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Inorganic-organic hybrid perovskite materials have been a topic of interest for the last few years due to their superior optoelectronic properties. However, the optical properties of perovskite materials are strongly dependent on the film morphology. A textured film morphology is expected to have higher light absorption as well as light out-coupling efficiency compared to a smooth film. There have been numerous methods for controlling and optimizing the film morphology to achieve high efficiency in solar cells and light emitting diodes. Here we have demonstrated that controlled anti-solvent treatment at low temperature can lead to Stranski-Krastanov growth in CH3NH3PbBr3 thin films with superior optical and electronic properties for light emitting diode applications. We have studied their photoluminescence properties at the micro- to nano-scale via fluorescence microscopy, hyper-spectral imaging and scanning near-field optical microscopy. We have demonstrated that the nanostructured micro-islands are highly emissive because of large quasi-Fermi level splitting (QFLS) due to the localization of free charges in the smaller crystals. We have shown that the photoluminescence as well as electroluminescence can be improved by at least seven-fold due to the presence of micro-islands on a smooth background film enhancing light out-coupling. Photo-induced photoluminescence enhancement is also observed in smooth films while micro-islands show photo-degradation.

Low dimensional (2D, 1D) lead halide perovskites are currently attracting huge research interest due to their enabling properties. Demonstrating synthetic control on the dimensionality/structure of...

Blue-color-emitting organic semiconductors are of significance for organic light-emitting diodes (OLEDs). In this study, through Suzuki coupling polymerization, three 1,4-naphthalene-based copolymers—namely, PNP(1,4)-PT, PNP(1,4)-TF, and PNP(1,4)-ANT—were designed and synthesized. The variation of comonomers, phenothiazine (PT), triphenylamine substituted fluorene (TF), and anthanthrene (ANT), effectively tuned the emitting color and device performance of poly(9-vinyl carbazole) (PVK)-based OLEDs. Especially, the polymer PNP(1,4)-TF, bearing perpendicular aryl side groups, showed a most twisted structural geometry, which enabled an ultra-high thermal stability and a best performance with blue emitting in PVK-host-based OLEDs. Overall, in this work, we demonstrate a promising blue-color-emitting polymer through structural geometry manipulation.

The modified Debus–Radziszewski reaction was used to design and synthesize novel truxene derived blue-emitting materials bearing phenanthroimidazole substituents. The materials were prepared non-catalytically under ambient conditions using a triamino based derivative of truxene as a key precursor in good yields. The 5, 5′, 10, 10′, 15, and 15′ positions of the truxene were alkylated to provide solubility to the molecules, making the materials solution processable. The substituted phenanthroimidazole moieties were introduced at the 2, 7, 12 positions of truxene to synthesize the target molecules. Three new materials were prepared by varying the phenyl group attached at the C2 position of the phenanthroimidazole moiety, designated as PT1 for the phenyl, PT2 for the 4-methoxyphenyl, and PT3 for the 4-cyanophenyl substituent. From the photophysical studies, PT3 was found to have dominant charge transfer characteristics in its excited state. Also, PT3 exhibited a photoluminescence quantum yield as high as 0.83. The optimized geometries from the computational studies revealed that the molecules are highly twisted, with dihedral angles of ∼75°. The HOMO–LUMO distributions were found to be well separated showing the bipolar characteristic of the compounds. The band gap values from computational studies were found to be in agreement with experimental values. The emission spectra in the solid state gave maxima at 402 nm for PT1, 412 nm for PT2, and 450 nm for PT3. The materials were thus found to be emitting in the blue region of the visible spectrum. The TCSPC and TRPL studies were carried out to explore further the excited states of the molecules, wherein radiative pathways were found to be dominant.

