Double Superconducting Dome of Quasi Two-Dimensional TaS2 in Non-Centrosymmetric van der Waals Heterostructure.

Two-dimensional van der Waals heterostructures (2D-vdWHs) based on transition metal dichalcogenides (TMDs) provide unparalleled control over electronic properties. However, the interlayer coupling is challenged by the interfacial misalignment and defects, which hinders a comprehensive understanding of the intertwined electronic orders, especially superconductivity and charge density wave (CDW). Here, by using pressure to regulate the interlayer coupling of non-centrosymmetric 6R-TaS2 vdWHs, we observe an unprecedented phase diagram in TMDs. This phase diagram encompasses successive suppression of the original CDW states from alternating H-layer and T-layer configurations, the emergence and disappearance of a new CDW-like state, and a double superconducting dome induced by different interlayer coupling effects. These results not only illuminate the crucial role of interlayer coupling in shaping the complex phase diagram of TMD systems but also pave a new avenue for the creation of a novel family of bulk heterostructures with customized 2D properties.

Exciton engineering of 2D Ruddlesden-Popper perovskites by synergistically tuning the intra and interlayer structures.

Designing two-dimensional halide perovskites for high-performance optoelectronic applications requires deep understanding of the structure-property relationship that governs their excitonic behaviors. However, a design framework that considers both intra and interlayer structures modified by the A-site and spacer cations, respectively, has not been developed. Here, we use pressure to synergistically tune the intra and interlayer structures and uncover the structural modulations that result in improved optoelectronic performance. Under applied pressure, (BA)2(GA)Pb2I7 exhibits a 72-fold boost of photoluminescence and 10-fold increase of photoconductivity. Based on the observed structural change, we introduce a structural descriptor χ that describes both the intra and interlayer characteristics and establish a general quantitative relationship between χ and photoluminescence quantum yield: smaller χ correlates with minimized trapped excitons and more efficient emission from free excitons. Building on this principle, we design a perovskite (CMA)2(FA)Pb2I7 that exhibits a small χ and an impressive photoluminescence quantum yield of 59.3%.

Photophysical Behavior of Triethylmethylammonium Tetrabromoferrate(III) under High Pressure.

The pressure-induced properties of hybrid organic-inorganic ferroelectrics (HOIFs) with tunable structures and selectable organic and inorganic components are important for device fabrication. However, given the structural complexity of polycrystalline HOIFs and the limited resolution of pressure data, resolving the structure-property puzzle has so far been the exception rather than the rule. With this in mind, we present a collection of in situ high-pressure data measured for triethylmethylammonium tetrabromoferrate(III), ([N(C2H5)3CH3][FeBr4]) (EMAFB) by unraveling its flexible physical and photophysical behavior up to 80 GPa. Pressure-driven X-ray diffraction and Raman spectroscopy disclose its soft and reversible structural distortion, creating room for delicate band gap modulation. During compression, orange turns dark red at ∼2 GPa, and further compression results in piezochromism, leading to opaque black, while decompressed EMAFB appears in an orange hue. Assuming that the mechanical softness of EMAFB is the basis for reversible piezochromic control, we present alternations in the electronic landscape leading to a 1.22 eV band narrowing at 20.3 GPa while maintaining the semiconducting character at 72 GPa. EMAFB exhibits an emission enhancement, manifested by an increase of photoluminescence up to 17.3 GPa, correlating with the onsets of structural distortion and amorphization. The stimuli-responsive behavior of EMAFB, exhibiting stress-activated modification of the electronic structure, can enrich the physical library of HOIFs suitable for pressure-sensing technologies.

Pressure-Modulated Anomalous Organic-Inorganic Interactions Enhance Structural Distortion and Second-Harmonic Generation in MHyPbBr3 Perovskite.

