Structural and electrical properties of reactive magnetron sputtered yttrium-doped HfO_2 films

Hafnium oxide thin films doped with different concentrations of yttrium are prepared on Si（100） substrates at room temperature using a reactive magnetron sputtering system.The effects of Y content on the bonding structure,crystallographic structure,and electrical properties of Y-doped HfO2 films are investigated.The x-ray photoelectron spectrum（XPS） indicates that the core level peak positions of Hf 4 f and O 1 s shift toward lower energy due to the structure change after Y doping.The depth profiling of XPS shows that the surface of the film is completely oxidized while the oxygen deficiency emerges after the stripping depths have increased.The x-ray diffraction and high resolution transmission electron microscopy（HRTEM） analyses reveal the evolution from monoclinic HfO2 phase towards stabilized cubic HfO2 phase and the preferred orientation of（111） appears with increasing Y content,while pure HfO2 shows the monoclinic phase only.The leakage current and permittivity are determined as a function of the Y content.The best combination of low leakage current of 10-7 A/cm^2 at 1 V and a highest permittivity value of 29 is achieved when the doping ratio of Y increases to 9 mol%.A correlation among Y content,phase evolution and electrical properties of Y-doped HfO2 ultra-thin film is investigated.

Resistive switching behavior and mechanism of HfO_(x) films with large on/off ratio by structure design

Different bilayer structures of HfO_(x)/Ti(TiO_(x)) are designed for hafnium-based memory to investigate the switching characteristics. The chemical states in the films and near the interface are characterized by x-ray photoelectron spectroscopy,and the oxygen vacancies are analyzed. Highly improved on/off ratio(~104) and much uniform switching parameters are observed for bilayer structures compared to single layer HfO_(x) sample, which can be attributed to the modulation of oxygen vacancies at the interface and better control of the growth of filaments. Furthermore, the reliability of the prepared samples is investigated. The carrier conduction behaviors of HfO_(x)-based samples can be attributed to the trapping and de-trapping process of oxygen vacancies and a filamentary model is proposed. In addition, the rupture of filaments during the reset process for the bilayer structures occur at the weak points near the interface by the recovery of oxygen vacancies accompanied by the variation of barrier height. The re-formation of fixed filaments due to the residual filaments as lightning rods results in the better switching performance of the bilayer structure.

Interfacial stress engineering toward enhancement of ferroelectricity in Al doped HfO_(2) thin films

Ferroelectric HfO_(2)has attracted much attention owing to its superior ferroelectricity at an ultra-thin thickness and good compatibility with Si-based complementary metal-oxide-semiconductor(CMOS)technology.However,the crystallization of polar orthorhombic phase(o-phase)HfO_(2)is less competitive,which greatly limits the ferroelectricity of the as-obtained ferroelectric HfO_(2)thin films.Fortunately,the crystallization of o-phase HfO_(2)can be thermodynamically modulated via interfacial stress engineering.In this paper,the growth of improved ferroelectric Al doped HfO_(2)(HfO_(2):Al)thin films on(111)-oriented Si substrate has been reported.Structural analysis has suggested that nonpolar monoclinic HfO_(2):Al grown on(111)-oriented Si substrate suffered from a strong compressive strain,which promoted the crystallization of(111)-oriented o-phase HfO_(2)in the as-grown HfO_(2):Al thin films.In addition,the in-plane lattice of(111)-oriented Si substrate matches well with that of(111)-oriented o-phase HfO_(2),which further thermally stabilizes the o-phase HfO_(2).Accordingly,an improved ferroelectricity with a remnant polarization(2P_(r))of 26.7C/cm^(2) has been obtained.The results shown in this work provide a simple way toward the preparation of improved ferroelectric HfO_(2)thin films.

Observing ferroelastic switching in Hf_(0.5)Zr_(0.5)O_(2) thin film

Hafnium zirconium oxides(HZO),which exhibit ferroelectric properties,are promising materials for nanoscale device fabrication due to their high complementary metal-oxide-semiconductor(CMOS) compatibility.In addition to piezoelectricity,ferroelectricity,and flexoelectricity,this study reports the observation of ferroelasticity using piezoelectric force microscopy(PFM) and scanning transmission electron microscopy(STEM).The dynamics of 90° ferroelastic domains in HZO thin films are investigated under the influence of an electric field.Switching of the retentive domains is observed through repeated wake-up measurements.This study presents a possibility of enhancing polarization in HZO thin films during wake-up processes.

