HETEROCYCLIC COMPOUNDS AND THEIR USE IN ELECTRO-OPTICAL OR OPTO-ELECTRONIC DEVICES

Abstract

Compounds exhibiting high hole mobility and/or high glass transition temperatures together with favourable HOMO, LUMO and triplet levels are provided which are 2-(4-Diphenylamino)phenyl-8-(1-thianthrenyl)- dibenzothiophene and 4-(1-Thianthrenyl)-bis(triphenylamine). The compounds may be used for hole transport layers e.g. in OLED devices.

Claims

1-28. (canceled)

29. A compound selected from the group consisting of 4-diphenylamino)phenyl-8-(1-thianthrenyl)-dibenzothiophene and 4-(1-thianthrenyl)-bis(triphenylamine).

30. The compound of claim 29, which is in pure form as a result of sublimation.

31. A hole transport material comprising a compound of claim 2, and a p-dopant which is an acceptor-type organic molecule.

32. The material of claim 31, wherein the dopant is present in an amount such that when the material is deposited to form a layer the dopant contributes about 10-40% to layer thickness, preferably about 33% to layer thickness,

33. The material of claim 31, comprising one or more of: (a) tetracyanoquinodimethane or tetrafluorotetracyano-quinodimethane; (b) a compound of any of the general formulae (i)-(vii) below: ##STR00012## wherein the groups R in any of the formulae in (i) to (v) can be the same or different and are selected from hydrogen; substituted and unsubstituted aliphatic groups; substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures; halogens; and thiophenyl groups; and wherein in formula (i) the methyl groups may be replaced by C.sub.1-C.sub.4 alkyl or monocyclic or polyclic aryl or heteroraryl which may be further substituted e.g. with alkyl, aryl or arylamino, or of the formula viii or ix ##STR00013## wherein the groups R.sub.1-R.sub.4 when appearing in either of the above formulae can be the same or different and are selected from hydrogen; substituted and unsubstituted aliphatic groups; substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures; halogens; and thiophenyl groups; (c) a teritiary amine which is ?-NPB or ?-NPB.

34. An optical light-emitting diode having first and second electrodes and between said electrodes a layer comprising a compound as claimed in claim 29.

35. The device of claim 34, wherein said layer is a hole transport layer.

36. The device of claim 34, having an emissive layer comprising a compound selected from the group consisting of (a) a fluorescent emitter; (b) a phosphorescent emitter; (c) an ion fluorescent (rare earth based) emitter; (d) quantum dots; (e) thermally activated fluorescent (TADF) materials.

37. The device of claim 34, having a hole injection layer comprising CuPC, ZnTpTP, 2-TNATA or ##STR00014##

38. The device of claim 34, which forms part of a flat panel display or of a lighting panel.

39. An organic photovoltaic device including a compound as claimed in claim 29.

40. An imaging member for forming an electrostatic latent image device including a compound as claimed in claim 29.

41. P n organic thin film transistor comprising a compound as claimed in claim 29.

42. A dye sensitised solar cell device comprising a compound as claimed in claim 29.

43. A printed device comprising a compound as claimed in claim 29.

44. A quantum dot based electroluminescent device comprising a compound as claimed in claim 29.

45. The device of claim 16, having a hole transport layer in which is incorporated said compound as claimed in claim 29.

46. An OLED device used as a light source to print conductive, resistive, dielectric, piezoelectric or pyroelectric films or lines or grids comprising a compound as claimed in claim 29.

