Ultraviolet Photoelectron Spectroscopy Research Articles

Spectroscopic Analysis of Electrical Phenomena and Oxygen Vacancy Generation for Self-Aligned Fully Solution-Processed Oxide Thin-Film Transistors.

This work unveils critical insights through spectroscopic analysis highlighting electrical phenomena and oxygen vacancy generation in self-aligned fully solution-processed oxide thin-film transistors (TFTs). Ar inductively coupled plasma treatment was conducted to fabricate an amorphous indium zinc oxide (a-InZnO) TFT in a self-aligned process. Results showed that the Ar plasma-activated a-InZnO regions became conductive, which means that a homogeneous layer can act as both channel and electrode in the device. Several techniques were employed to probe specific aspects of the source-drain-channel interface in the fully solution-processed TFTs. X-ray absorption near-edge structure and Extended X-ray absorption fine structure were conducted to investigate the existence of oxygen vacancies, which is the main driving factor in inducing a conductive region. X-ray photoelectron spectroscopy was also used to explain the oxygen refilling mechanism. Ultraviolet Photoelectron Spectroscopy was conducted to analyze the valence band maximum and work function. Integration of these results facilitated the construction of the energy band diagram at the interface, wherein a Schottky barrier height of ∼0.37 eV was observed. By leveraging these techniques, insights into the electronic properties and performance of next-generation transistors are gained, enabling their future widespread adoption.

Saturation Mobility of 100 cm2 V-1 s-1 in ZnO Thin-Film Transistors through Quantum Confinement by a Nanoscale In2O3 Interlayer Using Spray Pyrolysis.

In this study, we present a comprehensive study on the fabrication and characterization of heterojunction In2O3/ZnO thin-film transistors (TFTs) aimed at exploiting the quantum confinement effect to enhance device performance. By systematically optimizing the thickness of the crystalline In2O3 (c-In2O3) layer to create a narrow quantum well, we observed a significant increase in saturation mobility (μSAT) from 12.76 to 97.37 cm2 V-1 s-1. This enhancement, attributed to quantum confinement, was achieved through the deposition of a 3 nm c-In2O3 semiconductor via spray pyrolysis. Various In2O3 layer thicknesses (2-5 nm) were obtained by adjusting precursor solution concentration, flow rate, and number of spray cycles. Post annealing treatments were employed to reduce the defects at the interface and within the oxide film, enhancing device stability and performance. Transmission electron microscopy (TEM) confirmed the uniformity of the c-In2O3 film thickness, while variations in thickness significantly influenced TFT performance, particularly the turn-on voltage (VGS) due to changes in the carrier concentration. Ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS) supported the formation of a potential well with a two-dimensional electron gas (2DEG). The study of single and multiple superlattice structures of consecutive c-In2O3 and c-ZnO layers provided insights into the effects of multiple quantum wells on the TFT performance. This research presents an advanced approach to TFT optimization, highlighting high reliability, and environmental and bias stabilities. These lead to enhanced mobility and performance uniformity through the precise control of c-In2O3 layer thickness for the quantum confinement effect.

Dual efficacy of potassium-doping in perovskite solar cells: Reducing hysteresis and boosting open-circuit voltage

The incorporation of potassium into perovskite solar cells (PSCs) has been empirically validated to mitigate hysteresis phenomena and boost the power conversion efficiency (PCE). However, the doping mechanism of potassium ions in the perovskite film and their effect on photocarrier recombination remains a topic of debate. Here, we grew doped MAPbI3: K single crystals by inverse temperature crystallization using KI as a dopant, and then perovskite thin films were spin-coated with dissolved MAPbI3: K crystals as a precursor. The doped MAPbI3: K perovskite films exhibit better crystal quality with large columnar grains and lower defect density. Employing Hall effect, ultraviolet photoelectron spectroscopy, and Kelvin probe force microscopy measurements, we definitively demonstrate that K-doping transforms the conductivity type of the perovskite film from a marginally N-type to a distinct P-type semiconductor. Furthermore, this doping strategy induces a concurrent downward shift in both the conduction band minimum and valence band maximum. As a result, the PCE of the PSCs increases from 15.15% to an impressive 20.66%, and the J–V curve hysteresis almost disappears. Additionally, theoretical simulations using SCAPS-1D software reveal a profound modification in the device's energy band diagram after K+-doping. Specifically, the energy level offset between the perovskite layer and the electron transport layer diminishes from 0.24 to 0.14 eV, with a result of bigger quasi-Fermi energy level splitting. This, in turn, elevates the open-circuit voltage (Voc) of the doped perovskite solar cell, underscoring the profound impact of potassium doping on enhancing PSC performance.

