Probing Defects and Spin-Phonon Coupling in CrSBr via Resonant Raman Scattering

Understanding the stability limitations and defect formation mechanisms in 2D magnets is essential for their utilization in spintronic and memory technologies. Here, defects in mono- to multilayer CrSBr are correlated with structural, vibrational, and magnetic properties. Resonant Raman scattering is used to reveal distinct vibrational defect signatures. In pristine CrSBr, it is shown that bromine atoms mediate vibrational interlayer coupling, allowing for distinguishing between surface and bulk defect modes. Environmental exposure is shown to cause drastic degradation in monolayers, with the formation of intralayer defects. This is in contrast to multilayers that predominantly show bromine surface defects. Through deliberate ion irradiation, the formation of defect modes is tuned: these are strongly polarized and resonantly enhanced, reflecting the quasi--1D electronic character of CrSBr. Strikingly, pronounced signatures of spin-phonon coupling of the intrinsic phonon modes and the ion beam-induced defect modes are observed throughout the magnetic transition temperature. Overall, defect engineering of magnetic properties is possible, with resonant Raman spectroscopy serving as a direct fingerprint of magnetic phases and defects in CrSBr.     

Spin-Phonon Scattering-Induced Low Thermal Conductivity in a van der Waals Layered Ferromagnet Cr2Si2Te6

Layered van der Waals (vdW) magnets are prominent playgrounds for developing magnetoelectric, magneto-optic, and spintronic devices. In spintronics, particularly in spincaloritronic applications, low thermal conductivity (κ) is highly desired. Herein, by combining thermal transport measurements with density functional theory calculations, this study demonstrates low κ down to 1 W m⁻¹ K⁻¹ in a typical vdW ferromagnet Cr₂Si₂Te₆. In the paramagnetic state, development of magnetic fluctuations way above T_c = 33 K strongly reduces κ via spin-phonon scattering, leading to low κ ≈ 1 W m⁻¹ K⁻¹ over a wide temperature range, in comparable to that of amorphous silica. In the magnetically ordered state, emergence of resonant magnon-phonon scattering limits κ below ≈2 W m⁻¹ K⁻¹, which will be three times larger if magnetic scatterings are absent. Application of magnetic fields strongly suppresses the spin-phonon scattering, giving rise to large enhancements of κ. This study's calculations well capture these complex behaviors of κ by taking the temperature- and magnetic-field-dependent spin-phonon scattering into account. Realization of low κ, which is easily tunable by magnetic fields in Cr₂Si₂Te₆, may further promote spincaloritronic applications of vdW magnets. This study's theoretical approach may also provide a generic understanding of spin-phonon scattering, which appears to play important roles in various systems.     

Employing Polar Solvent Controlled Ionization in Precursors for Synthesis of High‐Quality Inorganic Perovskite Nanocrystals at Room Temperature

All inorganic cesium lead halide (CsPbX₃, X = Cl, Br, I) perovskite nanocrystals (PeNCs) are synthesized by employing polar solvent controlled ionization (PCI) method in precursors. The new strategy can be easily carried out at room temperature and allow to employ smaller amount of weaker polarity and a broader range of low‐boiling low‐toxic solvents. The as prepared CsPbX₃ PeNCs reveal tunable emission spectra from 380 to 700 nm and high quantum yields over 80% with narrow full width at half maximum (FWHM). Meanwhile, larger “effective Stokes shifts” of PeNCs in PCI method, which enlarges 200% more than other PeNCs in regular methods, are observed. Most interestingly, the PeNCs growth process is coupling with some typical crystals formations. The main morphologies of CsPbI₃ PeNCs are hybrid of nanorods and nanoparticles. The primary morphologies of CsPbBr_xI_3‐x and CsPbBr₃ PeNCs are nanowires, which are supposed to have great potentials for applying in laser arrays and highly sensitive photodetector applications. Furthermore, such superior optical is endowed to fabricate white light emitting diodes, which has wide color gamut covering up to 120% of the National Television Systems Committee color standard.     

