Understanding the evolution of the solid electrolyte-electrode interface is currently one of the most challenging obstacles in the development of solid-state batteries(SSBs).Here,we develop an X-ray Photoelectron Spec...Understanding the evolution of the solid electrolyte-electrode interface is currently one of the most challenging obstacles in the development of solid-state batteries(SSBs).Here,we develop an X-ray Photoelectron Spectroscopy(XPS)that allows for operando measurement during cycling.Based on theoretical analysis and the modulated electrode and detector co-grounding mode,the displacement of binding energy can be correlated with the surface electrostatic potential of the material,revealing the charge distribution and composition evolution of the space charge layer between the cathode and the electrolyte.In the investigation of typical LiCoO_(2)(LCO)/Li6PS5Cl(LPSC)/Li-In batteries,we observed the static potential difference and oxidative decomposition between LPSC and LCO,and the effectiveness of the LiNbO3 coating in reducing potential difference and inhibiting the diffusion of Co and oxidation of S species.Furthermore,our study also revealed that the potential drop between LiNi0⋅8Co0⋅1Mn0⋅1O_(2) and LPSC is smaller than that of LCO,whilst that between Li3InCl6 and LCO remains near zero.The proposed operando XPS method offers a novel approach for real-time monitoring of interface potential and species formation,providing rational guidance for the interface engineering in SSBs.展开更多
The possible configurations of pyrrole absorbed on a Si(100)surface have been investigated by x-ray photoelectron spectroscopy(XPS)and near-edge x-ray absorption fine structure(NEXAFS)spectra.The C-1s XPS and NEXAFS s...The possible configurations of pyrrole absorbed on a Si(100)surface have been investigated by x-ray photoelectron spectroscopy(XPS)and near-edge x-ray absorption fine structure(NEXAFS)spectra.The C-1s XPS and NEXAFS spectra of these adsorption configurations have been calculated by using the density functional theory(DFT)method and fullcore hole(FCH)approximation to investigate the relationship between the adsorption configurations and the spectra.The result shows that the XPS and NEXAFS spectra are structurally dependent on the configurations of pyrrole absorbed on the Si(100)surface.Compared with the XPS,the NEXAFS spectra are relatively sensitive to the adsorption configurations and can accurately identify them.The NEXAFS decomposition spectra produced by non-equivalent carbon atoms have also been calculated and show that the spectral features vary with the diverse types of carbon atoms and their structural environments.展开更多
Electrocatalysis is key to improving energy efficiency,reducing carbon emissions,and providing a sustainable way of meeting global energy needs.Therefore,elucidating electrochemical reaction mechanisms at the electrol...Electrocatalysis is key to improving energy efficiency,reducing carbon emissions,and providing a sustainable way of meeting global energy needs.Therefore,elucidating electrochemical reaction mechanisms at the electrolyte/electrode interfaces is essential for developing advanced renewable energy technologies.However,the direct probing of real-time interfacial changes,i.e.,the surface intermediates,chemical environment,and electronic structure,under operating conditions is challenging and necessitates the use of in situ methods.Herein,we present a new lab-based instrument commissioned to perform in situ chemical analysis at liquid/solid interfaces using ambient pressure X-ray photoelectron spectroscopy(APXPS).This setup takes advantage of a chromium source of tender X-rays and is designed to study liquid/solid interfaces by the“dip and pull”method.Each of the main components was carefully described,and the results of performance tests are presented.Using a three-electrode setup,the system can probe the intermediate species and potential shifts across the liquid electrolyte/solid electrode interface.In addition,we demonstrate how this system allows the study of interfacial changes at gas/solid interfaces using a case study:a sodium–oxygen model battery.However,the use of APXPS in electrochemical studies is still in the early stages,so we summarize the current challenges and some developmental frontiers.Despite the challenges,we expect that joint efforts to improve instruments and the electrochemical setup will enable us to obtain a better understanding of the composition–reactivity relationship at electrochemical interfaces under realistic reaction conditions.展开更多
Silicon nanopillars are fabricated by inductively coupled plasma （ICP） dry etching with the cesium chloride （CsCl） islands as masks originally from self-assembly. Wafers with nanopillar texture or planar surface a...Silicon nanopillars are fabricated by inductively coupled plasma （ICP） dry etching with the cesium chloride （CsCl） islands as masks originally from self-assembly. Wafers with nanopillar texture or planar surface are subjected to phosphorus （P） diffusion by liquid dopant source （POCl3） at 870 ℃ to form P-N junctions with a depth of 300 nm. The X-ray photoelectron spectroscopy （XPS） is used to measure the Si 2p core levels of P-N junction wafer with nanopillar texture and planar surface. With a visible light excitation, the P-N junction produces a new electric potential for photoelectric characteristic, which causes the Si 2p core level to have a energy shift compared with the spectrum without the visible light. The energy shift of the Si 2p core level is -0.27 eV for the planar P-N junction and -0.18 eV for the nanopillar one. The difference in Si 2p energy shift is due to more space lattice defects and chemical bond breaks for nanopillar compared with the planar one.展开更多
This paper reports how pyrite films were prepared by thermal sulfurization of magnetron sputtered iron films and characterized by X-ray absorption near edge structure spectra and X-ray photoelectron spectroscopy on a ...This paper reports how pyrite films were prepared by thermal sulfurization of magnetron sputtered iron films and characterized by X-ray absorption near edge structure spectra and X-ray photoelectron spectroscopy on a 4B9B beam line at the Beijing Synchrotron Radiation Facility. The band gap of the pyrite agrees well with the optical band gap obtained by a spectrophotometer. The octahedral symmetry of pyrite leads to the splitting of the d orbit into t2g and eg levels. The high spin and low spin states were analysed through the difference of electron exchange interaction and the orbital crystal field. Only when the crystal field splitting is higher than 1.5 eV, the two weak peaks above the white lines can appear, and this was approved by experiments in the present work.展开更多
