Symmetry Breaking and Spin-Orbit Coupling for Individual Vacancy-Induced In-Gap States in MoS2 Monolayers.

Spins confined to point defects in atomically thin semiconductors constitute well-defined atomic-scale quantum systems that are being explored as single-photon emitters and spin qubits. Here, we investigate the in-gap electronic structure of individual sulfur vacancies in molybdenum disulfide (MoS2) monolayers using resonant tunneling scanning probe spectroscopy in the Coulomb blockade regime. Spectroscopic mapping of defect wave functions reveals an interplay of local symmetry breaking by a charge-state-dependent Jahn-Teller lattice distortion that, when combined with strong (≃100 meV) spin-orbit coupling, leads to a locking of an unpaired spin-1/2 magnetic moment to the lattice at low temperature, susceptible to lattice strain. Our results provide new insights into the spin and electronic structure of vacancy-induced in-gap states toward their application as electrically and optically addressable quantum systems.

Near-Unity Emitting, Widely Tailorable, and Stable Exciton Concentrators Built from Doubly Gradient 2D Semiconductor Nanoplatelets.

The strength of electrostatic interactions (EIs) between electrons and holes within semiconductor nanocrystals profoundly affects the performance of their optoelectronic systems, and different optoelectronic devices demand distinct EI strength of the active medium. However, achieving a broad range and fine-tuning of the EI strength for specific optoelectronic applications is a daunting challenge, especially in quasi two-dimensional core-shell semiconductor nanoplatelets (NPLs), as the epitaxial growth of the inorganic shell along the direction of the thickness that solely contributes to the quantum confined effect significantly undermines the strength of the EI. Herein we propose and demonstrate a doubly gradient (DG) core-shell architecture of semiconductor NPLs for on-demand tailoring of the EI strength by controlling the localized exciton concentration via in-plane architectural modulation, demonstrated by a wide tuning of radiative recombination rate and exciton binding energy. Moreover, these exciton-concentration-engineered DG NPLs also exhibit a near-unity quantum yield, high photo- and thermal stability, and considerably suppressed self-absorption. As proof-of-concept demonstrations, highly efficient color converters and high-performance light-emitting diodes (external quantum efficiency: 16.9%, maximum luminance: 43,000 cd/m2) have been achieved based on the DG NPLs. This work thus provides insights into the development of high-performance colloidal optoelectronic device applications.

Thermopressure Coupling Effect Mimicking Natural Graphite Formation to Enhance the Storage K-Ion Performance of Carbonaceous Heterostructures.

Borrowing from natural mechanisms for material design can lead to functional mimicry and improvement. Inspired by graphite formation, a thermopressure coupling strategy under micropressure (<400 Pa) is applied to prepare carbon anodes. A thermopressure response is discovered based on the cellulose precursor. Here, homologous graphene quantum dot/hard carbon (GQD/HC) heterostructures are synthesized. Under 181.4 Pa and 1,200 °C, the product shows a capacity of 310 mAh g-1, while the capacity of the direct carbonization product is only 120 mAh g-1. Prominently, the GQD/HC heterostructure displays marked mechanical strength and flexibility. The experimental and theoretical results illustrate the ion and electron transfer, coordination environment, and electronic states in the GQD/HC heterostructure and elaborate on the origin of the enhanced performance. The thermopressure coupling under micropressure mimics graphite formation, but the heterostructure has better properties than traditional carbon materials. Additionally, micropressure injects new vitality into material research.

2D Material Infrared Photonics and Plasmonics.

Two-dimensional (2D) materials including graphene, transition metal dichalcogenides, black phosphorus, MXenes, and semimetals have attracted extensive and widespread interest over the past years for their many intriguing properties and phenomena, underlying physics, and great potential for applications. The vast library of 2D materials and their heterostructures provides a diverse range of electrical, photonic, mechanical, and chemical properties with boundless opportunities for photonics and plasmonic devices. The infrared (IR) regime, with wavelengths across 0.78 µm to 1000 µm, has particular technological significance in industrial, military, commercial, and medical settings while facing challenges especially in the limit of materials. Here, we present a comprehensive review of the varied approaches taken to leverage the properties of the 2D materials for IR applications in photodetection and sensing, light emission and modulation, surface plasmon and phonon polaritons, non-linear optics, and Smith-Purcell radiation, among others. The strategies examined include the growth and processing of 2D materials, the use of various 2D materials like semiconductors, semimetals, Weyl-semimetals and 2D heterostructures or mixed-dimensional hybrid structures, and the engineering of light-matter interactions through nanophotonics, metasurfaces, and 2D polaritons. Finally, we give an outlook on the challenges in realizing high-performance and ambient-stable devices and the prospects for future research and large-scale commercial applications.

