Picosecond photoluminescence measurements of hot carrier relaxation and auger recombination in GaSb

We have measured hot carrier relaxation and recombination of photoexcited carriers in GaSb using picosecond time-resolved photoluminescence. We find that these processes are greatly modified compared to other III–V materials by the conduction band structure which permits a large electron population at the L-minima. Rapid carrier cooling observed at early times is explained by efficient relaxation of electrons within the L-valleys. For carrier densities 10¹⁹cm⁻³ we find that the dominant recombination process at low temperatures (4K) is radiative, but at hihg temperatures Auger recombination becomes dominant. This is manifest in a dramatic reduction of luminescence intensity, faster recombination and very slow energy relaxation.     

Two Distinct Origins of Highly Localized Luminescent Centers within InGaN/GaN Quantum‐Well Light‐Emitting Diodes

The high light‐output efficiencies of In_xGa_1‐xN quantum‐well (QW)‐based light‐emitting diodes (LEDs) even in presence of a large number of nonradiative recombination centers (such as dislocations) has been explained by localization of carriers in radiative potential traps, the origins of which still remain unclear. To provide insights on the highly efficient radiative traps, spectrally resolved photoluminescence (PL) microscopy has been performed on green‐light‐emitting In_0.22Ga_0.78N QW LEDs, by selectively generating carriers in the alloy layers. PL imaging shows the presence of numerous inhomogeneously distributed low‐band‐gap traps with diverse radiative intensities. PL spectroscopy of a statistically relevant number of individual traps reveals a clear bimodal distribution in terms of both band‐gap energies and radiative recombination efficiencies, indicating the presence of two distinct classes of carrier localization centers within the same QW sample. Disparity in their relative surface coverage and photoemission “blinking” characteristics suggests that the deep traps originate from local compositional fluctuations of indium within the alloy, while the shallow traps arise from nanometer‐scale thickness variations of the active layers. This is further supported by Poisson–Schrödinger self‐consistent calculations and implies that radiative traps formed due to both local indium content and interface‐morphology‐related heterogeneities can coexist within the same QW sample.     

Intraband Cooling in All‐Inorganic and Hybrid Organic–Inorganic Perovskite Nanocrystals

Intraband relaxation in all‐inorganic cesium lead tribromide (CsPbBr₃) and hybrid organic–inorganic formamidinium lead tribromide (FAPbBr₃) nanocrystals is experimentally investigated for a range of particle sizes, excitation energies, sample temperatures, and excitation fluences. Hot carriers in CsPbBr₃ nanocrystals consistently exhibit slower cooling than FAPbBr₃ nanocrystals in the single electron–hole pair per nanocrystal regime. In both compositions, long‐lived hot carriers (>3 ps) are only observed at excitation densities corresponding to production of multiple electron–hole pairs per nanocrystal—and concomitant Auger recombination. These presented results are distinct from previous reports in bulk hybrid perovskite materials that convey persistent hot carriers at low excitation fluences. Time‐resolved photoluminescence confirms the rapid cooling of carriers in the low‐fluence (single electron–hole pair per nanocrystal) regime. Intraband relaxation processes, as a function of excitation energy, size, and temperature are broadly consistent with other nanocrystalline semiconductor materials.     

Hot carrier recombination radiation in GaAs diode

In order to analyze hot carrier effects on the recombination spectra, the electroluminescence from p⁺-n diode and the photoluminescence from n-GaAs under an electric field were measured at 77 K. A high carrier temperature up to 150 K was obtained under the forward bias current of 5200 A/cm². The experimentally determined distribution function from the radiative recombination spectrum was quantitatively interpreted with a Monte Carlo simulation, taking account of the dominant inelastic scattering with LO phonon and electron-electron interaction.     

Specific features of the spectra and relaxation kinetics of long-wavelength photoconductivity in narrow-gap HgCdTe epitaxial films and heterostructures with quantum wells

The spectra and relaxation kinetics of interband photoconductivity are investigated in narrow-gap Hg_{1 ? x} Cd _x Te epitaxial films with x = 0.19–0.23 and in structures with HgCdTe-based quantum wells (QWs), having an interband-transition energy in the range of 30–90 meV, grown by molecular-beam epitaxy on GaAs (013) substrates. A long-wavelength sensitivity band caused by impurities or defects is found in the spectra of the structures with quantum wells in addition to the interband photoconductivity. It is shown that the lifetimes of nonequilibrium carriers in the structures with QWs is less than in bulk samples at the same optical-transition energy. From the measured carrier lifetimes, the ampere-watt responsivity and the equivalent noise power for a film with x = 0.19 at a wavelength of 19 μm are estimated. When investigating the relaxation kinetics of the photoconductivity at 4.2 K in high excitation regime, it is revealed that radiative recombination is dominant over other mechanisms of nonequilibrium-carrier recombination.     

