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Definitions

• the present invention relates to a process for preparing an organic charge transporting film.
• solution processing is one of the leading technologies for fabricating large flat panel OLED displays by deposition of OLED solution onto a substrate to form a thin film followed by cross-linking and polymerization.
• solution processable polymeric materials are cross-linkable organic charge transporting compounds.
• US7037994 discloses an antireflection film-forming formulation comprising at least one polymer containing an acetoxymethylacenaphthylene or hydroxyl methyl acenaphthylene repeating unit and a thermal or photo acid generator (TAG, PAG) in a solvent.
• TAG thermal or photo acid generator
• the present invention provides a single liquid phase formulation useful for producing an organic charge transporting film; said formulation comprising: (a) a polymer resin having M w at least 3,000 and comprising arylmethoxy linkages; (b) an acid catalyst which is an organic Bronsted acid with pKa ⁇ 4; a Lewis acid comprising a positive aromatic ion and an anion which is (i) a tetraaryl borate having the formula
• R represents zero to five non-hydrogen substituents selected from D, F and CF 3 , (ii) BF 4 - , (iii) PF 6 - , (iv) SbF 6 - , (v) AsF 6 - or (vi) ClO 4 - ; or a thermal acid generator (TAG) which is an ammonium or pyridinium salt of an organic Bronsted acid with pKa ⁇ 2 or an ester of an organic sulfonic acid; and (c) a solvent.
• TAG thermal acid generator
• Percentages are weight percentages (wt%) and temperatures are in °C, unless specified otherwise. Operations were performed at room temperature (20-25 °C) , unless specified otherwise. Boiling points are measured at atmospheric pressure (ca. 101 kPa) . Molecular weights are in Daltons and molecular weights of polymers are determined by Size Exclusion Chromatography using polystyrene standards.
• a “polymer resin” is a monomer, oligomer or polymer which can be cured to form a cross-linked film. Preferably the polymer resins have at least two groups per molecule which are polymerizable by addition polymerization.
• polymerizable groups include an ethenyl group (preferably attached to an aromatic ring) , benzocyclobutenes, acrylate or methacrylate groups, trifluorovinylether, cinnamate/chalcone, diene, ethoxyethyne and 3-ethoxy-4-methylcyclobut-2-enone.
• Preferred resins contain at least one of the following structures
• R groups independently are hydrogen, deuterium, C 1 -C 30 alkyl, hetero-atom substituted C 1 -C 30 alkyl, C 1 -C 30 aryl, hetero-atom substituted C 1 -C 30 aryl or represent another part of the resin structure; preferably hydrogen, deuterium, C 1 -C 20 alkyl, hetero-atom substituted C 1 -C 20 alkyl, C 1 -C 20 aryl, hetero-atom substituted C 1 -C 20 aryl or represent another part of the resin structure; preferably hydrogen, deuterium, C 1 -C 10 alkyl, hetero-atom substituted C 1 -C 10 alkyl, C 1 -C 10 aryl, hetero-atom substituted C 1 -C 10 aryl or represent another part of the resin structure; preferably hydrogen, deuterium, C 1 -C 4 alkyl, hetero-atom substituted C 1 -C 4 alkyl, or represent another part of the resin structure.
• “R” groups independently are hydrogen, deuter
• An arylmethoxy linkage is a linkage having at least one benzylic carbon atom attached to an oxygen atom.
• the arylmethoxy linkage is an ether, an ester or a benzyl alcohol.
• the arylmethoxy linkage has two benzylic carbon atoms attached to an oxygen atom.
• a benzylic carbon atom is a carbon atom which is not part of an aromatic ring and which is attached to a ring carbon of an aromatic ring having from 5 to 30 carbon atoms (preferably 5 to 20) , preferably a benzene ring.
• organic charge transporting compound is a material which is capable of accepting an electrical charge and transporting it through the charge transport layer.
• charge transporting compounds include “electron transporting compounds” which are charge transporting compounds capable of accepting an electron and transporting it through the charge transport layer, and “hole transporting compounds” which are charge transporting compounds capable of transporting a positive charge through the charge transport layer.
• organic charge transporting compounds Preferably, organic charge transporting compounds.
• organic charge transporting compounds have at least 50 wt%aromatic rings (measured as the molecular weight of all aromatic rings divided by total molecular weight; non-aromatic rings fused to aromatic rings are included in the molecular weight of aromatic rings) , preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%.
