Multilayer coatings for flexible high-barrier materials

A multilayer, flexible, and transparent high-barrier system based on flexible plastic foils, polyethyleneterephthalate (PET) and ethylene-tetrafluoroethylene-copolymer (ETFE), combined with vacuum-deposited, inorganic SiO_x layers and hybrid ORMOCER® varnish layers were prepared in different orders on a semiproduction level. Barrier properties of prepared systems, as water vapour transmission (WVTR) and oxygen transmission (OTR), were measured and studied in connection with surface energy, surface topography, and water vapour adsorption properties. Correlations among layers sequence, barrier properties, and other parameters are presented, including some basic principles of permeation of substances through multilayer barrier systems. A combination of several inorganic and hybrid varnish layers is necessary to achieve the technological demands from a barrier standpoint. It is easier to suppress the oxygen transport than the water transport, due to the additional active penetration of water through hydrogen bonds and silanol creations at oxide interfaces, capillary condensation, and swelling with high internal pressure, leading to new defects.     

Quantitative measurement of local elasticity of SiOx film by atomic force acoustic microscopy

<正>In this paper the elastic properties of SiO_x film are investigated quantitatively for local fixed point and qualitatively for overall area by atomic force acoustic microscopy(AFAM) in which the sample is vibrated at the ultrasonic frequency while the sample surface is touched and scanned with the tip contacting the sample respectively for fixed point and continuous measurements.The SiO_x films on the silicon wafers are prepared by the plasma enhanced chemical vapour deposition(PECVD).The local contact stiffness of the tip-SiO_x film is calculated from the contact resonance spectrum measured with the atomic force acoustic microscopy.Using the reference approach,indentation modulus of SiO_x film for fixed point is obtained.The images of cantilever amplitude are also visualized and analysed when the SiO_x surface is excited at a fixed frequency.The results show that the acoustic amplitude images can reflect the elastic properties of the sample.     

Annealing effects on the optical and structural properties of Al2O3/SiO2 films as UV antireflection coatings on 4H-SiC substrates

Al₂O₃/SiO₂ films have been prepared by electron-beam evaporation as ultraviolet (UV) antireflection coatings on 4H-SiC substrates and annealed at different temperatures. The films were characterized by reflection spectra, ellipsometer system, atomic force microscopy (AFM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS), respectively. As the annealing temperature increased, the minimum reflectance of the films moved to the shorter wavelength for the variation of refractive indices and the reduction of film thicknesses. The surface grains appeared to get larger in size and the root mean square (RMS) roughness of the annealed films increased with the annealing temperature but was less than that of the as-deposited. The Al₂O₃/SiO₂ films maintained amorphous in microstructure with the increase of the temperature. Meanwhile, the transition and diffusion in film component were found in XPS measurement. These results provided the important references for Al₂O₃/SiO₂ films annealed at reasonable temperatures and prepared as fine antireflection coatings on 4H-SiC-based UV optoelectronic devices.     

Annealing effects on the structure and electrical characteristics of amorphous Er2O3 films

Amorphous Er 2 O 3 films are deposited on Si (001) substrates by using reactive evaporation.This paper reports the evolution of the structure,morphology and electrical characteristics with annealing temperatures in an oxygen ambience.X-ray diffraction and high resolution transimission electron microscopy measurement show that the films remain amorphous even after annealing at 700 C.The capacitance in the accumulation region of Er 2 O 3 films annealed at 450 C is higher than that of as-deposited films and films annealed at other temperatures.An Er 2 O 3 /ErO x /SiO x /Si structure model is proposed to explain the results.The annealed films also exhibit a low leakage current density (around 1.38 × 10 4 A/cm 2 at a bias of 1 V) due to the evolution of morphology and composition of the films after they are annealed.     

Optical characteristics of amorphous V2O5 thin films colored by an excimer laser

The V₂O₅ films were prepared by an RF sputtering method, and the amorphous films were colored by an UV excimer laser. The crystallinity of the as-grown V₂O₅ film was degenerated greatly by laser irradiation, as determined by X-ray diffraction (XRD) and Raman studies. The transmission and complex refractive index spectra of the V₂O₅ film were affected by variations in the microstructure, including the surface morphology, crystalline structure, and substoichiometry with an oxygen deficiency. Considerable emissions due to oxygen vacancies and band transition of photoluminescence (PL) peaks were observed, and the peaks were significantly changed after laser irradiation. The variations in the optical properties in both films may be attributed to oxygen deficiency induced by laser irradiation.     

