Phonon Bottleneck Research Articles

Temperature and excitation dependence of stimulated emission and spontaneous emission in InGaN epilayer**Project supported by the National Key Research Program of China (Grant No. 2016YFB0501604) and the National Natural Science Foundation of China (Grant Nos. 10874127 and 61227902).

Temperature and excitation dependent photoluminescence (PL) of InGaN epilayer grown on c-plane GaN/sapphire template by molecular beam epitaxy (MBE) has been systematically investigated. The emission spectra of the sample consisted of strong multiple peaks associated with one stimulated emission (SE) located at 430 nm and two spontaneous emissions (SPE) centered at about 450 nm and 480 nm, indicating the co-existence of shallow and deep localized states. The peak energy of SE exhibiting weak s-shaped variation with increasing temperature revealed the localization effect of excitons. Moreover, an abnormal increase of the SPE intensity with increasing temperature was also observed, which indicated that the carrier transfer between the shallow and deeper localized states exists. Temperature dependent time-resolved PL (TRPL) demonstrated the carrier transfer processes among the localized states. In addition, a slow thermalization of hot carriers was observed in InGaN film by using TRPL and transient differential reflectivity, which is attributed to the phonon bottleneck effect induced by indium aggregation.

Two‐Photon Photoemission Spectroscopy for Studying Energetics and Electron Dynamics at Semiconductor Interfaces

Time‐resolved two‐photon photoemission spectroscopy (tr‐2PPE) directly probes the kinetic energy and dynamics of photoemitted electrons. At the same time, the electronic structure and temporal occupation of surface‐near states can be accessed, which allows to unravel the fundamental processes governing electron dynamics and energetics in semiconductor surfaces. Here, recent studies on epitaxial III–V semiconductors and II–VI nanostructures are reviewed and the feasibility to study electron dynamics in III–V surface quantum wells (SQW) with tr‐2PPE is demonstrated. On InP(100), for example, surface states are filled by electrons relaxing from higher energetic bulk states. In the case of nanostructured materials, these effects play an even larger role due to the high surface to bulk ratio. For CdSe quantum dots, Auger recombination strongly competes with the exploitation of the quantum size dependent phonon bottleneck. The electron cooling dynamics in CdSe platelets are extremely fast and exhibit complete independence of Auger‐like processes. Finally, an InGaAs SQW/InP structure is shown to exhibit much longer lifetime of the quantum confined states. The SQW may act as a carrier accumulation layer for bulk electrons diffusing to the surface. Implications for future use in energy material systems for photovoltaic and photocatalytic applications are discussed.

Slow relaxation in a {Tb2Ba(α-fur)8}npolymer with Ln = Tb(iii) non-Kramers ions

We report the synthesis, crystal structure and magnetic properties of a new heteronuclear polymeric complex based on non-Kramers Tb ions and carboxylic α-fur = C4H3OCOO ligands: {[Tb2Ba(α-fur)8(H2O)4]·2H2O}n. The α-furoate ligands consolidate 1D zig-zag chains running along the c-axis, formed by Tb2 dimers separated by Ba ions. Ab initio calculations, in combination with the fit of experimental data, predict that the single-ion magnetic ground state is highly anisotropic () and consists of a quasi-doublet with a ΔTb/kB = 3.22 K gap, well separated from the next excited state, while the gap for the Tb2 dimer is Δ2Tb/kB = 2.58 K. Static magnetization and heat capacity measurements show that, magnetically, the system can be modeled as dimers of non-Kramers Tb ions, coupled by an antiferromagnetic intradimer interaction J'*/kB = -1.6 K. Dipolar interactions couple the Tb ions in the dimer with their first neighbour ions along the chain, with J''*/kB = -0.15 K, and with the surrounding ions out of the chain, with maximum J'''*/kB = -0.03 K. Ac susceptibility measurements in H = 0 performed down to 50 mK temperatures have enabled us to observe slow relaxation of magnetization, with an Orbach-like activation energy of U/kB = 1.1 K. It is assigned to the sluggish response of the 3D spin system due to a short-range ordering, possibly enhanced by the presence of disorder caused by defects in the polymeric chains. Under the application of a magnetic field, the system slowly relaxes by two distinct direct processes, strongly affected by a phonon bottleneck effect. We discuss the different relaxational phenomenology of the new complex in comparison with that of the isostructural {[Dy2Ba(α-fur)8(H2O)4]·2H2O}n, differing only in the Kramers nature of the ions, and the mononuclear {Ln(α-fur)3(H2O)3}n (Ln = Tb, Dy) complexes, previously reported.