• the resins are organic charge transporting compounds.
• the polymer resin has M w at least 5,000, preferably at least 10,000, preferably at least 20,000; preferably no greater than 10,000,000, preferably no greater than 1,000,000, preferably no greater than 500,000, preferably no greater than 400,000, preferably no greater than 300,000, preferably no greater than 200,000, preferably no greater than 100,000.
• the polymer resin comprises at least 50% (preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%) polymerized monomers which contain at least five aromatic rings, preferably at least six, preferably no more than 20, preferably no more than 15; other monomers not having this characteristic may also be present.
• a cyclic moiety which contains two or more fused rings is considered to be a single aromatic ring, provided that all ring atoms in the cyclic moiety are part of the aromatic system.
• the resin comprises at least 50%(preferably at least 70%) polymerized monomers which contain at least one of triarylamine, carbazole, indole and fluorene ring systems.
• the resin comprises a first monomer of formula NAr 1 Ar 2 Ar 3 , wherein Ar 1 , Ar 2 and Ar 3 independently are C 6 -C 50 aromatic substituents and at least one of Ar 1 , Ar 2 and Ar 3 contains a vinyl group attached to an aromatic ring.
• the resin comprises at least 50%of the first monomer, preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%.
• the resin is a copolymer of the first monomer and a second monomer of formula (I)
• a 1 is an aromatic ring system having from 5 to 20 carbon atoms and in which the vinyl group and the –CH 2 OA 2 group are attached to aromatic ring carbons and A 2 is hydrogen or a C 1 -C 20 organic substituent group.
• a 1 has five or six carbon atoms, preferably it is a benzene ring.
• a 2 is hydrogen or a C 1 -C 15 organic substituent group, preferably containing no atoms other than carbon, hydrogen, oxygen and nitrogen.
• the monomer of formula NAr 1 Ar 2 Ar 3 preferably comprises a benzyloxy linkage.
• the polymer comprises a monomer having formula (I) in which A 2 is a substituent of formula NAr 1 Ar 2 Ar 3 , as defined above, preferably linked to oxygen via an aromatic ring carbon or a benzylic carbon.
• the compound of formula NAr 1 Ar 2 Ar 3 contains a total of 4 to 20 aromatic rings; preferably at least 5 preferably at least 6; preferably no more than 18, preferably no more than 15, preferably no more than 13.
• the formulation further comprises a monomer or oligomer having M w less than 5,000, preferably less than 3,000, preferably less than 2,000, preferably less than 1,000; preferably a crosslinker having at least three polymerizable vinyl groups.
• the polymer resins are at least 99%pure, as measured by liquid chromatography/mass spectrometry (LC/MS) on a solids basis, preferably at least 99.5%, preferably at least 99.7%.
• the formulation of this invention contains no more than 10 ppm of metals, preferably no more than 5 ppm.
• Preferred polymer resins useful in the present invention include, e.g., the following structures, as well as polymers comprising Monomers A, B &C, as described in the Examples.
• Crosslinking agents which are not necessarily charge transporting compounds may be included in the formulation as well.
• these crosslinking agents have at least 60 wt%aromatic rings (as defined previously) , preferably at least 70%, preferably at least 75 wt%.
• the crosslinking agents have from three to five polymerizable groups, preferably three or four.
• the polymerizable groups are ethenyl groups attached to aromatic rings. Preferred crosslinking agents are shown below
• the anion is a tetraaryl borate having the formula
• R represents zero to five non-hydrogen substituents selected from F and CF 3 .
• R represents five substituents on each of four rings, preferably five fluoro substituents.
• the positive aromatic ion has from seven to fifty carbon atoms, preferably seven to forty.
• the positive aromatic ion is tropylium ion or an ion having the formula
• A is a substituent on one or more of the aromatic rings and is H, D, CN, CF 3 or (Ph) 3 C+(attached via Ph) ;
• X is C, Si, Ge or Sn.
• X is C.
• A is the same on all three rings.
• the organic Bronsted acid has pKa ⁇ 2, preferably ⁇ 0.
• the organic Bronsted acid is an aromatic, alkyl or perfluoroalkyl sulfonic acid; a carboxylic acid; a protonated ether; or a compound of formula Ar 4 SO 3 CH 2 Ar 5 , wherein Ar 4 is phenyl, alkylphenyl or trifluoromethylphenyl, and Ar 5 is nitrophenyl.
