White organic light-emitting devices with a bipolar transport layer between blue fluorescent and yellow phosphor-sensitized-fluorescent emitting layers

We report white organic light-emitting devices (WOLEDs) based on 4,4′-bis(2,2′-diphenylvinyl)-1,1′-biphenyl (DPVBi) and phosphorescence sensitized 5,6,11,12-tetraphenylnaphthacene (rubrene). By introducing a bipolar transport 4,4′-N,N′-dicarbazole-biphenyl (CBP) layer between the fluorescent and the phosphor-sensitized-fluorescent layers, additional light emission from the phosphorescence sensitized layer is observed. This can be attributed to the elimination of the Dexter energy transfer between these two emitters. White emission with Commission International de L’Eclairage coordinates of (0.22,0.33) and a maximum luminance of 22,360 cd/m² were obtained. The maximum current efficiency can reach 10.7 cd/A.     

Low driving voltage in organic light-emitting diodes using MoO3 as an interlayer in hole transport layer

Driving voltage of organic light-emitting diodes (OLEDs) was lowered by applying MoO₃ as an interlayer between hole injection layer (HIL) and hole transport layer (HTL). MoO₃ was effective as an interlayer between HIL and HTL due to its valence band of around 5.3 eV which is suitable for hole injection. Hole injection from HIL to HTL was enhanced by MoO₃ interlayer and driving voltage of green fluorescent device could be lowered by 1.3 V at 1000 cd/m² by using thin MoO₃ interlayer.     

Synthesis,crystal structure,photo- and electro-luminescence of 3-(4-(anthracen-10-yl)phenyl)-7-(N,N′-diethylamino)coumarin

A new coumarin derivative, 3-(4-(anthracen-10-yl)phenyl)-7-(N,N′-diethylamino)coumarin, was synthesized and characterized by FT-IR, ¹H NMR, element analysis and single crystal X-ray crystallography. The dihedral angle of coumarin ring and phenyl group is 30.83°, and the dihedral angle of phenyl group and anthracene skeleton is 76.99°. The photoluminescent (PL) and electroluminescent (EL) properties of the compound were investigated. The results show that the compound exhibits high fluorescence quantum yield (0.83), large Stokes shift and strong blue emission (466 nm). The electroluminescence devices comprised of vacuum vapor-deposited films using the compound as dopant were fabricated, showing blue emission that is identical to its photoluminescent spectrum in chloroform solutions. The electroluminescence device of indium tin oxide (ITO)/4,4′,4″-tris[2-naphthyl (phenyl)-amino]triphenylamine (2-TNATA) (5 nm)/N,N-bis-(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) (40 nm)/4,4-N,N-dicarbazole-biphenyl (CBP): dopant (1.0 wt%, 30 nm)/2-(4-biphenyl)-5-(4-t-butylphenyl)-1,3,4-oxadiazole (PBD) (30 nm)/LiF (1 nm)/Al (100 nm) gives a maximum luminous efficiency of 3.3 cd/A at the current density of 20 mA/cm², and maximum luminance of 5070 cd/m² at 16 V.     

Organic light-emitting device using new distyrylarylene host materials

Novel distyrylarylene-based blue host materials, 4,4′-bis(1,2-diphenylvinyl)-p-terphenyl (2), 4,4′-bis[1-phenyl-2-(p-tolyl)vinyl]-p-terphenyl (3) and 4,4′-bis[1-phenyl-2-(4,4′-biphenyl)vinyl]-p-terphenyl (4) were successfully synthesized using 4,4′-bisbenzoyl-p-terphenyl (1) through Wittig–Hornor reaction and a blue organic light-emitting diode (OLED) was made from them. The structure of the blue device is ITO/DNTPD/NPB/Host:DSA-Ph/Alq₃/Al-LiF. Here, NPB is used as a hole transport layer, DNTPD as the hole injection layer, DSA-Ph as the blue dopant, Alq₃ as the electron transport layer and Al as the cathode. The blue device doped with 5%-DSA-Ph shows a blue EL spectrum at 463 nm and a high efficiency of 4.14–5.13 cd/A.     