Organic-inorganic halide perovskites possess unique electronic configurations and high structural tunability, rendering them promising for photovoltaic and optoelectronic applications. Despite significant progress in optimizing the structural characteristics of the organic cations and inorganic framework, the role of organic-inorganic interactions in determining the structural and optical properties has long been underappreciated and remains unclear. Here, by employing pressure tuning, we realize continuous regulation of organic-inorganic interactions in a lead halide perovskite, MHyPbBr3 (MHy+ = methylhydrazinium, CH3NH2NH2+). Compression enhances the organic-inorganic interactions by strengthening the Pb-N coordinate bonding and N-H···Br hydrogen bonding, which results in a higher structural distortion in the inorganic framework. Consequently, the second-harmonic-generation (SHG) intensity experiences an 18-fold increase at 1.5 GPa, and the order-disorder phase transition temperature of MHyPbBr3 increases from 408 K under ambient pressure to 454 K at the industrially achievable level of 0.5 GPa. Further compression triggers a sudden non-centrosymmetric to centrosymmetric phase transition, accompanied by an anomalous bandgap increase by 0.44 eV, which stands as the largest boost in all known halide perovskites. Our findings shed light on the intricate correlations among organic-inorganic interactions, octahedral distortion, and SHG properties and, more broadly, provide valuable insights into structural design and property optimization through cation engineering of halide perovskites.

Anomalous Charge Transfer from Organic Ligands to Metal Halides in Zero-Dimensional [(C6 H5 )4 P]2 SbCl5 Enabled by Pressure-Induced Lone Pair-π Interaction.

Low-dimensional (low-D) organic metal halide hybrids (OMHHs) have emerged as fascinating candidates for optoelectronics due to their integrated properties from both organic and inorganic components. However, for most of low-D OMHHs, especially the zero-D (0D) compounds, the inferior electronic coupling between organic ligands and inorganic metal halides prevents efficient charge transfer at the hybrid interfaces and thus limits their further tunability of optical and electronic properties. Here, using pressure to regulate the interfacial interactions, efficient charge transfer from organic ligands to metal halides is achieved, which leads to a near-unity photoluminescence quantum yield (PLQY) at around 6.0 GPa in a 0D OMHH, [(C6 H5 )4 P]2 SbCl5 . In situ experimental characterizations and theoretical simulations reveal that the pressure-induced electronic coupling between the lone-pair electrons of Sb3+ and the π electrons of benzene ring (lp-π interaction) serves as an unexpected "bridge" for the charge transfer. Our work opens a versatile strategy for the new materials design by manipulating the lp-π interactions in organic-inorganic hybrid systems.

Manipulating Peierls Distortion in van der Waals NbOX2 Maximizes Second-Harmonic Generation.

Two-dimensional (2D) van der Waals (vdW) materials, featuring relaxed phase-matching conditions and highly tunable optical nonlinearity, endow them with potential applications in nanoscale nonlinear optical (NLO) devices. Despite significant progress, fundamental questions in 2D NLO materials remain, such as how structural distortion affects second-order NLO properties, which call for advanced regulation and in situ diagnostic tools. Here, by applying pressure to continuously tune the displacement of Nb atoms in 2D vdW NbOI2, we effectively modulate the polarization and achieve a 3-fold boost of the second-harmonic generation (SHG) at 2.5 GPa. By introducing a Peierls distortion parameter, λ, we establish a quantitative relationship between λ and SHG intensity. Importantly, we further demonstrate that the SHG enhancement can be achieved under ambient conditions by anionic substitution to tune the distortion in NbO(I1-xBrx)2 (x = 0-1) compounds, where the chemical tailoring simulates the pressure effects on the structural optimization. Consequently, NbO(I0.60Br0.40)2 with λ = 0.17 exhibits a giant SHG of over 2 orders of magnitude higher than that in monolayer WSe2, reaching the record-high value among reported 2D vdW NLO materials. This work unambiguously demonstrates the correlation between Peierls distortion and SHG property and, more broadly, opens new paths for the development of advanced NLO materials by manipulating the structure distortions.

Chirality-Dependent Structural Transformation in Chiral 2D Perovskites under High Pressure.

