Long-lived excitons in thermally annealed hydrothermal ZnO.

Applying thermal annealing to hydrothermal ZnO crystals an enhancement of exciton lifetime from 80 ps to 40 ns was achieved boosting PL quantum efficiency of the UV luminescence up to 70 %. The lifetime improvement is related to the reduced density of carrier traps by a few orders of magnitude as revealed by the reduction of the slow decay tail in pump probe decays coupled with weaker defects-related PL. The diffusion coefficient was determined to be 0.5 cm2/s, providing a large exciton diffusion length of 1.4 µm. The UV PL lifetime drop at the lowest exciton densities was explained by capture to traps. Release of holes from acceptor traps provided delayed exciton luminescence with ∼200 µs day time and 390 meV thermal activation energy. Pump-probe decays provided exciton absorption cross-section of 9 × 10-18 cm2 at 1550 nm wavelength and verified the PL decay times of excitons. Amplitudes and decay times of the microsecond slow decay tails have been correlated with the trap densities and their photoluminescence. A surface recombination velocity of 500 cm/s and the bimolecular free carrier recombination coefficient 0.7 × 10-11 cm3/s were calculated. Therefore, the properly annealed hydrothermally grown ZnO can be a viable and integral part of many functional devices as light-emitting diodes and lasers.

Impact of dopant-induced band tails on optical spectra, charge carrier transport, and dynamics in single-crystal CdTe.

Cadmium telluride (CdTe) semiconductors are used in thin-film photovoltaics, detectors, and other optoelectronic applications. For all technologies, higher efficiency and sensitivity are achieved with reduced charge carrier recombination. In this study, we use state-of-the-art CdTe single crystals and electro-optical measurements to develop a detailed understanding of recombination rate dependence on excitation and temperature in CdTe. We study recombination and carrier dynamics in high-resistivity (undoped) and arsenic (As)-doped CdTe by employing absorption, the Hall effect, time-resolved photoluminescence, and pump-probe in the 80-600 K temperature range. We report extraordinarily long lifetimes (30 µs) at low temperatures in bulk undoped CdTe. Temperature dependencies of carrier density and mobility reveal ionization of the main acceptors and donors as well as dominant scattering by ionized impurities. We also distinguish different recombination defects. In particular, shallow AsTe and deep VCd-AsCd acceptors were responsible for p-type conductivity. AX donors were responsible for electron capture, while nonradiative recombination centers (VCd-AsTe, As2 precipitates), and native defects (VCd-TeCd) were found to be dominant in p-type and n-type CdTe, respectively. Bimolecular and surface recombination rate temperature dependencies were also revealed, with bimolecular coefficient T-3/2 temperature dependence and 170 meV effective surface barrier, leading to an increase in surface recombination velocity at high temperatures and excitations. The results of this study allowed us to conclude that enhanced crucible rotation growth of As-doped CdTe is advantageous to As activation, leading to longer lifetimes and larger mobilities and open-circuit voltages due to lower absorption and trapping.

Highly efficient nanocrystalline CsxMA1-xPbBrx perovskite layers for white light generation.

Perovskite light converting layers optimization for cost-efficient white light emitting diodes (LED) was demonstrated. High excitation independent internal quantum efficiency (IQE) of 80% and weakly excitation dependent PL spectra suitable for white light generation were obtained in the mixed cation CsxMA1-xPbBr3 perovskite nanocrystal layers with optimal x = 0.3 being determined by effective surface passivation and phase mixing as revealed by x-ray diffraction. Enhancement of the PL homogeneity and the external quantum efficiency (EQE) were secured when using 2,2',2″-(1,3,5-Benzinetriyl)-tris(1-phenyl-1-H-benzimidazole (TPBi) additive in the layer preparation process. Excitation dependent PL intensity, decay time, and IQE revealed that the high emission efficiency of the layers originates from a dominant radiative localized exciton recombination (130 ns) weakly influenced by the nonradiative free carrier recombination (750 ns). Warm and cool white LEDs with correlated color temperature 3000 K and 5600 K, and color rendering index 82 and 74, respectively, were realized by using the optimized perovskite layers, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV) red emitter and a blue LED.

Carrier dynamics in highly excited TlInS2: evidence of 2D electron-hole charge separation at parallel layers.

We report a comprehensive study of the time-resolved photoluminescence (PL), carrier recombination, and carrier diffusion under diverse laser pulse excitation in TlInS2. The 2D-layered crystals were grown by the Bridgman method without or with the presence of a small amount of erbium in the melt. The investigation exposes large differences in two crystal types, although, a linear nonradiative lifetime and carrier diffusivity attain close values under high excitation with no contribution of the Auger recombination and the absence of the band gap narrowing effect. Moreover, at high pulse power, we detect imprinted transient grating fringes which are attributed to a new crystal phase formed by 2D electron-hole charge separation on local layers. The versatile model of the spontaneously polarized 2D-crystal has been developed to explain the observed features and ergodicity of charge dynamic processes. The model embraces the planar stacking fault (PSF) which edge provides a distortion and act as sink of strong recombination. The reduced occurrence of the PSFs in the erbium doped TlInS2 is the main attribute which determines the enhancement of PL by a factor of 50 and improves carrier diffusion along 2D-layers. The simulation permits evaluation of the PSF sizes of about 0.7 µm. The presented results allow improving 2D-crystal growth technology for novel sensor devices with separated excess charges.

Bismuth oxysulfide film electrodes with giant incident photon-to-current conversion efficiency: the dynamics of properties with deposition time.

It was demonstrated in our previous work that the photoelectrochemical (PEC) reduction processes occur with a giant incident photon-to-current conversion efficiency (IPCE ≫ 100%) at bismuth oxysulfide (BOS) semiconductor films in aqueous solutions containing acceptors of photoelectrons ([Fe(CN)6]3-). The anomalously high IPCE was related to the photoconductivity of the semiconductor. In this work, we analyze the dynamics of the chemical and phase composition of BOS films with variation of their deposition time, as well as the dependence of photocurrent on the film thickness and wavelength of the incident light. We demonstrate that in the case of illumination with a short-wavelength light (λ = 465 nm), the photocurrent is reduced down to a complete disappearance with an increase in the film thickness in the range of 0.3-1.3 µm, and for a fixed thickness of the bismuth oxysulfide film, the photocurrent decreases with the reduction of the wavelength indicating that photogeneration of the charge carriers over the entire thickness of the film is necessary for the giant IPCE effect. Using the light induced transient grating (LITG) method, the lifetime of the charge carriers (τ) was determined in the range of 25-80 ps depending on the film thickness, whereas the diffusion coefficient (D) does not exceed 1 cm2 s-1 meaning that the charge transport across the films is determined only by drift.

Diffusion Enhancement in Highly Excited MAPbI3 Perovskite Layers with Additives.

Carrier mobility is one of the crucial parameters determining the electronic device performance. We apply the light-induced transient grating technique to measure independently the carrier diffusion coefficient and lifetime, and to reveal the impact of additives on carrier transport properties in wet-cast CH3NH3PbI3 (MAPbI3) perovskite films. We use the high excitation regime, where diffusion length of carriers is controlled purely by carrier diffusion and not by the lifetime. We demonstrate a four-fold increase in diffusion coefficient due to the reduction of localization center density by additives; however, the density dependence analysis shows the dominance of localization-limited diffusion regime. The presented approach allows us to estimate the limits of technological improvement-carrier diffusion coefficient in wet-cast layers can be expected to be enhanced by up to one order of magnitude.