Effects of Oxygen Vacancy on the Electronic Structure of Monoclinic HfO_2 and Its Defect Energy States by the First Principles Calculation

The structural relaxation, electronic structures, formation energies and transition energy levels of monoclinic HfO2 with neutral and charged oxygen vacancies have been studied using the first principles calculation based on density-functional theory and generalized gradient approximation. The results show that oxygen vacancies with different charge states can be formed in m-HfO2 under both oxygen-rich and oxygen-poor conditions. Especially, lower formation energy is obtained in poor oxygen environment. In the presence of oxygen vacancies with different charge states, extra levels can be observed at different positions in the band gap. And the most stable charge states are obtained for varying Fermi levels in the HfO2 band gap. It is found that oxygen vacancy in m-HfO2 has a negative-U behavior.

Bipolar Resistive Switching Characteristics of TiN/HfO_(x)/ITO Devices for Resistive Random Access Memory Applications

Resistive switching characteristics of hafnium oxide are studied for possible nonvolatile memory device applications.The HfOx films with different oxygen contents are deposited by rf magnetron sputtering under different O_(2) flow rates.The films are amorphous,and the stoichiometric of the film is improved by increasing the O_(2) flow rate.Current-voltage characteristics of the TiN/HfOx/ITO device are investigated with 1 mA compliance.The bipolar resistive switching behavior is observed for the TiN/HfOx/ITO structure,and the resistive switching mechanism of the TiN/HfOx/ITO structure is explained by trap-controlled space charge limit current conduction.

Tribological property and wear mechanism of undercooled Ni-Pb monotectic alloys

The tribological properties of Ni-31.44%Pb monotectic alloys were measured by using a SRV reciprocating tribo-tester. The effects of load, sliding speed and melt undercooling on wear rate of the sample were investigated. The worn surface of Ni-31.44%Pb was examined using scanning electron microscope （SEM） and X-ray photoelectron spectroscope （XPS）. The results show that the wear properties of the samples undercooled by 80 K and 310 K are obviously superior, which is attributed to more efficient transfer of Pb from the bulk material to the worn surface. The lubricating film is identified as a mixture of Ni2O3 and PbO by XPS analysis. At the same load and sliding speed, the predominant wear mechanisms can be identified as oxidative wear for the lower and larger undercooling, and plastic deformation and fracture for the medium undercooling.

Microscopic Phase-field Simulation of Competition Mechanism Between Ll_2 and D0_(22) Structure in Ni-Cr-Al Alloy

Simulations are performed on temporal evolution of atom morphology and ordering parameters of Ni-14.5 Cr-16.5 Al alloy during early precipitation process at different temperatures based on microscopic phase-field theory; the relationship between precipitation sequence and mechanism of L12 and D022 structure and precipitation temperature are illuminated. The nonstoichiometric ordered L12 phases appear first with congruent ordering＋spinodal decomposition mechanism which is then followed by precipitation of D022 phases at ordering domain boundaries of L12 phases by spinodal decomposition mechanism at 1073 K and 1223 K. The nonstoichiometric L12 phases transform to stoichiometric ordering phases gradually. The incubation period of L12 and D022 phases is shorter at 1073 K than that 1223 K, and growth speed is higher at 1073 K. At 1373 K, L12 and D022 phases appear simultaneously by non-classical nucleation and growth mechanism. After that the particles of D022 phases diminish and disappear gradually; L12 phases grow and single L12 phases are remained at last.

Electronic and Optical Properties of Cubic SrHfO_3

In order to clarify the mechanism of optical transitions for cubic SrHfO_3, we have investigated the electronicstructure and optical properties of cubic SrHfO_3 using the plane-wave ultrasoft pseudopotential technique based on thefirst-principles density-functional theory (DFT).The ground-state properties, obtained by minimizing the total energy,are in favorable agreement with the previous work.From the band structure and charge densities as well as the theoryof crystal-field and molecular-orbital bonding, we have systematically studied how the optical transitions are affected bythe electronic structure and molecular orbitals.Our calculated complex dielectric function is in good agreement withthe experimental data and the optical transitions are in accord with the electronic structure.

First-Principles Calculations of Structural,Elastic and Electronic Properties of Tetragonal HfO_2 under Pressure

Structural, elastic and electronic properties of tetragonal Hf02 at applied hydrostatic pressure up to 50 GPa have been investigated using the plane-wave ultrasoft pseudopotential technique based on the first-principles density- functional theory （DFT）. The calculated ground-state properties are in good agreement with previous theoretical and experimental data. Six independent elastic constants of tetragonal Hf02 have been calculated at zero pressure and high pressure. From the obtained elastic constants, the bulk, shear and Young＇s modulus, Poisson＇s coefficients, acoustic velocity and Debye temperature have been calculated at the applied pressure. Band structure shows that tetragonal Hf02 is an indirect band gap. The variation of the gap versus pressure is well fitted to a quadratic function.

