Explaining the different efficiency behaviors of PHOLEDs with/without a hole injection barrier at the hole transport layer/emitter layer interface

In this work we investigate the different efficiency behaviors of the devices with and without hole injection barrier, utilizing in our investigation the archetypical 4,4′-bis(carbazol-9-yl)biphenyl:Tris(2-phenylpyridine)iridium(III) host–guest PHOLEDs system. The results show that the recombination of electrons and holes on the host material generally leads to higher device efficiency in comparison to the case where recombination happens on the guest material. The results also show that in devices where a hole injection barrier between the HTL and the host material in the EML exists, the emission mechanism gradually changes from one based on host e–h recombination to one based on guest e–h recombination as the guest concentration is increased. When host e–h recombination is dominant, although it tends to produce higher device efficiency, host e–h recombination is generally also associated with significant efficiency roll-off; the latter arises from quenching of the host triplet excitons primarily due to host–host TTA. As the concentration of the guest molecules increases and the creation of host triplet excitons subsides (since most e–h recombination occurs on the guest) host–host TTA decreases, hence also the efficiency roll-off. In such case, quenching is mostly caused by polarons residing on guest sites. At optimum guest concentrations (∼8% Vol.), a balance between host e–h recombination and guest e–h recombination is reached, and thus also minimal TTA and Triplet-Polaron Quenching. On the other hand, in devices where hole injection barrier between the HTL and the host in the EML is insignificant, emission mechanism is always based on host e–h recombination irrespective of the guest concentration, and therefore have higher efficiency and the efficiency does not depend on guest concentration. The absence of the injection barrier in these devices results in a wider recombination zone, and hence a lower exciton concentration in general, which in turn reduces host–host TTA and thus lowers efficiency roll-off. In contrast, guest–guest TTA is not found to play a significant role in device efficiency behavior.     

Analysis of exciton annihilation in high-efficiency sky-blue organic light-emitting diodes with thermally activated delayed fluorescence

We study external quantum efficiency (η_EQE) roll-off in organic light-emitting diodes (OLEDs) using thermally-activated delayed fluorescence (TADF) of 4,5-di (9H-carbazol-9-yl) phthalonitrile (2CzPN). Using 2CzPN intramolecular rate constants from optical analyses, we construct an exciton quenching model incorporating intersystem crossing and reverse intersystem crossing. The model indicates that singlet–triplet annihilation and triplet–triplet annihilation dominate η_EQE roll-off because of the relatively long 2CzPN triplet lifetime of 273 μs. This work yields a method to relax the exciton quenching process in TADF based OLEDs.     

Engineering Efficiency Roll‐Off in Organic Light‐Emitting Devices

Previous studies have identified triplet‐triplet annihilation and triplet‐polaron quenching as the exciton density‐dependent mechanisms which give rise to the efficiency roll‐off observed in phosphorescent organic light‐emitting devices (OLEDs). In this work, these quenching processes are independently probed, and the impact of the exciton recombination zone width on the severity of quenching in various OLED architectures is examined directly. It is found that in devices employing a graded‐emissive layer (G‐EML) architecture the efficiency roll‐off is due to both triplet‐triplet annihilation and triplet‐polaron quenching, while in devices which employ a conventional double‐emissive layer (D‐EML) architecture, the roll‐off is dominated by triplet‐triplet annihilation. Overall, the efficiency roll‐off in G‐EML devices is found to be much less severe than in the D‐EML device. This result is well accounted for by the larger exciton recombination zone measured in G‐EML devices, which serves to reduce exciton density‐driven loss pathways at high excitation levels. Indeed, a predictive model of the device efficiency based on the quantitatively measured quenching parameters shows the role a large exciton recombination zone plays in mitigating the roll‐off.     

