Semiconductor Surface States Research Articles

Direct Operando Identification of Reactive Electron Species Driving Photocatalytic Hydrogen Evolution on Metal-Loaded Oxides.

Performing operando spectroscopy under practical reaction conditions and extracting spectral components correlating with reaction activity are crucial in elucidating the reactive species in photocatalysis. However, the observation of weak signals corresponding to reactive photogenerated species is frequently hampered under reaction conditions owing to intense background signals originating from thermally induced species unrelated to the photoinduced reactions. Herein, by synchronizing the millisecond periodic excitations of photocatalysts with a Michelson interferometer used for FT-IR spectroscopy, we succeeded in significantly suppressing the signals derived from thermally excited electrons and observing the reactive photogenerated electrons contributing to the photocatalytic hydrogen evolution. This demonstration was achieved for metal-loaded oxide photocatalysts under steam methane reforming and water splitting conditions. Although it has long been conventionally believed that loaded metal cocatalysts function as sinks for reactive photogenerated electrons and active sites for reduction reactions, we found that the free electrons in the metal cocatalysts were not directly involved in the reduction reaction. Alternatively, the electrons shallowly trapped in the in-gap states of oxides contributed to enhancing the hydrogen evolution rate upon the loading of metal cocatalysts. We verified that the electron abundance in the in-gap states was clearly correlated to the reaction activity, suggesting that metal-induced semiconductor surface states formed in the periphery of the metal cocatalyst play key roles in the photocatalytic hydrogen evolution. Our microscopic insights shift a paradigm on the traditionally believed role of metal cocatalysts in photocatalysis and provide a fundamental basis for rational design of the metal/oxide interfaces as promising platforms for nonthermal hydrogen evolution.

Photo-emission electron gun and electron optical simulation for ultrafast scanning electron microscope

Ultrafast scanning electron microscope (USEM) integrates pump-probe technique with microscopic imaging, enabling the visualizing of photon-induced surface charge dynamics with high spatial and temporal resolution. This capability is crucial for high-resolution detection of semiconductor surface states and optoelectronic devices. This work discusses the parametric design of a thermionic emission electron gun that has been modified into a photoemission electron gun, based on a home-built ultrafast scanning electron microscope. Given that the dose of the photoemitting electron beam is usually much lower than that of thermionic emission, the transition to photoemission requires the removal of the self-bias voltage function of the original electron microscope power supply to ensure the normal operation of the Wehnelt electrode. We quantitatively analyze the dependence of bias voltage, cathode, Wehnelt electrode, and anode on the position, size and divergence angle of crossover, which helps to improve the parameter adjustment of the modified electron gun. The analysis results indicate that if the distance between the Wehnelt electrode and the anode is adjusted from 8 to 23 mm, the distance between the filament and wehnelt can be changes from 0.65 to 0.45 mm to cooperate with the bias adjustment, so that the normal use of high-resolution thermionic emission mode, low voltage mode and photoemission mode can be realized. Subsequently, the effect of the mirror’s position on the electron optical path is analyzed. It is found that when the anode is raised 1.4 mm above the mirror, the influence on the electron optical path can be ignored. Additionally, the zero-of-time and temporal broadening of the photo-electron pulse are further simulated. The results indicate that with the increase of bias voltage, the time zero of photoemission will be delayed and the temporal broadening will become larger. This study lays a foundation for the future development of ultrafast electron microscope and the design of photoemission electron sources.

