ABSTRACT
We explore the application of excitation correlation spectroscopy to detect nonlinear photophysical dynamics in two distinct semiconductor classes through time-integrated photoluminescence and photocurrent measurements. In this experiment, two variably delayed femtosecond pulses excite the semiconductor, and the time-integrated photoluminescence or photocurrent component arising from the nonlinear dynamics of the populations induced by each pulse is measured as a function of inter-pulse delay by phase-sensitive detection with a lock-in amplifier. We focus on two limiting materials systems with contrasting optical properties: a prototypical lead-halide perovskite (LHP) solar cell, in which primary photoexcitations are charge photocarriers, and a single-component organic-semiconductor diode, which features Frenkel excitons as primary photoexcitations. The photoexcitation dynamics perceived by the two detection schemes in these contrasting systems are distinct. Nonlinear-dynamic contributions in the photoluminescence detection scheme arise from contributions to radiative recombination in both materials systems, while photocurrent arises directly in the LHP but indirectly following exciton dissociation in the organic system. Consequently, the basic photophysics of the two systems are reflected differently when comparing measurements with the two detection schemes. Our results indicate that photoluminescence detection in the LHP system provides valuable information about trap-assisted and Auger recombination processes, but that these processes are convoluted in a nontrivial way in the photocurrent response and are therefore difficult to differentiate. In contrast, the organic-semiconductor system exhibits more directly correlated responses in the nonlinear photoluminescence and photocurrent measurements, as charge carriers are secondary excitations only generated through exciton dissociation processes. We propose that bimolecular annihilation pathways mainly contribute to the generation of charge carriers in single-component organic semiconductor devices. Overall, our work highlights the utility of excitation correlation spectroscopy in modern semiconductor materials research, particularly in the analysis of nonlinear photophysical processes, which are deterministic for their electronic and optical properties.
ABSTRACT
An anionic layered coordination polymer [Eu(BTEC)0.5(HCOO)(H2O)2] (1) has been successfully synthesized via a solvothermal method (H4BTEC = 1,2,4,5-benzenetetracarboxylic acid, HCOOH = formic acid). Compound 1 possesses two-dimensional layers, which further generate a three-dimensional supramolecular network by hydrogen bonds existing between carboxylic oxygen, formate anion and H2O molecules of two adjacent layers. Interestingly, 1 shows high luminescence quenching efficiency upon addition of Fe3+ ions when it was dispersed in water even in the presence of interfering ions such as Na+, Ag+, Ca2+, Cd2+, Co2+, Cu2+, Mg2+, Mn2+, Zn2+ and Al3+. When dispersed in DMSO solution, 1 displays excellent sensitivity and selectivity towards both Cu2+ and Fe3+ ions. Possible quenching mechanisms for detection of Fe3+ and Cu2+ ions were carefully investigated and proposed based on a dynamic quenching process, static quenching process and fluorescence inner filter effect. Moreover, the as-prepared particles can be used for visualizing latent fingerprints on various substrates. These results indicate that a Eu(iii)-based coordination polymer has great potential in detection and security application.
ABSTRACT
A stable 3D TbIII -based metal-organic framework [Tb(BPDC)2 ]â (CH3 )2 NH2 (DUT-101) was synthesized, and it is the first efficient dual-channel luminescence sensor for aqueous UO22+ ions. DUT-101 contains an anionic three-dimensional framework and protonated dimethylamine molecules embedded within the channels. The intense green emission of DUT-101 could be highly selectively and sensitively quenched by UO22+ ions even in the presence of other competing metal ions. A possible sensing mechanism was proposed based on both suppression of luminescence resonance energy transfer and enhancement of intermolecular electron transfer. Furthermore, visual green fluorescent test papers based on DUT-101 were fabricated and could be used to discriminate UO22+ ions among various metal ions.
ABSTRACT
We report a new synthetic protocol of Au99(SPh)42 nanoclusters with moderate efficiency (â¼15% yield based on HAuCl4), via a combination of the ligand-exchange and "size-focusing" processes. The purity of the as-prepared gold nanoclusters is characterized by matrix-assisted laser desorption ionization mass spectrometry and size exclusion chromatography.