Ultrafast Charge Transfer-Induced Unusual Nonlinear Optical Response in ReSe2/ReS2 Heterostructure.

Ultrafast charge transfer in van der Waals heterostructures can effectively engineer the optical and electrical properties of two-dimensional semiconductors for designing photonic and optoelectronic devices. However, the nonlinear absorption conversion dynamics with the pump intensity and the underlying physical mechanisms in a type-II heterostructure remain largely unexplored, yet hold considerable potential for all-optical logic gates. Herein, two-dimensional ReSe2/ReS2 heterostructure is designed to realize an unusual transition from reverse saturable absorption to saturable absorption (SA) with a conversion pump intensity threshold of approximately 170 GW/cm2. Such an intriguing phenomenon is attributed to the decrease of two-photon absorption (TPA) of ReS2 and the increase of SA of ReSe2 with the pump intensity. Based on the characterization results of X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, femtosecond transient absorption spectrum, Kelvin probe force microscopy, and density functional theory calculation, a type-II charge-transfer-energy level model is proposed combined with the TPA of ReS2 and SA of ReSe2 processes. The results reveal the critical role of ultrafast interfacial charge transfer in tuning the unusual nonlinear absorption and improving the SA of ReSe2/ReS2 under different excitation wavelengths. Our finding deepens the understanding of nonlinear absorption physical mechanisms in two-dimensional heterostructure materials, which may further diversify the nonlinear optical materials and photonic devices.

Engineering of Interface Barrier in Hybrid MXene/GaN Heterostructures for Schottky Diode Applications.

The Fermi level position at the interface of a heterostructure is a critical factor for device functionality, strongly influenced by surface-related phenomena. In this study, contactless electroreflectance (CER) was utilized for the first time to investigate the built-in electric field in MXene/GaN structures with the goal of understanding the carrier transfer across the MXene/GaN interface. Five MXenes with high work functions were examined: Cr2C, Mo2C, V2C, V4C3, and Ti3C2. The physicochemical properties of the MXene/GaN structures were analyzed by using X-ray and UV photoelectron spectroscopies. It was shown that upon the coverage of the GaN surface by all investigated MXenes, a shift in the position of the surface Fermi level occurs, consequently raising the interface barrier. Additionally, the physicochemical stability of MXenes on the GaN surface was studied after annealing the structures at 750 °C. Our findings indicate that the annealing process increases the barrier height and the ionization energies of all studied structures. Furthermore, it has been shown that removing excess MXene material from the surface did not significantly impact the built-in electric field, emphasizing the robust physicochemical stability of the MXenes on the GaN surface. To validate the potential of engineering of MXene/GaN interface barrier, Schottky diodes with MXenes exhibiting the highest barrier height (Mo2C and V2C) were demonstrated.

Rational Doping Strategy to Build the First Solution‐Processed p‐n Homojunction Architecture toward Silicon Quantum Dot Photodetectors

Semiconductor p‐n homojunction is a requisite building block of operating transistors and diodes which make up the modern electronic circuits and optoelectronic applications. However, it has been so far limited to bulk form of single crystals such as silicon (Si) or gallium arsenide. Herein, a brand‐new method of constructing p‐n homojunction architectures that breaks through the limitation is presented. Colloidal inks of p‐type and n‐type Si quantum dots (QDs) are synthesized by thermal disproportionation of (HSiO1.5)n doped with boron or phosphorus, followed by surface ligand engineering. Analysis combining UV photoelectron spectroscopy, electron spin resonance, and current–voltage characteristics confirms that an orthogonal solvent trick makes clean interfaces between n‐type and p‐type SiQD layers without disruption on film formation. The forward and reverse current–voltage characteristics of the diode, along with various spectroscopic characterizations, demonstrate the formation of the first p‐n homojunction of SiQDs. The self‐powered photodiode provides a tunable response specific to the wavelength.

