Highly Efficient Blue Fluorescent Organic Light-Emitting Devices Based on λ5-Phosphinine Derivatives.

Although λ5-phosphinine derivatives are known as a promising class of blue fluorescent emitters, those photoluminescent quantum yield (PLQY) values have been reached up to 92 %, however, only a few examples have been explored as an emitter for blue organic light-emitting device (OLED), and the external quantum efficiency (EQE) has been below 2.4 % so far. In this study, we newly developed two types of blue λ5-phosphinine derivatives namely CN-COCF3 and CO2Me-CHO, and investigated the photophysical properties in the solid states. The photophysical analyses in solid state films suggested that the strong electron-accepting nature of these λ5-phosphinine derivatives caused the inferior PLQY values, and the exciplex formation with the host and neighboring materials should be avoided to improve the device efficiency. By choosing suitable host and neighboring materials with deep ionization potentials, we successfully realized efficient blue fluorescent OLEDs with EQE of over 4 % and CIE (0.14, 0.18). This is among the best in λ5-phosphinine-based blue OLEDs so far.

Robust Spirobifluorene Core Based Hole Transporters with High Mobility for Long-Life Green Phosphorescent Organic Light-Emitting Devices.

Using a tailored high triplet energy hole transport layer (HTL) is a suitable way to improve the efficiency and extend the lifetime of organic light-emitting devices (OLEDs), which can use all molecular excitons of singlets and triplets. In this study, dibenzofuran (DBF)-end-capped and spirobifluorene (SBF) core-based HTLs referred as TDBFSBF1 and TDBFSBF2 were effectively developed. TDBFSBF1 exhibited a high glass transition temperature of 178 °C and triplet energy of 2.5 eV. Moreover, a high external quantum efficiency of 22.0 %, long operational lifetime at 50 % of the initial luminance of 89,000 h, and low driving voltage at 1000 cd m-2 of 2.95 V were achieved in green phosphorescent OLEDs using TDBFSBF1. Further, a high-hole mobility µh value of 1.9×10-3  cm2 V-1 s-1 was recorded in TDBFSBF2. A multiscale simulation successfully reproduced the experimental µh values and indicated that the reorganization energy was the primary factor in determining the mobility differences among these SBF core based HTLs.

Nonbonding/Bonding Molecular Orbital Regulation of Nitrogen-Boron-Oxygen-embedded Blue/Green Multiresonant TADF Emitters with High Efficiency and Color Purity.

Invited for the cover of this issue is the group of H. Sasabe and J. Kido at Yamagata University in Japan. The image depicts the molecular structures of N-B-O embedded multi-resonant thermally activated delayed fluorescent (MR-TADF) emitters, which achieved ultra-pure deep-blue/green emission with high efficiency in OLEDs. Read the full text of the article at 10.1002/chem.202201605.

Nonbonding/Bonding Molecular Orbital Regulation of Nitrogen-Boron-Oxygen-embedded Blue/Green Multiresonant TADF Emitters with High Efficiency and Color Purity.

In this study, we synthesized and characterized multiresonant thermally activated delayed fluorescent (TADF) materials embedded with nitrogen-boron-oxygen (N-B-O), exhibiting color-tunability between blue and green, namely NBO, m-DiNBO, and p-DiNBO. The three emitter materials showed a high photoluminescence quantum yield (PLQY) and a state-of-the-art narrow full width at half maximum (FWHM) of 96 %/25 nm, 87 %/17 nm, and 99 %/19 nm, respectively. For m-DiNBO and p-DiNBO, the emission color could be tuned from blue to green by regulating the nonbonding/bonding molecular orbital characters. Owing to the expanded planar molecular structure, m-DiNBO and p-DiNBO showed high horizontal dipole ratio (Θ) of 88 % and 92 %, respectively. OLEDs were prepared with NBO, m-DiNBO, and p-DiNBO, exhibiting high external quantum efficiencies of 16.8 %, 24.2 %, and 21.6 %, respectively. NBO and m-DiNBO exhibited pure-blue emission with CIE coordinates of (0.137, 0.142) and (0.126, 0.098), respectively. p-DiNBO showed pure-green emission with a CIE coordinate of (0.258, 0.665).

Constructing Soluble Anthracene-Based Blue Emitters Free of Electrically Inert Alkyl Chains for Efficient Evaporation- and Solution-Based OLEDs.