47. An OLED lighting panel comprising a compound as claimed in claim 29.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0010] How the invention mat be put into effect will now be described with reference to the accompanying drawings, in which:

[0011] FIG. 1 is a diagram showing plots along variously directed lines of hole mobility, melting point, glass transition temperature, HOMO level and LUMO level for the compounds ?-NPB, HTS-4, HTS-8 and HTS-11;

[0012] FIG. 2 is a bar chart showing HOMO and LUMO levels for various hole transport compounds;

[0013] FIG. 3 shows luminous efficiency for various OLED devices of Example 4; and

[0014] FIG. 4 is an energy band diagram for the OLED device of Example 4

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

[0015] The above compounds may be purified by sublimation. Their physical properties and those of related materials are summarised in the table below:

TABLE-US-00001 Compound ?-NPB HTS-4 HTS-8 HTS-10 HTS-11 HTS-13 M.P/? C. 279-283 Tg/? C. 122 135 96 124 107 Td/? C. 450 510 450 500 425 Band gap/eV 3.1 3.3 3.9 3.2 3.3 3.1

[0016] The above compounds may be used as hole transporters on their own or may comprise a hole transport material together with p-dopant which is an acceptor-type organic molecule. In the latter case, the dopant may be present in an amount such that when the material is deposited to form a layer the dopant contributes about 10-40% to layer thickness, e.g. in an amount such that when the material is deposited to form a layer the dopant contributes about 33% to layer thickness. The dopant may comprise tetracyanoquinodimethane or tetrafluorotetracyano-quinodimethane or it may comprise a compound of any of the general formulae (i)-(vii) below:

##STR00002##

wherein the groups R in any of the formulae in (i) to (v) can be the same or different and are selected from hydrogen; substituted and unsubstituted aliphatic groups; substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures; halogens; and thiophenyl groups; and wherein

[0017] in formula (i) the methyl groups may be replaced by C.sub.1-C.sub.4 alkyl or monocyclic or polyclic aryl or heteroraryl which may be further substituted e.g. with alkyl, aryl or arylamino, or of the formula viii or ix

##STR00003##

[0018] wherein the groups R.sub.1-R.sub.4 when appearing in either of the above formulae can be the same or different and are selected from hydrogen; substituted and unsubstituted aliphatic groups; substituted and unsubstituted aromatic, heterocyclic and polycyclic ring structures; halogens; and thiophenyl groups.

[0019] Such dopants may comprise a teritiary amine which is ?-NPB or ?-NPB.

[0020] The above compounds may be incorporated into an optical light-emitting diode OLED) having first and second electrodes and between said electrodes a layer comprising a compound as set out above or a doped material material as set out above, either compound or a mixture of them forming a hole transport layer. In such an OLED the emissive layer may be a fluorescent emitter, a phosphorescent emitter, an ion fluorescent (rare earth based) emitter, a quantum dot or a thermally activated fluorescent (TADF) material.

[0021] In such a device there may be provided a hole injection layer comprising PEDOT:PSS, CuPC, ZnTpTP, 2-TNATA, MoO.sub.3 or

##STR00004##

[0022] Known electron transport materials may provide an electron transport layer e.g. aluminium quinolate, zirconium quinolate. Organic electron transporters which may be used include 1,3,5-tris(N-phenylbenzimidizol-2-yl)benzene and any of the compounds shown below:

##STR00005##

[0023] As electron injection layer, any known electron injection material may be used, LiF being typical. Other possibilities include BaF.sub.2, CaF.sub.2, CsF, MgF.sub.2 and KF. The electron injection layer may be deposited direct onto the cathode and may also comprise a compound of the formula

##STR00006##

wherein

[0024] R.sub.1 is a 1-5 ring aryl (including polycyclic aryl or aryl-substituted polycyclic aryl), aralkyl or heteroaryl group which may be substituted with one or more C.sub.1-C.sub.4 alkyl or alkoxy substituents; and

[0025] R.sub.2 and R.sub.3 together form a 1-5 ring aryl (including polycyclic or aryl-substituted polycyclic aryl), aralkyl or heteroaryl group which may be substituted with one or more C.sub.1-C.sub.4 alkyl or alkoxy substituents. A compound of the above formula may be used alone or in combination with another electron injection material e.g. a quinolate such as lithium or zirconium quinolate. The Schiff base preferably comprises at least 30 wt % of the electron injection layer, more preferably at least 50 wt %.

