Hexylammonium Acetate-Regulated Buried Interface for Efficient and Stable Perovskite Solar Cells.

Due to current issues of energy-level mismatch and low transport efficiency in commonly used electron transport layers (ETLs), such as TiO2 and SnO2, finding a more effective method to passivate the ETL and perovskite interface has become an urgent matter. In this work, we integrated a new material, the ionic liquid (IL) hexylammonium acetate (HAAc), into the SnO2/perovskite interface to improve performance via the improvement of perovskite quality formed by the two-step method. The IL anions fill oxygen vacancy defects in SnO2, while the IL cations interact chemically with Pb2+ within the perovskite structure, reducing defects and optimizing the morphology of the perovskite film such that the energy levels of the ETL and perovskite become better matched. Consequently, the decrease in non-radiative recombination promotes enhanced electron transport efficiency. Utilizing HAAc, we successfully regulated the morphology and defect states of the perovskite layer, resulting in devices surpassing 24% efficiency. This research breakthrough not only introduces a novel material but also propels the utilization of ILs in enhancing the performance of perovskite photovoltaic systems using two-step synthesis.

Synthesis of two-dimensional MoO2 nanoplatelets and its multistep sulfurization into MoS2.

To control the growth of layered two-dimensional structures, such as transition metal dichalcogenide materials or heterostructures, understanding the growth mechanism is crucial. Here, we report the synthesis of ultra-thin MoO2 nanoplatelets through the sublimation of MoO3. Rhombus MoO2 nanoplatelets with the P21/c space group were characterized using various microscopic and spectroscopic techniques. Introducing sulfur sources into the chemical vapor deposition system also leads to the formation of monoclinic MoO2 nanoflakes due to the incomplete sulfurization of MoO3. With a gradual increase in the vapor concentration of sulfur, MoO3 undergoes stepwise reduction into MoS2/MoO2 and eventually into MoS2. Additionally, utilizing MoO2 as a precursor for Mo sources enables the formation of monolayer MoS2 single crystals. This work provides an effective approach for growing MoO2 nanoplatelets and elucidates the mechanism behind the stepwise sulfurization of MoO3.

Metal Clusters Effectively Adjust the Local Environment of Polymeric Carbon Nitride for Bifunctional Overall Water Splitting.

Compared with single-atom catalysts, clusters not only possess more metal-loadings and stability but also provide flexible active sites to break the linear scaling relationship of multistep reactions. However, exploring precise structure-activity relationships and the synergistic effect between clusters and nanosheets is still in its infancy. Here, based on first-principles and nonequilibrium Green's function simulation, the C2N-supported Fe and Co tetrahedral clusters exhibit remarkable bifunctional catalytic performance with a very low overpotential of hydrogen (0.12 and 0.07 V) /oxygen (0.20 and 0.55 V) evolution reactions (HER/OER), respectively. The C2N-regulated Fe and Co clusters have suitable d-band centers around the Fermi surface for HER. In turn, the Fe and Co clusters activate the subadjacent dual-carbon sites for OER. Simultaneously, the cluster enhances the electronic conductivity of C2N, and the initial current only needs ultralow bias voltage around 0.1-0.4 V. The desired metal cluster regulation strategy offers cost-effective potential for advancing clean energy technology.

Synthesis and Optimization of Cs2B'B″X6 Double Perovskite for Efficient and Sustainable Solar Cells.

Hybrid perovskite materials with high light absorption coefficients, long diffusion lengths, and high mobility have attracted much attention, but their commercial development has been seriously hindered by two major problems: instability and lead toxicity. This has led to lead-free halide double perovskite becoming a prominent competitor in the photovoltaic field. For lead-free double perovskites, Pb2+ can be heterovalent, substituted by non-toxic metal cations as a double perovskite structure, which promotes the flexibility of the composition. However, the four component elements and low solubility in the solvent result in synthesis difficulties and phase impurity problems. And material phase purity and film quality are closely related to the number of defects, which can limit the photoelectric performance of solar cells. Therefore, based on this point, we summarize the synthesis methods of Cs2B'B″X6 double perovskite crystals and thin films. Moreover, in the application of solar cells, the existing research mainly focuses on the formation process of thin films, band gap adjustment, and surface engineering to improve the quality of films and optimize the performance of devices. Finally, we propose that Cs2B'B″X6 lead-free perovskites offer a promising pathway toward developing highly efficient and stable perovskite solar cells.

