Thermally Activated Photoluminescence Induced by Tunable Interlayer Interactions in Naturally Occurring van der Waals Superlattice SnS/TiS2.

van der Waals (vdW) superlattices, comprising different 2D materials aligned alternately by weak interlayer interactions, offer versatile structures for the fabrication of novel semiconductor devices. Despite their potential, the precise control of optoelectronic properties with interlayer interactions remains challenging. Here, we investigate the discrepancies between the SnS/TiS2 superlattice (SnTiS3) and its subsystems by comprehensive characterization and DFT calculations. The disappearance of certain Raman modes suggests that the interactions alter the SnS subsystem structure. Specifically, such structural changes transform the band structure from indirect to direct band gap, causing a strong PL emission (∼2.18 eV) in SnTiS3. In addition, the modulation of the optoelectronic properties ultimately leads to the unique phenomenon of thermally activated photoluminescence. This phenomenon is attributed to the inhibition of charge transfer induced by tunable intralayer strains. Our findings extend the understanding of the mechanism of interlayer interactions in van der Waals superlattices and provide insights into the design of high-temperature optoelectronic devices.

Rational design of bimetallic MBene for efficient electrocatalytic nitrogen reduction.

Electrocatalytic nitrogen reduction reaction (NRR) is one of the most promising approaches to achieving green and efficient NH3 production. However, the designs of efficient NRR catalysts with high activity and selectivity still are severely hampered by inherent linear scaling relations among the adsorption energies of NRR intermediates. Herein, the properties of ten M3B4 type MBenes have been initially investigated for efficient N2 activation and reduction to NH3via first-principles calculations. We highlight that Cr3B4 MBene possesses remarkable NRR activity with a record-low limiting potential (-0.13 V). Then, this work proposes descriptor-based design principles that can effectively evaluate the catalytic activity of MBenes, which have been further employed to design bimetallic M2M'B4 MBenes. As a result, 5 promising candidates including Ti2YB4, V2YB4, V2MoB4, Nb2YB4, and Nb2CrB4 with excellent NRR performance have been extracted from 20 bimetallic MBenes. Further analysis illuminates that constructing bimetallic MBenes can selectively tune the adsorption strength of NHNH2** and NH2NH2**, and break the linear scaling relations between their adsorption energies, rendering them ideal for NRR. This work not only pioneers the application of MBenes as efficient NRR catalysts but also proposes rational design principles for boosting their catalytic performance.

An autotransferable alloy overlayer toward stable sodium metal anodes.

Sodium (Na) metal anodes receive significant attention due to their high theoretical specific energy and cost-effectiveness. However, the high reactivity of Na foil anodes and the irregular surfaces have posed challenges to the operability and reliability of Na metals in battery applications. In the absence of inert environmental protection conditions, constructing a uniform, dense, and sodiophilic Na metal anode surface is crucial for homogenizing Na deposition, but remains less-explored. Herein, we fabricated a Tin (Sn) nanoparticle-assembled film conforming to separator pores, which provided ample space for accommodating volumetric expansion during the Na alloying process. Subsequently, a seamless Na-Sn alloy overlayer was formed and transferred onto the Na foil during Na plating through a separator-assisted technique, thereby overcoming conventional operational limitations of metallic Na. As compared to traditional volumetrically expanded cracked ones, the present autotransferable, highly sodiophilic, ion-conductive, and seamless Na-Sn alloy overlayer serves as uniform nucleation sites, thereby reducing nucleation and diffusion barriers and facilitating the compact deposition of metallic Na. Consequently, the autotransferable alloy layer enables a high average Coulombic efficiency of 99.9 % at 3.0 mA cm-2 and 3.0 mAh cm-2 in the half cells as well as minimal polarization overpotentials in symmetric cells, both during prolonged cycling 1200 h. Furthermore, the assembled Na||Sn-1.0h-PP||Na3V2(PO4)3@C@CNTs full cell delivers high capacity retention of 97.5 % after 200 cycles at a high cathodic mass loading.

2D Lateral Heterojunction Arrays with Tailored Interface Band Bending.