Pressure driven rotational isomerism in 2D hybrid perovskites.

Multilayers consisting of alternating soft and hard layers offer enhanced toughness compared to all-hard structures. However, shear instability usually exists in physically sputtered multilayers because of deformation incompatibility among hard and soft layers. Here, we demonstrate that 2D hybrid organic-inorganic perovskites (HOIP) provide an interesting platform to study the stress-strain behavior of hard and soft layers undulating with molecular scale periodicity. We investigate the phonon vibrations and photoluminescence properties of Ruddlesden-Popper perovskites (RPPs) under compression using a diamond anvil cell. The organic spacer due to C4 alkyl chain in RPP buffers compressive stress by tilting (n = 1 RPP) or step-wise rotational isomerism (n = 2 RPP) during compression, where n is the number of inorganic layers. By examining the pressure threshold of the elastic recovery regime across n = 1-4 RPPs, we obtained molecular insights into the relationship between structure and deformation resistance in hybrid organic-inorganic perovskites.

Inorganic frameworks of low-dimensional perovskites dictate the performance and stability of mixed-dimensional perovskite solar cells.

Mixed-dimensional perovskites containing mixtures of organic cations hold great promise to deliver highly stable and efficient solar cells. However, although a plethora of relatively bulky organic cations have been reported for such purposes, a fundamental understanding of the materials' structure, composition, and phase, along with their correlated effects on the corresponding optoelectronic properties and degradation mechanism remains elusive. Herein, we systematically engineer the structures of bulky organic cations to template low-dimensional perovskites with contrasting inorganic framework dimensionality, connectivity, and coordination deformation. By combining X-ray single-crystal structural analysis with depth-profiling XPS, solid-state NMR, and femtosecond transient absorption, it is revealed that not all low-dimensional species work equally well as dopants. Instead, it was found that inorganic architectures with lesser structural distortion tend to yield less disordered energetic and defect landscapes in the resulting mixed-dimensional perovskites, augmented in materials with a longer photoluminescence (PL) lifetime, higher PL quantum yield (up to 11%), improved solar cell performance and enhanced thermal stability (T80 up to 1000 h, unencapsulated). Our study highlights the importance of designing templating organic cations that yield low-dimensional materials with much less structural distortion profiles to be used as additives in stable and efficient perovskite solar cells.

Reversible Photochromism in ⟨110⟩ Oriented Layered Halide Perovskite.

Extending halide perovskites' optoelectronic properties to stimuli-responsive chromism enables switchable optoelectronics, information display, and smart window applications. Here, we demonstrate a band gap tunability (chromism) via crystal structure transformation from three-dimensional FAPbBr3 to a ⟨110⟩ oriented FAn+2PbnBr3n+2 structure using a mono-halide/cation composition (FA/Pb) tuning. Furthermore, we illustrate reversible photochromism in halide perovskite by modulating the intermediate n phase in the FAn+2PbnBr3n+2 structure, enabling greater control of the optical band gap and luminescence of a ⟨110⟩ oriented mono-halide/cation perovskite. Proton transfer reaction-mass spectroscopy carried out to precisely quantify the decomposition product reveals that the organic solvent in the film is a key contributor to the structural transformation and, therefore, the chromism in the ⟨110⟩ structure. These intermediate n phases (2 ≤ n ≤ ∞) stabilize in metastable states in the FAn+2PbnBr3n+2 system, which is accessible via strain or optical or thermal input. The structure reversibility in the ⟨110⟩ perovskite allowed us to demonstrate a class of photochromic sensors capable of self-adaptation to lighting.

Layered P3-Type K0.4Fe0.1Mn0.8Ti0.1O2 as a Low-Cost and Zero-Strain Electrode Material for both Potassium and Sodium Storage.