Effects of O2/Ar ratio and annealing temperature on electrical properties of Ta2O5 film prepared by magnetron sputtering

The effects of the oxygen-argon ratio on electric properties of Ta2O5 film prepared by radio-frequency magnetron sputtering were investigated.The Ta2O5 partially transforms from the amorphous phase into the crystal phase when annealing temperatures are 800℃ or higher.The lattice constant of Ta2O5 decreases with the increase of the O2/Ar ratio,which indicates that oxygen gas in the working gas mixture contributes to reducing the density of oxygen vacancies during the deposition process.For the films deposited in working gas mixtures with different O2/Ar ratios and subsequently annealed at 700℃,the effective dielectric constant is increased from 14.7 to 18.4 with the increase of the O2/Ar ratio from 0 to 1.Considering the presence of an SiO2 layer between the film and the silicon substrate,the optimal dielectric constant of Ta2O5 film was estimated to be 31.Oxygen gas in the working gas mixture contributes to reducing the density of oxygen vacancies,and the oxygen vacancy density and leakage current of Ta2O5 film both decrease with the increase of the O2/Ar ratio.The leakage current decreases after annealing treatment and it is minimized at 700℃.However,when the annealing temperature is 800℃ or higher,it increases slightly,which results from the partially crystallized Ta2O5 layer containing defects such as grain boundaries and vacancies.     

Microstructure and photoluminescence of Er-doped SiOx films synthesized by ion beam assisted deposition

Er-doped SiO_x films were synthesized at 500℃ by ion beam assisted deposition technique and annealed at 800 and 1100℃ for 2h in the air atmosphere. The analysis by using energy dispersive x-ray spectroscopy showed that the ratio of Si to O decreased from 3 in the as-deposited films to about 1 in the annealed films. The investigation by using transmission electron microscopy and x-ray diffraction indicated that annealing induces a microstructure change from amorphous to crystalline. The grain sizes in the films were about 10 and 40nm when annealed at 800 and 1100℃, respectively. The films annealed at temperatures of 800 and 1100℃ exhibited a sharp photoluminescence (PL) at 1.533μm from the Er centres when pumped by 980nm laser. The influence of microstructure and grain size on the PL from Er-doped SiO_x films has been studied and discussed.     

AlNxOy thin films deposited by DC reactive magnetron sputtering

AlN_xO_y thin films were produced by DC reactive magnetron sputtering, using an atmosphere of argon and a reactive gas mixture of nitrogen and oxygen, for a wide range of partial pressures of reactive gas. During the deposition, the discharge current was kept constant and the discharge parameters were monitored. The deposition rate, chemical composition, morphology, structure and electrical resistivity of the coatings are strongly correlated with discharge parameters. Varying the reactive gas mixture partial pressure, the film properties change gradually from metallic-like films, for low reactive gas partial pressures, to stoichiometric amorphous Al₂O₃ insulator films, at high pressures. For intermediate reactive gas pressures, sub-stoichiometric AlN_xO_y films were obtained, with the electrical resistivity of the films increasing with the non-metallic/metallic ratio.     

Improving the gas barrier properties of a-SiOxCyNz film at low temperature using high energy and suitable nitrogen flow rate

Amorphous silicon oxycarbonitride thin films were synthesized on polyethylene terephthalate (PET) substrates at low temperatures (～80 °C) by plasma-enhanced chemical vapor deposition (PECVD). A high ion flux and suitable nitrogen flow rate improved the gas barrier properties and deposition rate of the resulting a-SiO_xC_yN_z film. The a-SiO_xC_yN_z films were deposited at a high deposition rate and low water WVTR properties as a result of the high ion flux and nitrogen chemistry. The high ion flux modified the chemical structure and nitrogen atomic composition of the resulting a-SiO_xC_yN_z film coatings. The substrate temperature was characterized using a thermometer. In addition, the coating properties were characterized by Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS) and the water vapor transmission rate (WVTR).     