Preparation,Characterization and Photothermal Study of PVA/Ti_(2)O_(3) Composite Films

In this work,flexible photothermal PVA/Ti_(2)O_(3) composite films with different amount(0 wt%,5 wt%,10 wt%,15 wt%)of Ti_(2)O_(3) particles modified by steric acid were prepared by a simple solution casting method.The microstructures,XRD patterns,FTIR spectra,UV-Vis-NIR spectra thermo-conductivity,thermo-stability and photothermal effects of these composite films were all characterized.These results indicated that Ti_(2)O_(3) particles were well dispersed throughout the polyvinyl alcohol(PVA)matrix in the PVA/Ti_(2)O_(3) composite films.And Ti_(2)O_(3) particles could also effectively improve the photothermal properties of the composite films which exhibited high light absorption and generated a high temperature(about 57.4℃for film with 15 wt%Ti_(2)O_(3) amount)on the surface when it was irradiated by a simulated sunlight source(1 kW/m^(2)).

Optimal parameter space for stabilizing the ferroelectric phase of Hf_(0.5)Zr_(0.5)O_(2) thin films under strain and electric fields

Hafnia-based ferroelectric materials, like Hf_(0.5)Zr_(0.5)O_(2)(HZO), have received tremendous attention owing to their potentials for building ultra-thin ferroelectric devices. The orthorhombic(O)-phase of HZO is ferroelectric but metastable in its bulk form under ambient conditions, which poses a considerable challenge to maintaining the operation performance of HZO-based ferroelectric devices. Here, we theoretically addressed this issue that provides parameter spaces for stabilizing the O-phase of HZO thin-films under various conditions. Three mechanisms were found to be capable of lowering the relative energy of the O-phase, namely, more significant surface-bulk portion of(111) surfaces, compressive c-axis strain,and positive electric fields. Considering these mechanisms, we plotted two ternary phase diagrams for HZO thin-films where the strain was applied along the in-plane uniaxial and biaxial, respectively. These diagrams indicate the O-phase could be stabilized by solely shrinking the film-thickness below 12.26 nm, ascribed to its lower surface energies. All these results shed considerable light on designing more robust and higher-performance ferroelectric devices.

Enhanced Electrical Properties of Bi_(2−x)Sb_(x)Te_(3)Nanoflake Thin Films Through Interface Engineering

The structure–property relationship at interfaces is difficult to probe for thermoelectric materials with a complex interfacial microstructure.Designing thermoelectric materials with a simple,structurally-uniform interface provides a facile way to understand how these interfaces influence the transport properties.Here,we synthesized Bi_(2−x)Sb_(x)Te_(3)(x=0,0.1,0.2,0.4)nanoflakes using a hydrothermal method,and prepared Bi_(2−x)Sb_(x)Te_(3)thin films with predominantly(0001)interfaces by stacking the nanoflakes through spin coating.The influence of the annealing temperature and Sb content on the(0001)interface structure was systematically investigated at atomic scale using aberration-corrected scanning transmission electron microscopy.Annealing and Sb doping facilitate atom diffusion and migration between adjacent nanoflakes along the(0001)interface.As such it enhances interfacial connectivity and improves the electrical transport properties.Interfac reactions create new interfaces that increase the scattering and the Seebeck coefficient.Due to the simultaneous optimization of electrical conductivity and Seebeck coefficient,the maximum power factor of the Bi_(1.8)Sb_(0.2)Te_(3)nanoflake films reaches 1.72 mW m^(−1)K^(−2),which is 43%higher than that of a pure Bi_(2)Te_(3)thin film.

Numerical Analysis on the Effect of n-Si on Cu(In, Ga)Se2 Based Thin-Films for High-Performance Solar Cells by 1D-SCAPS

We report the performances of a chalcopyrite Cu(In, Ga)Se2 CIGS-based thin-film solar cell with a newly employed high conductive n-Si layer. The data analysis was performed with the help of the 1D-Solar Cell Capacitance Simulator (1D-SCAPS) software program. The new device structure is based on the CIGS layer as the absorber layer, n-Si as the high conductive layer, i-In2S3, and i-ZnO as the buffer and window layers, respectively. The optimum CIGS bandgap was determined first and used to simulate and analyze the cell performance throughout the experiment. This analysis revealed that the absorber layer’s optimum bandgap value has to be 1.4 eV to achieve maximum efficiency of 22.57%. Subsequently, output solar cell parameters were analyzed as a function of CIGS layer thickness, defect density, and the operating temperature with an optimized n-Si layer. The newly modeled device has a p-CIGS/n-Si/In2S3/Al-ZnO structure. The main objective was to improve the overall cell performance while optimizing the thickness of absorber layers, defect density, bandgap, and operating temperature with the newly employed optimized n-Si layer. The increase of absorber layer thickness from 0.2 - 2 µm showed an upward trend in the cell’s performance, while the increase of defect density and operating temperature showed a downward trend in solar cell performance. This study illustrates that the proposed cell structure shows higher cell performances and can be fabricated on the lab-scale and industrial levels.