TixAl1-xN films have been prepared by RF reactive magnetron sputtering. X-ray diffraction results showed that TixAl1-xN thin films in this study were hexagonal wurtzite structure with the Ti content up to 0.18. X-ray ...TixAl1-xN films have been prepared by RF reactive magnetron sputtering. X-ray diffraction results showed that TixAl1-xN thin films in this study were hexagonal wurtzite structure with the Ti content up to 0.18. X-ray photoelectron spectrocopy studies provided that the Nls core-electron spectrum of TixAl1-xN thin film brodend with increasing Ti content, and the difference of the chemical shifts for Ti2p3/2 line between TiN and TixAl1-xN th77pj in film was 0.7 eV.展开更多
With the increasing interest in Cu2O-based devices for photovoltaic applications,the energy band alignment at the Cu2O/ZnO heterojunction has received more and more attention.In this work,a high-quality Cu2O/ZnO heter...With the increasing interest in Cu2O-based devices for photovoltaic applications,the energy band alignment at the Cu2O/ZnO heterojunction has received more and more attention.In this work,a high-quality Cu2O/ZnO heterojunction is fabricated on a c-Al2 O3 substrate by laser-molecular beam epitaxy,and the energy band alignment is determined by x-ray photoelectron spectroscopy.The valence band of ZnO is found to be 1.97 eV below that of Cu2O.A type-II band alignment exists at the Cu2O/ZnO heterojunction with a resulting conduction band offset of 0.77 eV,which is especially favorable for enhancing the efficiency of Cu2O/ZnO solar cells.展开更多
Different monolayers （ML） of Fe atoms were deposited on NiO （001） substrates or NiO underlayers using molecular beam epitaxy （MBE）, pulse laser deposition （PLD）, and magnetron sputtering （MS）. The magnetic p...Different monolayers （ML） of Fe atoms were deposited on NiO （001） substrates or NiO underlayers using molecular beam epitaxy （MBE）, pulse laser deposition （PLD）, and magnetron sputtering （MS）. The magnetic properties and microstructure of the films were studied. The apparent magnetic dead layer （MDL） is found to exist at the NiO/Fe interfaces of the MBE sample （about 2 ML MDL）, the PLD sample （about 3 ML MDL）, and the MS sample （about 4 ML MDL）. X-ray photoelectron spectroscopy indicates the presence of ionic Fe （Fe2＋ or Fe3＋） and metallic Ni at the NiO/Fe interfaces, which may be due to the chemical reactions between Fe and NiO layers. This also leads to the formation of MDL. The thickness of the MDL and the reaction products are related with the deposition energy of the atoms on the substrates. The interfacial reactions are effectively suppressed by inserting a thin Pt layer at the NiO/Fe interface.展开更多
The chemisorbed structure for an aromatic molecule on a silicon surface plays an important part in promoting the development of organic semiconductor material science. The carbon K-shell x-ray photoelectron spectrosc...The chemisorbed structure for an aromatic molecule on a silicon surface plays an important part in promoting the development of organic semiconductor material science. The carbon K-shell x-ray photoelectron spectroscopy（XPS） and the x-ray absorption near-edge structure（XANES） spectra of the interfacial structure of an s-triazine molecule adsorbed on Si（100） surface have been performed by the first principles, and the landscape of the s-triazine molecule on Si（100） surface has been described in detail. Both the XPS and XANES spectra have shown their dependence on different structures for the pristine s-triazine molecule and its several possible adsorbed configurations. By comparison with the XPS spectra, the XANES spectra display the strongest structural dependency of all of the studied systems and thus could be well applied to identify the chemisorbed s-triazine derivatives. The exploration of spectral components originated from non-equivalent carbons in disparate local environments has also been implemented for both the XPS and XANES spectra of s-triazine adsorbed configurations.展开更多
ZnO-based catalysts have been intensively studied because of their extraordinary performance in lower olefin synthesis,methanol synthesis and water-gas shift reactions.However,how ZnO catalyzes these reactions are sti...ZnO-based catalysts have been intensively studied because of their extraordinary performance in lower olefin synthesis,methanol synthesis and water-gas shift reactions.However,how ZnO catalyzes these reactions are still not well understood.Herein,we investigate the activations of CO_(2),O_(2)and CO on single crystalline ZnO polar surfaces at room temperature,through in-situ near-ambient-pressure X-ray photoelectron spectroscopy(NAP-XPS).It is revealed that O_(2)and CO_(2)can undergo chemisorption on ZnO polar surfaces at elevated pressures.On the ZnO(0001)surface,molecular CO_(2)(O_(2))can chemically interact with the top layer Zn atoms,leading to the formation of CO_(2)^(δ-)(O_(2)^(δ-))or partially dissociative atomic oxygen(O-)and hence the electron depletion layer in ZnO.Therefore,an apparent upward band-bending in ZnO(0001)is observed under the CO_(2)and O_(2)exposure.On the ZnO(0001)surface,the molecular chemisorbed CO_(2)(O_(2))mainly bond to the surface oxygen vacancies,which also results in an upward bandbending in ZnO(0001).In contrast,no band-bending is observed for both ZnO polar surfaces upon CO exposure.The electron-acceptor nature of the surface bounded molecules/atoms is responsible for the reversible binding energy shift of Zn 2 p_(3/2)and O 1 s in ZnO.Our findings can shed light on the fundamental understandings of CO_(2)and O_(2)activation on ZnO surfaces,especially the role of ZnO in heterogeneous catalytic reactions.展开更多
