Size effect of lead-free halide double perovskite on luminescence property

Lead-free halide double perovskites have gathered wide scientific interest since they are environmentally friendly and stable.However,compared to the lead perovskites,their optoelectronic properties are compromised.Herein we report a series of bulk lead-free mixed Bi-In halide double perovskites:Cs_2AgBi_(1-x)In_xCl_6(0x1).The Cs_2AgBi_(0.125)In_(0.875)Cl_6breaks the parity-forbidden transition and retains direct band gap structure,having warm-white light emission,with photoluminescence quantum efficiency(PLQE)of 70.3%,much higher than the PLQE of reported lead perovskite materials.Its exciton self-trapping dynamics is investigated.Meanwhile,the Cs_2AgBi_(0.125)In_(0.875)Cl_6nanocrystals and Cs_2AgBi_(0.125)In_(0.875)Cl_6microcrystals can be synthesized by modified hot injection and rapid cooling crystallization,respectively.The size effect of Cs_2AgBi_(0.125)In_(0.875)Cl_6is studied on the photoluminescence(PL)property.Additionally,the bulk material exhibits excellent stability on exposure to light,humidity and air for more than 3 months.It is a promising candidate as highly efficient warm white-light emitting material for road lighting.     

Excitonic coupling in polythiophenes: comparison of different calculation methods

In conjugated polymers the optical excitation energy transfer is usually described as Forster-type hopping between so-called spectroscopic units. In the simplest approach using the point-dipole approximation the transfer rate is calculated based on the interaction between the transition dipoles of two spectroscopic units. In the present work we compare this approach with three others: The line-dipole approximation, the Coulomb integral between the transition densities, and a quantum-chemical calculation of the interacting dimer as entity. The latter two approaches are based on the semiempirical method ZINDO. The line-dipole approximation is an attractive compromise between computational effort and precision for calculations of the excitonic coupling in extended conjugated polymers.     

Spectroscopic units in conjugated polymers: a quantum chemically founded concept?

In conjugated polymers the concept of spectroscopic units belonging to different spatial segments of the chain, which are responsible for the spectroscopic properties of the polymer, has been used to explain the spectral heterogeneity and the excitation migration by (F?rster type) hopping transfer. In the present work we study the possible mechanism of segmentation of polythiophene into spectroscopic units by using quantum-chemical methods (ZINDO). We found that static geometric defects such as kinks or torsions do not result in a significant localization of the excited states to a certain segment. Hence, we propose that a dynamic localization of excitation due to the interaction between the nuclear and electronic degrees of freedom is responsible for the formation of the spectroscopic units.     

Laser pulse control of exciton dynamics in a biological chromophore complex

Femtosecond laser pulse control of exciton dynamics in a biological chromophore complex is studied theoretically. The computations use the optimal control theory specified to open quantum systems and formulated in the framework of the rotating wave approximation. Based on the laser pulse induced formation of an excitonic wave packet the possibility to localize excitation energy at a certain chromophore within a photosynthetic antenna system (FMO complex of green bacteria) is investigated. Details of exciton dynamics driven by a polarization shaped pulse are discussed.     

Lead‐Free Silver‐Bismuth Halide Double Perovskite Nanocrystals

Lead‐free perovskite nanocrystals (NCs) were obtained mainly by substituting a Pb²⁺ cation with a divalent cation or substituting three Pb²⁺ cations with two trivalent cations. The substitution of two Pb²⁺ cations with one monovalent Ag⁺ and one trivalent Bi³⁺ cations was used to synthesize Cs₂AgBiX₆ (X=Cl, Br, I) double perovskite NCs. Using femtosecond transient absorption spectroscopy, the charge carrier relaxation mechanism was elucidated in the double perovskite NCs. The Cs₂AgBiBr₆ NCs exhibit ultrafast hot‐carrier cooling (<1 ps), which competes with the carrier trapping processes (mainly originate from the surface defects). Notably, the photoluminescence can be increased by 100 times with surfactant (oleic acid) added to passivate the defects in Cs₂AgBiCl₆ NCs. These results suggest that the double perovskite NCs could be potential materials for optoelectronic applications by better controlling the surface defects.     

Conformational fluctuations and large fluorescence spectral diffusion in conjugated polymer single chains at low temperatures

The fluorescence of single chains of the conductive polymer poly[2-methoxy-5-(2'-ethylhexyloxy)-1,4-phenylene vinylene] (MEH-PPV) was studied by means of single-molecule spectroscopy at 15 K. MEH-PPV was deposited onto a surface from a toluene solution and covered with a polymer cap layer of poly(vinyl alcohol) spin-coated from an aqueous solution for protection against air. Because MEH-PPV is insoluble in water, such sample preparation guarantees that MEH-PPV chains do not mix with the cap polymer. We found that this "host matrix free" environment results in substantially stronger fluorescence spectral diffusion than that observed for conjugated polymer single chains embedded into polymer matrices. The average spectral diffusion range was 500 cm(-1), and the maximum registered value reached 1100 cm(-1), which is approximately 6 times larger than the values reported before. We analyzed spectral diffusion by observation of temporal evolution of the fluorescence intensity, the position of the maximum, and the width of fluorescence spectra. We propose that the transition energy shifts are caused by the differences of the London dispersive forces in slightly different polymer chain conformations. Such conformational changes are possible even at low temperatures because the MEH-PPV single chains in our samples have more freedom for fluctuations than in the usual "in host" arrangement.     

Electron transfer in quantum-dot-sensitized ZnO nanowires: ultrafast time-resolved absorption and terahertz study

Photoinduced electron injection dynamics from CdSe quantum dots to ZnO nanowires is studied by transient absorption and time-resolved terahertz spectroscopy measurements. Ultrafast electron transfer from the CdSe quantum dots to ZnO is proven to be efficient already on a picoseconds time scale (τ = 3-12 ps). The measured kinetics was found to have a two-component character, whose origin is discussed in detail. The obtained results suggest that electrons are injected into ZnO via an intermediate charge transfer state.     

Control of electron transfer pathways in a dye-sensitized solar cell

Using shaped laser pulses, we increase the yield of ultrafast electron injection from the sensitizer to TiO2 nanocrystals in the core part of a dye-sensitized solar cell. The temporal structure of the optimized excitation pulse is in clear correlation with nuclear oscillations in the impulsively excited dye molecule. From DFT structure optimization and normal mode analyses we identified the modes which are responsible for the oscillations. The best pulse shape suggests Impulsive Stimulated (anti-Stokes) Raman scattering as a key process of optimization.     

Excited state and charge photogeneration dynamics in conjugated polymers

Conjugated polymers are becoming interesting materials for a range of optoelectronic applications. However, their often complex electronic and structural properties prevent establishment of straightforward property-function relationships. In this paper, we summarize recent results on the photophysics and excited state dynamics of conjugated polymers, in order to paint a picture of exciton formation, quenching, and generation of charge carriers.