Recent Progress in the Fabrication, Properties, and Devices of Heterostructures Based on 2D Materials

With a large number of researches being conducted on two?dimen?sional(2D) materials, their unique properties in optics, electrics, mechanics, and magnetics have attracted increasing attention. Accordingly, the idea of combining distinct functional 2D materials into heterostructures naturally emerged that pro?vides unprecedented platforms for exploring new physics that are not accessible in a single 2D material or 3D heterostructures. Along with the rapid development of controllable, scalable, and programmed synthesis techniques of high?quality 2D heterostructures, various heterostructure devices with extraordinary performance have been designed and fabricated, including tunneling transistors, photodetectors, and spintronic devices. In this review, we present a summary of the latest progresses in fabrications, properties, and applications of di erent types of 2D heterostruc?tures, followed by the discussions on present challenges and perspectives of further investigations.

Hydrogen Production via Hydrolysis and Alcoholysis of Light Metal-Based Materials:A Review

As an environmentally friendly and high-density energy carrier,hydrogen has been recognized as one of the ideal alternatives for fossil fuels.One of the major challenges faced by“hydrogen economy”is the development of efficient,low-cost,safe and selective hydrogen generation from chemical storage materials.In this review,we summarize the recent advances in hydrogen production via hydrolysis and alcoholysis of light-metal-based materials,such as borohydrides,Mg-based and Al-based materials,and the highly efficient regeneration of borohydrides.Unfortunately,most of these hydrolysable materials are still plagued by sluggish kinetics and low hydrogen yield.While a number of strategies including catalysis,alloying,solution modification,and ball milling have been developed to overcome these drawbacks,the high costs required for the“one-pass”utilization of hydrolysis/alcoholysis systems have ultimately made these techniques almost impossible for practical large-scale applications.Therefore,it is imperative to develop low-cost material systems based on abundant resources and effective recycling technologies of spent fuels for efficient transport,production and storage of hydrogen in a fuel cell-based hydrogen economy.

Spintronics in Two-Dimensional Materials

Spintronics,exploiting the spin degree of electrons as the information vector,is an attractive field for implementing the beyond Complemetary metal-oxide-semiconductor(CMOS)devices.Recently,two-dimensional(2D)materials have been drawing tremendous attention in spintronics owing to their distinctive spin-dependent properties,such as the ultralong spin relaxation time of graphene and the spin-valley locking of transition metal dichalcogenides.Moreover,the related heterostructures provide an unprecedented probability of combining the di erent characteristics via proximity e ect,which could remedy the limitation of individual 2D materials.Hence,the proximity engineering has been growing extremely fast and has made significant achievements in the spin injection and manipulation.Nevertheless,there are still challenges toward practical application;for example,the mechanism of spin relaxation in 2D materials is unclear,and the high-effciency spin gating is not yet achieved.In this review,we focus on 2D materials and related heterostructures to systematically summarize the progress of the spin injection,transport,manipulation,and application for information storage and processing.We also highlight the current challenges and future perspectives on the studies of spintronic devices based on 2D materials.

FLIM as a Promising Tool for Cancer Diagnosis and Treatment Monitoring

Fluorescence lifetime imaging microscopy(FLIM)has been rapidly developed over the past 30 years and widely applied in biomedical engineering.Recent progress in fluorophore-dyed probe design has widened the application prospects of fluorescence.Because fluorescence lifetime is sensitive to microenvironments and molecule alterations,FLIM is promising for the detection of pathological conditions.Current cancer-related FLIM applications can be divided into three main categories:(i)FLIM with autofluorescence molecules in or out of a cell,especially with reduced form of nicotinamide adenine dinucleotide,and flavin adenine dinucleotide for cellular metabolism research;(ii)FLIM with Förster resonance energy transfer for monitoring protein interactions;and(iii)FLIM with fluorophore-dyed probes for specific aberration detection.Advancements in nanomaterial production and efficient calculation systems,as well as novel cancer biomarker discoveries,have promoted FLIM optimization,offering more opportunities for medical research and applications to cancer diagnosis and treatment monitoring.This review summarizes cutting-edge researches from 2015 to 2020 on cancer-related FLIM applications and the potential of FLIM for future cancer diagnosis methods and anti-cancer therapy development.We also highlight current challenges and provide perspectives for further investigation.