Quasi‐2D Inorganic CsPbBr3 Perovskite for Efficient and Stable Light‐Emitting Diodes

Metal halide perovskites are rising as a competitive material for next‐generation light‐emitting diodes (LEDs). However, the development of perovskite LEDs is impeded by their fast carriers diffusion and poor stability in bias condition. Herein, quasi‐2D CsPbBr₃ quantum wells homogeneously surrounded by inorganic crystalline Cs₄PbBr₆ of large bandgap are grown. The centralization of carriers in nanoregion facilitates radiative recombination and brings much enhanced luminescence quantum yield. The external quantum efficiency and luminescence intensity of the LEDs based on this nanocomposite are one order of magnitude higher than the conventional low‐dimensional perovskite. Meanwhile, the use of inorganic nanocomposite materials brings much improved device operation lifetime under constant electrical field.     

Excitonic photoluminescence of silicon quantum-well structures

The exciton binding energy and the energies of radiative excitonic transitions in the separate SiO_x-Si-SiO_x quantum wells are calculated in the effective-mass approximation with the quadratic dispersion relation. Along with the real finite offsets of the bands in such quantum well structures, the effect of dielectric enhancement of the exciton binding energy due polarization of the heterointerfaces is taken into account. In addition, the dependence of the zero-phonon radiative excitonic recombination time on the width of the SiO_x-Si-SiO_x quantum well is calculated. This dependence exhibits unsteady (oscillating) behavior, which is caused by the indirect band gap of the silicon material. It is shown that the theoretically calculated energies of the radiative excitonic transitions in the SiO₂-Si-SiO₂ quantum wells match the experimentally determined energies for the quantum wells whose widths are larger than 1.5 nm. Good agreement between the theoretically calculated and experimental spectral dependences of photoluminescence in the SiO₂-Si-SiO₂ quantum wells is attained.     

Near‐Infrared Photoresponse of One‐Sided Abrupt MAPbI3/TiO2 Heterojunction through a Tunneling Process

Trap states in semiconductors usually degrade charge separation and collection in photovoltaics due to trap‐mediated nonradiative recombination. Here, it is found that perovskite can be heavily doped in low concentration with non‐ignorable broadband infrared absorption in thick films and their trap states accumulate electrons through infrared excitation and hot carrier cooling. A hybrid one‐sided abrupt perovskite/TiO₂ p‐N heterojunction is demonstrated that enables partial collection of these trap‐filled charges through a tunneling process instead of detrimental recombination. The tunneling is from broadband trap states in the wide depleted p‐type perovskite, across the barrier of the narrow depleted TiO₂ region (<5 nm), to the N‐type TiO₂ electrode. The trap states inject carriers into TiO₂ through tunneling and produce around‐unity peak external quantum efficiency, giving rise to near‐infrared photovoltaics. The near‐infrared response allows photodetecting devices to work in both diode and conductor modes. This work opens a new avenue to explore the near‐infrared application of hybrid perovskites.     

Particle conservation in the hot‐carrier solar cell

In conventional p–n junction solar cells, carrier multiplication by impact ionisation, is negligible, owing to the low temperature of the electron–hole pairs. This leads to particle conservation between the net number of absorbed photons and the number of electron–hole pairs withdrawn from the cell. In hot‐carrier solar cells, in which electrons are at a high temperature by assuming suppression of electron–phonon scattering, such particle conservation leads to peculiar results. Numerical calculations show that entire current–voltage characteristics with meaningful values of temperature and chemical potential do not exist. If the energy at which electron–hole pairs are extracted is smaller than the average energy of absorbed photons, the temperature of the electrons and holes becomes much larger than the tem perature of the sun. When the extraction energy is larger than the average energy of the absorbed photons, an entire current–voltage curve cannot always be obtained. It follows that impact ionisation and Auger recombination cannot be neglected when the thermal energy of the electron–hole pairs is comparable to the bandgap of the absorber. Accounting for these processes results in current–voltage characteristics that are well behaved. Copyright © 2005 John Wiley & Sons, Ltd.     

