Room‐Temperature Phase Demixing in Bulk Heterojunction Layers of Solution‐Processed Organic Photodetectors: the Effect of Active Layer Ageing on the Device Electro‐optical Properties

Herein, we address the reduction in the external quantum efficiency (EQE) of solution‐processed organic photodetectors caused by the room temperature phase demixing of components in the composite material of the photoactive layer. The reduction takes place under ambient conditions and after the completion of device fabrication. As a model system, we study photoactive blend films that consist of the electron acceptor N,N’‐bis(alkyl)‐3,4,9,10‐perylene tetracarboxylic diimide) (PDI) and the electron donor polymer poly(9,9’‐dioctylfluorene‐co‐benzothiadiazole) (F8BT). The ambient ageing of these photo­active layers is a consequence of the PDI component segregation; however, the final PDI domain size remains smaller than the resolution limit of optical microscopy. We find that the photophysical properties of the aged F8BT:PDI layer and the EQE of the aged device are significantly altered. The fabrication of F8BT:PDI layers from solvents of increasing boiling point allows for the spectroscopic monitoring of the ageing‐induced phase segregation (a‐PSG) process. For each solvent used, the extent of a‐PSG is correlated with the PDI dispersion in the F8BT matrix as received immediately after layer deposition. The tendency for room temperature phase demixing becomes stronger as PDI is more finely dispersed in the freshly spun F8BT:PDI layer. The evolution of the room temperature phase segregation of PDI has a negative impact on the photophysical processes that are essential for charge photogeneration in the F8BT:PDI photoactive layer.     

Correlating Emissive Non‐Geminate Charge Recombination with Photocurrent Generation Efficiency in Polymer/Perylene Diimide Organic Photovoltaic Blend Films

Evidence for a correlation between the dynamics of emissive non‐geminate charge recombination within organic photovoltaic (OPV) blend films and the photocurrent generation efficiency of the corresponding blend‐based solar cells is presented. Two model OPV systems that consist of binary blends of electron acceptor N′‐bis(1‐ethylpropyl)‐3,4,9,10‐perylene tetracarboxy diimide (PDI) with either poly(9,9‐dioctylfluorene‐co‐benzothiadiazole) (F8BT) or poly(9,9‐dioctylindenofluorene‐co‐benzothiadiazole) (PIF8BT) as electron donor are studied. For the F8BT:PDI and PIF8BT:PDI devices photocurrent generation efficiency is shown to be related to the PDI crystallinity. In contrast to the F8BT:PDI system, thermal annealing of the PIF8BT:PDI layer at 90 °C has a positive impact on the photocurrent generation efficiency and yields a corresponding increase in PL quenching. The devices of both blends have a strongly reduced photocurrent on higher temperature annealing at 120 °C. Delayed luminescence spectroscopy suggests that the improved efficiency of photocurrent generation for the 90 °C annealed PIF8BT:PDI layer is a result of optimized transport of the photogenerated charge‐carriers as well as of enhanced PL quenching due to the maintenance of optimized polymer/PDI interfaces. The studies propose that charge transport in the blend films can be indirectly monitored from the recombination dynamics of free carriers that cause the delayed luminescence. For the F8BT:PDI and PIF8BT:PDI blend films these dynamics are best described by a power‐law decay function and are found to be temperature dependent.     

High‐Performance Phototransistors Based on Single‐Crystalline n‐Channel Organic Nanowires and Photogenerated Charge‐Carrier Behaviors

The photoelectronic characteristics of single‐crystalline nanowire organic phototransistors (NW‐OPTs) are studied using a high‐performance n‐channel organic semiconductor, N,N′‐bis(2‐phenylethyl)‐perylene‐3,4:9,10‐tetracarboxylic diimide (BPE‐PTCDI), as the photoactive layer. The optoelectronic performances of the NW‐OPTs are analyzed by way of their current–voltage (I–V) characteristics on irradiation at different wavelengths, and comparison with corresponding thin‐film organic phototransistors (OPTs). Significant enhancement in the charge‐carrier mobility of NW‐OPTs is observed upon light irradiation as compared with when performed in the dark. A mobility enhancement is observed when the incident optical power density increases and the wavelength of the light source matches the light‐absorption range of the photoactive material. The photoswitching ratio is strongly dependent upon the incident optical power density, whereas the photoresponsivity is more dependent on matching the light‐source wavelength with the maximum absorption range of the photoactive material. BPE‐PTCDI NW‐OPTs exhibit much higher external quantum efficiency (EQE) values (≈7900 times larger) than thin‐film OPTs, with a maximum EQE of 263 000%. This is attributed to the intrinsically defect‐free single‐crystalline nature of the BPE‐PTCDI NWs. In addition, an approach is devised to analyze the charge‐transport behaviors using charge accumulation/release rates from deep traps under on/off switching of external light sources.     