Ultrafast lattice dynamics in lead selenide quantum dot

We monitored the femtosecond-laser-induced lattice dynamics in PbSe quantum dots by ultrafast electron diffraction. The electron-phonon coupling didn’t show phonon bottleneck. And lattice dilation exhibited unusual features. Heat transport to the substrate deviated significantly from Fourier’s Law.

On the absence of a phonon bottleneck in strongly confined CsPbBr3 perovskite nanocrystals.

In traditional solar cells, photogenerated energetic carriers (so-called hot carriers) rapidly relax to band edges via emission of phonons, prohibiting the extraction of their excess energy above the band gap. Quantum confined semiconductor nanocrystals, or quantum dots (QDs), were predicted to have long-lived hot carriers enabled by a phonon bottleneck, i.e., the large inter-level spacings in QDs should result in inefficient phonon emissions. Here we study the effect of quantum confinement on hot carrier/exciton lifetime in lead halide perovskite nanocrystals. We synthesized a series of strongly confined CsPbBr3 nanocrystals with edge lengths down to 2.6 nm, the smallest reported to date, and studied their hot exciton relaxation using ultrafast spectroscopy. We observed sub-ps hot exciton lifetimes in all the samples with edge lengths within 2.6-6.2 nm and thus the absence of a phonon bottleneck. Their well-resolved excitonic peaks allowed us to quantify hot carrier/exciton energy loss rates which increased with decreasing NC sizes. This behavior can be well reproduced by a nonadiabatic transition mechanism between excitonic states induced by coupling to surface ligands.

Phonon branch-resolved electron-phonon coupling and the multitemperature model

Electron-phonon $(e\text{\ensuremath{-}}p)$ interaction and transport are important for laser-matter interactions, hot-electron relaxation, and metal-nonmetal interfacial thermal transport. A widely used approach is the two-temperature model (TTM), where $e\text{\ensuremath{-}}p$ coupling is treated with a gray approach with a lumped coupling factor ${G}_{ep}$ and the assumption that all phonons are in local thermal equilibrium. However, in many applications, different phonon branches can be driven into strong nonequilibrium due to selective $e\text{\ensuremath{-}}p$ coupling, and a TTM analysis can lead to misleading or wrong results. Here, we extend the original TTM into a general multitemperature model (MTM), by using phonon branch-resolved $e\text{\ensuremath{-}}p$ coupling factors and assigning a separate temperature for each phonon branch. The steady-state thermal transport and transient hot electron relaxation processes in constant and pulse laser-irradiated single-layer graphene (SLG) are investigated using our MTM respectively. Results show that different phonon branches are in strong nonequilibrium, with the largest temperature rise being more than six times larger than the smallest one. A comparison with TTM reveals that under steady state, MTM predicts 50% and 80% higher temperature rises for electrons and phonons respectively, due to the ``hot phonon bottleneck'' effect. Further analysis shows that MTM will increase the predicted thermal conductivity of SLG by 67% and its hot electron relaxation time by 60 times. We expect that our MTM will prove advantageous over TTM and gain use among experimentalists and engineers to predict or explain a wide ranges of processes involving laser-matter interactions.

Low threshold and efficient multiple exciton generation in halide perovskite nanocrystals

Multiple exciton generation (MEG) or carrier multiplication, a process that spawns two or more electron–hole pairs from an absorbed high-energy photon (larger than two times bandgap energy Eg), is a promising way to augment the photocurrent and overcome the Shockley–Queisser limit. Conventional semiconductor nanocrystals, the forerunners, face severe challenges from fast hot-carrier cooling. Perovskite nanocrystals possess an intrinsic phonon bottleneck that prolongs slow hot-carrier cooling, transcending these limitations. Herein, we demonstrate enhanced MEG with 2.25Eg threshold and 75% slope efficiency in intermediate-confined colloidal formamidinium lead iodide nanocrystals, surpassing those in strongly confined lead sulfide or lead selenide incumbents. Efficient MEG occurs via inverse Auger process within 90 fs, afforded by the slow cooling of energetic hot carriers. These nanocrystals circumvent the conundrum over enhanced Coulombic coupling and reduced density of states in strongly confined nanocrystals. These insights may lead to the realization of next generation of solar cells and efficient optoelectronic devices.