Perovskite light-emitting diodes have almost reached the threshold for potential commercialization within a few years of research. However, there are still some unsolved puzzles such as large ideality factor and the presence of large negative capacitance especially at the low-frequency regime yet to be addressed. Here, we have fabricated a methylammonium lead tri-bromide perovskite n-i-p structure for light-emitting diodes from a smooth and textured emissive layer and demonstrated for the first time that these two factors are strongly dependent on the perovskite film morphology. Bias-dependent capacitance measurement also reveals the transition between negative to positive capacitance in textured films at the low-frequency regime. We have observed an anomalous capacitive behavior at the mid-frequency regime in smooth perovskite films but not in textured films. The relatively large ideality factor and anomalous capacitive behavior observed in perovskite light-emitting diodes are due to the presence of strong coupling between ions and electrons near the electrode interface. Therefore, the ideality factor and anomalous capacitance at the mid-frequency regime can be decreased by minimizing electronic-ionic coupling in textured perovskite films, while light outcoupling can be improved significantly.

Truxene (10,15-dihydro-5H-diindeno[ 1,2-a; 1', 2'-c] fluorene) derived blue emitting materials were designed and developed utilizing Suzuki and Buchwald-Hartwig type cross-coupling reactions. The target molecules T-1, T-2 and T-3 bearing N-carbazolyl, 1-pyrenyl and N-phenyl-N-(pyren-1-yl) substituents, respectively at 2,7,12-positions, were synthesized under mild conditions by palladium-catalyzed reactions in good yields. To improve the solution processability of the material, n-hexyl chains were used as substituents at 5,5'-, 10,10'-, 15,15'-positions. From UV-vis measurements, the absorption maxima were found to be at 330 nm for T-1, 356 nm for T-2 and 412 nm for T-3. The materials were found to be blue emitting with their emission maxima at 385 nm, 425 nm and 490 nm for T-1, T-2 and T-3, respectively. The excited state lifetimes were investigated using time correlated single photon counting and were found to be 10 ns, 1.4 ns and 5.4 ns for T-1, T-2 and T-3, respectively. The highest photoluminescence quantum yield was observed in the case of T-2 corresponding to a value of 0.97. The compounds T-2 and T-3 were used as active materials for the fabrication of solution processed, single layer blue light emitting diodes, with low turn-on voltage (2-3.3 V) and Commission Internationale de l'eclairage (CIE) coordinates corresponding to (0.16, 0.23) and (0.17, 0.36) for T-2 and T-3, respectively.

We demonstrate all thermal vapor-deposited CsSnBr 3 perovskite solar cells. The cell architecture consists of a planar CsSnBr 3 heterojunction where the perovskite layer is grown by thin sequential deposition of SnBr 2 and CsBr allowing for immediate reaction. While other halides of CsSnX 3 (e.g. X=Cl, I) are extremely air sensitive and change color within seconds, illumination tests performed on unencapsulated CsSnBr 3 devices in ambient air show no change over the span of hours. Further, we evaluate the impact of low-temperature annealing and incorporation of various fluoride passivating dopant profiles via vapor deposition. Our results demonstrate an exciting alternative pathway to develop all-inorganic lead-free perovskite photovoltaics.

A new method was developed for doping and fabricating hysteresis-free hybrid perovskite-based photovoltaic devices by using alkali metal halide salts as interface layer additives. Such salt layers introduced at the perovskite interface can provide excessive halide ions to fill vacancies formed during the deposition and annealing process. A range of solution-processed halide salts were investigated. The highest performance of methylammonium lead mixed-halide perovskite device was achieved with a NaI interlayer and showed a power conversion efficiency of 12.6% and a hysteresis of less than 2%. This represents a 90% improvement compared to control devices without this salt layer. Through depth-resolved mass spectrometry, optical modeling, and photoluminescence spectroscopy, this enhancement is attributed to the reduction of iodide vacancies, passivation of grain boundaries, and improved hole extraction. Our approach ultimately provides an alternative and facile route to high-performance and hysteresis-free perovskite solar cells.

