Effect of UV lamp irradiation during oxidation of Zr/Pt/Si structure on electrical properties of Pt/ZrO2/Pt/Si structure

Metal-insulator-metal (MIM) capacitors were fabricated using ZrO₂ films and the effects of structural and native defects of the ZrO₂ films on the electrical and dielectric properties were investigated. For preparing ZrO₂ films, Zr films were deposited on Pt/Si substrates by ion beam deposition (IBD) system with/without substrate bias voltages and oxidized at 200 °C for 60 min under 0.1 MPa O₂ atmosphere with/without UV light irradiation (λ = 193 nm, Deep UV lamp). The ZrO₂(∼12 nm) films on Pt(∼100 nm)/Si were characterized by X-ray diffraction pattern (XRD), field emission scanning electron microscopy (FE-SEM) and high-resolution transmission electron microscopy (HRTEM), capacitance-voltage (C-V) and current-voltage (I-V) measurements were carried out on MIM structures. ZrO₂ films, fabricated by oxidizing the Zr film deposited with substrate bias voltage under UV light irradiation, show the highest capacitance (784 pF) and the lowest leakage current density. The active oxygen species formed by UV irradiation are considered to play an important role in the reduction of the leakage current density, because they can reduce the density of oxygen vacancies.     

X-ray photoelectron spectroscopy of nano-multilayered Zr-O/Al-O coatings deposited by cathodic vacuum arc plasma

Nano-multilayered Zr-O/Al-O coatings with alternating Zr-O and Al-O layers having a bi-layer period of 6-7 nm and total coating thickness of 1.0-1.2 μm were deposited using a cathodic vacuum arc plasma process on rotating Si substrates. Plasmas generated from two cathodes, Zr and Al, were deposited simultaneously in a mixture of Ar and O₂ background gases. The Zr-O/Al-O coatings, as well as bulk ZrO₂ and Al₂O₃ reference samples, were studied using X-ray photoelectron spectroscopy (XPS). The XPS spectra were analyzed on the surface and after sputtering with a 4 kV Ar⁺ ion gun. High resolution angle resolved spectra were obtained at three take-off angles: 15°, 45° and 75° relative to the sample surface.It was shown that preferential sputtering of oxygen took place during XPS of bulk reference ZrO₂ samples, producing ZrO and free Zr along with ZrO₂ in the XPS spectra. In contrast, no preferential sputtering was observed with Al₂O₃ reference samples. The Zr-O/Al-O coatings contained a large amount of free metals along with their oxides. Free Zr and Al were observed in the coating spectra both before and after sputtering, and thus cannot be due solely to preferential sputtering.Transmission electron microscopy revealed that the Zr-O/Al-O coatings had a nano-multilayered structure with well distinguished alternating layers. However, both of the alternating layers of the coating contained of a mixture of aluminum and zirconium oxides and free Al and Zr metals. The concentration of Zr and Al changed periodically with distance normal to the coating surface: the Zr maximum coincided with the Al minimum and vice versa. However the concentration of Zr in both alternating layers was significantly larger than that of Al. Despite the large free metal concentration, the Knoop hardness, 21.5 GPa, was relatively high, which might be attributed to super-lattice formation or formation of a metal-oxide nanocomposite within the layers.     

Stabilization of a very high-k crystalline ZrO2 phase by post deposition annealing of atomic layer deposited ZrO2/La2O3 dielectrics on germanium

The impact of the ZrO₂/La₂O₃ film thickness ratio and the post deposition annealing in the temperature range between 400 °C and 600 °C on the electrical properties of ultrathin ZrO₂/La₂O₃ high-k dielectrics grown by atomic layer deposition on (1 0 0) germanium is investigated. As-deposited stacks have a relative dielectric constant of 24 which is increased to a value of 35 after annealing at 500 °C due to the stabilization of tetragonal/cubic ZrO₂ phases. This effect depends on the absolute thickness of ZrO₂ within the dielectric stack and is limited due to possible interfacial reactions at the oxide/Ge interface. We show that adequate processing leads to very high-k dielectrics with EOT values below 1 nm, leakage current densities in the range of 0.01 A/cm², and interface trap densities in the range of 2-5 × 10¹² eV⁻¹ cm⁻².     