• the TAG has a degradation temperature ⁇ 280 °C.
• Especially preferred acid catalysts for use in the present invention include, e.g., the following Bronsted acid, Lewis acid and TAGs.
• TAG is an organic ammonium salt.
• Preferred pyridinium salts include, e.g.,
• the amount of acid is from 0.5 to 10 wt%of the weight of the polymer, preferably less than 5 wt%, preferably less than 2 wt%.
• solvents used in the formulation have a purity of at least 99.8%, as measured by gas chromatography-mass spectrometry (GC/MS) , preferably at least 99.9%.
• solvents have an RED value (relative energy difference (vs. polymer) as calculated from Hansen solubility parameter using CHEMCOMP v2.8.50223.1) less than 1.2, preferably less than 1.0.
• RED value relative energy difference (vs. polymer) as calculated from Hansen solubility parameter using CHEMCOMP v2.8.50223.1
• Preferred solvents include aromatic hydrocarbons and aromatic-aliphatic ethers, preferably those having from six to twenty carbon atoms. Anisole, xylene and toluene are especially preferred solvents.
• the percent solids of the formulation i.e., the percentage of monomers and polymers relative to the total weight of the formulation, is from 0.5 to 20 wt%; preferably at least 0.8 wt%, preferably at least 1 wt%, preferably at least 1.5 wt%; preferably no more than 15 wt%, preferably no more than 10 wt%, preferably no more than 7 wt%, preferably no more than 4 wt%.
• the amount of solvent (s) is from 80 to 99.5 wt%; preferably at least 85 wt%, preferably at least 90 wt%, preferably at least 93 wt%, preferably at least 94 wt%; preferably no more than 99.2 wt%, preferably no more than 99 wt%, preferably no more than 98.5 wt%.
• the present invention is further directed to an organic charge transporting film and a process for producing it by coating the formulation on a surface, preferably another organic charge transporting film, and Indium-Tin-Oxide (ITO) glass or a silicon wafer.
• the film is formed by coating the formulation on a surface, baking at a temperature from 50 to 150°C (preferably 80 to 120°C) , preferably for less than five minutes, followed by thermal cross-linking at a temperature from 120 to 280°C; preferably at least 140°C, preferably at least 160°C, preferably at least 170°C; preferably no greater than 230°C, preferably no greater than 215°C.
• the thickness of the polymer films produced according to this invention is from 1 nm to 100 microns, preferably at least 10 nm, preferably at least 30 nm, preferably no greater than 10 microns, preferably no greater than 1 micron, preferably no greater than 300 nm.
• the spin-coated film thickness is determined mainly by the solid contents in solution and the spin rate. For example, at a 2000 rpm spin rate, 2, 5, 8 and 10 wt%polymer resin formulated solutions result in the film thickness of 30, 90, 160 and 220 nm, respectively.
• a reflux condenser was attached, the unit was sealed and removed from the glovebox.
• 4-vinylbenzyl chloride (1.05mL, 7.45mmol, 1.20equiv) was injected, and the mixture was refluxed until consumption of starting material.
• the reaction mixture was cooled (iced bath) and cautiously quenched with isopropanol. Sat. aq. NH 4 Cl was added, and the product was extracted with ethyl acetate. Combined organic fractions were washed with brine, dried with MgSO 4 , filtered, concentrated, and purified by chromatography on silica.
• B monomer (1.00 equiv) was dissolved in anisole (electronic grade, 0.25 M) .
• anisole electroactive grade, 0.25 M
• AIBN solution (0.20 M in toluene, 5 mol%) was injected.
• the mixture was stirred until complete consumption of monomer, at least 24 hours (2.5 mol%portions of AIBN solution can be added to complete conversion) .
• the polymer was precipitated with methanol (10x volume of anisole) and isolated by filtration. The filtered solid was rinsed with additional portions of methanol. The filtered solid was re-dissolved in anisole and the precipitation/filtration sequence repeated twice more. The isolated solid was placed in a vacuum oven overnight at 50 °C to remove residual solvent.
• Monomer A has the following structure
• Monomer B has the following structure:
• Monomer C has the following structure
• B-staged charge transporting polymers are formed by step-growth polymerization via [4+2] Diels-Alder reaction between BCB and styrene (Sty) in Monomers A, B &C.