Slow Magnetic Relaxation in Lanthanoid Crown Ether Complexes: Interplay of Raman and Anomalous Phonon Bottleneck Processes.

The combination of lanthanoid nitrates with 18-crown-6 (18-c-6) and tetrahalocatecholate (X4 Cat2- , X=Cl, Br) ligands has afforded two compound series [Ln(18-c-6)(X4 Cat)(NO3 )]⋅MeCN (X=Cl, 1-Ln; X=Br, 2-Ln; Ln=La, Ce, Nd, Gd, Tb, Dy). The 18-c-6 ligands occupy equatorial positions of a distorted sphenocorona geometry, whereas the charged ligands occupy the axial positions. The analogues of both series with Ln=Ce, Nd, Tb and Dy exhibit out-of-phase ac magnetic susceptibility signals in the presence of an applied magnetic field, indicative of slow magnetization relaxation. When diluted into a diamagnetic La host to reduce dipolar interactions, the Dy analogue exhibits slow relaxation up to 20 K in the absence of an applied dc field. Concerted magnetic measurements, EPR spectroscopy, and ab initio calculations have allowed elucidation of the mechanisms responsible for slow magnetic relaxation. A consistent approach has been applied to quantitatively model the relaxation data for different lanthanoid analogues, suggesting that the spin dynamics are governed by Raman processes at higher temperatures, transitioning to a dominant phonon bottleneck process as the temperature is decreased, with an observed T-6 rather than the usual T-2 dependence (T is temperature). This anomalous thermal dependence of the phonon bottleneck relaxation is consistent with anharmonic effects in the lattice dynamics, which was predicted by Van Vleck more than 70 years ago.

Elastic Softness of Hybrid Lead Halide Perovskites.

Much recent attention has been devoted towards unraveling the microscopic optoelectronic properties of hybrid organic-inorganic perovskites. Here we investigate by coherent inelastic neutron scattering spectroscopy and Brillouin light scattering, low frequency acoustic phonons in four different hybrid perovskite single crystals: MAPbBr_{3}, FAPbBr_{3}, MAPbI_{3}, and α-FAPbI_{3} (MA: methylammonium, FA: formamidinium). We report a complete set of elastic constants characterized by a very soft shear modulus C_{44}. Further, a tendency towards an incipient ferroelastic transition is observed in FAPbBr_{3}. We observe a systematic lower sound group velocity in the technologically important iodide-based compounds compared to the bromide-based ones. The findings suggest that low thermal conductivity and hot phonon bottleneck phenomena are expected to be enhanced by low elastic stiffness, particularly in the case of the ultrasoft α-FAPbI_{3}.

Effect of quantum confinement on lifetime of anharmonic decay of optical phonons in semiconductor nanostructures

The anharmonic decay of phonons underlies many important effects in semiconductors, e.g. hotspot formation, phonon bottleneck and thermal resistivity. In this article, we evaluate the effect of quantum confinement on the anharmonic decay transition probability in a cubic isotropic material. This article focuses on the anharmonic decay of longitudinal optical phonons, generated from hot electrons, are directly related to formation of hotspots in the active region of semiconductor devices. The confinement effect has been realized in double interface heterostructure quantum well (DHSQW) (e.g. AlAs/GaAs/AlAs) and free-standing quantum well (FSQW) (e.g. GaAs) structures as the confined phonon modes have different properties inside the structures. The longitudinal–optical phonon decay rate is reduced for the case of a DHSQW compared to bulk material and for a FSQW the decay rate has a strong dependence on wavevector value of the three phonons involved.

Generation of Coherent Optical Phonons in Methylammonium Lead Iodide Thin Films

A long-lived hot carrier in organic–inorganic hybrid perovskite materials is possibly assisted by the large polaron and hot phonon bottleneck. The phonon plays a significant role in the properties ...

Superatom Molecular Orbital as an Interfacial Charge Separation State.

