Nd掺杂对ZnSe薄膜微结构的影响

利用真空蒸发的方法制备ZnSe多晶薄膜,并采用双源法对薄膜进行了稀土元素Nd的掺杂。对薄膜进行了XRD测试,并计算了薄膜的晶粒尺寸、晶格常数以及内应力。结果表明,当原子配比Zn∶Se=0.9∶1时可制备较理想的ZnSe多晶薄膜,稀土Nd掺杂并未改变样品的物相结构,掺杂使得薄膜的晶粒尺寸减小,晶胞体积增加,内应力和晶格常数改变。实验还发现,适度的轻掺杂Nd可增加ZnSe薄膜的光透射性。     

Controlled Elemental Depth Profile in Sol–Gel-Derived PZT Films

Elemental depth profiles of PZT films prepared by two sol–gel formulations, differing in the zirconium precursor stabilization, were investigated by SIMS analysis. Early decomposition of the zirconium precursor yielded opposing gradients of zirconium and titanium, while simultaneous late decomposition of zirconium and titanium precursors provided profile uniformity. The gradients formed during initial crystallization are irreversible. Both types of films showed excellent hysteresis; however, uniform films exhibited a much higher dielectric constant, indicating superior piezoelectric properties. Non-uniform films displayed a complex CV pattern, consistent with an inhomogeneous structure. Finally, thermal decomposition of the individual metal precursors is crucial for controlling film uniformity.     

Preparation and Characterization of Sol—Gel-Derived Lead Magnesium Niobium Titanate Thin Films with Pure Perovskite Phase and Lead Oxide Cover Coat

A sol–gel-derived Pb(Mg_1/3Nb_2/3)_0.7Ti_0.3O₃ (PMNT) thin film was prepared using spin coating and a PbO cover coat technique. The amount of lead excess in the precursor solution had significant effects on the phase development and microstructure of the PMNT film. The PbO cover coat proved to be effective on suppressing the formation of pyrochlore phases. PMNT thin films with a pure perovskite structure were obtained by adding 30 mol% excess lead in the precursor solution and coating the PbO layer on the top of the film. The remnant polarization ( P _r), the dielectric constant (ɛ_r), and the dissipation factor (tan δ) of these thin films, which had a thickness of 150 nm, were determined to be 9 μC/cm², 1370, and 0.031, respectively.     

Effects of Individual Layer Thickness on the Microstructure and Optoelectronic Properties of Sol–Gel-Derived Zinc Oxide Thin Films

Zinc oxide (ZnO) thin films were prepared under different conditions on glass substrates using a sol–gel process. The microstructure of ZnO films was investigated by means of diffraction analysis, and plan-view and cross-sectional scanning electron microscopy. It was found that the preparation conditions strongly affected the structure and the optoelectronic properties of the films. A structural evolution in morphology from spherical to columnar growth was observed. The crystallinity of the films was improved and columnar film growth became more dominant as the zinc concentration and the substrate withdrawal speed decreased. The individual layer thickness for layer-by-layer homoepitaxy growth that resulted in columnar grains was <20 nm. The grain columns are grown through the entire film with a nearly unchanged lateral dimension through the full film thickness. The columnar ZnO grains are c -axis oriented perpendicular to the interface and possess a polycrystalline structure. Optical transmittance up to 90% in the visible range and electrical resistivity as low as 6.8 × 10⁻³·Ω·cm were obtained under optimal deposition conditions.     

Crystallization of Sol–Gel-Derived Barium Strontium Titanate Thin Films

Microstructural development of thin-film barium strontium titanate (Ba _x Sr_{1– x} TiO₃) as a function of strontium concentration and thermal treatment were studied, using transmission electron microscopy (TEM) and X-ray diffractometry (XRD). Thin films, ∼250 nm thick, were spin-coated onto Pt/Ti/SiO₂/Si substrates, using methoxypropoxide alkoxide precursors, and crystallized by heat-treating at 700°C. All films had the cubic perovskite structure, and their lattice parameters varied linearly with strontium content. Films with higher strontium concentrations had a larger average grain size. In situ TEM heating experiments, combined with differential thermal analysis/thermogravimetric analysis results, suggest that the gel films crystallize as an intermediate carbonate phase, Ba _x Sr_{1– x} TiO₂CO₃ (with a solid solution range from x = 1 to x = 0). Before decomposition at 600°C, this carbonate phase inhibits the formation of the desired perovskite phase.     

