from the group consisting of:
R Z,
..Z - R/ > .*.*
.
LA214 2
N - - - - ?
L4215
LA216
and -- Z Z _ - CardannotA US 2018 /0134954 A1 May 17 , 2018 35
- continued - continued
RN Z
?? Rb- diri
N
Rb
RCNS N Rh
and
RT Lii
[0087 ] wherein each Ra, Rb, Rc, and Rd may represent from mono substitution up to the maximum possible number of substitutions , or no substitution ; US 2018 /0134954 A1 May 17 , 2018 36
[0088 ] wherein Ra, R1, Rc, and Rg are each independently - continued selected from the group consisting of hydrogen , deuterium , LB5 halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy , ary loxy , amino , silyl, alkenyl, cycloalkenyl , heteroalkenyl, alkynyl, aryl, heteroaryl, acyl , carbonyl, carboxylic acids , ester , nitrile , isonitrile , sulfanyl, sulfinyl, sulfonyl, phos iz phino , and combinations thereof; and wherein any two adjacent substitutents of R?, Rb, Rc, and R , are optionally fused or joined to form a ring or form a multidentate ligand . [ 0089] In some embodiments , the ligand Lg is selected from the group consisting of: LB6
LB1
LB2
LB8 DzÇ D CD32
LB3
LB9
LB4 D3C
CD2. LB10 Z
- gogogogogogo. US 2018 / 0134954 A1 May 17, 2018
- continued - continued LB11 LB17
Z1
LB12
* LBi8
">,
L813
LB14 L819 DSC | CD ),
L815 *
LB16 L820
* US 2018 /0134954 A1 May 17 , 2018 38
- continued -continued LB21 LB26
LB22 LB27
D3C1 880B2 LB23
-
LB28
LB24
LB29
LB25 US 2018 / 0134954 A1 May 17, 2018
- continued -continued L830 L835
L836 L831
Z -
- |32?????? >,-
L832 L837
L833 L838
DC7 LB34 LB39
-' * C%?????? US 2018 / 0134954 A1 May 17, 2018 1040 - continued -continued L840 L845
L841
L846
L842
DC
LB47
DSC L843 |?xxx DC- -
L844 L848 US 2018 /0134954 A1 May 17 , 2018
- continued - continued LB53
and
D30 L850
LB54
w
LB51
D C
[0090 ] In some embodiments , the ligand Lc is selected from the group consisting of:
LB52 - -
- LC2
- - - - US 2018 / 0134954A1 May 17 , 2018
- continued -continued ??" L09
L4 Lcio
? ? ? ? ?????????????? LC11
LC6 LC12 and ????????? L LC13
= = = =
??? ? ???? [0091 ] In embodiments where the ligand L is selected from the group consisting of Lal through L4200, the com pound is selected from the group consisting of Compound A - 1 through Compound A - 140 ,400 ; where each Compound A - x has the formula Ir (L ) (LB )( L ) ; US 2018 / 0134954 A1 May 17, 2018 43
[ 0092] wherein X = 10, 800( k - 1 ) + 200( j - 1 ) + i, i is an integer - continued from 1 to 200 , j is an integer from 1 to 54 ; andk is an integer . L86 from 1 to 13 ; [ 0093 ] wherein L , has the following structure:
LB1
L87
LB
LR
L83
19
LB4 DSC D CD , LB10 *
LB5 5XXXX ?? L811 US 2018/ 0134954 A1 May 17 , 2018 44
- continued - continued L812 L817
? L813
L818
L814
z*
, ? L819 DC ) C3 L15
?