Intermolecular Interactions of Perylene diimides in Photovoltaic Blends of Fluorene Copolymers: Disorder Effects on Photophysical Properties,Film Morphology and Device Efficiency

In the present work, we correlate the photophysical and photovoltaic properties with the respective film morphologies of three different blends made of the fluorene copolymers poly(9,9′‐dioctylfluorene‐co‐benzothiadiazole) (F8BT), poly[9,9′‐dioctylfluorene‐co‐N‐(4‐butylphenyl)diphenylamine] (TFB), and poly[9,9′‐dioctyfluorene‐co‐bis‐N,N′‐(4‐butylphenyl)‐bis‐N,N‐phenyl‐1,4‐phenylenediamine] (PFB) when blended with a perylene tetracarboxylic diimide (PDI) derivative. Additional photophysical studies in reference PDI blends of the electronically inert poly(styrene) matrix address the enhanced PDI intermolecular solid‐state interactions. We resolve the process of resonance energy transfer from excited polymer hosts to PDI and the process of photoinduced hole transfer from PDI to the polymer hosts. We deduce the efficiency of charge‐transfer PDI photoluminescence (PL) quenching and we discuss the power‐law PL kinetics seen in the as‐spun systems. Next we determine the dependence of the device external quantum efficiency (EQE) of these blends, in a range of annealing temperatures and PDI loadings. Differential scanning calorimetry enables precise selection of annealing temperatures. Optical microscopy shows that annealing enhances the order characteristics in the PDI aggregates in the F8BT:PDI system. In the case of the TFB:PDI and PFB:PDI blends, AFM studies suggest the formation of PDI‐rich domains on the film/air interface. The degree of order in the π–π stacking of the PDI monomers is inferred by the UV–Vis and PL spectra of the blends. The extent of order characteristics in PDI aggregates is correlated with the thermal properties of the hosts that control PDI molecular mobility upon annealing. The efficient dispersion of disrupted PDI crystallites is proposed to form appropriate percolation networks that favor balanced extraction of photogenerated carriers.     

Effects of Arylene Diimide Thin Film Growth Conditions on n‐Channel OFET Performance

A series of eight perylene diimide (PDI)‐ and naphthalene diimide (NDI)‐based organic semiconductors was used to fabricate organic field‐effect transistors (OFETs) on bare SiO₂ substrates, with the substrate temperature during film deposition (T_d) varied from 70–130 °C. For the N,N′‐n‐octyl materials that form highly ordered films, the mobility (µ) and current on‐off ratio (I_on/I_off) increase slightly from 70 to 90 °C, and remain relatively constant between 90 and 130 °C. I_on/I_off and µ of dibromo‐PDI‐based OFETs decrease with increasing T_d, while films of N,N′‐1H,1H‐perfluorobutyl dicyanoperylenediimide (PDI‐FCN₂) exhibit dramatic I_on/I_off and µ enhancements with increasing T_d. Increased OFET mobility can be correlated with higher levels of molecular ordering and minimization of film morphology surface irregularities. Additionally, the effects of SiO₂ surface modification with trimethylsilyl and octadecyltrichlorosilyl monolayers, as well as with polystyrene, are investigated for N,N′‐n‐octyl dicyanoperylenediimide (PDI‐8CN₂) and PDI‐FCN₂ films deposited at T_d = 130 °C. The SiO₂ surface treatments have modest effects on PDI‐8CN₂ OFET mobilities, but modulate the mobility and morphology of PDI‐FCN₂ films substantially. Most importantly, the surface treatments result in substantially increased V_th and decreased I_off values for the dicyanoperylenediimide films relative to those grown on SiO₂, resulting in V_th > 0.0 V and I_on/I_off ratios as high as 10⁸. Enhancements in current modulation for these high‐mobility, air‐stable, and solution‐processable n‐type semiconductors, should prove useful in noise‐margin enhancement and further improvements in organic electronics.     

