Low Work Function Research Articles

Experimental and theoretical study on the facet‐dependent SERS activity of α‐Fe2O3 films

AbstractSemiconductors have attracted great attention for surface‐enhanced Raman scattering (SERS) applications due to their rich variety, adjustable band structure, good chemical stability, and biocompatibility. However, their intrinsic weak SERS activity limited the further development of semiconductor substrates. Here, the α‐Fe2O3 films with high {} and {} facet exposure ratios were fabricated through an electrodeposition method with the existence of NH4Cl and CH3COONa. The α‐Fe2O3{} and α‐Fe2O3{} films show excellent SERS properties with enhancement factor of 4.155×103 and 5.481×103, as well as the relatively low limit of detection down to 2 × 10−7 M for 4‐nitrobenzenethiol. Meanwhile, the lower relative standard deviation values (<10%) confirm the well uniformity of as‐prepared substrates. Ultraviolet photoelectron spectroscopy analysis reveals that the α‐Fe2O3{} possesses the lower work function, which could guarantee the efficient interfacial charge transfer between substrates and probe molecules. Moreover, first principles calculations further indicates that the charge transfer efficiency on {} facet can be effectively improved, and thus significantly enhance the SERS activity of α‐Fe2O3. The current study provides a strategy for the fabrication and application of semiconductor‐based SERS substrates.

Time dependence of SrVO3 thermionic electron emission properties

Single phase, polycrystalline perovskite oxide SrVO3, with its intrinsic low effective work function and facile synthesis process, is a promising thermionic electron emitter cathode candidate, in which previous works have shown evidence of an effective work function as low as 2.3 eV. In this work, we study the vacuum activation process of SrVO3 and find that it has promising emission stability over 15 days of continuous high temperature operation. We find that SrVO3 shows surface Sr and O segregation during its operation, which we hypothesize is needed to create a positive surface dipole, leading to a low effective work function. Emission repeatability from cyclic heating and cooling suggests the promising stability of the low effective work function surface, and additional observations of drift-free emission during 1 h of continuous emission testing at high temperature further demonstrate its excellent performance stability. This assessment of the emission stability over time and the interplay of evolving surface chemistry with emission behavior are necessary for understanding how best to prepare, process, and operate SrVO3 cathodes.

Influence of different terminations on the surface properties of MB2: first principles study

Metal diborides MB2 (M = Zr, V, Ta, Nb) are widely used in many optoelectronic devices. Investigation into their surface stability and morphology is the first and essential step in exploring their properties. In the present work, the periodic density functional theory method was performed to study the surface properties and optical properties of MB2 (M = Zr, V, Ta, Nb). The effects of different surface terminations are discussed, which indicates metal terminations have low work functions. The calculation of optical properties indicates that the four borides are suitable for spectral selective materials and optical storage materials. These findings provide valuable theoretical data for the design and application of MB2 in optoelectronic materials.

Beyond Conventional Carbon Activation: Creating Porosity without Etching Using Cesium Effect.

Facile synthesis of porous carbon with high yield and high specific surface area (SSA) from low-cost molecular precursors offers promising opportunities for their industrial applications. However, conventional activation methods using potassium and sodium hydroxides or carbonates suffer from low yields (<20%) and poor control over porosity and composition especially when high SSAs are targeted (>2000 m2 g-1) because nanopores are typically created by etching. Herein, a non-etching activation strategy is demonstrated using cesium salts of low-cost carboxylic acids as the sole precursor in producing porous carbons with yields of up to 25% and SSAs reaching 3008 m2 g-1. The pore size and oxygen content can be adjusted by tuning the synthesis temperature or changing the molecular precursor. Mechanistic investigation unravels the non-classical role of cesium as an activating agent. The cesium compounds that form in situ, including carbonates, oxides, and metallic cesium, have extremely low work function enabling electron injection into organic/carbonaceous framework, promoting condensation, and intercalation of cesium ions into graphitic stacks forming slit pores. The resulting porous carbons deliver a high capacity of 252 mAh g-1 (567 F g-1) and durability of 100000 cycles as cathodes of Zn-ion capacitors, showing their potential for electrochemical energy storage.