Lateral‐Polarity Structure of AlGaN Quantum Wells: A Promising Approach to Enhancing the Ultraviolet Luminescence

Aluminum‐gallium‐nitride alloys (Al _x Ga_{1– x} N, 0 ≤ x ≤ 1) can emit light covering the ultraviolet spectrum from 210 to 360 nm. However, these emitters have not fulfilled their full promise to replace the toxic and fragile mercury UV lamps due to their low efficiencies. This study demonstrates a promising approach to enhancing the luminescence efficiency of AlGaN multiple quantum wells (MQWs) via the introduction of a lateral‐polarity structure (LPS) comprising both III and N‐polar domains. The enhanced luminescence in LPS is attributed to the surface roughening, and compositional inhomogeneities in the N‐polar domain. The space‐resolved internal quantum efficiency (IQE) mapping shows a higher relative IQE in N‐polar domains and near inversion domain boundaries, providing strong evidence of enhanced radiative recombination efficiency in the LPS. These experimental observations are in good agreement with the theoretical calculations, where both lateral and vertical band diagrams are investigated. This work suggests that the introduction of the LPS in AlGaN‐based MQWs can provide unprecedented tunability in achieving higher luminescence performance in the development of solid state light sources.     

A probabilistic approach to determine radiative recombination carrier lifetimes in quantum well solar cells

In this paper the author places forth a new approach to determine the radiative recombination lifetimes of photo-generated carriers in quantum well solar cells. The calculations are performed for a hypothetical Al_xGa_1−xAs/GaAs quantum well solar cell. A similar device for which existing data is available is used for comparison. The foundation of the approach is the use of the original equations proposed by Shockley et al. using the assumption that photo-carrier generation is probabilistically controlled, a new approach to photo-carrier generation is derived and determination of the carrier lifetimes is possible. The results obtained for the AlGaAs/GaAs cell fall within accuracy of the existing experimental data.     

Energy Landscape of Vertically Anisotropic Polymer Blend Films toward Highly Efficient Polymer Light‐Emitting Diodes (PLEDs)

A blend of two hole‐dominant polymers is created and used as the light emissive layer in light‐emitting diodes to achieve high luminous efficiency up to 22 cd A^?1. The polymer blend F8_1?xSY_x is based on poly(9,9‐dioctylfluorene) (F8) and poly(para‐phenylene vinylene) derivative superyellow (SY). The blend system exhibits a preferential vertical concentration distribution. The resulting energy landscape modifies the overall charge transport behavior of the blend emissive layer. The large difference between the highest unoccupied molecular orbital levels of F8 (5.8 eV) and SY (5.3 eV) introduces hole traps at SY sites within the F8 polymer matrix. This slows down the hole mobility and facilitates a balance between the transport behavior of both the charge carriers. The balance due to such energy landscape facilitates efficient formation of excitons within the emission zone well away from the cathode and minimizes the surface quenching effects. By bringing the light‐emission zone in the middle of the F8_1?xSY_x film, the bulk of the film is exploited for the light emission. Due to the charge trapping nature of SY molecules in F8 matrix and pushing the emission zone in the center, the radiative recombination rate also increases, resulting in excellent device performance.     

Interplay between the hot phonon effect and intervalley scattering on the cooling rate of hot carriers in GaAs and InP

The influence of hot phonon effect and intervalley scattering on the hot carrier cooling rate was investigated using femtosecond time‐resolved photoluminescence spectroscopy in bulk GaAs and InP, two electronically similar but vibrationally distinct semiconductors. In both materials, a broad photoluminescence signal that extends from the band gap energy to values larger than the pump pulse energy was observed during the first few picoseconds after photoexcitation, for different excitation energies (1.7, 1.88, and 2.4 eV) at high carrier densities (>10¹⁹ cm⁻³). Different hot carrier relaxation times were observed in GaAs and InP for different excitation energies, demonstrating the influence of intervalley scattering phenomena in GaAs. When electrons were not energetic enough to access satellite valleys, longer decay transients were observed for InP compared with GaAs. This provides experimental evidence of the hot phonon effect in InP. Temperature transients were calculated by analyzing the topography of the two‐dimensional spectra. Copyright © 2011 John Wiley & Sons, Ltd.     