By varying the concentration of a solvent additive, we demonstrate the modulation of intermolecular (donor/acceptor (D/A) interface) and intramolecular (bulk) disorder in blends of the low-band gap polymer poly[2,6-(4,4-bis(2-ethylhexyl)-4H-cyclopental[2,1-b;3,4-b′]-dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) blended with [6,6]-phenyl-C71-butyric acid methyl ester (PC71BM). Using the solvent additive concentration of 1,8-diiodooctane (DIO) in the host-processing solvent, the disorder in the bulk and at the interface is studied in terms of Urbach energy, electroluminescence (EL) broadening, and EL quantum efficiency (ELQE). The Urbach energy varies from 80 to 39 meV for bulk and 39 to 51 meV for D/A interface. An interesting feature is that changes in the Urbach energy of the D/A interface are opposite to those of the Urbach energy of bulk; i.e., the disorder at the D/A interface increases as the disorder in the bulk decreases with increase in DIO concentration. Our study evidently suggested a...

We report a blue-emitting random copolymer (termed modified Aryl-F8) consisting of three repeat units of polydioctylfluorene (F8), Aryl-polydioctylfluorene (Aryl-F8), and an aromatic amine comonomer unit, poly(bis-N,Ν′-(4-butylphenyl)-bis-N,N′-phenyl-1,4 phenylenediamine) chemically linked to get an improved charge carrier balance without compromising on the photoluminescence (PL) quantum yield with respect to the Aryl-F8 homo-polymer. The measured photoluminescence quantum efficiency (∼70%) of the blue-emitting polymer is comparable to or greater than the individual monomer units. The time resolved PL spectra from the modified Aryl-F8 are similar to those of Arylated-poly(9,9′-dioctylfluorene-co-bis-N,N′-(4-butylphenyl)-bis-N,N′-phenyl-1,4 phenylenediamine) (PFB) even at a time scale of 100–250 ps, indicating an ultrafast energy transfer from the (Aryl-F8 or F8):Arylated-PFB interface to Arylated-PFB, i.e., endothermic transfer of non-radiative exciplex to a radiative molecular exciton. Furthermore, the presence of non-radiative exciplex is confirmed by the photoluminescence decay profile and temperature dependent PL spectra. The luminance efficiency achieved for the modified Aryl-F8 polymer light-emitting diodes is ∼11 cd A−1 with an external quantum efficiency (EQE) of ∼4.5%, whereas it is 0.05 cd/A with an EQE of ∼0.025% for Aryl-F8. Almost two orders of higher efficiency is achieved due to the improved charge carrier balance from the random copolymer without compromising on the photoluminescence yield.We report a blue-emitting random copolymer (termed modified Aryl-F8) consisting of three repeat units of polydioctylfluorene (F8), Aryl-polydioctylfluorene (Aryl-F8), and an aromatic amine comonomer unit, poly(bis-N,Ν′-(4-butylphenyl)-bis-N,N′-phenyl-1,4 phenylenediamine) chemically linked to get an improved charge carrier balance without compromising on the photoluminescence (PL) quantum yield with respect to the Aryl-F8 homo-polymer. The measured photoluminescence quantum efficiency (∼70%) of the blue-emitting polymer is comparable to or greater than the individual monomer units. The time resolved PL spectra from the modified Aryl-F8 are similar to those of Arylated-poly(9,9′-dioctylfluorene-co-bis-N,N′-(4-butylphenyl)-bis-N,N′-phenyl-1,4 phenylenediamine) (PFB) even at a time scale of 100–250 ps, indicating an ultrafast energy transfer from the (Aryl-F8 or F8):Arylated-PFB interface to Arylated-PFB, i.e., endothermic transfer of non-radiative exciplex to a radiative molecular exciton. Furthermore, the ...

Low dimensional lead halide perovskites have attracted huge research interest due to their structural diversity and remarkable photophysical properties. The ability to controllably change dimensionality/structure of perovskites remains highly challenging. Here, we report synthetic control on structure/dimensionality of ethylenediammonium (ED) lead bromide perovskite from a two dimensionally networked (2DN) sheet to a one dimensionally networked (1DN) chain structure. Intercalation of solvent molecules into the perovskite plays a crucial role in directing the final dimensionality/structure. This change in dimensionality reflects strongly in the observed differences in photophysical properties. Upon UV excitation, the 1DN structure emits white light due to easily formed "self-trapped" excitons. 2DN perovskites show band edge blue emission (similar to 410 nm). Interestingly, Mn2+ incorporated 2DN perovskites show a highly red-shifted Mn2+ emission peak at similar to 670 nm. Such a long wavelength Mn2+ emission peak is unprecedented in the perovskite family. This report highlights the synthetic ability to control the dimensionality/structure of perovskite and consequently its photophysical properties.

