High-efficiency and multi-function blue fluorescent material for organic electroluminescent devices

We demonstrate one high-efficiency blue fluorescent material, N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl)-N-phenylbenzenamine, with an emissive peak of 472 nm and the hole-transporting property speculated from different devices. It can function either as the single emissive layer or as the dye doped in N,N′-dicarbazolyl-4-4′-biphenyl (CBP). The former shows a maximum current efficiency and luminance of 7.06 cd/A (0.04 mA/cm²) and 16 930 cd/m², in contrast to 11.5 cd/A (4.35 mA/cm²) and 25 690 cd/m² for the latter. The better performance of the latter can be attributed to the bipolar carrier transport property of CBP and the hole-blocking and electron-transporting characteristic of 4,7-diphenyl-1,10-phenanthroline (BPhen), which resulting in a good balance of holes and electrons. Moreover, the Commission Internationale De L’Eclairage coordinates of the latter change slightly from (0.162, 0.3) to (0.148, 0.268) upon increasing the voltage from 3 V to 14 V.     

Efficient fluorescent white organic light-emitting diodes using co-host/emitter dual-role possessed di(triphenyl-amine)-1,4-divinyl-naphthalene

Efficient fluorescent white organic light-emitting diodes with low carrier-injection barriers were fabricated with device structure of indium tin oxide/N,N′-bis-(1-naphthy)-N,N′-diphenyl-1,1′-biphenyl-4-4′-diamine/white emission layer/1,3,5-tris(N-phenyl-benzimidazol-2-yl)benzene/lithium fluoride/aluminium. By blending in the blue host of 1-butyl-9,10-naphthalene-anthracene in the emissive layer an efficient electro-luminescent greenish-blue co-host of di(triphenyl-amine)-1,4-divinyl-naphthalene, with the doping of a trace amount of red dye of 4-(dicyano-methylene)-2-methyl-6-(julolidin-4-yl-vinyl)-4H-pyran, bright and colour-stable white emission with high power-efficiency of 14.6 lm/W at 100 cd/m² or current efficiency of 19.2 cd/A at 300 cd/m² or 18.7 cd/A at 10,000 cd/m² was obtained. The resulted synergistic increase in brightness and efficiency may be attributed to the presence of cascading new routes with comparatively lower electron injection barrier.     

Four-wavelength white organic light-emitting diodes using 4,4′-bis-[carbazoyl-(9)]-stilbene as a deep blue emissive layer

White organic light-emitting diodes (WOLEDs) with four wavelengths were fabricated by using three doped layers, which were obtained by separating recombination zones into three emitter layers. Among these emitters, blue emissions with two wavelengths (456 and 487 nm) were occurred in the 4,4′-bis(carbazoyl-(9))-stilbene (BCS) host doped with a perylene dye. Also, a green emission was originated from the tris(8-quinolinolato)aluminum (III) (Alq₃) host doped with a green fluorescent of 10-(2-benzothiazolyl)-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H,11H-[1]benzopyrano [6,7,8-ij]-quinolizin-11-one (C545T) dye. Finally, an orange emission was obtained from the N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) host doped with a 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidyl-9-enyl)-4H-pyran (DCJTB) dye. The white light could be emitted by simultaneously controlling the emitter thickness and concentration of fluorescent dyes in each emissive layer, resulting in partial excitations among those three emitter layers. Electroluminescent spectra of the device obtained in this study were not sensitive to driving voltage of the device. Also, the maximum luminance for the white OLED with the CIE coordinate of (0.34, 0.34) was 56,300 cd/m² at the applied bias voltage of 11.6 V. Also, its external quantum and the power efficiency at about 100 cd/m² were 1.68% and 2.41 lm/W, respectively.     