Magnetic properties of ZrO2-diluted magnetic semiconductors

Monoclinic zirconia (ZrO₂) as a potential host for diluted magnetic semiconductors (DMS) was investigated using density functional theory (DFT). Our calculations assessed the feasibility of long-range magnetic order at room temperature for transition metal ions substituting Zr. The defect-related d states split into e_g and t_2g bands. The exchange mechanism was shown to have strong nearest-neighbour coupling for several dopants reaching up to 150 meV for Fe. However, there was little to no long-range coupling extending beyond nearest-neighbour coordination, resulting in a non-physically high-defect concentration necessary for room temperature ferromagnetism.     

Study of structural and optical properties of ZnO films grown by pulsed laser deposition

Wurtzite zinc oxides films (ZnO) were deposited on silicon (0 0 1) and corning glass substrates using the pulsed laser deposition technique. The laser fluence, target-substrate distance, substrate temperature of 300 °C were fixed while varying oxygen pressures from 2 to 500 Pa were used. It is observed that the structural properties of ZnO films depend strongly on the oxygen pressure and the substrate nature. The film crystallinity improves with decreasing oxygen pressure. At high oxygen pressure, the films are randomly oriented, whereas, at low oxygen pressures they are well oriented along [0 0 1] axis for Si substrates and along [1 0 3] axis for glass substrates. A honeycomb structure is obtained at low oxygen pressures, whereas microcrystalline structures were obtained at high oxygen pressures. The effect of oxygen pressure on film transparency, band gap E_g and Urbach energies was investigated.     

Atomic force microscopy of living and fixed Xenopus laevis embryos

Xenopus laevis embryos are a rather simple and at the same time a very interesting animal model, which is widely used for research in developmental biology. Intensive coordinated cell movements take place during the multi-cellular organism development. Little is known of the cellular, molecular and biomechanical mechanisms of these movements. The conceptual framework for analysis of cell interactions within integrated populations is poorly developed. We have used atomic force microscopy (AFM) to observe the surface of fixed X. laevis embryos at different stages of their development. We have developed a new sample preparation protocol for these observations. The obtained images were compared with scanning electronic microscopy (SEM) data. Cell rearrangement during morphogenesis in vivo was also visualized by AFM. In the current paper we discuss facilities and challenges of using this technique for further embryo researching.     

On the existence of a homologous series of BamCum+nOy oxides with the cubic structure of the BaCuO2 oxide

Phase relations have been studied in the BaO–CuO_x system in the range of 42.0–83.0 mol.% CuO at P(O₂) = 21 kPa (air) by visual polythermal analysis (VPA), powder X-ray diffraction (XRD), differential thermal analysis (DTA), thermogravimetric analysis (TGA), chemical analysis (CA), and electron diffraction (ED) with simultaneous elemental analysis (EA) in a transmission electron microscope (TEM). The existence of discrete crystallization fields of barium–copper oxides of cation compositions Ba₄Cu₅O_y, Ba₅Cu₆O_y, Ba₇Cu₈O_y, Ba₁₂Cu₁₃O_y, and Ba₂₄Cu₂₅O_y, which have the cubic structure of the BaCuO₂ oxide, is revealed in the studied region of the system. The oxides may be represented as members of a Ba_mCu_m+nO_y homologous series. The BaCuO₂ oxide does not exist in the subsolidus region and does not have its own crystallization field. The oxygen-deficient oxide BaCuO_1.78 of the cation composition (Ba:Cu) 1:1 with the BaCuO₂ cubic structure is found in melted samples of the 50.0 mol.% CuO composition quenched at 1020–1060 °С.     