Anthracene derivatives are one of the most promising blue emitters employed in organic light-emitting devices (OLEDs) because of their electrochemical and thermal stabilities. However, their high crystallinity owing to their large π-planar structures severely impedes the progress in the development of solution-based systems. In this work, we developed two types of highly soluble multifunctional anthracene derivatives terminated with ortho-biphenyl and triphenylamine moieties and showed high solubility in general organic solvents such as toluene, tetrahydrofuran, and cyclohexanone at high concentrations (>10 mg mL-1 ), and showed blue emission with a peak wavelength of ∼465 nm and a high photoluminescence quantum yield that ranges up to 81 %. Notably, these emitters are suitable for fabricating both evaporation- and solution-based systems. The evaporation-based system OLED achieved a high external quantum efficiency (EQE) of 5.4 %. While the solution-processed system realized 4.8 %, exhibiting the best performance among the anthracene-based solution-processed OLEDs so far.

Four Dibenzofuran-Terminated High-Triplet-Energy Hole Transporters for High-Efficiency and Long-Life Organic Light-Emitting Devices.

The weak stability of a hole-transporter upon approaching the anion state is one of the major bottlenecks for developing long-life organic light-emitting devices (OLEDs). Therefore, in this study, we developed a series of thermally and electrically stable hole-transporters that are end-capped with four dibenzofuran units. These materials exhibit i) high bond dissociation energy (BDE) toward the anion state, ii) a high glass transition temperature (Tg >130 °C), and iii) high triplet energy (ET >2.7 eV), thereby enabling approximately 20 % high external quantum efficiency (EQE) and significantly prolonging the stability of both thermally activated delayed fluorescent (TADF) and phosphorescent OLEDs with an operation lifetime at 50 % (LT50 ) of 20 000-30 000 h at 1000 cd m-2 . In addition, investigating their structure-property relationship revealed that ionization potential (IP ), BDE, and Tg are critical prerequisites for the hole-transporter to prolong lifetime in OLEDs.

Bis(Triphenylamine)Benzodifuran Chromophores: Synthesis, Electronic Properties and Application in Organic Light-Emitting Diodes.

A series of bis(triphenylamine)benzodifuran chromophores have been synthesized and fully characterised. Starting from suitably functionalized benzodifuran (BDF) precursors, two triphenylamine (TPA) moieties are symmetrically coupled to a central BDF unit either at 4,8-positions through double bonds (1) and single bonds (2) respectively, or at 2,6-positions through double bonds (3). Their electronic absorption and photoluminescence properties as well as redox behaviour have been investigated in detail, indicating that the π-extended conjugation via vinyl linkers in 1 and 3 leads to comparatively strong electronic interactions between the relevant redox moieties TPA and BDF. Due to intriguing electronic properties and structural planarity, 3a has been applied as a dopant emitter in organic light-emitting diodes. A yellowish-green OLED exhibits a high external quantum efficiency (EQE) of 6.2%, thus exceeding the theoretical upper limit most likely due to energy transfer from an interface exciplex to an emissive layer and/or favorable horizontal orientation.

Asymmetric Spirobiacridine-based Delayed Fluorescence Emitters for High-performance Organic Light-Emitting Devices.

Invited for the cover of this issue is Hisahiro Sasabe, Junji Kido and co-workers at Yamagata University in Japan. This image depicts that the chemical structure of the acceptor is one of the most important keys to maximize the potential of triazine/acridine-based thermally activated delayed fluorescence (TADF) emitters realizing high external quantum efficiency (EQE) of over 30%. Read the full text of the article at 10.1002/chem.202101188.

Asymmetric Spirobiacridine-based Delayed Fluorescence Emitters for High-performance Organic Light-Emitting Devices.

Recently, researchers have focused on thermally activated delayed fluorescence (TADF) for efficient future lighting and displays. Among TADF emitters, a combination of triazine and acridine is a promising candidate for realizing high-efficiency organic light-emitting devices (OLEDs). However, simultaneous development of perfect horizontal orientation (Θ=100 %) and an external quantum efficiency (EQE) of over 40 % is still challenging. Here, to obtain insights for further improvements of a triazine/acridine combination, various asymmetric spirobiacridine (SBA)-based TADF emitters with a unity photoluminescence quantum yield and high Θ ratio of over 80 % were developed. Furthermore, the substitution effects of the triazine acceptor unit on the photophysical properties were studied, including molecular orientations and OLED performance. The corresponding OLED exhibited sky-blue emission with a high EQE of over 30 %.

Novel Series of Mononuclear Aluminum Complexes for High-Performance Solution-Processed Organic Light-Emitting Devices.