Facile construction of a sulfur vacancy defect-decorated CoSx@In2S3 core/shell heterojunction for efficient visible-light-driven photocatalytic hydrogen evolution.

Photoinduced electron-separation and -transport processes are two independent crucial factors for determining the efficiency of photocatalytic hydrogen production. Herein, a sulfur vacancy defect-decorated CoSx@In2S3 (CoSx@VS-In2S3) core/shell heterojunction photocatalyst was synthesized via an in situ sulfidation method followed by a liquid-phase corrosion process. Photocatalytic hydrogen evolution experiments showed that the CoSx@VS-In2S3 nanohybrids delivered an attractive photocatalytic activity of 4.136 mmol h-1 g-1 under visible-light irradiation, which was 8.23 times higher than that of the pristine In2S3 samples. As expected, VS could enhance the charge-separation efficiency of In2S3 through rearranging the electrons of the In2S3 basal plane, in addition to improving the electron-transfer efficiency, as visually verified by transient absorption spectroscopy. Mechanism studies based on density functional theory calculations confirmed that the In atoms adjacent to VS played a key role in the translation, rotation, and transformation of electrons for water reduction. This scalable strategy focused on defect engineering paves a new avenue for the design and assembly of 2D core/shell heterostructures for efficient and robust water-splitting photocatalysts.

Multilevel resistive switching in stable all-inorganic n-i-p double perovskite memristor.

Memristors are promising information storage devices for commercial applications because of their long endurance and low power consumption. Particularly, perovskite memristors have revealed excellent resistive switching (RS) properties owing to the fast ion migration and solution fabrication process. Here, an n-i-p type double perovskite memristor with "ITO/SnO2/Cs2AgBiBr6/NiOx/Ag" architecture was developed and demonstrated to reveal three resistance states because of the p-n junction electric field coupled with ion migration. The devices exhibited reliable filamentary with an on/off ratio exceeding 50. The RS characteristics remained unchanged after 1000 s read and 300 switching cycles. The synaptic functions were examined through long-term depression and potentiation measurements. Significantly, the device still worked after one year to reveal long-term stability because of the all-inorganic layers. This work indicates a novel idea for designing a multistate memristor by utilizing the p-n junction unidirectional conductivity during the forward and reverse scanning.

Single-Atom Phosphorus Defects Decorated CoP Cocatalyst Boosts Photocatalytic Hydrogen Generation Performance of Cd0.5 Zn0.5 S by Directed Separating the Photogenerated Carriers.

Design and preparation of an efficient and nonprecious cocatalysts, with structural features and functionality necessary for improving photocatalytic performance of semiconductors, remain a formidable challenge until now. Herein, for the first time, a novel CoP cocatalyst with single-atom phosphorus vacancies defects (CoP-Vp ) is synthesized and coupled with Cd0.5 Zn0.5 S to build CoP-Vp @Cd0.5 Zn0.5 S (CoP-Vp @CZS) heterojunctions photocatalysts via a liquid phase corrosion method following by an in suit growth process. The nanohybrids deliver an attractive photocatalytic hydrogen production activity of 2.05 mmol h-1 30 mg-1 under visible-light irradiation, which is 14.66 times higher than that of the pristine ZCS samples. As expected, CoP-Vp further enhances the charge-separation efficiency of ZCS, in addition to the improvement of the electron transfer efficiency, which is confirmed by the ultrafast spectroscopies. Mechanism studies based on density functional theory calculations verify that Co atoms adjacent with single-atom Vp play the key role in translation, rotation, and transformation of electrons for H2 O reduction. This scalable strategy focusing defect engineering provides a new insight into designing the highly active cocatalysts to boost the photocatalytic application.

Ferroelectric polarization effect on the photocatalytic activity of Bi0.9Ca0.1FeO3/CdS S-scheme nanocomposites.

