Impact of Crystal Surface on Photoexcited States in Organic–Inorganic Perovskites

Despite their outstanding photovoltaic performance, organic–inorganic perovskite solar cells still face severe stability issues and limitations in their device dimension. Further development of perovskite solar cells therefore requires a deeper understanding of loss mechanisms, in particular, concerning the origin and impact of trap states. Here, different surface properties of submicrometer sized CH₃NH₃PbI₃ particles are studied as a model system by photoluminescence spectroscopy to investigate the impact of the perovskite crystal surface on photoexcited states. Comparison of single crystals with either isolating or electron‐rich surface passivation indicates the presence of positively charged surface trap states that can be passivated in case of the latter. These surface trap states cause enhanced nonradiative recombination at room temperature, which is a loss mechanism for solar cell performance. In the orthorhombic phase, the origin of multiple emission peaks is identified as the recombination of free and bound excitons, whose population ratio critically depends on trap state properties. The dynamics of exciton trapping at 50 K are observed on a time‐scale of tens of picoseconds by a simultaneous population decrease and increase of free and bound excitons, respectively. These results emphasize the potential of surface passivation to further improve the performance of perovskite solar cells.     

Band‐Edge Exciton Fine Structure and Exciton Recombination Dynamics in Single Crystals of Layered Hybrid Perovskites

2D perovskite materials have recently reattracted intense research interest for applications in photovoltaics and optoelectronics. As a consequence of the dielectric and quantum confinement effect, they show strongly bound and stable excitons at room temperature. Here, the band‐edge exciton fine structure and in particular its exciton and biexciton dynamics in high quality crystals of (PEA)₂PbI₄ are investigated. A comparison of bulk and surface exciton lifetimes yields a room temperature surface recombination velocity of 2 × 10³ cm s^?1 and an intrinsic lifetime of 185 ns. Biexciton emission is evidenced at room temperature, with a binding energy of ≈45 meV and a lifetime of 80 ps. At low temperature, exciton state splitting is observed, which is caused by the electron–hole exchange interaction. Transient photoluminescence resolves the low‐lying dark exciton state, with a bright/dark splitting energy estimated to be 10 meV. This work contributes to the understanding of the complex scenario of the elementary photoexcitations in 2D perovskites.     

Ultrafast Spectroscopy of Photoexcitations in Organometal Trihalide Perovskites

Studying the room temperature broadband ultrafast transient response of photoexcitations in three perovskite films, namely MAPbI₃, MAPbI_1.1Br_1.9, and MAPbI_3?xCl_x (MA = CH₃NH₃), allowed unravelling the branching ratio between photogenerated carriers and excitons, a key factor for optoelectronic applications of perovskites. An instantaneously generated mid‐IR photoinduced absorption (PA) band, PA₁ is observed in all three perovskites, as well as a strong derivative‐like band of photoinduced bleaching (PB) and PA (PA₂) close to the corresponding absorption band edge. From the distinguished different decay dynamics of the PA bands in MAPbI₃, PA₁ is interpreted as due to the exciton transition, whereas PA₂ and PB are due to band‐filling effect caused by the photocarriers. In contrast, all bands in MAPbI_1.1Br_1.9 and MAPbI_3?xCl_x share the same dynamics and are therefore due to the same species, namely photogenerated excitons. The transient photoinduced polarization memory (POM) for both excitons and photocarriers as well as the steady‐state photoluminescence (PL) emission are observed in MAPbI₃, but not in MAPbI_1.1Br_1.9 and MAPbI_3?xCl_x because they possess cubic symmetry at room temperature. The estimated long excitons diffusion length (≈150 nm) in MAPbI₃ opens up the possibility of photocarriers generation at interfaces and grain boundaries even when the exciton binding energy is large compare to k_BT.     