Photoelectron Spectroscopic Study of the Interfacial Electronic Structures of Metal‐Ion Containing Polyelectrolytes on ITO Substrates

AbstractResearch in the field of organic electronics has witnessed dramatic improvements in device performance over the past several decades through an ever‐improving understanding of electron and hole movement and the development of new interfacial materials. In this study, a type of interfacial material that relies on ionic charges comprising metal:poly(styrenesulfonate) (PSS) polyelectrolytes are synthesized and investigated as structural analogs of the ubiquitously used poly(3,4‐ethylenedioxythiophene:polystyrenesulfonate) (PEDOT:PSS) hole transport layer, in order to investigate correlations between metal cation ions and the cationic PEDOT component. The metal ions selected for this study include Li, Mg, V, Mn, Co, Ni, Cu, Zn, Pd, Ag, Cs, and Pb ions. To analyze the interfacial energy level alignment, electronic band structure, and band bending at the Indium tin oxide (ITO)/metal:PSS interface, X‐ray photoelectron spectroscopy (XPS) and ultraviolet photoelectron spectroscopy (UPS) are employed. Alkali (earth) and post‐transition metals show deep highest occupied molecular orbital (HOMO) levels and low work function (WF) due to Fermi level balance, implying poor hole transport. Remarkably, Cu:PSS displays a unique electronic structure, suggesting potential as a hole transport layer with increased WF and low hole injection barrier. Period 5 transition metals mirror PEDOT:PSS trends, and Ag:PSS holds the potential to form effective ohmic contacts.

Converting formaldehyde in methanol with MoO2 under irradiation: A pollution-free strategy for cleaning air

Direct photocatalytic reduction of toxic formaldehyde (HCHO) in value-added chemicals and fuels is promising because that not only abates the environmental pollution, but also solves the energy shortage. Herein, self-supported MoO2 and MoO3 nanoparticles growing on Mo meshes were comparatively applied to the photocatalytic conversion of HCHO. Under UV–visble lights, MoO2 reduces HCHO in methanol (CH3OH) while MoO3 oxidizes HCHO in carbon oxide and water. Their contrary photocatalytic capacities were revealed. Compared with MoO3, the lower work function of MoO2 enables an electron-rich interface, realizing a complete reduction of 30 ppm HCHO to CH3OH in 30 min. Theoretical calculations clarify that a large number of delocalized electrons on MoO2 attracts HCHO molecule and activates its CO bond, facilitating subsequent hydrogenation and reduction of HCHO to CH3OH. As for MoO3, the wider bandgap and higher potential of valence band govern the photocatalytic oxidation of HCHO.

Investigation of Laser-Induced Graphene (LIG) on a Flexible Substrate and Its Functionalization by Metal Doping for Gas-Sensing Applications.

Graphene materials synthesized using direct laser writing (laser-induced graphene; LIG) make favorable sensor materials because of their large surface area, ease of fabrication, and cost-effectiveness. In particular, LIG decorated with metal nanoparticles (NPs) has been used in various sensors, including chemical sensors and electronic and electrochemical biosensors. However, the effect of metal decoration on LIG sensors remains controversial; hypotheses based on computational simulations do not always match the experimental results, and even the experimental results reported by different researchers have not been consistent. In the present study, we explored the effects of metal decorations on LIG gas sensors, with NO2 and NH3 gases as the representative oxidizing and reducing agents, respectively. To eliminate the unwanted side effects arising from metal salt residues, metal NPs were directly deposited via vacuum evaporation. Although the gas sensitivities of the sensors deteriorate upon metal decoration irrespective of the metal work function, in the case of NO2 gas, they improve upon metal decoration in the case of NH3 exposure. A careful investigation of the chemical structure and morphology of the metal NPs in the LIG sensors shows that the spontaneous oxidation of metal NPs with a low work function changes the behavior of the LIG gas sensors and that the sensors' behaviors under NO2 and NH3 gases follow different principles.

Enhanced sunlight-driven photocatalysis owing to synergetic effect of gold nanoparticles-incorporated ZnO/rGO ternary heterostructures

The combination of gold nanoparticles (Au NPs) incorporated ZnO/rGO heterostructures is unique for sunlight-driven photocatalysis (SPC). Here, hydrothermally synthesized pristine ZnO nanostructures (NSs), ZnO/rGO binary nanocomposites (BNCs) and ZnO/rGO/Au ternary nanocomposites (TNCs) of bandgap (Eg) values 3.56 eV, 3.37 eV and 3.17 eV, respectively are reported. These NSs are analyzed optically, structurally and morphologically via UV–Vis absorption spectroscopy, X-ray diffraction and SEM techniques, respectively. The SPC of methylene blue (MB) organic dye was considered using all three samples. The slow charge transfer over grain boundaries of ZnO results in the prohibition of photogenerated electron-hole pairs, exhibiting low photodegradation efficiency (87%). However, in BNCs the creation of alternative pathway of the carriers due to low work function level of rGO as compared to ZnO enhances the charge separation with an increased photocatalytic efficiency (92%). In contrast, TNCs show rather fast photodegradation efficiency (96%) as the photoexcited electrons on Au NPs surface migrate to the CB of ZnO because of the SPR stimulation of Au. These electrons easily shift to the conductive rGO layers and react with oxygen species (O2) producing superoxide radicals (•O2–). Thus, TNCs sample has appeared to be auspicious candidate for the photodegradation of organic pollutants in untreated water.