Theoretical studies of electronic structure and hole drift mobility of host hole transporting material 4,4′-N,N′-dicarbazol-biphenyl

The most commonly used host hole transport material, 4,4′-dicarbazole-1,1′-biphenyl (CBP), its structure, electronic transition mechanism and hole mobility were studied by means of ab initio HF, DFT B3LYP methods and Marcus theory. The lowest singlet excited state (S1) has been studied by the singles configuration interaction (CIS) method and time-dependent density functional theory (TD-DFT). The lowest singlet electronic transition (S0 → S1) is π–π* electronic transitions between carbazole and biphenyl parts involving the charge transfer from N atom to biphenyl. TD-B3LYP calculations predict an emission wavelength of 403.3 nm. This is comparable to 400 nm observed experimentally for photoluminescence. Using an incoherent transport model we calculated its hole mobility (μ). Both its reorganization energy and electronic coupling, especially the electronic couplings are considered and calculated in detail. It has high hole transport efficiency (μ = 8.60 × 10^?2 cm²/(V s)) and the result was rationalized in terms of the spatial extent of the highest occupied molecular orbital (HOMO) and molecular structural character.     

Control of efficiency characteristics in green phosphorescent organic light-emitting devices

The efficiency characteristics in green phosphorescent devices at low luminance as well as high luminance were investigated by using single, host-mixed and multiple emitting layer (EML) structure. 4,4′-Bis(N-carbazolyl)-1,1′-biphenyl (CBP) was used as a host suppressing electron injection and transport, whilst a host (GH) with a spirobifluorene-type backbone was used as a host enhancing electron injection and transport. When two hosts were optimally mixed (CBP:GH = 3:1) or a triple EML structure with GH–EML sandwiched between two CBP–EMLs were used, the improved current efficiency at high luminance was obtained and at the same time, the current efficiency at low luminance was maintained low.     

Movement of carrier recombination zone in organic light emitting devices by applied voltage

We fabricated organic light emitting devices that consist of three different emitting layers in series between hole transport layer (HTL) and electron transport layer (ETL), in order to investigate the carrier recombination zone in the devices. Since the three different emitting layers are constructed to emit different colors, the carrier recombination zone can be observed from the luminescence. The predominant recombination zone was found to be relatively far from the HTL–EML hetero-interface at low applied voltage (around 7 V). When the applied voltage increases to 11 V, the recombination zone tends to shift towards the hetero-interface. As the applied voltage increases further, interestingly the recombination zone tends to go back away from the HTL–EML interface due to the electron crossover to the HTL or electron diffusion back to the far side from the interface.     

New host materials with high triplet energy level for blue-emitting electrophosphorescent device

A series of new 9-phenylcarbazole (Cz-Ph)-based host materials with 1,2,4-trizole (TAZ) were synthesized for blue-emitting electrophosphorescent device. The substitution position of Cz-Ph on TAZ ring did not influence photoluminescence maximum (band gap) but the triplet energy level (T₁). The electron mobility of 3,5-bis-(3-(9-carbazoyl)-phenyl)-4-(4-butyl-phenyl)-4H-[1,2,4]triazole (6) is 10 times higher than the hole mobility. This is due to the electron transporting/hole blocking characteristics of TAZ moiety. The triplet energy level of the new host materials ranges from 2.8 to 3.0 eV which are suitable for blue-emitting electrophosphorescent devices. The time-resolved photoluminescence decay curve of 4% of FIrpic (iridium(III)bis[(4,6-difluorophenyl)-pyridinato-N,C2′]picolinate) doped in the film of compound 6 showed a single exponential decay curve with a lifetime of 1.2 μs. The absolute PL quantum efficiency (η_PL) of 6 doped with 4% of FIrpic was (82 ± 2%), which is significantly higher than the case of commonly used CBP (4,4′-bis-(9-carbazoyl)-biphenyl) (44 ± 2%). These results also strongly support that triplet excitons formed in FIrpic was not transferred to 6. For a device based on 6 (ITO/PEDOT:PSS (40 nm)/NPB (15 nm)/6:6% FIrpic (30 nm)/BAlq (35 nm)/LiF (1 nm)/Al (100 nm), the maximum photometric efficiency was 14.2 cd/A at a current density of 1.1 mA/cm², which is higher than that observed with a device based on CBP (ITO/PEDOT:PSS (40 nm)/NPB (30 nm)/CBP:6% FIrpic (40 nm)/BAlq (30 nm)/LiF (1 nm)/Al (100 nm)).     