Theε-Ga2O3 p-n heterojunctions(HJ)have been demonstrated using typical p-type oxide semiconductors(NiO or SnO).Theε-Ga2O3 thin film was heteroepitaxial grown by metal organic chemical vapor deposition(MOCVD)with thr...Theε-Ga2O3 p-n heterojunctions(HJ)have been demonstrated using typical p-type oxide semiconductors(NiO or SnO).Theε-Ga2O3 thin film was heteroepitaxial grown by metal organic chemical vapor deposition(MOCVD)with three-step growth method.The polycrystalline SnO and NiO thin films were deposited on theε-Ga2O3 thin film by electron-beam evaporation and thermal oxidation,respectively.The valence band offsets(VBO)were determined by x-ray photoelectron spectroscopy(XPS)to be 2.17 eV at SnO/ε-Ga2O3 and 1.7 eV at NiO/ε-Ga2O3.Considering the bandgaps determined by ultraviolet-visible spectroscopy,the conduction band offsets(CBO)of 0.11 eV at SnO/ε-Ga2O3 and 0.44 eV at NiO/ε-Ga2O3 were obtained.The type-Ⅱband diagrams have been drawn for both p-n HJs.The results are useful to understand the electronic structures at theε-Ga2O3 p-n HJ interface,and design optoelectronic devices based onε-Ga2O3 with novel functionality and improved performance.展开更多
The most important interface-related quantities determined by band alignment are the barrier heights for charge trans- port, given by the Fermi level position at the interface. Taking Pb（Zr, Ti）O3 （PZT） as a typic...The most important interface-related quantities determined by band alignment are the barrier heights for charge trans- port, given by the Fermi level position at the interface. Taking Pb（Zr, Ti）O3 （PZT） as a typical ferroelectric material and applying X-ray photoelectron spectroscopy （XPS）, we briefly review the interface formation and barrier heights at the inter- faces between PZT and electrodes made of various metals or conductive oxides. Polarization dependence of the Schottky barrier height at a ferroelectric/electrode interface is also directly observed using XPS.展开更多
Elemental analysis,nuclear magnetic resonance carbon spectroscopy(^(13)C-NMR),X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)experiments were carried out to determine the existen...Elemental analysis,nuclear magnetic resonance carbon spectroscopy(^(13)C-NMR),X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)experiments were carried out to determine the existence of aromatic structure,heteroatom structure and fat structure in coal.MS(materials studio)software was used to optimize and construct a 3D molecular structure model of coal.A method for establishing a coal molecular structure model was formed,which was“determination of key structures in coal,construction of planar molecular structure model,and optimization of three-dimensional molecular structure model”.The structural differences were compared and analyzed.The results show that with the increase of coal rank,the dehydrogenation of cycloalkanes in coal is continuously enhanced,and the content of heteroatoms in the aromatic ring decreases.The heteroatoms and branch chains in the coal are reduced,and the structure is more orderly and tight.The stability of the structure is determined by theπ-πinteraction between the aromatic rings in the nonbonding energy EN.Key Stretching Energy The size of EB determines how tight the structure is.The research results provide a method and reference for the study of the molecular structure of medium and high coal ranks.展开更多
The increased use of rechargeable batteries in portable electronic devices and the continuous develop-ment of novel applications （e.g. transportation and large scale energy storage）, have raised a strong de-mand for...The increased use of rechargeable batteries in portable electronic devices and the continuous develop-ment of novel applications （e.g. transportation and large scale energy storage）, have raised a strong de-mand for high performance batteries with increased energy density, cycle and calendar life, safety andlower costs. This triggers significant efforts to reveal the fundamental mechanism determining batteryperformance with the use of advanced analytical techniques. However, the inherently complex character-istics of battery systems make the mechanism analysis sophisticated and difficult. Synchrotron radiationis an advanced collimated light source with high intensity and tunable energies. It has particular ad-vantages in electronic structure and geometric structure （both the short-range and long-range structure）analysis of materials on different length and time scales. In the past decades, synchrotron X-ray tech-niques have been widely used to understand the fundamental mechanism and guide the technologicaloptimization of batteries. In particular, in situ and operando techniques with high spatial and temporalresolution, enable the nondestructive, real time dynamic investigation of the electrochemical reaction,and lead to significant deep insights into the battery operation mechanism. This review gives a brief introduction of the application of synchrotron X-ray techniques to the inves-tigation of battery systems. The five widely implicated techniques, including X-ray diffraction （XRD）, PairDistribution Function （PDF）, Hard and Soft X-ray absorption spectroscopy （XAS） and X-ray photoelectronspectroscopy （XPS） will be reviewed, with the emphasis on their in situ studies of battery systems during cycling.展开更多
Infrared(IR)absorption spectroscopy has been widely used for dynamic characterization of catalysts and mechanism of catalytic reactions.However,due to the strong infrared absorption of heterogeneous catalysts(mainly o...Infrared(IR)absorption spectroscopy has been widely used for dynamic characterization of catalysts and mechanism of catalytic reactions.However,due to the strong infrared absorption of heterogeneous catalysts(mainly oxides,or supported metal and metal oxides,etc.)below 1200 cm^(-1),and the intensity of regular infrared light source rapidly decays at low-wavenumber range,most in-situ infrared spectroscopy studies are limited to the detection of surface adsorbates in the range of 4000-900 cm^(-1).The change of catalytically active component itself(M-O,M-M bond,etc.,1200-50 cm^(-1))during the reaction is hard to be tracked under reaction conditions by in-situ IR.In this work,a home-made in-situ IR reactor was designed and a sample preparing method was developed.With such progresses,the changes of reactants,products,surface adsorbates,and catalysts themselves can be measured under the same reaction conditions with a spectral range of 4000-400 cm^(-1),providing a new opportunity for in-situ characterization of heterogeneous catalysis.CO oxidation on Pd/SiO_(2) and Cu/SiO_(2) catalysts were taken as examples,since both the two catalytic systems were extensively used commercially,and moreover reduction and oxidation of palladium and copper occur during the examined reaction conditions.The characteristic bands of Pd^(2+)-O(670,608 cm^(-1)),Cu^(+)-O(635 cm^(-1))and Cu^(2+)-O(595,535 cm^(-1))were observed by IR,and the changes during CO oxidation reaction were successfully monitored by IR.The oxidation/reduction of palladium and copper were also confirmed by ex-situ XPS.Moreover,Pd^(0) in Pd/SiO_(2) and Cu^(+)in Cu/SiO_(2) were found as the thermal dynamically stable phases under the examined conditions for CO oxidation.展开更多