Graphene/Hexagonal Boron Nitride Heterostructures for O2 Activation and CO Oxidation: Metal-Free Catalysts by Design.

Pristine graphene and h-BN monolayers are chemically inert to oxygen and thus exhibit very limited catalytic activity toward O2 activation. Herein, we show that graphene/h-BN heterostructures exhibit a surprising O2 activation capability. We theoretically designed ten graphene/h-BN heterostructures with three types of interfaces and investigated their catalytic activities toward O2 activation and CO-oxidation. In general, O2 can be molecularly chemisorbed and activated on electron-rich graphene/h-BN heterostructures. Electron-deficient graphene/h-BN heterostructures can lead to dissociative O2 adsorption with relatively low dissociation energy barriers (<0.4 eV). For CO-oxidation, the computed energy barrier can be as low as 0.67 eV. The high catalytic activities toward O2 stem from either electron-deficient heterostructures' accumulated electrons or electron richness and low work function for the electron-rich heterostructures. Although the catalytic activities of graphene/h-BN heterostructures depend strongly on the interface type, they are insensitive to the patterns of BN-substitutes, hence benefiting applicability of a wide range of heterostructures.

Fermi-level depinning in Mo/Si junctions by insertion of amorphous Si-rich Mo silicide film formed via gas-phase reactions of MoF6 with SiH4

We demonstrate the reduction of the electron Schottky barrier height (SBH) to 0.48 eV at Mo/n-type Si junctions through the insertion of a semimetal Si-rich Mo silicide (MoSi n , n = 7.9) film. Raman scattering measurements elucidated the persistence of the same amorphous structure within the MoSi n film even when subjected to temperatures as high as 900 °C. This excellent thermal stability yielded a notable result: preservation of the SBH modulation effect even following annealing at 700 °C. Moreover, we investigated the capacitance−voltage characteristics of MOS capacitors, revealing that MoSi n film has a remarkably low effective work function, measuring 4.1 eV when deposited onto SiO2. The deposition of MoSi n film was accomplished with an excellent coverage by using MoF6 and SiH4 gases. Thus, MoSi n film is a promising contact material in advanced CMOS transistors.

Post-annealing-free BaOxFy/LiF-based stack electron-selective contacts for high efficiency crystalline silicon solar cells featuring ultra-low contact resistivity

In silicon heterojunction and tunnel oxide passivating contact crystalline silicon (c-Si) solar cells based on successful passivating contacts technologies, an annealing activation step is indispensable to achieve a suitably low contact resistivity (ρc), which is a costly and non-ideal process. Here, combined with a calcium aluminium (Ca:Al) alloy electrode, a low work function barium oxide and lithium fluoride (BaOxFy/LiF) stack electron-selective contact (ESC) without an annealing activation step on c-Si solar cells clinches an ultra-low ρc of 1.4 mΩ·cm2 delivering a power conversion efficiency (PCE) of 20.5 %. The BaOxFy/LiF/Ca:Al stack structure is built by BaOx/LiF/Ca/Al hybrid structure via a facile continuous thermal evaporation process. As a proof of concept, the stacked BaOxFy/LiF/Ca:Al/Al contact is applied to the rear side of c-Si solar cells, achieving a PCE of 20.5 % with an open-circuit voltage of 625.7 mV, an impressive fill factor of 83.5 % and a short-circuit current density of 39.2 mA/cm2. With the aid of a transient photovoltage setup, the carrier recombination mechanism of the stacked BaOxFy/LiF/Ca:Al structure is explored. This work demonstrates an alternative idea for undoped ESCs, showing potential for next-generation cost-effective ultrathin-slice c-Si solar cells (∼80 μm) with high efficiency, and low-parasitic light absorption losses.

Characterization of a LaB6 tip as a thermionically enhanced photoemitter

There is a widespread interest in time-resolved electron spectroscopies such as ultrafast electron diffraction, ultrafast electron microscopy, and ultrafast electron energy loss spectroscopy. These techniques require pulsed electron beams with both high current and brightness. LaB6 is commonly used as a thermionic emitter because of its low work function and high electron yield. However, its use as a pulsed photocathode has not been widely explored. Here, we present measurements of the electron yield from a LaB6 filament exposed to 392 nm UV ultrafast laser pulses under a wide range of filament temperatures. We find that sample heating strongly enhances photoelectron yield, an effect known as thermionically enhanced photoemission. However, it also creates potentially undesirable, continuous thermionic background. We conclude that the ideal optimal operating conditions strongly depend on the type of measurement and require defining and quantifying an appropriate figure of merit.