Polymer light-emitting diodes with a phenyleneethynylene derivative as a novel hole blocking layer for efficiency enhancements

This paper reports on the use of an electron transport layer (ETL) in polymer light-emitting diodes based on poly(2,5-bis(3′,7′-dimethyl-octyloxy)1,4-phenylene-vinylene) (BDMO-PPV). This ETL is inserted between BDMO-PPV and a calcium cathode as a hole blocking layer (HBL). A novel phenyleneethynylene derivative (ImPE) is proposed and compared to well-known materials such as tris(8-hydroxyquinoline) aluminum (Alq₃) and bathocuproïne (BCP). Efficient hole blocking is achieved leading to yield improvements at low luminances. With a 8 nm-thick ImPE layer, at 1 cd/m², the power efficiency reaches 1.2 lm/W whereas a BDMO-PPV-only PLED exhibits a 0.13 lm/W power efficiency. ImPE enables to reach higher performances than Alq₃ for low luminances (<20 cd/m²). However, for luminances higher than 350 cd/m², it is demonstrated that the hole blocking in no more efficient because of a too strong electric field.     

Highly efficient blue electrophosphorescent devices with a novel host material

Highly efficient blue electrophosphorscent light emitting diodes with a new host material N,N′-dicarbazolyl-1,4-dimethene-benzene (DCB) were demonstrated. The energy transfer mechanism of the host–guest material system consisting of DCB and bis[(4,6-difluorophenyl)-pyridinato-N,C²′] (picolinato) Ir(III) (FIrpic) is an exothermic process. The device with a configuration of indium tin oxide/ N,N′-diphenyl-N,N′-bis(1,1′-biphenyl)-4,4′-diamine (NPB)/DCB:FIrpic/4,7-diphenyl-1,10-phenanthroline(BPhen)/Mg:Ag was optimized by adjusting the thickness of emitting layer and the dopant concentration. The device with the 8% (weight ratio) FIrpic and 30 nm emitting layer exhibits the maximum external quantum efficiency and current efficiency of 5.8% and 9.8 cd/A, respectively, at the luminance of 22 cd/m² driven at the voltage of 6.0 V.     

Synthesis and characterization of benzothiazole derivatives for blue electroluminescent devices

Two benzothiazole derivatives, 4-(benzo[d]thiazol-2-yl)-N-(4-(benzo[d]thiazol-2-yl)phenyl)-N-phenylbenzenamine (BBPA) and 4-(benzo[d]thiazol-2-yl)-N-(4-(benzo[d]thiazol-2-yl)phenyl)-N-naphthylbenzenamine (BBNA), were synthesized and characterized. Electroluminescent devices with compound BBPA or BBNA as the blue-emitting layer were fabricated. The triple-layer device, in which BBPA acted as the blue-emitter, NPB as the hole-transporting layer and TPBI as the electron-transporting layer (Device 1), showed a current efficiency of 5.24 cd/A, a power efficiency of 1.21 lm/W and an external quantum efficiency of 2.88% at a driving current density of 20 mA/cm². The double-layer device with BBNA as the emitting layer and electron-transporting layer and NPB as the hole-transporting layer (Device 4) exhibited a maximum brightness of 1430 cd/m² at 13 V with the CIE coordinates (0.21, 0.23).     

Synthesis,photoluminescent and electroluminescent properties of a novel europium(III) complex involving both hole- and electron-transporting functional groups

A novel europium(III) complex involving a carbazole fragment as hole-transporting group and an oxadiazole fragment as electron-transporting group was synthesized and used as red light-emitting material in organic light-emitting diodes (OLEDs). The complex is amorphous, and exhibits high glass transition temperature (T_g = 157 °C) and high thermal stability with a 5% weight loss temperature of 367 °C. Two devices, device 1: ITO/NPB (40 nm)/Eu(III) complex (30 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al (100 nm) and device 2: ITO/NPB (40 nm)/3% Eu(III) complex: CBP (30 nm)/BCP (10 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al (100 nm), were fabricated, where NPB is N,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine, Alq₃ is tris(8-hydroxyquinoline) Al(III), CBP is 4,4′-bis(carbazole-9-yl)-biphenyl, and BCP is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, respectively. In contrast with device 1, owing to less self-quenching and better charge confinement, device 2 shows improved performances: the maximum luminance of device 2 was dramatically increased from 199 to 1845 cd/m², the maximum current efficiency was increased from 0.69 to 2.62 cd/A, the turn-on voltage was decreased from 9.5 to 5.5 V, and higher color purity was attained.     

