Tuning the Excited State of Tetradentate Pd(II) Complexes for Highly Efficient Deep-Blue Phosphorescent Materials.

Deep-blue-light-emitting materials are urgently desired in high-performance organic light-emitting diodes (OLEDs) for full-color display and solid-state lighting applications. However, the development of stable and efficient deep-blue emitters remains a great challenge. Herein, a series of stable and efficient tetradentate Pd(II)-complex-based deep-blue emitters with rigid 5/6/6 metallocycles and no F atom were designed and synthesized. These deep-blue emitters employ various isoelectronic five-membered heteroaryl-ring-containing ligands to exhibit extremely narrow emission spectra peaking at 439-443 nm with a full width at half-maximum (fwhm) of only 22-38 nm in 2-methyltetrahydrofuran at room temperature. In particular, the design of an intramolecular hydrogen bond enabled the 1-phenyl-1,2,3-trazole-based Pd(II) complexes to achieve CIEy < 0.1 (0.069-0.078; CIE is Commission Internationale de L'Eclairage). Theoretical calculation and natural transition orbital analysis reveal that these deep-blue materials emit light exclusively from their ligand (carbazole)-centered (3LC) states. Moreover, the triplet excited-state property can be efficiently regulated through ligand modification with isoelectronic oxazole and thiazole rings or pyridine rings, resulting in sky-blue-to-yellow materials, which emit light originating from an admixture of metal-to-ligand charge-transfer (3MLCT) and intraligand charge-transfer states. The newly developed Pd(II) complexes are strongly emissive in various matrixes with a quantum efficiency of up to 51% and also highly thermally stable with a 5% weight-reduction temperature (ΔT5%) of up to 400 °C. Deep-blue OLEDs with CIEy < 0.1 employing Pd(II) complexes as emitters were successfully fabricated for the first time. This study demonstrates that the Pd(II) complexes can act as excellent phosphorescent light-emitting materials through rational molecular design and also provide a valuable method for the development of Pd(II)-complex-based efficient and stable deep-blue emitters.

Tuning State Energies for Narrow Blue Emission in Tetradentate Pyridyl-Carbazole Platinum Complexes.

Narrow, deep blue emitters are highly desired in the field of organic light emitting diodes for high quality full color display and solid-state lighting applications. PtNON is reported as a deep blue emitting phosphor but is limited by its broad emission spectrum, making it unsuitable for high quality full color display applications. In this work, we report a strategy to fine-tune the color and the emission line shape of PtNON derivatives by incorporating electron donating (methyl or methoxy) or withdrawing (trifluoromethyl) substituent groups at the positions para to the nitrogen of the pyridines in PtNON. These substitutions resulted in destabilization or stabilization of the charge transfer state (CT) relative to the ligand centered (LC) state, resulting in complexes with narrow or broad emission spectra in various media. PtNON-OMe emits predominantly from the LC state, giving a narrow emission spectrum with fwhm = 48 nm in any media. PtNON-Me emits largely from the LC state in nonpolar media (fwhm = 54 nm) and predominantly from the CT state in polar media (fwhm = 83 nm). Last, PtNON-CF3 emits solely from the CT state in any media, giving it a broad emission spectrum (fwhm = 98 nm). The photoluminescence quantum yields of PtNON-OMe, PtNON-Me, and PtNON-CF3 in 1% doped PMMA films are 89, 95 and 20% with emission lifetimes of 27.1, 7.17, and 0.96 µs, respectively.

Ground and excited states of zinc phthalocyanine, zinc tetrabenzoporphyrin, and azaporphyrin analogs using DFT and TDDFT with Franck-Condon analysis.

The electronic structure of eight zinc-centered porphyrin macrocyclic molecules are investigated using density functional theory for ground-state properties, time-dependent density functional theory (TDDFT) for excited states, and Franck-Condon (FC) analysis for further characterization of the UV-vis spectrum. Symmetry breaking was utilized to find the lowest energy of the excited states for many states in the spectra. To confirm the theoretical modeling, the spectroscopic result from zinc phthalocyanine (ZnPc) is used to compare to the TDDFT and FC result. After confirmation of the modeling, five more planar molecules are investigated: zinc tetrabenzoporphyrin (ZnTBP), zinc tetrabenzomonoazaporphyrin (ZnTBMAP), zinc tetrabenzocisdiazaporphyrin (ZnTBcisDAP), zinc tetrabenzotransdiazaporphyrin (ZnTBtransDAP), and zinc tetrabenzotriazaporphyrin (ZnTBTrAP). The two latter molecules are then compared to their phenylated sister molecules: zinc monophenyltetrabenzotriazaporphyrin (ZnMPTBTrAP) and zinc diphenyltetrabenzotransdiazaporphyrin (ZnDPTBtransDAP). The spectroscopic results from the synthesis of ZnMPTBTrAP and ZnDPTBtransDAP are then compared to their theoretical models and non-phenylated pairs. While the Franck-Condon results were not as illuminating for every B-band, the Q-band results were successful in all eight molecules, with a considerable amount of spectral analysis in the range of interest between 300 and 750 nm. The π-π(∗) transitions are evident in the results for all of the Q bands, while satellite vibrations are also visible in the spectra. In particular, this investigation finds that, while ZnPc has a D4h symmetry at ground state, a C4v symmetry is predicted in the excited-state Q band region. The theoretical results for ZnPc found an excitation energy at the Q-band 0-0 transition of 1.88 eV in vacuum, which is in remarkable agreement with published gas-phase spectroscopy, as well as our own results of ZnPc in solution with Tetrahydrofuran that are provided in this paper.