Effect of combination of noble metals and metal oxide supports on catalytic reduction of NO by H2

We investigated the effects of combination of noble metals M (Rh, Pd, Ir, Pt) and metal oxide supports S (Al₂O₃, SiO₂, ZrO₂, CeO₂) on the NO + H₂ reaction using planar catalysts with M/S two layered thin films on Si substrate. In this study, NO reduction ability per metal atom were evaluated with a specially designed apparatus employing pulse valves for the injection of reactant molecules onto catalysts and a time-of-flight mass spectrometer to measure multiple transient products: NH₃, N₂ and N₂O simultaneously as well as with an atomic force microscopy to observe the surface area of metal particles. The catalytic performances of Rh and Ir catalysts were hardly affected by a choice of a metal oxide support, while Pd and Pt catalysts showed different catalytic activity and selectivity depending on the metal oxide supports. This assortment is consistent with ability to dissociate NO depending on metals without the effect of any support materials. There, the metals to the left of Rh and Ir on the periodic table favor dissociation of NO and those to the right of Pd and Pt tend to show molecular adsorption of NO. Therefore, the catalytic property of noble metals could be assorted into two groups, i.e. Rh and Ir group whose own property would mainly dominate the catalytic performance, and Pd and Pt group whose interaction with metal oxides supports would clearly contribute to the reaction of NO with H₂. NO reduction activity of Pd and Pt was found to be promoted above that of Rh and Ir, provided that Pd and Pt were supported by CeO₂ and ZrO₂.     

980 nm激发下Er3+/Yb3+共掺杂ZrO2-Al2O3粉末的上转换发光特性

通过固相反应法制备了Er³⁺/Yb³⁺共掺杂ZrO₂-Al₂O₃粉末的样品，并对样品在980nm激光激发下的上转换发光特性进行了研究.从发射光谱可以发现，在可见光范围内有3个强的发光带，一个位于654nm附近的红光带和两个分别位于545nm、525nm附近的绿光带，分别对应于Er³⁺离子的以下辐射跃迁：⁴F_9/2→⁴I_15/2、⁴S_3/2→⁴I_15/2、 ²H_11/2→⁴I_15/2.其中又以Er³⁺离子的⁴F_9/2→⁴I_15/2跃迁产生的红色荧光辐射最强.对其上转换发光机制进行了分析，发现这三个发光过程都是双光子过程.对样品粉末进行了XRD检测，发现ZrO₂主要以立方相为主，并且计算得到了这种立方结构的晶格常数.Al₂O₃固溶于ZrO₂中，Al³⁺嵌入ZrO₂后产生氧空位，导致ZrO₂晶体的对称性降低，这种结构变化更有利于提高上转换效率，即上转换发光强度增强. 关键词： 3+/Yb³⁺')" href="#">Er³⁺/Yb³⁺ 上转换 2-Al₂O₃')" href="#">ZrO₂-Al₂O₃ 荧光 稀土     

First-principles study of the (0 0 1) surface of cubic SrZrO3

Density functional calculations have been used to investigate the (0 0 1) surface of cubic SrZrO₃ with both SrO and ZrO₂ termination. Surface structure and electronic structure have been obtained. The SrO surface is found to be similar to its counterpart in SrTiO₃, while there are marked differences between the ZrO₂ and TiO₂ terminations in SrZrO₃ and SrTiO₃, respectively, concerning surface relaxation and rumpling. For the ZrO₂-terminated surface of SrZrO₃, the covalency of the interaction between the outmost Zr and the O beneath is enhanced as a result of their bond contraction. The band gap reduction and the presence of the surface states are also discussed in relation with the behavior of the electrostatic potential.     

XPS investigation of diffusion of two-layer ZrO2/SiO2 and SiO2/ZrO2 sol–gel films

Two-layer ZrO₂/SiO₂ and SiO₂/ZrO₂ films were deposited on K9 glass substrates by sol–gel dip coating method. X-ray photoelectron spectroscopy (XPS) technique was used to investigate the diffusion of ZrO₂/SiO₂ and SiO₂/ZrO₂ films. To explain the difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films, porous ratio and surface morphology of monolayer SiO₂ and ZrO₂ films were analyzed by using ellipsometry and atomic force microscopy (AFM). We found that for the ZrO₂/SiO₂ films there was a diffusion layer with a certain thickness and the atomic concentrations of Si and Zr changed rapidly; for the SiO₂/ZrO₂ films, the atomic concentrations of Si and Zr changed relatively slowly, and the ZrO₂ layer had diffused through the entire SiO₂ layer. The difference of diffusion between ZrO₂/SiO₂ and SiO₂/ZrO₂ films was influenced by the microstructure of SiO₂ and ZrO₂.     