Highly efficient blue electroluminescence based on a new anthracene derivative

A novel blue-light-emitting material, 2,3,6,7-tetramethyl-9,10-dinaphthyl-anthracene (TMADN), was synthesized and characterized. Organic light-emitting diode (OLED), which has a double-layer structure, has been fabricated. In this OLED, the homemade TMADN was used as the light-emitting material and 4,7-diphenyl-1,10-phenanthroline (DPA) was used as the hole blocking/electron transporting material, N,N′-biphenyl-N,N′-bis-(1-naphenyl)-[1,1′-biphenyl]-4,4′-diamine (NPB) was used as the hole transporting material. The peak emission of electroluminescence (EL) is at about 456 nm and the CIE coordinates are (0.171, 0.228). The brightness of the device is up to 5600 cd/m² at 17 V with the maximum EL efficiency of 2.2 cd/A.     

Organic tunable electroluminescent diodes from polyfluorene derivatives

We report on the electroluminescent properties of recently synthesized fluorine-based π-conjugated polymers. The spectral emission varies from blue to yellow depending on the composition of the alternated copolymers containing thiophene or phenylene moieties. The luminance of the devices can be enhanced by adequate balancing of the hole and electron injection/transport. Incorporation of a hole transporting molecule in the polymer and insertion of an insulating buffer layer in the device resulted in enhancement of the luminous efficiency. A 30-fold enhancement of the luminance was obtained by inserting an electron transporting layer. The highest luminance reached was 1640 cd/m² at 17 V and was obtained with a green emitter, poly(2,2′-(5,5′-bithienylene)-2,7-(9,9-dioctylfluorene)) (PBTF).     

Synthesis and electroluminescence of thiophene-based bipolar small molecules with different arylamine moieties

A series of fluorescent dyes consisted of a thiophene unit, an 1,3,4-oxadiazole unit and four different arylamine moieties were prepared using a facile multi-steps synthetic route with high yield. The four arylamine structures studied were triphenylamine, N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine, diphenyl(1-naphthyl)amine and 9-phenylcarbazole. Experimental results shown that their HOMOs varied from 5.21 to 5.73 eV strongly affected by the arylamine chemistry while their LUMOs remained relatively unchanged. Their corresponding emission colors ranged from UV (393 nm) to bluish green (483 nm). In general, the thiophene unit enhanced the overall thermal stability of the compounds. According to cyclic voltammetry, the compounds are predominantly hole-transporting while OLED results indicated cpd 10 possess both hole and electron transport properties. Single layer OLED fabricated from 10 resulted in ca. 2000 cd/m² (luminous intensity) and 1.10 cd/A (current efficiency) max, whereas, a multilayer OLED using 10 as the hole transporting layer achieved over 7400 cd/m² and 2.3 cd/A max.     

Low voltage organic light emitting diode using p–i–n structure

Efficient n-type doping has been achieved by doping Liq in electron transport material Alq₃. Detailed investigation of current density–voltage characteristics of electron only devices with different doping concentrations of Liq in Alq₃ has been performed. An increase in current density by two orders of magnitude has been achieved with 33 wt% of Liq doped in Alq₃. Organic light emitting diode with p–i–n structure was fabricated using F₄-TCNQ doped α-NPD as hole transport layer, Ir(ppy)₃ doped CBP as emitting layer and 33 wt% Liq doped Alq₃ as electron transport layer. Comparison of OLEDs fabricated using undoped Alq₃ and 33 wt% Liq doped Alq₃ as electron transport layer shows reduction in turn on voltage from 5 to 2.5 V and enhancement of power efficiency from 5.8 to 10.6 lm/W at 5 V.     