TiBCN films were deposited on Si(100) and cemented carbide substrates by using multi-cathodic arc ion plating in C_2H_2 and N_2atmosp^here. Their structure and mechanical properties were studied systematically under d...TiBCN films were deposited on Si(100) and cemented carbide substrates by using multi-cathodic arc ion plating in C_2H_2 and N_2atmosp^here. Their structure and mechanical properties were studied systematically under different N_2 flow rates. The results showed that the Ti BCN films were adhered well to the substrates. Rutherford backscattering sp^ectroscopy was employed to determine the relative concentration of Ti, B, C and N in the films.The chemical bonding states of the films were explored by X-ray photoelectron sp^ectroscopy, revealing the presence of bonds of Ti N, Ti(C,N), BN, pure B, sp^2C–C and sp^3C–C, which changed with the N_2 flow rate. Ti BCN films contain nanocrystals of Ti N/Ti CN and Ti B_2/Ti(B,C)embedded in an amorphous matrix consisting of amorphous BN and carbon at N_2 flow rate of up to 250 sccm.展开更多
The geometric and electronic structures of several possible adsorption configurations of the pyrazine(C4H4N2)molecule covalently attached to Si(100)surface,which is of vital importance in fabricating functional nano-d...The geometric and electronic structures of several possible adsorption configurations of the pyrazine(C4H4N2)molecule covalently attached to Si(100)surface,which is of vital importance in fabricating functional nano-devices,have been investigated using X-ray spectroscopies.The Carbon K-shell(1s)X-ray photoelectron spectroscopy(XPS)and near-edge X-ray absorption fine structure(NEXAFS)spectroscopy of predicted adsorbed structures have been simulated by density functional theory with cluster model calculations.Both XPS and NEXAFS spectra demonstrate the structural dependence on different adsorption configurations.In contrast to the XPS spectra,it is found that the NEXAFS spectra exhibiting conspicuous dependence on the structures of all the studied pyrazine/Si(100)systems can be well utilized for structural identification.In addition,according to the classification of carbon atoms,the spectral components of carbon atoms in different chemical environments have been investigated in the NEXAFS spectra as well.展开更多
High-quality needle-like CuTaS3 single crystals have been synthesized through a chemical vapor transport（CVT） process.Crystallographic data show the special double chains of edge-sharing TaS6 octahedra.The detailed ...High-quality needle-like CuTaS3 single crystals have been synthesized through a chemical vapor transport（CVT） process.Crystallographic data show the special double chains of edge-sharing TaS6 octahedra.The detailed XPS analysis of CuTaS3 was undertaken and the valence states can be described by Cu＋Ta5＋3S2-.In addition,CuTaS3 crystals were characterized with Raman spectroscopy.展开更多
The role of microstructural features on in-vitro degradation and surface film development of a thermomechanically processed Mg-4Zn-0.5Ca-0.8Mn alloy has been investigated employing electrochemical studies,scanning ele...The role of microstructural features on in-vitro degradation and surface film development of a thermomechanically processed Mg-4Zn-0.5Ca-0.8Mn alloy has been investigated employing electrochemical studies,scanning electron microscopy and X-ray photoelectron spectroscopy.The specimen forged at 523 K temperature developed a coarse unimodal microstructure consisting of basal oriented grains,whereas the specimens forged at 623 K and 723 K temperatures exhibited bimodal microstructures containing randomly oriented fine grains and basal oriented coarse grains.The bimodal microstructures exerted higher resistance to corrosion compared to the unimodal microstructure in presence of a protective surface film.The optimum size distribution of fine and coarse grains as well as the prevalence of basal oriented grains led to the lowest anodic current density in the specimen forged at 623 K.The morphology of Ca_(2)Mg_(6)Zn_(3)precipitates governed the cathodic kinetics by controlling the anode to cathode surface area ratio.Despite the specimen forged at 723 K comprised comparatively lower fraction of precipitates than at 623 K,the mesh-like precipitate morphology increased the effective cathodic surface area,leading to enhanced localised corrosion in the former specimen.Optimal microstructural features developed at 623 K forging temperature formed a well-protective surface film with lower Mg(OH)_(2)to MgO ratio,exhibiting distinctly high polarization resistance and superior cytocompatibility in terms of cell-proliferation and cell-differentiation.展开更多
Electroless deposition has been used to deposit Ni-P films on glass slides using the reducing agent sodium hypophosphite. This has been done with a purpose to use Ni-P films as back contact for silicon carbide radiati...Electroless deposition has been used to deposit Ni-P films on glass slides using the reducing agent sodium hypophosphite. This has been done with a purpose to use Ni-P films as back contact for silicon carbide radiation detectors. By keeping deposition time, temperature, pH and concentration of the precursor solution constant, the film deposition has been done. XPS studies were done to analyze the composition and stoichiometry of Ni-P thin films.展开更多
基金the financial support from the National Natural Science Foundation of China(No.12174057,22179020)Natural Science Foundation of Fujian Province(Grant No.2021L3011).