Electrical and thermal characteristics of LaB6 thermionic hollow cathodes operating in He, D2, Ar, and Xe at 4–200 Pa and 0.25–5 A cm−2

We report characteristics of lanthanum hexaboride (LaB6) cathodes for conditions relevant to a high-voltage, high-current switching device. LaB6 is selected because of its relatively low work function, stability in the presence of many common gas impurities, and a low evaporation rate (long life) at operating temperatures. We have investigated the effect of cathode geometry, gas type, pressure, and current on a LaB6 hollow cathode in a diode configuration with an opposing planar anode. The gas is stagnant at a relatively low pressure of 4–200 Pa (0.03–1.5 Torr) because of device high-voltage standoff requirements. In all cases, the plasma voltage decreases to a plateau value with increasing current where a practical device would operate. The plateau voltage aligns with the fill gas excitation or ionization voltage, depending on conditions. At high current, the cathode temperature exceeds that required for thermionic emission to supply the total current, a behavior that is understood by accounting for back-diffusing bulk electrons.

Characterisation of a Cs–Implanted Cu Photocathode

The generation of high-brightness electron beams is a crucial area of particle accelerator research and development. Photocathodes which offer high levels of quantum efficiency when illuminated at visible wavelengths are attractive as the drive laser technology is greatly simplified. The higher laser power levels available at longer wavelengths create headroom allowing use of manipulation techniques to optimise the longitudinal and transverse beam profiles, and so minimise electron beam emittance. Bi–alkali photocathodes which offer quantum efficiency ∼ 10 % under illumination at 532 nm are an example of this. Another solution is the use of modified photoemissive surfaces. Caesium has a low work function and readily photoemits when illuminated at green wavelengths (∼532nm). Caesium oxide has an even lower work function and emits at red wavelengths (∼635nm). We present data on our work to create a hybrid copper photocathode surface modified by implantation of caesium ions, measuring the surface roughness and probing its structure using MEIS. We measure the energy spread of photoemitted electrons, the QE as a function of illumination wavelength, and the practicality of this surface as a photocathode by assessing its lifetime on exposure to oxygen.

The tuned Schottky barrier of a CoP co-catalyst via the bridge of ohmic contact from molybdenum metal for enhanced photocatalytic hydrogen evolution

The Schottky barrier between CoP and g-C3N4 is tuned via nanometallic Mo with a low work function.

Improvement of Ti/Al/Ti Ohmic contacts on AlGaN/GaN heterostructures by insertion of a thin carbon interfacial layer

This Letter reports on the improvement of the morphological and electrical behavior in Ti/Al/Ti Ohmic contacts on AlGaN/GaN heterostructures by the insertion of a thin carbon interfacial layer. In particular, the presence of a carbon layer between the Ti/Al/Ti metal stack and the AlGaN surface leads to the lowering of the annealing temperature (down to 450 °C) required to obtain linear I–V curves and to the improvement of the contacts surface morphology. The temperature dependence of the specific contact resistance was explained by the thermionic field emission, with a reduction in the barrier height ΦB down to 0.62 eV in the annealed contacts with the interfacial carbon layer. The experimental evidence has been justified with the formation of a thin low work function TiC layer, which enhances the current conduction through the metal/AlGaN interface.

Ultra-low work function of caesiated surfaces and impact of selected gas species

Modern high-power negative hydrogen ion sources rely predominantly on the surface production of negative hydrogen ions. Hence, low work function converter surfaces are mandatory, for which the alkali metal Cs is commonly evaporated into the ion source to lower the work function of refractory metals by surface adsorption. To study the work function behaviour upon caesiation under the typically given non-ultra-high vacuum conditions, investigations are performed at a dedicated laboratory experiment. In a vacuum environment dominated by water vapour, the work function evolution is found to be dependent on the flux ratio of Cs to H2O onto the surface. For sufficiently high flux ratios, ultra-low work functions in the range of 1.25±0.10 eV are generated with excellent reproducibility. In the absence of Cs evaporation, the work function gradually increases under the influence of the residual gases, and re-caesiation processes lead to lower quantum efficiencies and higher work functions of typically 1.9–2.1 eV. While the addition of hydrogen and deuterium gas at several Pa as well as the leakage of inert gases (argon and nitrogen) into the vacuum system have a negligible influence on the caesiation process, small amounts of oxygen with partial pressures of ∼10-2–10-1 Pa lead to an instant reduction of the Cs density in the gas phase by several orders of magnitude and to an increase in the work function of the order of 1 eV. After the oxygen exposure is terminated, however, the Cs density and work function fully recover within several minutes.