Light metal complexes, such as lithium (Li), sodium (Na), magnesium (Mg), and aluminum (Al) complexes, are attractive candidates for the fabrication of thermally activated delayed fluorescent (TADF) materials. Nevertheless, mononuclear Al complexes with delayed fluorescence have not been developed so far. In this study, we successfully developed a novel series of highly luminescent Al complexes with two phenylacridine-modified asymmetric acetylacetonate-type ligands. These complexes exhibit high photoluminescence quantum yields (PLQYs) of up to 79 % in the solid state with a short delayed fluorescence lifetime of approximately 4 µs. Solution-processed organic light-emitting devices (OLEDs) using these Al complexes exhibit excellent performance with an external quantum efficiency of 17.5 % at 100 cd m-2 . This is the best performance in light metal-based TADF OLEDs reported so far. The results are expected to guide the advancement of the next-generation solid-state lighting technology.

π-Extended Carbazole Derivatives as Host Materials for Highly Efficient and Long-Life Green Phosphorescent Organic Light-Emitting Diodes.

High-performance organic light-emitting diodes (OLEDs) that use phosphorescent and/or thermally activated delayed fluorescence emitters are capable of realizing 100 % electron-to-photon conversion. The host materials in these OLEDs play crucial roles in determining OLED performance. Carbazole derivatives are frequently used as host materials, among which 3,3-bis(9H-carbazol-9-yl)biphenyl (mCBP) is often used for lifetime testing in scientific studies. In this study, the π conjugation of the carbazole unit was expanded to enhance OLED lifetime by designing and developing two benzothienocarbazole (BTCz)-based host materials, namely m1BTCBP and m4BTCBP. Among these host materials, m1BTCBP formed a highly efficient [Ir(ppy)3 ]-based OLED with an operational luminescence half-life (LT50 ) of over 300 h at an initial luminance of approximately 12000 cd m-2 (current density: 25 mA cm-2 ). The LT50 value at 1000 cd cm-2 was estimated to be about 23 000 h. This performance is clearly higher than that of mCBP-based OLEDs (LT50 ≈8500 h).

Molecular Orientations of Delayed Fluorescent Emitters in a Series of Carbazole-Based Host Materials.

Molecular orientation is one of the most crucial factors to boost the efficiency of organic light-emitting devices. However, active control of molecular orientation of the emitter molecule by the host molecule is rarely realized so far, and the underlying mechanism is under discussion. Here, we systematically investigated the molecular orientations of thermally activated delayed fluorescence (TADF) emitters in a series of carbazole-based host materials. Enhanced horizontal orientation of the TADF emitters was achieved. The degree of enhancement observed was dependent on the host material used. Consequently, our results indicate that π-π stacking, CH/n (n = O, N) weak hydrogen bonds, and multiple CH/π contacts greatly induce horizontal orientation of the TADF emitters in addition to the molecular shape anisotropy. Finally, we fabricated TADF-based organic light-emitting devices with an external quantum efficiency (ηext) of 26% using an emission layer with horizontal orientation ratio (Θ) of 79%, which is higher than that of an almost randomly oriented emission layer with Θ of 62% (ηext = 22%).

Room-Temperature Phosphorescence from a Series of 3-Pyridylcarbazole Derivatives.

Exploration of pure metal-free organic molecules that exhibit strong room-temperature phosphorescence (RTP) is an emerging research topic. In this regard, unveiling the design principles for an efficient RTP molecule is an essential, but challenging, task. A small molecule is an ideal platform to precisely understand the fundamental role of each functional component because the parent molecule can be easily derivatized. Here, the RTP behaviors of a series of 3-pyridylcarbazole derivatives are presented. Experimental studies in combination with theoretical calculations reveal the crucial role of the n orbital on the central pyridine ring in the dramatic enhancement of the intersystem crossing between the charge-transfer-excited singlet state and the locally excited triplet states. Single-crystal X-ray crystallographic studies apparently indicate that both the pyridine ring and fluorine atom contribute to the enhancement of the RTP because of the restricted motion owing to weak C-H⋅⋅⋅N and H⋅⋅⋅F hydrogen-bonding interactions. The single crystal of the fluorine-substituted derivative shows an ultra-long phosphorescent lifetime (τP ) of 1.1 s and a phosphorescence quantum yield (ΦP ) of 1.2 %, whereas the bromine-substituted derivative exhibits τP of 0.15 s with a ΦP of 7.9 %. We believe that this work provides a fundamental and universal guideline for the generation of pure organic molecules exhibiting strong RTP.