Visible photoluminescence of selectively etched porous <Emphasis Type="Italic">nc</Emphasis>-Si-Sio<Subscript>x</Subscript> structures

The results of the first studies of the effect of selective etching on photoluminescence in porous nc- Si–SiO_x structures containing Si nanoclusters (nc-Si) in the SiO_x matrix are reported. In the initial samples at room temperature, intense photoluminescence bands are observed with peaks at 840 and 660 nm corresponding to radiative recombination of free charge carriers (or charge carriers bound to excitons) excited in nc- Si. After selective etching of the nc- Si–SiO_x structures in 1% HF solution, these bands are noticeably shifted to higher energies of the spectrum. It is suggested that the evolution of the spectra is due to the decrease in the Si nanoparticle dimensions on etching of the oxide and additional oxidation of nc- Si. The results show that selective etching of the oxide matrix can be used to control the radiation spectra of porous nc- Si–SiO_x structures.     

Inelastic scattering of hot electrons by neutral donors in heavily silicon-doped GaAs/AlAs quantum wells

The energy and momentum relaxation of hot electrons in n-type GaAs/AlAs quantum wells is studied. Hot photoluminescence due to the recombination of hot electrons with holes bound on Si acceptors is observed in structures with a high level of doping with silicon. Using the method of magnetic depolarization of hot photoluminescence, the probability of scattering of hot electrons is found to decrease substantially with increasing temperature in the range 4–80 K. This effect is shown to be due to the ionization of donors. It is established that the probability of inelastic scattering by neutral donors is several times greater than the probability of quasielastic electron-electron scattering. Fiz. Tekh. Poluprovodn. 33, 1235–1239 (October 1999)     

Temperature‐Dependent Charge‐Carrier Dynamics in CH3NH3PbI3 Perovskite Thin Films

The photoluminescence, transmittance, charge‐carrier recombination dynamics, mobility, and diffusion length of CH₃NH₃PbI₃ are investigated in the temperature range from 8 to 370 K. Profound changes in the optoelectronic properties of this prototypical photovoltaic material are observed across the two structural phase transitions occurring at 160 and 310 K. Drude‐like terahertz photoconductivity spectra at all temperatures above 80 K suggest that charge localization effects are absent in this range. The monomolecular charge‐carrier recombination rate generally increases with rising temperature, indicating a mechanism dominated by ionized impurity mediated recombination. Deduced activation energies E_a associated with ionization are found to increase markedly from the room‐temperature tetragonal (E_a ≈ 20 meV) to the higher‐temperature cubic (E_a ≈ 200 meV) phase adopted above 310 K. Conversely, the bimolecular rate constant decreases with rising temperature as charge‐carrier mobility declines, while the Auger rate constant is highly phase specific, suggesting a strong dependence on electronic band structure. The charge‐carrier diffusion length gradually decreases with rising temperature from about 3 μm at ?93 °C to 1.2 μm at 67 °C but remains well above the optical absorption depth in the visible spectrum. These results demonstrate that there are no fundamental obstacles to the operation of cells based on CH₃NH₃PbI₃ under typical field conditions.     

Plasmonic Au/TiO2‐Dumbbell‐On‐Film Nanocavities for High‐Efficiency Hot‐Carrier Generation and Extraction

Plasmon‐induced hot carriers have vast potential for light‐triggered high‐efficiency carrier generation and extraction, which can overcome the optical band gap limit of conventional semiconductor‐based optoelectronic devices. Here, it is demonstrated that Au/TiO₂ dumbbell nanostructures assembled on a thin Au film serve as an efficient optical absorber and a hot‐carrier generator in the visible region. Upon excitation of localized surface plasmons in such coupled particle‐on‐film nanocavities, the energetic conduction electrons in Au can be injected over the Au/TiO₂ Schottky barrier and migrated to TiO₂, participating in the chemical reaction occurring at the TiO₂ surface. Compared with the same dumbbell nanostructures on an indium tin oxide (ITO) film, such nanocavities exhibit remarkable enhancement in both photocurrent amplitude and reaction rate that arise from increased light absorption and near‐field amplification in the presence of the Au film. The incident‐wavelength‐dependent photocurrent and reaction rate measurements jointly reveal that Au‐film‐mediated near‐field localization facilitates more efficient electron–hole separation and transport in the dumbbells and also promotes strong d‐band optical transitions in the Au film for generation of extra hot electrons. Such nanocavities provide a new plasmonic platform for effective photoexcitation and extraction of hot carriers and also better understanding of their fundamental science and technological implications in solar energy harvesting.     