Fluorene-based cathode interlayer polymers for high performance solution processed organic optoelectronic devices

A hydrophilic polyfluorene-based conjugated polyelectrolyte (CPE) Poly[9,9-bis(4′-(6″-(diethanolamino)hexyloxy) phenyl)fluorene], PPFN-OH (Scheme 1) has been synthesized and utilized as cathode interlayer for both polymer light emitting diodes (PLEDs) and solar cells (PSCs). For comparison, another CPE namely Poly[9,9-bis(6′-(diethanolamino)hexyl)fluorene] (PFN-OH) has also been investigated. They comprise the same polyfluorene backbone structures with, respectively, diethanolaminohexyl (PFN-OH) and diethanolaminohexoxyphenyl (PPFN-OH) substituents attached to the C9 carbon of the fluorene repeat unit. In comparison to reference devices with more reactive Ca/Al cathodes, utilizing these CPEs as interlayers allowed an Al cathode to be used for blue light emission PLEDs, yielding 51% and 92% enhancement of maximum luminous efficiency (LE) for PFN-OH and PPFN-OH, respectively. The PLEDs with PPFN-OH showed both higher maximum LE and maximum luminance (L) (LE = 2.53 cd/A at 6.2 V, L = 9917 cd/m² at 8.3 V) than devices with PFN-OH (2.00 cd/A at 4.1 V, 3237 cd/m² at 7.2 V). The PPFN-OH PLEDs also showed no significant roll-off in efficiency with increasing current density up to 400 mA/cm², indicating excellent electron injection ability and stability for this interlayer. The insertion of alkoxy-phenyl groups at the C9-position in PPFN-OH is clearly advantageous. This simple modification significantly improves the CPE cathode interlayer performance. Parallel investigations of the electron extraction properties of PPFN-OH in inverted architecture PSCs with PCDTBT:PC₇₀BM bulk heterojunction active layers demonstrated a power conversion efficiency enhancement of ∼19% (from 4.99% to 5.95%) for indium tin oxide cathode devices compared with reference devices using Ca/Al cathodes. These results confirm PPFN-OH to be a promising interlayer material for high performance solution processed organic optoelectronic devices.     

Blue light-emitting OLED using new spiro[fluorene-7,9′-benzofluorene] host and dopant materials

A new spiro-type compound, 2-(10-biphenylanthracene)-spiro[fluorene-7,9′-benzofluorene] (BH-3B) containing anthracene moiety was prepared for the blue host material. Also new dopant materials, 2-[4′-(phenyl-4-vinylbenzeneamine)phenyl-spiro[fluorene-7,9′-benzofluorene] (BH-3BD) and 4-[2-naphthyl-4′(phenyl-4-vinylbenzeneamine)]phenyl (BD-1N) were successfully synthesized and a blue OLEDs were made from them. The structure of the device was as follows; ITO/DNTPD/α-NPD/Host:5% dopant/Alq₃/Al-LiF. Among all of the devices, the device obtained from BH-3B host doped with 5% BH-3BD showed the best electroluminescence characteristics. The emission peak of EL is at 456 nm and the CIE value is (0.15, 0.14). The brightness of the device is up to 5407 cd/m² at 10 V with the maximum EL efficiency of 3.4 cd/A.     

A hybrid white organic light-emitting diode with stable color and reduced efficiency roll-off by using a bipolar charge carrier switch

A hybrid white organic light-emitting diode (WOLED) with an emission layer (EML) structure composed of red phosphorescent EML/green phosphorescent EML/spacer/blue fluorescent EML was demonstrated. This hybrid WOLED shows high efficiency, stable spectral emission and low efficiency roll-off at high luminance. We have attributed the significant improvement to the wide distribution of excitons and the effective control of charge carriers in EMLs by using mixed 4,4′,4″-tri(9-carbazoyl) triphenylamine (TCTA) and bis[2-(2-hydroxyphenyl)-pyridine] beryllium (Bepp₂) as the host of phosphorescent EMLs as well as the spacer. The bipolar mixed TCTA:Bepp_2, which was proved to be a charge carrier switch by regulating the distribution of charge carriers and then the exciton recombination zone, plays an important role in improving the efficiency, stabilizing the spectrum and reducing the efficiency roll-off at high luminous. The hybrid WOLED exhibits a current efficiency of 30.2 cd/A, a power efficiency of 32.0 lm/W and an external quantum efficiency of 13.4% at a luminance of 100 cd/m², and keeps a current efficiency of 30.8 cd/A, a power efficiency of 27.1 lm/W and an external quantum efficiency of 13.7% at a 1000 cd/m². The Commission Internationale de l’Eclairage (CIE) coordinates of (0.43, 0.43) and the color rendering index (CRI) of 89 remain nearly unchanged in the whole range of luminance.     