[0026] In the formula set out above, R.sub.1 may be polycyclic aryl e.g. naphthyl, anthracenyl, tetracenyl, pentacenyl or a perylene or pyrene compound or may have up to 5 aromatic rings arranged in a chain e.g. biphenyl. It is preferably phenyl or substituted phenyl. R.sub.2 and R.sub.3 together may form the same groups as R.sub.1 and are preferably phenyl or substituted phenyl. Where substituents are present they may be methyl, ethyl, propyl or butyl, including t-butyl substituted, or may be methoxy, ethoxy, propoxy or butoxy including t-butoxy substituted. Particular compounds include

##STR00007##

[0027] In many embodiments, aluminium is used as the cathode either on its own or alloyed with elements such as magnesium or silver, although in some embodiments other cathode materials e.g. calcium may be employed. In an embodiment the cathode may comprise a first layer of alloy e.g. LiAg, MgAg or AlMg closer to the electron injection or electron transport layer and a second layer of pure aluminium further from the electron injection or electron transport layer. Cells in which graphene serves as cathode are also within the invention.

[0028] The above compounds may be incorporated into a device which forms part of a flat panel display, a lighting panel, an organic photovoltaic device, an electrostatic latent image device, an organic thin film transistor, a dye sensitised solar cell device, a printed device, or a quantum dot based electroluminescent device. Such an OLED device may be used as a light source to print conductive, resistive, dielectric, piezoelectric or pyroelectric films or lines or grids.

[0029] It is believed that one or both of the compounds described herein can be incorporated into or used as a hole transport layer in a quantum dot electroluminescent device or QLED. More specifically, a representative QLED is described in US Patent Application No. 2009/009057 (Lee et al.,) which describes a QLED comprising: a substrate, a hole injection electrode, a hole transport layer, a quantum dot luminescent layer, an electron transport layer, and an electron injection electrode. Materials suggested for the hole transport layer include poly(3,4-ethylenedioxythiophene) (PEDOT)/polystyrene parasulfonate (PSS), poly-N-vinylcarbazole, polyphenylenevinylene, polyparaphenylene, polymethacrylate, poly(9,9-octylfluorene), poly(spiro-fluorene), N,N-diphenyl-N,N-bis 3-methylphenyl-1,1-biphenyl-4,4-diamine (TPD), N,N-di(naphthalene-1-yl)-N-N-diphenyl-benzidine, tris(3-methylphenylphenylamino)-triphenylamine (m-MTDATA), poly-9,9-dioctylfluorene-co-N-(4-butylphenyl)diphenylamine (TFB), copper phthalocyanine, polyvinylcarbazole (PVK), and derivatives thereof and starburst materials. The quantum dot luminescent layer may include a material selected from the group consisting of a II-VI group compound semiconductor nanocrystal, a III-V group compound semiconductor nanocrystal, a IV-VI group compound semiconductor nanocrystal, a IV group compound semiconductor nanocrystal, and a mixture thereof; metal oxides, including ZnO, SiO.sub.2, SnO.sub.2, WO.sub.3, ZrO.sub.2, HfO.sub.2, Ta.sub.2O.sub.5, BaTiO.sub.3, BaZrO.sub.3, Al.sub.2O.sub.3, Y.sub.2O.sub.3 and ZrSiO.sub.4 and mixtures thereof. The present compounds or a mixture of them and optionally a p-dopant which is an acceptor-type organic molecule may be incorporated into the hole transport layer as alternative to, in addition to or in admixture with the compounds mentioned above, see also U.S. Pat. No. 7,569,248 (fang et al., Samsung), U.S. Pat. No. 8,552,416 (Kin et al., L G Display Co.) and Kathirgamanathan, Electroluminescent Organic and Quantum Dot LEDs: The State of the Art, J. Display Technologies, 11, No. 5, 480-493. Such QLED devices may be incorporated into display panels or used for lighting.