Hot electron cooling by energy loss to heat through electron-phonon (e-ph) interaction is an important mechanism that can limit the efficiency of solar energy conversion. To avoid such energy loss, sufficient charge separation needs to be realized by extracting hot carriers from the photoconverter before they cool, which requires fast interfacial charge transfer and slow internal hot carrier relaxation. Using ab initio time-dependent nonadiabatic molecular dynamics and taking C60/MoS2 as a prototype system, we show that the superatom molecular orbitals (SAMOs) of fullerenes, which are bound by the central potential of the whole molecule induced by the charge screening, are ideal media for charge separation. The diffuse character of SAMOs results in extremely weak e-ph interaction and therefore acts as a "phonon bottleneck" for hot electron cooling. Furthermore, it also leads to significant hybridization with other atoms at the interface that induces fast charge transfer. The interfacial charge-transfer rate at the C60/MoS2 interface is found to be 2 orders of magnitude faster than the hot electron cooling from s-SAMO in C60. This conclusion is generally applicable for different carbon nanostructures that have SAMOs. The proposed SAMO-induced charge separation provides unique and essential insights into the material design and function for solar energy conversion.

Nonbolometric bottleneck in electron-phonon relaxation in ultrathin WSi films

We developed the model of the internal phonon bottleneck to describe the energy exchange between the acoustically soft ultrathin metal film and acoustically rigid substrate. Discriminating phonons in the film into two groups, escaping and nonescaping, we show that electrons and nonescaping phonons may form a unified subsystem, which is cooled down only due to interactions with escaping phonons, either due to direct phonon conversion or indirect sequential interaction with an electronic system. Using an amplitude-modulated absorption of the sub-THz radiation technique, we studied electron-phonon relaxation in ultrathin disordered films of tungsten silicide. We found an experimental proof of the internal phonon bottleneck. The experiment and simulation based on the proposed model agree well, resulting in tau_{e-ph} = 140-190 ps at T_C = 3.4 K, supporting the results of earlier measurements by independent techniques.

Effect of a Phonon Bottleneck on Exciton and Spin Generation in Self-Assembled In1−xGaxAs Quantum Dots

Semiconductor quantum dots (QDs) hold great potential for solid-state light-emitting devices and optical and spin-based quantum information processing, but the efficiency of QD-based spin LEDs remains limited, and their physics not fully understood. Using tunable laser spectroscopy, the authors discover that here an intrinsic obstacle to spin generation is $p\phantom{\rule{0}{0ex}}h\phantom{\rule{0}{0ex}}o\phantom{\rule{0}{0ex}}n\phantom{\rule{0}{0ex}}o\phantom{\rule{0}{0ex}}n$ $b\phantom{\rule{0}{0ex}}o\phantom{\rule{0}{0ex}}t\phantom{\rule{0}{0ex}}t\phantom{\rule{0}{0ex}}l\phantom{\rule{0}{0ex}}e\phantom{\rule{0}{0ex}}n\phantom{\rule{0}{0ex}}e\phantom{\rule{0}{0ex}}c\phantom{\rule{0}{0ex}}k$, a lack of phonon-mediated relaxation pathways that can arise in a zero-dimensional system. This insight provides design rules for energy-level engineering in spin-optoelectronic applications of QDs, yielding about a threefold increase in spin generation efficiency, even at elevated temperatures.

Observation of enhanced hot phonon bottleneck effect in 2D perovskites

We thoroughly investigated the carrier-phonon relaxation process in 2D halide perovskites with the general formula of (BA)2(MA)n-1PbnI3n+1, where n = 2, 3, and 4, by femtosecond transient absorption spectroscopy. A significant enhancement of the hot phonon bottleneck effect is observed in the natural multiple quantum well with n = 2 and 3. Specifically, the sample with n = 3 shows a 1000 ps hot carrier relaxation time to reach room temperature, which is 10 times longer compared with its three-dimensional counterpart. We believe that both the organic cation and quantum confinement effect are responsible for this phenomenon. The acoustic phonon cannot propagate due to the decrease in group velocity caused by the confinement effect in such a quantum well structure. In addition, the confined acoustic phonons can up-convert to optical phonons due to the presence of a “hybrid phonon” induced by the organic cation. This result suggests a promising way to obtain long-live hot carrier materials.

