Fabrication of Au thin film gratings by pulsed laser interference

We report that one-dimensional (1D) and two-dimensional (2D) metal thin film gratings can be directly fabricated by interfering Nd-YAG pulsed laser beams (wavelength = 1064 nm, pulse width = 6 ns) incident from the backside of glass substrate. This process utilizes a laser-induced thermo-elastic force which plays a role to detach the film from the substrate. Micro-scale Au transmission gratings with a minimum feature size of 1 μm could be generated by interference-driven periodic detachment. The fabrication of tube-structured patterns as well as stripes was also possible by adjusting the pulse power and this is explained with the effect of film cohesion.     

Growth and characterization of pulsed laser deposited ZnO thin films

One of the most important and promising materials from metal oxides is ZnO with specific properties for near UV emission and absorption optical devices. The properties of ZnO thin films strongly depend on the deposition method. Among them, pulsed laser deposition (PLD) plays an important role for preparing various kinds of ZnO films, e.g. doped, undoped, monocrystalline, and polycrystalline. Different approaches — ablation of sintered ZnO pellets or pure metallic Zn as target material are described. This contribution is comparing properties of ZnO thin films deposited from pure Zn target in oxygen atmosphere and those deposited from sintered ZnO target. There is a close connection between final thin film properties and PLD conditions. The surface properties of differently grown ZnO thin films are measured by secondary ion mass spectrometry (SIMS), atomic force microscopy (AFM) and scanning electron microscopy (SEM). Furthermore, different approaches — ablation of sintered ZnO pellet or pure metallic Zn as target materials are described. The main results characterize typical properties of ZnO films versus technological parameters are presented. Presented at 5-th International Conference Solid State Surfaces and Interfaces, November 19–24, 2006, Smolenice Castle, Slovakia     

Effects of deposition temperature on the structural and morphological properties of thin ZnO films fabricated by pulsed laser deposition

ZnO thin films were grown on Si(1 0 0) substrates using pulsed laser deposition in O₂ gas ambient (10 Pa) and at different substrate temperatures (25, 150, 300 and 400 °C). The influence of the substrate temperature on the structural and morphological properties of the films was investigated using XRD, AFM and SEM. At substrate temperature of T=150 °C, a good quality ZnO film was fabricated that exhibits an average grain size of 15.1 nm with an average RMS roughness of 3.4 nm. The refractive index and the thickness of the thin films determined by the ellipsometry data are also presented and discussed.     

Highly conductive and transparent laser ablated nanostructured Al: ZnO thin films

Al doped ZnO thin films are prepared by pulsed laser deposition on quartz substrate at substrate temperature 873 K under a background oxygen pressure of 0.02 mbar. The films are systematically analyzed using X-ray diffraction, atomic force microscopy, micro-Raman spectroscopy, UV-vis spectroscopy, photoluminescence spectroscopy, z-scan and temperature-dependent electrical resistivity measurements in the temperature range 70-300 K. XRD patterns show that all the films are well crystallized with hexagonal wurtzite structure with preferred orientation along (0 0 2) plane. Particle size calculations based on XRD analysis show that all the films are nanocrystalline in nature with the size of the quantum dots ranging from 8 to 17 nm. The presence of high frequency E₂ mode and longitudinal optical A₁ (LO) modes in the Raman spectra suggest a hexagonal wurtzite structure for the films. AFM analysis reveals the agglomerated growth mode in the doped films and it reduces the nucleation barrier of ZnO by Al doping. The 1% Al doped ZnO film presents high transmittance of ∼75% in the visible and near infrared region and low dc electrical resistivity of 5.94 × 10⁻⁶ Ω m. PL spectra show emissions corresponding to the near band edge (NBE) ultra violet emission and deep level emission in the visible region. Nonlinear optical measurements using the z-scan technique shows optical limiting behavior for the 5% Al doped ZnO film.     

Direct laser interference patterning of poly(3,4-ethylene dioxythiophene)-poly(styrene sulfonate) (PEDOT-PSS) thin films

We have developed a patterning procedure based on selective ablation using interference patterns with ns-laser pulses to fabricate periodic arrays on large areas of poly(3,4-ethylene dioxythiophene)-poly(4-styrene sulfonic acid) (PEDOT-PSS) thin films over a metallic gold–palladium layer. Single pulse laser-ablation experiments were performed to study the ablation characteristics of the thin films as a function of the film thickness. The ablation threshold fluence of the PEDOT-PSS films was found to be dependent on thickness with values ranging from 43 mJ/cm² to 252 mJ/cm². Additionally, fluences at which the PEDOT-PSS films could be ablated without inducing damage in the underlying metallic films were observed (128 mJ/cm² and 402 mJ/cm² for film thicknesses of 70 nm and 825 nm, respectively). Linear periodic arrays with line spacings of 7.82 μm and 13.50 μm were also fabricated. The surface topography of these arrays was analyzed using scanning electron and atomic force microscopy. For thicker polymeric layers, several peeled sub-layers of the conjugated polymer with average thicknesses of about 165–185 nm were observed in the ablation experiments. The size and scale of structures produced by this technique could be suitable for several biomedical applications and devices in which controlling cell adhesion, promoting cell alignment, or improving biocompatibility are important.     