Two-dimensional (2D) lateral heterojunction arrays, characterized by well-defined electronic interfaces, hold significant promise for advancing next-generation electronic devices. Despite this potential, the efficient synthesis of high-density lateral heterojunctions with tunable interfacial band alignment remains a challenging. Here, a novel strategy is reported for the fabrication of lateral heterojunction arrays between monolayer Si2Te2 grown on Sb2Te3 (ML-Si2Te2@Sb2Te3) and one-quintuple-layer Sb2Te3 grown on monolayer Si2Te2 (1QL-Sb2Te3@ML-Si2Te2) on a p-doped Sb2Te3 substrate. The site-specific formation of numerous periodically arranged 2D ML-Si2Te2@Sb2Te3/1QL-Sb2Te3@ML-Si2Te2 lateral heterojunctions is realized solely through three epitaxial growth steps of thick-Sb2Te3, ML-Si2Te2, and 1QL-Sb2Te3 films, sequentially. More importantly, the precisely engineering of the interfacial band alignment is realized, by manipulating the substrate's p-doping effect with lateral spatial dependency, on each ML-Si2Te2@Sb2Te3/1QL-Sb2Te3@ML-Si2Te2 junction. Atomically sharp interfaces of the junctions with continuous lattices are observed by scanning tunneling microscopy. Scanning tunneling spectroscopy measurements directly reveal the tailored type-II band bending at the interface. This reported strategy opens avenues for advancing lateral epitaxy technology, facilitating practical applications of 2D in-plane heterojunctions.

Z-scheme Al2SeTe/GaSe and Al2SeTe/InS van der Waals heterostructures for photocatalytic water splitting.

Designing Z-scheme van der Waals (vdW) heterostructured photocatalysts is a promising strategy for developing highly efficient overall water splitting. Herein, by employing density functional theory calculations, we systematically investigated the stability, electronic structures, photocatalytic and optical properties of Al2SeTe, GaSe, and InS monolayers and their corresponding vdW heterostructures. Interestingly, electronic structures show that all vdW heterostructures have direct band gaps, which is conducive to the transition of electrons from the valence band to the conduction band. Notably, Al2TeSe/GaSe and Al2TeSe/InS vdW heterostructures possess large overpotentials for Z-scheme photocatalytic water splitting, as proved by the results of band edge positions and band structure bending. Moreover, these vdW heterostructures exhibit good optical absorption in ultraviolet and visible light regions. We believe that our findings will open a new avenue for the modulation and development of Al2TeSe/GaSe and Al2TeSe/InS vdW heterostructures for photocatalytic water splitting.

Tailoring Li Deposition by Regulating Structural Connectivity of Electrochemical Li Reservoir in Li-metal Batteries.

Irregular Li deposition is the major reason for poor reversibility and cycle instability in Li metal batteries, even leading to safety hazards, the causes of which have been extensively explored. The structural disconnection induced by completely dissolving Li in the traditional testing protocol is a key factor accounting for irregular Li growth during the subsequent deposition process. Herein, the critical role played by the structural connectivity of electrochemical Li reservoir in subsequent Li deposition behaviors is elucidated and a morphology-performance correlation is established. The structural connection and resultant well-distributed morphology of the in situ electrochemical Li reservoir ensure efficient electron transfer and Li+ diffusion pathway, finally leading to homogenized Li nucleation and growth. Tailoring the geometry of Li reservoir can improve the coulombic efficiency and cyclability of anode-free Li metal batteries by optimizing Li deposition behavior.

Design principles of heterointerfacial redox chemistry for highly reversible lithium metal anode.

High electrochemical reversibility is required for the application of high-energy-density lithium (Li) metal batteries; however, inactive Li formation and SEI (solid electrolyte interface)-instability-induced electrolyte consumption cause low Coulombic efficiency (CE). The prior interfacial chemical designs in terms of alloying kinetics have been used to enhance the CE of Li metal anode; however, the role of its redox chemistry at heterointerfaces remains a mystery. Herein, the relationship between heterointerfacial redox chemistry and electrochemical transformation reversibility is investigated. It is demonstrated that the lower redox potential at heterointerface contributes to higher CE, and this enhancement in CE is primarily due to the regulation of redox chemistry to Li deposition behavior rather than the formation of SEI films. Low oxidation potential facilitates the formation of the surface with the highly electrochemical binding feature after Li stripping, and low reduction potential can maintain binding ability well during subsequent Li plating, both of which homogenize Li deposition and thus optimize CE. In particular, Mg hetero-metal with ultra-low redox potential enables Li metal anode with significantly improved CE (99.6%) and stable cycle life for 700 cycles at 3.0 mA cm-2. This work provides insight into the heterointerfacial design principle of next-generation negative electrodes for highly reversible metal batteries.

Contact engineering for 2D Janus MoSSe/metal junctions.