Charge transport studies in thermally evaporated 2,2′,7,7′-tetrakis-(N,N-di-4-methoxyphenylamino)-9,9′-spirobifluorene (spiro-MeOTAD) thin film

Charge transport mechanism in 2,2′,7,7′-tetrakis-(N,N-di-4-methoxyphenyl amino)-9,9′-spirobifluorene (spiro-MeOTAD) has been investigated as a function of temperature and organic layer thicknesses. Hole only devices of different thicknesses were fabricated in configuration ITO/spiro-MeOTAD/Au by vacuum evaporation technique. The hole current is space charge limited which provides a direct measurement of the hole mobility μ as a function of electric field and temperature. Gaussian disorder model has been used to explain the temperature and field dependent behavior of mobility. The values of energetic disorder (σ = 0.088 eV), positional disorder (Σ = 3.35) and mobility prefactor (μ₀ = 0.0147 cm²/V s) have been evaluated using this model.     

Synthesis,photophysical and electrophosphorescent properties of a novel fluorinated rhenium(I) complex

A novel fluorinated rhenium complex, i.e., Re-BFPP (BFPP, 2, 3-bis(4-fluorophenyl)pyrazino[2,3-f][1,10]phenanthroline) was designed, synthesized and characterized by ¹H NMR and mass spectroscopy. The light-emitting and electrochemical properties of this complex were studied. The organic light-emitting diodes (OLEDs) employing Re-BFPP as a dopant emitter with the structures of ITO/m-MTDATA (10 nm)/NPB (20 nm)/CBP: X wt.% Re-BFPP (30 nm)/Bphen (10 nm)/Alq₃ (30 nm)/LiF (1 nm)/Al (100 nm) were successfully fabricated and a broad electroluminescent peak at 553 nm was observed. The 10 wt.% Re-BFPP doped device exhibited the maximum luminance of 6342 cd/m² and a peak current efficiency of 17.9 cd/A, corresponding to the power efficiency of 8.1 lm/W.     

Highly efficient organic light-emitting diodes using novel hole-transporting materials

A new class of tetraminobiphenyl derivatives, which contains a 3,3′,5,5′-tetraminobiphenyl core, has been synthesized and examined as a hole-transporting material for organic light-emitting diodes. We fabricated the organic light-emitting diode (OLED) cells with tetraminobiphenyl derivatives as hole-injecting layer, hole-transporting layer and hole-injecting and transporting layer for green device with tris(8-quinolinolato)aluminum (Alq₃) doped with 1% of Coumarin 545T (C545T) as green emitting layer. Tetraminobiphenyls were found to be useful as a novel hole-transporting material. The electroluminescent device with the 3,3′,5,5′-tetrakis(p-tolyldiamino)biphenyl (TTAB) as a hole-transporting layer was more efficient than that with the analogous triarylamine, N,N′-di(naphthalene-1-yl)-N,N′-diphenyl benzidine (NPB). The external luminous efficiency of the device IV having TTAB as one hole-injecting and transporting layer can reach 14.55 cd/A, which is higher than the standard device I (11.66 cd/A) using two layers, a hole-injecting layer and a hole-transporting layer.     

Determination of electron and hole energy levels in mesoporous nanocrystalline TiO2 solid-state dye solar cell

A study of a hybrid heterojunction solar cell based on nanocrystalline mesoporous TiO₂ and the hole conductor spiro-OMeTAD (2,2′7,7′-tetrakis(N,N′-di-p-methoxyphenyl-amine)-9,9′-spiro-bifluorene) has been realized. Impedance and cyclic voltammetry techniques were used to measure the interfacial properties of the hybrid heterojunction and establish the energy levels of the solid-state electrolyte. It was observed that the energy levels of the organic hole transport material are changed when it forms a film deposited onto indium-doped tin oxide (ITO). Moreover, the HOMO level of the mono oxidized spiro-OMeTAD is well coupled with the HOMO level of the dye N719 (Ru(4,4′-dicarboxy-2,2′-bipyridyI)₂(SCN)₂) which implies that it is not convenient to increase the doping of the hole conductor much further than this first oxidized state. This doping level (n ≈ 10¹⁹ cm⁻³) also assures a high enough hole conductivity. The implications of our results to the solid-state dye solar cell performance are discussed.