BiFeO3 (BFO), as a kind of narrow band-gap semiconductor material, has gradually emerged advantages in the application of photocatalysis. In this paper, Ca doped BFO nanoparticles Bi0.9Ca0.1FeO3 (BCFO) were prepared by sol-gel method. And BCFO and CdS nanocomposites with two morphologies were obtained by controlling the time of loading CdS under a low temperature liquid phase process. It is found that the band gap becomes narrower after doping Ca into BFO, which is conducive to the absorption of visible light. Among all the samples, the composite of CdS nanowires and BCFO nanoparticles obtained by reaction time of 10 min has the best photocatalytic performance. The degradation rate of Methyl Orange solution was 94% after 90 min under visible light irradiation, which was much higher than that of pure BCFO and CdS. Furthermore, significant enhancement in the degradation rate (100% degradation in 60 min) can be achieved in poled samples after electric polarization process. The highest degradation rate is due to the promoted separation of photogenerated carriers induced by the internal polarization field and the formation of S-scheme heterostructure between BCFO and CdS. Such BCFO-CdS nanocomposites may bring new insights into designing highly efficient photocatalyst.

Spatial Relation Controllable Di-Defects Synergy Boosts Electrocatalytic Hydrogen Evolution Reaction over VSe2 Nanoflakes in All pH Electrolytes.

Defect engineering of transition metal dichalcogenides (TMDCs) is important for improving electrocatalytic hydrogen evolution reaction (HER) performance. Herein, a facile and scalable atomic-level di-defect strategy over thermodynamically stable VSe2 nanoflakes, yielding attractive improvements in the electrocatalytic HER performance over a wide electrolyte pH range is reported. The di-defect configuration with controllable spatial relation between single-atom (SA) V defects and single Se vacancy defects effectively triggers the electrocatalytic HER activity of the inert VSe2 basal plane. When employed as a cathode, this di-defects decorated VSe2 electrocatalyst requires overpotentials of 67.2, 72.3, and 122.3 mV to reach a HER current density of 10 mA cm-2 under acidic, alkaline, and neutral conditions, respectively, which are superior to most previously reported non-noble metal HER electrocatalysts. Theoretical calculations reveal that the reactive microenvironment consists of two adjacent SA Mo atoms with two surrounding symmetric Se vacancies, yielding optimal water dissociation and hydrogen desorption kinetics. This study provides a scalable strategy for improving the electrocatalytic activity of other TMDCs with inert atoms in the basal plane.

Recent Advances in g-C3N4 for the Application of Perovskite Solar Cells.

In this study, graphitic carbon nitride (g-C3N4) was extensively utilized as an electron transport layer or interfacial buffer layer for simultaneously realizing photoelectric performance and stability improvement of perovskite solar cells (PSCs). This review covers the different g-C3N4 nanostructures used as additive and surface modifier layers applied to PSCs. In addition, the mechanism of reducing the defect state in PSCs, including improving the crystalline quality of perovskite, passivating the grain boundaries, and tuning the energy level alignment, were also highlighted in this review. Currently, the power conversion efficiency of PSCs based on modified g-C3N4 has been increased up to 22.13%, and its unique two-dimensional (2D) package structure has enhanced the stability of PSCs, which can remain stable in the dark for over 1500 h. Finally, the potential challenges and perspectives of g-C3N4 incorporated into perovskite-based optoelectronic devices are also included in this review.

Two-dimensional IV-VA3 monolayers with enhanced charge mobility for high-performance solar cells.

High-performance photovoltaics (PVs) constitute a subject of extensive research efforts, in which silicon (Si)-based solar cells (SCs) have been widely commercialized. However, the low carrier mobility of Si-based SCs can limit the effective charge separation, thereby negatively impacting the device performance. Here, via calculating the physicochemical and PV performance based on density functional theory, we demonstrate SCs based on two-dimensional (2D) group IV and V compounds with an AX3 configuration. Firstly, the cleavage energies of AX3 (A = Si, Ge; X = P, As, and Sb) are calculated to be less than 1 J m-2, providing an experimental feasibility to be exfoliated from the corresponding bulk. Secondly, electronic and optical properties have been systematically investigated. To be specific, the band gap of monolayer AX3 falls in the range of 1.11-1.27 eV, which is comparable with that of Si. Significantly, the electron mobility of monolayer AX3 can reach as high as ∼30 000 cm2 V-1 s-1, which is one order of magnitude higher than that of Si. Furthermore, the optical absorbance of monolayer SiAs3, SiP3 and GeAs3 exhibits high coefficients in visible light. Therefore, we believe that our designed AX3-based PV systems with power conversion efficiency of 20% can offer great potential in the application of high-performance two-dimension-based PVs.

Sandwich-Polarized Heterojunction: Efficient Charge Separation and Redox Capability Protection for Photocatalytic Overall Water Splitting.