L816 L820
? US 2018 /0134954 A1 May 17 , 2018 45
- continued - continued LB21 LB26
LB22
LB27
D3C1 LB23
-
LB28
LB24
LB25 LB29 US 2018 / 0134954 A1 May 17, 2018 46
- continued -continued L830 L835
L836 L831
Z -
- |32?????? >,-
L832 L837
L833 L838
DC7 LB34 LB39
-' * C%?????? US 2018 / 0134954 A1 | May 17, 2018 47
- continued -continued L840 L845
L841
L846
L842
DC
L847
DC, LB43 DSC - W ?? )? ???? L844 L848 US 2018 /0134954 A1 May 17 , 2018 48
- continued - continued L849 LB53
and
D30 L850Lose
LB54
w
LB51
D C
[0094 ] wherein Lck has the following structure :
- - - LB52LB52
- LO2 US 2018 / 0134954A1 May 17 , 2018
- continued -continued ???
L4 Li
LC6
113
and
L ?????????? Lc13
??? ? ???? [0095 ] In embodiments where the ligand L is selected from the group consisting of Lan through L4200 , the com pound has the formula Ir( L )( LB )( LE ), wherej is not equal to???????? j' ; US 2018 /0134954 A1 May 17 , 2018 50
[0096 ] wherein i is an integer from 1 to 200 , j is an integer - continued from 1 to 54 ; and j' is an integer from 1 to 54 ; LB6 [ 0097 ] wherein LB ; or L Bir has the following structure :
LB1
Z.
-
LB7
LB2
LBS
LB3
.
L89
9800.09.09ODzC LB4
LB10
LB5 Jo0804620 LB11 US 2018 /0134954 A1 May 17 , 2018
- continued - continued LB12 LB17
LB13
LB18
LB14
.7
LB19 D3C D -CD3 , LB15
LB16 LB20 US 2018 /0134954 A1 May 17 , 2018 52
- continued -continued LB21 LB26
Z,
LB22
LB27
D3C1 LB23
-
LB28
LB24
LB25 L829 US 2018 / 0134954 A1 May 17, 2018 53
- continued -continued L830 L835
L836 L831
Z -
-
>,-
L832 L837
L833 L838
DC7 LB34 LB39
-' * C%?????? |
US 2018 / 0134954 A1 May 17, 2018 54
- continued -continued L840 IQ L845
L841
L846
L842 DC Q L847
DC, LB43 DSC - W ???? L844 Q L848 US 2018 /0134954 A1 May 17 , 2018 55
- continued -continued L849 LB53
and
D30 L850
LB54
w
LB51
D307
[ 0098 ] In embodiments where the ligand LB is selected from the group consisting of Lbl to LB54, the compound has the formula Ir (LB ; ) ( LB ; - ) ( LB ; " ) ; [0099 ] wherein each of j, j ', and j" is an integer from 1 to 54 ; and [0100 ] wherein j, j' , and j" are different. [0101 ] According to another aspect of the present disclo sure , an OLED is disclosed , the OLED comprises: an anode ; LB52 a cathode ; and an organic layer , disposed between the anode and the cathode , comprising a compound having the formula M (LA ) , (LB ), (LC ) : [ 0102] wherein the ligand L4 is
-
22- - pot US 2018 /0134954 A1 May 17 , 2018 56
the ligand Lg is [0116 ] wherein n is from 1 to 10 ; and [0117 ] wherein Ar? and Arz are independently selected RC from the group consisting of benzene , biphenyl, naphtha lene, triphenylene , carbazole, and heteroaromatic analogs thereof. [0118 ] In some embodiments of the OLED , the organic layer further comprises a host , wherein host comprises at 02- - - least one chemical group selected from the group consisting of triphenylene , carbazole, dibenzothiphene , dibenzofuran , dibenzoselenophene , azatriphenylene , azacarbazole , aza poto dibenzothiophene , aza -dibenzofuran , and aza -dibenzosele nophene . and the ligand Lc is [0119 ] In some embodiments of the OLED , the organic layer further comprises a host, wherein the host is selected 1901 from the group consisting of:
- - - -
RZ [0103 ] wherein M is a metal having an atomic number greater than 40 ; [ 0104 ] wherein x is 0 , 1 , or 2 ; [ 0105 ] wherein y is 1 , 2 , or 3 ; [0106 ] wherein z is 0, 1, or 2 ; [ 0107 ] wherein x + y + z is the oxidation state of the metal M ; [0108 ] wherein LA is different from LB , and when x , y , or z is larger than 1 , each plurality of LÀ, LB, or Lc are also different; [0109 ] wherein rings A , B , C , and D are each indepen dently a 5 or 6 -membered carbocyclic or heterocyclic ring ; [ 0110 ] wherein R4, RP , RC, and RD each independently represent mono substitution up to the maximum