Layered transition metal oxides are ideal Na+/K+ host materials due to their high theoretical capacities and appropriate working potentials, and the pursuit of cost-effective and environmentally friendly alternatives with high energy density and structural stability has remained a hot topic. Herein, we design and synthesize a low-cost and zero-strain cathode material, P3-type K0.4Fe0.1Mn0.8Ti0.1O2, which demonstrates superior properties for both potassium and sodium storage. The cathode delivers a reversible potassium storage capacity of 117 mA h g-1 at 20 mA g-1 and a fast rate capability of 71 mA h g-1 at 1000 mA g-1. In situ X-ray diffraction reveals a solid-solution transition with a negligible volume change of 0.5% upon K+ insertion/deinsertion that ensures long cycling stability over 300 cycles. When the material is employed for sodium storage, a spontaneous ion-exchange process with Na+-containing electrolytes occurs. Thanks to the positive effects of the remaining K+ ions that protect the layered structure from collapse as well as expand the interlayer structure, and the resulting K0.12Na0.28Fe0.1Mn0.8Ti0.1O2 demonstrates a high sodium storage capacity of 160 mA h g-1 and superior cycling stability with capacity retention of 81% after 300 cycles as well as fast kinetics.

Formation of Corrugated n = 1 2D Tin Iodide Perovskites and Their Use as Lead-Free Solar Absorbers.

Major strides have been made in the development of materials and devices based around low-dimensional hybrid group 14 metal halide perovskites. Thus far, this work has mostly focused on compounds containing highly toxic Pb, with the analogous less toxic Sn materials being comparatively poorly evolved. In response, the study herein aims to (i) provide insight into the impact of templating cations upon the structure of n = 1 2D tin iodide perovskites (where n refers to the number of contiguous two-dimensional (2D) inorganic layers, i.e., not separated by organic cations) and (ii) examine their potential as light absorbers for photovoltaic (PV) cells. It was discovered through systematic tuning of organic dications that imidazolium rings are able to induce the formation of (110)-oriented materials, including examples of "3 × 3" corrugated Sn-I perovskites. This structural outcome is a consequence of a combination of supramolecular interactions of the two endocyclic N atoms of the imidazolium rings with the Sn-I framework, and the comparatively high tendency of Sn2+ ions to stereochemically express their 5s2 lone pairs . More importantly, the resulting materials feature very short separations between their 2D inorganic layers with iodide-iodide (I···I) contacts as small as 4.174 Å, which is among the shortest ever recorded for 2D tin iodide perovskites. These proximate inorganic distances, combined with the polarizable nature of the imidazolium moiety, eases the separation of photogenerated charge within the materials. This is evident from the measurement of excitonic activation energies as low as 83(10) meV for ImEA[SnI4]. When combined with superior light absorption capabilities relative to their lead congeners, this allowed the fabrication of lead-free solar cells with incident photon-to-current and power conversion efficiencies of up to 70% and 2.26%, respectively, which are among the highest values reported for pure n = 1 2D group 14 metal halide perovskites. In fact, these values are superior to the corresponding lead iodide material, which demonstrates that 2D Sn-based materials have significant potential as less toxic alternatives to their Pb counterparts.

Electronic States Modulation by Coherent Optical Phonons in 2D Halide Perovskites.

Excitonic effects underpin the fascinating optoelectronic properties of 2D perovskites that are highly favorable for photovoltaics and light-emitting devices. Analogous to switching in transistors, manipulating these excitonic properties in 2D perovskites using coherent phonons could unlock new applications. Presently, a detailed understanding of this underlying mechanism remains modest. Herein, the origins of the carrier-phonon coupling in 2D perovskites using transient absorption (TA) spectroscopy are explicated. The exciton fine structure is modulated by coherent optical phonons dominated by the vibrational motion of the PbI6 octahedra via deformation potential. Originating from impulsive stimulated Raman scattering, these coherent vibrations manifest as oscillations in the TA spectrum comprising of the generation and detection processes of coherent phonons. This two-step process leads to a unique pump- and probe-energy dependence of the phonon modulation determined by the imaginary part of the refractive index and its derivative, respectively. The phonon frequency and lattice displacement of the inorganic octahedra are highly dependent on the organic cation. This study injects fresh insights into the exciton-phonon coupling of 2D perovskites relevant for emergent optoelectronics development.