Influence of plasma treatment of ITO surface on the growth and properties of hole transport layer and the device performance of OLEDs

Surface energy of indium tin oxide (ITO) surfaces treated by different plasmas, including argon (Ar–P), hydrogen (H₂–P), carbon tetrafluoride (CF₄–P), and oxygen (O₂–P), was measured and analyzed. The initial growth mode of hole transport layers (HTLs) was investigated by atomic force microscope observation of thermally deposited 2 nm thick N,N′-bis(1-naphthyl)-N,N′-diphenyl-1,1′-biphenyl-4,4′-diamine (NPB) on the plasma treated ITO surfaces. The results show that different plasma treatments of ITO influence the growth of HTLs in significantly different ways through the modification of surface energy, especially the polar component. The O₂–P and CF₄–P were found to be most effective in enhancing surface polarity through decontamination and increased dipoles, leading to more uniform and denser nucleation of NPB on the treated ITO surfaces. It was further found that increased density of nucleation sites resulted in a decreased driving voltage of OLEDs. Under the same fabricating conditions, a lowest driving voltage of 4.1 V was measured at a luminance of 200 cd/m² for the samples treated in CF₄–P, followed by the samples treated in O₂–P (5.6 V), Ar–P (6.4 V), as-clean (7.0 V) and H₂–P (7.2 V) plasma, respectively. The mechanisms behind the improved performance were proposed and discussed.     

High efficiency fluorescent white organic light-emitting diodes with red,green and blue separately monochromatic emission layers

Highly efficient fluorescent white organic light-emitting diodes (WOLEDs) have been fabricated by using three red, green and blue, separately monochromatic emission layers. The red and blue emissive layers are based on 4-(dicyanomethylene)-2-tert-butyl-6-(1,1,7,7-tetramethyljulolidin-4-yl-vinyl)-4H-pyran (DCJTB) doped N,N′-di(naphthalene-1-yl)-N,N′-diphenyl-benzidine (NPB) and p-bis(p-N,N-diphenyl-amino-styryl) benzene (DSA-ph) doped 2-methyl-9,10-di(2-naphthyl) anthracene (MADN), respectively; and the green emissive layer is based on tris(8-hydroxyquionline)aluminum(Alq₃) doped with 10-(2-benzothiazolyl)-2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H,5H,1[H-(1)-benzopyropyrano(6,7-8-i,j)quinolizin-1]-one (C545T), which is sandwiched between the red and the blue emissive layers. It can be seen that the devices show stable white emission with Commission International de L’Eclairage coordinates of (0.41, 0.41) and color rendering index (CRI) of 84 in a wide range of bias voltages. The maximum power efficiency, current efficiency and quantum efficiency reach 15.9 lm/W, 20.8 cd/A and 8.4%, respectively. The power efficiency at brightness of 500 cd/m² still arrives at 7.9 lm/W, and the half-lifetime under the initial luminance of 500 cd/m² is over 3500 h.     

Extremely low driving voltage electrophosphorescent green organic light-emitting diodes based on a host material with small singlet–triplet exchange energy without p- or n-doping layer

In order to achieve low driving voltage, electrophosphorescent green organic light-emitting diodes (OLEDs) based on a host material with small energy gap between the lowest excited singlet state and the lowest excited triplet state (ΔE_ST) have been fabricated. 2-biphenyl-4,6-bis(12-phenylindolo[2,3-a] carbazole-11-yl)- 1,3,5-triazine (PIC–TRZ) with ΔE_ST of only 0.11 eV has been found to be bipolar and used as the host for green OLEDs based on tris(2-phenylpyridinato) iridium(III) (Ir(ppy)₃). A very low onset voltage of 2.19 V is achieved in devices without p- or n-doping. Maximum current and power efficiencies are 68 cd/A and 60 lm/W, respectively, and no significant roll-off of current efficiency (58 cd/A at 1000 cd/m² and 62 cd/A at 10,000 cd/m²) have been observed. The small roll-off is due to the improved charge balance and the wide charge recombination zone in the emissive layer.     

