Structure-property relationships in dicyanopyrazinoquinoxalines and their hydrogen-bonding-capable dihydropyrazinoquinoxalinedione derivatives.

Presented here is the design, synthesis, and study of a variety of novel hydrogen-bonding-capable π-conjugated N-heteroacenes, 1,4-dihydropyrazino[2,3-b]quinoxaline-2,3-diones (DPQDs). The DPQDs were accessed from the corresponding weakly hydrogen-bonding dicyanopyrazinoquinoxaline (DCPQ) suspensions with excess potassium hydroxide, resulting in moderate to good yields. Both families of compounds were analyzed by UV-vis and NMR spectroscopy, where the consequences of hydrogen bonding capability could be assessed through the structure-property studies. Conversion of the DCPQs into hydrogen-bonding capable DPQDs results in modulation of frontier MO energies, higher molar extinction coefficients, enhanced crystallinity, and on-average higher thermal stability (where in some cases the 5% weight loss temperature is increased by up to 100 °C). Single crystal X-ray diffraction data could be obtained for three DPQDs. One reveals pairwise hydrogen bonding in the solid state as well as a herringbone packing arrangement rendering it a promising candidate for additional studies in the context of organic optoelectronic devices.

Dicyanorhodanine-Pyrrole Conjugates for Visible Light-Driven Quantitative Photoswitching in Solution and the Solid State.

Small molecule photoswitches capable of toggling between two distinct molecular states in response to light are versatile tools to monitor biological processes, control photochemistry, and design smart materials. In this work, six novel dicyanorhodanine-based pyrrole-containing photoswitches are reported. The molecular design avails both the Z and E isomers from synthesis, where each can be isolated using chromatographic techniques. Inter- and intramolecular hydrogen bonding (H-bonding) interactions available to the E and Z isomers, respectively, uniquely impart thermal stability to each isomer over long time periods. Photoisomerization could be assessed by solution NMR and UV-vis spectroscopic techniques along with complementary ground- and excited-state computational studies, which show good agreement. Quantitative E → Z isomerization occurs upon 523 nm irradiation of the parent compound (where R = H) in solution, whereas Z → E isomerization using 404 nm irradiation offers a photostationary state (PSS) ratio of 84/16 (E/Z). Extending the π-conjugation of the pyrrole unit (where R = p-C6H4-OMe) pushes the maximum absorption to the yellow-orange region of the visible spectrum and allows bidirectional quantitative isomerization with 404 and 595 nm excitation. Comparator molecules have been prepared to report how the presence or absence of H-bonding affects the photoswitching behavior. Finally, studies of the photoswitches in neat films and photoinactive polymer matrices reveal distinctive structural and optical properties of the Z and E isomers and ultimately afford reversible photoswitching to spectrally unique PSSs using visible light sources including the Sun.

Thin-Film Morphology and Optical Properties of Photoisomerizable Donor-Acceptor Oligothiophenes.

It was recently reported that the most popular electron-accepting units introduced to π-conjugated oligomers studied for organic photovoltaic applications are susceptible to unwanted and even destructive photochemical reactions. The consequences of Z/E photoisomerization of the popular 2-(1,1-dicyanomethylene)rhodanine (RCN) unit on the optical and morphological properties of a homologous series of RCN-functionalized oligothiophenes are studied here. Oligomers consisting of one, two, or three thiophene units were studied as pure Z isomers and with E isomer compositions of 25, 53, and 45%, respectively, for Z/E mixtures. Solutions of Z isomers and Z/E mixtures were characterized by UV-vis and photoluminescence spectroscopy, wherein changes to optical properties were evaluated on the basis of E isomer content. X-ray diffraction of thin-film Z/E mixtures reveals crystalline domains of both Z and E forms after thermal annealing for mono- and bithiophene oligomers, with greater interplanar spacing for E crystalline domains than the Z counterparts along the substrate normal direction. The surface morphology viewed by atomic force microscopy also shows fiberlike structures for the E form with a much larger aspect ratio than for the Z domains in the bithiophene oligomer. Optical characterization reveals drastic changes in the solid state upon introduction of the E form for the mono- and bithiophene derivatives, whereas subtle consequences are noted for the terthiophene analogue. Most notably, a 132 nm redshift in maximum absorption occurs for the bithiophene oligomer films containing 53% E isomer compared to the pure Z counterpart. Finally, although solid-state photoisomerization experiments find no evidence of Z → E isomerization in polycrystalline Z films, E → Z isomerization is observed and becomes more restrictive in films with higher crystallinity (i.e., after thermal annealing). This structure-property study, which elucidates the consequences of the RCN configuration on solid-state packing and optical properties, is expected to guide the development of more efficient and stable organic optoelectronic devices.