Growth and electronic structure of the nodal line semimetal in monolayer Cu2Si on Cu(111)

Cu2Si, a single-layer two-dimensional material with a honeycomb structure, has been proposed to have Dirac nodal line fermions. In this study, the synchrotron radiation X-ray photoelectron spectroscopy, ultraviolet photoelectron spectroscopy, and angle-resolved photoemission spectroscopy (SR-XPS, SR-UPS, and SR-ARPES) techniques were used to investigate the dynamic process of in situ deposition of single-layer Cu2Si on a Cu(111) crystal surface via molecular beam epitaxy (MBE). Cu2Si existed as a monolayer (ML) alloy, and there were competing mechanisms of distinct chemical states of silicon in different growth periods, according to a detailed examination of the experimental SR-XPS and SR-UPS spectra. Additionally, a weak interaction between the Cu2Si ML and Cu(111) was demonstrated via SR-ARPES and first-principles computations. The unique electronic structure of the Cu2Si ML was not destroyed by either this weak interaction or the disordered silicon produced on the surface during the growth process. The study of the Cu2Si growth kinetics provides a guarantee and a basis for the future exploration of the exotic properties of Cu2Si.

Non-damaged preparation and energy band structure modulation of silicon-based nitrogen-terminated diamond films

The surface terminal structure of diamond film determines its surface physical properties. In this paper, the surface of silicon-based polycrystalline diamond film was nitrided by radio frequency (RF) plasma, and the evolution of the diamond surface termination structure under different nitridation temperatures and times was investigated. In-situ X-ray photoelectron spectroscopy (XPS) analysis showed that nitridation at 600 °C is beneficial for the more effective formation of nitrogen terminal diamond (N-diamond) structure dominated by CN bonds on the diamond surface. In-situ ultraviolet photoelectron spectroscopy (UPS) indicated that the electron affinity of diamond surface can gradually change from negative to positive with prolonged nitridation time. The increased positive electron affinity (PEA) of surface terminations made it more difficult for electrons to escape from the diamond surface, resulting in a significant decrease in the intensity of the secondary electron peak. Furthermore, AFM and Raman measurements indicated that nitridation treatment does not significantly improve the surface roughness of diamond or form graphite phase, which realized the preparation of non-damaged N-diamond.

Is the oxygen plasma cleaning technique indicated for any electrochemical purpose?: The case of FTO electrodes

Fluorine-doped tin oxide (FTO) is among the most used transparent conductive oxides (TCOs) in phototovoltaic devices such as photoelectrochemical and solar cells. Preparation of films on these TCOs can be achieved by several deposition techniques including electrodeposition. Among the several cleaning and activation procedures before a thin film deposition there is the oxygen plasma treatment, which has been successfully applied on several kind of substrate materials. Surprisingly, the use of this step on TCOs previously to the electrodeposition of a film is not a usual practice. Here we present a detailed study on the consequences of oxygen plasma process over FTO electrodes that are subsequently employed in several electrochemical reactions of practical importance. Open circuit potential (OCP) measurements from oxygen plasma treated FTO have proven the resorption of ions and/or solvent molecules in aqueous electrolyte following a pseudo-second order kinetic. Electrochemical reactions were quite sensible to the oxygen plasma treatment, even under mild conditions. In all cases FTO become deactivated for such electrochemical processes independently of the plasma set up employed except for metal electrodeposition. Partial recovering of the electrochemical response of FTO in the ferri/ferro system after annealing at 450 °C explains why oxygen plasma process is worthy only for other deposition techniques such as spray pyrolysis where similar temperatures are employed. Electrochemical Impedance Spectroscopy (EIS) analysis revealed a decrease of the majority carrier density (ND). This is mainly attributed to the oxyanion implantation on oxygen vacancies sites during the plasma process thus explaining the loss of activation of FTO. Energy level diagrams reveal the decrease of degeneracy of FTO towards an n-type semiconducting SnO2 film which is also supported by ultraviolet photoelectron spectroscopy (UPS). A band gap energy dependence with the plasma conditions allowed to check the filling of oxygen vacancies on the FTO surface without discard the loss of fluorine. Anodic polarization in acid media proved the impossibility of oxygen vacancies restitution, being the dominating process the partial etching of FTO.