Small molecule interlayer for solution processed phosphorescent organic light emitting device

Using a 4,4′,4′′-tris(N-carbazolyl)-triphenylamine (TCTA) small molecule interlayer, we have fabricated efficient green phosphorescent organic light emitting devices by solution process. Significantly a low driving voltage of 3.0 V to reach a luminance of 1000 cd/m² is reported in this device. The maximum current and power efficiency values of 27.2 cd/A and 17.8 lm/W with TCTA interlayer (thickness 30 nm) and 33.7 cd/A and 19.6 lm/W with 40 nm thick interlayer are demonstrated, respectively. Results reveal a way to fabricate the phosphorescent organic light emitting device using TCTA small molecule interlayer by solution process, promising for efficient and simple manufacturing.     

Optoelectronic characteristics of MEH-PPV polymer LEDs with thin,doped composition-graded a-SiC:H carrier injection layers

The optoelectronic characteristics of poly(2-methoxy-5-(2′ethyl-hexoxy)-1,4-phenylene-vinylene) (MEH-PPV) polymer LEDs (PLEDs) have been improved by employing thin doped composition-graded (CG) hydrogenated amorphous silicon–carbide (a-SiC:H) films as carrier injection layers and O₂-plasma treatment on indium–tin-oxide (ITO) transparent electrode, as compared with previously reported ones having doped constant-optical-gap a-SiC:H carrier injection layers. For PLEDs with an n-type a-SiC:H electron injection layer (EIL) only, the electroluminescence (EL) threshold voltage and brightness were improved from 7.3 V, 3162 cd/m² to 6.3 V, 5829 cd/m² (at a current density J = 0.6 A/cm²), respectively, by using the CG technique. The enhancement of EL performance of the CG technique was due to the increased electron injection efficiency resulting from a smoother barrier and reduced recombination of charge carriers at the EIL and MEH-PPV interface. Also, surface modification of the ITO transparent electrode by O₂-plasma treatment was used to further improve the EL threshold voltage and brightness of this PLED to 5.1 V, 6250 cd/m² (at J = 0.6 A/cm²). Furthermore, by employing the CG n[p]-a-SiC:H film as EIL [hole injection layer (HIL)] and O₂-plasma treatment on the ITO electrode, the brightness of PLEDs could be enhanced to 9350 cd/m² (at a J = 0.3 A/cm²), as compared with the 6450 cd/m² obtained from a previously reported PLED with a constant-optical-gap n-a-SiCGe:H EIL and p-a-Si:H HIL.     

Carrier transport of inverted quantum dot LED with PEIE polymer

An inverted-type quantum-dot light-emitting-diode (QD LED), employing low-work function organic material polyethylenimine ethoxylated (PEIE) as electron injection layer, was fabricated by all solution processing method, excluding anode electrode. From transmission electron microscopy (TEM) and scanning electron microscopy (SEM) studies, it was confirmed that CdSe@ZnS QDs with 7 nm size were uniformly distributed as a monolayer on PEIE layer. In this inverted QD LED, two kinds of hybrid organic materials, [poly (9,9-di-n-octyl-fluorene-alt-benzothiadiazolo)(F8BT) + poly(N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine (poly-TPD)] and [4,4′-N,N′-dicarbazole-biphenyl (CBP) + poly-TPD], were adopted as hole transport layer having high highest occupied molecular orbital (HOMO) level for improving hole transport ability. At a low-operating voltage of 8 V, the device emits orange and red spectral radiation with high brightness up to 2450 and 1420 cd/m², and luminance efficacy of 1.4 cd/A and 0.89 cd/A, respectively, at 7 V applied bias. Also, the carrier transport mechanisms for the QD LEDs are described by using several models to fit the experimental I–V data.     

