Carrier-lattice Interaction Research Articles

Lattice Manipulation with Di-Tertiary Ammonium Spacer in Bismuth Bromide Perovskite Directs Efficient Charge Transport and Suppressed Ion Migration for Photodetector Applications.

Bismuth halide hybrid perovskites have emerged as promising alternatives to their lead halide homologs because of high chemical stability, low toxicity, and structural diversity. However, their advancements in optoelectronic field are plagued with poor charge transport, due to considerable microstrain triggered by bulky spacer. Herein, the di-tertiary ammonium spacer (N,N,N',N'-tetramethyl-1,4-butanediammonium, TMBD) is explored to direct stable 1D bismuth bromide lattice structure with relaxed microstrain. Compared to the primary pentamethylenediamine (PD)2+, the (TMBD)2+ adopting alternating alignment enables a unique H-bonds mode to distort the configuration of inorganic layers to form corner-sharing [BiBr5] near-regular chains with narrower bandgap, lower exciton binding energy, and reduced carrier-lattice interactions, thereby facilitating charge-carrier transport. Moreover, the (TMBD)2+ spacers largely suppress ion migration in perovskite lattice, as substantiated by the experimental and theoretical investigations. Consequently, (TMBD)BiBr5 single crystal photodetector delivers a 185-fold increase in current on/off ratio with respect to (PD)BiBr5 under white light irradiation, considerable responsivity (≈82.97mA W-1), detectivity (≈8.06 ×1011 Jones) under weak light (0.02mW cm-2) irradiation, in the top rank of the reported hybrid bismuth halide perovskites. This finding offers novel design criterion for high-performance lead-free perovskites.

Exploring the lead-free halide Cs2MGaBr6 (M = Li, Na) double perovskites for sustainable energy applications

In recent years, there has been a growing emphasis on the exploration of sustainable and eco-friendly materials well-suited for advanced applications in the realms of thermoelectrics and optoelectronics. Lead-free halide double perovskites have emerged as a compelling class of materials in this context. Nevertheless, despite their potential utility, thorough investigations into their thermal transport characteristics remain limited. In this systematic investigation, we employ density functional theory (DFT) and post-DFT techniques to elucidate the essential stability parameters, transport properties, and carrier-lattice interactions of the metal halide-based Cs2MGaBr6 (X = Li, Ga) double perovskites. Our assessment of structural stability involves a meticulous description of stability index parameters and the optimization of pristine structures using the GGA-PBE potential. Additionally, we calibrate the electronic structure while taking spin–orbit coupling (SOC) effects into consideration by using a combination of GGA and GGA + mBJ potentials. Our findings reveal that the TB-mBJ derived band gaps of 1.82 eV and 1.78 eV for Cs2LiGaBr6 and Cs2NaGaBr6 reside within the visible spectrum, prompting further investigation into their thermal transport characteristics. Moreover, we analyze the phonon characteristics and vibrational modes, extending our investigation to examine the electron–phonon coupling strength. The scrutiny of the Fröhlich coupling constant and the Feynman polaron radius unveils a stronger electron–phonon coupling strength. In the domain of thermoelectrics, the significant figure of merit (zT) values of 1.08 and 1.04 for Cs2LiGaBr6 and Cs2NaGaBr6, respectively, emphasize the considerable potential of these materials for deployment in renewable energy applications. Furthermore, our computational investigation into optical properties, including the dielectric constant, optical absorption, and refractive index, demonstrates optimal performance within the visible spectrum. Specifically, elevated absorption coefficient values of 30×10\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$30\ imes 10$$\\end{document}4cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\ ext{cm}}}^{-1}$$\\end{document} for Cs2LiGaBr6 and 40×10\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$40\ imes 10$$\\end{document}4cm-1\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\ ext{cm}}}^{-1}$$\\end{document} for Cs2NaGaBr6 are noted across visible and infrared spectra, highlighting their promising potential in optoelectronic and solar cell technologies.