文摘Understanding the evolution of the solid electrolyte-electrode interface is currently one of the most challenging obstacles in the development of solid-state batteries(SSBs).Here,we develop an X-ray Photoelectron Spectroscopy(XPS)that allows for operando measurement during cycling.Based on theoretical analysis and the modulated electrode and detector co-grounding mode,the displacement of binding energy can be correlated with the surface electrostatic potential of the material,revealing the charge distribution and composition evolution of the space charge layer between the cathode and the electrolyte.In the investigation of typical LiCoO_(2)(LCO)/Li6PS5Cl(LPSC)/Li-In batteries,we observed the static potential difference and oxidative decomposition between LPSC and LCO,and the effectiveness of the LiNbO3 coating in reducing potential difference and inhibiting the diffusion of Co and oxidation of S species.Furthermore,our study also revealed that the potential drop between LiNi0⋅8Co0⋅1Mn0⋅1O_(2) and LPSC is smaller than that of LCO,whilst that between Li3InCl6 and LCO remains near zero.The proposed operando XPS method offers a novel approach for real-time monitoring of interface potential and species formation,providing rational guidance for the interface engineering in SSBs.
基金Project supported by the Shandong Provincial Natural Science Foundation,China(Grant Nos.ZR2022MA025 and ZR2020MA077).
文摘The possible configurations of pyrrole absorbed on a Si(100)surface have been investigated by x-ray photoelectron spectroscopy(XPS)and near-edge x-ray absorption fine structure(NEXAFS)spectra.The C-1s XPS and NEXAFS spectra of these adsorption configurations have been calculated by using the density functional theory(DFT)method and fullcore hole(FCH)approximation to investigate the relationship between the adsorption configurations and the spectra.The result shows that the XPS and NEXAFS spectra are structurally dependent on the configurations of pyrrole absorbed on the Si(100)surface.Compared with the XPS,the NEXAFS spectra are relatively sensitive to the adsorption configurations and can accurately identify them.The NEXAFS decomposition spectra produced by non-equivalent carbon atoms have also been calculated and show that the spectral features vary with the diverse types of carbon atoms and their structural environments.
文摘Electrocatalysis is key to improving energy efficiency,reducing carbon emissions,and providing a sustainable way of meeting global energy needs.Therefore,elucidating electrochemical reaction mechanisms at the electrolyte/electrode interfaces is essential for developing advanced renewable energy technologies.However,the direct probing of real-time interfacial changes,i.e.,the surface intermediates,chemical environment,and electronic structure,under operating conditions is challenging and necessitates the use of in situ methods.Herein,we present a new lab-based instrument commissioned to perform in situ chemical analysis at liquid/solid interfaces using ambient pressure X-ray photoelectron spectroscopy(APXPS).This setup takes advantage of a chromium source of tender X-rays and is designed to study liquid/solid interfaces by the“dip and pull”method.Each of the main components was carefully described,and the results of performance tests are presented.Using a three-electrode setup,the system can probe the intermediate species and potential shifts across the liquid electrolyte/solid electrode interface.In addition,we demonstrate how this system allows the study of interfacial changes at gas/solid interfaces using a case study:a sodium–oxygen model battery.However,the use of APXPS in electrochemical studies is still in the early stages,so we summarize the current challenges and some developmental frontiers.Despite the challenges,we expect that joint efforts to improve instruments and the electrochemical setup will enable us to obtain a better understanding of the composition–reactivity relationship at electrochemical interfaces under realistic reaction conditions.
基金supported by the National Natural Science Foundation of China(Grant No.50972144)
文摘Silicon nanopillars are fabricated by inductively coupled plasma （ICP） dry etching with the cesium chloride （CsCl） islands as masks originally from self-assembly. Wafers with nanopillar texture or planar surface are subjected to phosphorus （P） diffusion by liquid dopant source （POCl3） at 870 ℃ to form P-N junctions with a depth of 300 nm. The X-ray photoelectron spectroscopy （XPS） is used to measure the Si 2p core levels of P-N junction wafer with nanopillar texture and planar surface. With a visible light excitation, the P-N junction produces a new electric potential for photoelectric characteristic, which causes the Si 2p core level to have a energy shift compared with the spectrum without the visible light. The energy shift of the Si 2p core level is -0.27 eV for the planar P-N junction and -0.18 eV for the nanopillar one. The difference in Si 2p energy shift is due to more space lattice defects and chemical bond breaks for nanopillar compared with the planar one.
基金Project supported by the National Natural Science Foundation of China (Grant No 102750770)
文摘This paper reports how pyrite films were prepared by thermal sulfurization of magnetron sputtered iron films and characterized by X-ray absorption near edge structure spectra and X-ray photoelectron spectroscopy on a 4B9B beam line at the Beijing Synchrotron Radiation Facility. The band gap of the pyrite agrees well with the optical band gap obtained by a spectrophotometer. The octahedral symmetry of pyrite leads to the splitting of the d orbit into t2g and eg levels. The high spin and low spin states were analysed through the difference of electron exchange interaction and the orbital crystal field. Only when the crystal field splitting is higher than 1.5 eV, the two weak peaks above the white lines can appear, and this was approved by experiments in the present work.