Broad Range Tuning of Phase Transition Property in VO2 Through Metal‐Ceramic Nanocomposite Design

Vanadium dioxide (VO₂) is a well‐studied Mott‐insulator because of the very abrupt physical property switching during its semiconductor‐to‐metal transition (SMT) around 341 K (68 °C). In this work, through novel oxide‐metal nanocomposite designs (i.e., Au:VO₂ and Pt:VO₂), a very broad range of SMT temperature tuning from ≈ 323.5 to ≈ 366.7 K has been achieved by varying the metallic secondary phase in the nanocomposites (i.e., Au:VO₂ and Pt:VO₂ thin films, respectively). More surprisingly, the SMT T_c can be further lowered to ≈ 301.8 K (near room temperature) by reducing the Au particle size from 11.7 to 1.7 nm. All the VO₂ nanocomposite thin films maintain superior phase transition performance, i.e., large transition amplitude, very sharp transition, and narrow width of thermal hysteresis. Correspondingly, a twofold variation of the complex dielectric function has been demonstrated in these metal‐VO₂ nanocomposites. The wide range physical property tuning is attributed to the band structure reconstruction at the metal‐VO₂ phase boundaries. This demonstration paved a novel approach for tuning the phase transition property of Mott‐insulating materials to near room temperature transition, which is important for sensors, electrical switches, smart windows, and actuators.     

Photoluminescence and X-ray luminescence of Pb0.30Cd0.70I2 solid solutions. Comparative study

The nature and relative contributions (RCs) of various radiative recombination processes to the photoluminescence (PL) spectra for bulk nanostructured Pb_0.30Cd_0.70I₂ solid solutions have been established at different temperatures. The analysis indicates that the PL is caused by free, bound and self-trapped excitons as well as by donor-acceptor pairs emission with the participation of shallow and deep acceptor centers. It was shown that X-ray luminescence (XRL) spectra are also determined by these recombination processes. However, their RC and the temperature evolution are considerably different. Besides, XRL spectra contain an intense long-wavelength band associated with the emission of many LO-phonons. It was shown that the deep luminescence surface states, associated with the self-trapped excitons and deep intrinsic defects, mainly determine the intensity of XRL spectra both at 80 K and room temperature. The results obtained open the way to the optimization of the scintillator properties of the investigated materials.     

Optical spectroscopy of excitonic states in CuInSe2

Optical properties of structurally perfect CuInSe₂ single crystals were studied in the temperature range of 4.2–300 K with the use of photoluminescence, optical absorption, optical reflection, and wavelength-modulated optical reflection (WMOR). The intense lines of free excitons A (～1.0414 eV) and B (～1.0449 eV) with a half-width of ～0.7 meV at 4.2 K are found to be related to two extrema of valence band split by a crystal field. The excitons emission line C (～1.2779 eV) in WMOR spectra are related to a lower valence band split-off by spin-orbit interaction. Within the context of the quasi-cubic Hopfield model, the parameters of valence band splitting Δ_CF=5.2 meV and Δ_SO=234.7 meV defined by the crystal and spin-orbit interaction, respectively, are calculated. In the region of the fundamental absorption edge, the lines of bound excitons are found with a half-width ～0.3 meV that is indicative of a high quality of grown CuInSe₂ crystals.     

Organic Thin‐Film Photovoltaic Cells Based on Oligothiophenes with Reduced Bandgap

The best polymeric solar cells reported so far are based on a so‐called bulk heterojunction of a polythiophene as donor and a soluble fullerene derivative as acceptor. However, these cells still suffer from an unsatisfying photovoltage, typically below 0.7 V. Here, we show that we can achieve higher photovoltages using a new terthiophene end‐capped with electron withdrawing dicyanovinyl groups (DCV3T) that increase both the ionization energy and even more strongly the electron affinity of the compound. The new material is tested in cells using a photoactive heterojunction to separate the excitons generated in the oligomer and a p‐doped wide‐gap transport layer. The solar cells show an open circuit voltage of up to 1.04 V and a broad spectral sensitivity band ranging from 420 nm to 650 nm. Solar cells based on such oligothiophenes are promising candidates for stacked organic solar cells tailored to the sun‐spectrum. Moreover, we present first examples of a new concept for organic solar cells: By blending DCV3T with fullerene C₆₀, an enhanced generation of triplet excitons on the oligomer can be achieved via a back and forth transfer of excitons (ping‐pong‐effect).     