Low Roll‐Off Perovskite Quantum Dot Light‐Emitting Diodes Achieved by Augmenting Hole Mobility

The external quantum efficiencies (EQEs) of perovskite quantum dot light‐emitting diodes (QD‐LEDs) are close to the out‐coupling efficiency limitation. However, these high‐performance QD‐LEDs still suffer from a serious issue of efficiency roll‐off at high current density. More injected carriers produce photons less efficiently, strongly suggesting the variation of ratio between radiative and non‐radiative recombination. An approach is proposed to balance the carrier distribution and achieve high EQE at high current density. The average interdot distance between QDs is reduced and this facilitates carrier transport in QD films and thus electrons and holes have a balanced distribution in QD layers. Such encouraging results augment the proportion of radiative recombination, make devices with peak EQE of 12.7%, and present a great device performance at high current density with an EQE roll‐off of 11% at 500 mA cm^?2 (the lowest roll‐off known so far) where the EQE is still over 11%.     

Interplay of Structural and Optoelectronic Properties in Formamidinium Mixed Tin–Lead Triiodide Perovskites

Mixed lead–tin triiodide perovskites are promising absorber materials for low bandgap bottom cells in all‐perovskite tandem photovoltaic devices. Key structural and electronic properties of the FAPb_1−xSn_xI₃ perovskite are presented here as a function of lead:tin content across the alloy series. Temperature‐dependent photoluminescence and optical absorption measurements are used to identify changes in the bandgap and phase transition temperature. The large bandgap bowing parameter, a crucial element for the attainment of low bandgaps in this system, is shown to depend on the structural phase, reaching a value of 0.84 eV in the low‐temperature phase and 0.73 eV at room temperature. The parabolic nature of the bowing at all temperatures is compatible with a mechanism arising from bond bending to accommodate the random placement of unevenly sized lead and tin ions. Charge‐carrier recombination dynamics are shown to fall into two regimes. Tin‐rich compositions exhibit fast, monoexponential recombination that is almost temperature‐independent, in accordance with high levels of electrical doping. Lead‐rich compositions show slower, stretched‐exponential charge‐carrier recombination that is strongly temperature‐dependent, in accordance with a multiphonon assisted process. These results highlight the importance of structure and composition for control of bandgap bowing and charge‐carrier recombination mechanisms in low bandgap absorbers for all‐perovskite tandem solar cells.     

Over 30% External Quantum Efficiency Light‐Emitting Diodes by Engineering Quantum Dot‐Assisted Energy Level Match for Hole Transport Layer

In the study of hybrid quantum dot light‐emitting diodes (QLEDs), even for state‐of‐the‐art achievement, there still exists a long‐standing charge balance problem, i.e., sufficient electron injection versus inefficient hole injection due to the large valence band offset of quantum dots (QDs) with respect to the adjacent carrier transport layer. Here the dedicated design and synthesis of high luminescence Zn_1?x Cd_xSe/ZnSe/ZnS QDs is reported by precisely controlled shell growth, which have matched energy level with the adjacent hole transport layer in QLEDs. As emitters, such Zn_1?xCd_xSe‐ based QLEDs exhibit peak external quantum efficiencies (EQE) of up to 30.9%, maximum brightness of over 334 000 cd m^?2, very low efficiency roll‐off at high current density (EQE ≈25% @ current density of 150 mA cm^?2), and operational lifetime extended to ≈1 800 000 h at 100 cd m^?2. These extraordinary performances make this work the best among all solution‐processed QLEDs reported in literature so far by achieving simultaneously high luminescence and balanced charge injection. These major advances are attributed to the combination of an intermediate ZnSe layer with an ultrathin ZnS outer layer as the shell materials and surface modification with 2‐ethylhexane‐1‐thiol, which can dramatically improve hole injection efficiency and thus lead to more balanced charge injection.