Deciphering heterojunction layered double hydroxide-polyaniline-carbon nanotubes for phosphorus capture in capacitive deionization

The capacitive deionization (CDI) has emerged as a robust technology due to its effective performance in removing and recovering phosphate in wastewater. However, there are still challenges in achieving fast charge transfer and high capacity phosphorus storage simultaneously. In this study, a layered double hydroxide-polyaniline-carbon nanotubes composite material (ZnFe-PANI/CNT) with heterojunction and pseudocapacitive characteristics was fabricated via a simple and effective precipitation strategy. The existence of heterojunction and pseudocapacitance of ZnFe-PANI/CNT was confirmed through material performance testing Moreover, with its fast charge transfer and high ion storage performance, it was achieved high phosphate adsorption efficiency (94 %) and sustainable electrode regeneration in low concentration phosphate wastewater. Ultraviolet photoelectron spectroscopy (UPS) and density functional theory revealed the ability to accelerate charge transfer, which was contributed by the heterojunction ZnFe-PANI/CNT. In addition, it was found that the synergies of electrostatic attraction, ligand exchange and surface complexation contributed to the high phosphate capture ability in the acidic environments. The binuclear bidentate or mononuclear bidentate structures dominated the surface configuration of phosphate adsorption at pH 4–9.

Effects of Antisolvent Treatment on Copper(I) Thiocyanate Hole Transport Layer in n-i-p Perovskite Solar Cells.

Copper(I) thiocyanate (CuSCN) is considered an efficient HTL of low cost and with high stability in perovskite solar cells (PSCs). However, the diethyl sulfide solvent used for CuSCN preparation is known to cause damage to the underlying perovskite layer in n-i-p PSCs. Antisolvent treatment of CuSCN during spin-coating can effectively minimize interfacial interactions. However, the effects of antisolvent treatment are not sufficiently understood. In this study, the effects of five different antisolvents were investigated. Scanning electron microscopy and X-ray diffraction analyses showed that the antisolvent treatment improved the crystallinity of the CuSCN layer on the perovskite layer and reduced damage to the perovskite layer. However, X-ray and ultraviolet photoelectron spectroscopy analyses showed that antisolvent treatment did not affect the chemical bonds or electronic structures of CuSCN. As a result, the power conversion efficiency of the PSCs was increased from 14.72% for untreated CuSCN to 15.86% for ethyl-acetate-treated CuSCN.

Synergistic effect of graphdiyne (C2H2n-2) based hollow spherical Cu2O/GDY and NiS dual cocatalysts boosting photocatalytic hydrogen evolution

The control of carrier separation morphology and efficiency is a key strategy for preparing high-performance photocatalysts. In this study, Cu2O/graphdiyne was introduced into NiS in the form of hollow nanospheres, creating a novel composite material. This method improved upon the traditional graphdiyne fabrication processes that typically use copper foil. Through the hollow spherical structure, both internal and external surface light scattering and reflection were significantly enhanced, indirectly enhancing the light absorption rate of the photocatalyst and photocatalytic activity. Ultraviolet-visible spectroscopy and photoelectrochemical results showed that using NiS as the external cocatalyst and Cu2O as the internal cocatalyst are the driving factors for the hydrogen evolution reaction, with a synergistic effect that accelerated the reaction. Such synergistic catalytic effects are rare in traditional photocatalytic systems, indicating their potential application value in enhancing catalytic efficiency. The overall performance was more than 22 times that of Cu2O/graphdiyne alone and more than 2.6 times that of NiS. Additionally, the electronic band structures and reaction mechanisms can be elucidated through Density Functional Theory (DFT) calculations, Ultraviolet Photoelectron Spectroscopy (UPS) and UV-Vis spectroscopy. These findings not only offer practical guidance but also underscore the significance of precisely manipulating the components of composite catalysts to optimize performance.