The flourish of two-dimensional (2D) materials provides a versatile platform for building high-performance electronic devices in the atomic thickness regime. However, the presence of the high Schottky barrier at the interface between the metal electrode and the 2D semiconductors, which dominates the injection and transport efficiency of carriers, always limits their practical applications. Herein, we show that the Schottky barrier can be controllably lifted in the heterostructure consisting of Janus MoSSe and 2D vdW metals by different means. Based on density functional theory calculations and machine learning modelings, we studied the electrical contact between semiconducting monolayer MoSSe and various metallic 2D materials, where a crossover from Schottky to Ohmic/quasi-Ohmic contact is realized. We demonstrated that the band alignment at the interface of the investigated metal-semiconductor junctions (MSJs) deviates from the ideal Schottky-Mott limit because of the Fermi-level pinning effects induced by the interface dipoles. Besides, the effect of the thickness and applied biaxial strain of MoSSe on the electronic structure of the junctions are explored and found to be powerful tuning knobs for electrical contact engineering. It is highlighted that using the sure-independence-screening-and-sparsifying-operator machine learning method, a general descriptor WM3/exp(Dint) was developed, which enables the prediction of the Schottky barrier height for different MoSSe-based MSJ. These results provide valuable theoretical guidance for realizing ideal Ohmic contacts in electronic devices based on the Janus MoSSe semiconductors.

Experimental Realization of Monolayer α-Tellurene.

2D materials emerge as a versatile platform for developing next-generation devices. The experimental realization of novel artificial 2D atomic crystals, which does not have bulk counterparts in nature, is still challenging and always requires new physical or chemical processes. Monolayer α-tellurene is predicted to be a stable 2D allotrope of tellurium (Te), which has great potential for applications in high-performance field-effect transistors. However, the synthesis of monolayer α-tellurene remains elusive because of its complex lattice configuration, in which the Te atoms are stacked in tri-layers in an octahedral fashion. Here, a self-assemble approach, using three atom-long Te chains derived from the dynamic non-equilibrium growth of an a-Si:Te alloy as building blocks, is reported for the epitaxial growth of monolayer α-tellurene on a Sb2 Te3 substrate. By combining scanning tunneling microscopy/spectroscopy with density functional theory calculations, the surface morphology and electronic structure of monolayer α-tellurene are revealed and the underlying growth mechanism is determined. The successful synthesis of monolayer α-tellurene opens up the possibility for the application of this new single-element 2D material in advanced electronic devices.

Breaking linear scaling relations by strain engineering on MXene for boosting N2 electroreduction.

The development of N2 reduction reaction (NRR) electrocatalysts with excellent activity and selectivity is of great significance, but adsorption-energy linear scaling relations between reaction intermediates severely hamper the realization of this aspiration. Here, we propose an elegant strain engineering strategy to break the linear relations in NRR to promote catalytic activity and selectivity. Our results show that the N-N bond lengths of adsorbed N2 with side-on and end-on configurations exhibit opposite variations under strains, which is illuminated by establishing two different N2 activation mechanisms of "P-P" (Pull-Pull) and "E-E" (Electron-Electron). Then, we highlight that strain engineering can break the linear scaling relations in NRR, selectively optimizing the adsorption of key NH2NH2** and NH2* intermediates to realize a lower limiting potential (UL). Particularly, the catalytic activity-selectivity trade-off of NRR on MXene can be circumvented, resulting in a low UL of -0.25 V and high Faraday efficiency (FE), which is further elucidated to originate from the strain-modulated electronic structures. Last but not least, the catalytic sustainability of MXene under strain has been guaranteed. This work not only provides fundamental insights into the strain effect on catalysis but also pioneers a new avenue toward the rational design of superior NRR catalysts.

Magnetic-ferroelectric synergic control of multilevel conducting states in van der Waals multiferroic tunnel junctions towards in-memory computing.

van der Waals (vdW) multiferroic tunnel junctions (MFTJs) based on two-dimensional materials have gained significant interest due to their potential applications in next-generation data storage and in-memory computing devices. In this study, we construct vdW MFTJs by employing monolayer Mn2Se3 as the spin-filter tunnel barrier, TiTe2 as the electrodes and In2S3 as the tunnel barrier to investigate the spin transport properties based on first-principles quantum transport calculations. It is highlighted that apparent tunneling magnetoresistance (TMR) and tunneling electroresistance (TER) effects with a maximum TMR ratio of 6237% and TER ratio of 1771% can be realized by using bilayer In2S3 as the tunnel barrier under finite bias. Furthermore, the physical origin of the distinguished TMR and TER effects is unraveled from the k||-resolved transmission spectra and spin-dependent projected local density of states analysis. Interestingly, four distinguishable conductance states reveal the implementation of four-state nonvolatile data storage using one MFTJ unit. More importantly, in-memory logic computing and multilevel data storage can be achieved at the same time by magnetic switching and electrical control, respectively. These results shed light on vdW MFTJs in the applications of in-memory computing as well as multilevel data storage devices.