Barium Hydroxide as an Interlayer Between Zinc Oxide and a Luminescent Conjugated Polymer for Light‐Emitting Diodes

A study of hybrid light‐emitting diodes (HyLEDs) fabricated with and without solution‐processible Cs₂CO₃ and Ba(OH)₂ inorganic interlayers is presented. The interlayers are deposited between a zinc oxide electron‐injection layer and a fluorescent emissive polymer poly(9‐dioctyl fluorine–alt‐benzothiadiazole) (F8BT) layer, with a thermally evaporated MoO₃/Au layer used as top anode contact. In comparison to Cs₂CO₃, the Ba(OH)₂ interlayer shows improved charge carrier balance in bipolar devices and reduced exciton quenching in photoluminance studies at the ZnO/Ba(OH)₂/F8BT interface compared to the Cs₂CO₃ interlayer. A luminance efficiency of ≈28 cd A^?1 (external quantum efficiency (EQE) ≈ 9%) is achieved for ≈1.2 μm thick single F8BT layer based HyLEDs. Enhanced out‐coupling with the aid of a hemispherical lens allows further efficiency improvement by a factor of 1.7, increasing the luminance efficiency to ≈47cd A^?1, corresponding to an EQE of 15%. The photovoltaic response of these structures is also studied to gain an insight into the effects of interfacial properties on the photoinduced charge generation and back‐recombination, which reveal that Ba(OH)₂ acts as better hole blocking layer than the Cs₂CO₃ interlayer.     

Achieving a High Fill Factor and Stability in Perylene Diimide–Based Polymer Solar Cells Using the Molecular Lock Effect between 4,4′‐Bipyridine and a Tri(8‐hydroxyquinoline)aluminum(III) Core

Two novel perylene diimide (PDI)–based derivatives, Alq₃‐PDI and Alq₃‐PDI 2, are synthesized by flanking a 3D tri(8‐hydroxyquinoline)aluminum(III) (Alq₃) core with PDI and a helical PDI dimer (PDI2) to construct high‐performance small molecular nonfullerene acceptors (SMAs). The 3D Alq₃ core significantly suppresses the molecular aggregation of the resulting SMAs, leading to a well‐mixed blend with a PTTEA donor polymer and weak phase separation. Compared with Alq₃‐PDI , the extended π‐conjugation of Alq₃‐PDI2 results in higher‐order molecular packing, which improves the absorption and phase separation behavior. Thus, the Alq₃‐PDI2 devices have higher J_sc and FF values and better device performance, which are further enhanced by a small amount of 4,4′‐bipyridine (Bipy) as an additive. The coordination between Bipy and the Alq₃ core promotes molecular packing and phase separation, which lower charge recombination and enhanced charge collection in the resulting devices. Therefore, a largely improved J_sc of 15.74 mA cm^?2 and very high FF of 71.27% are obtained in the Alq₃‐PDI2 devices, resulting in a power conversion efficiency of 9.54%, which is the best value reported for PDI‐based polymer solar cells. The coordination can also serve as a “molecular lock,” which prevents molecular motion and thus improves device stability.     

n‐Doping of a Low‐Electron‐Affinity Polymer Used as an Electron‐Transport Layer in Organic Light‐Emitting Diodes

n‐Doping electron‐transport layers (ETLs) increases their conductivity and improves electron injection into organic light‐emitting diodes (OLEDs). Because of the low electron affinity and large bandgaps of ETLs used in green and blue OLEDs, n‐doping has been notoriously more difficult for these materials. In this work, n‐doping of the polymer poly[(9,9‐dioctylfluorene‐2,7‐diyl)‐alt‐(benzo[2,1,3]thiadiazol‐4,7‐diyl)] (F8BT) is demonstrated via solution processing, using the air‐stable n‐dopant (pentamethylcyclopentadienyl)(1,3,5‐trimethylbenzene)ruthenium dimer [RuCp*Mes]₂. Undoped and doped F8BT films are characterized using ultraviolet and inverse photoelectron spectroscopy. The ionization energy and electron affinity of the undoped F8BT are found to be 5.8 and 2.8 eV, respectively. Upon doping F8BT with [RuCp*Mes]₂, the Fermi level shifts to within 0.25 eV of the F8BT lowest unoccupied molecular orbital, which is indicative of n‐doping. Conductivity measurements reveal a four orders of magnitude increase in the conductivity upon doping and irradiation with ultraviolet light. The [RuCp*Mes]₂‐doped F8BT films are incorporated as an ETL into phosphorescent green OLEDs, and the luminance is improved by three orders of magnitude when compared to identical devices with an undoped F8BT ETL.     