Chiral perovskites have attracted considerable attention owing to their potential applications in spintronic- and polarization-based optoelectronic devices. However, the structural chirality/asymmetry transfer mechanism between chiral organic ammoniums and achiral inorganic frameworks is still equivocal, especially under extreme conditions, as the systematic structural differences between chiral and achiral perovskites have been rarely explored. Herein, we successfully synthesized a pair of new enantiomeric chiral perovskite (S/R-3PYEA)PbI4 (3PYEA2+ = C5NH5C2H4NH32+) and an achiral perovskite (rac-3PYEA)PbI4. Hydrostatic pressure was used, for the first time, to systematically investigate the differences in the structural evolution and optical behavior between (S/R-3PYEA)PbI4 and (rac-3PYEA)PbI4. At approximately 7.0 GPa, (S/R-3PYEA)PbI4 exhibits a chirality-dependent structural transformation with a bandgap "red jump" and dramatic piezochromism from translucent red to opaque black. Upon further compression, a previously unreported chirality-induced negative linear compressibility (NLC) is achieved in (S/R-3PYEA)PbI4. High-pressure structural characterizations and first-principles calculations demonstrate that pressure-driven homodirectional tilting of homochiral ammonium cations strengthens the interactions between S/R-3PYEA2+ and Pb-I frameworks, inducing the formation of new asymmetric hydrogen bonds N-H···I-Pb in (S/R-3PYEA)PbI4. The enhanced asymmetric H-bonding interactions further break the symmetry of (S/R-3PYEA)PbI4 and trigger a greater degree of in-plane and out-of-plane distortion of [PbI6]4- octahedra, which are responsible for chirality-dependent structural phase transition and NLC, respectively. Nevertheless, the balanced H-bonds incurred by equal proportions of S-3PYEA2+ and R-3PYEA2+ counteract the tilting force, leading to the absence of chirality-dependent structural transition, spectral "red jump", and NLC in (rac-3PYEA)PbI4.

Modulating Charge-Density Wave Order and Superconductivity from Two Alternative Stacked Monolayers in a Bulk 4Hb-TaSe2 Heterostructure via Pressure.

Two-dimensional (2D) van der Waals heterostructures (VDWHs) containing a charge-density wave (CDW) and superconductivity (SC) have revealed rich tunability in their properties, which provide a new route for optimizing their novel exotic states. The interaction between SC and CDW is critical to its properties; however, understanding this interaction within VDWHs is very limited. A comprehensive in situ study and theoretical calculation on bulk 4Hb-TaSe2 VDWHs consisting of alternately stacking 1T-TaSe2 and 1H-TaSe2 monolayers are investigated under high pressure. Surprisingly, the superconductivity competes with the intralayer and adjacent-layer CDW order in 4Hb-TaSe2, which results in substantially and continually boosted superconductivity under compression. Upon total suppression of the CDW, the superconductivity in the individual layers responds differently to the charge transfer. Our results provide an excellent method to efficiently tune the interplay between SC and CDW in VDWHs and a new avenue for designing materials with tailored properties.

Giant Tunability of Charge Transport in 2D Inorganic Molecular Crystals by Pressure Engineering.

The unique intermolecular van der Waals force in emerging two-dimensional inorganic molecular crystals (2DIMCs) endows them with highly tunable structures and properties upon applying external stimuli. Using high pressure to modulate the intermolecular bonding, here we reveal the highly tunable charge transport behavior in 2DIMCs for the first time, from an insulator to a semiconductor. As pressure increases, 2D α-Sb2 O3 molecular crystal undergoes three isostructural transitions, and the intermolecular bonding enhances gradually, which results in a considerably decreased band gap by 25 % and a greatly enhanced charge transport. Impressively, the in situ resistivity measurement of the α-Sb2 O3 flake shows a sharp drop by 5 orders of magnitude in 0-3.2 GPa. This work sheds new light on the manipulation of charge transport in 2DIMCs and is of great significance for promoting the fundamental understanding and potential applications of 2DIMCs in advanced modern technologies.

Reconfiguring band-edge states and charge distribution of organic semiconductor-incorporated 2D perovskites via pressure gating.

Two-dimensional (2D) semiconductor heterostructures are key building blocks for many electronic and optoelectronic devices. Reconfiguring the band-edge states and modulating their interplay with charge carriers at the interface in a continuous manner have long been sought yet are challenging. Here, using organic semiconductor-incorporated 2D halide perovskites as the model system, we realize the manipulation of band-edge states and charge distribution via mechanical-rather than chemical or thermal-regulation. Compression induces band-alignment switching and charge redistribution due to the different pressure responses of organic and inorganic building blocks, giving controllable emission properties of 2D perovskites. We propose and demonstrate a "pressure gating" strategy that enables the control of multiple emission states within a single material. We also reveal that band-alignment transition at the organic-inorganic interface is intrinsically not well resolved at room temperature owing to the thermally activated transfer and shuffling of band-edge carriers. This work provides important fundamental insights into the energetics and carrier dynamics of hybrid semiconductor heterostructures.