High-Efficiency Sky Blue-To-Green Fluorescent Emitters Based on 3-Pyridinecarbonitrile Derivatives.

The pyridinecarbonitrile derivative is well known as an acceptor unit in fluorescent materials. However, its use in thermally activated delayed fluorescent (TADF) emitters is very limited compared with its benzenecarbonitrile counterparts. Very recently, we developed a series of 4-pyridinecarbonitrile, so-called isonicotinonitrile derivatives, as a highly efficient sky blue-to-green TADF emitters realizing low-drive-voltage organic light-emitting devices (OLEDs). In this work, we contributed new design and development for three 3-pyridinecarbonitrile-based TADF emitters named 2AcNN, 2PXZNN, and 5PXZNN. Among these emitters, a sky blue emitter, 2AcNN, showed a maximum external quantum efficiency (η ext,max) of 12% with CIE (0.19, 0.36). While green emitters, 5PXZNN and 2PXZNN, realized highly efficient TADF OLEDs with a η ext,max of 16-20%. Introduction of electron-donor moiety into the 2-position of 3-pyridinecarbonitrile contributes a larger overlapping of frontier molecular orbitals (FMOs) and stronger intramolecular charge transfer (ICT) interaction generating efficient TADF emitters.

Control of Molecular Orientation in Organic Semiconductor Films using Weak Hydrogen Bonds.

Use of the intrinsic optoelectronic functions of organic semiconductor films has not yet reached its full potential, mainly because of the primitive methodology used to control the molecular aggregation state in amorphous films during vapor deposition. Here, a universal molecular engineering methodology is presented to control molecular orientation; this methodology strategically uses noncovalent, intermolecular weak hydrogen bonds in a series of oligopyridine derivatives. A key is to use two bipyridin-3-ylphenyl moieties, which form self-complementary intermolecular weak hydrogen bonds, and which do not induce unfavorable crystallization. Another key is to incorporate a planar anisotropic molecular shape by reducing the steric hindrance of the core structure for inducing π-π interactions. These synergetic effects enhance horizontal orientation in amorphous organic semiconductor films and significantly increasing electron mobility. Through this evaluation process, an oligopyridine derivative is selected as an electron-transporter, and successfully develops highly efficient and stable deep-red organic light-emitting devices as a proof-of-concept.

A Series of Dibenzofuran-Based n-Type Exciplex Host Partners Realizing High-Efficiency and Stable Deep-Red Phosphorescent OLEDs.

Deep-red to near-infrared (NIR) OLEDs, which yield emission peak wavelengths beyond λ=660 nm, are applicable as unique light sources in plant growth or health monitoring systems. Compared with other visible-spectrum OLEDs, however, research in the field of deep-red OLEDs is not as advanced. In this work, three new types of dibenzofuran-based host materials are developed as n-type exciplex host partners. Combining these with the deep-red iridium complex bis(2,3-diphenylquinoxaline)iridium(dipivaloylmethane) ([(DPQ)2 Ir(dpm)]) and N,N'-di(naphalene-1-yl)-N,N'-diphenylbenzidine (α-NPD) as a p-type exciplex host partner, a highly efficient deep-red OLED can be realized with a maximum external quantum efficiency (ηext,max ) of over 16 % with Comission Internationale de l'Éclairge (CIE) coordinates of (0.71, 0.28). In addition, the effect of the doping concentration and the p/n ratio of the exciplex host on the efficiency and the lifetime of the OLEDs are investigated. Consequently, the optimized device exhibits a ηext,max of over 15 % and a six-time longer lifetime operating at high brightness of 100 cd m-2 compared with other state-of-the-art deep-red OLEDs.

Comparison of the Solution and Vacuum-Processed Squaraine:Fullerene Small-Molecule Bulk Heterojunction Solar Cells.

Squaraine dyes have shown promising properties for high performance organic solar cells owing to their advantages of intense absorption and high absorption coefficients in the visible and near-infrared (NIR) regions. In this work, to directly compare the photovoltaic performance of solution- and vacuum-processed small-molecule bulk heterojunction (SMBHJ) solar cells, we employed a squaraine small molecular dye, 2,4-bis[4-(N,N-diisobutylamino)-2,6-dihydroxyphenyl] squaraine (DIBSQ), as an electron donor combined with fullerene acceptors to fabricate SMBHJ cells either from solution or vacuum deposition process. The solution-processed SMBHJ cell possesses a power conversion efficiency (PCE) of ~4.3%, while the vacuum-processed cell provides a PCE of ~6.3%. Comparison of the device performance shows that the vacuum-processed SMBHJ cells possess higher short-circuit current density, fill factor and thus higher PCE than the solution-processed devices, which should be assigned to more efficient charge transport and charge extraction in the vacuum-processed SMBHJ cells. However, solution-processed SMBHJ cells demonstrate more pronounced temperature-dependent device performance and higher device stability. This study indicates the great potential of DIBSQ in photovoltaic application via both of solution and vacuum processing techniques.