Exploring cyclometalated Ir complexes as donor materials for organic solar cells.

The performance of small molecular organic photovoltaic materials is typically limited by their low exciton diffusion lengths, poor solubility, and poor energy level alignment with fullerenes so that the design and synthesis of new materials remain a top priority. To overcome these limitations, we explored the use of an iridium complex as a donor material with the potential for compatibility with solution processing, long exciton diffusion length and easy molecular modification for tunable optical or electrical properties. A bilayer device with a cyclometalated iridium complex and C60 resulted in a power conversion efficiency as high as 2.8%. Furthermore, a VOC of 1 V was achieved in the bilayer device despite an estimated exciton energy of only 1.55 eV, and the device showed minimal temperature and light intensity dependence.

Phosphorescent Pt(II) and Pd(II) Complexes for Efficient, High-Color-Quality, and Stable OLEDs.

Phosphorescent organic light-emitting diodes (OLEDs) are leading candidates for next-generation displays and solid-state lighting technologies. Much of the academic and commercial pursuits in phosphorescent OLEDs have been dominated by Ir(III) complexes. Over the past decade recent developments have enabled square planar Pt(II) and Pd(II) complexes to meet or exceed the performance of Ir complexes in many aspects. In particular, the development of N-heterocyclic carbene-based emitters and tetradentate cyclometalated Pt and Pd complexes have significantly improved the emission efficiency and reduced their radiative lifetimes making them competitive with the best reported Ir complexes. Furthermore, their unique and diverse molecular design possibilities have enabled exciting photophysical attributes including narrower emission spectra, excimer -based white emission, and thermally activated delayed fluorescence. These developments have enabled the fabrication of efficient and "pure" blue OLEDs, single-doped white devices with EQEs of over 25% and high CRI, and device operational lifetimes which show early promise that square planar metal complexes can be stable enough for commercialization. These accomplishments have brought Pt complexes to the forefront of academic research. The molecular design strategies, photophysical characteristics, and device performance resulting from the major advancements in emissive Pt and Pd square planar complexes are discussed.

Efficient and stable single-doped white OLEDs using a palladium-based phosphorescent excimer.

A tetradentate Pd(ii) complex, Pd3O3, which exhibits highly efficient excimer emission is synthesized and characterized. Pd3O3 can achieve blue emission despite using phenyl-pyridine emissive ligands which have been a mainstay of stable green and red phosphorescent emitter designs, making Pd3O3 a good candidate for stable blue or white OLEDs. Pd3O3 exhibits strong and efficient phosphorescent excimer emission expanding the excimer based white OLEDs beyond the sole class of Pt complexes. Devices of Pd3O3 demonstrate peak external quantum efficiencies as high as 24.2% and power efficiencies of 67.9 Lm per W for warm white devices. Furthermore, Pd3O3 devices in a carefully designed stable structure achieved a device operational lifetime of nearly 3000 h at 1000 cd m-2 without any outcoupling enhancement while simultaneously achieving peak external quantum efficiencies of 27.3% and power efficiencies over 81 Lm per W.

High-Performance Sub-Micrometer Channel WSe2 Field-Effect Transistors Prepared Using a Flood-Dike Printing Method.

Printing technology has potential to offer a cost-effective and scalable way to fabricate electronic devices based on two-dimensional (2D) transition metal dichalcogenides (TMDCs). However, limited by the registration accuracy and resolution of printing, the previously reported printed TMDC field-effect transistors (FETs) have relatively long channel lengths (13-200 µm), thus suffering low current-driving capabilities (≤0.02 µA/µm). Here, we report a "flood-dike" self-aligned printing technique that allows the formation of source/drain metal contacts on TMDC materials with sub-micrometer channel lengths in a reliable way. This self-aligned printing technique involves three steps: (i) printing of gold ink on a WSe2 flake to form the first gold electrode, (ii) modifying the surface of the first gold electrode with a self-assembled monolayer (SAM) to lower the surface tension and render the surface hydrophobic, and (iii) printing of gold ink close to the SAM-treated first electrode at a certain distance. During the third step, the gold ink would first spread toward the edge of the first electrode and then get stopped by the hydrophobic SAM coating, ending up forming a sub-micrometer channel. With this printing technique, we have successfully downscaled the channel length to ∼750 nm and achieved enhanced on-state current densities of ∼0.64 µA/µm (average) and high on/off current ratios of ∼3 × 105 (average). Furthermore, with our high-performance printed WSe2 FETs, driving capabilities for quantum-dot light-emitting diodes (LEDs), inorganic LEDs, and organic LEDs have been demonstrated, which reveals the potential of using printed TMDC electronics for display backplane applications.