Colloidal Bi2S3 Nanocrystals: Quantum Size Effects and Midgap States

Among solution‐processed nanocrystals containing environmentally benign elements, bismuth sulfide (Bi₂S₃) is a very promising n‐type semiconductor for solar energy conversion. Despite the prompt success in the fabrication of optoelectronic devices deploying Bi₂S₃ nanocrystals, the limited understanding of electronic properties represents a hurdle for further materials developments. Here, two key materials science issues for light‐energy conversion are addressed: bandgap tunability via the quantum size effect, and photocarrier trapping. Nanocrystals are synthesized with controlled sizes varying from 3 to 30 nm. In this size range, bandgap tunability is found to be very small, a few tens of meV. First principles calculations show that a useful blueshift, in the range of hundreds of meV, is achieved in ultra‐small nanocrystals, below 1.5 nm in size. Similar conclusions are envisaged for the class of pnictide chalcogenides with a ribbon‐like structure [Pn₄Ch₆]_n (Pn = Bi, Sb; Ch = S, Se). Time‐resolved differential transmission spectroscopy demonstrates that only photoexcited holes are quickly captured by intragap states. Photoexcitation dynamics are consistent with the scenario emerging in other metal–chalcogenide nanocrystals: traps are created in metal‐rich nanocrystal surfaces by incomplete passivation by long fatty acid ligands. In large nanocrystals, a lower bound to surface trap density of one trap every sixteen Bi₂S₃ units is found.     

A Room Temperature Route toward In Situ Crystallization of Perovskite Nanocrystals Induced by Acrylic Acid for Flexible Free-Standing Luminescent Gels

Perovskite nanocrystals (PNCs) with unique and excellent optical properties have emerged as appealing luminescent materials in optoelectronic fields. However, high temperature processing, complicated procedures, and the use of toxic solvents are typically involved in the preparation of PNCs and their related optoelectronic devices. In this study, a one-step method is developed for the preparation of flexible photoluminescence gel based on PNCs at ambient conditions, which is a promising alternative to the current PNCs preparation strategy in terms of experimental friendliness, ease of production, and the potential for flexible devices. Acrylic acid (AA) is used for in situ crystallization of PNCs. The interaction between H⁺ of AA and perovskite-solvent complex determines the nucleation and growth of PNCs. This crystallization mechanism is systematically studied by varying acid category, adjusting solvent kind, and regulating the ratio of PNCs and gels. To give a proof of practicability, flexible free-standing PNCs-gel composites with excellent luminescent and mechanical properties are prepared with the AA treatment. Moreover, the PNCs-gel shape can be customized, which greatly expands the structural flexibility and functionalities of fabricated devices.     

Broadband Defects Emission and Enhanced Ligand Raman Scattering in 0D Cs3Bi2I9 Colloidal Nanocrystals

Excitonic 0D and 2D lead‐halide perovskites have been recently developed and investigated as new materials for light generation. Here broadband (>1 eV) emission from newly synthesized 0D lead‐free colloidal Cs₃Bi₂I₉ nanocrystals (NCs) is reported. The nature of their emissive states as well as the relative dynamics which are currently hotly debated are investigated. In particular, it is found that the broadband emission is made by the coexistence of emissive excitons and sub‐bandgap emissive trap‐states. Remarkably, evidence of enhanced Raman scattering from the ligands is observed when attached to the NCs surface, an effect that is preliminarily attributed to strong exciton‐ligands electronic coupling in these systems.     

Strained Interface Defects in Silicon Nanocrystals

The surface of silicon nanocrystals embedded in an oxide matrix can contain numerous interface defects. These defects strongly affect the nanocrystals’ photoluminescence efficiency and optical absorption. Dangling‐bond defects are nearly eliminated by H₂ passivation, thus decreasing absorption below the quantum‐confined bandgap and enhancing PL efficiency by an order of magnitude. However, there remain numerous other defects seen in absorption by photothermal deflection spectroscopy; these defects cause non‐radiative recombination that limits the PL efficiency to <15%. Using atomistic pseudopotential simulations, we attribute these defects to two specific types of distorted bonds: Si‐Si and bridging Si‐O‐Si bonds between two Si atoms at the nanocrystal surface.     

Self-Assemblies of Fe3O4 Nanocrystals: Toward Nanoscale Precision of Photothermal Effects in the Tumor Microenvironment

Fe₃O₄ nanocrystals are self-assembled into two different conformations: colloidosome and supraball that confer them with distinct properties determining their photo-induced heating capacities. These self-assemblies are assessed for photothermal therapy, an adjuvant strategy for tumor therapy. The tumor microenvironment is a heterogeneous ecosystem including immune cells and the extracellular matrix. The interactions between photothermal therapy agents and the different components of the tumor microenvironment determine the outcome of this therapy. In this study, the fate of both colloidosomes and supraballs within the tumor microenvironment in comparison to their Fe₃O₄ nanocrystal building blocks is revealed. This study highlights how these two hybrid self-assemblies target different compartments of the tumor microenvironment and trigger local photothermal damages that are inaccessible for isolated nanocrystals and not predicted by global temperature measurements.     