High‐Quality Whispering‐Gallery‐Mode Lasing from Cesium Lead Halide Perovskite Nanoplatelets

Semiconductor micro/nano‐cavities with high quality factor (Q) and small modal volume provide critical platforms for exploring strong light‐matter interactions and quantum optics, enabling further development of coherent and quantum photonic devices. Constrained by exciton binding energy and thermal fluctuation, only a handful of wide‐band semiconductors such as ZnO and GaN have stable excitons at room temperature. Metal halide perovskite with cubic lattice and well‐controlled exciton may provide solutions. In this work, high‐quality single‐crystalline cesium lead halide CsPbX₃ (X = Cl, Br, I) whispering‐gallery‐mode (WGM) microcavities are synthesized by vapor‐phase van der Waals epitaxy method. The as‐grown perovskites show strong emission and stable exciton at room temperature over the whole visible spectra range. By varying the halide composition, multi‐color (400–700 nm).WGM excitonic lasing is achieved at room temperature with low threshold (~ 2.0 μJ cm^?2) and high spectra coherence (~0.14–0.15 nm). The results advocate the promise of inorganic perovskites towards development of optoelectronic devices and strong light‐matter coupling in quantum optics.     

Photoluminescent properties of ZnO thin films grown on SiO2/Si(100) by metal-organic chemical vapor deposition

We report on the photoluminescent (PL) properties of ZnO thin films grown on SiO₂/Si(100) substrates using low pressure metal-organic chemical vapor deposition. The growth temperature of the films was as low as 400°C. From the PL spectra of the films at 10–300 K, strong PL peaks due to free and bound excitons were observed. The origin of the near bandedge emission peaks was investigated measuring temperature-dependent PL spectra. In addition, the Zn O films demonstrated a stimulated emission peak at room temperature. Upon illumination with an excitation density of 1 MW/cm², a strong, sharp peak was observed at 3.181 eV.     

Conductive Nanostructures of MMX Chains

Crystals of [Pt₂(n‐pentylCS₂)₄I] show a transition from semiconductor to metallic with the increase of the temperature (conductivity is 0.3–1.4 S · cm^?1 at room temperature) and a second metallic–metallic transition at 330 K, inferred by electrical conductivity measurements. X‐ray diffraction studies carried out at different temperatures (100, 298, and 350 K) confirm the presence of three different phases. The valence‐ordering of these phases is analyzed using structural, magnetic, and electrical data. Density functional theory calculations allow a further analysis of the band structure derived for each phase. Nanostructures adsorbed on an insulating surface show electrical conductivity. These results suggest that MMX‐polymer‐based nanowires could be suitable for device applications.     

Amplified Spontaneous Emission Based on 2D Ruddlesden–Popper Perovskites

2D Ruddlesden–Popper perovskites (RPPs) are a class of quantum‐well (QW) materials, composed of layered perovskite QWs encapsulated between two hydrophobic organic layers. Different from widely investigated 3D‐perovskites with free carriers at room temperature, 2D‐RPPs exhibit strongly bound electron–hole pairs (excitons) for high‐performance solar cells and light emitting diodes (LEDs). Herein, it is reported that self‐organized multiple QWs in 2D‐RPP thin films naturally form an energy cascade, which enables an ultrafast energy transfer process from higher energy‐bandgap QWs to lower energy‐bandgap QWs. Therefore, photoexcitations are concentrated on lower‐bandgap QWs, facilitating the build‐up of population inversion. Room‐temperature amplified spontaneous emission (ASE) from 2D‐RPP thin films is achieved at dramatically low thresholds, with gain coefficients as high as >300 cm^?1, and stoichiometrically tunable ASE wavelengths from visible to near‐infrared spectral range (530–810 nm). In view of the high efficiency reported for LEDs, these solution‐processed 2D‐RPP thin films may hold the key to realize electrically driven lasers.     

