Multiphoton excited singlet/triplet mixed self-trapped exciton emission.

Multiphoton excited luminescence is of paramount importance in the field of optical detection and biological photonics. Self-trapped exciton (STE) emission with self-absorption-free advantages provide a choice for multiphoton excited luminescence. Herein, multiphoton excited singlet/triplet mixed STE emission with a large full width at half-maximum (617 meV) and Stokes shift (1.29 eV) has been demonstrated in single-crystalline ZnO nanocrystals. Temperature dependent steady state, transient state and time-resolved electron spin resonance spectra demonstrate a mixture of singlet (63%) and triplet (37%) mixed STE emission, which contributes to a high photoluminescence quantum yield (60.5%). First-principles calculations suggest 48.34 meV energy per exciton stored by phonons in the distorted lattice of excited states, and 58 meV singlet-triplet splitting energy for the nanocrystals being consistent with the experimental measurements. The model clarifies long and controversial debates on ZnO emission in visible region, and the multiphoton excited singlet/triplet mixed STE emission is also observed.

Stabilized tilted-octahedra halide perovskites inhibit local formation of performance-limiting phases.

Efforts to stabilize photoactive formamidinium (FA)­based halide perovskites for perovskite photovoltaics have focused on the growth of cubic formamidinium lead iodide (α-FAPbI3) phases by empirically alloying with cesium, methylammonium (MA) cations, or both. We show that such stabilized FA-rich perovskites are noncubic and exhibit ~2° octahedral tilting at room temperature. This tilting, resolvable only with the use of local nanostructure characterization techniques, imparts phase stability by frustrating transitions from photoactive to hexagonal phases. Although the bulk phase appears stable when examined macroscopically, heterogeneous cation distributions allow microscopically unstable regions to form; we found that these transitioned to hexagonal polytypes, leading to local trap-assisted performance losses and photoinstabilities. Using surface-bound ethylenediaminetetraacetic acid, we engineered an octahedral tilt into pure α-FAPbI3 thin films without any cation alloying. The templated photoactive FAPbI3 film was extremely stable against thermal, environmental, and light stressors.

The importance of relativistic effects on two-photon absorption spectra in metal halide perovskites.

Despite intense research into the optoelectronic properties of metal halide perovskites (MHPs), sub-bandgap absorption in MHPs remains largely unexplored. Here we recorded two-photon absorption spectra of MHPs using the time-resolved microwave conductivity technique. A two-step upward trend is observed in the two-photon absorption spectrum for methylammonium lead iodide, and some analogues, which implies that the commonly used scaling law is not applicable to MHPs. This aspect is further confirmed by temperature-dependent conductivity measurements. Using an empirical multiband tight binding model, spectra for methylammonium lead iodide were calculated by integration over the entire Brillouin zone, showing compelling similarity with experimental results. We conclude that the second upward trend in the two-photon absorption spectrum originates from additional optical transitions to the heavy and light electron bands formed by the strong spin-orbit coupling. Hence, valuable insight can be obtained in the opto-electronic properties of MHPs by sub-bandgap spectroscopy, complemented by modelling.

Reversible Removal of Intermixed Shallow States by Light Soaking in Multication Mixed Halide Perovskite Films.

The highest reported efficiencies of metal halide perovskite (MHP) solar cells are all based on mixed perovskites, such as (FA,MA,Cs)Pb(I1-x Br x )3. Despite demonstrated structural changes induced by light soaking, it is unclear how the charge carrier dynamics are affected across this entire material family. Here, various (FA,MA,Cs)Pb(I1-x Br x )3 perovskite films are light-soaked in nitrogen, and changes in optoelectronic properties are investigated through time-resolved microwave conductivity (TRMC) and optical and structural techniques. To fit the TRMC decay kinetics obtained for pristine (FA,MA,Cs)Pb(I1-x Br x )3 for various excitation densities, additional shallow states have to be included, which are not required for describing TRMC traces of single-cation MHPs. These shallow states can, independently of x, be removed by light soaking, which leads to a reduction in the imbalance between the diffusional motion of electrons and holes. We interpret the shallow states as a result of initially well-intermixed halide distributions, which upon light soaking segregate into domains with distinct band gaps.

A Highly Emissive Surface Layer in Mixed-Halide Multication Perovskites.