A host material with a small singlet–triplet exchange energy for phosphorescent organic light-emitting diodes: Guest,host, and exciplex emission

A host material containing a triazine core and three phenylcarbazole arms, called 2,4,6-tris(3-(carbazol-9-yl)phenyl)-triazine (TCPZ), was developed for phosphorescent organic light-emitting diodes (OLEDs). Ultra-low driving voltages were achieved by utilizing TCPZ as the host due to its decreased singlet–triplet exchange energy (ΔE_ST) and low-lying lowest unoccupied molecular orbital (LUMO) energy level. Interaction between the RGB triplet emitters and TCPZ were studied in both photoluminescent and electroluminescent processes. Transient photoluminescence (PL) measurement of the co-deposited film of fac-tris(2-phenylpyridine) iridium (Ir(PPy)₃):TCPZ exhibits a shoulder at 565 nm whose lifetime is about two times longer than that of the Ir(PPy)₃ triplet excitons and can be attributed to the triplet exciplex formed between Ir(PPy)₃ and TCPZ. Such exciplex was also found for the green phosphorescent OLED, giving the most efficient phosphorescent OLED with triplet exciplex emission hitherto. Different from the PL process, a broad featureless band with a maximum at 535 nm was found for the OLED based on an EML of iridium(III) bis(4,6-(di-fluorophenyl)pyridinato-N,C²′)picolinate (FIrpic):TCPZ, which can be attributed to the emission from the singlet excited state of TCPZ formed by direct hole-electron recombination. A multi-emitting-layer white OLED was also fabricated by utilizing FIrpic and tris(1-phenylisoquinolinolato-C²,N)iridium(III) (Ir(piq)₃) as the complementary triplet emitters and TCPZ as the host. Different from most of ever reported white OLEDs fabricated with blue/red complementary triplet emitters that exhibit color rendering index (CRI) lower than 70, a high CRI of 82 is achieved due to the combination of blue and red phosphorescence emissions from FIrpic and Ir(piq)₃, and the emerging green fluorescence emission from TCPZ.     

Achieving above 30% external quantum efficiency for inverted phosphorescence organic light-emitting diodes based on ultrathin emitting layer

High efficiency inverted phosphorescence organic light-emitting diodes (PhOLEDs) based on ultrathin undoped and doped emitting layer (EML) have been developed. Compared to conventional device, the inverted PhOLED with 0.5 nm undoped EML exhibits significantly larger external quantum efficiency (EQE), due to effective energy transfer from the excited host to the emitter. According to the atomic force microscopy image of EML, the 0.5 nm emitter sandwiched by two hosts can be considered as the emitter doped in two hosts. The inverted device with intentionally doped ultrathin EML (1.5 nm) exhibits the maximum EQE of 31.1%, which is attributed to optimized charge balance and preferred horizontal orientation of emitter. However, such inverted device has large efficiency roll-off at high brightness because of triplet–triplet annihilation process within the ultrathin EML. This can be improved by broadening the doped EML. The inverted device with 10.5 nm doped EML has about EQE of 20 % at 10,000 cd/m². It is expected that our inverted PhOLED will promote development of high efficiency active-matrix organic light-emitting diodes based on the n-type Indium Gallium Zinc Oxide thin film transistor.     

Delayed luminescence in a molecularly doped polymer (TAPC in polycarbonate)

Decay of the delayed luminescence of 1,1-bis(di-4-tolylaminophenyl)cyclohexane, both doped into a polycarbonate binder and matrix-isolated in an MTHF glass, has been studied upon excitation with the 308 nm line of an excimer laser. Time-resolved emission spectra have also been recorded. In the early time regime, 30 ns < t < 10 μs, the decay of the emission, identified as delayed fluorescence rather than phosphorescence, follows a power-law characteristic of geminate pair recombination in a disordered medium. Singlet–singlet excitation fusion is considered to be the main pathway for geminate pair formation. Fusion of triplet excitations becomes important for e–h pair formation at long times only (10 μs < t < 10 ms). The rate of triplet–triplet encounters carries a time dependence characteristic of the random walk of excitations in a disordered solid.     