Temperature‐Insensitive (K,Na)NbO3‐Based Lead‐Free Piezoactuator Ceramics

The development of lead‐free piezoceramics has attracted great interest because of growing environmental concerns. A polymorphic phase transition (PPT) has been utilized in the past to tailor piezoelectric properties in lead‐free (K,Na)NbO₃ (KNN)‐based materials accepting the drawback of large temperature sensitivity. Here a material concept is reported, which yields an average piezoelectric coefficientd₃₃ of about 300 pC/N and a high level of unipolar strain up to 0.16% at room temperature. Most intriguingly, field‐induced strain varies less than 10% from room temperature to 175 °C. The temperature insensitivity of field‐induced strain is rationalized using an electrostrictive coupling to polarization amplitude while the temperature‐dependent piezoelectric coefficient is discussed using localized piezoresponse probed by piezoforce microscopy. This discovery opens a new development window for temperature‐insensitive piezoelectric actuators despite the presence of a polymorphic phase transition around room temperature.     

Photoluminescences from AlxGa1−xP liquid phase epitaxial layers

Homogenous Al_xGa_1-xP liquid phase epitaxial layers have been obtained with the temperature difference method under controlled vapor pressure (TDM-CVP). Very clear fine structures near band edge in photoluminescence spectra have been observed at 77 K for the first time. Photoluminescence measurement results confirmed that the free exciton recombination without phonon assistance plays an important role in the luminescence at 77 K and becomes dominant at room temperature. It is considered that zero-phonon assisted free exciton recombination is intensified by some local perturbations to electrical potentials against carriers or excitons introduced by Al atoms in Al_xGa_1-xP layers, which can give momentum change necessary for recombination.     

Plasmonic‐Induced Photon Recycling in Metal Halide Perovskite Solar Cells

Organic–inorganic metal halide perovskite solar cells have emerged in the past few years to promise highly efficient photovoltaic devices at low costs. Here, temperature‐sensitive core–shell Ag@TiO₂ nanoparticles are successfully incorporated into perovskite solar cells through a low‐temperature processing route, boosting the measured device efficiencies up to 16.3%. Experimental evidence is shown and a theoretical model is developed which predicts that the presence of highly polarizable nanoparticles enhances the radiative decay of excitons and increases the reabsorption of emitted radiation, representing a novel photon recycling scheme. The work elucidates the complicated subtle interactions between light and matter in plasmonic photovoltaic composites. Photonic and plasmonic schemes such as this may help to move highly efficient perovskite solar cells closer to the theoretical limiting efficiencies.     

Efficient near IR photoluminescence from gallium nitride layers doped with arsenic

Photoluminescence in the 1.2–1.4 eV spectral range from GaN:As layers grown on (0001) Al₂O₃ substrates was observed and studied. The photoluminescence is attributed to radiative recombination in GaAs nanocrystallites, self-organized in the GaN matrix during growth. The photoluminescence intensity attains a maximum at a growth temperature of ～780°C, which is explained by the competition between several temperature-dependent processes that affect the formation of GaAs nanocrystallites. Sharp emission lines were observed at the high-energy edge of the photoluminescence band. These lines are caused by an emission of bound excitons in the GaAs nanocrystallites and by phonon replicas of the bound-exciton emission. The energies of the corresponding optical phonons are typical of GaAs. The photoluminescence-excitation spectra exhibit features related to resonantly excited free and bound excitons as well as to excitons formed simultaneously with the emission of optical phonons.     