Nested order-disorder framework containing a crystalline matrix with self-filled amorphous-like innards.

Solids can be generally categorized by their structures into crystalline and amorphous states with different interactions among atoms dictating their properties. Crystalline-amorphous hybrid structures, combining the advantages of both ordered and disordered components, present a promising opportunity to design materials with emergent collective properties. Hybridization of crystalline and amorphous structures at the sublattice level with long-range periodicity has been rarely observed. Here, we report a nested order-disorder framework (NOF) constructed by a crystalline matrix with self-filled amorphous-like innards that is obtained by using pressure to regulate the bonding hierarchy of Cu12Sb4S13. Combined in situ experimental and computational methods demonstrate the formation of disordered Cu sublattice which is embedded in the retained crystalline Cu framework. Such a NOF structure gives a low thermal conductivity (~0.24 W·m-1·K-1) and a metallic electrical conductivity (8 × 10-6 Ω·m), realizing the collaborative improvement of two competing physical properties. These findings demonstrate a category of solid-state materials to link the crystalline and amorphous forms in the sublattice-scale, which will exhibit extraordinary properties.

New Lead-free Organic-Inorganic Hybrid Semiconductor Single Crystals for a UV-Vis-NIR Broadband Photodetector.

Organic-inorganic hybrid semiconducting (OIHS) materials, which can detect broader spectral regions, are highly desired in several applications including biomedical imaging, night vision, and optical communications. Although lead (Pb)-halide perovskites have reached a mature research stage, high toxicity of Pb hinders their large-scale viability. Tin (Sn)-based perovskites are the most common OIHS broadband light absorbers that replace toxic Pb; however, they are extremely unstable due to the notorious Sn2+ oxidation. Herein, a novel, non-toxic, and solution-processed millimeter-sized OIHS single crystal [Ga(C3H7NO)6](I3)3 has been grown at room temperature. Both the absorption measurement and density functional theory calculations have confirmed a narrow indirect band gap of 1.32 eV. The corresponding photodetector based on this single crystal demonstrated excellent performance including an ultraviolet-visible-near infrared (UV-vis-NIR) response between 325 and 1064 nm, fast response time (trise/tdecay = 3.8 ms/5.4 ms), and profound air storage stability (41 h), thus outperforming most common photodetectors based on Sn-based perovskites. This work not only provides a profound understanding of this novel organic-inorganic single-crystal material but also demonstrates its great potential to realize the high-performance UV-vis-NIR broadband photodetectors.

Pressure-Enhanced Photocurrent in One-Dimensional SbSI via Lone-Pair Electron Reconfiguration.

Understanding the relationships between the local structures and physical properties of low-dimensional ferroelectrics is of both fundamental and practical importance. Here, pressure-induced enhancement in the photocurrent of SbSI is observed by using pressure to regulate the lone-pair electrons (LPEs). The reconfiguration of LPEs under pressure leads to the inversion symmetry broken in the crystal structure and an optimum bandgap according to the Shockley-Queisser limit. The increased polarization caused by the stereochemical expression of LPEs results in a significantly enhanced photocurrent at 14 GPa. Our research enriches the foundational understanding of structure-property relationships by regulating the stereochemical role of LPEs and offers a distinctive approach to the design of ferroelectric-photovoltaic materials.

Improved Polarization in the Sr6 Cd2 Sb6 O7 Se10 Oxyselenide through Design of Lateral Sublattices for Efficient Photoelectric Conversion.

Highly-polarizable materials are favorable for photoelectric conversion due to their efficient charge separation, while precise design of them is still a big challenge. Herein a novel polar oxyselenide, Sr6 Cd2 Sb6 O7 Se10 , is rationally designed. It contains lateral sublattices of polarizable [Sb2 OSe4 ]4- chains and highly-orientated [CdSe3 ]4- chains. The intense polarization was evaluated by significant second-harmonic generation (SHG) signal (maximum: 12.6×AgGaS2 ) in broad spectrum range. The polarization was found to mainly improve the carrier separation with a much longer recombination lifetime (76.5 µs) than that of the nonpolar compound Sr2 Sb2 O2 Se3 (18.0 µs), resulting in better photoelectric performance. The single-crystal photoelectric device exhibited excellent response covering broad spectrum in 500-1000 nm with stable reproducibility. This work provides some new insights into the structure design of highly-polarizable heteroanionic materials for photoelectric conversion.