Crystallization and Microstructure Development of Sol–Gel-Derived Titanium Dioxide Thin Films with Single and Multiple Layers

Sol–gel TiO₂ thin films were fabricated at 650°C using sol that was derived from the Ti(O ⁱ Pr)₄-diethanolamine-H₂O- ⁱ PrOH system. Repeated deposition and rapid heating resulted in columnar grains, whereas slow heating—at a rate of 10°–20°C/min—caused equiaxed grains to form. Slow heating caused the film to crystallize as anatase. The anatase-to-rutile ratio of the rapidly heated film increased with increased deposition thickness and repeated depositions. The tendency of the thicker film to crystallize as rutile during rapid heating was attributed to the rapid grain growth of fine anatase grains.     

Crystallization Behavior of Sol–Gel-Derived Strontium Barium Niobate Thin Films

The crystallization of sol–gel-derived strontium barium niobate (SBN) thin films on various substrates is enhanced by a two-step heating process. Also, SBN films with c -axis preferred orientation are obtained on MgO (100) substrates. The crystallized phase and the degree of orientation are dependent on crystallization temperature and film composition. The crystallization temperature required to form a single tetragonal tungsten bronze (TTB) SBN phase increases with an increase of Sr content due to the distorted SBN structure. However, in the case of the film on MgO substrate, the oriented crystallization which forms the single tetragonal phase occurs at a lower crystallization temperature than those of polycrystalline films because of lattice matching between the film and the substrate. Its optical and ferroelectric properties were also investigated. They vary depending on film composition, due to the effect of the distorted SBN structure.     

Microstructure of Solution-Processed Lead Zirconate Titanate (PZT) Thin Films

Lead zirconate titanate (PZT) thin films with a composition near the morphotropic phase boundary (Zr/Ti = 53/47) were fabricated by spin deposition of an alkoxide-derived solution and annealed at 650°C for 30 min. A complex microstructure is observed in which micrometer-scale rosettes of the desired perovskite phase are surrounded by nanocrystalline (10 to 15 nm) grains of pyrochlore structure. Transmission electron microscopy (TEM) demonstrates that the perovskite rosettes—features of approximately circular cross section which grow rapidly within the confined conditions of the thin film—are single crystals despite being highly porous. Pockets of lead-deficient pyrochlore extend throughout the thickness of the film. The only effects of Nb (2%) doping on the microstructure are to increase the fraction of the perovskite phase and the perovskite grain size. Despite the highly irregular shape of the perovskite particles and the presence of some pyrochlore, reasonable ferroelectric properties are measured (spontaneous polarization P _s∼ 0.2 C/m²).     

Fabrication and Ultraviolet Absorption of Sol–Gel-Derived Germanium Oxide Glass Thin Films

Germanium oxide glass thin films were prepared by the sol–gel method and annealed under reduced atmosphere to create more oxygen-deficient defects. The densification and crystallization were examined depending on sintering and annealing conditions. Thus, homogeneous germanium oxide thin films with a high content of oxygen vacancies were fabricated. Ultraviolet absorption and oxygen vacancies of the films were investigated as a function of annealing temperature and time. Optical absorption in the 5-eV region due to the formation of oxygen vacancies is enhanced with increasing annealing temperature and time. The formation energy of oxygen vacancies is calculated to be about 1.0 eV.     

Texture Development, Microstructure Evolution, and Crystallization of Chemically Derived PZT Thin Films

Two solution-based methods, metallo-organic decomposition and sol—gel processes, were used to study the effects of precursor solution type on the microstructure evolution and texture development of oriented PZT films. Microstructure development and perovskite content are strongly dependent on the heating rate. Fast heating rate forms a dense fine-grained microstructure with (111) orientation. Intermediate-temperature pyrolysis followed by a fast heating rate forms clustered or island structures of submicrometer grains with (100) orientation. Intermediate-temperature pyrolysis followed by a very slow heating rate forms larger spherical rosettes with random orientations. Pt_5–7Pb is a (111) textured transient intermetallic phase that nucleates PZT(111) texture. PbO is a (001) textured layer compound that nucleates PZT(100) texture. The texture selection of PZT films is independent of precursor systems but sensitive to the film thickness especially when sol—gel precursors and oxidizing atmosphere are used. Correlation and comparison of oriented sol—gel and MOD PZT films with electrical properties are also made.     