The role of high pressure on a low molecular weight nematic liquid crystalline organic semiconductor, ethyl-hexyl substituted polyfluorene (PF2/6) is investigated using photoluminescence (PL), Raman scattering, and X-ray scattering studies at pressures from 1 to 8 GPa. The PL and the Raman data under pressure are consistent with each other with no abrupt changes in the pressure coefficients of PL or Raman peaks. The PL energies redshift and broaden, consistent with both enhanced intra- and interchain interactions. The Raman peak positions yield pressure coefficients similar to other phenyl based π-conjugated polymers. The broadening of a doublet peak in the 1135 cm−1 region indicates a more planar backbone conformation with increasing pressure. X-ray scattering indicates that the torsion angle between adjacent repeats reduces with increasing pressure and reverts back with decompression. The intermolecular structure is weakly ordered (frozen nematic) and essentially maintained with increasing pressure, in contrast to a high molecular weight PF2/6. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014, 52, 1014–1023

Control of unwanted low-energy emission originating due to trap states is crucial for improving the emission efficiency and for maintaining the color purity in blue light-emitting diodes. Here, a truxene-based emitter (T-pyrene) that is a good candidate for the blue emitter is investigated using photophysical studies. Steady-state absorption of the emitter reveals the presence of a charge-transfer state, and the photoluminescence spectrum suggests an occurrence of a strong interchain/exciplex state. Time-resolved photoluminescence (TRPL) and fluence-dependent measurements of the material in the dilute solution show the presence of multiple excitonic processes contributing to the delayed fluorescence. Similar studies on the pristine film suggest that the delayed fluorescence is dominated by the presence of the traps. By blending the oligomer with a higher bandgap polymer matrix, poly(9-vinyl carbazole) (PVK), a type I heterojunction at the T-pyrene:PVK interface is obtained that confines the generated excitons in T-pyrene. With this architecture, device efficiencies with T-pyrene (20 wt. %):PVK show significantly enhanced efficiency than those of the pristine device. We elucidate the relevance of the matrix:T-pyrene system using TRPL and fluence-dependent studies on T-pyrene (20 wt. %):PVK. Time-resolved emission spectra on the T-pyrene (20 wt. %):PVK films do not show red-shifted emission with time delays, which suggests the passivation of the quenching sites due to the dispersion of T-pyrene in PVK to prevent the intermolecular interactions.

Effects of substitutions of rare earth (RE) elements (Y, La, Ce, and Nd) to the Zr-based AB2 multi-phase metal hydride (MH) alloys on the structure, gaseous phase hydrogen storage (H-storage), and electrochemical properties were studied and compared. Solubilities of the RE atoms in the main Laves phases (C14 and C15) are very low, and therefore the main contributions of the RE additives are through the formation of the RENi phase and change in TiNi phase abundance. Both the RENi and TiNi phases are found to facilitate the bulk diffusion of hydrogen but impede the surface reaction. The former is very effective in improving the activation behaviors. −40 °C performances of the Ce-doped alloys are slightly better than the Nd-doped alloys but not as good as those of the La-doped alloys, which gained the improvement through a different mechanism. While the improvement in ultra-low-temperature performance of the Ce-containing alloys can be associated with a larger amount of metallic Ni-clusters embedded in the surface oxide, the improvement in the La-containing alloys originates from the clean alloy/oxide interface as shown in an earlier transmission electron microscopy study. Overall, the substitution of 1 at% Ce to partially replace Zr gives the best electrochemical performances (capacity, rate, and activation) and is recommended for all the AB2 MH alloys for electrochemical applications.