Strong self-trapping by deformation potential limits photovoltaic performance in bismuth double perovskite.

Bismuth-based double perovskite Cs2AgBiBr6 is regarded as a potential candidate for low-toxicity, high-stability perovskite solar cells. However, its performance is far from satisfactory. Albeit being an indirect bandgap semiconductor, we observe bright emission with large bimolecular recombination coefficient (reaching 4.5 ± 0.1 × 10-11 cm3 s-1) and low charge carrier mobility (around 0.05 cm2 s-1 V-1). Besides intermediate Fröhlich couplings present in both Pb-based perovskites and Cs2AgBiBr6, we uncover evidence of strong deformation potential by acoustic phonons in the latter through transient reflection, time-resolved terahertz measurements, and density functional theory calculations. The Fröhlich and deformation potentials synergistically lead to ultrafast self-trapping of free carriers forming polarons highly localized on a few units of the lattice within a few picoseconds, which also breaks down the electronic band picture, leading to efficient radiative recombination. The strong self-trapping in Cs2AgBiBr6 could impose intrinsic limitations for its application in photovoltaics.

In-plane optical anisotropy in ReS2 flakes determined by angle-resolved polarized optical contrast spectroscopy.

Various in-plane anisotropic properties are observed for the layered semiconducting transition metal dichalcogenide (TMD), rhenium disulfide (ReS2) due to its reduced symmetry. The understanding of these unique anisotropic behaviors in ReS2 will promote its applications in optoelectronics. In this work, angle-resolved polarized optical contrast spectroscopy has proved to be an efficient, quantitative, and non-destructive method to probe the optical anisotropy in ReS2 flakes with different thicknesses. The contrast value of ReS2 displays the maximum intensity when the polarization of incident light is along the Re-Re chain direction, while the contrast shows the minimum value when the polarization is perpendicular. An empirical equation for in-plane anisotropic refractive index calculation has been proposed and the angle-resolved polarized optical contrasts of 1-3-layer ReS2 are calculated. The calculation results show good agreements with the experimental observations. This indicates that the proposed equation is indeed appropriate for the quantitative understanding of birefringence and dichroism in ReS2 flakes. Our results not only shed light on the identification of crystal axes in anisotropic materials by using angle-resolved polarized contrast spectroscopy, but also provide quantitative information about anisotropy in anisotropic materials such as ReS2.

New Metallic Ordered Phase of Perovskite CsPbI3 under Pressure.

Pressure-induced electronic structure transition from insulating phase to metal state is a potential new paradigm for halide perovskites. The metallization based on these materials may afford a novel motif toward realizing new electronic properties even superconductivity phenomenon. Herein, how static compression modulates the crystal and electronic structure of typical perovskite semiconductors cesium lead iodine (CsPbI3) by both experimental and theoretical studies is reported. The comprehensive studies discover the insulator-metal transition of CsPbI3 at 39.3 GPa, and reveal the key information behind the electronic transition. The perovskite's precise structural evolution is tracked upon compression, from orthorhombic Pnma phase to monoclinic C2/m structure before the metallic transition. More interestingly, the C2/m phase has the most distorted octahedra and the shortest Pb-I bond length relative to the average bond length that is ever reported in a halide perovskite structure. The electronic transition stems from the structural changes accompanied by the anomalously self-distorted octahedra. These studies show that pressure can significantly alter the structural and electronic properties of these technologically important perovskites.

Improving Polysulfides Adsorption and Redox Kinetics by the Co4 N Nanoparticle/N-Doped Carbon Composites for Lithium-Sulfur Batteries.