Gate modulation of barrier height of unipolar vertically stacked monolayer ReS2/MoS2 heterojunction

This study investigates vertically stacked CVD grown ReS2/MoS2 unipolar heterostructure device as Field Effect Transistor (FET) device wherein ReS2 on top acts as drain and MoS2 at bottom acts as source. The electrical measurements of ReS2/MoS2 FET device were carried out and variation in Ids (drain current) Vs Vds (drain voltage) for different Vgs (gate voltage) revealing the n-type device characteristics. Furthermore, the threshold voltage was calculated at the gate bias voltage corresponding to maximum transconductance (gm) value which is ~ 12 V. The mobility of the proposed ReS2/MoS2 heterojunction FET device was calculated as 60.97 cm2 V−1 s−1. The band structure of the fabricated vDW heterostructure was extracted utilizing ultraviolet photoelectron spectroscopy and the UV–visible spectroscopy revealing the formation of 2D electron gas (2DEG) at the ReS2/MoS2 interface which explains the high carrier mobility of the fabricated FET. The field effect behavior is studied by the modulation of the barrier height across heterojunction and detailed explanation is presented in terms of the charge transport across the heterojunction.

Comprehensive study of SrF2 growth on highly oriented pyrolytic graphite (HOPG): Temperature-dependent van der Waals epitaxy

This study explores the molecular beam epitaxy (MBE) growth of SrF2 on highly oriented pyrolytic graphite (HOPG) highlighting the temperature-dependent variations in growth morphology, crystalline structure and electronic properties. The comprehensive characterization of SrF2/HOPG interfaces was carried out using atomic force microscopy (AFM), reflection high-energy electron diffraction (RHEED), ultraviolet photoelectron spectroscopy (UPS) and X-ray photoelectron spectroscopy (XPS). The spectroscopy data suggest that the chemical interaction of the fluoride with the substrate is weak at each deposited thickness and temperature of the substrate during the deposition, indicating a growth under a van der Waals epitaxial regime. SrF2 nanostructures deposited on HOPG depict a distinctive bulk-like character, concerning their crystallinity and composition, even at the very initial growth stage. Remarkably, temperature plays a crucial role in driving the growth patterns, moving from coalescence of dendritic islands at room temperature to induce nearly 1D rows along the step-edges of HOPG terraces at higher temperatures (400 °C).

Investigation on the carrier dynamics and energy band of the CVD-grown large area WS2/Bi2O2Se heterostructure

Bismuth oxyselenide (Bi2O2Se) emerged as a prominent member of the quasi-2D layered material family, possesses appealing characteristics for optoelectronic applications including impressive environmental stability and high carrier mobility. Recently, although significant advancements have been made in the initial research on the optoelectronic characteristics of Bi2O2Se-based heterostructures, there remains a lack of comprehensive study on the carrier dynamics and energy band within these structures. In this work, large-area (1 cm × 1 cm) continuous Bi2O2Se and monolayer WS2 films were grown by chemical vapor deposition (CVD) method, and the related WS2/Bi2O2Se heterostructures were successfully constructed. Triple decay processes with lifetimes ofτ1 ∼ 298 ps, τ2∼37 ps andτ3 ∼ 1.58 ns are observed through time-resolved photoluminesce (TRPL), which were attributed to the recombination of neutral excitons, trions, and interlayer excitons, respectively. Then, the energy band structure was investigated through x-ray photoelectron spectroscopy, revealing a type-Ⅱ band alignment at the heterointerface. The valence band offset was 0.19 eV, while conduction band offset was approximately 1.09 eV as confirmed by ultraviolet photoelectron spectroscopy. As a result, the WS2/Bi2O2Se junction enhances charge transfer and interlayer interactions by the aid of interface build-in electric field. These results showcase the potential of integrating Bi2O2Se with other 2D semiconductors to form heterostructures possessing novel charge dynamic behaviors, and provide valuable understanding into the functionality of optoelectronic devices that rely on these 2D heterostructures.