Diffused Phase Transition Boosts Thermal Stability of High‐Performance Lead‐Free Piezoelectrics

High piezoelectricity of (K,Na)NbO₃ (KNN) lead‐free materials benefits from a polymorphic phase transition (PPT) around room temperature, but its temperature sensitivity has been a bottleneck impeding their applications. It is found that good thermal stability can be achieved in CaZrO₃‐modified KNN lead‐free piezoceramics, in which the normalized strain d ₃₃* almost keeps constant from room temperature up to 140 °C. In situ synchrotron X‐ray diffraction experiments combined with permitivity measurements disclose the occurrence of a new phase transformation under an electrical field, which extends the transition range between tetragonal and orthorhombic phases. It is revealed that such an electrically enhanced diffused PPT contributed to the boosted thermal stability of KNN‐based lead‐free piezoceramics with high piezoelectricity. The present approach based on phase engineering should also be effective in endowing other lead‐free piezoelectrics with high piezoelectricity and good temperature stability.     

Freestanding Single Crystalline Fe–Pd Ferromagnetic Shape Memory Membranes – Role of Mechanical and Magnetic Constraints Across the Martensite Transition

Substrate‐attached and freestanding single crystalline Fe₇₀Pd₃₀ ferromagnetic shape memory alloy membranes, which were synthesized by molecular beam epitaxy on MgO (001) and later released from their substrates, are characterized with respect to their structural, thermal and magnetic properties. Residing in the two‐phase region of austenite and the correct martensite phase with face centered tetragonal (fct) structure at room temperature, they reveal martensite transition with little hysteresis at 326 K and 320 K, respectively. Comparing substrate‐attached with freestanding films, which show fundamentally different magnetic fingerprints, it is proposed that domain structure is capable of posing a bias on the austenite → fct‐martensite phase transition by favoring martensite variants with their easy axis aligned along the field – just as the substrate constitutes a mechanical constraint on the transition. If confirmed, this would suggest thermo‐magnetic actuation as an alternative where only moderate magnetic fields are feasible, but moderate temperature changes are possible.     

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.     

Intrinsically Low Thermal Conductivity in BiSbSe3: A Promising Thermoelectric Material with Multiple Conduction Bands

Bi₂Se₃, as a Te‐free alternative of room‐temperature state‐of‐the‐art thermoelectric (TE) Bi₂Te₃, has attracted little attention due to its poor electrical transport properties and high thermal conductivity. Interestingly, BiSbSe₃, a product of alloying 50% Sb on Bi sites, shows outstanding electron and phonon transports. BiSbSe₃ possesses orthorhombic structure and exhibits multiple conduction bands, which can be activated when the carrier density is increased as high as ≈3.7 × 10²⁰ cm^?3 through heavily Br doping, resulting in simultaneously enhancing the electrical conductivities and Seebeck coefficients. Meanwhile, an extremely low thermal conductivity (≈0.6–0.4 W m^?1 K^?1 at 300–800 K) is found in BiSbSe₃. Both first‐principles calculations and elastic properties measurements show the strong anharmonicity and support the ultra‐low thermal conductivity of BiSbSe₃. Finally, a maximum dimensionless figure of merit ZT ～ 1.4 at 800 K is achieved in BiSb(Se_0.94Br_0.06)₃, which is comparable to the most n‐type Te‐free TE materials. The present results indicate that BiSbSe₃ is a new and a robust candidate for TE power generation in medium‐temperature range.     

Microchannel gate temperature analysis

Photoemission spectra of a GaAs gate material of a metal semiconductor field effect transistor (MESFET) were analyzed to nondestructively assess the submicron-size local gate temperature. Utilizing the micromanipulator, the laser beam was precisely adjusted to probe the exact position of the device gate. The emission spectral bands due to the interaction among photons, free excitons and impurity bound excitons in GaAs gate materials were measured and identified both at 299.1 K and 84.8 K. The shift of the band was found to be 16.30 meV for the free excitons when the device was not powered, while the band shift of the gate was 7.38 meV when the device was powered at 84.8 K. Simple first order calculations based on the theory of temperature shift of the bound excitons, predicts an inversely proportional relationship between the emission bandshift and temperature. Measurements using this technique found an increase of 97.0 K.