不同氧气流量对直流磁控溅射TiO2薄膜的影响

采用直流反应磁控溅射法,以高纯Ti为靶材,高纯O₂为反应气体,制备了TiO₂薄膜.研究了氧气流量对薄膜结晶取向、表面形貌和光学性能的影响.研究发现,TiO₂薄膜主要呈锐钛矿TiO₂(101)择优取向,当氧气流量较小时,薄膜中还含有金属Ti(100),氧气流量较大时,薄膜含TiO₂(101)和TiO₂(004),成多晶态;薄膜的粗糙度和颗粒大小都随氧气流量的增大而增大;薄膜在400~1100nm可见-近红外波段有较高的透射率并且其吸收峰随着氧气流量的增大而红移,当氧气流量为5sccm时,平均透射率最高.     

Substrate effects on the oxygen gas sensing properties of SnO2/TiO2 thin films

In this study, SnO₂/TiO₂ thin films are fabricated on SiO₂/Si and Corning glass 1737 substrates using a R.F. magnetron sputtering process. The gas sensing properties of these films under an oxygen atmosphere with and without UV irradiation are carefully examined. The surface structure, morphology, optical transmission characteristics, and chemical compositions of the films are analyzed by atomic force microscopy, scanning electron microscopy and PL spectrometry. It is found that the oxygen sensitivity of the films deposited on Corning glass 1737 substrates is significantly lower than that of the films grown on SiO₂/Si substrates. Therefore, the results suggest that SiO₂/Si is an appropriate substrate material for oxygen gas sensors fabricated using thin SnO₂/TiO₂ films.     

Low temperature deposited Zr-B film applicable to extremely thin barrier for copper interconnect

We have prepared thin Zr-B films at low temperatures as a new material applicable to an extremely thin barrier against Cu diffusion in Si-ULSI metallization. The obtained Zr-B films mainly consist of the ZrB₂ phase with a nanocrystalline texture on SiO₂ and a fiber texture on Cu. The resistivity of the Zr-B films depends on the substrate of SiO₂ or Cu. The constituent ratio of B/Zr is almost 2, though the contaminants of oxygen, nitrogen, and carbon are incorporated in the film. The nanocrystalline structure of the Zr-B film on SiO₂ is stable due to annealing at temperatures up to 500 °C for 30 min. We applied the 3-nm thick Zr-B film to a diffusion barrier between Cu and SiO₂, and the stable barrier properties were confirmed. We can demonstrate that the thin Zr-B film is a promising candidate for thin film application to a metallization material in Si-ULSIs.     

Structure, morphology and optical properties of SiO2−x thin films prepared by plasma-assisted pulsed laser deposition

The amorphous silicon oxide SiO_2−x thin films were prepared by the plasma-assisted pulsed laser deposition (PLD) method. X-ray diffraction spectrometry (XRD), scanning electron microscopy (SEM), atomic force microscopy (AFM), UV-VIS-NIR scanning spectrophotometry and ellipsometry were used to characterize the crystallinity, microscopic morphology and optical properties of obtained thin films. The influences of substrate temperatures, oxygen partial pressures and oxygen plasma assistance on the compositions of silicon oxide (SiO_2−x) thin films were investigated. Results show that the deposited thin films are amorphous and have high surface quality. Stoichiometric silicon dioxide (SiO₂) thin film can be obtained at elevated temperature of 200 °C in an oxygen plasma-assisted atmosphere. Using normal incidence transmittance, a novel and simple method has been proposed to evaluate the value of x in transparent SiO_2−x thin films on a non-absorbing flat substrate.     