Efficient hole transport layers for silicon heterojunction solar cells by surface plasmonic modification in MoOx/Au NPs/MoOx stacks

This study explores the integration of Au nanoparticles (NPs) into molybdenum oxide (MoOx) thin films to form a MoOx/Au NPs/MoOx (MAM) stack. This stack serves as a hole transport layer (HTL) in silicon heterojunction solar cells, aiming to address the challenges of safety concerns and inefficient carrier transport. Ultraviolet photoelectron spectroscopy and X-ray photoelectron spectroscopy spectra demonstrate that the incorporation of Au NPs notably raises the work function of MAM to 5.85 eV and stabilize Mo6+ concentrations at 94.07%. In addition, Au NPs effectively act as a shield against detrimental interactions with Ag, thereby improving the interfacial stability between the back electrode and HTL. This strategic enhancement facilitates the formation of surface plasmon polaritons, reduces the contact resistance to 41.19 mΩ cm2, and boosts the quantum efficiency by injecting hot electrons and intensifying the surface electric field. These advancements lead to a significant enhancement in the fill factor and short-circuit current, leading to the development of a heterojunction solar cell with an increased efficiency (Eff) from 19.81% to 22.03%. This investigation underscores the transformative potential of engineered nanomaterials in elevating the performance and stability of photovoltaic devices, promoting the wider adoption of renewable energy technologies.

Controlling charge migration and CO2 conversion through surface decoration of 2D-hydrotalcite on bismuth oxybromide for enhanced artificial photosynthesis

Photocatalytic reduction of CO2 in pure H2O media to produce chemicals presents an appealing avenue for simultaneously alleviating energy and environmental crises. However, the rapid recombination of photogenerated charge carriers presents a significant challenge in this promising field. Heterojunction engineering has emerged as an effective approach to address this dilemma. Here, by decorating 2D NiAl-layered double hydroxides (NAL) onto bismuth oxybromide (BOB), we have created a S-scheme heterojunction (N1B1 composite). This catalyst affords CO2-to-CO yields of 102.30 μmol g−1 with a selectivity of 100 %. Ultraviolet photoelectron spectroscopy (UPS) and in-situ irradiated X-ray photoelectron spectroscopy (ISI-XPS) reveal that charge transfer occurs efficiently from BOB to 2D-NAL upon light irradiation. The designed N1B1 heterojunction achieves 7.3-fold and 2.1-fold increase in the internal electric field strength compared to bare 2D-NAL and BOB, respectively, which should be accountable for the improved charge migration. Additionally, pulsed chemisorption and in-situ Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) show the presence of multiple carbonate intermediates with activated OCO bonds upon N1B1 composite, with *CO2− being identified as the most crucial species for CO production.

Investigating Cu-Site Doped Cu-Sb-S Nanoparticles Using Photoelectron and Electron Paramagnetic Resonance Spectroscopy.

Tetrahedrite (Cu12Sb4S13) and famatinite (Cu3SbS4) are good candidates for green energy applications because they possess promising thermoelectric and photovoltaic properties as well as contain earth-abundant and nontoxic constituents. Herein, X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and electron paramagnetic resonance spectroscopy (EPR) methods examined inherent electronic properties and interatomic magnetic interactions of Cu-site doped tetrahedrite and famatinite nanomaterials. An energy-efficient modified polyol method was utilized for the synthesis of tetrahedrite and famatinite nanoparticles doped on the Cu-site with Zn, Fe, Ni, Mn, and Co. This is the first parallel study of tetrahedrite and famatinite nanomaterials with XPS, UPS, and EPR methods alongside a systematic analysis of dopant-dependent effects on the electronic structure and magnetic interactions for each material. XPS showed that the Cu and Sb species in tetrahedrite and famatinite possess different oxidation states, while UPS characterization reveals larger dopant-dependent shifts in the work function for tetrahedrite nanoparticles (4.21 to 4.79 eV) than for famatinite nanoparticles (4.57 to 4.77 eV). Finally, all famatinite nanoparticles display an EPR signal, indicating trace amounts of paramagnetic Cu(II) present below the detection limit of XPS. For tetrahedrite, EPR signatures were observed only for the Zn-doped and Mn-doped nanoparticles, suggesting signal broadening from Cu-Cu spin exchange or spin-lattice relaxation. This study demonstrates the complementary nature of XPS and EPR techniques for studying the oxidation states of metals in solid-state nanomaterials. Comparing the electronic and magnetic properties of tetrahedrite and famatinite while studying the impact of dopant incorporation will guide future endeavors in designing sustainable, high-performance materials for renewable energy applications.