Effect of Tamm Surface States on Landau Damping in Metal–Semiconductor Nanostructures

AbstractThe hot electron generation in plasmonic nanoparticles is the key to efficient plasmonic photocatalysis. Here, the effect of Tamm states (TSs) at the metal–semiconductor interface on hot electron generation and Landau damping (LD) in metal nanoparticles is studied theoretically for the first time. TSs can lead to resonant hot electron generation and to the LD rate enhanced by several times. The resonant hot electron generation is reinforced by thetransitionabsorption due to the jump of the permittivity at the metal–semiconductor interface. Since electron states in the metal and the quasi‐discrete TS are coupledcoherently(“bound state in continuum”), the absorption spectrum of light by electrons has a Fano‐type shape. The results demonstrate clearly the importance of taking into account details of the semiconductor band structure and surface states at the metal–semiconductor interface, including Tamm surface states, for a proper description of the hot carrier generation and LD. The results are in correspondence with earlier experimental works on coherent electron transport and chemical‐induced damping in plasmonic nanostructures. Thus, by judicious selection of semiconductor materials with Tamm surface states one can engineer decay rates and hot carrier production for important applications, such as photodetection and photochemistry.

The impact of semiconductor surface states on vacuum field emission

This work presents a theoretical analysis of the impact of surface states on vacuum field emission currents in semiconductors. In wide and ultra-wide bandgap semiconductors such as GaN and AlGaN, low electron affinity has been proposed as a benefit for field emission into vacuum. However, in these materials, the surface Fermi level at the surface is pinned well below the conduction band, and the surface depletion barriers due to the surface Fermi level pinning can be comparable to or higher than the electron affinity. Therefore, analysis of field emission requires consideration of not only the vacuum potential barrier set by electron affinity, but also the depletion region near the semiconductor surface. In this paper, we develop analytical models to predict field emission currents with careful consideration of the impact of surface states on the energy band alignment. The results are used to provide guidelines for design of field emitters that could benefit from the low electron affinity of semiconductors such as Al(Ga)N.

Negative Schottky barrier height and surface inhomogeneity in n-silicon M–I–S structures

The alleviation effect on the Schottky barrier height (SBH) (ΦB) using ultrathin titanium dioxide and hafnium dioxide dielectrics in a single layer and a bilayer stack was demonstrated. ΦB in the Pt/n-Si contact was reduced from 0.53 to −0.058, 0.3, and −0.12 eV using 3 nm TiO2, 1 nm HfO2, and high-k/high-k bilayer insertion, respectively. A maximum of 122% reduction in ΦB was obtained using bilayer dielectric insertion, which is the highest ever reduction reported so far in a Schottky diode. This was achieved by effectively passivating the semiconductor surface states by HF cleaning followed by inserting an ultrathin film produced from the novel Atomic Layer Deposition (ALD) technique. The Gaussian distribution (GD) of barrier heights all over the interface has been investigated for both Metal–Semiconductor (M–S) and Metal–Insulator–Semiconductor (M–I–S) contacts. The nonlinear behavior in a conventional Richardson plot was observed with lower values of the Richardson constant (A*). We have reported the surface inhomogeneity in both M–S and M–I–S contacts through temperature dependency of diode characteristics. The standard deviation (σ) as evidence for the Gaussian distribution of barrier heights was determined using the ln(Is/T2) vs q/2kT plot. The results were validated by a modified Richardson plot where the values of A* obtained were found to be in close agreement with the known values. As the ALD technique is known for conformity and uniformity of thin films, the dielectric insertion has proved effective in mitigating the SBH. However, the inhomogeneity in both M–S and M–I–S points to the role of dipole formation at the interface.

Revisiting the physical origin and nature of surface states in inverted-band semiconductors

We revisit the problem of surface states in semiconductors with inverted band structures, such as $\alpha$-Sn and HgTe. We unravel the confusion that arose over the past decade regarding the origin of the surface states, their topological nature, and the role of strain. Within a single minimalistic description, we reconcile different solutions found in the 1980s with the results obtained from modern-day numerical simulations, allowing us to unambiguously identify all branches of surface states around the $\Gamma$-point of the Brillouin zone in different regimes. We also show that strain is a smooth "deformation" to the surface states, following the usual continuity principle of physics, and not leading to any drastic change of the physical properties in these materials, in contrast to what has recently been advanced in the literature. We consider biaxial in-plane strain that is either tensile or compressive, leading to different branches of surface states for topological insulators and Dirac semimetals, respectively. Our model can help in interpreting numerous experiments on topological surface states originating from inverted-band semiconductors.