High‐Mobility Air‐Stable Naphthalene Diimide‐Based Copolymer Containing Extended π‐Conjugation for n‐Channel Organic Field Effect Transistors

A high‐performance naphthalene diimide (NDI)‐based conjugated polymer for use as the active layer of n‐channel organic field‐effect transistors (OFETs) is reported. The solution‐processable n‐channel polymer is systematically designed and synthesized with an alternating structure of long alkyl substituted‐NDI and thienylene–vinylene–thienylene units (PNDI‐TVT). The material has a well‐controlled molecular structure with an extended π‐conjugated backbone, with no increase in the LUMO level, achieving a high mobility and highly ambient stable n‐type OFET. The top‐gate, bottom‐contact device shows remarkably high electron charge‐carrier mobility of up to 1.8 cm² V^?1 s^?1 (I_on/I_off = 10⁶) with the commonly used polymer dielectric, poly(methyl methacrylate) (PMMA). Moreover, PNDI‐TVT OFETs exhibit excellent air and operation stability. Such high device performance is attributed to improved π–π intermolecular interactions owing to the extended π‐conjugation, apart from the improved crystallinity and highly interdigitated lamellar structure caused by the extended π–π backbone and long alkyl groups.     

Origins of Improved Hole‐Injection Efficiency by the Deposition of MoO3 on the Polymeric Semiconductor Poly(dioctylfluorene‐alt‐benzothiadiazole)

The electronic structure of the interfaces formed after deposition of MoO₃ hole‐injection layers on top of a polymer light‐emitting material, poly(dioctylfluorene‐alt‐benzothiadiazole) (F8BT), is studied by ultraviolet photoelectron spectroscopy (UPS), X‐ray photoelectron spectroscopy and metastable atom electron spectroscopy. Significant band bending is induced in the F8BT film by MoO₃ “acceptors” that spontaneously diffuse into the F8BT “host” probably driven by kinetic energy of the deposited hot MoO₃. Further deposition leads to the saturation of the band bending accompanied by the formation of MoO₃ overlayers. Simultaneously, a new electronic state in the vicinity of the Fermi level appears on the UPS spectra. Since this peak does not appear in the bulk MoO₃ film, it can be assigned as an interface state between the MoO₃ overlayer and underlying F8BT film. Both band bending and the interface state should result from charge transfer from F8BT to MoO₃, and they appear to be the origin of the hole‐injection enhancement by the insertion of MoO₃ layers between the F8BT light‐emitting diodes and top anodes.     

High‐Throughput Combinatorial Optimizations of Perovskite Light‐Emitting Diodes Based on All‐Vacuum Deposition

Light‐emitting diodes (LEDs) based on lead halide perovskites demonstrate outstanding optoelectronic properties and are strong competitors for display and lighting applications. While previous halide perovskite LEDs are mainly produced via solution processing, here an all‐vacuum processing method is employed to construct CsPbBr₃ LEDs because vacuum processing exhibits high reliability and easy integration with existing OLED facilities for mass production. The high‐throughput combinatorial strategies are further adopted to study perovskite composition, annealing temperature, and functional layer thickness, thus significantly speeding up the optimization process. The best rigid device shows a current efficiency (CE) of 4.8 cd A^?1 (EQE of 1.45%) at 2358 cd m^?2, and best flexible device shows a CE of 4.16 cd A^?1 (EQE of 1.37%) at 2012 cd m^?2 with good bending tolerance. Moreover, by choosing NiO_x as the hole‐injection layer, the CE is improved to 10.15 cd A^?1 and EQE is improved to a record of 3.26% for perovskite LEDs produced by vacuum deposition. The time efficient combinatorial approaches can also be applied to optimize other perovskite LEDs.     