利用PtOEP掺杂改善Spiro发光器件的发光效率

为了利用有机三线态发光提高有机发光器件的发光效率,用磷光材料掺杂到聚合物主体中作为发光层,制备有机电致发光器件.在测量器件的电流-电压特性、发光亮度-电压特性和电致发光谱的基础上,计算了器件的外量子效率,研究了磷光材料的掺杂浓度对器件发光效率的影响.结果表明,对特定的材料体系,适当控制掺杂浓度,可以同时观察到荧光和磷光光谱,使掺杂器件的外量子效率在纯聚合物发光器件的基础上得到明显提高.     

利用PtOEP掺杂改善Spiro发光器件的发光效率

为了利用有机三线态发光提高有机发光器件的发光效率,用磷光材料掺杂到聚合物主体中作为发光层,制备有机电致发光器件.在测量器件的电流-电压特性、发光亮度-电压特性和电致发光谱的基础上,计算了器件的外量子效率,研究了磷光材料的掺杂浓度对器件发光效率的影响.结果表明,对特定的材料体系,适当控制掺杂浓度,可以同时观察到荧光和磷光光谱,使掺杂器件的外量子效率在纯聚合物发光器件的基础上得到明显提高.     

A new thermally crosslinkable hole injection material for OLEDs

A new thermal cross-linkable hole injection monomer VB-DATA derived from famous m-MTDATA as core peripherally functionalized with styryl (vinylbenzene) moiety as polymerizable group has been synthesized and characterized. The propensity of VB-DATA thin films formation is sensitive to the nature of solvent, in which the dichloroethane solution gave smooth polymeric thin films with surface roughness of RMS ∼0.84 nm by spin-casting followed by thermal treatment at 190 °C. The introduction of oxygen-linked vinylbenzene group shifted HOMO energy level of VB-DATA to −5.1 eV along with good nondispersive hole transport property (μ_h ∼ 10^–6 cm² V^–1 s^–1) makes it suitable for serving as HIL on top of ITO electrode. The replacement of PEDOT:PSS by thermally cross-linked VB-DATA films showed comparable OLEDs performance, giving more flexibility on material selection for future OLEDs applications, especially solution-processed ones.     

Color stable and highly efficient hybrid white organic light-emitting devices using heavily doped thermally activated delayed fluorescence and ultrathin non-doped phosphorescence layers

Blue/orange complementary fluorescence/phosphorescence hybrid white organic light-emitting devices with excellent color stability and high efficiency have been fabricated, which are based on an easily fabricated multiple emissive layer (EML) configuration with an ultrathin non-doped orange phosphorescence EML selectively inserted between heavily doped blue thermally activated delayed fluorescence (TADF) EMLs. Through systematic investigation and improvement on luminance-dependent color shift and efficiency deterioration, a slight Commission Internationale de 1′Eclairage coordinates shift of (0.008, 0.003) at a practical luminance range from 1000 to 10000 cd/m², a maximum power efficiency of 45.8 lm/W, a maximum external quantum efficiency (EQE) of 15.7% and an EQE above 12% at 1000 cd/m² have been achieved. The heavily doped blue TADF emitters which act as the main charge transport channels and recombination sites in the host with high-lying lowest triplet excited state, take advantage of the bipolar transport ability to broaden the major charge recombination region, which alleviates triplet energy loss. The selectively inserted ultrathin non-doped orange EML makes its emission mechanism dominated by Förster energy transfer, which is effective to keep color stable under different drive voltages.     