Unveiling strain-enhanced moiréexciton localization in twisted van der Waals homostructures

Moirésuperlattices,arising from the controlled twisting of van der Waals homostructures at specific angles,have emerged as a promising platform for quantum emission applications.Concurrently,the manipulation of strain provides a versatile strategy to finely adjust electronic band structures,enhance exciton luminescence efficiency,and establish a robust foundation for two-dimensional quantum light sources.However,the intricate interplay between strain and moirépotential remains partially unexplored.Here,we introduce a meticulously designed fusion of strain engineering and the twisted 2L-WSe_(2)/2L-WSe_(2) homobilayers,resulting in the precise localization of moiréexcitons.Employing low-temperature photoluminescence spectroscopy,we unveil the emergence of highly localized moiré-enhanced emission,characterized by the presence of multiple distinct emission lines.Furthermore,our investigation demonstrates the effective regulation of moirépotential depths through strain engineering,with the potential depths of strained and unstrained regions differing by 91%.By combining both experimental and theoretical approaches,our study elucidates the complex relationship between strain and moirépotential,thereby opening avenues for generating strain-induced moiréexciton single-photon sources.

Effect of layered-coupling in twisted WSe_(2) moiré superlattices

Recently,the discovery of a variety of moiré-related properties in the twisted vertical stacking of two different monolayers has attracted considerable attention.The introduction of small twist angles in transition metal dichalcogenide(TMD)heterostructures leads to the emergence of moirépotentials,which provide a fascinating platform for the study of strong interactions of electrons.While there has been extensive research on moiréexcitons in twisted bilayer superlattices,the capture and study of moiréexcitons in homostructure superlattices with layer-coupling effects remain elusive.Here,we present the observation of moiréexcitons in the twisted 1L-WSe_(2)/1L-WSe_(2)and 1L-WSe_(2)/2L-WSe_(2)homostructures with various layer-coupling interactions.The results reveal that the moirépotential increases(~260%)as the number of underlying layers decreases,indicating the effect of layer coupling on the modulation of the moirépotential.The effects of the temperature and laser power dependence as well as valley polarization on moiréexcitons were further demonstrated,and the crucial spectral features observed were explained.Our findings pave the way for exploring quantum phenomena and related applications of quantum information.

Evidence for interlayer coupling and moiréexcitons in twisted WS_(2)/WS_(2)homostructure superlattices

The formation of moirésuperlattices in twisted van der Waals(vdW)homostructures provides a versatile platform for designing the electronic band structure of two-dimensional(2D)materials.In graphene and transition metal dichalcogenides(TMDs)moirésystems,twist angle has been shown to be a key parameter for regulating the moirésuperlattice.However,the effect of the modulation of the twist angle on moirépotential and interlayer coupling has not been the subject of experimental investigation.Here,we report the observation of the modulation of moirépotential and intralayer excitons in the WS_(2)/WS_(2)homostructure.By accurately adjusting the torsion angle of the homobilayers,the depth of the moirépotential can be modulated.The confinement effect of the moirépotential on the intralayer excitons was further demonstrated by the changing of temperature and valley polarization.Furthermore,we show that a detection of atomic reconstructions by the low-frequency Raman mapping to map out inhomogeneities in moirélattices on a large scale,which endows the uniformity of interlayer coupling.Our results provide insights for an in-depth understanding of the behaviors of moiréexcitons in the twisted van der Waals homostructure,and promote the study of electrical engineering and topological photonics.

Exploring the regulatory effect of stacked layers on moiréexcitons in twisted WSe_(2)/WSe_(2)/WSe_(2)homotrilayer

Moirésuperlattices in van der Waals structures have emerged as a powerful platform for studying the novel quantum properties of two-dimensional materials.The periodic moirépatterns generated by these structures lead to the formation of flat mini-bands,which alter the electronic energy bands of the material.The resulting flat electronic bands can greatly enhance strong correlative interactions between electrons,leading to the emergence of exotic quantum phenomena,including moiréphonons and moiréexcitons.While extensive research has been conducted on the exotic quantum phenomena in twisted bilayers of transition metal dichalcogenides(TMDs),and the regulatory effect of stacked layers on moiréexcitons remains unexplored.In this study,we report the fabrication of a twisted WSe_(2)/WSe_(2)/WSe_(2) homotrilayer with two twist angles and investigate the influence of stacked layers on moiréexcitons.Our experiments reveal multiple moiréexciton splitting peaks in the twisted trilayer,with moirépotential depths of 78 and 112 meV in the bilayer and trilayer homostructures,respectively.We also observed the splitting of the moiréexcitons at 90 K,indicating the presence of a deeper moirépotential in the twisted trilayer.Moreover,we demonstrate that stacked layers can tune the moiréexcitons by manipulating temperature,laser power,and magnetic field.Our results provide a new physical model for studying moirésuperlattices and their quantum properties,which could potentially pave the way for the development of quantum optoelectronics.