Tailoring Broadband Nonlinear Optical Characteristics and Ultrafast Photocarrier Dynamics of Bi2 O2 S Nanosheets by Defect Engineering.

Low-dimensional bismuth oxychalcogenides have shown promising potential in optoelectronics due to their high stability, photoresponse, and carrier mobility. However, the relevant studies on deep understanding for Bi2 O2 S is quite limited. Here, comprehensive experimental and computational investigations are conducted in the regulated band structure, nonlinear optical (NLO) characteristics, and carrier dynamics of Bi2 O2 S nanosheets via defect engineering, taking O vacancy (OV) and substitutional Se doping as examples. As the OV continuously increased to ≈35%, the optical bandgaps progressively narrow from ≈1.21 to ≈0.81 eV and NLO wavelengths are extended to near-infrared regions with enhanced saturable absorption. Simultaneously, the relaxation processes are effectively accelerated from tens of picoseconds to several picoseconds, as the generated defect energy levels can serve as both additional absorption cross-sections and fast relaxation channels supported by theoretical calculations. Furthermore, substitutional Se doping in Bi2 O2 S nanosheets also modulate their optical properties with the similar trends. As a proof-of-concept, passively mode-locked pulsed lasers in the ≈1.0 µm based on the defect-rich samples (≈35% OV and ≈50% Se-doping) exhibit excellent performance. This work deepens the insight of defect functions on optical properties of Bi2 O2 S nanosheets and provides new avenues for designing advanced photonic devices based on low-dimensional bismuth oxychalcogenides.

Predicted superconductivity in one-dimensional A3Hf2B3-type electrides.

Inorganic electrides are considered potential superconductors due to the unique properties of their anionic electrons. However, most electrides require external high-pressure conditions to exhibit considerable superconducting transition temperatures (Tc). Therefore, searching for superconducting electrides under low or moderate external pressures is of significant research interest and importance. In this work, a series of A3Hf2B3-type compounds (A = Mg, Ca, Sr, Ba; B = Si, Ge, Sn, Pb) were constructed and systematically studied based on density functional theory calculations. According to the analysis of the electronic structures and phonon dispersion spectrums, stable one-dimensional electrides Ca3Hf2Ge3, Ca3Hf2Sn3, and Sr3Hf2Pb3, were screened out. Interestingly, the superconductivity of these electrides were predicted from electron phonon coupling calculations. It is highlighted that Sr3Hf2Pb3 showed the highest Tc, reaching 4.02 K, while the Tc values of Ca3Hf2Ge3 and Ca3Hf2Sn3 were 1.16 K and 1.04 K, respectively. Moreover, the Tc value of Ca3Hf2Ge3 can be increased to 1.96 K under 20 GPa due to the effect of phonon softening. This work enriches the types of superconducting electrides and has important guiding significance for the research on constructing electrides and related superconducting materials.

Enriching 2D transition metal borides via MB XMenes (M = Fe, Co, Ir): Strong correlation and magnetism.

Recently, two-dimensional (2D) FeSe-like anti-MXenes (or XMenes), composed of late d-block transition metal M and p-block nonmetal X elements, have been both experimentally and theoretically investigated. Here, we select three 2D borides FeB, CoB and IrB for a deeper investigation by including strong correlation effects, as a fertile ground for understanding and applications. Using a combination of Hubbard corrected first-principles calculations and Monte Carlo simulations, FeB and CoB are found to be ferro- and anti-ferro magnetic, contrasting with the non-magnetic nature of IrB. The metallic FeB XMene monolayer, superior to most of the MXenes or MBenes, exhibits robust ferromagnetism, driven by intertwined direct-exchange and super-exchange interactions between adjacent Fe atoms. The predicted Curie temperature (TC) of the FeB monolayer via the Heisenberg model reaches an impressive 425 K, with the easy-axis oriented out-of-plane and high magnetic anisotropic energy (MAE). The asymmetry in the spin-resolved transmission spectrum induces a thermal spin current, providing an opportunity for spin filtration. This novel 2D FeB material is expected to hold great promise as an information storage medium and find applications in emerging spintronic devices.