Efficient nondoped organic light-emitting diodes with Cu complex emitter

In Cu^I complex based organic light emitting diodes (OLEDs) a host matrix is traditionally thought to be required to achieve high efficiency. Herein, it is found that the device ITO/MoO₃ (1 nm)/4,4′-N,N′-dicarbazole-biphenyl (CBP, 35 nm)/[Cu(μ-I)dppb]₂ (dppb = 1,2-bis[diphenylphosphino]benzene, 20 nm)/1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene (TPBi, 65 nm)/LiF (1 nm)/Al (100 nm) with a vacuum thermal evaporated nondoped Cu^I complex emissive layer (EML) showed external quantum efficiency and current efficiency of 8.0% and 24.3 cd/A at a brightness of 100 cd/m², respectively, which are comparable to the maximum efficiencies reported in an optimized doped OLED with the same emitter, higher efficiency than the OLED with a [Cu(μ-I)dppb]₂:CBP EML, and much higher efficiencies than the nondoped OLED with a bis(2-phenylpyridine)(acetylacetonate)iridium [Ir(ppy)₂(acac)] EML. A series of reference films and single carrier devices were fabricated and studied to understand the difference between Cu^I and Ir^III complex based nondoped OLEDs.     

Effect of Electric Field on Coulomb‐Stabilized Excitons in Host/Guest Systems for Deep‐Blue Electrophosphorescence

Here, a study of the electric field induced quenching on the phosphorescence intensity of a deep‐blue triplet emitter dispersed in different host materials is presented. The hosts are characterized by a higher triplet excitonic level with respect to the emitter, ensuring efficient energy transfer and exciton confinement, whereas they differ in the highest occupied molecular orbital (HOMO) alignment, forming type I and type II host/guest heterostructures. While the type I structure shows negligible electric field induced quenching, a quenching up to 25% for the type II at a field of 2 MV/cm is reported. A similar quenching behaviour is also reported for thin films of the pure emitter, revealing an important luminescence loss mechanism for aggregated emitter molecules. These results are interpreted by considering Coulomb stabilized excitons in the type II heterostructure and in the pure emitter, that become very sensitive to dissociation upon application of the field. These results clarify the role of external electric field quenching on the phosphorescence of triplet emitters and provide useful insights for the design of deep‐blue electrophosphorescent devices with a reduced efficiency roll‐off.     

Photophysical Properties of a Series of Poly(ladder‐type phenylene)s

The photophysical properties, i.e., the fluorescence and phosphorescence of a series of blue light‐emitting poly(ladder‐type phenylene)s have been investigated employing continuous‐wave (cw) and time‐resolved photoluminescence (PL) spectroscopy in solid state and dilute solution. The chemically well‐defined polymers vary from two to five bridged phenyl‐rings per monomer unit bearing aryl‐ or alkyl‐substitution at the bridge‐head carbon atoms. It has been found that the fluorescence energy of the polymers and of the corresponding monomers deviates from a simple 1/N dependence, if the number N of bridged‐phenylene rings is increased beyond a certain limit. Time‐resolved fluorescence spectroscopy on thin films showed that apart from the blue fluorescence of the polymers an additional lower energy emission feature exists, which cannot be assigned to keto‐defects and which seems to be an inherent solid state property of this class of materials. Delayed time‐resolved photoluminescence spectroscopy allowed the detection of phosphorescence energies and lifetimes for all investigated polymers. Photoinduced absorption spectroscopy on thin films showed that the triplet‐triplet absorption red‐shifts with increasing monomer length but reaches a constant value for polymers with N ≥ 4. Amplification of light via amplified spontaneous emission (ASE) from thin film slab waveguide structures could be demonstrated for all ladder‐type polymers but the onset threshold value for ASE varies significantly with the polymer structure.     