Surface States Enhanced Dynamic Schottky Diode Generator with Extremely High Power Density Over 1000 W m-2.

The overloaded energy cost has become the main concern of the now fast developing society, which make novel energy devices with high power density of critical importance to the sustainable development of human society. Herein, a dynamic Schottky diode based generator with ultrahigh power density of 1262.0 W m−2 for sliding Fe tip on rough p‐type silicon is reported. Intriguingly, the increased surface states after rough treatment lead to an extremely enhanced current density up to 2.7 × 105 A m−2, as the charged surface states can effectively accelerate the carriers through large atomic electric field, while the reflecting directions are regulated by the built‐in electric field of the Schottky barrier. This research provides an open avenue for utilizing the surface states in semiconductors in a subversive way, which can co‐utilize the atomic electric field and built‐in electric field to harvest energy from the mechanical movements, especially for achieving an ultrahigh current density power source.

Zn+-O- Dual-Spin Surface State Formation by Modification of ZnO Nanoparticles with Diboron Compounds.

ZnO semiconductor oxides are versatile functional materials that are used in photoelectronics, catalysis, sensing, etc. The Zn+-O- surface electronic states of semiconductor oxides were formed on the ZnO surface by Zn 4s and O 2p orbital coupling with the diboron compound's B 2p orbitals. The formation of spin-coupled surface states was based on the spin-orbit interaction on the interface, which has not been reported before. This shows that the semiconductor oxide's spin surface states can be modulated by regulating surface orbital energy. The Zn+-O- surface electronic states were confirmed by electron spin resonance results, which may help in expanding the fundamental research on spintronics modulation and quantum transport.

Tight-binding electronic band structure and surface states of Cu-chalcopyrite semiconductors

We report theoretical calculations of the electronic band structure and surface states of Cu-chalcopyrite semiconductors. The systems under consideration are CuGaS2, CuAlSe2, and CuGaS2 doped with Cr. The calculations are carried out using semi-empirical Tight-Binding formalism. By reproducing the band gap of these systems obtained by ab-initio calculations we report the Tight-Binding parameters required for the band structure calculations. We present bulk band structure calculations of the above mentioned semiconductors, and we analyze the (001) and (110) surface states of the corresponding semi-infinite semiconductors.

Facile synthesis of bismuth oxyhalide nanosheet films with distinct conduction type and photo-induced charge carrier behavior

A modified successive ionic layer adsorption and reaction (SILAR) method was developed to fabricate 2D ordered BiOX (X = CI, Br, I) nanosheet array films on FTO substrates at room temperature. The formation of BiOX films were characterized by X-ray powder diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), UV-vis absorption spectroscopy, and X-ray photoelectron spectroscopy (XPS). The semiconductor surface states determine the type of semiconductor. Although BiOCI, BiOBr and BiOI belong to the bismuth oxyhalide semiconductor family and possess similar crystal and electronic structures, they show different conductivity types due to their respective surface states. Mott-Schottky curve results demonstrate that the BiOCl and BiOI nanosheet arrays display n-type semiconductor properties, while the BiOBr films exhibit p-type semiconductor properties. Assisted by surface photovoltage (SPV) and transient photovoltage (TPV) techniques, the photoinduced charge transfer dynamics on the surface/interface of the BiOX/FTO nanosheet films were systematically and comparatively investigated. As revealed by the results, both the separation and transfer dynamics of the photo-induced carrier are influenced by film thickness.