Improved conductivity and suppressed dissolution of lithium polysulfides is highly desirable for high-performance lithium-sulfur (Li-S) batteries. Herein, by a facile solvent method followed by nitridation with NH3 , a 2D nitrogen-doped carbon structure is designed with homogeneously embedded Co4 N nanoparticles derived from metal organic framework (MOF), grown on the carbon cloth (MOF-Co4 N). Experimental results and theoretical simulations reveal that Co4 N nanoparticles act as strong chemical adsorption hosts and catalysts that not only improve the cycling performance of Li-S batteries via chemical bonding to trap polysulfides but also improve the rate performance through accelerating the conversion reactions by decreasing the polarization of the electrode. In addition, the high conductive nitrogen-doped carbon matrix ensures fast charge transfer, while the 2D structure offers increased pathways to facilitate ion diffusion. Under the current density of 0.1C, 0.5C, and 3C, MOF-Co4 N delivers reversible specific capacities of 1425, 1049, and 729 mAh g-1 , respectively, and retains 82.5% capacity after 400 cycles at 1C, as compared to the sample without Co4 N (MOF-C) values of 61.3% (200 cycles). The improved cell performance corroborates the validity of the multifunctional design of MOF-Co4 N, which is expected to be a potentially promising cathode host for Li-S batteries.

Pressure-Engineered Structural and Optical Properties of Two-Dimensional (C4H9NH3)2PbI4 Perovskite Exfoliated nm-Thin Flakes.

Resolving the structure-property relationships of two-dimensional (2D) organic-inorganic hybrid perovskites is essential for the development of photovoltaic and photoelectronic devices. Here, pressure (0-10 GPa) was applied to 2D hybrid perovskite flakes mechanically exfoliated from butylammonium lead halide single crystals, (C4H9NH3)2PbI4, from which we observed a series of changes of the strong excitonic emissions in the photoluminescence spectra. By correlating with in situ high-pressure X-ray diffraction results, we examine successfully the relationship between structural modifications in the inorganic PbI42- layer and their excitonic properties. During the transition between Pbca (1b) phase and Pbca (1a) phase at around 0.1 GPa, the decrease in ⟨Pb-I-Pb⟩ bond angle and increase in Pb-I bond length lead to an abrupt blue shift of the excitonic bandgap. The presence of the P21/a phase above 1.4 GPa increases the ⟨Pb-I-Pb⟩ bond angle and decreases the Pb-I bond length, leading to a deep red shift of the excitonic bandgap. The total band gap narrowing of ∼350 meV to 2.03 eV at 5.3 GPa before amorphization, facilitates (C4H9NH3)2PbI4 as a much better solar absorber. Moreover, phase transitions inevitably modify the carrier lifetime of (C4H9NH3)2PbI4, where an initial 150 ps at ambient phase is prolongated to 190 ps in the Pbca (1a) phase along with enhanced photoluminescence (PL), originating from pressure-induced strong radiative recombination of trapped excitons.The onset of P21/a phase shortens significantly the carrier lifetime to 53 ps along with a weak PL emission due to pressure-induced severe lattice distortion and amorphization. High-pressure study on (C4H9NH3)2PbI4 nm-thin flakes may provide insights into the mechanisms for synthetically designing novel 2D hybrid perovskite based photoelectronic devices and solar cells.

Double-Shelled Phosphorus and Nitrogen Codoped Carbon Nanospheres as Efficient Polysulfide Mediator for High-Performance Lithium-Sulfur Batteries.

Lithium-sulfur batteries are regarded as very promising energy storage devices due to their high energy density, low cost, and environmental friendliness; however, their insulating properties and the instability of sulfur-based electrodes impede the practical applications of Li-S batteries. Here, a versatile strategy to synthesize double-shelled nitrogen and phosphorus codoped carbon spheres (NPDSCS) as an efficient sulfur host for Li-S batteries is reported. With strong trapping, good affinity, high adsorption for polysulfides, and the bifunctional catalyzing for sulfur redox processes, the developed NPDSCS cathodes with a high S loading of 72.4% exhibit large specific discharge capacity of 1326 mAh g-1 at 0.1C, high Coulombic efficiency, good rate capability, and excellent cycling performance with a reversible capacity of 814 mAh g-1 at 1C after 500 cycles.

Coherent Spin and Quasiparticle Dynamics in Solution-Processed Layered 2D Lead Halide Perovskites.