High-Purity and Saturated Deep-Blue Luminescence from trans-NHC Platinum(II) Butadiyne Complexes: Properties and Organic Light Emitting Diode Application.

Two new platinum(II) compounds with trans-(NHC)2Pt(C≡C-C≡C-R)2 (where NHC = N-heterocyclic carbene and R = phenyl or trimethylsilyl) architecture exhibit sharp blue-green or saturated deep-blue phosphorescence with high color purity. The photoluminescence of both compounds is dominated by an intense 0-0 band with distinct but weaker vibronic progressions in both tetrahydrofuran (THF) and poly(methyl methacrylate) (PMMA) matrix. The full width at half-maximum (fwhm) of the photoluminescence of trans-(NHC)2Pt(C≡C-C≡C-trimethylsilyl)2 are 10 nm at room temperature and 4 nm at 77 K, while the trans-(NHC)2Pt(C≡C-C≡C-phenyl)2 shows a fwhm of 14 nm at room temperature and 8 nm at 77 K. The Commission International de L'Eclairage (CIE) coordinates of trans-(NHC)2Pt(C≡C-C≡C-phenyl)2 are (0.222, 0.429) in PMMA, and trans-(NHC)2Pt(C≡C-C≡C-trimethylsilyl)2 has a deep-blue CIE of (0.163, 0.077) in PMMA. When doped into PMMA, the phosphorescence quantum yield of the complex with trimethylsilyl-butadiyne ligand increases dramatically to 57% from 0.25% in THF, while the complex with phenyl-butadiyne ligand has similar quantum yields in PMMA (32%) and THF (37%). Organic light-emitting diodes (OLEDs) employing these two complexes as the emitters were successfully fabricated with electroluminescence that closely matches the corresponding photoluminescence. The OLEDs based on trans-(NHC)2Pt(C≡C-C≡C-trimethylsilyl)2 display highly pure deep-blue electroluminescence (fwhm = 12 nm) with CIE coordinates of (0.172, 0.086), approaching the most stringent National Television System Committee (NTSC) coordinates for "pure" blue of (0.14, 0.08).

Highly Emissive and Stable Organic-Perovskite Nanocomposite Thin Films with Phosphonium Passivation.

Organometal halide perovskite materials, in particular colloidal perovskite nanocrystals (NCs), have been investigated extensively as next-generation light-emitting materials. However, producing highly efficient and stable perovskite thin films from colloidal NCs is not trivial, as dissociation of surfactants often occurs during the thin-film formation. Here, we demonstrate a facile solution-processing approach to prepare perovskite nanocomposite thin films by using phosphonium as the capping ligand for methylammonium lead bromide (MAPbBr3) NCs. The photoluminescence and stability of thin films containing in situ formed perovskite NCs were greatly enhanced after phosphonium passivation, with the photoluminescence quantum efficiency reaching 78% and only 5% decrease of the intensity after one month's exposure in ambient conditions. Electrically driven light-emitting diodes (LEDs) based on pristine perovskite neat thin films and organic-perovskite nanocomposite thin films were fabricated, and we observed a 10-fold improvement in the external quantum efficiency of these LEDs (from 0.6% to 6.3%) resulting from the in situ formation of perovskite NCs with phosphonium passivation.