P-n codoping induced enhancement of ferromagnetism in Mn-doped In2O3: A first-principles study

We have performed first-principles density functional theory calculation in order to investigate the feasibility of “p-n codoping method” in improving magnetic property of In₂O₃ based diluted magnetic semiconductors. We find that the ferromagnetic state is favored in Mn-doped In₂O₃, and Sn doping can increase magnetic moment in Mn-doped In₂O₃. These findings are in line with our earlier experimental observation. Along with previous works, we now have enough evidences to support that p-n codoping is a valid method to improve magnetism of oxides based diluted magnetic semiconductors.     

Synthesis and magnetic properties of Li-Mn-Zn spinel oxides

LiMn_2−XZn_XO₄ (X<0.5) compounds were prepared by sol-gel method. The specimens with a large substitution degree (X>0.2) led to symmetry reduction from Fdm to P2₁3 in the spinel oxide, while those with a small substitution degree (X<0.1) had Fdm cubic symmetry. The Zn²⁺-substitution led to the enhancement of the low-temperature magnetic susceptibility and a shift in the Weiss constant from negative to positive, indicating that the dominant exchange interaction changed from antiferromagnetic to ferromagnetic. For the compounds with X=0.5, the spontaneous magnetization was 4.48μ_B and the Curie temperature was approximately 21 K. The experimentally obtained magnetization value was close to the value calculated under the assumption that the spins of the Mn⁴⁺ ions were aligned in ferromagnetic form. In addition, the magnetic properties of Li-Mn-Zn spinel oxides were briefly discussed, and compared with those of Li-Mn-M (M=Ni, Mg) spinel oxides.     

Raman scattering and room temperature ferromagnetism in Co-doped SrTiO3 particles

Raman scattering has been used to study the influence of cobalt, an effective dopant to obtain SrTiO₃ magnetic oxide, on the lattice dynamics of SrTiO₃. It is found that Co doping increases the lattice defects and induces a Raman vibration mode of 690 cm⁻¹. On the other hand, the ferromagnetism dependence on the x and annealing temperature was clearly and coherently observed in SrTi_1−xCo_xO₃ (x = 0, 0.01, 0.03 and 0.05) nanoparticles. It is found that the ferromagnetism of SrTi_1−xCo_xO₃ nanoparticles is weakly related to crystal deformation and oxygen vacancies in SrTiO₃. So, F-center model can explain the origin of the ferromagnetism in the prepared Co-doped SrTiO₃ samples. At the same time, the finding of large room-temperature ferromagnetism (1.6 emu/g) in this system would stimulate further interest in the area of more complicated ternary oxides.     

Surface functionalization of porous ZrO2-TiO2 membranes using γ-aminopropyltriethoxysilane in palladium electroless deposition

A pre-treatment technique was developed to facilitate the electroless deposition of Pd layers onto ZrO₂-TiO₂ ceramic membrane surfaces in the preparation of novel multi-functional porous membranes. Surface functionalization using an aqueous solution of γ-aminopropyltriethoxysilane (γ-APTES) aided the surface immobilization of the Pd activation particles and the subsequent electroless deposition of metal layers onto the hydroxyl-rich membrane surface. The attractiveness of γ-APTES functionalization, in the electroless deposition of metal layers, was thus demonstrated. Characterization techniques employed in the structural study of the surface-modified membranes included SEM, EDS, dynamic analysis in micro-PIXE, and XRD. Special membrane techniques such as electrokinetic analysis and single-gas permeation measurements were also used in the study of surface modification. These membranes were developed for application in tasks associated with the hydrogen economy.     