Mixed-halide lead perovskites have attracted significant attention in the field of photovoltaics and other optoelectronic applications due to their promising bandgap tunability and device performance. Here, the changes in photoluminescence and photoconductance of solution-processed triple-cation mixed-halide (Cs0.06 MA0.15 FA0.79 )Pb(Br0.4 I0.6 )3 perovskite films (MA: methylammonium, FA: formamidinium) are studied under solar-equivalent illumination. It is found that the illumination leads to localized surface sites of iodide-rich perovskite intermixed with passivating PbI2 material. Time- and spectrally resolved photoluminescence measurements reveal that photoexcited charges efficiently transfer to the passivated iodide-rich perovskite surface layer, leading to high local carrier densities on these sites. The carriers on this surface layer therefore recombine with a high radiative efficiency, with the photoluminescence quantum efficiency of the film under solar excitation densities increasing from 3% to over 45%. At higher excitation densities, nonradiative Auger recombination starts to dominate due to the extremely high concentration of charges on the surface layer. This work reveals new insight into phase segregation of mixed-halide mixed-cation perovskites, as well as routes to highly luminescent films by controlling charge density and transfer in novel device structures.

Photoluminescence from Radiative Surface States and Excitons in Methylammonium Lead Bromide Perovskites.

In view of its band gap of 2.2 eV and its stability, methylammonium lead bromide (MAPbBr3) is a possible candidate to serve as a light absorber in a subcell of a multijunction solar cell. Using complementary temperature-dependent time-resolved microwave conductance (TRMC) and photoluminescence (TRPL) measurements, we demonstrate that the exciton yield increases with lower temperature at the expense of the charge carrier generation yield. The low-energy emission at around 580 nm in the cubic phase and the second broad emission peak at 622 nm in the orthorhombic phase originate from radiative recombination of charges trapped in defects with mobile countercharges. We present a kinetic model describing both the decay in conductance as well as the slow ingrowth of the TRPL. Knowledge of defect states at the surface of various crystal phases is of interest to reach higher open-circuit voltages in MAPbBr3-based cells.

Dopant compensation in alloyed CH3NH3PbBr3-xClx perovskite single crystals for gamma-ray spectroscopy.

Organic-inorganic halide perovskites (OIHPs) bring an unprecedented opportunity for radiation detection with their defect-tolerance nature, large mobility-lifetime product, and simple crystal growth from solution. Here we report a dopant compensation in alloyed OIHP single crystals to overcome limitations of device noise and charge collection, enabling γ-ray spectrum collection at room temperature. CH3NH3PbBr3 and CH3NH3PbCl3 are found to be p-type and n-type doped, respectively, whereas dopant-compensated CH3NH3PbBr2.94Cl0.06 alloy has over tenfold improved bulk resistivity of 3.6 × 109 Ω cm. Alloying also increases the hole mobility to 560 cm2 V-1 s-1, yielding a high mobility-lifetime product of 1.8 × 10-2 cm2 V-1. The use of a guard ring electrode in the detector reduces the crystal surface leakage current and device dark current. A distinguishable 137Cs energy spectrum with comparable or better resolution than standard scintillator detectors is collected under a small electric field of 1.8 V mm-1 at room temperature.

Surface plasmon effect of carbon nanodots.

Luminescent ZnO quantum dots (QDs) have been prepared, and the fluorescence intensity of the QDs can be increased greatly with the introduction of carbon nanodots, while the fluorescence lifetime of the QDs decreases significantly. The fluorescence enhancement and lifetime decrement can be attributed to the surface plasmon effect of the carbon nanodots, and the calculated surface plasmon resonance frequency of the nanodots matches well with the fluorescence spectrum of the ZnO QDs.

Highly sensitive ultraviolet photodetectors fabricated from ZnO quantum dots/carbon nanodots hybrid films.

Ultraviolet photodetectors have been fabricated from ZnO quantum dots/carbon nanodots hybrid films, and the introduction of carbon nanodots improves the performance of the photodetectors greatly. The photodetectors can be used to detect very weak ultraviolet signals (as low as 12 nW/cm(2)). The detectivity and noise equivalent power of the photodetector can reach 3.1 × 10(17) cmHz(1/2)/W and 7.8 × 10(-20) W, respectively, both of which are the best values ever reported for ZnO-based photodetectors. The mechanism for the high sensitivity of the photodetectors has been attributed to the enhanced carrier-separation at the ZnO/C interface.