• the polymers obtained were as follows.
• HTL formulation solution Charge transporting B polymer solid powders were directly dissolved into anisole to make a 2 wt% stock solution.
• HTL homopolymers the solution was stirred at 80°C for 5 to 10 min in N 2 for complete dissolving.
• Organic acids were directly dissolved into anisole to make a 2 wt%stock solution.
• the anisole solvent was replaced by 2-heptanone for complete dissolving.
• the resulting formulation solution was filtered through 0.2um PTFE syringe filter prior to depositing onto Si wafer.
• the resulting HTL formulation was prepared using toluene for HTL homopolymer and anisole for B-staged HTL copolymer, sealed in N 2 and then kept in refrigerator for 4 weeks before proceeding to the following thermal cross-linking and strip tests.
• the use of toluene rather than anisole is expected to accelerate the aging process of the formulation.
• the total film loss after anisole stripping should be ⁇ 1 nm, preferably ⁇ 0.5nm.
• B1 homopolymer gives almost 100% film loss after 205°C/10min thermal treatment, indicating the benzyl ether is non-reactive in absence of acid catalyst and no cross-linking occurs.
• B1 homopolymer gives significant cross-linking upon the addition of HB acid.
• the total film loss decreases with increasing HB level and cross-linking temperature and time.
• Fully cross-linked B1 homopolymer film with good solvent resistance can be achieved at 5wt% HB and 190°C/10min, 2wt% HB and 205°C/5min, 1 wt% HB and 205°C/10min.
• B1 homopolymer gives almost 100% film loss after 205°C/10min thermal treatment, indicating the benzyl ether is non-reactive in absence of acid catalyst and no cross-linking occurs.
• B1 homopolymer gives significant cross-linking upon the addition of TB acid.
• the total film loss decreases with increasing TB level and cross-linking temperature and time.
• B1 homopolymer film with good solvent resistance can be achieved at 5wt% TB and 190°C/5min, 2wt% TB and 205°C/5min.
• B1 homopolymer +TB gives similar performance to that of B1 homopolymer +HB
• B1 homopolymer + TB film prepared using aged formulation and cross-linked at 205°C10min still gives identical optical properties to the film prepared using fresh formulation.
• Low and High MW B2 Homopolymer film with good solvent resistance can be achieved at 5wt% HB and 205°C/5min, 2wt% HB and 205°C/10min for low MW polymer; 2wt% HB and 190°C/10min, 1wt% HB and 205°C/10min for high MW polymer.
• High MW B2 +HB performs better than that of low MW B2+HB.
• B2 Homopolymer gives significant cross-linking upon the addition of TB acid.
• the total film loss decreases with increasing TB level and cross-linking temperature and time.
• Fully cross-linked B2 Homopolymer film with good solvent resistance can be achieved at 5wt% TB and 205°C/5min for low MW polymer; 2wt% TB and 190°C/10min for high MW polymer.
• High MW B2 Homopolymer +TB performs better than that of low MW HTL-SP-28 (1: 0) +TB.
• B2 Homopolymer +TB gives similar performance to that of B2 Homopolymer +HB.
• Formulation of low MW B2 homopolymer and TB acid that is aged after 29 days still gives nearly fully cross-linked film with good solvent resistance after 205°C10min thermal treatment, similar to the performance of the film prepared using fresh formulation.
• the low MW B2 homopolymer + TB film prepared using aged formulation and cross-linked at 205°C10min still gives identical optical properties to the film prepared using fresh formulation.
• the good shelf stability of low MW B2 homopolymer in presence of highly reactive TB acid can be attributed to the absence of typical reactive cross-linkable group such as styrene, acrylic etc.
• High MW B2 homopolymer gives significant cross-linking upon the addition of 10wt% DDSA acid at 205°C/10min, result in ⁇ 2 nm total film loss.
• High MW B2 homopolymer +DDSA does not perform as good as that of high MW B2 homopolymer +HB or TB, presumably due to the incompatibility between HTL polymer and DDSA.
• High MW B2 homopolymer gives more than 85% film loss in presence of 10wt% AVAND TGA at 205°C/10min, which temperature is significantly lower than TGAs’decomposition temperature.