Localization-enhanced moiréexciton in twisted transition metal dichalcogenide heterotrilayer superlattices

The stacking of twisted two-dimensional(2D)layered materials has led to the creation of moirésuperlattices,which have become a new platform for the study of quantum optics.The strong coupling of moirésuperlattices can result in flat minibands that boost electronic interactions and generate interesting strongly correlated states,including unconventional superconductivity,Mott insulating states,and moiréexcitons.However,the impact of adjusting and localizing moiréexcitons in Van der Waals heterostructures has yet to be explored experimentally.Here,we present experimental evidence of the localization-enhanced moiréexcitons in the twisted WSe_(2)/WS_(2)/WSe_(2)heterotrilayer with type-II band alignments.At low temperatures,we observed multiple excitons splitting in the twisted WSe_(2)/WS_(2)/WSe_(2)heterotrilayer,which is manifested as multiple sharp emission lines,in stark contrast to the moiréexcitonic behavior of the twisted WSe_(2)/WS_(2)heterobilayer(which has a linewidth 4 times wider).This is due to the enhancement of the two moirépotentials in the twisted heterotrilayer,enabling highly localized moiréexcitons at the interface.The confinement effect of moirépotential on moiréexcitons is further demonstrated by changes in temperature,laser power,and valley polarization.Our findings offer a new approach for localizing moiréexcitons in twist-angle heterostructures,which has the potential for the development of coherent quantum light emitters.

Enhanced valley polarization in WSe_(2)/YIG heterostructures via interfacial magnetic exchange effect

Exploiting the valley degrees of freedom as information carriers provides new opportunities for the development of valleytronics.Monolayer transition metal dichalcogenides(TMDs)with broken space-inversion symmetry exhibit emerging valley pseudospins,making them ideal platforms for studying valley electronics.However,intervalley scattering of different energy valleys limits the achievable degree of valley polarization.Here,we constructed WSe_(2)/yttrium iron garnet(YIG)heterostructures and demonstrated that the interfacial magnetic exchange effect on the YIG magnetic substrate can enhance valley polarization by up to 63%,significantly higher than that of a monolayer WSe_(2)on SiO_(2)/Si(11%).Additionally,multiple sharp exciton peaks appear in the WSe_(2)/YIG heterostructures due to the strong magnetic proximity effect at the magnetic-substrate interface that enhances exciton emission efficiency.Moreover,under the effect of external magnetic field,the magnetic direction of the magnetic substrate enhances valley polarization,further demonstrating that the magnetic proximity effect regulates valley polarization.Our results provide a new way to regulate valley polarization and demonstrate the promising application of magnetic heterojunctions in magneto-optoelectronics.

Valleytronics in transition metal dichalcogenides materials

Valley degree of freedom in the first Brillouin zone of Bloch electrons offers an innovative approach to information storage and quantum computation.Broken inversion symmetry together with the presence of time-reversal symmetry endows Bloch electrons non-zero Berry curvature and orbital magnetic moment,which contribute to the valley Hall effect and optical selection rules in valleytronics.Furthermore,the emerging transition metal dichalcogenides(TMDs)materials naturally become the ideal candidates for valleytronics research attributable to their novel structural,photonic and electronic properties,especially the direct bandgap and broken inversion symmetry in the monolayer.However,the mechanism of inter-valley relaxation remains ambiguous and the complicated manipulation of valley predominantly incumbers the realization of valleytronic devices.In this review,we systematically demonstrate the fundamental properties and tuning strategies(optical,electrical,magnetic and mechanical tuning)of valley degree of freedom,summarize the recent progress of TMD-based valleytronic devices.We also highlight the conclusion of present challenges as well as the perspective on the further investigations in valleytronics.

High-performance polarization-sensitive photodetector based on a few-layered PdSe2 nanosheet

The extraordinary optical and electronic properties of anisotropic two-dimensional materials,such as black phosphorus,ReS2,and GeSe,enable them a promising component of polarization-sensitive photodetectors.However,these applications are significantly limited by the challenges of air-stability,response time,and linearly dichroic ratio.Interestingly,palladium diselenide(PdSe2)with high air stability is an emerging material that has robust in-plane anisotropy induced by its asymmetric pentagonal lattice structure.We have successfully prepared a few-layer PdSe2 using micromechanical exfoliation,and here we demonstrate the strong linear dichroism behavior of PdSe2 by polarization-resolved absorption spectra measurements.Such unique linear dichroism,endows the PdSe2 photodetector powerful ability to detect polarized light.The photodetector based on 5L PdSe2,as tested with polarization-dependent photocurrent mapping,exhibited competitive capability to detect polarized light,achieving a significant photocurrent on/off ratio(>10^2),the quite fast response time(<11 ms)and robust linearly dichroic ratios(/max//min≈1.9 at 532 nm).These results are essential advance in the development of polarization-sensitive photodetector,a crucial step towards opening up a new avenue for the application of 2D optoelectronic devices.