Photocatalytic overall water splitting is a potential strategy to address energy crisis and environmental issues. However, it remains a great challenge to design an efficient photocatalyst, which not only possesses large spatial separation of photogenerated electrons and holes (PEH) to suppress recombination, but also can preserve the redox capability to drive the reaction. Herein, we design a new type of sandwich-polarized heterojunction by inserting a polarized semiconductor into the interlayer of the conventional photocatalyst. The inserted sublayer with out-of-plane polarization can induce a large electrostatic potential difference between the top and bottom photocatalytic sublayers. Then, the band edges of the top and bottom sublayers can be shifted to form the type II band alignment. Also, the valence band maximum and conduction band minimum will be located on different photocatalytic sublayers to facilitate the spatial separation of PEH. Simultaneously, different from the conventional type II heterojunction that reduces the redox capability, the electrostatic potential difference also acts as an auxiliary booster to offset the reduced redox potential of PEH. Taking the C2N/In2Se3/C2N heterojunction as an example, the polarized In2Se3 effectively promotes the interface transfer of PEH in 1-5 ps and extends the lifetime of PEH to ∼186 ns, which is about six times that of bilayer C2N. Simultaneously, the redox power of C2N is well preserved. Our work offers a promising scheme to advance the photocatalytic overall water splitting.

Internal Interactions between Mixed Bulky Organic Cations on Passivating Defects in Perovskite Solar Cells.

In perovskite solar cells (PSCs), bulky organic cation halide salt additions play a significant role in suppressing nonradiative recombination by passivating intrinsic defects in perovskites. Herein, a passivation treatment is developed by applying mixed bulky cations [guanidinium cation (GA+) and phenylethylammonium cations (PEA+)] as the additive for perovskite thin films. The internal interactions between the two bulky cations could result in lower carrier trap-state densities, a sharper Urbach tail, and better carrier transport in perovskite films in comparison with a control film. As a result, in comparison to the control device, which has a power conversion efficiency (PCE) of 18.92%, the mixed-cation-based device exhibits a dramatic enhancement of PCE of 20.64%. Importantly, after 720 h of storage in an ambient atmosphere with a relative humidity (RH) of 60-80% at room temperature, the mixed-cation-based device retains 62.7% of its original performance, whereas the control devices decay to less than 40% of their original performance.

Tunable magnetoelectric coupling and electrical features in an ultrathin Cr2Si2Te6/In2Se3 heterostructure.

Two-dimensional (2D) van der Waals (vdW) heterostructures based on multiferroic materials have potential applications in novel low-dimensional spintronic devices. In this work, we have investigated a strong magnetoelectric coupling and electrical dependence between single layer (1L) Cr2Si2Te6 and In2Se3. By switching the direction of ferroelectric polarization in In2Se3, we observed a significant magneto-crystalline anisotropy energy (MAE) enhancement of Cr2Si2Te6. The analysis of the spin-resolved orbital-decomposed band structure shows stronger magnetoelectric coupling between the In2Se3 and Cr2Si2Te6 layers. The modulation of the electrical features could also be achieved in the switching of the ferroelectric polarization. Furthermore, the switching of Ohmic-Schottky contacts in the heterojunction with different polarization states was successfully achieved under the effect of strain engineering. Based on these findings, we design a novel 2D ferroelectric-ferromagnetic heterojunction that exploits the controllability and nonvolatility of ferroelectrics to modulate the electrical properties of the device. These findings indicate the high application potential of Cr2Si2Te6/In2Se3 multiferroic heterojunctions in spintronics.

Two-dimensional InSb/GaAs- and InSb/InP-based tandem photovoltaic device with matched bandgap.

The past several years have witnessed remarkable research efforts to develop high-performance photovoltaics (PVs), to curtail the energy crisis by avoiding dependence on traditional fossil fuels. In this regard, there is an urgent need to accelerate research progress on new low-dimensional semiconductors with superior electronic and optical properties. Herein, combining abundant related PV experimental data in the literature and our systematic theoretical calculations, we propose two-dimensional (2D) InSb/GaAs and InSb/InP-based tandem PVs with high solar-to-electric efficiency up to near 30.0%. Firstly, according to first-principles calculations, the stability, electronic and optical properties of single-layer group-III-V materials (XY, X = Ga and In, Y = N, P, As, Sb, and Bi) are systematically introduced. Next, due to the high bandgap (Eg) of GaAs and InP being a perfect match with the low Eg of InSb, InSb/GaAs- and InSb/InP-based tandem PVs are constructed. In addition, the complementary absorption spectra of these two subcells can facilitate the achievement of high tandem power conversion efficiency. Furthermore, we have analyzed in detail the influencing factors for PCE and the physical mechanism of the optimized match between the top and bottom subcells in the tandem configurations. Our designed 2D-semiconductor-based PVs can be expected to bring a new perspective for future commercialized high-efficiency energy devices.