• High MW B2 homopolymer gives significant cross-linking with 6 to 7 nm film loss in presence of 10wt%AVAND TGA at 250°C/20min, which temperature is near TGAs’decomposition temperature.
• High MW B2 homopolymer +AVAND TGA does not perform as well as high MW B2 homopolymer +HB or TB, presumably due to the TGAs’high decomposition temperature.
• High MW Comp homopolymer gives more than 60% film loss in presence of 10wt% HB and TB at 205°C/10min.
• High MW B3 polymer and B6 polymer gives further enhanced cross-linking upon the addition of TB acid.
• the total film loss further decreases with increasing TB level and cross-linking temperature and time.
• Fully cross-linked B3 or B6 film with good solvent resistance can be achieved at 10wt% TB and 170°C/15min, 2wt% TB and 190°C/10min for B3; 5wt% TB and 170°C/15min, 2wt% TB and 190°C/10min for B6.
• High MW B3 polymer and B6 polymer +TB performs better than that of B1 homopolymer, due to the additional acid catalyzed benzyloxy cross-linking.
• Fully cross-linked film with good solvent resistance can be achieved at 10wt% TB and 205°C/5min, for both B4 and B7.
• Medium MW B8 gives cross-linking after 205°C/5 to 20min thermal treatment due to the BCB self-reaction in absence of acid catalyst. However, the cross-linking is not good enough to give fully cross-linked film, resulting in >5 nm film loss. Under the same conditions, medium MW B5 gives no cross-linking, resulting in almost 100% film loss.
• Fully cross-linked film with good solvent resistance can be achieved at 10wt% TB and 190°C/15min for B8; 10wt% TB and 205°C/20min for B5.
• B9 homopolymer gives almost 100% film loss after 190C to 220°C/10min thermal treatment, indicating the benzyl ether is non-reactive in absence of acid catalyst and no cross-linking occurs.
• B9 homopolymer gives significant cross-linking upon the addition of HB acid.
• the total film loss decreases with increasing HB level and cross-linking temperature and time.
• Fully cross-linked B1 homopolymer film with good solvent resistance can be achieved at 5wt% HB and 205°C/10min, 2wt% HB and 220°C/10min.
• B10 copolymer gives almost 100% film loss after 190C to 220°C/10min thermal treatment, indicating the benzyl ether is non-reactive in absence of acid catalyst and no cross-linking occurs.
• B10 copolymer gives significant cross-linking upon the addition of HB acid.
• the total film loss decreases with increasing HB level and cross-linking temperature and time.
• Fully cross-linked B10 copolymer film with good solvent resistance can be achieved at 5wt% HB and 190°C/10min, 2wt% HB and 205°C/10min, 1wt% HB and 220°C/10min.
• B-staged A, B & C give cross-linking after 205°C/5 to 20min thermal treatment due to the combined BCB and styrene reactions in absence of acid catalyst.
• the cross-linking is not good enough to give fully cross-linked film, resulting in 4 to 7 nm loss for those B-staged at 105°C for 5hr and > 10 nm loss for those B-staged at 105°C for 40hr.
• B-staged A, B & C gives significantly improved cross-linking upon the addition of 5 or 10wt% TB acid.
• B-staged A, B & C +TB performs better than those of B-staged copolymer only, due to the additional acid catalyzed benzyl ether cross-linking.
• B-staged A, B & C gives cross-linking after 205°C/5 to 20min thermal treatment due to the combined BCB and styrene reactions in absence of acid catalyst.
• the cross-linking is not good enough to give fully cross-linked film, resulting in about 4 nm loss.
• B-staged A, B & C gives significantly improved cross-linking upon the addition of 8.2wt% HB acid at 205°Cfor > 20min.
• Fully cross-linked B-staged A, B & C film with good solvent resistance can only be achieved at 8.2wt% HB and 205°C/40min, 8.2wt% HB and 220°C/10min.
• B-staged A, B & C +HB performs better than those of B-staged copolymer only, due to the additional acid catalyzed benzyl ether cross-linking.
• Formulations of B-staged A, B & C and TB acid that are aged after 31 days give nearly 100% film loss after 205°C10min thermal treatment, significantly worse than the performance of the films prepared using fresh formulation.
• B3, B4, B6 & B7 homopolymers are more advantageous for shelf-stability due to high stability of benzyl ether and absence of reactive cross-linkable groups.