反应溅射VN/SiO2纳米多层膜的微结构与力学性能

采用V和SiO₂靶通过反应溅射方法制备了一系列具有不同SiO₂和VN调制层厚的VN/SiO₂纳米多层膜. 利用X射线衍射、X射线能量色散谱、高分辨电子显微镜和微力学探针表征了多层膜的微结构和力学性能. 结果表明：在Ar，N₂混和气体中，射频反应溅射的SiO₂薄膜不会渗氮. 单层膜时以非晶态存在的SiO₂，当其厚度小于1nm时，在多层膜中因VN晶体层的模板效应被强制晶化，并与VN层形成共格外延生长. 相应地，多层膜的硬度得到明显提高，最高硬度达34GPa. 随SiO₂层厚度的进一步增加，SiO₂层逐渐转变为非晶态，破坏了与VN层的共格外延生长结构，多层膜硬度也随之降低. VN调制层的改变对多层膜的生长结构和力学性能也有影响，但并不明显. 关键词： 2纳米多层膜')" href="#">VN/SiO₂纳米多层膜 共格外延生长 非晶晶化 超硬效应     

Si基铁电Bi3.15Nd0.85Ti3O12多层薄膜的一致取向生长和性能的研究

采用脉冲激光沉积(PLD)技术，利用LSCO/CeO₂/YSZ多异质缓冲层，在Si(100)基 片上成功地制备了c轴一致取向的Bi_3.15Nd_0.85Ti₃O12(BNT)铁电薄膜.利用X射线衍射(XRD)和扫描电镜(SEM)分析测定了薄膜的相结构 、取向和形貌特征，考察了沉积温度和氧分压对BNT薄膜微结构、取向和形貌的影响，确定 了BNT薄膜的最佳沉积条件.对在优化的条件下制备得到的BNT薄膜的C-V曲线测试得到了典型 的蝴蝶形曲线，表明该薄膜具有较好的电极化反转存储特性.最后讨论了BNT薄膜铁电性能与 薄膜取向的相关性. 关键词： 3.15Nd_0.85Ti₃O₁₂')" href="#">Bi_3.15Nd_0.85Ti₃O₁₂ 铁电薄 膜 多层异质结 脉冲激光沉积     

Hf1−xSixOy dielectric films deposited by UV-photo-induced chemical vapour deposition (UV-CVD)

Hf_1−xSi_xO_y is an attractive candidate material for high-k dielectrics. We report in this work the deposition of ultra-thin Hf_1−xSi_xO_y films (0.1 ≤ x ≥ 0.6) on silicon substrate at 450 °C by UV-photo-induced chemical vapour deposition (UV-CVD) using 222 nm excimer lamps. Silicon(IV) and hafnium(IV) organic compounds were used as the precursors. Films from around 5 to 40 nm in thickness with refractive indices from 1.782 to 1.870 were grown. The deposition rate was found to be of 6 nm/min at a temperature of 450 °C. The physical, interfacial and electrical properties of hafnium silicate (Hf_1−xSi_xO_y) thin films were investigated by using X-ray photoelectron spectroscopy, ellipsometry, FT-IR, C-V and I-V measurements. XRD showed that they were basically amorphous, while Fourier transform infrared spectroscopy (FT-IR), clearly revealed Hf-O-Si absorption in the photo-CVD deposited Hf_1−xSi_xO_y films. Surface and interfacial properties were analysed by TEM and XPS. It is found that carbon content in the films deposited by UV-CVD is very low and it also decreases with increasing Si/(Si + Hf) ratio, as low as about 1 at.% at the Si/(Si + Hf) ratio of 60 at.%.     

Oxygen flux influence on the morphological, structural and optical properties of Zn1−xMgxO thin films grown by plasma-assisted molecular beam epitaxy

The Zn_1−xMg_xO thin films were grown on Al₂O₃ substrate with various O₂ flow rates by plasma-assisted molecular beam epitaxy (P-MBE). The growth conditions were optimized by the characterizations of morphology, structural and optical properties. The Mg content of the Zn_1−xMg_xO thin film increases monotonously with decreasing the oxygen flux. X-ray diffractometer (XRD) measurements show that all the thin films are preferred (0 0 2) orientated. By transmittance and absorption measurements, it was found that the band gap of the film decreases gradually with increasing oxygen flow rate. The surface morphology dependent on the oxygen flow rate was also studied by field emission scanning electron microscopy (FE-SEM). The surface roughness became significant with increasing oxygen flow rate, and the nanostructures were formed at the larger flow rate. The relationship between the morphology and the oxygen flow rate of Zn_1−xMg_xO films was discussed.     