Suppression of the Keto‐Emission in Polyfluorene Light‐Emitting Diodes: Experiments and Models

The spectral characteristics of polyfluorene (PF)‐based light‐emitting diodes (LEDs) containing a defined low concentration of either keto‐defects or of the polymer poly(9,9‐octylfluorene‐co‐benzothiadiazole) (F8BT) are presented. Both types of blend layers were tested in different device configurations with respect to the relative and absolute intensities of green and blue emission components. It is shown that blending hole‐transporting molecules into the emission layer at low concentration or incorporation of a suitable hole‐transporting layer reduces the green emission contribution in the electroluminescence (EL) spectrum of the PF:F8BT blend, which is similar to what is observed for the keto‐containing PF layer. We conclude that the keto‐defects in PF homopolymer layers mainly constitute weakly emissive electron traps, in agreement with the results of quantum‐mechanical calculations.     

High‐Sensitivity p–n Junction Photodiodes Based on PbS Nanocrystal Quantum Dots

Chemically synthesized nanocrystal quantum dots (NQDs) are promising materials for applications in solution‐processable optoelectronic devices such as light emitting diodes, photodetectors, and solar cells. Here, we fabricate and study two types of p‐n junction photodiodes in which the photoactive p‐layer is made from PbS NQDs while the transparent n‐layer is fabricated from wide bandgap oxides (ZnO or TiO₂). By using a p–n junction architecture we are able to significantly reduce the dark current compared to earlier Schottky junction devices without reducing external quantum efficiency (EQE), which reaches values of up to ～80%. The use of this device architecture also allows us to significantly reduce noise and obtain high detectivity (>10¹² cm Hz^1/2 W^?1) extending to the near infrared past 1 μm. We observe that the spectral shape of the photoresponse exhibits a significant dependence on applied bias, and specifically, the EQE sharply increases around 500–600 nm at reverse biases greater than 1 V. We attribute this behavior to a “turn‐on” of an additional contribution to the photocurrent due to electrons excited to the conduction band from the occupied mid‐gap states.     

Thiocyanate‐Free Ru(II) Sensitizers with a 4,4′‐Dicarboxyvinyl‐2,2′‐bipyridine Anchor for Dye‐Sensitized Solar Cells

A new class of thiocyanate‐free Ru(II) sensitizers with 4,4′‐dicarboxyvinyl‐2,2′‐bipyridine anchor and two trans‐oriented pyrid‐2‐yl pyrazolate (or triazolate) functional chromophores is synthesized, characterized, and evaluated in dye‐sensitized solar cells (DSCs). Despite their enhanced red response and absorptivity when compared to the parent sensitizer TFRS‐2 that possesses standard 4,4′‐dicarboxyl‐2,2′‐bipyridine anchor and shows the best conversion efficiency of η = 9.82%, the newly synthesized carboxyvinyl‐pyrazolate sensitizers, TFRS‐11 – TFRS‐13 , exhibit inferior performance characteristics in terms of short‐circuit current density (J_SC), open‐circuit voltage (V_OC), and power conversion efficiency (η), the latter being recorded to be in the range 5.60–7.62%. The reduction in device efficiencies is attributed to a combination of poor packing of these sensitizers on the TiO₂ surface and less positive ground‐state oxidation potentials, which, respectively, increase charge recombination with I₃^? in electrolytes and impede the regeneration of sensitizers by I^? anions. The latter obstacle can be circumvented in part by the replacement of the pyrazolates with triazolates, forming the TFRS‐14 sensitizer, which exhibits an improved J_SC, V_OC, and η of 16.4 mAcm^?2, 0.77 V, and 9.02%, respectively.     

Rational Design of Small Molecular Donor for Solution‐Processed Organic Photovoltaics with 8.1% Efficiency and High Fill Factor via Multiple Fluorine Substituents and Thiophene Bridge