possible number of substitutions, or no substitution ; [0111 ] wherein Z and Z2 are each independently selected from the group consisting of carbon or nitrogen ; [0112 ] wherein C is an anionic donor carbon atom , C2 is a neutral carbene carbon atom ; [0113 ] wherein each of R4, RB , RC, R ” , R®, R ”, and R2 are independently selected from the group consisting of hydro gen , deuterium , halide , alkyl, cycloalkyl, heteroalkyl, aryl alkyl, alkoxy, aryloxy, amino , silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, car boxylic acids, ester, nitrile , isonitrile , sulfanyl, sulfinyl, sulfonyl, phosphino , and combinations thereof; and wherein any adjacent substitutents are optionally joined or fused into a ring [0114 ] In some embodiments of the OLED , the organic layer further comprises a host, wherein the host comprises a triphenylene containing benzo - fused thiophene or benzo fused furan ; [0115 ] wherein any substituent in the host is an unfused substituent independently selected from the group consisting of CH2n + 1 , OC, H2n + 1 , OArt , NoC, H2n + 1 ) 2, N ( Ar ) ( Ara ) , CH = CH - C „ H2n + 19 C = CC7H2n + 1 , Ar? , Ar? - Ar2 , and C „H2n - Ar?, or the host has no substitutions; US 2018 / 0134954 A1 May 17, 2018 0515: AM 57 | _ May 17, 2018 "- continued -continued
N
NC
NT ? US 2018 /0134954 A1 May 17 , 2018 58
- continued - continued og Bocono and combinations thereof. [0120 ] In some embodiments of the OLED , the organic layer further comprises a host, wherein the host comprises a metal complex . [0121 ] According to another aspect, a formulation com prising a compound having the formula M (LA ) ,( LB ) ,( L .) , is disclosed , wherein the ligand L4 is
posto 22- - -
the ligand LB is
Poto - - - US 2018 /0134954 A1 May 17 , 2018 59 and the ligand Lc is consisting of benzene, biphenyl, naphthalene , triphenylene, carbazole , and heteroaromatic analogs thereof. The host can be an inorganic compound . For example a Zn containing inorganic material e. g. ZnS . [0135 ] The host can be a compound comprising at least R ! one chemical group selected from the group consisting of - - - - triphenylene, carbazole , dibenzothiophene, dibenzofuran , dibenzoselenophene , azatriphenylene , azacarbazole , aza dibenzothiophene , aza -dibenzofuran , and aza -dibenzosele nophene. The host can include a metal complex . The host [ 0122 ] wherein M is a metal having an atomic number can be , but is not limited to , a specific compound selected greater than 40 ; from the group consisting of: 10123 ] wherein x is 0 , 1 , or 2 ; 10124 ] wherein y is 1 , 2 , or 3 ; [ 0125 ] wherein z is 0 , 1 , or 2 ; [0126 ] wherein x + y + z is the oxidation state of the metal M ; [ 0127 wherein L , is different from LR, and when x , y , or z is larger than 1 , each plurality of L? , LB , or Lc are also different ; [0128 ] wherein rings A , B , C , and D are each indepen dently a 5 or 6 -membered carbocyclic or heterocyclic ring ; [0129 ] wherein R4 , RB , RC, and RD each independently represent mono substitution up to the maximum possible number of substitutions, or no substitution ; [ 0130 ] wherein Z and Z are each independently selected from the group consisting of carbon or nitrogen ; [0131 ] wherein C is an anionic donor carbon atom , Cº is a neutral carbene carbon atom ; wherein each of R4 , RP , Rº, R ” , RY , R ' , and RZ are independently selected from the group consisting of hydrogen , deuterium , halide , alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, aryloxy , amino , silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl , aryl, heteroaryl, acyl, carbonyl, carboxylic acids, ester , nitrile , isonitrile , sulfanyl, sulfinyl, sulfonyl, phosphino , and com binations thereof; and wherein any adjacent substitutents are optionally joined or fused into a ring . [0132 ] In some embodiments , the compound can be an emissive dopant. In some embodiments , the compound can produce emissions via phosphorescence , fluorescence , ther mally activated delayed fluorescence , i. e ., TADF (also referred to as E - type delayed fluorescence ) , triplet - triplet annihilation , or combinations of these processes . [0133 ] The OLED disclosed herein can be incorporated into one or more of a consumer product, an electronic component module , and a lighting panel . The organic layer can be an emissive layer and the compound can be an emissive dopant in some embodiments , while the compound can be a non - emissive dopant in other embodiments . [ 0134 ] The organic layer can also include a host. In some 800 embodiments , two or more hosts are preferred . In some embodiments , the hosts used maybe a ) bipolar, b ) electron transporting , c ) hole transporting or d ) wide band gap materials that play little role in charge transport. In some embodiments , the host can include a metal complex . The host can be a triphenylene containing benzo - fused thiophene or benzo - fused furan . Any substituent in the host can be an unfused substituent independently selected from the group como consisting of C „ H2n + 19 OC „ H2n + 1 , OAr? , N ( C „ H2n + 1 ) 2 , N ( Art ) ( Ara ), CH = CH2C , H2n + 1 , C = C – C , Ha+ 1 , Art , Ar - Arz, and C H2n - Ar?, or the host has no substitution . In the preceding substituents n can range from 1 to 10 ; and Ar, and Arz can be independently selected from the group load h USUS201012954 2018 /0134954 A1 MayMay 17 17,, 2018 2018 - continued -continued a
T
NC
N Locate US 2018 /0134954 A1 May 17 , 2018
- continued -continued 8 ö
and combinations thereof. [0136 ] Additional information on possible hosts is pro vided below . [0137 ] The formulation can include one or more compo nents selected from the group consisting of a solvent, a host, a hole injection material, hole transport material, and an electron transport layer material, disclosed herein . [0138 ] Combination with Other Materials [ 0139 ] The materials described herein as useful for a particular layer in an organic light emitting device may be used in combination with a wide variety of other materials present in the device . For example , emissive dopants dis closed herein may be used in conjunction with a wide variety of hosts , transport layers , blocking layers , injection layers , electrodes and other layers that may be present. The mate rials described or referred to below are non - limiting examples of materials that may be useful in combination with the compounds disclosed herein , and one of skill in the art can readily consult the literature to identify other mate rials that may be useful in combination . [0140 ] Conductivity Dopants : [0141 ] A charge transport layer can be doped with con ductivity dopants to substantially alter its density of charge carriers, which will in turn alter its conductivity . The con ductivity is increased by generating charge carriers in the matrix material, and depending on the type of dopant, a change in the Fermi level of the semiconductor may also be achieved . Hole -transporting layer can be doped by p - type conductivity dopants and n -type conductivity dopants are used in the electron - transporting layer. 0142 ] Non - limiting examples of the conductivity dopants that may be used in an OLED in combination with materials disclosed herein are exemplified below together with refer ences that disclose those materials : EP01617493 , EP01968131, EP2020694 , EP2684932 , US20050139810 , US20070160905 , US20090167167 , US2010288362 , WO06081780 , WO2009003455 , WO2009008277 , WO2009011327 , WO2014009310 , US2007252140 , US2015060804 and US2012146012 . US 2018/ 0134954 A1 May 17, 2018
-continued
E
?? F F ? ? ?
