Nonradiative Recombination Channels Research Articles

Photostimulated control of luminescence quantum yield for colloidal Ag2S/2-MPA quantum dots.

In this paper, we present the results on photoinduced formation of colloidal Ag2S quantum dots with sizes of 1.5–3 nm passivated by 2-mercaptopropionic acid (Ag2S/2-MPA) in the presence of ethylene glycol. The synthetized colloidal Ag2S/2-MPA QDs have NIR recombination luminescence with its maximum near 800 nm. The control of absorption and luminescence properties of the QDs is achieved by photoactivation. It is shown that photoexposure of colloidal solution of Ag2S/2-MPA QDs leads to an increase in the QD size and monodispersity along side with the growth of the luminescence quantum yield from 1% to 7.9%. Enhancement of the luminescence quantum yield is accompanied by an increase in the average luminescence lifetime up to 190 ns, which is due to the blocking of the nonradiative recombination channel with the radiative recombination rate being (3–5.5) × 105 s−1. It is shown that the purification of the Ag2S/2-MPA solution by a dialysis membrane from regenerated cellulose leads to an increase in the sample monodispersity, as well as stops the photoinduced growth of QDs, and also reduces the degradation of their photoluminescence.

Enhanced excitonic emission efficiency in porous GaN

We investigate the optical properties of porous GaN films of different porosities, focusing on the behaviors of the excitonic features in time-integrated and time-resolved photoluminescence. A substantial enhancement of both excitonic emission intensity and recombination rate, along with insignificant intensity weakening under temperature rise, is observed in the porous GaN films. These observations are in line with (i) the local concentration of electric field at GaN nanoparticles and pores due to the depolarization effect, (ii) the efficient light extraction from the nanoparticles. Besides, the porosification enlarges the surface of the air/semiconductor interface, which further promotes the extraction efficiency and suppresses non-radiative recombination channels. Our findings open a way to increasing the emission efficiency of nanophotonic devices based on porous GaN.

Giant Light-Emission Enhancement in Lead Halide Perovskites by Surface Oxygen Passivation.

Surface condition plays an important role in the optical performance of semiconductor materials. As new types of semiconductors, the emerging metal-halide perovskites are promising for next-generation optoelectronic devices. We discover significantly improved light-emission efficiencies in lead halide perovskites due to surface oxygen passivation. The enhancement manifests close to 3 orders of magnitude as the perovskite dimensions decrease to the nanoscale, improving external quantum efficiencies from <0.02% to over 12%. Along with about a 4-fold increase in spontaneous carrier recombination lifetimes, we show that oxygen exposure enhances light emission by reducing the nonradiative recombination channel. Supported by X-ray surface characterization and theoretical modeling, we propose that excess lead atoms on the perovskite surface create deep-level trap states that can be passivated by oxygen adsorption.

Photoluminescence properties of ZnS:Mn single crystal effected by defect drift in electric and pulsed magnetic fields

Luminescence properties of ZnS:Mn single crystal are studied before and after drift of defects in electric field additionally influenced by pulsed magnetic field. It is detected that besides the change of luminescence center quantity the efficiency of channels of radiative and non-radiative recombination at the anode and cathode areas changes also due to the change of the Fermi energy position in these areas of the crystal. Simultaneous presence of two types of manganese ions in ZnS:Mn crystal possessing different local symmetry is found. These ions are sensitizers for different by nature emitting centers for self-activation (SA) and Mn-related photoluminescence. Selectivity in transfer of excitation to a particular emission center (SA or Mn) is defined by the efficiency of resonance excitation transfer.

Spectral Characteristics and Thermal Quenching of Luminescence in Rb0.993Pr0.007Pb2Br5 and Rb0.993Pr0.007Pb2Cl2.5Br2.5 Crystals

Crystals with the compositions Rb0.993Pr0.007Pb2Br5 and Rb0.993Pr0.007Pb2Cl2.5Br2.5 have been grown by the Bridgman method, and the absorption, luminescence excitation, and photoluminescence spectra of these materials in the case of the Stokes mechanism of optical excitation in the blue spectral region have been analyzed. The intensity of the visible luminescence bands of the Pr3+ praseodymium ions has been shown to depend on the nature of the nearest neighbor atoms in their crystalline environment. This effect is tentatively attributed to changes in the probability of radiative transitions in the rare-earth ion. The temperature dependences of emission intensity obtained for the crystals demonstrate that the contributions of nonradiative recombination channels depend on the transition, which also leads to changes in the emission color of the compounds.