[0030] How the invention may be put into effect will now be described with reference to the accompanying examples

EXAMPLE 1 (Reference)

Synthesis of 2,8-Dibromodibenzothiophene

[0031] ##STR00008##

[0032] To a slurry of dibenzothiophene (15.0 g; 0.0814 mol) in chloroform (80 ml) was slowly added bromine (10.5 ml; 32.6 g; 0.18 mol) in chloroform (20 ml). The red-brown reaction mixture was stirred at room temperature for 24 h and then solvent removed by distillation at atmospheric pressure. The residue was washed three times with methanol until the filtrate became almost colourless. The off-white solid was dried under vacuum at 75? C. Yield 20.5 g (74%). The product was sublimed to give an analytically pure colourless solid, 18.2 g (89%). M.p 223? C. (DSC, onset) and 227? C. (DSC, peak) [Lit., 226? C. TCI]

2,8-Bis(1-thianthrenyl)dibenzothiophene [HIS-8]

[0033] ##STR00009##

[0034] To a solution of 2,8-Dibromodibenzothiophene (1.0 g; 2.9 mmol) in ethyleneglycol dimethyl ether (50 ml) at 60? C. was added 1-thianthreneboronic acid (1.6 g; 6.1 mmol) and tetrkis(triphenylphosphine)palladium (0.34 g; 0.29 mmol) followed by a solution of potassium carbonate (3.2 g; 23 mmol) in water (20 ml). The reaction mixture slowly darkened and became greenish in colour. The mixture was magnetically stirred and refluxed under nitrogen for 20 hours, after which solvent was removed from the cooled reaction mixture under reduced pressure. The residue was dissolved in dichloromethane (150 ml), extracted with water and then brine, after which the organic phase was dried over anhydrous magnesium sulphate. Removal of the solvent gave a greenish residue which was purified by column chromatography over silica gel using dichloromethane-petroleum ether (40-60? C.) (4:1) as eluent. A crude product was obtained by trituration with diethyl ether-petroleum ether (40-60? C.) to give an off-white solid, (1.3 g; 73%) which was further purified by sublimation at 300? C. (1.6?10.sup.?6 barr) to give a glassy solid, 0.48 g which did not show any melting peak on the DSC. Its glass transition temperature Tg was 133? C.

[0035] Found: C, 70.10; H, 3.41; S, 26.53. C.sub.36H.sub.20S.sub.5 requires C, 70.55; H, 3.29; S, 26.16%. UV: ?max/nm (?) (CH.sub.2Cl.sub.2); 294 (sh) (30,989), 263 (97,473) and 230 (35,934); UV: ?max/nm (thin film); 303 and 268; Band gap: 3.85 eV FL: ?max/nm (?) (CH.sub.2Cl.sub.2); 441 (excitation wavelength: 350 nm), ?max/nm (?) (powder) 439 (excitation wavelength: 350 nm); ?max/nm (?) (thin film), 434, (excitation wavelength: 350 nm). CV: electrolyte (100 mM-Tetrabutylammonium tetrafluoroborate), analyte (1 mM), Solvent-dichloromethane: HOMO: ?6,06 eV and LUMO: ?2.2 eV Calculated from optical absorption edge of the thin film; TGA/? C. (% weight loss): 486 (5) and 510 (10).

EXAMPLE 2

2-(4-diphenylamino)phenyl-8-(1-Thianthrenyl)-dibenzothiophene (HTS-11)

[0036] ##STR00010##

[0037] A mixture of 2-bromo-8-(1-thianthrenyl)dibenzothiophene (4.0 g, 8.38 mmole) and tetrakistriphenylphosphinepalladium (0.485 g; 0.420 mmol) was heated in 1,2-dimethoxyethane (50 ml) at about 50? C. for 10 minutes. Then, 4-(diphenylamino)phenylboronic acid (2.2 g; 7.54 mmol) in 1,2-dimethoxyethane (10 ml) was added followed by potassium carbonate (5.8 g; 41.97 mmol) in water (10 nil). The resulting mixture was refluxed under nitrogen for 20 hours. The solvent removed from the cooled reaction mixture and the residue dissolved in dichloromethane and washed with water. The organic phase again washed with brine and dried over anhydrous magnesium sulphate and solvent removed to give the crude product. This was subjected to column chromatography over silica gel using CH.sub.2Cl.sub.2-Petroleum ether (40-60? C.). The eluent containing the product was evaporated using rotary evaporator and the residue was magnetically stirred with methanol overnight to give a fluorescent white solid, 3.3 g (61%). The product was further purified by sublimation at 355? C. and 2.0?10.sup.?6 Torr to give colourless glassy solid, 1.3 g, sublimation yield of around 40%. The product did not show any melting peak in the DSC, but showed a Tg at 124? C.