Exciton and Polaron Quenching in Doping‐Free Phosphorescent Organic Light‐Emitting Diodes from a Pt(II)‐Based Fast Phosphor

By introducing a neat Pt(II)‐based phosphor with a remarkably short decay lifetime, a simplified doping‐free phosphorescent organic light‐emitting diode (OLED) with a forward viewing external quantum efficiency (EQE) and power efficiency of 20.3 ± 0.5% and 63.0 ± 0.4 lm W^?1, respectively, is demonstrated. A quantitative analysis of how triplet‐triplet annihilation (TTA) and triplet‐polaron annihilation (TPA) affect the device EQE roll‐off at high current densities is performed. The contributions from loss of charge balance associated with charge leakage and field‐induced exciton dissociation are found negligible. The rate constants k_TTA and k_TPA are determined by time‐resolved photoluminescence experiments of a thin film and an electrically‐driven unipolar device, respectively. Using the parameters extracted experimentally, the EQE is modeled versus electric current characteristics of the OLEDs by taking both TTA and TPA into account. Based on this model, the impacts of the emitter lifetime, quenching rate constants, and exciton formation zone upon device efficiency are analyzed. It is found that the short lifetime of the neat emitter is key for the reduction of triplet quenching.     

Ferroelectric and leakage current characteristics of (Pb0.72La0.28)Ti0.93O3 thin films prepared by a sol-gel process

(Pb_1 − xLa_x)Ti_1 − x/4O₃(x = 28 mol%, denoted as PLT) thin films were grown on Pt/Ti/SiO₂/Si substrates by using a sol-gel process. The Pt/PLT/Pt film capacitor showed well-saturated hysteresis loops at an applied electric field of 500 kV/cm with spontaneous polarization (P_s), remanent polarization (P_r) and coercive electric field (E_c) values of 9.23 μC/cm², 0.53 μC/cm² and 19.7 kV/cm, respectively. At 100 kHz, the dielectric constant and dissipation factor of the film were 748 and 0.026, respectively. The leakage current density is lower than 1.0 × 10⁻⁷ A/cm²over the electric field range of 0 to 200 kV/cm. And the Pt/PLT interface exist a Schottky emission characteristics.     

Enhancement of Phosphorescence by Surface‐Plasmon Resonances in Colloidal Metal Nanoparticles: The Role of Aggregates

The spectroscopic and near‐field scanning optical microscopy (NSOM) studies of phosphorescent films doped with colloidal gold nanoparticles (NPs) are presented. Films with a high concentration of 2,3,7,8,12,13,17,18‐octaethyl‐21H,23H‐porphine platinum(II ) dispersed in a neutral polymer poly[(methyl methacrylate)‐co‐(ethyl acrylate)] demonstrate a twofold increase of the phosphorescence quantum yield after the addition of aggregated NPs. In materials doped with unaggregated particles, a decrease of the emission yield is observed. Theoretical modeling of the phosphorescence transients suggests a minimization of the triplet–triplet quenching owing to the presence of fast processes that decrease the concentration of chromophores in the excited state and may be both of radiative and non‐radiative origin. NSOM examination of the films reveals increased light emission around large NP clusters. This observation demonstrates significant enhancement of the spontaneous emission rates by the large aggregates, although unaggregated NPs introduce mostly phosphorescence quenching sites.     

Metal deposition for optoelectronic devices using a low vacuum vapor phase deposition (VPD) system

A vapor phase deposition (VPD) system has been used to deposit magnesium and zinc films and prepare optoelectronic devices under low vacuum conditions, i.e. 1 torr. An analysis of the metal films via SEM, AFM, XRD and four-point probe resistivity measurements revealed comparable characteristics to metal films deposited in a vacuum thermal evaporation (VTE) system. Magnesium cathodes were fabricated for organic light emitting diodes (OLEDs) and organic photovoltaic (OPV) devices. OLEDs were fully made in either the VPD or VTE system employing aluminum tris-(8 hydroxyquinoline) [Alq₃] as the green fluorescent emitter or fac-tris(2-phenylpyridine)iridium [Ir(ppy)₃] as the green emitting phosphor. Analysis of the OLED devices made in the VPD system showed external quantum efficiencies (EQE = 0.9 ± 0.1%) and (EQE = 7.6 ± 0.6%) at a luminance of 100 cd/m² for the fluorescent and phosphorescent devices, respectively. In addition, organic photovoltaics (OPVs) were fully fabricated by both methods employing copper phthalocyanine (CuPc) and C₆₀ as the donor/acceptor materials. Analysis of the OPV devices made in the VPD system showed a power efficiency of 0.5 ± 0.1%, an open circuit voltage of 0.45 ± 0.05% and a fill factor of 0.50 ± 0.05%.     