CoFe2O4 Nanocrystals Mediated Crystallization Strategy for Magnetic Functioned ZSM‐5 Catalysts

Zeolites have many applications in the petrochemical and fine chemical industry and their functionalization does expand the spectrum of potentials. However, the integration of functional nanocrystals into zeolite frameworks with controlled size, dispersion, and crystallization behavior still remains a significant challenge. Here, a new synthesis of magnetic functioned ZSM‐5 zeolite catalysts via a CoFe₂O₄ nanocrystal mediated crystallization strategy is reported. It is found that high crystallinity of CoFe₂O₄ nanocrystals results in a well‐dispersed encapsulation of them into a single‐crystal of ZSM‐5 due to non‐further‐grown nanocrystals during the fast ZSM‐5 growth. On the contrary, low crystallinity of CoFe₂O₄ nanocrystals leads to the polycrystalline zeolite growth due to the secondary growth of nanocrystals accompanied by the zeolite crystallization and large lattice mismatch between them. The successful encapsulation of small CoFe₂O₄ nanocrystals (≈4 nm) into single crystals lies on the preattachment of them into solid silica gel. During the growth of ZSM‐5 crystals, no secondary growth of nanocrystals happens and its motion is restricted. The encapsulation of magnetic CoFe₂O₄ nanocrystals not only endows magnetic function into zeolites for the first time, but also does not impact catalytic performance of ZSM‐5 in acetalization of cyclohexanone with methanol, which is highly promising in catalytic industries.     

Coupling Ferroelectric to colloidal Nanocrystals as a Generic Strategy to Engineer the Carrier Density Landscape

The design of infrared nanocrystals-based (NCs) photodiodes faces a major challenge related to the identification of barriers with a well-suited band alignment or strategy to finely control the carrier density. Here, this study explores a general complementary approach where the carrier density control is achieved by coupling an NC layer to a ferroelectric material. The up-and-down change in ferroelectric polarization directly impacts the NC electronic structure, resulting in the formation of a lateral pn junction. This effect is uncovered directly using nano X-ray photoemission spectroscopy, which shows a relative energy shift of 115 meV of the NC photoemission signal over the two different up- and down-polarized ferroelectric regions, a shift as large as the open circuit value obtained in the diode stack. The performance of this pn junction reveals enhanced responsivity and reduced noise that lead to a factor 40 increase in the detectivity value.     

Stable Alignment of Tautomers at Room Temperature in Porphyrin 2D Layers

A major challenge in molecular electronics is to develop logic devices based on a truly intramolecular switching mechanism. Recently, a new type of molecular device has been proposed where the switching characteristic is mediated by the bistability in the position of the two hydrogen atoms which can occupy different, energetically equivalent positions (tautomerization) in the inner cavity of porphyrins and naphthalocyanines. Up to now, such a reaction has only been exploited at low temperatures and induced or detected through atomic scale manipulation. In addition, the unpredictability of the tautomer orientation currently excludes molecular interconnection to functional electronic circuits. Here, full evidence is provided that, following a newly proposed growth strategy, 2D layers of metal‐free tetraphenylporphyrins (H₂TPP) show frozen tautomerization even at room temperature on macroscopic domains, with the H atoms aligned along a direction settled a priori. This behavior is ascribed to the buckling of the molecule, anchored to the substrate, which removes the degeneracy between the two tautomer alignments. On this basis, a new way to exploit uniaxially oriented H₂TPP tautomers in a first elementary logic device is proposed.     

Induced SER‐Activity in Nanostructured Ag–Silica–Au Supports via Long‐Range Plasmon Coupling

A novel Ag–silica–Au hybrid device is developed that displays a long‐range plasmon transfer of Ag to Au leading to enhanced Raman scattering of molecules largely separated from the optically excited Ag surface. A nanoscopically rough Ag surface is coated by a silica spacer of variable thickness from ～1 to 21 nm and a thin Au film of ～25 nm thickness. The outer Au surface is further functionalized by a self‐assembled monolayer (SAM) for electrostatic binding of the heme protein cytochrome c (Cyt c) that serves as a Raman probe and model enzyme. High‐quality surface‐enhanced resonance Raman (SERR) spectra are obtained with 413 nm excitation, demonstrating that the enhancement results exclusively from excitation of Ag surface plasmons. The enhancement factor is estimated to be 2 × 10⁴–8 × 10³ for a separation of Cyt c from the Ag surface by 28–47 nm, corresponding to an attenuation of the enhancement by a factor of only 2–6 compared to Cyt c adsorbed directly on a SAM‐coated Ag electrode. Upon immobilization of Cyt c on the functionalized Ag–silica–Au device, the native structure and redox properties are preserved as demonstrated by time‐ and potential‐dependent SERR spectroscopy.     