F
? F FF ?? ??
??? ?? ? =N =
N - N ,
N N ? =? NCCEFI CFACN . F FIF
| F F, ? FF FCF F N >ook FFF1 FI ??? ??
F ?N F ?? NN* = S US 2018 /0134954 A1 May 17 , 2018 US 20180136956 AT 63 - continued - continued F FF ARAr Ap3Ar3 F Ar Arl 4 7 > 7 Ap Aro ARAr no Ty N - Art LietusN 403 ZF Aro — N N — Arº , and F F = Ar? Ané 4r4 V- Aus
- F 3
Z- F F F 4r6 V - 4R - N. N - 49 F F Agosto Ar? 48 [0146 ] Each of Arl to Arº is selected from the group consisting of aromatic hydrocarbon cyclic compounds such and as benzene, biphenyl, triphenyl, triphenylene , naphthalene , anthracene, phenalene , phenanthrene , fluorene , pyrene , chrysene , perylene, and azulene ; the group consisting of aromatic heterocyclic compounds such as dibenzothio phene, dibenzofuran , dibenzoselenophene , furan , thiophene , benzofuran , benzothiophene , benzoselenophene , carbazole , - indolocarbazole , pyridylindole , pyrrolodipyridine , pyrazole , N imidazole , triazole , oxazole , thiazole , oxadiazole , oxatriaz ole , dioxazole , thiadiazole , pyridine , pyridazine , pyrimidine , pyrazine , triazine , oxazine , oxathiazine , oxadiazine, indole , benzimidazole , indazole , indoxazine , benzoxazole , ben zisoxazole , benzothiazole , quinoline , isoquinoline, cinno line , quinazoline , quinoxaline , naphthyridine, phthalazine , pteridine , Xanthene , acridine , phenazine , phenothiazine , Quo phenoxazine , benzofuropyridine , furodipyridine , benzoth [0143 ] HIL /HTL : ienopyridine , thienodipyridine , benzoselenophenopyridine , [0144 ] A hole injecting / transporting material to be used in and selenophenodipyridine ; and the group consisting of 2 to the present invention is not particularly limited , and any 10 cyclic structural units which are groups of the same type compound may be used as long as the compound is typically or different types selected from the aromatic hydrocarbon used as a hole injecting/ transporting material. Examples of cyclic group and the aromatic heterocyclic group and are bonded to each other directly or via at least one of oxygen the material include, but are not limited to : a phthalocyanine atom , nitrogen atom , sulfur atom , silicon atom , phosphorus or porphyrin derivative ; an aromatic amine derivative; an atom , boron atom , chain structural unit and the aliphatic indolocarbazole derivative ; a polymer containing fluorohy cyclic group . Each Ar may be unsubstituted or may be drocarbon ; a polymer with conductivity dopants ; a conduct substituted by a substituent selected from the group consist ing polymer , such as PEDOT/ PSS ; a self- assembly mono ing of deuterium , halide , alkyl, cycloalkyl, heteroalkyl, mer derived from compounds such as phosphonic acid and arylalkyl, alkoxy , aryloxy, amino , silyl, alkenyl, cycloalk silane derivatives ; a metal oxide derivative , such as MoO ; enyl, heteroalkenyl, alkynyl, aryl, heteroaryl, acyl, carbonyl, a p - type semiconducting organic compound , such as 1 , 4 , 5 , carboxylic acids, ester , nitrile , isonitrile , sulfanyl, sulfinyl, 8 , 9 , 12 -Hexaazatriphenylenehexacarbonitrile ; a metal com sulfonyl, phosphino , and combinations thereof. plex , and a cross -linkable compounds. [0147 ] In one aspect, Arl to Arº is independently selected [0145 ] Examples of aromatic amine derivatives used in from the group consisting of: HIL or HTL include , but not limit to the following general structures :