Layered 2D halide perovskites with their alternating organic and inorganic atomic layers that form a self-assembled quantum well system are analogues of the purely inorganic 2D transition metal dichalcogenides. Within their periodic structures lie a hotbed of photophysical phenomena such as dielectric confinement effect, optical Stark effect, strong exciton-photon coupling, etc. Detailed understanding into the strong light-matter interactions in these hybrid organic-inorganic semiconductor systems remains modest. Herein, the intricate coherent interplay of exciton, spin, and phonon dynamics in (C6H5C2H4NH3)2PbI4 thin films using transient optical spectroscopy is explicated. New insights into the hotly debated origins of transient spectral features, relaxation pathways, ultrafast spin relaxation via exchange interaction, and strong coherent exciton-phonon coupling are revealed from the detailed phenomenological modeling. Importantly, this work unravels the complex interplay of spin-quasiparticle interactions in these layered 2D halide perovskites with large spin-orbit coupling.

Advanced Energy Storage Devices: Basic Principles, Analytical Methods, and Rational Materials Design.

Tremendous efforts have been dedicated into the development of high-performance energy storage devices with nanoscale design and hybrid approaches. The boundary between the electrochemical capacitors and batteries becomes less distinctive. The same material may display capacitive or battery-like behavior depending on the electrode design and the charge storage guest ions. Therefore, the underlying mechanisms and the electrochemical processes occurring upon charge storage may be confusing for researchers who are new to the field as well as some of the chemists and material scientists already in the field. This review provides fundamentals of the similarities and differences between electrochemical capacitors and batteries from kinetic and material point of view. Basic techniques and analysis methods to distinguish the capacitive and battery-like behavior are discussed. Furthermore, guidelines for material selection, the state-of-the-art materials, and the electrode design rules to advanced electrode are proposed.

High-Pressure-Induced Comminution and Recrystallization of CH3 NH3 PbBr3 Nanocrystals as Large Thin Nanoplates.

High pressure (HP) can drive the direct sintering of nanoparticle assemblies for Ag/Au, CdSe/PbS nanocrystals (NCs). Instead of direct sintering for the conventional nanocrystals, this study experimentally observes for the first time high-pressure-induced comminution and recrystallization of organic-inorganic hybrid perovskite nanocrystals into highly luminescent nanoplates with a shorter carrier lifetime. Such novel pressure response is attributed to the unique structural nature of hybrid perovskites under high pressure: during the drastic cubic-orthorhombic structural transformation at ≈2 GPa, (301) the crystal plane fully occupied by organic molecules possesses a higher surface energy, triggering the comminution of nanocrystals into nanoslices along such crystal plane. Beyond bulk perovskites, in which pressure-induced modifications on crystal structures and functional properties will disappear after pressure release, the pressure-formed variants, i.e., large (≈100 nm) and thin (<10 nm) perovskite nanoplates, are retained and these exhibit simultaneous photoluminescence emission enhancing (a 15-fold enhancement in the photoluminescence) and carrier lifetime shortening (from ≈18.3 ± 0.8 to ≈7.6 ± 0.5 ns) after releasing of pressure from 11 GPa. This pressure-induced comminution of hybrid perovskite NCs and a subsequent amorphization-recrystallization treatment offer the possibilities of engineering the advanced hybrid perovskites with specific properties.

Ordered and Atomically Perfect Fragmentation of Layered Transition Metal Dichalcogenides via Mechanical Instabilities.

Thermoplastic polymers subjected to a continuous tensile stress experience a state of mechanical instabilities, resulting in neck formation and propagation. The necking process with strong localized strain enables the transformation of initially brittle polymeric materials into robust, flexible, and oriented forms. Here we harness the polymer-based mechanical instabilities to control the fragmentation of atomically thin transition metal dichalcogenides (TMDs). We develop a simple and versatile nanofabrication tool to precisely fragment atom-thin TMDs sandwiched between thermoplastic polymers into ordered and atomically perfect TMD nanoribbons in arbitrary directions regardless of the crystal structures, defect content, and original geometries. This method works for a very broad spectrum of semiconducting TMDs with thicknesses ranging from monolayers to bulk crystals. We also explore the electrical properties of the fabricated monolayer nanoribbon arrays, obtaining an on/off ratio of ∼106 for such MoS2 arrays based field-effect transistors. Furthermore, we demonstrate an improved hydrogen evolution reaction with the resulting monolayer MoS2 nanoribbons, thanks to the largely increased catalytic edge sites formed by this physical fragmentation method. This capability not only enriches the fundamental study of TMD extreme and fragmentation mechanics, but also impacts on future developments of TMD-based devices.