Crystal Engineering of BiVO4 for Photochemical Sensing of H2 S Gas at Ultra-low Concentration.

We report a photochemical bismuth vanadate (BiVO4 ) sensing material, which possesses a large proportion of (110) and (011) facets combined with the additional (111) facets, for the selective detection of ultra-low concentration hydrogen sulfide (H2 S) driven by visible light. Specifically, the obtained octadecahedron BiVO4 (Octa-BiVO4 ) performs a high response value (67) and short response time (47.4 s) to 100 ppm H2 S with good stability for nearly 100 days, as well as undisturbedness by moist air. With the combination of experimental and theoretical calculation results, the adsorption and carrier transfer behaviors of H2 S molecules on the Octa-BiVO4 crystal surface are investigated. By adjusting the ratio of different crystal facets and controlling the facets with characteristic adsorption, we achieve improved anisotropic photoinduced carrier separation and high selectivity for a specific gas. Furthermore, this facial facet engineering can be extended to the synthesis of other sensing materials, offering huge opportunities for fundamental research and technological applications.

Unraveling the Emerging Photocatalytic, Thermoelectric, and Topological Properties of Intercalated Architecture MZX (M = Ga and In; Z = Si, Ge and Sn; X = S, Se, and Te) Monolayers.

The continuous advancements in studying two-dimensional (2D) materials pave the way for groundbreaking innovations across various industries. In this study, by employing density functional theory calculations, we comprehensively elucidate the electronic structures of MZX (M = Ga and In; Z = Si, Ge, and Sn; X = S, Se, and Te) monolayers for their applications in photocatalytic, thermoelectric, and spintronic fields. Interestingly, GaSiS, GaSiSe, InSiS, and InSiSe monolayers are identified to be efficient photocatalysts for overall water splitting with band gaps close to 2.0 eV, suitable band edge positions, and excellent optical harvest ability. In addition, the InSiTe monolayer exhibits a ZT value of 1.87 at 700 K, making it highly appealing for applications in thermoelectric devices. It is further highlighted that GaSnTe, InSnS, and InSnSe monolayers are predicted to be 2D topological insulators (TIs) with bulk band gaps of 115, 54, and 152 meV, respectively. Current research expands the family of 2D GaGeTe materials and establishes a path toward the practical utilization of MZX monolayers in energy conversion and spintronic devices.

Stable Harsh-Temperature Lithium Metal Batteries Enabled by Tailoring Solvation Structure in Ether Electrolytes.

For lithium metal batteries (LMBs), the elevated operating temperature results in severe capacity fading and safety issues due to unstable electrode-electrolyte interphases and electrolyte solvation structures. Therefore, it is crucial to construct advanced electrolytes capable of tolerating harsh environments to ensure stable LMBs. Here, we proposed a stable localized high-concentration electrolyte (LHCE) by introducing the highly solvating power solvent diethylene glycol dimethyl ether (DGDME). Computational and experimental evidence discloses that the original DGDME-LHCE shows favorable features for high-temperature LMBs, including high Li+-binding stability, electro-oxidation resistance, thermal stability, and nonflammability. The tailored solvated sheath structure achieves the preferred decomposition of anions, inducing the stable (cathode and Li anode)/interphases simultaneously, which enables a homogeneous Li plating-stripping behavior on the anode side and a high-voltage tolerance on the cathode side. For the Li||Li cells coupled with DGDME-LHCE, they showcase outstanding reversibility (a long lifespan of exceeding 1900 h). We demonstrate exceptional cyclic stability (∼95.59%, 250 cycles), high Coulombic efficiency (>99.88%), and impressive high-voltage (4.5 V) and high-temperature (60 °C) performances in Li||NCM523 cells using DGDME-LHCE. Our advances shed light on an encouraging ether electrolyte tactic for the Li-metal batteries confronted with stringent high-temperature challenges.

Synergism of Edge Effect and Interlayer Engineering of VS2 on CNFs for Rapid and Precise NO2 Detection.