474
IR An US 2018 /0134954 A1 May 17 , 2018 64
- continued [0150 ] wherein Met is a metal, which can have an atomic weight greater than 40 ; ( Y101 - Y102) is a bidentate ligand , Y100 and Y102 are independently selected from C , N , O , P, and S ; L 101 is an ancillary ligand; k' is an integer value from 1 to the maximum number of ligands that may be attached to the metal ; and k ' + k " is the maximum number of ligands com that may be attached to the metal. [0151 ] In one aspect, (Y101 - Y102) is a 2 -phenylpyridine derivative. In another aspect , (Y101 - Y102) is a carbene ligand . In another aspect, Met is selected from Ir , Pt, Os, and Zn . In a further aspect, the metal complex has a smallest oxidation potential in solution vs . Fc + /Fc couple less than about 0 . 6 V . [0152 ] Non - limiting examples of the HIL and HTL mate rials that may be used in an OLED in combination with materials disclosed herein are exemplified below together coche with references that disclose those materials : CN102702075 , DE102012005215, EP01624500 , EP01698613 , EP01806334 , EP01930964, EP01972613 , EP01997799 , EP02011790 , EP02055700 , EP02055701 , EP1725079 , and EP2085382 , EP2660300 , EP650955 , JP07 -073529 , JP2005112765 , JP2007091719 , JP2008021687 , JP2014 - 009196 , KR20110088898 , KR20130077473 , TW201139402 , U .S . Ser . No . 06 / 517 ,957 , US20020158242 , US20030162053 , US20050123751, US20060182993 , US20060240279 , US20070145888 , US20070181874 , 11017101 - x108 US20070278938 , US20080014464, US20080091025 , to 7107 US20080106190 , US20080124572 , US20080145707 , US20080220265, US20080233434 , US20080303417 , XL 104 y105 :X106 US2008107919 , US20090115320 , US20090167161, US2009066235, US2011007385 , US20110163302 , [ 0148 ] wherein k is an integer from 1 to 20 ; X101 to X108 US2011240968 , US2011278551, US2012205642 , is C ( including CH ) or N ; Z101 is NAr !, O , or S ; Arl has the US2013241401, US20140117329 , US2014183517 , U . S . same group defined above . Pat. No. 5 , 061, 569, U . S . Pat. No . 5 ,639 ,914 , W005075451 , [0149 ] Examples ofmetal complexes used in HIL or HTL W007125714 , WO008023550 , WO08023759 , include, but are not limited to the following general formula : WO2009145016 , WO2010061824 , WO2011075644 , WO2012177006 , WO2013018530 , WO2013039073 , Ty101 WO2013087142 , WO2013118812 , WO2013120577 , [ Met — (L101 ) k " WO2013157367, WO2013175747 , WO2014002873 , [( y1021 *, . WO2014015935 , WO2014015937 , WO2014030872 , WO2014030921 , WO2014034791, WO2014104514 , Qoys WO2014157018 . US 2018 /0134954 A1 May 17 , 2018
-continued
Quadrano onwoord US 2018 / 0134954 A1 May 17, 2018 66 --continued
O?
. US 2018 / 0134954 A1 May 17, 2018 67
- continued
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+ MoO,
T CI
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=z
2 US 2018 / 0134954 A1 May 17, 2018 69 ?? -continued '
Br
F
F F
| F F F F ? F US 2018 /0134954 A1 May 17 , 2018 70
-continued US 2018 / 0134954 A1 May 17, 2018
-continued V?
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- continued
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- continued
D ON m US 2018 / 0134954 A1 May 17, 2018 75 .