基金This work was supported by the National Natural Science Foundation of China under grant No.10474074the Hubei Natural Science Foundation under grant No.2001ABB060.
文摘TixAl1-xN films have been prepared by RF reactive magnetron sputtering. X-ray diffraction results showed that TixAl1-xN thin films in this study were hexagonal wurtzite structure with the Ti content up to 0.18. X-ray photoelectron spectrocopy studies provided that the Nls core-electron spectrum of TixAl1-xN thin film brodend with increasing Ti content, and the difference of the chemical shifts for Ti2p3/2 line between TiN and TixAl1-xN th77pj in film was 0.7 eV.
基金Project supported by the National Natural Science Foundation of China(Grant No.11404302)the Laser Fusion Research Center Funds for Young Talents,China(Grant No.RCFPD1-2017-9)
文摘With the increasing interest in Cu2O-based devices for photovoltaic applications,the energy band alignment at the Cu2O/ZnO heterojunction has received more and more attention.In this work,a high-quality Cu2O/ZnO heterojunction is fabricated on a c-Al2 O3 substrate by laser-molecular beam epitaxy,and the energy band alignment is determined by x-ray photoelectron spectroscopy.The valence band of ZnO is found to be 1.97 eV below that of Cu2O.A type-II band alignment exists at the Cu2O/ZnO heterojunction with a resulting conduction band offset of 0.77 eV,which is especially favorable for enhancing the efficiency of Cu2O/ZnO solar cells.
基金supported by the National Natural Science Foundation of China (Nos.50871014, 50831002, 50971021, and 50901007)the Funding Project for Academic Human Resources Development in Institutions of Higher Learning under the Jurisdiction of Beijing Municipality (No.PHR201007122)
文摘Different monolayers （ML） of Fe atoms were deposited on NiO （001） substrates or NiO underlayers using molecular beam epitaxy （MBE）, pulse laser deposition （PLD）, and magnetron sputtering （MS）. The magnetic properties and microstructure of the films were studied. The apparent magnetic dead layer （MDL） is found to exist at the NiO/Fe interfaces of the MBE sample （about 2 ML MDL）, the PLD sample （about 3 ML MDL）, and the MS sample （about 4 ML MDL）. X-ray photoelectron spectroscopy indicates the presence of ionic Fe （Fe2＋ or Fe3＋） and metallic Ni at the NiO/Fe interfaces, which may be due to the chemical reactions between Fe and NiO layers. This also leads to the formation of MDL. The thickness of the MDL and the reaction products are related with the deposition energy of the atoms on the substrates. The interfacial reactions are effectively suppressed by inserting a thin Pt layer at the NiO/Fe interface.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11874242,11804196,and 11804197)
文摘The chemisorbed structure for an aromatic molecule on a silicon surface plays an important part in promoting the development of organic semiconductor material science. The carbon K-shell x-ray photoelectron spectroscopy（XPS） and the x-ray absorption near-edge structure（XANES） spectra of the interfacial structure of an s-triazine molecule adsorbed on Si（100） surface have been performed by the first principles, and the landscape of the s-triazine molecule on Si（100） surface has been described in detail. Both the XPS and XANES spectra have shown their dependence on different structures for the pristine s-triazine molecule and its several possible adsorbed configurations. By comparison with the XPS spectra, the XANES spectra display the strongest structural dependency of all of the studied systems and thus could be well applied to identify the chemisorbed s-triazine derivatives. The exploration of spectral components originated from non-equivalent carbons in disparate local environments has also been implemented for both the XPS and XANES spectra of s-triazine adsorbed configurations.
基金financial supports from the National Natural Science Foundation of China(Grant no.91645102 and 22002031)the Singapore National Research Foundation under the grant of NRF2017NRF-NSFC001-007the NUS Flagship Green Energy Programme。
文摘ZnO-based catalysts have been intensively studied because of their extraordinary performance in lower olefin synthesis,methanol synthesis and water-gas shift reactions.However,how ZnO catalyzes these reactions are still not well understood.Herein,we investigate the activations of CO_(2),O_(2)and CO on single crystalline ZnO polar surfaces at room temperature,through in-situ near-ambient-pressure X-ray photoelectron spectroscopy(NAP-XPS).It is revealed that O_(2)and CO_(2)can undergo chemisorption on ZnO polar surfaces at elevated pressures.On the ZnO(0001)surface,molecular CO_(2)(O_(2))can chemically interact with the top layer Zn atoms,leading to the formation of CO_(2)^(δ-)(O_(2)^(δ-))or partially dissociative atomic oxygen(O-)and hence the electron depletion layer in ZnO.Therefore,an apparent upward band-bending in ZnO(0001)is observed under the CO_(2)and O_(2)exposure.On the ZnO(0001)surface,the molecular chemisorbed CO_(2)(O_(2))mainly bond to the surface oxygen vacancies,which also results in an upward bandbending in ZnO(0001).In contrast,no band-bending is observed for both ZnO polar surfaces upon CO exposure.The electron-acceptor nature of the surface bounded molecules/atoms is responsible for the reversible binding energy shift of Zn 2 p_(3/2)and O 1 s in ZnO.Our findings can shed light on the fundamental understandings of CO_(2)and O_(2)activation on ZnO surfaces,especially the role of ZnO in heterogeneous catalytic reactions.