Laser-induced damage threshold in HfO_2/SiO_2 multilayer films irradiated by β-ray

Post-processing can effectively improve the resistance to laser damage in multilayer films used in a high power laser system. In this work, HfO_2/SiO_2 multilayer films are prepared by e-beam evaporation and then β-ray irradiation is employed as the post-processing method. The particle irradiation affects the laser induced damage threshold(LIDT),which includes defects, surface roughness, packing density and residual stress. The residual stress that is relaxed during irradiation changes from compressive stress into tensile stress. Our results indicate that appropriate tensile stress can improve LIDT remarkably. In view of the fact that LIDT rises from 8 J/cm^2 to 12 J/cm^2, i.e., 50% increase, after the film has been irradiated by 2.2×10^(13)/cm^2 β-ray, the particle irradiation can be used as a controllable and desirable postprocessing method to improve the resistance to laser induced damage.

Effects of water vapor in high vacuum chamber on the properties of HfO_2 films

The influence of water vapor content in high vacuum chamber during the coating process on physical properties of HfO2 films was investigated. Coatings were deposited on BK7 substrates by electron beam evaporation and photoelectric maximum control method. An in situ residual gas analyzer （RGA） was used to monitor the residual gas composition in the vacuum chamber. The optical properties, microstructure, absorption and laser-induced damage threshold （LIDT） of the samples were characterized by Lambda 900 spectrophotometer, X-ray diffraction （XRD）, surface thermal lensing （STL） technique and 1064-nm Qswitched pulsed laser at a pulse duration of 12 ns respectively. It was found that a cold trap is an effective equipment to suppress water vapor in the vacuum chamber during the pumping process, and the coatings deposited in the vacuum atmosphere with relatively low water vapor composition show higher refractive index and smaller grain size. Meanwhile, the higher LIDT value is corresponding to lower absorbance.

Uniform deposition of ultra-thin TiO_(2) film on mica substrate by atmospheric pressure chemical vapor deposition: Effect of precursor concentration

The performance of pearlescent pigment significantly affected by the grain size and the roughness of deposited film. The effect of TiCl_(4) concentration on the initial deposition of TiO_(2) on mica by atmospheric pressure chemical vapor deposition(APCVD) was investigated. The precursor concentration significantly affected the deposition and morphology of TiO_(2) grains assembling the film. The deposition time for fully covering the surface of mica decreased from 120 to 10 s as the TiCl_(4) concentration increased from 0.38%to 2.44%. The grain size increased with the TiCl_(4) concentration. The AFM and TEM analysis demonstrated that the aggregation of TiO_(2) clusters at the initial stage finally result to the agglomeration of fine TiO_(2) grains at high TiCl_(4) concentrations. Following the results, it was suggested that the nucleation density and size was easy to be adjusted when the TiCl_(4) concentration is below 0.90%.

Effects of HfO_2 buffer layers on the dielectric property and leakage current of Ba_(0.6)Sr_(0.4)TiO_3 thin films by pulsed laser deposition

Ba0.6Sr0.4TiO3 （BST） thin films with and without HfO 2 buffer layer were fabricated on Pt/Ti/SiO2/Si substrates by pulsed laser deposition. Dependences of HfO 2 thickness on the dielectric property and leakage current of BST thin films were focused. The dielectric constant of BST thin films increased and then decreased with the increase of HfO 2 thickness, while the dielectric relaxation was gradually improved. The loss tangent and leakage current under positive bias decreased with the HfO 2 thickness increasing. The leakage current analysis based on the Schottky emission indicated an improvement of the BST/Pt interface with HfO 2 buffer layer. The loss tangent, tunability and figure of merit of optimized HfO 2 buffered BST thin film achieved 0.009 8, 21.91% （E max = 200 kV/cm）, 22.40 at 10 6 Hz, respectively.