Photoinduced Degradation of the Optical Properties of Colloidal Ag2S and CdS Quantum Dots Passivated by Thioglycolic Acid

The results of studying degradation of the optical properties of colloidal Ag2S and CdS quantum dots (QDs) 2.6–3.2 nm in size passivated by thioglycolic acid (TGA) are presented. The photoluminescence intensity of colloidal Ag2S QDs has been found to decrease under laser irradiation at a wavelength of 445 nm, beginning with the effective power of 10 mW. The observed effect is interpreted as a photochemical reaction of formation of new nonradiative-recombination channels in Ag2S QDs upon excitation. It is established for colloidal CdS QDs passivated by TGA that a decrease in the optical density in the entire absorption spectrum and the luminescence intensity is accompanied by precipitation of the colloidal particles in a cell and related to photodegradation of the passivating shell.

Composition-Dependent Energy Splitting between Bright and Dark Excitons in Lead Halide Perovskite Nanocrystals.

Perovskite semiconductor nanocrystals with different compositions have shown promise for applications in light-emitting devices. Dark excitonic states may suppress light emission from such nanocrystals by providing an additional nonradiative recombination channel. Here, we study the composition dependence of dark exciton dynamics in nanocrystals of lead halides by time-resolved photoluminescence spectroscopy at cryogenic temperatures. The presence of a spin-related dark state is revealed by magneto-optical spectroscopy. The energy splitting between bright and dark states is found to be highly sensitive to both halide elements and organic cations, which is explained by considering the effects of size confinement and charge screening, respectively, on the exchange interaction. These findings suggest the possibility of manipulating dark exciton dynamics in perovskite semiconductor nanocrystals by composition engineering, which will be instrumental in the design of highly efficient light-emitting devices.

Effect of ambient conditions on a violet emission band from ZnO nanorods

A photoluminescence study of ZnO nanorods prepared using a hydrothermal method was performed in air and vacuum ambient. It was found that UV illumination in vacuum gives rise to appearance of a violet emission band at ~ 405 nm (3.06 eV) and increase in the near band edge emission intensity. The violet emission vanishes after exposure to air, but restoring the PL spectrum's initial form requires a long time (> 44 h). The violet emission band is attributed to zinc vacancy defects formed from the hydrogen passivated VZn-H centers due to UV illumination in vacuum. The impact of the ambient conditions on the PL spectrum and intensity indicates that, it is likely, the UV illumination in vacuum also gives rise to desorption of surface oxygen and reducing the surface depletion width, which lead to blocking the non-radiative recombination channels.

Enhancing the Performance of CdSe/CdS Dot-in-Rod Light-Emitting Diodes via Surface Ligand Modification.

The surface ligands on colloidal nanocrystals (NCs) play an important role in the performance of NC-based optoelectronic devices such as photovoltaic cells, photodetectors, and light-emitting diodes (LEDs). On one hand, the NC emission depends critically on the passivation of the surface to minimize trap states that can provide nonradiative recombination channels. On the other hand, the electrical properties of NC films are dominated by the ligands that constitute the barriers for charge transport from one NC to its neighbor. Therefore, surface modifications via ligand exchange have been employed to improve the conductance of NC films. However, in LEDs, such surface modifications are more critical because of their possible detrimental effects on the emission properties. In this work, we study the role of surface ligand modifications on the optical and electrical properties of CdSe/CdS dot-in-rods (DiRs) in films and investigate their performance in all-solution-processed LEDs. The DiR films maintain high photoluminescence quantum yield, around 40-50%, and their electroluminescence in the LED preserves the excellent color purity of the photoluminescence. In the LEDs, the ligand exchange boosted the luminance, reaching a fourfold increase from 2200 cd/m2 for native surfactants to 8500 cd/m2 for the exchanged aminoethanethiol (AET) ligands. Moreover, the efficiency roll-off, operational stability, and shelf life are significantly improved, and the external quantum efficiency is modestly increased from 5.1 to 5.4%. We relate these improvements to the increased conductivity of the emissive layer and to the better charge balance of the electrically injected carriers. In this respect, we performed ultraviolet photoelectron spectroscopy (UPS) to obtain a deeper insight into the band alignment of the LED structure. The UPS data confirm similar flat-band offsets of the emitting layer to the electron- and hole-transport layers in the case of AET ligands, which translates to more symmetric barriers for charge injection of electrons and holes. Furthermore, the change in solubility of the NCs induced by the ligand exchange allows for a layer-by-layer deposition process of the DiR films, which yields excellent homogeneity and good thickness control and enables the fabrication of all the LED layers (except for cathode and anode) by spin-coating.