Influence of Pressure on the Structural,Electronic and Mechanical Properties of Cubic SrHfO_(3):A First-Principles Study

The structural,electronic and mechanical properties of cubic SrHfO_(3) under hydrostatic pressure up to 70 GPa are investigated using the first-principles density functional theory(DFT).The calculated lattice parameter,elastic constants and mechanical properties of cubic SrHfO_(3) at zero pressure are in good agreement with the available experimental data and other calculational values.As pressure increases,cubic SrHfO_(3) will change from an indirect band gap(Γ-R)compound to a direct band gap(Γ-Γ)compound.Charge densities reveal the coexistence of covalent bonding and ionic bonding in cubic SrHfO_(3).With the increase of pressure,both the covalent bonding(HfO)and ionic bonding(SrO)are strengthened.Cubic SrHfO_(3) is mechanically stable when pressure is lower than 55.1 GPa,whereas that is instable when pressure is higher than 55.1 GPa.With the increasing pressure,enthalpy,bulk modulus,shear modulus and Young's modulus increase,whereas the lattice parameter decreases.Moreover,cubic SrHfO_(3) under pressure has higher hardness and better ductility than that at zero pressure.

Effects of Film Thickness and Ar/O2 Ratio on Resistive Switching Characteristics of HfOx-Based Resistive-Switching Random Access Memories

Cu/HfOx/n^＋Si devices are fabricated to investigate the influence of technological parameters including film thickness and Ar/02 ratio on the resistive switching （RS） characteristics of HfOx films, in terms of switch ratio, endurance properties, retention time and multilevel storage. It is revealed that the RS characteristics show strong dependence on technological parameters mainly by altering the defects （oxygen vacancies） in the film. The sample with thickness of 2Onto and Ar/O2 ratio of 12：3 exhibits the best RS behavior with the potential of multilevel storage. The conduction mechanism of all the films is interpreted based on the filamentary model.

Influence of Rapid Thermal Annealing on the Structure and Electrical Properties of Ce-Doped HfO2 Gate Dielectric

Ce-doped Hf02 （HfCeO） films are prepared by radio-frequency magnetron sputtering. The influences of rapid thermal annealing on the structure and electrical properties of HfCeO films are investigated. The results show that the incorporation of Ce into Hf02 increases the crystallization temperature of Hf02, and the cubic phase of Hf02 can be stabilized by incorporating Ce into Hf02. After high temperature annealing, Hf 4f core level spectra shift to a higher energy, whereas O 1s core level spectra shift to a lower energy. With increasing annealing temperatures, the effective permittivity increases, whereas the flat-band voltage shift and effective oxide charge density decrease. Moreover, the leakage current density of the HfCeO films decreases initially, and then increases as the annealing temperature increases.

Mechanisms of eutectic lamellar destabilization upon rapid solidification of an undercooled Ag-39.9 at.% Cu eutectic alloy

The eutectic Ag-Cu alloys exhibiting fine Ag-Cu lamellar eutectic structure formed upon rapid solidification have great potentials being used in various engineering fields.However,the desired fine primary lamellar eutectic structure(PLES)is usually replaced by a coarse anomalous eutectic structure(AES)when the undercooling prior to solidification exceeds a certain value.The forming mechanism of AES in the undercooled eutectic Ag-Cu alloy has been a controversial issue.In this work,the undercooled Ag-39.9 at.% Cu eutectic alloy is solidified under different cooling conditions by using techniques of melt fluxing and copper mold casting.The results show that the coupled eutectic growth of this alloy undergoes a transition from a slow eutectic-cellular growth(ECG)to a rapid eutectic-dendritic growth(EDG)above a undercooling of 72 K,accompanying with an abrupt change of the distribution and amount of AES in as-solidified microstructures.Two kinds of primary lamellar eutectic structures are formed by ECG and EDG during recalescence,respectively.The destabilization of PLES that causes the formation of AES is ascribed to two different mechanisms based on the microstructural examination and theoretical calculations.Below 72 K,the destabilization of PLES formed by slow ECG is caused by the mechanism of"termination migration"driven by interfacial energy.While above 72 K,the destabilization of PLES formed by rapid EDG is attributed to the unstable perturbation of interface driven by interfacial energy and solute supersaturation.

Stress Distribution in the Cruciform Specimen under Transverse Tension Stress for SiC/Ti-6Al-4V Composites

The cruciform specimen was selected to obtain the transverse tensile behavior of SiC fiber reinforced titanium matrix composites. Moreover, the means of combining the unilaterally coupled finite element method with the transverse tensile test was developed to evaluate the interfacial normal bond strength of composites. The results showed that the initial non-linearity in the transverse stress-strain curve of SiC/Ti-6Al-4V occurs at the stress of 350 MPa. The means of combining the unilaterally coupled finite element method with the transverse tensile test is an effective method to predict the interfacial normal bond strength of composites. In addition, the interface failure mechanism of composites was analyzed in detail.