Transparent Thermally Tunable Microwave Absorber Prototype Based on Patterned VO2 Film

Transparent microwave absorbers that exhibit high optical transmittance and microwave absorption capability are ideal,although having a fixed absorption performance limits their applicability.Here,a simple,transparent,and thermally tunable microwave absorber is proposed,based on a patterned vanadium dioxide(VO_(2))film.Numerical calculations and experiments demonstrate that the proposed VO_(2)absorber has a high optical transmittance of 84.9%at 620 nm;its reflection loss at 15.06 GHz can be thermally tuned from–4.257 to–60.179 dB,and near-unity absorption is achieved at 523.750 K.Adjusting only the patterned VO_(2)film duty cycle can change the temperature of near-unity absorption.Our VO_(2)absorber has a simple composition,a high optical transmittance,a thermally tunable microwave absorption performance,a large modulation depth,and an adjustable temperature tuning range,making it promising for application in tunable sensors,thermal emitters,modulators,thermal imaging,bolometers,and photovoltaic devices.

Thickness effect on solar-blind photoelectric properties of ultrathinβ-Ga_(2)O_(3)films prepared by atomic layer deposition

Theβ-Ga_(2)O_(3)films with different thicknesses are prepared by an atomic layer deposition system.The influence of film thickness on the crystal quality is obvious,indicating that the thicker films perform better crystal quality,which is verified from x-ray diffraction(XRD)and scanning electron microscope(SEM)results.The Ga_(2)O_(3)-based solar blind photodetectors with different thicknesses are fabricated and studied.The experimental results show that the responsivity of the photodetectors increases exponentially with the increase of the film thickness.The photodetectors with inter-fingered structure based on 900 growth cyclesβ-Ga_(2)O_(3)active layers(corresponding film thickness of 58 nm)exhibit the best performances including a low dark current of 134 fA,photo-to-dark current ratio of 1.5×10^(7),photoresponsivity of 1.56 A/W,detectivity of 2.77×10^(14)Jones,and external quantum efficiency of 764.49%at a bias voltage of 10 V under 254-nm DUV illumination.The photoresponse rejection ratio(R_(254)/R_(365))is up to 1.86×10^(5).In addition,we find that the photoelectric characteristics also depend on the finger spacing of the MSM structure.As the finger spacing decreases from 50μm to10μW,the photoresponsivity,detectivity,and external quantum efficiency increase significantly.

Centimeter-sized Cs_(3)Cu_(2)I_(5)single crystals grown by oleic acid assisted inverse temperature crystallization strategy and their films for high-quality X-ray imaging

Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.

Tensile stress regulated microstructures and ferroelectric properties of Hf_(0.5)Zr_(0.5)O_(2) films

The discovery of ferroelectricity in HfO_(2) based materials reactivated the research on ferroelectric memory.However,the complete mechanism underlying its ferroelectricity remains to be fully elucidated.In this study,we conducted a systematic study on the microstructures and ferroelectric properties of Hf_(0.5)Zr_(0.5)O_(2)(HZO)thin films with various annealing rates in the rapid thermal annealing.It was observed that the HZO thin films with higher annealing rates demonstrate smaller grain size,reduced surface roughness and a higher portion of orthorhombic phase.Moreover,these films exhibited enhanced polarization values and better fatigue cycles compared to those treated with lower annealing rates.The grazing incidence x-ray diffraction measurements revealed the existence of tension stress in the HZO thin films,which was weakened with decreasing annealing rate.Our findings revealed that this internal stress,along with the stress originating from the top/bottom electrode,plays a crucial role in modulating the microstructure and ferroelectric properties of the HZO thin films.By carefully controlling the annealing rate,we could effectively regulate the tension stress within HZO thin films,thus achieving precise control over their ferroelectric properties.This work established a valuable pathway for tailoring the performance of HZO thin films for various applications.

Effects of irradiation on superconducting properties of small-grained MgB_(2) thin films

We investigate the effect of ion irradiation on MgB_(2) thin films with small grains of approximately 122 nm and 140 nm.The flux pinning by grain boundaries is insignificant in the pristine MgB_(2) films due to good inter-grain connectivity,but is significantly improved after 120-keV Mn-ion irradiation.The scaling behavior of the flux pinning force density for the ion-irradiated MgB_(2) thin films with nanoscale grains demonstrates the predominance of pinning by grain boundaries,in contrast to the single-crystalline MgB_(2) films where normal point pinning was dominant after low-energy ion irradiation.These results suggest that irradiation-induced defects can accumulate near the grain boundaries in metallic MgB_(2) superconductors.