Energy level alignment at the interface of cadmium sulphide single crystal and phthalocyanines: The role of the crystal surface states

Ultraviolet photoelectron spectroscopy was used to study energy levels of (0001) and (0001_) surfaces of bare CdS crystal terminated with Cd and S atoms, respectively, as well as energy level alignment at hybrid interfaces of CdS crystal and donor zinc phthalocyanine (PcZn) or acceptor fluoro-substituted zinc phtalocyanine (F-PcZn) layers, respectively. The data allowed us to distinguish a slight difference between ionization potential of the Cd- and S-terminated facets of the crystal and different contribution of these surfaces to formation of the interfacial dipole at the hybrid interfaces. Ionization potential for the S-terminated surface was slightly higher as compared to the Cd-terminated one for the same crystal, and a more positive dipole was always created on the S-terminated surface independent of whether the donor or acceptor phthalocyanine was used. The results showed that PcZn and F-PcZn render a dual effect at the CdS surface. First, the molecules created a dipole at the interface, however, the sign of this dipole was opposite for PcZn and F-PcZn, respectively. Second, the both molecules contributed to the formation of a depletion layer near the crystal surface. The role of the surface states of the crystal in the above effects has been elucidated. Interaction of PcZn and CdS surface was associated with the pinning of the upper occupied level of the surface states to the positive charge transfer state corresponding to the oxidized HOMO level of the molecule at the interface, whereas interaction of F-PcZn and CdS surface with the pinning of the upper occupied level of the surface states to the negative charge transfer corresponding to the reduced LUMO level of the molecule at the interface, i.e., similar to what is observed for the metal-organic interfaces, where an upper occupied level of semiconductor surface states in our case plays the role of Fermi level in metal.

Temperature and doping dependent changes in surface recombination during UV illumination of (Al)GaN bulk layers

We have studied the effect of continuous illumination with above band gap energy on the emission intensity of polar (Al)GaN bulk layers during the photoluminescence experiments. A temporal change in emission intensity on time scales from seconds to hours is based on the modification of the semiconductor surface states and the surface recombination by the incident light. The temporal behavior of the photoluminescence intensity varies with the parameters such as ambient atmosphere, pretreatment of the surface, doping density, threading dislocation density, excitation power density, and sample temperature. By means of temperature-dependent photoluminescence measurements, we observed that at least two different processes at the semiconductor surface affect the non-radiative surface recombination during illumination. The first process leads to an irreversible decrease in photoluminescence intensity and is dominant around room temperature, and the second process leads to a delayed increase in intensity and becomes dominant around T = 150–200 K. Both processes become slower when the sample temperature decreases from room temperature. They cease for T < 150 K. Stable photoluminescence intensity at arbitrary sample temperature was obtained by passivating the analyzed layer with an epitaxially grown AlN cap layer.

Tuning the work function of GaN with organic molecular acceptors

We demonstrate the capability of two molecular organic acceptors [1,4,5,8,9,12-hexaazatriphenylenehexacarbonitrile and 2,2\ensuremath{'}-(perfluoronaphthalene-2,6-diylidene)dimalononitrile] to tune the work function (\ensuremath{\Phi}) of intrinsically doped GaN(0001) and for comparison of intrinsically doped ZnO(0001). With ultraviolet photoelectron spectroscopy we determine the accessible \ensuremath{\Phi} range as 4.2--6.0 eV for GaN and 3.9--6.3 eV for ZnO. The contribution to the \ensuremath{\Phi} change (\ensuremath{\Delta}\ensuremath{\Phi}) of acceptor-induced surface band bending within GaN was significantly smaller than in ZnO (0.35 versus 1 eV), which we attribute to surface gap states. We introduce a model that takes these surface states into account and thus allows quantifying the impact of the semiconductor bulk doping level and surface state density on \ensuremath{\Delta}\ensuremath{\Phi}. The lower the doping level is, the lower the surface state density needs to be to reduce the band bending contribution to \ensuremath{\Delta}\ensuremath{\Phi}. This limits the maximum value of \ensuremath{\Phi} tuning for GaN with molecular acceptors, whereas, on the other hand, it renders the method robust against surface structural disorder.