Interplay between Singlet and Triplet Excited States in Interface Exciplex OLEDs with Fluorescence,Phosphorescence, and TADF Emitters

Interface exciplex represents a promising host material for organic light-emitting diodes (OLEDs) with barrier-free charge injection and highly confined recombination region. However, the efficiency of radiative recombination in pristine exciplex is usually low and needs to be improved by doping various emitters. In this study, the interface exciplex OLEDs doped with fluorescence, phosphorescence, and thermally activated delayed fluorescence (TADF) emitters is fabricated to investigate the relationship between their excited-state properties and electroluminescence efficiencies. A maximum external quantum efficiency of 20% is achieved in interface exciplex OLEDs doped with TADF emitter, which corresponds to nearly 100% exciton utilization and is superior to those of fluorescence and phosphorescence emitters. Furthermore, optical spectroscopy and magneto-electroluminescence method are used to study the advantages of TADF emitter in interface exciplex host. The large dipole of TADF emitter is beneficial for harvesting energy from the charge-transfer state at the interface, and its reverse intersystem crossing avoids the accumulation of triplet excitons that leads to triplet-triplet annihilation in interface exciplex OLEDs. These results demonstrate that the photophysical process needs to be carefully considered in designing high-performance emitters for exciplex host materials, and it may bring in-depth understanding on improving exciton utilization and electroluminescence efficiency in interface exciplex OLEDs.     

Substituent effect of fluorine ligand on spectroscopic properties of Pt(N^C^N)Cl complexes,a theoretical study

Time-Dependent Density Functional Theory (TDDFT) method was used to investigate the substituent effect of fluorine ligand on geometrical structures, electronic properties, electroluminescent properties, absorption and emission spectra of six tridentate cyclometalated Pt(II) complexes. M062X hybrid functional was proved to be suitable for calculating the lowest triplet excited state (T₁) characters in TDDFT calculations. The energies of d–d transitions both in absorption and emission were larger than HOMO–LUMO energy gaps, so d–d transitions did not easily occur. With the introduction of fluorine ligand, the energy levels did not show regularity changes, while the IP (ionization potentials) values and EA (electron affinities) values increased correspondingly. The phosphorescence emissions of the complexes were all assigned as ³ILCT mixed with ³MLCT. In addition, one dimeric form of cyclometalated Pt(II) complexes have also been investigated.     

Investigating the Role of Emissive Layer Architecture on the Exciton Recombination Zone in Organic Light‐Emitting Devices

An experimental approach to determine the spatial extent and location of the exciton recombination zone in an organic light‐emitting device (OLED) is demonstrated. This technique is applicable to a wide variety of OLED structures and is used to examine OLEDs which have a double‐ (D‐EML), mixed‐ (M‐EML), or graded‐emissive layer (G‐EML) architecture. The location of exciton recombination in an OLED is an important design parameter, as the local optical field sensed by the exciton greatly determines the efficiency and angular distribution of far‐field light extraction. The spatial extent of exciton recombination is an important parameter that can strongly impact exciton quenching and OLED efficiency, particularly under high excitation. A direct measurement of the exciton density profile is achieved through the inclusion of a thin, exciton sensitizing strip in the OLED emissive layer which locally quenches guest excitons and whose position in the emissive layer can be translated across the device to probe exciton formation. In the case of the G‐EML device architecture, an electronic model is developed to predict the location and extent of the exciton density profile by considering the drift, diffusion, and recombination of charge carriers within the device.