Controllable preparation of ultrathin 2D BiOBr crystals for high-performance ultraviolet photodetector

Ternary layered compound materials(bismuth oxyhalides and metal phosphorus trichalcogenides)stand out in electronic and optoelectronic fields due to their interesting physical properties.However,few studies focus on the preparation of high-quality two-dimensional(2D)BiOBr crystals with a typical layered structure,let alone their optoelectronic applications.Here,for the first time,high-quality 2D BiOBr crystals with ultrathin thicknesses(less than 10 nm)and large domain sizes(~100μm)were efficiently prepared via a modified space-confined chemical vapor deposition(SCCVD)method.It is demonstrated that a moderate amount of H2O molecules in the SCCVD system greatly promote the formation of high-quality 2D BiOBr crystals because of the strong polarity of H2O molecules.In addition,a linear relationship between the thickness of BiOBr nanosheets and Raman shift of A1g(1)mode was found.Corresponding theoretical calculations were carried out to verify the experimental data.Furthermore,the BiOBr-based photodetector was fabricated,exhibiting excellent performances with a responsivity of 12.4 A W-1 and a detectivity of 1.6×1013 Jones at 365 nm.This study paves the way for controllable preparation of high-quality 2D BiOBr crystals and implies intriguing opportunities of them in optoelectronic applications.

Charge transport and bipolar switching mechanism in a Cu/HfO_2/Pt resistive switching cell

Bipolar resistance switching characteristics are investigated in Cu/sputtered-HfO_2/Pt structure in the application of resistive random access memory（RRAM）.The conduction mechanism of the structure is characterized to be SCLC conduction.The dependence of resistances in both high resistance state（HRS） and low resistance state（LRS） on the temperature and device area are studied.Then,the composition and chemical bonding state of Cu and Hf at Cu/HfO_2 interface region are analyzed by x-ray photoelectron spectroscopy（XPS）.Combining the electrical characteristics and the chemical structure at the interface,a model for the resistive switching effect in Cu/HfO_2/Pt stack is proposed.According to this model,the generation and recovery of oxygen vacancies in the HfO_2 film are responsible for the resistance change.

Advances and challenges on springback control for creep age forming of aluminum alloy

Creep age forming(CAF)is an advanced forming technology that combines creep deformation and age hardening processes.When compared with the conventional forming technologies including roll bending and shot-peen forming,CAF has many advantages of low residual stress,excellent dimensional stability,good service performance and short production cycle.It is an optimal technique for precise manufacturing for shape and properties of large-scale complicated thinwalled components of light-weight and high strength aluminum alloys in the aviation and aerospace industries.Nevertheless,CAF has an inevitable disadvantage that a large amount of springback occurs after unloading,which brings a challenge on the accurate shape forming and property tailoring of components.Therefore,how to achieve accurate prediction and control of springback has always been a bottleneck hindering the development of CAF to more industrial applications.After the factors of affecting springback and measures of reducing springback are summarized from the internal and external aspects,constitutive models for predicting springback and springback compensation methods for CAF of aluminum alloy panel components are reviewed.Then,a review of research progresses on tool design for CAF is presented.Finally,in view of the key issue that it is difficult to predict and control the shape and properties of components during CAF,the technical challenges are discussed and future development trends of CAF are prospected.

Annealing Effects on Structural,Optical Properties and Laser-Induced Damage Threshold of MgF2 Thin Films

The chemical structures, optical properties and laser-induced damage thresholds of magnesium fluoride films annealed at different temperatures were investigated. The results showed that the stoichiometry of MgF2 film changed a little with the increase in annealing temperature. Analysis of the optical properties indicated that excellent antireflection behavior of the film in the range of 200-400 nm can be obtained by the samples coated with MgF2 film. The refractive index increased and the extinction coefficient decreased with increasing annealing temperature. Compared with the asdeposited films, the laser-induced damage threshold was improved after annealing process and decreased with the increase in annealing temperature, which was probably due to the denser film and more absorption centers under higher annealing temperature.