Observation of double indirect interlayer exciton in MoSe_(2)/WSe_(2) heterostructure

Interlayer excitons(IXS)are electron–hole pairs bound in the spatial separation layer by the Coulomb effect,and their lifetime is several orders of magnitude longer than that of direct excitons,providing an essential platform for long-lived exciton devices.The recent emergence of the van der Waals heterostructure(HS),which combines two layers of different transitional metal dichalcogenides(TMDs),has created new opportunities for IX research.Herein,we demonstrate the observation of double indirect interlayer excitons in the MoSe_(2)/WSe_(2)HS using photoluminescence(PL)spectroscopy.The intensities of the two peaks are essentially the same,and the energy difference is 22 meV,which is perfectly in line with the calculation result of density functional theory.Furthermore,the experience of variable excitation power also proves that the splitting of the IXs originates from the conduction band spin-splitting of MoSe_(2).The observation results provide a promising platform for further exploring the new physical properties and optoelectronic phenomena of TMD HS.

PdSe_(2)/MoSe_(2) vertical heterojunction for self-powered photodetector with high performance

Van der Waals’two-dimensional(2D)material heterostructure engineering offers an effective strategy for the design of multifunctional and high-performance optoelectronic devices.However,2D heterostructure photodetectors with a photoconductive effect tend to suffer from high driving source-drain voltages and significant dark noise currents.Herein,a self-powered photodetector with high performance was fabricated based on vertically stacked graphene/MoSe_(2)/PdSe_(2)/graphene heterojunctions through a dry transfer method.The fabricated device displays current rectification characteristics in darkness(on/off ratio>10^(3))and superior photovoltaic behaviors under illumination.In addition,benefitting from the strong built-in field,the Gr/PdSe_(2)/MoSe_(2)/Gr heterojunction photodetector is able to respond to a broad spectrum from visible to near-infrared(NIR)with a remarkable responsivity of 651 mA·W^(−1),a high specific detectivity of 5.29×10^(11) Jones and a fast response speed of 41.7/62.5μs.Moreover,an enhanced responsivity of 1.16 A·W^(−1) has been obtained by a reverse voltage(−1 V)and further evaluation on image recognition has also demonstrated the great application potential of the Gr/MoSe_(2)/PdSe_(2)/Gr heterojunction photodetector.The findings are expected to bring new opportunities for the development of highly sensitive,high-speed and energy-efficient photodetectors for comprehensive applications.

High population and dispersion of pentacoordinated Al~Ⅴ species on the surface of ?ame-made amorphous silica-alumina

Pentacoordinated Al(Al~Ⅴ)species in silica-alumina are promising to promote the formation of acid sites or act as surface defects for tailoring single-atom catalysts.However,pentahedral coordination(Al~Ⅴ)is rarely observed in conventionally prepared silica-alumina.Here,we show that high population and dispersion of Al~Ⅴ species on the surface of amorphous silica-alumina(ASA)can be achieved by means of flame spray pyrolysis.High resolution TEM/EDX,high magnetic-field NMR and DFT calculations are employed to characterize the structure of as-prepared ASAs.Solid-state ^(27)Al multi-quantum MAS NMR experiments show that most of the Al~Ⅴspecies are formed independently from the alumina phase and are accessible for guest molecules on the surface.Upon water adsorption,these Al~Ⅴ species are transformed to Al~Ⅵ species,structurally similar to surface Al~Ⅳ species,as confirmed by DFT calculations.The outstanding catalytic activity of as-synthesized ASA is demonstrated using the in situ H/D exchange reaction with deuterated benzene as an example.The Al~Ⅴ-rich ASA provides a much lower activation energy(～30 kJ/mol)than that reported for zeolite H-ZSM-5(～60 kJ/mol).The superior catalytic performance is attributed to the high Al~Ⅴcontent promoting the surface active sites in ASA.The knowledge gained on the synthesis of Al~Ⅴ-rich ASAs and the nature of aluminum coordination in these materials could pave the way to more efficient silica-alumina based catalysts.