Field-Dipole Interactions at p-GaAs (100) Electrode in Sodium Dodecyl Sulfate Acid Solution

Electrochemical impedance spectroscopy (EIS), X-ray photoelectron spectroscopy (XPS) and atomic force microscopy (AFM) have been used to investigate the effects of the sodium dodecyl sulfate (SDS) at the electrified p-GaAs(100) / H2SO4 interface. The analysis of the EIS data revealed that the surfactant adsorption brings about a pronounced decrease of the capacitive contributions of the semiconductor surface state (Fig. 1 B) accompanied by a shift to more positive potentials of the Mott-Schottky plot (Fig. 1 A). According to the XPS (Fig 1 C) and AFM data, SDS forms a well-ordered protective overlayer on p-GaAs(100) which prevents the surface oxidation in air. However, the field-dipole interactions acting under the applied potential control become preponderant at the electrified GaAs / solution interface yielding distinct effects at the end of the direct and forward potential scans as seen in Fig 1 C. These results suggest that SDS interaction with GaAs substrate might be an efficient tool to improve both the electronic properties of the semiconductor and its protection against the surface oxidation in air. Acknowledgements This work was supported by a grant of the Romanian National Authority for Scientific Research, CNCS – UEFISCDI, project number PN-II-ID-PCE-2011-3-0304 Figure 1

Gated Hall effect of nanoplate devices reveals surface-state-induced surface inversion in iron pyrite semiconductor.

Understanding semiconductor surface states is critical for their applications, but fully characterizing surface electrical properties is challenging. Such a challenge is especially crippling for semiconducting iron pyrite (FeS2), whose potential for solar energy conversion has been suggested to be held back by rich surface states. Here, by taking advantage of the high surface-to-bulk ratio in nanostructures and effective electrolyte gating, we develop a general method to fully characterize both the surface inversion and bulk electrical transport properties for the first time through electrolyte-gated Hall measurements of pyrite nanoplate devices. Our study shows that pyrite is n-type in the bulk and p-type near the surface due to strong inversion and yields the concentrations and mobilities of both bulk electrons and surface holes. Further, solutions of the Poisson equation reveal a high-density of surface holes accumulated in a 1.3 nm thick strong inversion layer and an upward band bending of 0.9-1.0 eV. This work presents a general methodology for using transport measurements of nanostructures to study both bulk and surface transport properties of semiconductors. It also suggests that high-density of surface states are present on surface of pyrite, which partially explains the universal p-type conductivity and lack of photovoltage in polycrystalline pyrite.

Transient Response in Aqueous Solution of an Anions Porous Silicon Based Sensor

A porous silicon based sensor has been developed to detect anions in a salt solution by the application of DC pulses on a Semiconductor/Electrolyte system. The sensor performance can be explained invoking a model where charge accumulation in the semiconductor surface states directly affects their geometric capacitances. By varying anions concentrations in salt solution, the results show a fairly constant value of substrate resistance, whereas variations in those geometric capacitances depend on the anion concentration. The constancy of substrate resistance and variability of geometric capacitance constitute key points for the development of an anion solution sensor.

The energetics and kinetics of uranyl reduction on pyrite, hematite, and magnetite surfaces: A powder microelectrode study

There are many studies describing the influence of parameters such as pH, pCO2, and complexing ligands on the sorption of the aqueous uranyl species onto mineral surfaces. However, few of these studies describe the reduction reaction mechanisms and the factors that influence the rate of reduction, despite the fact that the oxidation state of uranium is the most important factor controlling the mobility of uranium. In this study, the energetics and kinetics of the U(VI) reduction half-reaction on pyrite, hematite, and magnetite were investigated by electrochemical methods using a powder microelectrode (PME) as the working electrode. Anodic and cathodic peaks corresponding to the 1e- redox couple, U(VI)/U(V), were identified in cyclic voltammograms of pyrite, hematite, and magnetite at pH 4.5. A second oxidation peak, corresponding to the oxidation of U(IV), was identified and provides evidence for the formation of reduced uranium phase(s) on the mineral surfaces. In addition, uranium-containing precipitates were identified on pyrite surfaces after polarization in a PME. This study identifies the disproportionation of U(V) species on the surface as a possible rate-limiting step in the two-step U(VI) reduction mechanism: (1) charge transfer to form U(V) followed by, (2) a disproportionation reaction that forms U(IV) and U(VI). The Tafel slope (i.e., the derivative of the electrode potential with respect to log[current]) was used to evaluate electrochemical mechanisms. High Tafel slopes (>220mV/(logunit of current) on all minerals evaluated) suggest that uranyl reduction is mediated by insulating (hydr)oxide layers that are present on the semiconducting mineral surfaces. The onset potential for uranyl reduction was determined for pyrite (>+0.1V vs. Ag/AgCl), and hematite and magnetite (between−0.02 and−0.1V vs. Ag/AgCl). The onset potential values establish a baseline kinetic parameter that can be used to evaluate how solution conditions (e.g., dissolved reductants, complexing ligands, and polarizing ions) affect the kinetics of uranyl reduction.The results of this study demonstrate the potential for using PMEs to evaluate redox potentials and mechanisms for U(VI) reduction by Fe-oxides and sulfides under more complex solution conditions as well as other environmentally-relevant mineral-analyte systems. However, it should be noted that the determination of redox kinetics using Butler–Volmer theory has limitations when applied to semiconductor mineral electrodes. Charge depletion in semiconductor surface states can affect the kinetic values obtained for redox reactions on the surface. These limitations and a discussion of the flat band potential are considered in the interpretation of U redox kinetics in this study.