Stability of La2O3 and GeO2 passivated Ge surfaces during ALD of ZrO2 high-k dielectric

La₂O₃ grown by atomic layer deposition (ALD) and thermally grown GeO₂ are used to establish effective electrical surface passivations on n-type (1 0 0)-Ge substrates for high-k ZrO₂ dielectrics, grown by ALD at 250 °C substrate temperature. The electrical characterization of MOS capacitors indicates an impact of the Ge-surface passivation on the interfacial trap density and the frequency dependent capacitance in the inversion regime. Lower interface trap densities can be obtained for GeO₂ based passivation even though a chemical decomposition of the oxidation states occur during the ALD of ZrO₂. As a consequence the formation of a ZrGeO_x compound inside the ZrO₂ matrix and a decline of the interfacial GeO₂ are observed. The La₂O₃ passivation provides a stable amorphous lanthanum germanate phase at the Ge interface but also traces of Zr germanate are indicated by X-ray-Photoelectron-Spectroscopy and Transmission-Electron-Microscopy.     

Enhancement of the electrochemical performance in MgO stabilized ZrO2 oxygen sensors by co-doping trivalent metal oxides

The present work looked at the co-doping effect of the typical trivalent metal oxides on the electrochemical performance of 8 mol% of MgO stabilized ZrO₂ (Mg-PSZ) electrolyte ceramics used for oxygen sensors. An appreciable increase in the ionic conductivity occurred on substituting MgO with trivalent metal oxides except La₂O₃ in the Mg-PSZ electrolyte ceramics across the measured temperature range. The conductivity was related to the co-dopant ionic radius and the ionic conductivity increased with the co-dopant ionic radius of the trivalent metal oxides, reached a maximum at about 1.02 Å, and thereafter decreased. Through comparison and analysis, the Y₂O₃ exhibited excellent superiority than other trivalent metal oxides and the oxygen sensor assembled by 1Y7Mg-PSZ electrolyte possessed more excellent response speed and stability.     

Iron isotope effect on Tc in optimally-doped (Ba,K)Fe2As2 (Tc = 38 K) and SmFeAsO1−y (Tc = 54 K) superconductors

We report the iron isotope effect on a transition temperature (T_c) in an optimally-doped (Ba,K)Fe₂As₂ (T_c = 38 K) and SmFeAsO_1−y (T_c = 54 K) superconductors. In order to obtain the reliable isotope shift in T_c, twin samples with different iron isotope mass are synthesized in the same conditions (simultaneously) under high-pressure. We have found that (Ba,K)Fe₂As₂ shows an inverse iron isotope effect α_Fe = −0.18 ± 0.03 while SmFeAsO_1−y shows a small iron isotope effect α_Fe = −0.02 ± 0.01, where the isotope exponent α is defined by T_c ∼ M^−α (M is the isotopic mass). The results show that α_Fe changes in the iron-based superconductors depending on the system. The distinct iron isotope effects imply the exotic coupling mechanism in the iron-based superconductors.     

High temperature ferromagnetism in cubic Mn-doped ZrO2 thin films

Theory has predicted that high temperature ferromagnetism (FM) should be found in cubic fake-diamonds, Mn-doped ZrO₂. Experimentally, it is shown that Mn-doped ZrO₂ ceramics are not ferromagnetic, but the nanosized Mn-doped ZrO₂ thin films grown on LaAlO₃ substrates can be ferromagnets with T_C above 400 K. The largest saturated magnetic moment (M_s) is huge as of about 230 emu/cm³ for the Mn_0.05Zr_0.95O₂ films, and it decreases as the Mn content increases. The intrinsic FM is strongly associated with the cubic structure of Mn-doped ZrO₂, and the Mn–Mn interactions via oxygen intermediates are important. No electrical conductivity is observed. Mn-doped ZrO₂ thin films can be truly considered as excellent candidates for spintronic applications.     

Superacid Catalyst SO42-/ZrO2-La2O3 Prepared by Ultrasonic Co-precipitation and Low Temperature Aging

低温陈化超声波共沉淀法制得SO₄^2-/ZrO^2-La₂O₃前驱体, 经H₂SO₄处理, 在不同温度下焙烧得到纳米晶催化剂SO₄^2-/ZrO^2-La₂O₃;用Hammett指示剂法测定其酸性. 用XRD、BET、TEM、IR和XPS对样品进行表征,其催化活性用醋酸和甘油的酯化反应进行了评价. 结果表明经超声波搅拌和低温(-15 ºC)陈化,650 ºC焙烧4 h得到的固体超强酸表现出较高催化活性.