.. . - continued ?? US 2018 / 0134954 A1 May 17, 2018
- continued ????? ? US 2018 /0134954 A1 May 17 , 2018 77
-continued
QuaGoleado US 2018/ 0134954 A1 May 17, 2018 78
- continued
??? US 2018 /0134954 A1 May 17 , 2018 79 Pontian- continued 2006 US 2018/ 0134954 A1 May 17 , 2018 80
-continued
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[0153 ] EBL : azole , thiadiazole , pyridine, pyridazine, pyrimidine , pyra [ 0154 ] An electron blocking layer ( EBL ) may be used to zine, triazine , oxazine, oxathiazine , oxadiazine , indole , ben reduce the number of electrons and / or excitons that leave the zimidazole, indazole, indoxazine , benzoxazole , emissive layer. The presence of such a blocking layer in a benzisoxazole , benzothiazole, quinoline , isoquinoline , cin noline, quinazoline , quinoxaline, naphthyridine , phthala device may result in substantially higher efficiencies, and /or zine , pteridine , xanthene , acridine , phenazine , phenothiaz longer lifetime, as compared to a similar device lacking a ine , phenoxazine , benzofuropyridine, furodipyridine , blocking layer . Also , a blocking layer may be used to confine benzothienopyridine , thienodipyridine , benzoselenophen emission to a desired region of an OLED . In some embodi opyridine , and selenophenodipyridine ; and the group con ments , the EBL material has a higher LUMO ( closer to the sisting of 2 to 10 cyclic structural units which are groups of vacuum level) and/ or higher triplet energy than the emitter the same type or different types selected from the aromatic closest to the EBL interface . In some embodiments , the EBL hydrocarbon cyclic group and the aromatic heterocyclic material has a higher LUMO ( closer to the vacuum level ) group and are bonded to each other directly or via at least and or higher triplet energy than one or more of the hosts one of oxygen atom , nitrogen atom , sulfur atom , silicon closest to the EBL interface . In one aspect, the compound atom , phosphorus atom , boron atom , chain structural unit used in EBL contains the same molecule or the same and the aliphatic cyclic group . Each option within each functional groups used as one of the hosts described below . group may be unsubstituted or may be substituted by a [0155 ] Host: substituent selected from the group consisting of deuterium , [ 0156 ] The light emitting layer of the organic EL device of halide, alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy , ary the present invention preferably contains at least a metal loxy , amino , silyl, alkenyl, cycloalkenyl, heteroalkenyl, complex as light emitting material , and may contain a host alkynyl, aryl, heteroaryl, acyl, carbonyl, carboxylic acids, material using the metal complex as a dopant material. ester , nitrile, isonitrile , sulfanyl, sulfinyl, sulfonyl, phos Examples of the host material are not particularly limited , phino , and combinations thereof. and any metal complexes or organic compounds may be [0163 ] In one aspect , the host compound contains at least used as long as the triplet energy of the host is larger than one of the following groups in the molecule : that of the dopant. Any host material may be used with any dopant so long as the triplet criteria is satisfied . [0157 ] Examples of metal complexes used as host are preferred to have the following general formula :