Study of the surface damage threshold and mechanism of KDP crystal under ultrashort laser irradiation

Here, we investigate the mechanism of surface damage threshold anisotropy induced by ultrashort laser in potassium dihydrogen phosphate (KDP) crystal. Carrier-lattice nonequilibrium interaction is simulated based on Brillouin light-scattering (BLS) spectroscopy and a complete self-consistent model to obtain the time evolution of carrier density and temperature as well as lattice temperature. The results indicate that the trend of the lattice temperature is consistent with the experimental phenomena. Meanwhile, the electron-phonon coupling effect, in addition to the electron density traditionally considered, is an important factor affecting damage and is a major contributor to the anisotropy of the damage threshold.

Highly Stable and Efficient Formamidinium-Based 2D Ruddlesden-Popper Perovskite Solar Cells via Lattice Manipulation.

Formamidinium (FA)-based 2D perovskites have emerged as highly promising candidates in solar cells. However, the insertion of 2D spacer cations into the perovskite lattice concomitantly introduces microstrain and unfavorable orientations that hinder efficiency and stability. In this study, by finely tuning the FA-based 2D perovskite lattice through spacer cation engineering, a stable lattice structure with balanced distortion, microstrain relaxation, and reduced carrier-lattice interactions is achieved. These advancements effectively stabilize the inherently soft lattice against light and thermal-aging stress. To reduce the photocurrent loss induced by undesired crystal texture, a polarity-matched molecular-type selenourea (SENA) additive is further employed to modulate the crystallization kinetics. The introduction of the SENA significantly inhibits the disordered crystallization induced by spacer cations and drives the templated growth of the quantum well structure with a vertical orientation. This controlled crystallization process effectively reduces crystal defects and enhances charge separation. Ultimately, the optimized FA-based perovskite photovoltaic devices achieve a remarkable power conversion efficiency (PCE) of 20.03% (certified steady-state efficiency of 19.30%), setting a new record for low-n 2D perovskite solar cells. Furthermore, the devices exhibit less than 1% efficiency degradation after operating at maximum power point for 1000 h and maintain excellent stability after thermal aging and cycles of cold-warm shock, respectively.

Spin-dependent polaron transport in helical molecules

We study thermal effects on spin transport along a deformable helical molecule in the presence of chiral-induced spin–orbit coupling. The carrier–lattice interaction is modeled by the well-established Peyrard–Bishop–Holstein model within the Langevin approach to include temperature as a stochastic noise. The carrier–lattice interaction causes the occurrence of polaron states in the molecule. We demonstrate the existence of two well-differentiated spin-dependent polaron transport regimes as a function of temperature. In the low-temperature regime, the spatial separation of the two spin-dependent polaron wave-packets results in a nonzero spin current. On the contrary, the spin current becomes negligible if the temperature of the system is high enough. Finally, we characterize this transition and estimate the critical temperature at which it takes place.

The superposed electric field effect on the charge transport and polaron formation in molecular crystals

We study the polaron formation and its mobility in a one-dimensional molecular crystal subjected to superposed static and harmonic electric fields. Such molecular chain exhibits intermolecular vibrational degrees of freedom, which makes the carrier-lattice interaction an important parameter of the system. By exploring field settings in which the preferential transport occurs, we show the existence of different small polaron formations, including those that travel close to the sound velocity or that are stationary by self-trapping. Electric fields magnitudes and carrier-lattice coupling have also been analyzed, which allowed to show a phase diagram that describes the existing regimes. In addition to thresholds between the mobile and stationary polaron regimes, this phase diagram unveils an unusual aspect: a metastable polaron formation.

Lead-Free Potassium Alloyed Cs2AgBiBr6: Tunable Optoelectronic Properties and Carrier-Lattice Interaction

The role of the carrier-lattice interaction and associated self-trapped excitons (STEs) in broadband white-light emission in perovskite halides is one of the key aspects when aiming to develop next generation semiconductors for lighting applications. Herein, we provide microscopic insight on optoelectronic properties and electron–phonon interactions in potassium (K+) alloyed Cs2AgBiBr6, while evaluating its potential as a single material tunable light emitter. While K+ partially occupying the Cs+ site leads to blue-light emission at low K+ ion concentrations, a sudden photoluminescence broadening and white-light emission occur at relatively higher alloying concentrations where K+ starts to occupy Ag+ sites. Simulation reveals an anomalous increase in carrier lattice coupling strength (via the Fröhlich mechanism) when K+ replaces Ag+. This along with the increased density of STEs (aided by strong electron–phonon coupling and more octahedral distortion) and induced free exciton (FE) emission is proposed to play a major role behind the observed photoluminescence (PL) broadening and white-light emission. This study should stimulate further research on single material based white-light emitters for next generation solid-state lighting applications.