XPS Study of Electroless Deposited Sb2Se3 Thin Films for Solar Cell Absorber Material

As a thin film solar cell absorber material, antimony selenide (Sb2Se3) has become a potential candidate recently because of its unique optical and electrical properties and easy fabrication method. X-ray photoelectron spectroscopy (XPS) was used to determine the stoichiometry and composition of electroless Sb2Se3 thin films using depth profile studies. The surface layers were analyzed nearly stoichiometric. But the abundant amount of antimony makes the inner layer electrically more conductive.

Optical and electrical properties of BaSnO_(3) and In_2O_(3) mixed transparent conductive films deposited by filtered cathodic vacuum arc technique at room temperature

For the crystalline temperature of BaSnO_(3)(BTO)was above 650℃,the transparent conductive BTO-based films were always deposited above this temperature on epitaxy substrates by pulsed laser deposition or molecular beam epitaxy till now which limited there application in low temperature device process.In the article,the microstructure,optical and electrical of BTO and In_(2)O_(3) mixed transparent conductive BaInSnO_(x)(BITO)film deposited by filtered cathodic vacuum arc technique(FCVA)on glass substrate at room temperature were firstly reported.The BITO film with thickness of 300 nm had mainly In_(2)O_(3) polycrystalline phase,and minor polycrystalline BTO phase with(001),(011),(111),(002),(222)crystal faces which were first deposited at room temperature on amorphous glass.The transmittance was 70%–80%in the visible light region with linear refractive index of 1.94 and extinction coefficient of 0.004 at 550-nm wavelength.The basic optical properties included the real and imaginary parts,high frequency dielectric constants,the absorption coefficient,the Urbach energy,the indirect and direct band gaps,the oscillator and dispersion energies,the static refractive index and dielectric constant,the average oscillator wavelength,oscillator length strength,the linear and the third-order nonlinear optical susceptibilities,and the nonlinear refractive index were all calculated.The film was the n-type conductor with sheet resistance of 704.7Ω/□,resistivity of 0.02Ω⋅cm,mobility of 18.9 cm2/V⋅s,and carrier electron concentration of 1.6×10^(19) cm^(−3) at room temperature.The results suggested that the BITO film deposited by FCVA had potential application in transparent conductive films-based low temperature device process.

The effects of radio frequency atmospheric pressure plasma and thermal treatment on the hydrogenation of TiO_(2) thin film

The effects of radio frequency(RF)atmospheric pressure(AP)He/H_(2)plasma and thermal treatment on the hydrogenation of TiO_(2)thin films were investigated and compared in this work.The color of the original TiO_(2)film changes from white to black after being hydrogenated in He/H_(2)plasma at160 W(gas temperature~381℃)within 5 min,while the color of the thermally treated TiO_(2)film did not change significantly even in pure H_(2)or He/H_(2)atmosphere with higher temperature(470℃)and longer time(30 min).This indicated that a more effective hydrogenation reaction happened through RF AP He/H_(2)plasma treatment than through pure H_(2)or He/H_(2)thermal treatment.The color change of TiO_(2)film was measured based on the Commission Internationale d’Eclairage L*a*b*color space system.Hydrogenated TiO_(2)film displayed improved visible light absorption with increased plasma power.The morphology of the cauliflower-like nanoparticles of the TiO_(2)film surface remained unchanged after plasma processing.X-ray photoelectron spectroscopy results showed that the contents of Ti3+species and Ti-OH bonds in the plasma-hydrogenated black TiO_(2)increased compared with those in the thermally treated TiO_(2).X-ray diffraction(XRD)patterns and Raman spectra indicated that plasma would destroy the crystal structure of the TiO_(2)surface layer,while thermal annealing would increase the overall crystallinity.The different trends of XRD and Raman spectra results suggested that plasma modification on the TiO_(2)surface layer is more drastic than on its inner layer,which was also consistent with transmission electron microscopy results.Optical emission spectra results suggest that numerous active species were generated during RF AP He/H_(2)plasma processing,while there were no peaks detected from thermal processing.A possible mechanism for the TiO_(2)hydrogenation process by plasma has been proposed.Numerous active species were generated in the bulk plasma region,accelerated in the sheath region,and bumped toward the TiO_(2)film,which will react with the TiO_(2)surface to form OVs and disordered layers.This leads to the tailoring of the band gap of black TiO_(2)and causes its light absorption to extend into the visible region.