• Type A ITO/AQ1200/HTL molecule (evaporative, ) /EML/ETL/Al
• Type B ITO/AQ1200/HTL polymer (soluble, ) /EML/ETL/Al
• Type C ITO/AQ1200/HTL polymer + acid p-dopant /EML/ETL/Al
• HIL Hole Injection Layer
• Emission Material Layer Emission Material Layer
• ETL Electron Transporting Layer
• cathode Al cathode Al
• Type A device was fabricated with evaporated HTL (same HTL core as HTL polymer) as evaporative control
• Type B device was fabricated with solution processed HTL polymer as soluble control
• Type C device was fabricated with solution processed HTL polymer plus 2 to 10wt%acid p-dopant.
• Type A-C devices Current density-voltage (J-V) characteristics, luminescence efficiency versus luminance curves, and luminescence decay curves of Type A-C devices were measured to evaluate the key device performance, specifically the driving voltage (at 1000 nit) , current efficiency (at 1000 nit) and lifetime (15000 nit, after 10 hr) .
• Type A to C Hole-Only Device (HOD) without EML and ETL layers were also prepared and tested for evaluating the hole mobility of the acid p-doped HTL.
• Example 18 Formulation of B-staged A, B&C and TB as HTL in OLED, HOD Device
• Cross-linked B-staged A, B&C (Device 5, 6) gives reduced hole mobility than non cross-linked B-staged A, B&C (Device 4) in term of higher driving voltage.
• TB doped cross-linked B-staged A, B&C (Device 7) gives higher hole mobility than cross-linked B-staged A, B&C (Device 5, 6) in term of lower driving voltage.
• TB doped cross-linked B-staged Monomers A, B&C (Device 7) gives longer lifetime than cross-linked B-staged A, B&C (Device 5, 6) , which almost matches the evaporative control (Device 2) .
• the hole mobility of TB doped cross-linked B-staged A, B&C gives higher hole mobility than the evaporative control (Device 1) in term of low driving voltage.
• Example 19 Formulation of High MW B6 Copolymer and TB as HTL in OLED, HOD Device
• TB doped cross-linked high MW B6 copolymer (Device 8) gives higher hole mobility than cross-linked high MW B6 copolymer itself (Device 5) in term of lower driving voltage.
• TB doped cross-linked high MW B6 copolymer (Device 8) gives longer lifetime than cross-linked high MW B6 copolymer (Device 5) , which almost matches the evaporative control (Device 2) .
• TB doped cross-linked high MW B6 copolymer gives similar performance to evaporative control (Device 1, 2) in term of turn-on voltage, efficiency and lifetime.
• the hole mobility of TB doped cross-linked high MW B6 gives higher hole mobility than the evaporative control (Device 1) in term of lower driving voltage.
• Example 20 Formulation of Low MW B2, Medium MW B4, B7 and TB as HTL in OLED, HOD Device
• TB doped cross-linked low MW B2 homopolymer (Device 9) and medium MW B4, B7 copolymer (Device 10, 11) gives higher hole mobility than cross-linked low MW B2 (Device 6) and medium MW B4, B7 ( Device 7, 8) in term of lower driving voltage.
• TB doped cross-linked low MW B2 (Table 5-2 Device 9) and medium MW B4, B7 ( Device 10, 11) gives longer lifetime than cross-linked low MW B2 (Device 6) and medium MW B4, B7 (Device 7, 8) , which almost matches the evaporative control (Device 2) .
• TB doped cross-linked low MW B2, medium MW B4, B7 gives similar performance to evaporative control (Device 1, 2) in term of turn-on voltage, efficiency and lifetime.
• TB doped cross-linked low MW B2 homopolymer (Device 8) and medium MW B4, B7 copolymer (Device 9, 10) gives higher hole mobility than cross-linked low MW B2 (Device 5) and medium MW B4, B7 (Device 6, 7) , as well as non-cross-linked low MW B2 (Device 2) and medium MW B4, B7 (Device 3, 4) in term of lower driving voltage.
• Example 21 Formulation of High MW B1 and TB/HB as HTL in OLED Device
• TB/HB doped cross-linked high MW B1 (Device 5, 6) gives similar performance to evaporative control (Device 2) in terms of driving voltage and lifetime.
• the efficiency is higher for TB/HB doped cross-linked high MW B1 (Device 5, 6 vs. 2) .

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