Impressive performance of hybrid perovskite solar cells reported in recent years still awaits a comprehensive understanding of its microscopic origins. In this work, the intrinsic Hall mobility and ...photocarrier recombination coefficient are directly measured in these materials in steady-state transport studies. The results show that electron-hole recombination and carrier trapping rates in hybrid perovskites are very low. The bimolecular recombination coefficient (10(-11) to 10(-10) cm(3) s(-1)) is found to be on par with that in the best direct-band inorganic semiconductors, even though the intrinsic Hall mobility in hybrid perovskites is considerably lower (up to 60 cm(2) V(-1) s(-1)). Measured here, steady-state carrier lifetimes (of up to 3 ms) and diffusion lengths (as long as 650 μm) are significantly longer than those in high-purity crystalline inorganic semiconductors. We suggest that these experimental findings are consistent with the polaronic nature of charge carriers, resulting from an interaction of charges with methylammonium dipoles.
This paper presents new developments in inorganic scintillators widely used for radiation detection. It addresses major emerging research topics outlining current needs for applications and material ...sciences issues with the overall aim to provide an up-to-date picture of the field. While the traditional forms of scintillators have been crystals and ceramics, new research on films, nanoparticles, and microstructured materials is discussed as these material forms can bring new functionality and therefore find applications in radiation detection. The last part of the contribution reports on the very recent evolutions of the most advanced theories, methods, and analyses to describe the scintillation mechanisms.
The recently discovered phenomenon of broadband white-light emission at room temperature in the (110) two-dimensional organic–inorganic perovskite (N-MEDA)PbBr4 (N-MEDA = N ...1-methylethane-1,2-diammonium) is promising for applications in solid-state lighting. However, the spectral broadening mechanism and, in particular, the processes and dynamics associated with the emissive species are still unclear. Herein, we apply a suite of ultrafast spectroscopic probes to measure the primary events directly following photoexcitation, which allows us to resolve the evolution of light-induced emissive states associated with white-light emission at femtosecond resolution. Terahertz spectra show fast free carrier trapping and transient absorption spectra show the formation of self-trapped excitons on femtosecond time-scales. Emission-wavelength-dependent dynamics of the self-trapped exciton luminescence are observed, indicative of an energy distribution of photogenerated emissive states in the perovskite. Our results are consistent with photogenerated carriers self-trapped in a deformable lattice due to strong electron–phonon coupling, where permanent lattice defects and correlated self-trapped states lend further inhomogeneity to the excited-state potential energy surface.
The aim of this study was to develop a widely accepted prognostic nomogram for extranodal NK/T-cell lymphoma, nasal-type (NKTCL). The clinical data from 1383 patients with NKTCL treated at 10 ...participating institutions between 2000 and 2011 were reviewed. A nomogram was developed that predicted overall survival (OS) based on the Cox proportional hazards model. To contrast the utility of the nomogram against the widely used Ann Arbor staging system, the International Prognostic Index (IPI) and the Korean Prognostic Index (KPI), we used the concordance index (C-index) and a calibration curve to determine its predictive and discriminatory capacity. The 5-year OS rate was 60.3% for the entire group. The nomogram included five important variables based on a multivariate analysis of the primary cohort: stage; age; Eastern Cooperative Oncology Group performance status; lactate dehydrogenase; and primary tumor invasion. The calibration curve showed that the nomogram was able to predict 5-year OS accurately. The C-index of the nomogram for OS prediction was 0.72 for both cohorts, which was superior to the predictive power (range, 0.56-0.64) of the Ann Arbor stage, IPI and KPI in the primary and validation cohorts. The proposed nomogram provides an individualized risk estimate of OS in patients with NKTCL.
The absorption of one photon by a semiconductor material usually creates one electron–hole pair. However, this general rule breaks down in a few organic semiconductors, such as pentacene and ...tetracene, where one photon absorption may result in two electron–hole pairs. This process, where a singlet exciton transforms to two triplet excitons, can have quantum yields as high as 200%. Singlet fission may be useful to solar cell technologies to increase the power conversion efficiency beyond the so-called Shockley-Queisser limit. Through time-resolved two-photon photoemission (TR-2PPE) spectroscopy in crystalline pentacene and tetracene, our lab has recently provided the first spectroscopic signatures in singlet fission of a critical intermediate known as the multiexciton state (also called a correlated triplet pair). More importantly, we found that population of the multiexciton state rises at the same time as the singlet state on the ultrafast time scale upon photoexcitation. This observation does not fit with the traditional view of singlet fission involving the incoherent conversion of a singlet to a triplet pair. However, it provides an experimental foundation for a quantum coherent mechanism in which the electronic coupling creates a quantum superposition of the singlet and the multiexciton state immediately after optical excitation. In this Account, we review key experimental findings from TR-2PPE experiments and present a theoretical analysis of the quantum coherent mechanism based on electronic structural and density matrix calculations for crystalline tetracene lattices. Using multistate density functional theory, we find that the direct electronic coupling between singlet and multiexciton states is too weak to explain the experimental observation. Instead, indirect coupling via charge transfer intermediate states is two orders of magnitude stronger, and dominates the dynamics for ultrafast multiexciton formation. Density matrix calculation for the crystalline tetracene lattice satisfactorily accounts for the experimental observations. It also reveals the critical roles of the charge transfer states and the high dephasing rates in ensuring the ultrafast formation of multiexciton states. In addition, we address the origins of microscopic relaxation and dephasing rates, and adopt these rates in a quantum master equation description. We show the need to take the theoretical effort one step further in the near future by combining high-level electronic structure calculations with accurate quantum relaxation dynamics for large systems.