[0038] Found: C, 79.37; H, 3.67; N, 2.45; S, 16.04%, also obtained C, 77.52; H, 4.13; N, 1.89; and S, 16.04%. C.sub.42H.sub.27NS.sub.3, requires C, 78.59; H, 4.24; N, 2.18; and S, 14.99%. UV: ?.sub.max(CH.sub.2Cl.sub.2)/nm (?/dm.sup.3 mol.sup.?1 cm.sup.?1) 338 (25,536) 291 sh (30,643) and 261 (72,321). ?.sub.max(Thin film)/nm: 336 sh, 291 (sh) and 261 nm. Optical band gap: 3.26 eV. FL: ?.sub.max/nm (CH.sub.2Cl.sub.2) em: 413; ex/nm: 300; ?.sub.max/nm (Powder) em: 419, ex/nm: 300; ?.sub.max/nm (Thin film) em: 414, ex/nm: 300. TGA/? C. (% weight loss): 461 (1%) and 509 (5)

EXAMPLE 3

4-(1-thianthrenyl)-bis(triphenyl amine) [HTS-13]

[0039] ##STR00011##

(a) To a slurry of 4,4-dibromotriphenylamine (5.3 g; 0.013 mole) in 2-methoxyethanol (50 ml) was added tetrakis(triphenylphosphine) palladium (0.76 g; 0.00066 mole) followed by 1-thianthrenylboronic acid (3.42 g; 0.013 mole) in 2-methoxy ethanol (30 ml). Then sodium tert-butoxide (2.4 g; 0.025 mole) was added followed by 2-methoxy ethanol (20 ml). The reaction mixture was refluxed under nitrogen for 20 hrs. The solution at the beginning became homogeneous then cloudy finally dark green in colour. The solvent removed under reduced pressure using the rotary evaporator and the residue extracted with dichloromethane. The dichloromethane solution was washed with brine and water then dried over anhydrous magnesium sulphate. The solvent after filtration of magnesium sulphate was evaporated in a rotary evaporator to give dark green solid. The solid was purified by column chromatography using petroleum ether-dichloromethane (3:2) to give a colourless solid, 3.4 g (48%)
(b) 4-Bromo-4-(1-thianthrenyl)triphenyl amine (3.3 g; 0.0061 mole) was taken-up in dimethoxy ethane (40 ml) and warmed at about 50? C. for 10 min, then (PPh.sub.3).sub.4Pd (0.75 g; 0.00065 mole) was added followed by toluene (20 ml). A clear solution was obtained but within 10 min it became dark in colour. 4-(diphenylamino)phenylboronic acid (1.60 g; 0.0055 mole) in toluene (20 ml) was added followed by potassium carbonate 92.6 g; 0.018 mole) in water (10 ml). The reaction mixture magnetically stirred and refluxed for 20 hrs. The solvent removed from the reaction mixture using rotary evaporator and the residue was dissolved in dichloromethane, washed with water twice and dried over anhydrous magnesium sulphate. The solvent filtered from magnesium sulphate and removed using rotary evaporator to give the crude product. The product was subjected to flash chromatography using CH.sub.2Cl.sub.2-Petroleum ether (40-60? C.) [1:1] to give the product as viscous liquid. This was cooled and magnetically stirred with methanol and small amounts of petroleum ether (40-60? C.) to give an amorphous white solid. The solid was filtered off and dried under vacuum at 80? C. to give 3.1 g of product (72%). The product was further purified by sublimation at 280? C. (4.8?10?7 Torr) to give a glassy solid 1.3 g (42%). The compound did not show any melting peak in DSC, but showed a glass transition temperature (Tg) at 107? C.