Preparation and characterization of amine-functionalized SiO2/TiO2 films for formaldehyde degradation

This paper investigated the gaseous formaldehyde degradation by the amine-functionalized SiO₂/TiO₂ photocatalytic films for improving indoor air quality. The films were synthesized via the co-condensation reaction of methyltrimethoxysilane (MTMOS) and 3-aminopropyltrimethoxysilane (APTMS). The physicochemical properties of prepared photocatalysts were characterized with N₂ adsorption/desorption isotherms measurement, X-ray diffraction (XRD) and Fourier Transform Infrared spectroscopy (FT/IR). The effect of amine-functional groups and the ratio of MTMOS/APTMS precursors on the formaldehyde adsorption and photocatalytic degradation were investigated. The results showed that the formaldehyde adsorption and photocatalytic degradation of the APTMS-functionalized SiO₂/TiO₂ film was higher than that of SiO₂/TiO₂ film due to the surface adsorption on amine sites and the relatively high of the specific surface area of the APTMS-functionalized SiO₂/TiO₂ film (15 times higher than SiO₂/TiO₂). The enhancement of the formaldehyde degradation of the film can be attributed to the synergetic effect of adsorption and subsequent photocatalytic decomposition. The repeatability of photocatalytic film was also tested and the degradation efficiency was 91.0% of initial efficiency after seven cycles.     

Effect of O2 gas partial pressure on structures and dielectric characteristics of rf sputtered ZrO2 thin films

Amorphous and polycrystalline zirconium oxide thin films have been deposited by reactive rf magnetron sputtering in a mixed argon/oxygen or pure oxygen atmosphere with no intentional heating of the substrate. The films were characterized by high-resolution transmission electron microscopy (HR-TEM), atomic force microscopy (AFM), spectroscopic ellipsometry (SE), and capacitance versus voltage (C-V) measurements to investigate the variation of structure, surface morphology, thickness of SiO₂-like interfacial layer as well as dielectric characteristics with different oxygen partial pressures. The films deposited at low oxygen partial pressures (less than 15%) are amorphous and dense with a smooth surface. In contrast, the films prepared at an oxygen partial pressure higher than 73% are crystallized with the microstructure changing from the mixture of monoclinic and tetragonal phases to a single monoclinic structure. The film structural transition is believed to be consequences of decrease in the oxygen vacancy concentration in the film and of increase of the energetically neutral particles in the plasma due to an increased oxygen partial pressure. SE measurements showed that significant interfacial SiO₂ growth has taken place above approximately 51%. The best C-V results in terms of relative dielectric constant values are obtained for thin films prepared at an oxygen partial pressure of 15%.     

Effects of vanadium doping on structure and electrical properties of SrBi4Ti4O15 thin films

The effects of vanadium(V) doping into SrBi₄Ti₄O₁₅ (SBTi) thin films on the structure, ferroelectric, leakage current, dielectric, and fatigue properties have been studied. X-ray diffraction result showed that the crystal structure of the SBTi thin films with and without vanadium is the same. Enhanced ferroelectricity was observed in the V-doped SrBi₄Ti₄O₁₅ (SrBi_4−x/3Ti_4−xV_xO₁₅, SBTiV-x (x = 0.03, 0.06, and 0.09)) thin films compared to the pure SrBi₄Ti₄O₁₅ thin film. The values of remnant polarization (2P_r) and coercive field (2E_c) of the SBTiV-0.09 thin film capacitor were 40.9 μC/cm² and 105.6 kV/cm at an applied electric field of 187.5 kV/cm, respectively. The 2P_r value is over five times larger than that of the pure SBTi thin film capacitor. At 100 kHz, the values of dielectric constant and dielectric loss were 449 and 0.04, and 214 and 0.06 for the SBTiV-0.09 and the pure SBTi thin film capacitors, respectively. The leakage current density of the SBTiV-0.09 thin film capacitor measured at 100 kV/cm was 6.8 × 10⁻⁹ A/cm², which is more than two and a half orders of magnitude lower than that of the pure SBTi thin film capacitor. Furthermore, the SBTiV-0.09 thin film exhibited good fatigue endurance up to 10¹⁰ switching cycles. The improved electrical properties may be related to the reduction of internal defects such as bismuth and oxygen vacancies with changes in the grain size by doping of vanadium into SBTi.