基金Project supported by the National Natural Science Foundation of China(Grant No.61774172)the Guangdong Provincial Department of Science and Technology,China(Grant Nos.2019B010132002 and 2016B090918106)+1 种基金the Pengcheng Scholar Funding(2018)Shenzhen Science and Technology Innovation Committee,China(Grant No.KQJSCX20180323174713505).
文摘Theε-Ga2O3 p-n heterojunctions(HJ)have been demonstrated using typical p-type oxide semiconductors(NiO or SnO).Theε-Ga2O3 thin film was heteroepitaxial grown by metal organic chemical vapor deposition(MOCVD)with three-step growth method.The polycrystalline SnO and NiO thin films were deposited on theε-Ga2O3 thin film by electron-beam evaporation and thermal oxidation,respectively.The valence band offsets(VBO)were determined by x-ray photoelectron spectroscopy(XPS)to be 2.17 eV at SnO/ε-Ga2O3 and 1.7 eV at NiO/ε-Ga2O3.Considering the bandgaps determined by ultraviolet-visible spectroscopy,the conduction band offsets(CBO)of 0.11 eV at SnO/ε-Ga2O3 and 0.44 eV at NiO/ε-Ga2O3 were obtained.The type-Ⅱband diagrams have been drawn for both p-n HJs.The results are useful to understand the electronic structures at theε-Ga2O3 p-n HJ interface,and design optoelectronic devices based onε-Ga2O3 with novel functionality and improved performance.
基金Project supported by the German Science Foundation(DFG)within the Collaborative Research Center SFB 595(Electrical Fatigue of Functional Materials)the National Natural Science Foundation of China(Grant Nos.11274287,11174001,and 11204313)the National Basic Research Program of China(Grant No.2012CB927402)
文摘The most important interface-related quantities determined by band alignment are the barrier heights for charge trans- port, given by the Fermi level position at the interface. Taking Pb（Zr, Ti）O3 （PZT） as a typical ferroelectric material and applying X-ray photoelectron spectroscopy （XPS）, we briefly review the interface formation and barrier heights at the inter- faces between PZT and electrodes made of various metals or conductive oxides. Polarization dependence of the Schottky barrier height at a ferroelectric/electrode interface is also directly observed using XPS.
基金supported by the National Natural Science Foundation of China(41872174 and 42072189)the Program for Innovative Research Team(in Science and Technology)in the Universities of Henan Province,China(21IRTSTHN007)the Program for Innovative Research Team(in Science and Technology)of Henan Polytechnic University(T2020-4)。
文摘Elemental analysis,nuclear magnetic resonance carbon spectroscopy(^(13)C-NMR),X-ray photoelectron spectroscopy(XPS)and Fourier transform infrared spectroscopy(FTIR)experiments were carried out to determine the existence of aromatic structure,heteroatom structure and fat structure in coal.MS(materials studio)software was used to optimize and construct a 3D molecular structure model of coal.A method for establishing a coal molecular structure model was formed,which was“determination of key structures in coal,construction of planar molecular structure model,and optimization of three-dimensional molecular structure model”.The structural differences were compared and analyzed.The results show that with the increase of coal rank,the dehydrogenation of cycloalkanes in coal is continuously enhanced,and the content of heteroatoms in the aromatic ring decreases.The heteroatoms and branch chains in the coal are reduced,and the structure is more orderly and tight.The stability of the structure is determined by theπ-πinteraction between the aromatic rings in the nonbonding energy EN.Key Stretching Energy The size of EB determines how tight the structure is.The research results provide a method and reference for the study of the molecular structure of medium and high coal ranks.
基金the National Natural Science Foundation of China (Grant nos.21233004,21303147 and 21473148,etc.)the National Key Research and Development Program (Grant no.2016YFB0901500)
文摘The increased use of rechargeable batteries in portable electronic devices and the continuous develop-ment of novel applications （e.g. transportation and large scale energy storage）, have raised a strong de-mand for high performance batteries with increased energy density, cycle and calendar life, safety andlower costs. This triggers significant efforts to reveal the fundamental mechanism determining batteryperformance with the use of advanced analytical techniques. However, the inherently complex character-istics of battery systems make the mechanism analysis sophisticated and difficult. Synchrotron radiationis an advanced collimated light source with high intensity and tunable energies. It has particular ad-vantages in electronic structure and geometric structure （both the short-range and long-range structure）analysis of materials on different length and time scales. In the past decades, synchrotron X-ray tech-niques have been widely used to understand the fundamental mechanism and guide the technologicaloptimization of batteries. In particular, in situ and operando techniques with high spatial and temporalresolution, enable the nondestructive, real time dynamic investigation of the electrochemical reaction,and lead to significant deep insights into the battery operation mechanism. This review gives a brief introduction of the application of synchrotron X-ray techniques to the inves-tigation of battery systems. The five widely implicated techniques, including X-ray diffraction （XRD）, PairDistribution Function （PDF）, Hard and Soft X-ray absorption spectroscopy （XAS） and X-ray photoelectronspectroscopy （XPS） will be reviewed, with the emphasis on their in situ studies of battery systems during cycling.