[0040] Found: C, 81.20; H, 4.80; N, 3.93; S, 10.16%. C.sub.48H.sub.34N.sub.2S.sub.2 requires, C, 82.02; H, 4.88; N, 3.98; and S, 9.12%. UV: ?.sub.max (Toluene)/nm (?/dm.sup.3 mol.sup.?1 cm.sup.?1) 324.50 (36,506). ?.sub.max (Thin film)/nm: 324.50 and 265.50 nm. Optical band gap: 3.1 eV. FL: ?.sub.max/nm (toluene) em: 394 and 410 (sh); ex/nm: 320; ?.sub.max/nm (Powder) em: 427, ex/nm: 320; ?.sub.max/nm (Thin film) em: 428 and 410 (sh), ex/nm: 320. TGA/? C. (% weight loss): 382 (5) and T.sub.d at 498? C.

EXAMPLE 4

Efficiency of OLED Devices

[0041] Oleds were fabricated using as hole transport layers ?-NPB, HTS-8 and HTS-11. The layers were as follows (HIL means hole injection layer, HTL mentis hole transport layer, EML means emissive layer and ETL means electron transport layer):

[0042] Anode: ITO on glass

[0043] HIL: PEDOT:PSS ?40 nm, spin coated

[0044] HTL NPB (50 nm), HTS-8 (10-22 nm) or HTS-11 (10-30 nm)

[0045] EML: TCTA:TPBi (3:7):Ir(ppy)2acac, doping 10%

[0046] ETL: TPBi (30 nm)

[0047] Cathode: LiF (0.5 nm)/Al (100 nm)

[0048] In the above listing PEDOT means poly(3,4-ethylenedioxythiophene) and PSS means poly(4-styrenesulfonate), TCTA means tris(4-carbazoyl-9-ylphenylamine) and TPBi means 1,3,5-tris(N-phenylbenzimidizol-2-yl)benzene. The PEDOT:PSS is spin coated and the HIS-8 is also spin coated in chlorobenzene. Device performance for various cells is shown below:

TABLE-US-00002 V.sub.T/V (Turn-on V.sub.D/V Maximum @1000 cd m.sup.?2 @10000 cd m.sup.?2 HTS Voltage) @1000 nits C/E (cd/A) P/E (lm/w) C/E (cd/a) P/E (lm/W) C/E (cd/A) P/E (lm/W) a-NPB (50 nm) a 2.69 4.28 52.68 51.13 52.23 38.32 36.80 16.79 a-NPB (50 nm) b 2.48 4.66 58.93 68.07 47.02 31.70 35.89 18.93 HTS-04 (10 nm) a 3.06 4.88 54.72 52.41 54.34 34.97 48.65 24.28 HTS-04 (50 nm) a 3.23 5.35 58.98 51.46 56.09 32.96 45.31 19.02 HTS-11 (10 nm) b 2.65 4.11 70.75 69.29 68.95 52.71 58.81 29.07 HTS-11 (30 nm) b 2.96 4.56 68.27 62.12 67.00 46.24 60.37 32.48 HTS-08* (10 nm) b 3.01 4.75 40.66 25.85 38.92 25.73 36.49 15.77 HTS-08* (20 nm) b 3.12 6.45 48.43 30.91 45.84 22.31 36.72 14.44 *Spin coated (Chlorobenzene) film. a) ITO/PEDOT:PSS(50 nm)/HTS-04/CBP:lr(ppv).sub.3(12%)(20 nm)/TPBi(40 nm)/LiF(1 nm)/Al b) ITO/PEDOT:PSS(40 nm)/HTS/TCTA:TPBi(3:7):lr(ppv).sub.2acac(10%)(Total thickness 20 nm)/TPBi(30 nm)/LiF(0.5 nm)/Al

[0049] The cells provide green emission. Efficiency in a representative cell is shown in FIG. 3 and is in the order HTS-11>HTS-822 ?-NPB and an energy band diagram for the cell appears as FIG. 4. A plot of current efficiency against luminance appears as FIG. 5.