Cooling,Scattering, and Recombination—The Role of the Material Quality for the Physics of Tin Halide Perovskites

Tin‐based perovskites have long remained a side topic in current perovskite optoelectronic research. With the recent efficiency improvement in thin film solar cells and the observation of a long hot carrier cooling time in formamidinium tin iodide (FASnI₃), a thorough understanding of the material's photophysics becomes a pressing matter. Since pronounced background doping can easily obscure the actual material properties, it is of paramount importance to understand how different processing conditions affect the observed behavior. Using photoluminescence spectroscopy, thin films of FASnI₃ fabricated through different protocols are therefore investigated. It is shown that hot carrier relaxation occurs much faster in highly p‐doped films due to carrier–carrier scattering. From high quality thin films, the longitudinal optical phonon energy and the electron–phonon coupling constant are extracted, which are fundamental to understanding carrier cooling. Importantly, high quality films allow for the observation of a previously unreported state of microsecond lifetime at lower energy in FASnI₃, that has important consequences for the discussion of long lived emission in the field of metal halide perovskites.     

Blue light‐emitting poly(p‐phenylenevinylene) derivative with oxadiazole and carbazole pendant groups

A blue light‐emitting statistical poly(p‐phenylenevinylene) (PPV) copolymer with hole‐transporting carbazole and electron‐transporting oxadiazole pendant groups attached to the kinked m‐terphenyl unit was prepared by Heck coupling between 1,4‐divinylbenzene and dibromides. The latter were synthesized through pyrylium salts. The polymer had optical band gap of 2.89 eV and emission maximum at 446 nm in THF solution and 434 nm in thin film. It showed a pure blue emission with no aggregates or excimers formed even in solid state because of the long and bulky pendant groups. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3842–3849, 2006     

Photochemistry and photophysics of poly(organophosphazenes) and related compounds: A review. I. Monomolecular processes

In this review we report an outline of the synthesis, UV-Vis spectral characterization, and light-induced reactivity in monomolecular processes of poly(organophosphazenes). The photoreactivity of phosphazene polymers, both in solution and in solid state, strongly depends on the nature of the chromophore attached to the phosphorus atoms of the inorganic –P=N – backbone. In fact, polyphosphazenes not bearing mobile hydrogen atoms in the side moieties undergo, in the first excited singlet state, homolytic eleavage of the bonds connecting the substituents to the inorganic backbone: free radicals of the substituents and phosphazene macroradicals are formed. Moreover, for polyphosphazenes containing labile hydrogens in the side groups, C–H bond scission takes place with the formation of free hydrogens and radicals located in the phosphazene substituents. From these species degradation or crosslinking of the macromolecules will follow according to the experimental conditions.This review is in three parts. Parts II and III will appear sequentially in the next two issues of this journal.     

Advanced Photoresponsive Materials Using the Metal–Organic Framework Approach

When fabricating macroscopic devices exploiting the properties of organic chromophores, the corresponding molecules need to be condensed into a solid material. Since optical absorption properties are often strongly affected by interchromophore interactions, solids with a well-defined structure carry substantial advantages over amorphous materials. Here, the metal–organic framework (MOF)-based approach is presented. By appropriate functionalization, most organic chromophores can be converted to function as linkers, which can coordinate to metal or metal-oxo centers so as to yield stable, crystalline frameworks. Photoexcitations in such chromophore-based MOFs are surveyed, with a special emphasis on light-switchable MOFs from photochromic molecules. The conventional powder form of MOFs obtained using solvothermal approaches carries certain disadvantages for optical applications, such as limited efficiency resulting from absorption and light scattering caused by the (micrometer-sized) powder particles. How these problems can be avoided by using MOF thin films is demonstrated.     

两种蔡酰亚胺类化合物及其聚合物荧光性质的研究

本文以１,８萘酰亚胺为原料,合成了两种萘酰亚胺类型的化合物,系统地研究了它们在不同溶剂中的吸收光谤和荧光光谱。并以这两种化合物单体为基础,通过共聚合成了它们与甲基丙烯酸甲酯和Ｎ－乙烯基咔唑的嵌段共聚物。研究了聚合物在溶液和薄膜中的荧光性质。结果证明,所得共聚物不但保持了单体的基本荧光特性,其溶解性、成膜性、热稳定性等都得到了大大改善,是一种有应用前景的有机发光半导体材料。此外,本文还利用荧光猝灭的     

Excited States Computation of Models of Phenylalanine Protein Chains: TD-DFT and Composite CC2/TD-DFT Protocols