文摘Infrared(IR)absorption spectroscopy has been widely used for dynamic characterization of catalysts and mechanism of catalytic reactions.However,due to the strong infrared absorption of heterogeneous catalysts(mainly oxides,or supported metal and metal oxides,etc.)below 1200 cm^(-1),and the intensity of regular infrared light source rapidly decays at low-wavenumber range,most in-situ infrared spectroscopy studies are limited to the detection of surface adsorbates in the range of 4000-900 cm^(-1).The change of catalytically active component itself(M-O,M-M bond,etc.,1200-50 cm^(-1))during the reaction is hard to be tracked under reaction conditions by in-situ IR.In this work,a home-made in-situ IR reactor was designed and a sample preparing method was developed.With such progresses,the changes of reactants,products,surface adsorbates,and catalysts themselves can be measured under the same reaction conditions with a spectral range of 4000-400 cm^(-1),providing a new opportunity for in-situ characterization of heterogeneous catalysis.CO oxidation on Pd/SiO_(2) and Cu/SiO_(2) catalysts were taken as examples,since both the two catalytic systems were extensively used commercially,and moreover reduction and oxidation of palladium and copper occur during the examined reaction conditions.The characteristic bands of Pd^(2+)-O(670,608 cm^(-1)),Cu^(+)-O(635 cm^(-1))and Cu^(2+)-O(595,535 cm^(-1))were observed by IR,and the changes during CO oxidation reaction were successfully monitored by IR.The oxidation/reduction of palladium and copper were also confirmed by ex-situ XPS.Moreover,Pd^(0) in Pd/SiO_(2) and Cu^(+)in Cu/SiO_(2) were found as the thermal dynamically stable phases under the examined conditions for CO oxidation.
基金supported by the National Natural Science Foundation of China(Nos.11375135 and 11275141)International Cooperation Program of the Ministry of Science and Technology of China(No.2015DFR00720)Fundamental Research Funds for the Central Universities
文摘TiBCN films were deposited on Si(100) and cemented carbide substrates by using multi-cathodic arc ion plating in C_2H_2 and N_2atmosp^here. Their structure and mechanical properties were studied systematically under different N_2 flow rates. The results showed that the Ti BCN films were adhered well to the substrates. Rutherford backscattering sp^ectroscopy was employed to determine the relative concentration of Ti, B, C and N in the films.The chemical bonding states of the films were explored by X-ray photoelectron sp^ectroscopy, revealing the presence of bonds of Ti N, Ti(C,N), BN, pure B, sp^2C–C and sp^3C–C, which changed with the N_2 flow rate. Ti BCN films contain nanocrystals of Ti N/Ti CN and Ti B_2/Ti(B,C)embedded in an amorphous matrix consisting of amorphous BN and carbon at N_2 flow rate of up to 250 sccm.
基金the National Natural Science Foundation of China(No.11874242,No.11804196,No.11804197)support provided by China Scholarship Council(CSC)for Yong Ma to Royal Institute of Technology(KTH)is acknowledgedsupport of the Taishan Scholar Project of Shandong Province。
文摘The geometric and electronic structures of several possible adsorption configurations of the pyrazine(C4H4N2)molecule covalently attached to Si(100)surface,which is of vital importance in fabricating functional nano-devices,have been investigated using X-ray spectroscopies.The Carbon K-shell(1s)X-ray photoelectron spectroscopy(XPS)and near-edge X-ray absorption fine structure(NEXAFS)spectroscopy of predicted adsorbed structures have been simulated by density functional theory with cluster model calculations.Both XPS and NEXAFS spectra demonstrate the structural dependence on different adsorption configurations.In contrast to the XPS spectra,it is found that the NEXAFS spectra exhibiting conspicuous dependence on the structures of all the studied pyrazine/Si(100)systems can be well utilized for structural identification.In addition,according to the classification of carbon atoms,the spectral components of carbon atoms in different chemical environments have been investigated in the NEXAFS spectra as well.
基金Supported by the National Natural Science Foundation of China(Nos.20471022, 40673051 and 20121103)the Program for New Century Excellent Talents(NCET) in Universities of China
文摘High-quality needle-like CuTaS3 single crystals have been synthesized through a chemical vapor transport（CVT） process.Crystallographic data show the special double chains of edge-sharing TaS6 octahedra.The detailed XPS analysis of CuTaS3 was undertaken and the valence states can be described by Cu＋Ta5＋3S2-.In addition,CuTaS3 crystals were characterized with Raman spectroscopy.
文摘The role of microstructural features on in-vitro degradation and surface film development of a thermomechanically processed Mg-4Zn-0.5Ca-0.8Mn alloy has been investigated employing electrochemical studies,scanning electron microscopy and X-ray photoelectron spectroscopy.The specimen forged at 523 K temperature developed a coarse unimodal microstructure consisting of basal oriented grains,whereas the specimens forged at 623 K and 723 K temperatures exhibited bimodal microstructures containing randomly oriented fine grains and basal oriented coarse grains.The bimodal microstructures exerted higher resistance to corrosion compared to the unimodal microstructure in presence of a protective surface film.The optimum size distribution of fine and coarse grains as well as the prevalence of basal oriented grains led to the lowest anodic current density in the specimen forged at 623 K.The morphology of Ca_(2)Mg_(6)Zn_(3)precipitates governed the cathodic kinetics by controlling the anode to cathode surface area ratio.Despite the specimen forged at 723 K comprised comparatively lower fraction of precipitates than at 623 K,the mesh-like precipitate morphology increased the effective cathodic surface area,leading to enhanced localised corrosion in the former specimen.Optimal microstructural features developed at 623 K forging temperature formed a well-protective surface film with lower Mg(OH)_(2)to MgO ratio,exhibiting distinctly high polarization resistance and superior cytocompatibility in terms of cell-proliferation and cell-differentiation.
文摘Electroless deposition has been used to deposit Ni-P films on glass slides using the reducing agent sodium hypophosphite. This has been done with a purpose to use Ni-P films as back contact for silicon carbide radiation detectors. By keeping deposition time, temperature, pH and concentration of the precursor solution constant, the film deposition has been done. XPS studies were done to analyze the composition and stoichiometry of Ni-P thin films.