Efficient and long-lifetime full-color light-emitting diodes using high luminescence quantum yield thick-shell quantum dots.

We report full-color quantum-dot-based light-emitting diodes (QLEDs) with high efficiency and long-lifetime by employing high quantum-yield core/shell QDs with thick shells. The increased shell thickness improves the confinement of excitons in the QD cores, and helps to suppress Auger recombination and Förster resonant energy transfer among QDs. Along with optimizing the QD emitting layer thickness and hole transport materials, we achieved significant improvements in device performance as a result of increasing the QD shell thickness to above 5 nm. By using poly[9,9-dioctylfluorene-co-N-[4-(3-methylpropyl)]-diphenylamine] (TFB) as a HTL with a 38 nm thick QD layer, these QLEDs show maximum current efficiencies of 18.9 cd A-1, 53.4 cd A-1, and 2.94 cd A-1, and peak external quantum efficiencies (EQEs) of 10.2%, 15.4%, and 15.6% for red, green, and blue QLEDs, respectively, all of which are well maintained over a wide range of luminances from 102 to 104 cd m-2. To the best of our knowledge, this is the first report of blue QLEDs with ηEQE > 15%. Most importantly, these devices also possess long lifetimes with T70 (the time at which the brightness is reduced to 70% of its initial value) of 117 h (red, with an initial luminance of 8000 cd m-2), 84 h (green, 6000 cd m-2) and 47 h (blue, 420 cd m-2). With further optimization of QD processing and device structures, these LEDs based on thick-shell QDs show great promise for use in next-generation full-color displays and lighting devices.

Super color purity green quantum dot light-emitting diodes fabricated by using CdSe/CdS nanoplatelets.

Colloidal nanoplatelets (NPLs) have recently been introduced as semiconductor emissive materials for the fabrication of quantum dot light-emitting diodes (QLED) on account of their ultra-narrow photoluminescence (PL) linewidth. In this paper, we report a multilayer all solution-processed green QLED based on colloidal CdSe/CdS core/shell NPLs with a narrow PL full-width-at-half-maximum (FWHM) of 12 nm. Our characterization results reveal that this kind of NPL containing QLED exhibit a low operating voltage of 2.25 V and a maximum luminance up to 33 000 cd m(-2), and peak external quantum efficiency (EQE) of 5%, corresponding to 12.5 cd A(-1) in luminance efficiency. Particularly, these devices show ultra-high color purity for electroluminescence (EL) with FWHM of 14 nm. As extremely narrow EL and ultra-pure color is highly attractive in the applications of LED industries, this work signifies the unique potential application of one new class of colloidal core/shell NPLs in achieving bright and efficient LEDs with superior color saturation.

High-efficiency, low turn-on voltage blue-violet quantum-dot-based light-emitting diodes.

We report high-efficiency blue-violet quantum-dot-based light-emitting diodes (QD-LEDs) by using high quantum yield ZnCdS/ZnS graded core-shell QDs with proper surface ligands. Replacing the oleic acid ligands on the as-synthesized QDs with shorter 1-octanethiol ligands is found to cause a 2-fold increase in the electron mobility within the QD film. Such a ligand exchange also results in an even greater increase in hole injection into the QD layer, thus improving the overall charge balance in the LEDs and yielding a 70% increase in quantum efficiency. Using 1-octanethiol capped QDs, we have obtained a maximum luminance (L) of 7600 cd/m(2) and a maximum external quantum efficiency (ηEQE) of (10.3 ± 0.9)% (with the highest at 12.2%) for QD-LEDs devices with an electroluminescence peak at 443 nm. Similar quantum efficiencies are also obtained for other blue/violet QD-LEDs with peak emission at 455 and 433 nm. To the best of our knowledge, this is the first report of blue QD-LEDs with ηEQE > 10%. Combined with the low turn-on voltage of ∼2.6 V, these blue-violet ZnCdS/ZnS QD-LEDs show great promise for use in next-generation full-color displays.