Asymmetric contact-induced selective doping of CVD-grown bilayer WS2 and its application in high-performance photodetection with an ultralow dark current.

Two-dimensional (2D) transition metal dichalcogenides (TMDs) are excellent candidates for high-performance optoelectronics due to their high carrier mobility, air stability and strong optical absorption. However, photodetectors made with monolayer TMDs often exhibit a high dark current, and thus, there is a scope for further improvement. Herein, we developed a 2D bilayer tungsten disulfide (WS2) based photodetector (PD) with asymmetric contacts that exhibits an exceptionally low dark current and high specific detectivity. High-quality and large-area monolayer and bilayer WS2 flakes were synthesized using a thermal chemical vapor deposition system. Compared to conventional symmetric contact electrodes, utilizing metal electrodes with higher and lower work functions relative to bilayer WS2 aids in achieving asymmetric lateral doping in the WS2 flakes. This doping asymmetry was confirmed through the photoluminescence spectral profile and Raman mapping analysis. With the asymmetric contacts on bilayer WS2, we find evidence of selective doping of electrons and holes near the Ti and Au contacts, respectively, while the WS2 region away from the contacts remains intrinsic. When compared with the symmetric contact case, the dark current in the WS2 PD with asymmetric (Au, Ti) contact decreases by an order of magnitude under reverse bias with a concomitant increase in the photocurrent, resulting in an improved on/off ratio of ∼105 and overall improved device performance under identical illumination conditions. We explained this improved performance based on the energy band alignment showing a unidirectional charge flow under light illumination. Our results indicate that the planar device structure and compatibility with current nanofabrication technologies can facilitate its integration into advanced chips for futuristic low-power optoelectronic and nanophotonic applications.

Temperature-dependent work function, thermionic emission and bulk modulus of TiC: a study on the identification of free valence electrons and localized valence electrons and their roles played in carbides.

By analyzing the projected states of valence electrons (fatband structures), the localized valence electrons and the free valence electrons of TiC were identified, respectively. After defining the volumes and the magnitudes of localized valence electrons and free valence electrons, the influences of the temperature, including the thermal expansion and the atomic thermal vibration, on the localized valence electron density and the free valence electron density were investigated, respectively. Based on the metallic plasma model (MPM), the temperature-dependent work functions and the thermionic emission current densities of TiC were calculated in terms of temperature-dependent free valence electron densities. The results were in good agreement with experimental results. Furthermore, as it was observed, the linear dependence of the bulk modulus on the localized valence electron density demonstrated that the bulk modulus of TiC was determined by the localized valence electron density. The different roles played by the free valence electrons and the localized valence electrons in the work function and the bulk modulus of TiC could be attributed to their different contributions to the kinetic energy density of valence electrons. The influences of the temperature on the work function, thermionic emission and bulk modulus of TiC indicated that the transition metal carbides with lower free valence electron density, higher localized valence electron density and heavier atomic mass were desired to achieve lower work function, higher current density and higher stability.

Signature of low-dimensional quasi-F centers in zirconium-rich electrides.

Electrides are a class of materials consisting of non-nuclear excess electrons as quasi-F centers or Farbe centers within a positively charged lattice framework, and have significant applications in the fields of electrochemistry, spintronics, and electrode materials. Using first-principles quantum mechanical calculations, we have demonstrated exotic electronic structures of zirconium-rich electrides, Zr2X (X = O, Se, and Te), and obtained the quantitative values of charge transfer (oxidation states), and projected density of states associated with the localized quasi F-centers. The localized interstitial anionic electrons exhibit significant charge transfer values of approximately -1.88, -2.01, and -1.79 per atom in Zr2O, Zr2Se, and Zr2Te, respectively, and contribute actively in the electronic band structures and density of states at the Fermi level. From the 2D contour plot of the electron localization function (ELF), it has been predicted that the spatial distribution of the quasi-F centers stabilizes in the form of a one-dimensional pattern, with localized ELF sites interconnected with delocalized electron channels. Further, low work-function values of Zr2X, ranging from 2.7-3.4 eV, confirm the electride properties of these binary compounds, promising applications in electro-catalytic oxidations and anode materials in batteries. These unique electronic properties of anionic electrons free from nuclear binding in Zr2X have not been reported yet in the literature.