Large bandgap oscillations in two-dimensional Dion–Jacobson phase perovskites caused by coherent longitudinal acoustic phonons [Invited

Two-dimensional Dion–Jacobson (D-J) phase perovskites are prospective photovoltaic and optoelectronic materials. To study their mechanical properties and carrier-lattice interactions, we conduct femtosecond spectroscopic experiments on the films of a D-J perovskite. After optical excitation, a ∼33 meV bandgap oscillation is observed in the film by transient absorption spectroscopy. With the help of transient reflection methods, we reveal that the oscillation originates from the transport of coherent longitudinal acoustic phonons through the film. Large bandgap oscillation indicates a strong coupling between carriers and lattice, and significant bandgap modulation by strains in D-J perovskites.

Carrier transport and electron–lattice interactions of nonlinear optical crystals CdGeP2, ZnGeP2, and CdSiP2

Terahertz time-domain spectroscopy is employed to investigate temperature-dependent properties of bulk chalcopyrite crystals ( C d G e P 2 , Z n G e P 2 , and C d S i P 2 ). The complex spectra provide refraction and absorption as a function of temperature, from which electron–phonon coupling and average phonon energies are extracted and linked to the mechanics of the A- and B-site cations. AC conductivity spectra provide carrier densities and electron scattering times, the temperature dependence of which are associated with unintentional shallow dopants. Temperature dependence of the scattering time is converted into carrier mobility and modeled with microscopic transport mechanisms such as polar optical phonon, acoustic phonons, deformation potential, ionized impurity, and dislocation scattering. Hence, analysis links the terahertz optical and electronic properties to relate microscopic carrier transport and carrier–lattice interactions.

Ultrafast carrier and spin dynamics in GaMnAs across the Curie temperature

The carrier and spin dynamics of the diluted ferromagnetic semiconductor GaMnAs are crucial to understanding its ferromagnetic nature, especially near the Curie temperature (TC). Herein, transient differential reflectivity measurements and the temporal evolution of Kerr rotation are shown using ultrafast optical spectroscopy at various temperatures. The energy and angular momentum transfer routes after femtosecond laser pumping are revealed. The hole dynamics consist of two processes: a fast process that arises from carrier recombination and a slow process caused by carrier–lattice interactions. The spin dynamics are determined from the spin–orbital coupling and spin–lattice interactions in the ferromagnetic and paramagnetic phases, respectively. Critical phenomena are observed from the competition between the hole-mediated ferromagnetic orders and thermal perturbations near TC. These experimental results provide deep insights into the ultrafast decay behavior in GaMnAs, which is regarded as one of the most promising spintronic materials.

Lattice Dynamics and Electron-Phonon Coupling in Lead-Free Cs2AgIn1-xBixCl6 Double Perovskite Nanocrystals.

Recently, lead free all-inorganic double perovskites have revolutionized photovoltaic research, showing promising light emitting efficiency and tunability via modification of inherent structural and chemical properties. Here, we report a combined experimental and theoretical study on the variation of carrier-lattice interaction and optoelectronic properties of Cs2AgIn1-xBixCl6 double perovskite nanocrystals with varying alloying concentrations. Our UV-vis study confirms the parity allowed first direct transition for x ≤ 0.25. Using a careful analysis of Raman spectra assisted with first-principles simulations, we assign the possible three types of active modes to intrinsic atomic vibrations; 2 T2g modes (one for translational motion of "Cs" and other for octahedral breathing), 1 Eg and 1 A1g mode for various stretching of Ag-Cl octahedra. Ab-initio simulation reveals dominant carrier-phonon scattering via Fröhlich mechanism near room temperature, with longitudinal optical phonons being effectively activated around 230 K. We observe a noticeable increase in hole mobility (∼4 times) with small Bi alloying, attributed to valence band (VB) maxima acquiring Bi-s orbital characteristics, thus resulting in a dispersive VB. We believe that our results should help to gain a better understanding of the intrinsic electronic and lattice dynamical properties of these compounds and provide a base toward improving the overall performance of double perovskite nanocrystals.