Electron overheating during field emission from carbon island films due to phonon bottleneck effect

Electron overheating during field emission from carbon island films due to phonon bottleneck effect

The Role of a Phonon Bottleneck in Relaxation Processes for Ln-Doped NaYF4 Nanocrystals

The localized inner 4f shell transitions of lanthanide ions are largely independent of the local surroundings. The luminescence properties of Ln3+ ions doped into nanocrystals (NCs) are therefore similar to those in bulk crystals. Quantum size effects, responsible for the unique size-dependent luminescence of semiconductor NCs, are generally assumed not to influence the optical properties of Ln3+-doped insulator NCs. However, phonon confinement effects have been reported to hamper relaxation between closely spaced Stark levels in Ln3+-doped NCs. At cryogenic temperatures emission and excitation from higher Stark levels was observed for Ln3+ ions in NCs only and were explained by a cutoff in the acoustic phonon spectrum. Relaxation would be inhibited as no resonant low energy (long wavelength) acoustic phonon modes can exist in nanometer sized crystals, and this prevents relaxation by direct phonon emission between closely spaced Stark levels. This phenomenon is known as a phonon bottleneck. Here, we investigate the role of phonon confinement in Ln-doped NCs. High resolution emission spectra at temperatures down to 2.2 K are reported for various Ln3+ ions (Er3+, Yb3+, Eu3+) doped into monodisperse 10 nm NaYF4 NCs and compared with spectra for bulk (microcrystalline) material. Contrary to previous reports, we find no evidence for phonon bottleneck effects in the emission spectra. Emission from closely spaced higher Stark levels is observed only at high excitation powers and is explained by laser heating. The present results indicate that previously reported effects in NCs may not be caused by phonon confinement.

Spin-orbit coupling and electric-dipole spin resonance in a nanowire double quantum dot

We study the electric-dipole transitions for a single electron in a double quantum dot located in a semiconductor nanowire. Enabled by spin-orbit coupling (SOC), electric-dipole spin resonance (EDSR) for such an electron can be generated via two mechanisms: the SOC-induced intradot pseudospin states mixing and the interdot spin-flipped tunneling. The EDSR frequency and strength are determined by these mechanisms together. For both mechanisms the electric-dipole transition rates are strongly dependent on the external magnetic field. Their competition can be revealed by increasing the magnetic field and/or the interdot distance for the double dot. To clarify whether the strong SOC significantly impact the electron state coherence, we also calculate relaxations from excited levels via phonon emission. We show that spin-flip relaxations can be effectively suppressed by the phonon bottleneck effect even at relatively low magnetic fields because of the very large g-factor of strong SOC materials such as InSb.

Ultrafast selective extraction of hot holes from cesium lead iodide perovskite films

Lead halide perovskites have some unique properties which are very promising for optoelectronic applications such as solar cells, LEDs and lasers. One important and expected application of perovskite halide semiconductors is solar cell operation including hot carriers. This advanced solar cell concept allows overcoming the Shockley–Queisser efficiency limit, thereby achieving energy conversion efficiency as high as 66% by extracting hot carriers. Understanding ultrafast photoexcited carrier dynamics and extraction in lead halide perovskites is crucial for these applications. Here, we clarify the hot carrier cooling and transfer dynamics in all-inorganic cesium lead iodide (CsPbI3) perovskite using transient absorption spectroscopy and Al2O3, poly(3-hexylthiophene-2,5-diyl) (P3HT) and TiO2 as selective contacts. We find that slow hot carrier cooling occurs on a timescale longer than 10 ps in the cases of CsPbI3/Al2O3 and CsPbI3/ TiO2, which is attributed to hot phonon bottleneck for the high photoexcited carrier density. An efficient ultrafast hole transfer from CsPbI3 to the P3HT hole extracting layer is observed. These results suggest that hot holes can be extracted by appropriate selective contacts before energy dissipation into the halide perovskite lattice and that CsPbI3 has a potential for hot carrier solar cell applications.

Slow Cooling of Hot Polarons in Halide Perovskite Solar Cells.

Halide perovskites show unusual thermalization kinetics for above-bandgap photoexcitation. We explain this as a consequence of excess energy being deposited into discrete large polaron states. The crossover between low-fluence and high-fluence “phonon bottleneck” cooling is due to a Mott transition where the polarons overlap (n ≥ 1018 cm–3) and the phonon subpopulations are shared. We calculate the initial rate of cooling (thermalization) from the scattering time in the Fröhlich polaron model to be 78 meV ps–1 for CH3NH3PbI3. This rapid initial thermalization involves heat transfer into optical phonon modes coupled by a polar dielectric interaction. Further cooling to equilibrium over hundreds of picoseconds is limited by the ultralow thermal conductivity of the perovskite lattice.