Light-Emitting Artificial Synapses for Neuromorphic Computing.

As the key connecting points in the neuromorphic computing systems, synaptic devices have been investigated substantially in recent years. Developing optoelectronic synaptic devices with optical outputs is becoming attractive due to many benefits of optical signals in systems. Colloidal quantum dots (CQDs) are potential luminescent materials for information displays. Light-emitting diodes based on CQDs have become appealing candidates for optoelectronic synaptic devices. Moreover, light-emitting transistors exhibit great application potential in these synaptic devices. From this perspective, light-emitting artificial synapses were discussed on the basis of these structures in the devices. Their mechanisms, performance, and future development were analysed and prospected in detail.

Direct formation of interlayer exciton in two-dimensional van der Waals heterostructures.

In atomically thin two-dimensional van der Waals (2D vdW) heterostructures, spatially separated interlayer excitons play an important role in the optoelectronic performance and show great potential for the exploration of many-body quantum phenomena. A commonly accepted formation mode for interlayer excitons is via a two-step intralayer exciton transfer mechanism, namely, photo-excited intralayer excitons are initially generated in individual sublayers, and photogenerated electrons and holes are then separated into opposite sublayers based on the type-II band alignment. Herein, we expand the concept of interlayer exciton formation and reveal that bright interlayer excitons can be generated in one step by direct interlayer photoexcitation in 2D vdW heterostructures that have strong interlayer coupling and a short photoexcitation channel. First-principles and many-body perturbation theory calculations demonstrate that indium selenide/antimonene and indium selenide/black phosphorus heterostructures are two promising systems that show an exceptionally large interlayer transition probability (>500 Debye2). This study enriches the understanding of interlayer exciton formation and provides a new avenue to acquiring strong interlayer excitons in artificial 2D vdW heterostructures.

Memristive Artificial Synapses for Neuromorphic Computing.

Neuromorphic computing simulates the operation of biological brain function for information processing and can potentially solve the bottleneck of the von Neumann architecture. This computing is realized based on memristive hardware neural networks in which synaptic devices that mimic biological synapses of the brain are the primary units. Mimicking synaptic functions with these devices is critical in neuromorphic systems. In the last decade, electrical and optical signals have been incorporated into the synaptic devices and promoted the simulation of various synaptic functions. In this review, these devices are discussed by categorizing them into electrically stimulated, optically stimulated, and photoelectric synergetic synaptic devices based on stimulation of electrical and optical signals. The working mechanisms of the devices are analyzed in detail. This is followed by a discussion of the progress in mimicking synaptic functions. In addition, existing application scenarios of various synaptic devices are outlined. Furthermore, the performances and future development of the synaptic devices that could be significant for building efficient neuromorphic systems are prospected.

Room Temperature Processed Double Electron Transport Layers for Efficient Perovskite Solar Cells.

Zinc Oxide (ZnO) has been regarded as a promising electron transport layer (ETL) in perovskite solar cells (PSCs) owing to its high electron mobility. However, the acid-nonresistance of ZnO could destroy organic-inorganic hybrid halide perovskite such as methylammonium lead triiodide (MAPbI3) in PSCs, resulting in poor power conversion efficiency (PCE). It is demonstrated in this work that Nb2O5/ZnO films were deposited at room temperature with RF magnetron sputtering and were successfully used as double electron transport layers (DETL) in PSCs due to the energy band matching between Nb2O5 and MAPbI3 as well as ZnO. In addition, the insertion of Nb2O5 between ZnO and MAPbI3 facilitated the stability of the perovskite film. A systematic investigation of the ZnO deposition time on the PCE has been carried out. A deposition time of five minutes achieved a ZnO layer in the PSCs with the highest power conversion efficiency of up to 13.8%. This excellent photovoltaic property was caused by the excellent light absorption property of the high-quality perovskite film and a fast electron extraction at the perovskite/DETL interface.