The present benchmark calculations testify to the validity of time-dependent density functional theory (TD-DFT) when exploring the low-lying excited states potential energy surfaces of models of phenylalanine protein chains. Among three functionals suitable for systems exhibiting charge-transfer excited states, LC-ωPBE, CAM-B3LYP, and ωB97X-D, which were tested on a reference peptide system, we selected the ωB97X-D functional, which gave the best results compared to the approximate coupled-cluster singles and doubles (CC2) method. A quantitative agreement for both the geometrical parameters and the vibrational frequencies was obtained for the lowest singlet excited state (a ππ* state) of the series of capped peptides. In contrast, only a qualitative agreement was met for the corresponding adiabatic zero-point vibrational energy (ZPVE)-corrected excitation energies. Two composite protocols combining CC2 and DFT/TD-DFT methods were then developed to improve these calculations. Both protocols substantially reduced the error compared to CC2 and experiment, and the best of both even led to results of CC2 quality at a lower cost, thus providing a reliable alternative to this method for very large systems.     

Synthesis,electroluminescence, and photovoltaic cells of new vinylene‐copolymers with 4‐(anthracene‐10‐yl)‐2,6‐diphenylpyridine segments

Three new soluble vinylene‐copolymers F , C, and P that contain 4‐(anthracene‐10‐yl)‐2,6‐diphenylpyridine as common segment and fluorene, carbazole, or phenylene, respectively, as alternating segment were prepared by Heck coupling. The glass transition temperature was high for F and C (110 and 117°C), whereas was lower than 25°C for P . The polymers were stable up to ～ 300°C. They emitted blue–green light with maximum located at wavelength of 456–550 nm, which was of the order F < C < P . The photoluminescence quantum efficiency in THF solution was ～ 30% for F and P and only 5% for C . All three copolymers were used as active layers for polymer light emitting diodes (PLEDs) and organic photovoltaic cells. The double PLEDs with configuration of indium‐tin oxide (ITO)/poly(ethylenedioxythiophene (PEDOT) : poly(styrenesulfonate)(PSS)/Copolymer F , C , or P /TPBI(1,3,5‐tris(2‐N‐phenylbenzimidazolyl)benzene)/Ca/Al were fabricated. Copolymer P emitted green light with maximum brightness of 28 cd/m² and a current yield of 0.85 cd/A. Organic photovoltaics with the configuration of ITO/PEDOT : PSS/Copolymer and [6,6]‐phenyl‐C61‐butyric acid methyl ester blend (1 : 1) /Ca/Al were also fabricated. Copolymer P showed the highest power conversion efficiency of 0.034%. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Photophysics of Two-Dimensional Perovskites—Learning from Metal Halide Substitution

2D perovskites offers a rich playing field to explore exciton physics and they possess a great potential for a variety of opto-electronic applications. Whilst their photophysics shows intricate interactions of excitons with the lattice, most reports have so far relied on single compound studies. With the exception of variations of the organic spacer cations, the effect of constituent substitution on the photophysics and the nature of emitting species, in particular, have remained largely under-explored. Here PEA₂PbBr₄, PEA₂PbI₄, and PEA₂SnI₄ (where PEA stands for phenylethylammonoium) are studied through a variety of optical spectroscopy techniques to reveal a complex set of excitonic transitions at low temperature. Weak high-energy features are attributed to vibronic transitions breaking Kasha's, for which the responsible phonons cannot be accessed through simple Raman spectroscopy. Bright peaks at lower energy are due to two distinct electronic states, of which the upper is a convolution of the free exciton and a localized dark state and the lower is attributed to recombination involving shallow defects. This study offers deeper insights into the photophysics of 2D perovskites through compositional substitution and highlights critical limits to the communities’ current understanding of processes in these compounds.     

Guidance for Mutual Disposition of Chromophores for Singlet Fission

The choice of chromophores and of their mutual geometrical arrangement for optimized singlet fission (SF) rates are considered. The electronic matrix element that enters the Fermi golden rule for the rate of SF is worked out algebraically for a simple model, but the density of states factor is not analyzed here. The model treats only the highest occupied and lowest unoccupied orbitals of the partners. It provides an approximate formula that requires only the knowledge of the expansion coefficients of these orbitals and of overlap integrals between atomic orbitals on the partners to obtain an estimate of the electronic matrix element. An illustrative application to a pair of ethylene molecules suggests that favored geometries will be those in which one of the AOs on the first ethylene overlaps with both AOs on the second ethylene, while the other AO on the first ethylene overlaps with at least one, and preferably both, AOs of the second ethylene as little as possible.