Synthesis of Two-Dimensional CsPb2X5 (X = Br and I) with a Stable Structure and Tunable Bandgap by CsPbX3 Phase Separation.

Perovskite-related materials with various dimensionalities have attracted sustained attention owing to their extraordinary electronic and optoelectronic properties, but it is still challenging in the synthesis of compounds with desired compositions and structures. Herein, a two-dimensional (2D) CsPb2I5 perovskite has been synthesized by the conversion of CsPbI3 at high-pressure and high-temperature (high P-T) conditions, which is quenchable at ambient conditions. In situ synchrotron X-ray diffraction shows that high-pressure monoclinic CsPbI3 converts into tetragonal CsPb2I5 and cubic CsI at 8.7 GPa upon heating from 644 to 666 K. Keeping the tetragonal structure stable, CsPb2I5 exhibits tunable optical properties with the bandgap changing from ∼2.4 eV at ambient pressure to ∼1.4 eV at 36.9 GPa. Further experiments demonstrate similar structural evolution in the typical three-dimensional CsPbBr3 perovskite into 2D CsPb2Br5 at high P-T conditions, indicating that the conversion of CsPbX3 (X = Br and I) into CsPb2X5 is ubiquitous.

Regulating off-centering distortion maximizes photoluminescence in halide perovskites.

Metal halide perovskites possess unique atomic and electronic configurations that endow them with high defect tolerance and enable high-performance photovoltaics and optoelectronics. Perovskite light-emitting diodes have achieved an external quantum efficiency of over 20%. Despite tremendous progress, fundamental questions remain, such as how structural distortion affects the optical properties. Addressing their relationships is considerably challenging due to the scarcity of effective diagnostic tools during structural and property tuning as well as the limited tunability achievable by conventional methods. Here, using pressure and chemical methods to regulate the metal off-centering distortion, we demonstrate the giant tunability of photoluminescence (PL) in both the intensity (>20 times) and wavelength (>180 nm/GPa) in the highly distorted halide perovskites [CH3NH3GeI3, HC(NH2)2GeI3, and CsGeI3]. Using advanced in situ high-pressure probes and first-principles calculations, we quantitatively reveal a universal relationship whereby regulating the level of off-centering distortion towards 0.2 leads to the best PL performance in the halide perovskites. By applying this principle, intense PL can still be induced by substituting CH3NH3 + with Cs+ to control the distortion in (CH3NH3)1-xCsxGeI3, where the chemical substitution plays a similar role as external pressure. The compression of a fully substituted sample of CsGeI3 further tunes the distortion to the optimal value at 0.7 GPa, which maximizes the emission with a 10-fold enhancement. This work not only demonstrates a quantitative relationship between structural distortion and PL property of the halide perovskites but also illustrates the use of knowledge gained from high-pressure research to achieve the desired properties by ambient methods.

Regulating Exciton-Phonon Coupling to Achieve a Near-Unity Photoluminescence Quantum Yield in One-Dimensional Hybrid Metal Halides.

Low-dimensional hybrid metal halides are emerging as a highly promising class of single-component white-emitting materials for their unique broadband emission from self-trapped excitons (STEs). Despite substantial progress in the development of these metal halides, many challenges remain to be addressed to obtain a better fundamental understanding of the structure-property relationship and realize the full potentials of this class of materials. Here, via pressure regulation, a near 100% photoluminescence quantum yield (PLQY) of broadband emission is achieved in a corrugated 1D hybrid metal halide C5 N2 H16 Pb2 Br6 , which possesses a highly distorted structure with an initial PLQY of 10%. Compression reduces the overlap between STE states and ground state, leading to a suppressed phonon-assisted non-radiative decay. The PL evolution is systematically demonstrated to be controlled by the pressure-regulated exciton-phonon coupling which can be quantified using Huang-Rhys factor S. Detailed studies of the S-PLQY relation for a series of 1D hybrid metal halides (C5 N2 H16 Pb2 Br6 , C4 N2 H14 PbBr4 , C6 N2 H16 PbBr4 , and (C6 N2 H16 )3 Pb2 Br10 ) reveal a quantitative structure-property relationship that regulating S factor toward 28 leads to the maximum emission.