A Distributed Bulk-Oxide Trap Model for $\hbox{Al}_{2} \hbox{O}_{3}$ InGaAs MOS Devices

This paper presents a distributed circuit model for bulk-oxide traps based on tunneling between the semiconductor surface and trap states in the gate dielectric film. The model is analytically solved at dc. It is shown that the distributed bulk-oxide trap model correctly depicts the frequency dispersion in the capacitance- and conductance-voltage data of Al <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> O <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> -InGaAs MOS devices that do not fit the conventional interface state model. The slope degradation or stretch-out of the measured capacitance-voltage curve near flatband can be also explained by the distributed bulk-oxide trap model.

Effect of electron–phonon interaction on surface states in wurtzite nitride semiconductors under pressure

A variational theory is proposed to study the electronic surface states in semi-infinite wurtzite nitride semiconductors under the hydrostatic pressure. The electronic surface state energy level is calculated, by taking the effects of the electron–Surface–Optical–phonon interaction, structural anisotropy and the hydrostatic pressure into account. The numerical computation has been performed for the electronic surface state energy levels, coupling constants and the average penetrating depths of the electronic surface state wave functions under the hydrostatic pressure for wurtzite GaN, AlN and InN, respectively. The results show that electron–Surface–Optical–phonon interaction lowers the electronic surface state energy levels. It is also found that the electronic surface state energy levels decrease with the hydrostatic pressure in wurtzite GaN and AlN. But for wurtzite InN, the case is contrary. It is shown that the hydrostatic pressure raised the influence of electron–phonon interaction on the electronic surface states obviously. The effect of electron–Surface–Optical–phonon interaction under the hydrostatic pressure on the electronic surface states cannot be neglected, in specially, for materials with strong electron–phonon coupling and wide band gap.

Charge transport at the interface of n-GaAs (100) with an aqueous HCl solution: Electrochemical impedance spectroscopy study

Charge transport processes at the interface of n-GaAs (100) with an aqueous HCl solution are studied by electrochemical impedance spectroscopy. It is found that when open-circuit potential and anodic potentials are applied to the semiconductor the impedance spectra contain two capacitive semicircles corresponding to the capacitances of the space charge layer and surface states. In the case of open-circuit potential, semiconductor band bending at the interface with the solution is about 0.7 eV and the density of occupied surface states in the dark and under daylight conditions is 1.6 and 2.8 × 1012 cm2 eV−1, respectively. When cathode potentials are applied to GaAs, hydrogen evolution begins at the semiconductor/electrolyte interface and an additional inductive loop appears in the impedance spectra. At the same time, the density of occupied surface states increases considerably both due to a straightening of the semiconductor bands and to the appearance of As-H bonds. Thus, charge transport through the n-GaAs (100)/aqueous HCl solution interface is always mediated by semiconductor surface states.