Compositional dependence of Raman frequencies in SixGe1-x alloys

正Increases in Si content and the calculated Raman spectra acquired from the Si_xGe_(1-x) alloys reveal that the frequencies of the Ge-Si and Si-Si modes are up-shifted obviously,meanwhile that of the Ge-Ge optical mode is down-shifted,which is strongly dependent on their microstructural changes.The linear decrease and increase caused by their force constant(bond lengths and bond angles) changes,which can be used as a fingerprint to identify the average Si content.The complex microstructural changes induced by increasing Si content can be clearly displayed by Raman spectra transformation.     

Lattice Dynamics,Phonon Chirality,and Spin–Phonon Coupling in 2D Itinerant Ferromagnet Fe3GeTe2

Fe₃GeTe₂ has emerged as one of the most fascinating van der Waals crystals due to its 2D itinerant ferromagnetism, topological nodal lines, and Kondo lattice behavior. However, lattice dynamics, chirality of phonons, and spin–phonon coupling in this material, which set the foundation for these exotic phenomena, have remained unexplored. Here, the first experimental investigation of the phonons and mutual interactions between spin and lattice degrees of freedom in few‐layer Fe₃GeTe₂ is reported. The results elucidate three prominent Raman modes at room temperature: two A_1g(Γ) and one E_2g(Γ) phonons. The doubly degenerate E_2g(Γ) mode reverses the helicity of incident photons, indicating the pseudoangular momentum and chirality. Through analysis of temperature‐dependent phonon energies and lifetimes, which strongly diverge from the anharmonic model below Curie temperature, the spin–phonon coupling in Fe₃GeTe₂ is determined. Such interaction between lattice oscillations and spin significantly enhances the Raman susceptibility, allowing to observe two additional Raman modes at the cryogenic temperature range. In addition, laser radiation‐induced degradation of Fe₃GeTe₂ in ambient conditions and the corresponding Raman fingerprint is revealed. The results provide the first experimental analysis of phonons in this novel 2D itinerant ferromagnet and their applicability for further fundamental studies and application development.     

Evidence for the Band‐Edge Exciton of CuInS2 Nanocrystals Enables Record Efficient Large‐Area Luminescent Solar Concentrators

Ternary I‐III‐VI₂ nanocrystals (NCs), such as CuInS₂, are receiving attention as heavy‐metals‐free materials for solar cells, luminescent solar concentrators (LSCs), LEDs, and bio‐imaging. The origin of the optical properties of CuInS₂ NCs are however not fully understood. A recent theoretical model suggests that their characteristic Stokes‐shifted and long‐lived luminescence arises from the structure of the valence band (VB) and predicts distinctive optical behaviours in defect‐free NCs: the quadratic dependence of the radiative decay rate and the Stokes shift on the NC radius. If confirmed, this would have crucial implications for LSCs as the solar spectral coverage ensured by low‐bandgap NCs would be accompanied by increased re‐absorption losses. Here, by studying stoichiometric CuInS₂ NCs, it is revealed for the first time the spectroscopic signatures predicted for the free band‐edge exciton, thus supporting the VB‐structure model. At very low temperatures, the NCs also show dark‐state emission likely originating from enhanced electron‐hole spin interaction. The impact of the observed optical behaviours on LSCs is evaluated by Monte Carlo ray‐tracing simulations. Based on the emerging device design guidelines, optical‐grade large‐area (30×30 cm²) LSCs with optical power efficiency (OPE) as high as 6.8% are fabricated, corresponding to the highest value reported to date for large‐area devices.     