Highly efficient hybrid solar cells with tunable dipole at the donor-acceptor interface.

Effects of molecular dipole at the conjugated polymer-nanocrystal interface on the energy level alignment, the exciton dissociation process, and consequently the photovoltaic performance of poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT):CdSe quantum dot bulk heterojunction hybrid solar cells are systemically studied. Power conversion efficiency up to 4.0% is achieved when 4-fluorobenzenethiol is used for ligand exchange.

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.

Enhancing the efficiency of solution-processed polymer:colloidal nanocrystal hybrid photovoltaic cells using ethanedithiol treatment.

Advances in colloidal inorganic nanocrystal synthesis and processing have led to the demonstration of organic-inorganic hybrid photovoltaic (PV) cells using low-cost solution processes from blends of conjugated polymer and colloidal nanocrystals. However, the performance of such hybrid PV cells has been limited due to the lack of control at the complex interfaces between the organic and inorganic hybrid active materials. Here we show that the efficiency of hybrid PV devices can be significantly enhanced by engineering the polymer-nanocrystal interface with proper chemical treatment. Using two different conjugated polymers, poly(3-hexylthiophene) (P3HT) and poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT), we show that treating the polymer:nanocrystal hybrid film in an ethanedithiol-containing acetonitrile solution can increase the efficiency of the hybrid PV devices by 30-90%, and a maximum power conversion efficiency of 5.2 ± 0.3% was obtained in the PCPDTBT:CdSe devices at 0.2 sun (AM 1.5G), which was slightly reduced to 4.7 ± 0.3% at 1 sun. The ethanedithiol treatment did not result in significant changes in the morphology and UV-vis optical absorption of the hybrid thin films; however, infrared absorption, NMR, and X-ray photoelectron spectroscopies revealed the effective removal of organic ligands, especially the charged phosphonic acid ligands, from the CdSe nanorod surface after the treatment, accompanied by the possible monolayer passivation of nanorod surfaces with Cd-thiolates. We attribute the hybrid PV cell efficiency increase upon the ethanedithiol treatment to the reduction in charge and exciton recombination sites on the nanocrystal surface and the simultaneous increase in electron transport through the hybrid film.

Macroscopic volume change of dynamic hydrogels induced by reversible DNA hybridization.

Molecular recognition is fundamental to the specific interactions between molecules, of which the best known examples are antibody-antigen binding and cDNA hybridization. Reversible manipulation of the molecular recognition events is still a very challenging topic, and such studies are often performed at the molecular level. An important consideration is the collection of changes at the molecular level to provide macroscopic observables. This research makes use of photoresponsive molecular recognition for the fabrication of novel photoregulated dynamic materials. Specifically, a dynamic hydrogel was prepared by grafting azobenzene-tethered ssDNA and its cDNA to the hydrogel network. The macroscopic volume of the hydrogel can be manipulated through the photoreversible DNA hybridization controlled by alternate irradiation of UV and visible light. The effects of synthetic parameters including the concentration of DNA, polymer monomer, and permanent cross-linker are also discussed.

Enhancing light extraction in top-emitting organic light-emitting devices using molded transparent polymer microlens arrays.

The light extraction efficiency in organic light-emitting devices (OLEDs) is enhanced by up to 2.6 times when a close-packed, hemispherical transparent polymer microlens array (MLA) is molded on the light-emitting surface of a top-emitting device. The microlens array helps to extract the waveguided optical emission in the organic layers and the transparent top electrode, and can be manufactured in large area with low cost.

Solution-processed, nanostructured hybrid solar cells with broad spectral sensitivity and stability.