A series of tetrafluorine‐substituted small molecules with a D₁‐A‐D₂‐A‐D₁ linear framework based on indacenodithiophene and difluorobenzothiadiazole is designed and synthesized for application as donor materials in solution‐processed small‐molecule organic solar cells. The impacts of thiophene π‐bridge and multiple fluorinated modules on the photophysical properties, the energy levels of the highest occupied molecular orbitals (HOMO) and lowest unoccupied molecular orbitals (LUMO), charge carrier mobility, the morphologies of blend films, and their photovoltaic properties as electron donor material in the photoactive layer are investigated. By incorporating multiple fluorine substituents of benzothiadiazole and inserting two thiophene spacers, the fill factor (FF), open‐circuit voltage, and short‐circuit current density are dramatically improved in comparison with fluorinated‐free materials. With the solvent vapor annealing treatment, further enhancement in charge carrier mobility and power conversion efficiency (PCE) are achieved. Finally, a high PCE of 8.1% with very‐high FF of 0.76 for BIT‐4F‐ T/PC₇₁BM is achieved without additional additive, which is among one of the highest reported for small‐molecules‐based solar cells with PCE over 8%. The results reported here clearly indicate that high PCE in solar cells based small molecules can be significantly increased through careful engineering of the molecular structure and optimization on the morphology of blend films by solvent vapor annealing.     

Charge‐Carrier Balance and Color Purity in Polyfluorene Polymer Blends for Blue Light‐Emitting Diodes

A study of an efficient blue light‐emitting diode based on a fluorescent aryl polyfluorene (aryl‐F8) homopolymer in an inverted device architecture is presented, with ZnO and MoO₃ as electron‐ and hole‐injecting electrodes, respectively. Charge‐carrier balance and color purity in these structures are achieved by incorporating poly(9,9‐dioctylfluorene‐co‐N‐(4‐butylphenyl)‐diphenylamine (TFB) into aryl‐F8. TFB is known to be a hole‐transporting material but it is found to act as a hole trap on mixing with aryl‐F8. Luminance efficiency of ≈6 cd A^?1 and external quantum efficiency (EQE) of 3.1% are obtained by adding a small amount (0.5% by weight) of TFB into aryl‐F8. Study of charge injection and transport in the single‐carrier devices shows that the addition of a small fraction of hole traps is necessary for charge‐carrier balance. Optical studies using UV–vis and fluorescence spectroscopic measurements, photoluminescence quantum yield, and fluorescence decay time measurements indicate that TFB does not affect the optical properties of the aryl‐F8, which is the emitting material in these devices. Luminance efficiency of up to ≈11 cd A^?1 and EQE values of 5.7% are achieved in these structures with the aid of improved out‐coupling using index‐matched hemispheres.     

Multifunctional Triphenylamine/Oxadiazole Hybrid as Host and Exciton‐Blocking Material: High Efficiency Green Phosphorescent OLEDs Using Easily Available and Common Materials

A new triphenylamine/oxadiazole hybrid, namely m‐TPA‐o‐OXD, formed by connecting the meta‐position of a phenyl ring in triphenylamine with the ortho‐position of 2,5‐biphenyl‐1,3,4‐oxadiazole, is designed and synthesized. The new bipolar compound is applicable in the phosphorescent organic light‐emitting diodes (PHOLEDs) as both host and exciton‐blocking material. By using the new material and the optimization of the device structures, very high efficiency green and yellow electrophosphorescence are achieved. For example, by introducing 1,3,5‐tris(N‐phenylbenzimidazol‐2‐yl)benzene (TPBI) to replace 2, 9‐dimethyl‐4,7‐diphenyl‐1, 10‐phenanthroline (BCP)/tris(8‐hydroxyquinoline)aluminium (Alq₃) as hole blocking/electron transporting layer, followed by tuning the thicknesses of hole‐transport 1, 4‐bis[(1‐naphthylphenyl)amino]biphenyl (NPB) layer to manipulate the charge balance, a maximum external quantum efficiency (η_EQE,max) of 23.0% and a maximum power efficiency (η_p,max) of 94.3 lm W⁻¹ are attained for (ppy)₂Ir(acac) based green electrophosphorescence. Subsequently, by inserting a thin layer of m‐TPA‐o‐OXD as self triplet exciton block layer between hole‐transport and emissive layer to confine triplet excitons, a η_EQE,max of 23.7% and η_p,max of 105 lm W⁻¹ are achieved. This is the highest efficiency ever reported for (ppy)₂Ir(acac) based green PHOLEDs. Furthermore, the new host m‐TPA‐o‐OXD is also applicable for other phosphorescent emitters, such as green‐emissive Ir(ppy)₃ and yellow‐emissive (fbi)₂Ir(acac). A yellow electrophosphorescent device with η_EQE,max of 20.6%, η_c,max of 62.1 cd A⁻¹, and η_p,max of 61.7 lm W⁻¹, is fabricated. To the author’s knowledge, this is also the highest efficiency ever reported for yellow PHOLEDs.     