In this Letter, we demonstrate highly efficient, polarization-insensitive planar lenses (metalenses) at red, green, and blue wavelengths (λ = 660, 532, and 405 nm). Metalenses with numerical ...apertures (NA) of 0.85 and 0.6 and corresponding efficiencies as high as 60% and 90% are achieved. These metalenses are less than 600 nm-thick and can focus incident light down to diffraction-limited spots as small as ∼0.64λ and provide high-resolution imaging. In addition, the focal spots are very symmetric with high Strehl ratios. The single step lithography and compatibility with large-scale fabrication processes make metalenses highly promising for widespread applications in imaging and spectroscopy.
The absorption of a photon usually creates a singlet exciton (S
) in molecular systems, but in some cases S
may split into two triplets (2×T
) in a process called singlet fission. Singlet fission is ...believed to proceed through the correlated triplet-pair
(TT) state. Here, we probe the
(TT) state in crystalline hexacene using time-resolved photoemission and transient absorption spectroscopies. We find a distinctive
(TT) state, which decays to 2×T
with a time constant of 270 fs. However, the decay of S
and the formation of
(TT) occur on different timescales of 180 fs and <50 fs, respectively. Theoretical analysis suggests that, in addition to an incoherent S
→
(TT) rate process responsible for the 180 fs timescale, S
may couple coherently to a vibronically excited
(TT) on ultrafast timescales (<50 fs). The coexistence of coherent and incoherent singlet fission may also reconcile different experimental observations in other acenes.
Singlet fission (SF) has the potential to significantly enhance the photocurrent in single-junction solar cells and thus raise the power conversion efficiency from the Shockley–Queisser limit of 33% ...to 44%. Until now, quantitative SF yield at room temperature has been observed only in crystalline solids or aggregates of oligoacenes. Here, we employ transient absorption spectroscopy, ultrafast photoluminescence spectroscopy, and triplet photosensitization to demonstrate intramolecular singlet fission (iSF) with triplet yields approaching 200% per absorbed photon in a series of bipentacenes. Crucially, in dilute solution of these systems, SF does not depend on intermolecular interactions. Instead, SF is an intrinsic property of the molecules, with both the fission rate and resulting triplet lifetime determined by the degree of electronic coupling between covalently linked pentacene molecules. We found that the triplet pair lifetime can be as short as 0.5 ns but can be extended up to 270 ns.
The event rate, energy distribution and time-domain behaviour of repeating fast radio bursts (FRBs) contain essential information regarding their physical nature and central engine, which are as yet ...unknown
. As the first precisely localized source, FRB 121102 (refs.
) has been extensively observed and shows non-Poisson clustering of bursts over time and a power-law energy distribution
. However, the extent of the energy distribution towards the fainter end was not known. Here we report the detection of 1,652 independent bursts with a peak burst rate of 122 h
, in 59.5 hours spanning 47 days. A peak in the isotropic equivalent energy distribution is found to be approximately 4.8 × 10
erg at 1.25 GHz, below which the detection of bursts is suppressed. The burst energy distribution is bimodal, and well characterized by a combination of a log-normal function and a generalized Cauchy function. The large number of bursts in hour-long spans allows sensitive periodicity searches between 1 ms and 1,000 s. The non-detection of any periodicity or quasi-periodicity poses challenges for models involving a single rotating compact object. The high burst rate also implies that FRBs must be generated with a high radiative efficiency, disfavouring emission mechanisms with large energy requirements or contrived triggering conditions.
In an attempt to tailor low-cost, precious-metal-free electrocatalysts for water electrolysis in acid, molybdenum carbide ( beta -Mo sub(2)C) nanoparticles are prepared by in situcarburization of ...ammonium molybdate on carbon nanotubes and XC-72R carbon black without using any gaseous carbon source. The formation of Mo sub(2)C is investigated by thermogravimetry and in situX-ray diffraction. X-ray absorption analysis reveals that Mo sub(2)C nanoparticles are inlaid or anchored into the carbon supports, and the electronic modification makes the surface exhibit a relatively moderate Mo-H bond strength. It is found that carbon nanotube-supported Mo sub(2)C showed superior electrocatalytic activity and stability in the hydrogen evolution reaction (HER) compared to the bulk Mo sub(2)C. An overpotential of 63 mV for driving 1 mA cm super(-2) of current density was measured for the nanotube-supported Mo sub(2)C catalysts; this exceeds the activity of analogous Mo sub(2)C catalysts. The enhanced electrochemical activity is facilitated by unique effects of the anchored structure coupled with the electronic modification.
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