Colorful Squaraines Dyes for Efficient Solution-Processed All Small-Molecule Semitransparent Organic Solar Cells.

Semitransparent organic solar cells (ST-OSCs) exhibit highly promising applications to develop integrated photovoltaics and power-generating windows. However, the development of ST-OSCs is significantly lagging behind opaque OSCs, especially for all small-molecule ST-OSCs. Here, four unique squaraines dyes (IDPSQ, SQ-BP, D-BDT-SQ, and AzUSQ) were successfully used as donors in ST-OSCs, whose colors can be tuned from purple to blue, green, and dark green, respectively. While using ultrathin Ag as a transparent electrode, the ST-OSCs fabricated using IDPSQ:PC71BM, SQ-BP:PC71BM, D-BDT-SQ:PC71BM, and AzUSQ:PC71BM yield power conversion efficiencies (PCEs) of 2.96, 4.36, 4.91, and 1.71%, respectively, and their colors are purple, cyan, brown, and light brown, respectively. Compared to their opaque OSCs (PCEs of 3.95, 5.45, 5.84, and 1.91%, respectively), the reduction in the PCEs are as low as 25, 20, 16, and 10%, respectively. Furthermore, each of these ST-OSCs exhibit good average visible transmittance (AVT) of 25-30%, favorable CIE color coordinates, and a color rendering index (CRI) of 71-97%. Finally, by changing the thickness of the Ag electrode, an impressive PCE of 4.9% along with an AVT of 25% and a CRI of 97% can be obtained in D-BDT-SQ:PC71BM-based ST-OSCs, which is the highest PCE among all small-molecule ST-OSCs.

A Novel Sterically Bulky Hole Transporter to Remarkably Improve the Lifetime of Thermally Activated Delayed Fluorescent OLEDs at High Brightness.

For the practical application of organic light emitting devices (OLEDs) based on thermally activated delayed fluorescence (TADF) for large area TV and solid state lighting, low power consumption as well as the operation lifetime at high brightness over 1000 cd m-2 must be improved. Here, we have developed a novel hexaphenylbenzene-based sterically bulky hole-transport layer named 4DBTHPB with deep ionization potential of 5.8 eV and high triplet energy of 2.7 eV. By using 4DBTHPB, we can realize a highly efficient and stable TADF OLED exhibiting external quantum efficiency of 21.6 % and power efficiency of 54.3 lm W-1 and operation lifetime at 50 % (LT50 ) of approximately 10 000 h at an initial luminance of 1000 cd m-2 . These performances are comparable to those of the state-of-the-art green phosphorescent OLEDs reported in the scientific literatures.

A Series of Lithium Pyridyl Phenolate Complexes with a Pendant Pyridyl Group for Electron-Injection Layers in Organic Light-Emitting Devices.

We report a new series of lithium pyridyl phenolate complexes with a pendant pyridyl group, Li2BPP, Li3BPP, and Li4BPP, in which the pendant pyridines are substituted at the 2-, 3-, and 4-positions, respectively. The most important difference between these complexes is their molecular planarity; Li3BPP and Li4BPP adopt twisted bipyridine structures, whereas Li2BPP adopts a planar structure owing to the steric hindrance and chelating effect of bipyridine on the Li core. The planar structure leads to crystallization through π-π stacking interactions, and the small differences in the molecular structures of the pendant pyridine rings cause drastic differences in the physical properties of thin solid films of these complexes. We applied these complexes as electron-injection layers (EILs) in Ir(ppy)3-based organic light-emitting devices. When thin EILs were used, Li3BPP and Li4BPP afforded lower driving voltages than Li2BPP; the order of the driving voltages followed the order of their electron affinity values. Moreover, the dependence of driving voltage on the EIL thickness was investigated for each complex. Among the three LiBPP derivatives, Li2BPP-based devices showed almost negligible EIL thickness dependence, which may be attributable to the high crystallinity of Li2BPP. All LiBPP-based devices also showed higher stability than conventional 8-quinolinolato lithium-based devices.