Although two-dimensional (2D) transition-metal dichalcogenides (TMDs) exhibit attractive prospects for gas-sensing applications, the rapid and precise sensing of TMDs at low loss remains challenging. Herein, a NO2 sensor based on an expanded VS2 (VS2-E)/carbon nanofibers (CNFs) composite (abbreviated as VS2-E-C) with ultrafast response/recovery at a low-loss state is reported. In particular, the impact of the CNF content on the NO2-sensing performance of VS2-E-C was thoroughly explored. Expanded VS2 nanosheets were grafted onto the surface of hollow CNFs, and the combination boosted the charge transport, exposing abundant active edges of VS2, which enhanced the adsorption of NO2 efficiently. The activity of the VS2 edge is further confirmed by stronger NO2 adsorption with a more negative adsorption energy (-3.42 eV) and greater than the basal VS2 surface (-1.26 eV). Moreover, the exposure of rich edges induced the emergence of the expanded interlayers, which promoted the adsorption/desorption of NO2 and the interaction of gas molecules within VS2-E-C. The synergism of edge effect and interlayer engineering confers the VS2-E-C3 sensor with ultrafast response/recovery speed (9/10 s) at 60 °C, high sensitivity (∼2.50 to 15 ppm NO2), good selectivity/stability, and a low detection limit of 23 ppb. The excellent "4S" functions indicate the promising prospect of the VS2-E-C3 sensor for fast and precise NO2 detection at low-loss condition.

Establishing theoretical landscapes for identifying basal plane active sites in MBene toward multifunctional HER, OER, and ORR catalysts.

Exploring multifunctional electrocatalysts to realize efficient hydrogen evolution reaction (HER), oxygen evolution reaction (OER), and oxygen reduction reaction (ORR) is urgently desired for developing novel renewable energy storage and conversion technologies. However, integrating these three merits in one single catalyst remains a big challenge due to the difficulty in balancing the adsorption strengths of multiple reaction intermediates. Herein, through first-principles calculations, we systematically investigated the electrocatalytic activity of M2B2, M3B4, and M4B6 type MBenes (M = Cr, Mn, Fe, Co, and Ni) for multifunctional HER, OER, and ORR. The results indicate that most of the investigated MBenes show outstanding catalytic activity for HER with hydrogen adsorption Gibbs free energy close to the optimal value (0 eV). Thereinto, Ni2B2 and Co3B4 MBenes can be promising multifunctional HER/OER/ORR electrocatalysts, and Fe3B4 MBene is expected to be a promising bifunctional electrocatalyst for HER/ORR. Especially, Ni2B2 MBene is even better than the benchmark RuO2 catalyst with ultralow low overpotentials of 0.26 and 0.30 V for OER and ORR, respectively. Then, we proposed that the overpotentials of OER/ORR can be well described by the varied ΔGOH* on MBene, which has been further illuminated through the d-band center and charge transfer analysis. Importantly, new scaling relations between the adsorption energies of OOH* and O* on MBenes have been established, where ΔGOOH* and ΔGO* possess different slopes versus ΔGOH*, allowing the significantly lower overpotentials of OER and ORR to be achieved. This work provides not only promising multifunctional HER/OER/ORR electrocatalysts but also new scaling relations to achieve the rational design of MBene-based electrocatalysts.

Out-of-plane polarization modulated band alignments inß-In2X3/α-In2X3(X = S and Se) vdW heterostructures.

The construction of two-dimensional (2D) van der Waals (vdW) heterostructures is an effective strategy to overcome the intrinsic disadvantages of individual 2D materials. Herein, by employing first-principles calculations, the electronic structures and potential applications in the photovoltaic field of theß-In2X3/α-In2X3(X = S and Se) vdW heterostructures have been systematically unraveled. Interestingly, the band alignments ofß-In2S3/α-In2S3,ß-In2Se3/α-In2Se3, andß-In2Se3/α-In2S3heterostructures can be transformed from type-I to type-II by switching the polarization direction ofα-In2X3layers. It is highlighted that the light-harvesting ability of theß-In2X3/α-In2X3vdW heterostructures is significantly higher than the corresponding monolayers in nearly the entire visible light region. Interestingly, type-IIß-In2S3/α-In2Se3↓ heterostructure can achieve the power conversion efficiency of 17.9%, where theα-In2Se3layer acts as a donor and theß-In2S3layer displays as the acceptor. The present research not only provides an in-depth understanding that the out-of-plane polarization ofα-In2X3monolayers can efficiently modulate the band edge alignment of theß-In2X3/α-In2X3vdW heterostructures, but also paves the way for the application of these heterostructures in the field of photovoltaics and optoelectronics.