光声喇曼效应中光束的空间耦合与几何匹配

推导出在两束高斯光束作用下相干喇曼跃迁几率的空间分布函数，讨论了聚焦作用以及泵浦光束和斯托克斯光束间的空间耦合、几何参数匹配对光声喇曼信号的影响。结果表明，光声喇曼光谱（PARS）信号主要产生于两激光束焦面附近的相互作用区域；当两光束的共焦参数相等时，喇曼转换效率最高，随着两光束几何参数失匹配茺的增加，RARS信号将减弱。另外，光束间的空间耦合需要精确调整以获得最佳的PARS信号输出，尤其是横向偏差的影响特别敏感。     

Low-Voltage Magnetoelectric Coupling in Fe0.5Rh0.5/0.68PbMg1/3Nb2/3O3-0.32PbTiO3 Thin-Film Heterostructures

The rapid development of computing applications demands novel low-energy consumption devices for information processing. Among various candidates, magnetoelectric heterostructures hold promise for meeting the required voltage and power goals. Here, a route to low-voltage control of magnetism in 30 nm Fe_0.5Rh_0.5/100 nm 0.68PbMg_1/3Nb_2/3O₃-0.32PbTiO₃ (PMN-PT) heterostructures is demonstrated wherein the magnetoelectric coupling is achieved via strain-induced changes in the Fe_0.5Rh_0.5 mediated by voltages applied to the PMN-PT. We describe approaches to achieve high-quality, epitaxial growth of Fe_0.5Rh_0.5 on the PMN-PT films and, a methodology to probe and quantify magnetoelectric coupling in small thin-film devices via studies of the anomalous Hall effect. By comparing the spin-flop field change induced by temperature and external voltage, the magnetoelectric coupling coefficient is estimated to reach ≈7 × 10⁻⁸ s m⁻¹ at 325 K while applying a −0.75 V bias.     

Cr_2O_3掺杂对钡硼硅微晶玻璃的性能影响

采用固相合成法制备了高膨胀系数钡硼硅微晶玻璃材料。通过对该微晶玻璃进行X线衍射仪(XRD)、扫描电子显微镜(SEM)测试分析研究铬掺杂对BaO-B2O3-SiO2力、热、电性能及微观机理的影响。结果显示,热膨胀系数与介电损耗随Cr2O3含量增加而增大,研究表明,加入Cr2O3会促进该体系晶粒的生长,并促使晶相由石英晶相转变为方石英晶相,方石英热膨胀系数较高,其晶相含量增多导致热膨胀系数增大。该体系Cr2O3质量分数为0.5%时,制备出具有较高热膨胀系数(18.44×10-6/℃),较高抗弯强度(187 MPa),较低相对介电常数(5.5)的封装材料。     

Core/Shell Perovskite Nanocrystals: Synthesis of Highly Efficient and Environmentally Stable FAPbBr3/CsPbBr3 for LED Applications

Lead halide perovskite nanocrystals (PeNCs) are promising materials for applications in optoelectronics. However, their environmental instability remains to be addressed to enable their advancement into industry. Here the development of a novel synthesis method is reported for monodispersed PeNCs coated with all inorganic shell of cesium lead bromide (CsPbBr₃) grown epitaxially on the surface of formamidinium lead bromide (FAPbBr₃) NCs. The formed FAPbBr₃/CsPbBr₃ NCs have photoluminescence in the visible range 460–560 nm with narrow emission linewidth (20 nm) and high optical quantum yield, photoluminescence quantum yield (PLQY) up to 93%. The core/shell perovskites have enhanced optical stability under ambient conditions (70 d) and under ultraviolet radiation (50 h). The enhanced properties are attributed to overgrowth of FAPbBr₃ with all‐inorganic CsPbBr₃ shell, which acts as a protective layer and enables effective passivation of the surface defects. The use of these green‐emitting core/shell FAPbBr₃/CsPbBr₃ NCs is demonstrated in light‐emitting diodes (LEDs) and significant enhancement of their performance is achieved compared to core only FAPbBr₃‐LEDs. The maximum current efficiency observed in core/shell NC LED is 19.75 cd A^‐1 and the external quantum efficiency of 8.1%, which are approximately four times and approximately eight times higher, respectively, compared to core‐only devices.     

Evaluation of Zn{N[Si(CH3)3]2}2 as ap-type dopant in OMVPE growth of ZnSe

We have grown nominally undoped ZnSe on GaAs from the precursors H₂Se and Et₂Zn. Replacement of Et₂Zn by Zn[N(TMS)₂]₂ produced crystalline ZnSe of a lesser quality. Data indicate incorporation of nitrogen into the films when Et₂Zn is utilized as the main zinc source with Zn[N(TMS)₂]₂ being introduced at dopant levels. Characterization techniques employed include NMR, XRD, SIMS, SEM, PL, RGA, GC/MS, and Raman spectroscopy.