Enhanced Photocurrent of All-Inorganic Two-Dimensional Perovskite Cs2PbI2Cl2 via Pressure-Regulated Excitonic Features.

Pressure processing is efficient to regulate the structural and physical properties of two-dimensional (2D) halide perovskites which have been emerging for advanced photovoltaic and light-emitting applications. Increasing numbers of studies have reported pressure-induced and/or enhanced emission properties in the 2D halide perovskites. However, no research has focused on their photoresponse properties under pressure tuning. It is also unclear how structural change affects their excitonic features, which govern the optoelectronic properties of the halide perovskites. Herein, we report significantly enhanced photocurrents in the all-inorganic 2D perovskite Cs2PbI2Cl2, achieving over 3 orders of magnitude increase at the industrially achievable level of 2 GPa in comparison with its initial photocurrent. Lattice compression effectively regulates the excitonic features of Cs2PbI2Cl2, reducing the exciton binding energy considerably from 133 meV at ambient conditions to 78 meV at 2.1 GPa. Impressively, such a reduced exciton binding energy of 2D Cs2PbI2Cl2 is comparable to the values of typical 3D perovskites (MAPbBr3 and MAPbI3), facilitating the dissociating of excitons into free carriers and enhancing the photocurrent. Further pressurization leads to a layer-sliding-induced phase transition and an anomalous negative linear compression, which has not been observed so far in other halide perovskites. Our findings reveal the dramatically enhanced photocurrents in the 2D halide perovskite by regulating its excitonic features and, more broadly, provide new insights into materials design toward extraordinary properties.

Phase transition mechanism and bandgap engineering of Sb2S3 at gigapascal pressures.

Earth-abundant antimony trisulfide (Sb2S3), or simply antimonite, is a promising material for capturing natural energies like solar power and heat flux. The layered structure, held up by weak van-der Waals forces, induces anisotropic behaviors in carrier transportation and thermal expansion. Here, we used stress as mechanical stimuli to destabilize the layered structure and observed the structural phase transition to a three-dimensional (3D) structure. We combined in situ x-ray diffraction (XRD), Raman spectroscopy, ultraviolet-visible spectroscopy, and first-principles calculations to study the evolution of structure and bandgap width up to 20.1 GPa. The optical band gap energy of Sb2S3 followed a two-step hierarchical sequence at approximately 4 and 11 GPa. We also revealed that the first step of change is mainly caused by the redistribution of band states near the conduction band maximum. The second transition is controlled by an isostructural phase transition, with collapsed layers and the formation of a higher coordinated bulky structure. The band gap reduced from 1.73 eV at ambient to 0.68 eV at 15 GPa, making it a promising thermoelectric material under high pressure.

Pressure-Regulated Dynamic Stereochemical Role of Lone-Pair Electrons in Layered Bi2O2S.

Lone-pair electrons (LPEs) ns2 in subvalent 14 and 15 groups lead to highly anharmonic lattice and strong distortion polarization, which are responsible for the groups' outstanding thermoelectric and optoelectronic properties. However, their dynamic stereochemical role in structural and physical properties is still unclear. Here, by introducing pressure to tune the behavior of LPEs, we systematically investigate the lone-pair stereochemical role in a Bi2O2S. The gradually suppressed LPEs during compression show a nonlinear repulsive electrostatic force, resulting in two anisotropic structural transitions. An orthorhombic-to-tetragonal phase transition happens at 6.4 GPa, caused by the dynamic cation centering. This structural transformation effectively modulates the optoelectronic properties. Further compression beyond 13.2 GPa induces a 2D-to-3D structural transition due to the disappearance of the Bi-6s2 LPEs. Therefore, the pressure-induced LPE reconfiguration dominates these anomalous variations of lattice, electronic, and optical properties. Our findings provide new insights into the materials optimization by regulating the characters of LPEs.