Optical properties of an ensemble of G-centers in silicon

We addressed the carrier dynamics in so-called G-centers in silicon (consisting of substitutional-interstitial carbon pairs interacting with interstitial silicons) obtained via ion implantation into a silicon-on-insulator wafer. For this point defect in silicon emitting in the telecommunication wavelength range, we unravel the recombination dynamics by time-resolved photoluminescence spectroscopy. More specifically, we performed detailed photoluminescence experiments as a function of excitation energy, incident power, irradiation fluence and temperature in order to study the impact of radiative and non-radiative recombination channels on the spectrum, yield and lifetime of G-centers. The sharp line emitting at 969 meV ($\sim$1280 nm) and the broad asymmetric sideband developing at lower energy share the same recombination dynamics as shown by time-resolved experiments performed selectively on each spectral component. This feature accounts for the common origin of the two emission bands which are unambiguously attributed to the zero-phonon line and to the corresponding phonon sideband. In the framework of the Huang-Rhys theory with non-perturbative calculations, we reach an estimation of 1.6$\pm$0.1 $\angstrom$ for the spatial extension of the electronic wave function in the G-center. The radiative recombination time measured at low temperature lies in the 6 ns-range. The estimation of both radiative and non-radiative recombination rates as a function of temperature further demonstrate a constant radiative lifetime. Finally, although G-centers are shallow levels in silicon, we find a value of the Debye-Waller factor comparable to deep levels in wide-bandgap materials. Our results point out the potential of G-centers as a solid-state light source to be integrated into opto-electronic devices within a common silicon platform.

Switchable dissociation of excitons bound at strained CdTe/CdS interfaces.

Charge carrier dynamics of semiconductor nano-heterostructures are determined by band alignment and lattice mismatch of the adjacent materials. However, quantum efficiencies for the separation of excited charge carriers at such an interface are hard to predict and cannot yet be easily controlled. In this work we examine nanorods with a severely strained, axial CdTe/CdS interface using femtosecond transient absorption spectroscopy. We show that charge separation is mitigated by equal contributions of valence band distortion and formation of coulomb pairs across the interface. Left undisturbed such localised excitons relax rapidly via non-radiative recombination channels. By adding a competitive hole acceptor that disrupts the coulomb interaction we overcome the synergetic co-localisation of the carriers and realise charge separation. The thus created long-lived state can be exploited for a broad range of applications such as photocatalysis, water splitting, and switchable nanodevices.

A comparative study of one-step and two-step approaches for MAPbI3 perovskite layer and its influence on the performance of mesoscopic perovskite solar cell

The mesoscopic perovskite solar cells (M-PSCs) were synthesized with MAPbI3 perovskite layers as light harvesters, which were grown with one-step and two-step solution process, respectively. A comparative study was performed through the quantitative correlation of resulting device performance and the crystalline quality of perovskite layers. Comparing with the one-step counterpart, a pronounced improvement in the steady-state power conversion efficiencies (PCEs) by 56.86% was achieved with two-step process, which was mainly resulted from the significant enhancement in fill factor (FF) from 48% to 77% without sacrificing the open circuit voltage (Voc) and short circuit current (Jsc). The enhanced FF was attributed to the reduced non-radiative recombination channels due to the better crystalline quality and larger grain size with the two-step processed perovskite layer. Moreover, the superiority of two-step over one-step process was demonstrated with rather good reproducibility.

Decay of electronic excitations in colloidal thioglycolic acid (TGA)-capped CdS/ZnS quantum dots

Investigations of dynamics of exciton relaxation in colloidal thioglycolic acid (TGA)-capped CdS/ZnS core/shell systems with diameter of 3.6 nm by means of femtosecond transient absorption spectroscopy, thermostimulated luminescence (TSL), and decay of luminescence are presented in this paper. It was found that the intensity of trap-state luminescence increases when one and two ZnS monolayers are formed. Also, the lifetime of trap-state luminescence increases. Two types of trap states with different depths were found, using thermostimulated luminescence technique. Localized states of the first type with depth of 0.085 eV do not change their concentration during sell formation. In contrast, trap state of the second type with depth of 0.125 eV are almost completely removed. It was found that the electron lifetime, investigated femtosecond transient absorption is not changed during formation of ZnS shell. It was concluded that localized states are channels of non-radiative recombination, direct quenching the center of trap-state luminescence. The absence of exciton luminescence is caused by rapid localization of holes at luminescence center.