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.     

Highly Efficient Simple‐Structure Blue and All‐Phosphor Warm‐White Phosphorescent Organic Light‐Emitting Diodes Enabled by Wide‐Bandgap Tetraarylsilane‐Based Functional Materials

Two host materials of {4‐[diphenyl(4‐pyridin‐3‐ylphenyl)silyl]phenyl}diphenylamine (p‐PySiTPA) and {4‐[[4‐(diphenylphosphoryl)phenyl](diphenyl)silyl]phenyl}diphenylamine (p‐POSiTPA), and an electron‐transporting material of [(diphenylsilanediyl)bis(4,1‐phenylene)]bis(diphenylphosphine) dioxide (SiDPO) are developed by incorporating appropriate charge transporting units into the tetraarylsilane skeleton. The host materials feature both high triplet energies (ca. 2.93 eV) and ambipolar charge transporting nature; the electron‐transporting material comprising diphenylphosphine oxide units and tetraphenylsilane skeleton exhibits a high triplet energy (3.21 eV) and a deep highest occupied molecular orbital (HOMO) level (‐6.47 eV). Using these tetraarylsilane‐based functional materials results in a high‐efficiency blue phosphorescent device with a three‐organic‐layer structure of 1,1‐bis[4‐[N,N‐di(p‐tolyl)‐amino]phenyl]cyclohexane (TAPC)/p‐POSiTPA: iridium(III) bis(4′,6′‐difluorophenylpyridinato)tetrakis(1‐pyrazolyl)borate (FIr6)/SiDPO that exhibits a forward‐viewing maximum external quantum efficiency (EQE) up to 22.2%. This is the first report of three‐organic‐layer FIr6‐based blue PhOLEDs with the forward‐viewing EQE over 20%, and the device performance is among the highest for FIr6‐based blue PhOLEDs even compared with the four or more than four organic‐layer devices. Furthermore, with the introduction of bis(2‐(9,9‐diethyl‐9H‐fluoren‐2‐yl)‐1‐phenyl‐1H‐benzoimidazol‐N,C³)iridium acetylacetonate [(fbi)₂Ir(acac)] as an orange emitter, an all‐phosphor warm‐white PhOLED achieves a peak power efficiency of 47.2 lm W^?1, which is close to the highest values ever reported for two‐color white PhOLEDs.     

Solution‐Processed,Alkali Metal‐Salt‐Doped,Electron‐Transport Layers for High‐Performance Phosphorescent Organic Light‐Emitting Diodes

High‐performance, blue, phosphorescent organic light‐emitting diodes (PhOLEDs) are achieved by orthogonal solution‐processing of small‐molecule electron‐transport material doped with an alkali metal salt, including cesium carbonate (Cs₂CO₃) or lithium carbonate (Li₂CO₃). Blue PhOLEDs with solution‐processed 4,7‐diphenyl‐1,10‐phenanthroline (BPhen) electron‐transport layer (ETL) doped with Cs₂CO₃ show a luminous efficiency (LE) of 35.1 cd A^?1 with an external quantum efficiency (EQE) of 17.9%, which are two‐fold higher efficiency than a BPhen ETL without a dopant. These solution‐processed blue PhOLEDs are much superior compared to devices with vacuum‐deposited BPhen ETL/alkali metal salt cathode interfacial layer. Blue PhOLEDs with solution‐processed 1,3,5‐tris(m‐pyrid‐3‐yl‐phenyl)benzene (TmPyPB) ETL doped with Cs₂CO₃ have a luminous efficiency of 37.7 cd A^?1 with an EQE of 19.0%, which is the best performance observed to date in all‐solution‐processed blue PhOLEDs. The results show that a small‐molecule ETL doped with alkali metal salt can be realized by solution‐processing to enhance overall device performance. The solution‐processed metal salt‐doped ETLs exhibit a unique rough surface morphology that facilitates enhanced charge‐injection and transport in the devices. These results demonstrate that orthogonal solution‐processing of metal salt‐doped electron‐transport materials is a promising strategy for applications in various solution‐processed multilayered organic electronic devices.