Effects of Acetic Acid on the Crystallization Temperature of Sol–Gel-Derived MgO Nano-Powders and Thin Films

The influences of acetic acid addition to Mg-methoxide on the stability of the precursor and the crystallization behavior of sol–gel-derived MgO nano-powders and thin films were investigated using X-ray powder diffraction, transmission electron microscopy, Fourier-transformed infrared spectroscopy, and thermogravimetry. The addition of acetic acid enhanced the stability of the alkoxide against precipitation. Moreover, during postheat treatment of the gel powders treated with acetic acid, a significantly lowered crystallization temperature (250°C) was observed as compared to the untreated counterpart (350°C). The low-temperature crystallization of MgO, induced by the modification of Mg-methoxide with acetic acid, was related to the decomposition of organics at a lower temperature. These results could be explained in terms of the decrease of the O–R bond strength depending on the increase in the alkyl group size. MgO thin films having a high degree of crystallinity were successfully obtained from the Mg-methoxide treated with acetic acid at 300°C. The low-temperature crystallization of sol–gel-derived MgO thin films showed the feasibility for their application as a protective layer in alternative current plasma display panel cells.     

In–Situ Transmission Electron Microscopy Crystallization Studies of Sol–Gel-Derived Barium Titanate Thin Films

Barium titanate (BaTiO₃) thin films that were derived from methoxypropoxide precursors were deposited onto (100) Si, Pt/Ti/SiO₂/(100) Si, and molecular-beam-epitaxy-grown (MBE-grown) (100) BaTiO₃ on (100) Si substrates by spin coating. The crystallization behavior of the amorphous-gel films was characterized using in-situ transmission electron microscopy heating experiments, glancing-angle X-ray diffraction, and differential thermal analysis/thermogravimetric analysis. Amorphous-gel films crystallized at a temperature of ∼600°C to an intermediate nanoscale (5–10 nm) barium titanium carbonate phase, presumably BaTiO₂CO₃, that subsequently transformed to nanocrystalline (20–60 nm) BaTiO₃. Random nucleation in the bulk of the gel film was observed on all substrates. In addition, oriented growth of BaTiO₃ was concurrently observed on MBE-grown BaTiO₃ on (100) Si. High-temperature decomposition of the intermediate carbonate phase contributed to nanometer-scale residual porosity in the films. High concentrations of water of hydrolysis inhibited the formation of the intermediate carbonate phase; however, these sols precipitated and were not suitable for spin coating.     

Cl离子掺杂对钙钛矿薄膜结构及光学性能的影响

有机-无机杂化钙钛矿光吸收层薄膜的结构、形貌及结晶度对电池的光电性能起决定性作用.采用一步溶液法通过改变CH3 NH3 I和PbCl2的摩尔比调控钙钛矿前驱体溶液中Cl离子的掺杂量,从而制备钙钛矿光吸收层薄膜.利用荧光光谱(PL)、X射线衍射(XRD)、扫描电子显微镜(SEM)及EDS能谱分别对钙钛矿溶液的荧光性能、薄膜的结构、表面形貌及反应后Cl离子的含量进行表征.结果表明,随着CH3 NH3 I和PbCl2的摩尔比的增加,前驱体溶液的荧光强度逐渐减弱(激发波长为325 nm);晶体结构由立方相CH3 NH3 PbCl3转换成了纯的四方相CH3 NH3 PbI3钙钛矿薄膜,晶粒尺寸增大,晶格应变随之增加;表面覆盖率逐渐升高,薄膜表面无针状结构出现;薄膜中Cl离子的含量逐渐减少,改善了薄膜的质量.     

射频磁控溅射制备PZT铁电薄膜的工艺研究

在SiO2/Si基片上采用直流对靶溅射技术制备出Pt/Ti底电极;应用射频磁控溅射方法,利用快速热处理(RTA)工艺,制备出了具有良好铁电性能的Pb(Zr0.52Ti0.48)O3铁电薄膜.将样品进行10min快速热退火处理,退火温度700℃.测试分析表明:薄膜厚度比较均匀、表面基本平整、没有裂纹和孔洞、致密性好、薄膜样品的矫顽场强(Ec)为28.6kV/cm,剩余极化强度(Pr)为18.7μC/cm2,自发极化强度(Ps)为37.5μC/cm2,是制备铁电薄膜存储器的优选材料.     