Transition of dynamic recrystallization mechanism during hot deformation of Incoloy 028 alloy

Dynamic recrystallization(DRX)plays significant roles in manipulating of microstructures during hot deformation and the result mechanical properties;however,the underling mechanism leading to multi scale-microstructures remains poorly understood.Here,the DRX mechanism under wide processing conditions(i.e.950-1200°C,0.001-10 s-1)in Incoloy 028 alloy was investigated,where the relationships among flow stress,Z parameter and grain size,as well as the evolution of characteristic microstructures(grain size,sub-grain boundaries,and high angle grain boundaries),are established.As the values of Z parameters decrease(corresponding to decreased flow stresses),three typical softening mechanisms successively occur,ranging from continuous DRX controlled by dislocation glide,discontinuous DRX dominated by dislocation motion(climb and cross/multiple slip)and grain boundary migration,to dynamic normal/abnormal grain growth resulting from grain boundary migration,with transition regions where two adjacent mechanisms occur simultaneously.Correspondingly,these above three softening mechanisms result in ultrafine,fine and coarse grains,respectively.The present findings demonstrate a comprehensive understanding of DRX mechanism over a wide range of processing conditions,and further provide a new guideline for preparing single crystals.

Effects of dealloying and heat treatment parameters on microstructures of nanoporous Pd

Microstructures of nanoporous Pd are essentially important for its physical and chemical properties.In this work,we show that the microstructures of nanoporous Pd can be tuned by adjusting compositions of the precursor alloys,and dealloying and heat treatment parameters.Both the ligament and pore sizes decrease with increasing the electrochemical potential upon dealloying and the concentration of noble component in the precursor alloys.Heat treatment causes coarsening of the nanoporous structure.Above a critical temperature,the nanoporous structures are subjected to significant coarsening.Below the critical temperature,surface diffusion is believed to dominate the coarsening process.Above the critical temperature,the nanoporous structure coarsens remarkably at a rather high rate,which is ascribed to a multiple-mechanism controlled process.

First-Principles Calculations on Electronic,Chemical Bonding and Optical Properties of Cubic Hf_3N_4

Electronic, chemicM bonding and optical properties of cubic Hf3N4 （ c-Hf3N4 ） are calculated using the first- principles based on the density functional theory （DFT）. The optimized lattice parameter is in good agreement with the available experimental and cedculational values. Band structure shows that c-Hf3N4 has direct band gap. Densities of states （DOS） and charge densities indicate that the bonding between Hf and N is ionic. The optical properties including complex dielectric function, refractive index, extinction coefficient, absorption coefficient, and refleetivity are predicted. Prom the theory of crystal-field and molecular-orbited bonding, the optical transitions of c-Hf3N4 affected by the electronic structure and molecular orbited are studied. It is found that the absorptive transitions of c-Hf3N4 compound are predominantly composed of the transitions from N T2 2p valence bands to Hf T2 （dxy, dxz, dyz） conduction bands.

On the mechanism of Si-promoted destabilization of TiC_(x)particles in Al alloys

TiC_(x)is an excellent composite strengthening particle and grain refiner for Al alloys.However,the stability of TiC_(x)is poor when solute Si exists in Al alloy melts,which significantly depresses its strengthening and grain refining effects.In this work,the destabilization mechanisms of the TiC_(x)particles in Al-Si alloy melt with a composition of Al-7Si-7.5TiC were explored via experiments,first-principles calculations and thermodynamic calculations.The experimental results show that Si atoms diffuse into TiC_(x)and Ti atoms are released into the Al melt to form a Ti-rich transition zone during the insulation of TiC_(x)in Al-Si melt,and the TiAlySiz and Al_(4)C_(3)phases are solidified in the Ti-rich zone and at Ti-rich zone/TiC_(x)interface,respectively.The first principles calculations show that the low formation energy of C vacancies facilitates the rapid diffusion of Si atoms in TiC_(x),while the doping of Si atoms reduces the energy barrier of diffusion of Ti atoms in TiC_(x)and promotes the formation of Ti-rich zones.The thermodynamic calculations show that the wide crystallization temperature range of the destabilized product TiAlySiz phase is the key to continuous decomposition of TiC_(x)particles.In addition,the driving force of the main destabilization reaction of TiC_(x)in the Al-Si alloys is about 44 times higher than that in the Al alloys without Si addition.This indicates that the presence of solute Si remarkably promotes the subsequent decomposition process of TiC_(x)in the Al-Si alloy melts.

Nucleation/growth design by thermo-kinetic partition

Departing from nucleation and growth involved in phase transformations (PTs) and/or plastic deformations (PDs), thermodynamics, kinetics, and thermo-kinetic partition are described. It has been shown that the thermo-kinetic partition reflects the scale of the so-called thermo-kinetic correlation, and by combining with the reference state of PT or PD, corresponds to so-called generalized stability. Regarding the universality of nucleation/growth and thermo-kinetic partition, the principle of high thermodynamic driving force-high generalized stability has been reinterpreted by integrating nucleation and growth, separating nucleation and growth, and designing so-called negative driving forces, respectively. As such, the current materials design is classified, summarized, and prospected. This work is helpful to realize high strength and high plasticity by designing nucleation and growth.