[ Y103 1 Met — (L101 ) k " Ly104 , fotolato [0158 ] wherein Met is a metal; (Y103 - Y104 ) is a bidentate ligand , Y103 and Y104 are independently selected from C , N , O , P , and S ; L101 is an another ligand ; k ' is an integer value from 1 to the maximum number of ligands that may be attached to the metal; and k ' + k " is the maximum number of ligands that may be attached to the metal. [0159 ] In one aspect, the metal complexes are : foto A — (L101 ) 3 - K Zn — ( L 101) 2 - F o\ N tom 17 [ 0160 ] wherein ( 0 - N ) is a bidentate ligand , having metal coordinated to atoms O and N . [ 0161 ] In another aspect, Met is selected from Ir and Pt. In a further aspect, ( Y103 - Y104 ) is a carbene ligand . [0162 ] Examples of other organic compounds used as host R 101 are selected from the group consisting of aromatic hydro carbon cyclic compounds such as benzene , biphenyl, triph & 00 enyl, triphenylene, tetraphenylene , naphthalene, anthracene, phenalene , phenanthrene , fluorene , pyrene , chrysene , perylene , and azulene ; the group consisting of aromatic R101 [ heterocyclic compounds such as dibenzothiophene , diben R105 zofuran , dibenzoselenophene , furan , thiophene , benzofuran , R102 - Si — + R104 Si + R107 benzothiophene , benzoselenophene , carbazole , indolocarba zole , pyridylindole , pyrrolodipyridine , pyrazole, imidazole , R 103 R106 triazole, oxazole , thiazole , oxadiazole , oxatriazole , diox US 2018 /0134954 A1 May 17 , 2018 83
-continued - continued 012101 X105 x 106 +7 =+ 1107 and xley 104 7102 xios
ZO 2012101 - X108 + 7107 +10 X1 y 104 X y104 X105105 . 1106 x 108 x 105 X107 go X106 [0164 ] wherein each of R101 to R107 is independently x1017101 z102X106 selected from the group consisting of hydrogen , deuterium , 10= -1101 X107 halide , alkyl, cycloalkyl, heteroalkyl, arylalkyl, alkoxy, ary loxy , amino , silyl, alkenyl, cycloalkenyl , heteroalkenyl, X103 flog: 106 alkynyl, aryl, heteroaryl, acyl , carbonyl, carboxylic acids, y 104 ester , nitrile , isonitrile , sulfanyl, sulfinyl, sulfonyl, phos phino , and combinations thereof, and when it is aryl or heteroaryl, it has the similar definition as Ar’ s mentioned above . K is an integer from 0 to 20 or 1 to 20 ; kt" is an integer from 0 to 20 . xl01 to X108 is selected from C (including CH ) or N . 101 2101 [0165 ) Z101 and 2102 is selected from NR101, 0 , or S . +10 = TQ 0166 ] Non - limiting examples of the host materials that may be used in an OLED in combination with materials x2 disclosed herein are exemplified below together with refer ences that disclose those materials : EP2034538 , EP2034538A , EP2757608 , JP2007254297 , v 105 KR20100079458 , KR20120088644 , KR20120129733 , KR20130115564, TW201329200 , US20030175553 , X106 108 US20050238919 , US20060280965 , US20090017330 , 710 US20090030202 , US20090167162 , US20090302743 , US20090309488 , US20100012931, US20100084966 , US20100187984 . US2010187984 , US2012075273 , US2012126221 , US2013009543, US2013105787 , US2013175519 , US2014001446 , US20140183503 , US20140225088, US2014034914 , U .S . Pat. No. 7 , 154 , 114 , 7107 WO2001039234 , WO2004093207 , WO2005014551, 470106 WO2005089025 , WO2006072002 , WO2006114966 , x10i z101 X108 WO2007063754, WO2008056746 , WO2009003898 , #102 4201 WO2009021126 , WO2009063833 , WO2009066778 , WO2009066779 , WO2009086028 , WO2010056066 , 103 7102 WO2010107244 . WO2011081423 , WO2011081431 . WO2011086863 , WO2012128298 , WO2012133644 , WO2012133649 , WO2013024872 , WO2013035275 , 0840 800gWO2013081315 , WO2013191404 , WO2014142472 , US 2018 / 0134954 A1 May 17, 2018 . . 84
.-continued
?? . ???? ??? US 2018 /0134954 A1 May 17 , 2018
- continued
Ne US 2018 / 0134954 A1 May 17, 2018 86
-continued
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- N . US 2018 / 0134954 A1 May 17, 2018 Lates R 08- continued ??? US 2018/ 0134954 A1 May 17 , 2018
- continued
= N ? ? US 2018 / 0134954 A1 May 17, 2018 89 ????????-continued ???
= ?? Q US 2018 /0134954 A1 May 17 , 2018 90
-continued Bonogood N
cog US 2018 / 0134954 A1 May 17, 2018
-continued c ???? US 2018 / 0134954 A1 May 17, 2018 92
- continued AN 88 ??????NN NTN ??