Microstructure Development in Unsupported Thin Films

To better understand the role of the substrate in the microstructural evolution of thin films, unsupported nanocrystalline yttrium-stabilized zirconia (ZrO₂:16%Y or YSZ) films were examined as a function of temperature and annealing time. Grain growth, texturing, and pinhole formation were measured using transmission electron microscopy (TEM) and electron diffraction. Films were produced and subsequently annealed on metallic grids using a previously developed technique that results in near full density films at low annealing temperatures. Microstructural evolution in these films was unique compared with constrained films. Grains were found to spheroidize much more readily, ultimately resulting in the formation of porosity and pinholes. Grain growth was found to stagnate at a size particular to each annealing temperature, presumably due to the effects of Zener pinning. It is proposed that the lack of substrate strain and confinement effects allows for the dominance of surface energetics with respect to microstructural evolution.     

Effect of Zn, Sr, and Y Addition on Electrical Properties of PZT Thin Films

We have investigated methods to increase the efficiency of piezoelectric micromachined ultrasonic transducers (pMUTs). pMUTs are driven by a thin piezoelectric layer on a Si membrane. The efficiency of pMUTs can be increased using a film with better ferroelectric properties. We have used Zn, Sr, and Y doping on PZT-based thin films along the morphotropic phase boundary (MPB) composition to increase their piezoelectric properties. The results obtained were then extended to compositions on both sides of the MPB. The sol–gel method was used to prepare precursor solutions, which were then spin coated on a Pt(100)/Ti/SiO₂/Si substrate to prepare the PZT thin films. It was found that Zn and Sr together had the most significant effect on the ferroelectric properties in which a saturation polarization of 108 μC/cm² and remanent polarization of 54 μC/cm² were achieved.     

Influences of Cr Doping on the Electrical Properties in BiFeO3 Thin Films

Cr-doped BiFeO₃ (BFO) thin films were deposited on Pt(200)/TiO₂/SiO₂/Si(100) substrates by a chemical solution deposition method. The dielectric constant and dissipation factor of the BFO thin films decrease from 165 and 0.054 (undoped) to 100 and 0.02 (3 mol% Cr-doped) at a frequency of 10 kHz as the Cr content increases. The leakage current and ferroelectric properties were improved significantly by means of Cr doping. The leakage current density of 4.1×10^-6 A/cm² for the 3 mol% Cr-doped BFO thin film is about four orders of magnitude lower than that of undoped BFO thin film at an external electric field of 100 kV/cm. The 3 mol% Cr-doped BFO thin film exhibited a well-saturated hysteresis loop with a large remanent polarization (P_r) of 61 μC/cm² at room temperature. The reason for the improved leakage current and ferroelectric properties in Cr-doped BFO thin films can be attributed to the reduced oxygen vacancies in the films by Cr doping.

Communicated by Dr. George W. Taylor     

Preparation and Optical Nonlinear Property of Sol–Gel-Derived Cu─SiO2 Thin Films

Cu-metal-doped glass films having a Cu:Si atomic ratio of 0.05 ± 0.002 were successfully prepared by a sol-gel method using a dipping technique. The appearance of surface plasmon of Cu metal at about 570 nm was observed after heat treatment at or above 700°C. The third-order nonlinear susceptibility (x³) was as high as 5.0 × 10^–8 esu at 570 nm.     

不同退火温度In掺杂ZnO薄膜的表面形貌和光学性质

用X射线衍射仪(XRD)、扫描电子显微镜(SEM)和紫外-可见分光光度计观察4%(原子分数)In掺杂ZnO薄膜的微结构、表面形貌和光学性质.微结构分析表明:薄膜仍为六角纤锌矿结构,由于In杂质的掺入,使得薄膜结晶度劣化,退火温度对薄膜微结构影响较小;表面形貌观察结果显示:薄膜表面凹凸不平,450 ℃退火处理薄膜表面最平坦,尺寸在50～100 nm之间小颗粒致密、均匀地分布于起伏的表面;紫外可见透射谱研究结果表明:随着退火温度升高,薄膜光学带宽E_g由3.267 eV减小到3.197 eV,该结果可能与薄膜表面残余应力发生变化密切相关.     

Al-Sc共掺杂ZnO透明导电薄膜的掺杂机制

采用溶胶-凝胶法制备Al-Sc共掺杂ZnO透明导电薄膜,考察了结晶性、晶界状态、紫外-可见光透射光谱及Hall效应,并讨论其掺杂机制,结果表明:Sc单独掺杂时,晶粒尺寸变小,结晶性变差,晶粒表面包裹一层非晶相,透射光谱存在较大的吸收谷,无导电性;Al-Sc共掺杂时,晶粒表面无非晶相,c轴择优取向性和晶界状态变优,透射光...