How Lattice Dynamics Moderate the Electronic Properties of Metal-Halide Perovskites.

Metal-halide perovskites have emerged as highly promising semiconductors with excellent optoelectronic properties. This Perspective outlines how the dynamic response of the ionic lattice affects key electronic properties such as exciton binding energies and charge-carrier mobilities in hybrid perovskites. Such links are shown to derive from the frequency-dependence of the dielectric function, which is governed by contributions from electronic interband transitions, polar vibrations of the metal-halide sublattice, organic cation collective reorientations, and ionic movement. The influence of each of these contributions to charge-carrier screening and carrier-lattice interactions is discussed, which allows for general trends with material composition to be revealed. Overall, this Perspective highlights the challenges and questions arising from the peculiar combination of a soft polar metal-halide sublattice interspersed with rotationally mobile dipolar molecules that is encountered in hybrid metal-halide perovskites.

Correlation among the effective mass (m⁎), λab and Tc of superconducting cuprates in a Casimir energy scenario

The relevance of the Casimir effect, discovered in 1948, has recently been pointed out in studies on materials such as graphene and high-temperature superconducting cuprates. In particular, the relationship between Casimir energy and the energy of a superconducting condensate with anisotropy characterized by high bidimensionality has already been discussed in certain theoretical scenarios. Using this proposal, this work describes the relationship between the effective mass of the charge carriers (m⁎=αme) and the macroscopic parameters characteristic of several families of high-Tc superconducting cuprates (Cu-HTSC) that have copper and oxygen superconducting planes (Cu-O). We have verified that an expression exists that correlates the effective mass, the London penetration length in the plane λab, the critical temperature Tc and the distance d between the equivalent superconducting planes of Cu-HTSC. This study revealed that the intersection between the asymptotic behavior of α as a function of Tc and the line describing the optimal value of α≃2 (m⁎≃2me) indicates that a nonadiabatic region exists, which implies a carrier-lattice interaction and where the critical temperature can have its highest value in Cu-HTSC.

Polaronic Charge Carrier-Lattice Interactions in Lead Halide Perovskites.

Almost ten years after the renaissance of the popular perovskite-type semiconductors based on lead salts with the general formula AMX3 (A=organic or inorganic cation; M=divalent metal; X=halide), many facets of photophysics continue to puzzle researchers. In this Minireview, light is shed on the low mobilities of charge carriers in lead halide perovskites with special focus on the lattice properties at non-zero temperature. The polar and soft lattice leads to pronounced electron-phonon coupling, limiting carrier mobility and retarding recombination. We propose that the proper picture of excited charge carriers at temperature ranges that are relevant for device operations is that of a polaron, with Fröhlich coupling constants between 1<α<3. Under the aspect of light-emitting diode application, APbX3 perovskite show moderate second order (bimolecular) recombination rates and high third-order (Auger) rate constants. It has become apparent that this is a direct consequence of the anisotropic polar A-site cation in organic-inorganic hybrid perovskites and might be alleviated by replacing the organic moiety with an isotropic cation.

Direct Experimental Evidence for Photoinduced Strong-Coupling Polarons in Organolead Halide Perovskite Nanoparticles.

Echoing the roaring success of their bulk counterparts, nano-objects built from organolead halide perovskites (OLHP) present bright prospects for surpassing the performances of their conventional organic and inorganic analogues in photodriven technologies. Unraveling the photoinduced charge dynamics is essential for optimizing the optoelectronic functionalities. However, mapping the carrier-lattice interactions remains challenging, owing to their manifestations on multiple length scales and time scales. By correlating ultrafast time-resolved optical and X-ray absorption measurements, this work reveals the photoinduced formation of strong-coupling polarons in CH3NH3PbBr3 nanoparticles. Such polarons originate from the self-trapping of electrons in the Coulombic field caused by the displaced inorganic nuclei and the oriented organic cations. The transient structural change detected at the Pb L3 X-ray absorption edge is well-captured by a distortion with average bond elongation in the [PbBr6]2- motif. General implications for designing novel OLHP nanomaterials targeting the active utilization of these quasi-particles are outlined.