Construction of 2D/2D S-scheme Bi2MoO6/Zn-TCPP heterojunction via in-situ self-assembly growth strategy to enhance interface effect for efficient photocatalytic hydrogen production

Two-dimensional/two-dimensional (2D/2D) heterojunctions are considered to be an effective strategy for forming strong interface effects and facilitating photogenerated carrier separation. However, it is usually limited by the size mismatch of the materials, even at the expense of its redox capability. Herein, 2D/2D S-scheme heterojunction photocatalyst Bi2MoO6/Zn-TCPP (BMO/ZTP) composed of 2D Bi2MoO6 and 2D Zn-TCPP (TCPP: tetrakis (4-carboxyphenyl) porphyrin) (MOFs) was constructed by in-situ self-assembly growth strategy. The size-compatible 2D/2D composites had abundant surface active sites and strong interactions. In addition, band bending and interfacial electric field (IEF) effect based on S-scheme heterojunction could accelerate the separation and migration of photogenerated carriers in BMO/ZTP. The best hydrogen precipitation rate of the BMO/ZTP was 10900.94 umol·g−1·h−1, which was 38.90 and 3.24 times higher than that of Bi2MoO6 (280.26 umol·g−1·h−1) and Zn-TCPP (3360.34 umol·g−1·h−1), respectively. The results indicated that 2D/2D BMO/ZTP S-scheme heterojunction could enhance the interface effect and retain strong reducing electrons to achieve efficient photocatalytic hydrogen production, which was confirmed by ultraviolet photoelectron spectroscopy (UPS), Tafel curve, electron spin resonance (ESR) and time-resolved photoluminescence (TRPL) characterization and density functional theory (DFT) calculations. This work provided a general strategy for constructing 2D Bi2MoO6 and 2D MOFs S-scheme heterojunctions to enhance interface effects for achieving efficient photocatalytic hydrogen production.

Green and solid state reduction of GO monolayers sandwiched between Arachidic acid LB layers

A novel, single step and environment friendly solid state approach for reduction of graphene oxide (GO) monolayers has been demonstrated, in which, arachidic acid/GO/arachidic acid (AA/GO/AA) sandwich structure obtained by Langmuir-Blodgett (LB) technique was heat treated at moderate temperatures to obtain RGO sheets. Heat treatment of AA/GO/AA sandwich structure at 200 °C results in substantial reduction of GO, with concurrent removal of AA molecules. Such developed RGO sheets possess sp2-C content of ∼69 %, O/C ratio of ∼0.17 and significantly reduced I(D)/I(G) ratio of ∼1.1. Ultraviolet photoelectron spectroscopy (UPS) studies on RGO sheets evidenced significant increase in density of states in immediate vicinity of Fermi level and decrease in work function after reduction. Bottom gated field effect transistors fabricated with isolated RGO sheets displayed charge neutrality point at a positive gate voltage, indicating p-type nature, consistent with UPS and electrostatic force microscopy (EFM) measurement results. The RGO sheets obtained by heat treatment of AA/GO/AA sandwich structure exhibited conductivity in the range of 2–7 S/cm and field effect mobility of 0.03–2 cm2/Vs, which are comparable with values reported for RGO sheets obtained by various chemical/thermal reduction procedures. The extent of GO reduction is determined primarily by proximity of AA molecules and found to be unaltered with either escalation of heat treatment temperature or increase of AA content in sandwich structure. The single-step GO reduction approach demonstrated in this work is an effective way for development of RGO monolayers with high structural quality towards graphene-based electronic device applications.