Evidence for moiréintralayer excitons in twisted WSe_(2)/WSe_(2) homobi layer superlattices

Recent advances in twisted van der Waals heterostructure superlattices have emerged as a powerful and attractive platform for exploring novel condensed matter physics due to the interplay between the moirépotential and Coulomb interactions.The moirésuperlattices act as a periodic confinement potential in space to capture interlayer excitons(IXs),resulting in moiréexciton arrays,which provide opportunities for quantum emitters and many-body physics.The observation of moiréIXs in twisted transition-metal dichalcogenide(TMD)heterostructures has recently been widely reported.However,the capture and study of the moiréintralayer excitons based on TMD twisted homobilayer(T-HB)remain elusive.Here,we report the observation of moiréintralayer excitons in a WSe_(2)/WSe_(2) T-HB with a small twist angle by measuring PL spectrum.The multiple split peaks with an energy range of 1.55-1.73 eV are different from that of the monolayer WSe_(2) exciton peaks.The split peaks were caused by the trapping of intralayer excitons via the moirépotential.The confinement effect of the moirépotential on the moiréintralayer excitons was further demonstrated by the changing of temperature,laser power,and valley polarization.Our findings provide a new avenue for exploring new correlated quantum phenomena and their applications.

Enhanced interlayer neutral excitons and trions in MoSe_(2)/MoS_(2)/MoSe_(2)trilayer heterostructure

Van der Waals heterostructures have recently emerged,in which two distinct transitional metal dichalcogenide(TMD)monolayers are stacked vertically to generate interlayer excitons(IXs),offing new opportunites for the design of optoelectronic devices.However,the bilayer heterostructure with type-II band alignment can only produce low quantum yield.Here,we present the observation of interlayer neutral excitons and trions in the MoSe_(2)/MoS_(2)/MoSe_(2)trilayer heterostructure(Tri-HS).In comparison to the 8 K bilayer heterostructure,the addition of a MoSe_(2)layer to the Tri-HS can significantly increase the quantum yield of IXs.It is believed the two symmetrical type-II band alignments formed in the Tri-HS could effectively promote the IX radiation recombination.By analyzing the photoluminescence(PL)spectrum of the IXs at cryogenic temperature and the power dependence,the existence of the interlayer trions was confirmed.Our results provide a promising platform for the development of more efficient optoelectronic devices and the investigation of new physical properties of TMDs.

Observation of interlayer excitons in trilayer type-Ⅱ transition metal dichalcogenide heterostructures

Vertically stacked transition metal dichalcogenide(TMD)heterostructures provide an opportunity to explore optoelectronic properties within the two-dimensional limit.In such structures,spatially indirect interlayer excitons(IXs)can be generated in adjacent layers because of strong Coulomb interactions.However,due to the complexity of the multilayered heterostructure(HS),the capture and study of the IXs in trilayer type-Ⅱ HSs have so far remained elusive.Here,we present the observation of the IXs in trilayer type-Ⅱ staggered band alignment of MoS_(2)/MoSe_(2)/WSe_(2) van der Waals(vdW)HSs by photoluminescence(PL)spectroscopy.The central energy of IX is 1.33 eV,and the energy difference between the extracted double peaks is 23 meV.We confirmed the origin of IX through PL properties and calculations by the density functional theory,we also studied the dependence of the IX emission peak on laser power and temperature.Furthermore,the polarization-resolved PL spectra of HS were also investigated,and the maximum polarizability of the emission peak of WSe_(2) reached 11.40%at 6 K.Our findings offer opportunities for the study of new physical properties of excitons in TMD HSs and therefore are valuable for exploring the potential applications of TMDs in optoelectronic devices.

Dynamic control of moirépotential in twisted WS_(2)-WSe_(2)heterostructures

Moirésuperlattices are formed by a lattice mismatch or twist angle in two-dimensional materials,which can generate periodical moirépotentials leading to strong changes in the band structure,resulting in new quantum phenomena.However,the experimental engineering of in-situ deformation of moiréheterostructures remains deficient.Here,we demonstrate a dynamic local deformation of the twisted heterostructures using a diamond anvil cell(DAC),enabling in-situ dynamic modulation of moirépotential in twisted WS_(2)–WSe_(2)heterostructures at room temperature.Deformation of the twisted heterostructure increases the moirépotential,causing a red shift of the moiréexciton resonance,and observed the red shift of the intralayer exciton resonance up to 16.3 meV(less than 1.1 GPa).The blue shift of the interlayer excitons of twisted WS_(2)–WSe_(2)heterostructures shows an evident transition of the pressure sensitive exciton,induced by the dominant effect of modifying the band structure on optical properties.Combined with the spectral changes of pressurized Raman,which further demonstrated that the DAC can efficiently regulate the interlayer coupling.Our results offer an effective strategy for in-situ dynamic modulation of moirépotential,providing a promising platform for the development of novel quantum devices.