Characterization of carrier transport properties in strained crystalline Si wall-like structures in the quasi-quantum regime

We report the transport characteristics of both electrons and holes through narrow constricted crystalline Si “wall-like” long-channels that were surrounded by a thermally grown SiO2 layer. The strained buffering depth inside the Si region (due to Si/SiO2 interfacial lattice mismatch) is where scattering is seen to enhance some modes of the carrier-lattice interaction, while suppressing others, thereby changing the relative value of the effective masses of both electrons and holes, as compared to bulk Si. In the narrowest wall devices, a considerable increase in conductivity was observed as a result of higher carrier mobilities due to lateral constriction and strain. The strain effects, which include the reversal splitting of light- and heavy-hole bands as well as the decrease of conduction-band effective mass by reduced Si bandgap energy, are formulated in our microscopic model for explaining the experimentally observed enhancements in both conduction- and valence-band mobilities with reduced Si wall thickness. Also, the enhancements of the valence-band and conduction-band mobilities are found to be associated with different aspects of theoretical model.

Increased Deep-Level Hole Trapping by Combined Negative-Bias Temperature and Channel Hot-Hole Stress

Trapping of holes at deep energy states under negative-bias-temperature instability (NBTI) is examined in the presence of a nonzero drain bias [i.e., channel hot-hole (CHH) effect]. While the total density of switching hole traps is unchanged after the combined NBTI and CHH stress (implying no additional creation of such traps for the conditions studied), evidence shows that the density of deep-level switching hole traps is increased. Enhanced carrier-lattice interaction under hot-hole injection is believed to induce the greater structural relaxation inherent to specific precursor sites for these deep-level hole traps. Implications of this observation are briefly discussed.

Photo-structural changes in chalcogenide glasses during illumination

A theory is developed for the processes of the creation of light induced defects, photo-darkening and volume expansion during illumination of chalcogenide glasses. Considering a linear chain of the sample, it is shown that the charge carrier–lattice interaction plays a common role in all the three processes. Results are compared with the experimental results and other theories.

Intraband magnetospectroscopy of singly and doubly chargedn-type self-assembled quantum dots

The influence of quantum dot occupancy and incident light polarization on the carrier-lattice interactions in electron-doped $\mathrm{InAs}$ quantum dots grown on $\mathrm{GaAs}$ has been investigated up to $28\phantom{\rule{0.3em}{0ex}}\mathrm{T}$ by far-infrared magnetotransmission spectroscopy. An enhancement of the electron-phonon coupling with increased electron population from one to two electrons per dot is observed, in close agreement with the predicted $\sqrt{2}$ increase due to the antisymmetrization of the electron wave function in the two-electron quantum dot system. This contrasts with two-dimensional systems in which the polaron coupling strength is reduced with increasing electron density due to the screening effect of multiple carriers on the electron-phonon interaction. A clear change of the polarization dependence for transitions from the ground to the first excited state from linear to circular has been observed as the Zeeman splitting becomes larger than the zero-field excited state splitting energy.

NUMERICAL ANALYSIS ON HEAT TRANSFER CHARACTERISTICS OF A SILICON FILM IRRADIATED BY PICO-TO FEMTOSECOND PULSE LASERS

This work aims to investigate the heat transfer characteristics of a silicon microstructure irradiated by picosecond-to-femtosecond ultrashort laser pulses from a microscopic point of view. Carrier-lattice nonequilibrium interactions are simulated with a set of governing equations for the carrier and lattice temperatures to obtain the time evolutions of the lattice temperatures, the carrier number densities, and carrier temperatures. In particular, the relaxation time for approaching the thermal equilibrium between carriers and lattices is introduced to estimate duration of the nonequilibrium state. An appropriate regime map to make a distinction between one-peak and two-peak structures is also established for picosecond laser pulses. It is noted that a substantial increase in carrier temperature is observed for pulse lasers of a few picoseconds duration, whereas the lattice temperature rise is relatively small with decreasing laser pulse widths. It is also found that the laser fluence significantly affects the N 3 decaying rate of the Auger recombination, the carrier temperature distribution exhibits two peaks as a function of time due to the Auger heating as well as the direct laser heating of carriers, and finally, both laser fluence and pulse width play an important role in controlling the nonequilibrium between carriers and lattices.