Multiple exciton generation regions in phosphorescent white organic light emitting devices

We demonstrate a white electrophosphorescent organic light emitting device (WOLED) with a three-section emission layer (EML) where excitons are formed in the multiple emission regions. The EML consists of a stepped progression of highest occupied and lowest unoccupied molecular orbital energies of the ambipolar hosts. Analysis shows that (36 ± 6)% of the excitons form in the blue emitting region, while (64 ± 6)% form in the green emitting region at 100 mA/cm². The doping of the red, green and blue phosphors, each in its own host, allows for efficient utilization of excitons formed in these multiple regions. Based on this architecture, the WOLED has an internal quantum efficiency close to unity. The WOLED has total external quantum and power efficiencies of η_ext,t = (26 ± 1)% and η_p,t = (63 ± 3) lm/W at 12 cd/m², decreasing to η_ext,t = (23 ± 1)% and η_p,t = (37 ± 2) lm/W at 500 cd/m². When an undoped electron transport layer is used, the peak efficiency is η_ext,t = (28 ± 1)%. Due to the distributed exciton formation in the EML, the WOLED exhibits higher total efficiency than monochromatic devices employing the same red, green and blue dopant–host combinations.     

High-performance inverted top-emitting green electrophosphorescent organic light-emitting diodes with a modified top Ag anode

Green electrophosphorescent inverted top-emitting organic light-emitting diodes with a Ag/1,4,5,8,9,11-hexaazatriphenylene hexacarbonitrile (HAT-CN) anode are demonstrated. A high current efficacy of 124.7 cd/A is achieved at a luminance of 100 cd/m² when an optical outcoupling layer of N,N′-di-[(1-naphthyl)-N,N′-diphenyl]-1,1′-biphenyl-4,4′-diamine (α-NPD) is deposited on the anode. The devices have a low turn-on voltage of 3.0 V and exhibit low current efficacy roll-off through luminance values up to 10,000 cd/m². The angle dependent spectra show deviation from Lambertian emission and color change with viewing angle. Hole-dominated devices with Ag/HAT-CN electrodes show current densities up to three orders of magnitude higher than devices without HAT-CN.     

Enhanced pure red electroluminescence intensity of Eu(o-BBA)3(phen) by red dye co-doping and inorganic semiconductor as charge carrier function layer

There is an emission peak at 494 nm in the electroluminescence (EL) of PVK [poly(n-vinylcarbazole)]: Eu(o-BBA)₃(phen) besides PVK exciton emission and Eu³⁺ characteristic emissions. Both the peaking at 494 nm emission and PVK emission influenced the color purity of red emission from Eu(o-BBA)₃(phen). In order to restrain these emissions and obtain high intensity red emission, 4-(dicyanomethylene)-2-t-butyl-6-(1,1,7,7,-tetramethyljulolidy-9-enyl)-4Hpyran (DCJTB) and Eu(o-BBA)₃(phen) were co-doped in PVK solution and used as the active emission layer. The EL intensity of co-doped devices reached to 420 cd/m² at 20 V driving voltage. The chromaticity coordinates of EL was invariable (x = 0.55, y = 0.36) with the increase of driving voltage. For further improvement of EL intensity, organic–inorganic hybrid devices (ITO/active emission layer/ZnS/Al) were fabricated. The EL intensity was increased by a factor of 2.5 [(420 cd/m²)/(168 cd/m²)] when the Eu complex was doped with an efficient dye DCJTB, and by a factor of ≈4 [(650 cd/m²)/(168 cd/m²)] when in addition ZnS layer was deposited on such an emitting layer prior to evaporation of the Al cathode.     

Low and small resistance hole-injection barrier for NPB realized by wide-gap p-type degenerate semiconductor,LaCuOSe:Mg

LaCuOSe:Mg is a wide-gap p-type semiconductor with a high conductivity and a large work function. Potential of LaCuOSe:Mg as a transparent hole-injection electrode of organic light-emitting diodes (OLEDs) was examined by employing N,N′-diphenyl-N,N′-bis (1,1′-biphenyl)-4,4′-diamine (NPB) for a hole transport layer. Photoemission spectroscopy revealed that an oxygen plasma treated surface of LaCuOSe:Mg formed a hole-injection barrier as low as 0.3 eV, which is approximately a half of a conventional ITO/NPB interface. Hole-only devices composed of a LaCuOSe:Mg/NPB/Al structure showed a low threshold voltage ∼0.2 V and high-density current drivability of 250 mA cm⁻² at 2 V, which is larger by two orders of magnitude than that of ITO/NPB/Al devices. These results demonstrate that LaCuOSe:Mg has great potential as an efficient transparent anode for OLEDs and other organic electronic devices.     