Demonstration of omnidirectional photoluminescence (ODPL) spectroscopy for precise determination of internal quantum efficiency of radiation in GaN single crystals

For rating unambiguous performance of a light-emitting semiconductor material, determination of the absolute quantum efficiency (AQE) of radiation, which is basically a product of internal quantum efficiency (IQE) and light-extraction efficiency, is the most delightful way. Here, we propose the use of omnidirectional photoluminescence (ODPL) spectroscopy for quantifying AQE of the near-band-edge (NBE) emission, in order to evaluate bulk GaN crystals and wafers. When the measurement was carried out in the air, the AQE showed a continuous decrease most likely due to the formation of extrinsic nonradiative recombination channels at the surface by photo-pumping. However, such an influence was suppressed by measuring ODPL in an inert ambient such as nitrogen or in vacuum. Consequently, AQE was revealed to depend on the photo-pumping density. The increase in AQE of the NBE emission caused by the increase in the excess carrier concentration was significant, indicating gradual saturation of nonradiative recombination centers in the bulk of GaN. The highest AQE value (8.22%) ever reported for the NBE emission of GaN at room temperature, which corresponds to IQE of 70.9%, was eventually obtained from the GaN wafer grown by hydride vapor phase epitaxy on a GaN seed crystal manufactured by the acidic ammonothermal method, when the cw photo-pumping density was 66 W/cm2.

Optimization of post-deposition annealing in Cu2ZnSnS4 thin film solar cells and its impact on device performance

In this work we present an optimization of the post-deposition annealing, in Cu2ZnSnS4 (CZTS) thin film solar cells, applied at different stages of the solar cell preparation, namely, bare CZTS absorber, CZTS/CdS heterojunction and CZTS/CdS/i-ZnO/ITO complete solar cell. We performed current-density measurements, scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), Raman scattering, photoluminescence (PL) and X-ray photoelectron spectroscopy (XPS) studies to enlighten the mechanisms by which solar cells performance improvement comes about. As a result, we concluded that the optimum post-deposition annealing for CZTS is at 300°C for 15min and at atmospheric pressure. The highest efficiency gain was obtained when the absorber layer composition is close to the ideal one and when a single annealing step is performed on complete solar cells, where, we obtained efficiency improvements from below 1% to over 6.6%. Despite the observed improvement in device performance for annealing at intermediate stages it is, however, less pronounced than for full cell annealing. In this process we demonstrate very substantial cell performance improvements. XRD results show a shift of all Bragg peaks to lower diffraction angle values, after post-deposition annealing. Also, the intensity of the peaks decreases and their full width at half maximum increases. PL measurements show that, post-deposition annealing, leads to a clear reduction of the non-radiative recombination channels and that the electronic structure is dominated by fluctuating potentials. XPS measurements reveal an interdiffusion of Cu, Zn and possibly Cd across the interface between buffer and CZTS absorber layers as the source of the significant observed cell performance enhancement.

"Supertrap" at Work: Extremely Efficient Nonradiative Recombination Channels in MAPbI3 Perovskites Revealed by Luminescence Super-Resolution Imaging and Spectroscopy.

Organo-metal halide perovskites are some of the most promising materials for the new generation of low-cost photovoltaic and light-emitting devices. Their solution processability is a beneficial trait, although it leads to a spatial inhomogeneity of perovskite films with a variation of the trap state density at the nanoscale. Comprehending their properties using traditional spectroscopy therefore becomes difficult, calling for a combination with microscopy in order to see beyond the ensemble-averaged response. We studied photoluminescence (PL) blinking of micrometer-sized individual methylammonium lead iodide (MAPbI3) perovskite polycrystals, as well as monocrystalline microrods up to 10 μm long. We correlated their PL dynamics with structure employing scanning electron and optical super-resolution microscopy. Combining super-resolution localization imaging and super-resolution optical fluctuation imaging (SOFI), we could detect and quantify preferential emitting regions in polycrystals exhibiting different types of blinking. We propose that blinking in MAPbI3 occurs by the activation/passivation of a "supertrap" which presumably is a donor-acceptor pair able to trap both electrons and holes. As such, nonradiative recombination via supertraps, in spite being present at a rather low concentrations (1012-1015 cm-3), is much more efficient than via all other defect states present in the material at higher concentrations (1016-1018 cm-3). We speculate that activation/deactivation of a supertrap occurs by its temporary dissociation into free donor and acceptor impurities. We found that supertraps are most efficient in structurally homogeneous and large MAPbI3 crystals where carrier diffusion is efficient, which may therefore pose limitations on the efficiency of perovskite-based devices.