Hybrid organic-inorganic solar cells, as an alternative to all-organic solar cells, have received significant attention for their potential advantages in combining the solution-processability and versatility of organic materials with high charge mobility and environmental stability of inorganic semiconductors. Here we report efficient and air-stable hybrid organic-inorganic solar cells with broad spectral sensitivity based on a low-gap polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b']-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) and spherical CdSe nanoparticles. The solvents used for depositing the hybrid PCPDTBT:CdSe active layer were shown to strongly influence the film morphology, and subsequently the photovoltaic performance of the resulted solar cells. Appropriate post-deposition annealing of the hybrid film was also shown to improve the solar cell efficiency. The inclusion of a thin ZnO nanoparticle layer between the active layer and the metal cathode leads to a significant increase in device efficiency especially at long wavelengths, due to a combination of optical and electronic effects including more optimal light absorption in the active layer and elimination of unwanted hole leakage into the cathode. Overall, maximum power conversion efficiencies up to 3.7 ± 0.2% and spectral sensitivity extending above 800 nm were achieved in such PCPDTBT:CdSe nanosphere hybrid solar cells. Furthermore, the devices with a ZnO nanoparticle layer retained ∼70% of the original efficiency after storage under ambient laboratory conditions for over 60 days without any encapsulation.

Hybrid polymer-nanocrystal materials for photovoltaic applications.

Hybrid polymer-nanocrystal photovoltaic (PV) cells have received much attention during the past decade as promising low-cost solar energy harvesting devices, and showed significant progress with power conversion efficiency reaching 5% recently. This review starts from the introduction of hybrid materials to their application in electronic devices, with particular focus on bulk-heterojunction hybrid polymer-nanocrystal PV devices. The synthesis, surface chemistry, and electronic properties of colloidal inorganic nanocrystals are described. The recent development of hybrid PV devices will be discussed from the perspective of tailoring both inorganic nanocrystals and conjugated polymers, controlling polymer-nanocrystal hybrid morphology, engineering polymer-nanocrystal interface, and optimizing device architecture. Finally, future directions for further advancing hybrid PV technology to potential commercialization are also discussed.

Efficient near-infrared polymer and organic light-emitting diodes based on electrophosphorescence from (tetraphenyltetranaphtho[2,3]porphyrin)platinum(II).

The new metalloporphyrin Pt(tptnp), where tptnp = tetraphenyltetranaphtho[2,3]porphyrin, has been prepared and subjected to photophysical and electrooptical device studies. In degassed toluene solution at room temperature Pt(tptnp) features efficient phosphorescence emission with lambda(max) 883 nm with a quantum efficiency of 0.22. The complex has been used as the active phosphor in polymer and organic light-emitting diodes. Polymer light-emitting diodes based on a spin-coated emissive layer consisting of a blend of Pt(tptnp) doped in poly(9-vinylcarbazole) and 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole exhibit near-IR emission with lambda(max) 896 nm, with a maximum external quantum efficiency (EQE) of 0.4% and a maximum radiant emittance of 100 muW/cm(2). Organic light-emitting diodes prepared via vapor deposition of all layers and that feature an optimized multilayer hole injection and electron blocking layer heterostructure with an emissive layer consisting of 4,4'-bis(carbazol-9-yl)biphenyl (CBP) doped with Pt(tptnp) exhibit a maximum EQE of 3.8% and a maximum radiant emittance of 1.8 mW/cm(2). The polymer and organic light-emitting diodes characterized in this study exhibit record high efficiency for devices that emit in the near-IR at lambda >800 nm.

Effect of the charge balance on high-efficiency blue-phosphorescent organic light-emitting diodes.

The charge balance in blue-phosphorescent devices was studied using single-carrier devices, and the results show that the transport is highly hole dominant. The effect of the charge balance on the device performance was further demonstrated using different electron-transport materials with different electron mobilities. By optimization of the charge balance, a maximum current efficiency of 60 Cd A(-1) at a luminance of 500 cd m(-2) was achieved.