Efficient Red-Emitting Platinum Complex with Long Operational Stability.

A tetradentate cyclometalated Pt(II) complex, PtN3N-ptb, was developed as an emissive dopant for stable and efficient red phosphorescent OLEDs. Devices employing PtN3N-ptb in electrochemically stable device architectures achieved long operational lifetimes with estimated LT97, of over 600 h at luminances of 1000 cd/m(2). Such long operational lifetimes were achieved utilizing only literature reported host, transporting and blocking materials with known molecular structures. Additionally, a thorough study of the effects of various host and transport materials on the efficiency, turn on voltage, and stability of the devices was carried out. Ultimately, maximum forward viewing EQEs as high as 21.5% were achieved, demonstrating that Pt(II) complexes can act as stable and efficient dopants with operational lifetimes comparable or superior to those of the best literature-reported Ir(III) complexes.

Harvesting all electrogenerated excitons through metal assisted delayed fluorescent materials.

Highly efficient and stable palladium complexes that exhibit both phosphorescence and delayed fluorescence are developed. It is demonstrated that the emission from the two processes can be separately tuned through rational ligand modification. External quantum efficiencies over 20% are achieved and stable devices demonstrate an operational lifetime to 90% initial luminance estimated at over 20 000 h at 100 cd m(-2) .

Photocurrent enhancements of organic solar cells by altering dewetting of plasmonic Ag nanoparticles.

Incorporation of metal nanoparticles into active layers of organic solar cells is one of the promising light trapping approaches. The size of metal nanoparticles is one of key factors to strong light trapping, and the size of thermally evaporated metal nanoparticles can be tuned by either post heat treatment or surface modification of substrates. We deposited Ag nanoparticles on ITO by varying nominal thicknesses, and post annealing was carried out to increase their size in radius. PEDOT: PSS was employed onto the ITO substrates as a buffer layer to alter the dewetting behavior of Ag nanoparticles. The size of Ag nanoparticles on PEDOT: PSS were dramatically increased by more than three times compared to those on the ITO substrates. Organic solar cells were fabricated on the ITO and PEDOT: PSS coated ITO substrates with incorporation of those Ag nanoparticles, and their performances were compared. The photocurrents of the cells with the active layers on PEDOT: PSS with an optimal choice of the Ag nanoparticles were greatly enhanced whereas the Ag nanoparticles on the ITO substrates did not lead to the photocurrent enhancements. The origin of the photocurrent enhancements with introducing the Ag nanoparticles on PEDOT: PSS are discussed.

Efficient and stable white organic light-emitting diodes employing a single emitter.

Using a single tetradentate platinum emitter dubbed Pt7O7, efficient and stable white organic light-emitting diodes are developed. The excimer-based white devices achieve an external quantum efficiency (EQE) of 24.5%, coordinates of (0.37, 0.42) based on the Commission internationale de l'éclairage (CIE) system, and a color rendering index (CRI) of 70. Moreover, devices of Pt7O7 in a stable structure demonstrate operational lifetimes (50% initial luminance) of 36 h at an elevated driving current of 20 mA cm2, which corresponds to over 10,000 h at 100 cd m2.

Efficient "pure" blue OLEDs employing tetradentate Pt complexes with a narrow spectral bandwidth.

Efficient deep-blue-emitting tetradentate platinum complexes with a narrow spectral bandwidth are presented, which demonstrate CIEx ≈ 0.15 and CIEy < 0.1. Ultimately, an organic light-emitting diode (OLED) with 24.8% peak external quantum efficiency and CIE coordinates of (0.147, 0.079) is fabricated using PtON7-dtb.

Efficient zinc phthalocyanine/C60 heterojunction photovoltaic devices employing tetracene anode interfacial layers.

We report the development of efficient small molecular organic photovoltaic devices incorporating tetracene anode interfacial layers. Planar heterojunction devices employing the tetracene anode interfacial layer achieved an EQE enhancement of 150% in the spectral region corresponding to ZnPc absorption. We demonstrate that this enhancement is due to the combined effect of the tetracene layer providing exciton-blocking at the anode/donor interface and potentially an increase in the exciton diffusion length in the ZnPc layer due to increased crystallinity and more preferred molecular stacking orientation. A power conversion efficiency of 4.7% was achieved for a planar heterojunction of a modified zinc phthalocyanine based material and C60 when employing the tetracene anode interfacial layer. By utilizing a planar-mixed heterojunction structure a peak EQE of nearly 70% and a power conversion efficiency of 5.8% was achieved.

Single-doped white organic light-emitting device with an external quantum efficiency over 20%.

A white OLED with a maximum EQE of 20.1%, CIE coordinates of (0.33, 0.33) and CRI of 80 is fabricated based on platinum(II) bis(N-methyl-imidazolyl)benzene chloride (Pt-16). The device emission spectrum and the chemical structure of Pt-16 are shown in the inset of the efficiency versus luminance graph.