Temperature and excitation power dependence of photoluminescence of ZnO nanorods synthesized by pattern assisted hydrothermal method

Abstract Pattern assisted ZnO nanorods (NRs) growth are performed using electron beam lithography (EBL) and hydrothermal method. The patterns of lines, circles and squares are prepared on polycrystalline ZnO seed layer using PMMA as photoresist. It is found that the ZnO NRs can only grow on the area with ZnO seed layer, not on the PMMA surface. The TEM results show that the ZnO NRs have single crystal structures with good orientation along the c-axis. The excitation power dependence of photoluminescence (PL) spectra of ZnO NRs shows that with excitation power increasing, the near band edge emission increases rapidly than the defects related visible emissions. The temperature dependence of PL spectra was measured in the temperature range of 13–300 K. The dependence of peak position and peak energy of exciton bound (D0X) emission of ZnO NRs on temperature were analyzed. Two non-radiative recombination channels for the D0X emission are discussed in detail.

Role of oxygen vacancies on light emission mechanisms in SrTiO3 induced by high-energy particles

Light emission under MeV hydrogen and oxygen ions in stoichiometric SrTiO3 are identified at temperatures of 100 K, 170 K and room-temperature. MeV ions predominately deposit their energies to electrons in SrTiO3 with energy densities orders of magnitude higher than from UV or x-ray sources but comparable to femtosecond lasers. The ionoluminescence (IL) spectra can be resolved into three main Gaussian bands at 2.0 eV, 2.5 eV and 2.8 eV, whose relative contributions strongly depend on irradiation temperature, electronic energy loss and irradiation fluence. Two main bands, observed at 2.5 eV and 2.8 eV, are intrinsic and associated with electron–hole recombination in the perfect SrTiO3 lattice. The 2.8 eV band is attributed to recombination of free (conduction) electrons with an in-gap level, possibly related to self-trapped holes. Self-trapped excitons (STEs) are considered suitable candidates for the 2.5 eV emission band, which implies a large energy relaxation in comparison to the intrinsic edge transition. The dynamics of electronic excitation, governs a rapid initial rise of the intensity; whereas, accumulated irradiation damage (competing non-radiative recombination channels) accounts for a subsequent intensity decrease. The previously invoked role of isolated oxygen vacancies for the blue luminescence (2.8 eV) does not appear consistent with the data. An increasing well-resolved band at 2.0 eV dominates at 170 K and below. It has been only previously observed in heavily strained and amorphous SrTiO3, and is, here, attributed to transitions from d(t2g) conduction band levels to d(eg) levels below the gap. In accordance with ab initio theoretical calculations they are associated to trapped electron states in relaxed Ti3+ centers at an oxygen vacancy within distorted TiO6 octahedra. The mechanism of defect evolution monitored during real-time IL experiments is presented. In conclusion, the light emission data confirm that IL is a useful tool to investigate lattice disorder in irradiated SrTiO3.

Temperature dependence of luminescence intensity in ZnMoO4 crystals

Luminescence of ZnMoO4 crystals (of stoichiometric composition, with excess of molybdenum and doped with tungsten) under X-ray irradiation in the temperature interval from 4 to 400 K was studied. The difference in the composition has little influence on the luminescence properties of the samples. An increase of the 1.93eV emission band intensity was observed in the temperature interval from 8K to 90K. Two mechanisms, concurrence with excitonic emission and concurrence with non-radiative recombination channel, were considered to explain the observation. Theoretical formulas were obtained to describe the temperature dependence of luminescence intensity. The experimental data are well described by the developed theoretical model which assumes recombination of free charge carriers with carriers of opposite sign localized on shallow traps. The high temperature quenching of luminescence is well described by the Mott formula.

Enhancement of 1.5 μm emission under 980 nm resonant excitation in Er and Yb co-doped GaN epilayers

The Erbium (Er) doped GaN is a promising gain medium for optical amplifiers and solid-state high energy lasers due to its high thermal conductivity, wide bandgap, mechanical hardness, and ability to emit in the highly useful 1.5 μm window. Finding the mechanisms to enhance the optical absorption efficiency at a resonant pump wavelength and emission efficiency at 1.5 μm is highly desirable. We report here the in-situ synthesis of the Er and Yb co-doped GaN epilayers (Er + Yb:GaN) by metal-organic chemical vapor deposition (MOCVD). It was observed that the 1.5 μm emission intensity of the Er doped GaN (Er:GaN) under 980 nm resonant pump can be boosted by a factor of 7 by co-doping the sample with Yb. The temperature dependent PL emission at 1.5 μm in the Er + Yb:GaN epilayers under an above bandgap excitation revealed a small thermal quenching of 12% from 10 to 300 K. From these results, it can be inferred that the process of energy transfer from Yb3+ to Er3+ ions is highly efficient, and non-radiative recombination channels are limited in the Er + Yb:GaN epilayers synthesized in-situ by MOCVD. Our results point to an effective way to improve the emission efficiency of the Er doped GaN for optical amplification and lasing applications.