High general and special color rendering index white organic light-emitting device with bipolar homojunction emitting layers

High general and special color rendering index (CRI) together with gamut area index (GAI) is demanded for lighting source. In a tolerable Duv, an efficient warm white organic light-emitting device (WOLED) with a high CRI and GAI is developed by using a bipolar homojunction emitting layers, i.e., junction between different emitting layers with the same bipolar host material. At a low drive voltage of 4 V, the WOLED shows a high luminance of 1594 cd/m² and a power efficiency of 12.95 lm/W, and, it shows a high general CRI of 82, a special CRI R₉ of 75, an average of R₉ to R₁₂ of 69 and a GAI of 95. Besides, the WOLED shows relative stable color coordinates due to the elimination of the charges accumulation at interface between different emitting layers. And the current efficiency roll-off of the WOLED is also reduced due to the balance of carrier injection and transport in emitting layers.     

Cadmium-free quantum dots based violet light-emitting diodes: High-efficiency and brightness via optimization of organic hole transport layers

Bright and efficient violet quantum dot (QD) based light-emitting diodes (QD-LEDs) with heavy-metal-free ZnSe/ZnS have been demonstrated by choosing different hole transport layers, including poly(4-butyl-phenyl-diphenyl-amine) (poly-TPD), poly[9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB), and poly-N-vinylcarbazole (PVK). Violet QD-LEDs with maximum luminance of about 930 cd/m², the maximum current efficiency of 0.18 cd/A, and the peak EQE of 1.02% when poly-TPD was used as HTL. Higher brightness and low turn-on voltage (3.8 V) violet QD-LEDs could be fabricated when TFB was used as hole transport material. Although the maximum luminance could reach up to 2691 cd/m², the devices exhibited only low current efficiency (∼0.51 cd/A) and EQE (∼2.88%). If PVK is used as hole transport material, highly efficient violet QD-LEDs can be fabricated with lower maximum luminance and higher turn-on voltages compared with counterpart using TFB. Therefore, TFB and PVK mixture in a certain proportion has been used as HTL, turn-on voltage, brightness, and efficiency all have been improved greatly. The QD-LEDs is fabricated with 7.39% of EQE and 2856 cd/m² of maximum brightness with narrow FWHM less than 21 nm. These results represent significant improvements in the performance of heavy-metal-free violet QD-LEDs in terms of efficiency, brightness, and color purity.     

Highly efficient green top-emitting organic light-emitting devices with metal electrode structure

In this work, the electrical and optical characteristics of top-emitting organic light-emitting device (TEOLED) using metal Ag as anode with different thicknesses have been investigated. The emission peak of fabricated TEOLED is 512 nm for a full-width at half-maximum (FWHM) of 48 nm in forward direction. The TEOLED turns on at 3 V with luminance of 2.38 cd/m² and reaches 16,300 cd/m² at 9 V. The maximum of current efficiency is 5.2 cd/A at 7 V, corresponding to the external quantum efficiency of 1.72%.     

Green phosphorescent iridium dendrimers containing dendronized benzoimidazole-based ligands for OLEDs

A series of novel non-conjugated functionalized benzoimidazole-based dendrimers containing peripheral benzyl ether type dendrons have been synthesized and characterized. These compounds undergo cyclometalation with iridium trichloride to form iridium(III) complexes. The emission wavelengths of these dendrimers are in the range from 510 to 530 nm, and the photoluminescence quantum yields (PLQYs) in the range from 0.45 to 0.80. Dendrimers (Gn)₂Ir(acac) and (Gn)₃Ir exhibit a reversible one-electron oxidation wave at ∼0.55 V and ∼0.37 V (vs. Ag/AgNO₃), respectively. With a device configuration of indium tin oxide/poly(3,4-ethylenedioxythiophene):poly(styrene sulfonic acid)/4,4′-bis(N-carbarzolyl)biphenyl:(G2)₃Ir 20 wt% dopant/1,3,5-tris(2-N-phenyl-benzoimidazolyl)benzene/LiF/Al has a maximum external quantum efficiency (EQE) of 17.6% and a maximum current efficiency of 61.5 cd/A.