Thermal conductivity of thermoelectric Al‐substituted ZnO thin films

ZnO:Al thin films with a low electrical resistivity were grown by magnetron sputtering on sapphire substrates. The cross‐plane thermal conductivity (κ = 4.5 ± 1.3 W/mK) at room temperature is almost one order of magnitude lower than for bulk materials. The thermoelectric figure of merit ZT at elevated temperatures was estimated from in‐plane power factor and the cross‐plane thermal conductivity at room temperature. It is expected that the thermal conductivity drops with increasing temperature and is lower in‐plane than cross‐plane. Consequently, the thin film ZT is at least three times higher than for bulk samples at intermediate temperatures. (© 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Properties of ZnO thin films deposited on (glass,ITO and ZnO:Al) substrates

ZnO thin films were deposited on glass, ITO (In₂O₃; Sn) and on ZnO:Al coated glass by spray pyrolysis. The substrates were heated at 350 °C. Structural characterization by X-ray diffraction (XRD) measurements shows that films crystallize in hexagonal structure with a preferential orientation along (0 0 2) direction. XRD peak-shift analysis revealed that films deposited on glass substrate (−0.173) were compressive, however, films deposited onto ITO (0.691) and on ZnO:Al (0.345) were tensile. Scanning electron microscopies (SEM) show that the morphologies of surface are porous in the form of nanopillars. The transmittance spectra indicated that the films of ZnO/ITO/glass and ZnO/ZnO:Al/glass exhibit a transmittance around 80% in the visible region. An empirical relationship modeled by theoretical numerical models has been presented for estimating refractive indices (n) relative to energy gap. All models indicate that the refractive index deceases with increasing energy band gap (E_g).     

退火对ZnO:Al薄膜光致发光性能的影响

 采用溶胶-凝胶工艺在石英衬底上制备ZnO:Al（AZO）薄膜,通过不同温度的退火处理,研究了退火对AZO薄膜结构和光致发光特性的影响。XRD图谱表明：所制备的薄膜具有c轴高度择优取向,随着退火温度的升高,(002)峰的强度逐渐增强,同时(002)峰的半高宽逐渐减小,表明晶粒在不断增大。未退火样品的光致发光（PL）谱由361 nm附近的紫外带边发射峰和500 nm附近的深能级发射峰组成。样品经退火后,以500 nm为中心的绿带发射逐渐减弱,而带边发射强度有所增强,并且逐渐红移到366 nm附近,与吸收边移动的测试结果相吻合。对经过不同时间退火的样品分析表明,AZO薄膜的发光特性与退火时间也有很大关系,时间过短可见波段的发射较强,但时间过长会使晶粒发生团聚,导致紫外发射峰强度减弱。     

The transparence comparison of Ga- and Al-doped ZnO thin films

The Ga-doped ZnO (GZO) and Al-doped ZnO (AZO) thin films were grown on quartz glass substrates by pulsed laser deposition under different oxygen partial pressures (PO₂). The transparent performances of films versus properties of structure and conductivity were discussed. With the increase of PO₂, the transmittance of both GZO films and AZO films increased to maximum and then decreased which were in according with the change of crystallization quality. The transmittance of GZO films was higher than that of AZO films, which were not dominated by the impurity ions induced by doping. AFM images and surface roughness mean square coefficients showed that the surfaces of GZO films were smoother than that of AZO films, which were due to the dopant Ga acting as the surfactant and smoothed the GZO films surface.     

Ordered ultra thin ZnO films on metal substrate

Ultra thin ZnO films were prepared on metal Mo(1 1 0) substrate under ultrahigh vacuum conditions either by depositing Zn in 10⁻⁵ Pa oxygen or by oxidizing pre-deposited Zn films. The films were characterized in situ by various surface analytical techniques, including Auger electron spectroscopy, X-ray and ultraviolet photoelectron spectroscopies, low energy electron diffraction and high resolution electron energy loss spectroscopy. The results indicate that a long-range ordered and stoichiometric ZnO films are formed along its [0 0 0 1] direction. The annealing experiments show that as-prepared ZnO films are thermal stable until 800 K. This study provides constructive information to further understand the growth mechanism of ZnO films on different substrates.     

Nano-scale and surface precipitation of metallic particles in laser interference patterned noble metal-based thin films

Laser interference patterning (also known as “laser interference metallurgy”) is used to locally tailor the microstructure of oxide (Pd_0.25Pt_0.75O_x) and nitride (Cu₃N) thin films to induce a chemical decomposition, which is responsible for a decrease of electrical resistivity. This technique allows hereby a laser-induced chemical decomposition of as-deposited oxide and nitride films, resulting locally in a porous microstructure due to the simultaneous emission of gaseous nitrogen and oxygen. The process locally generates at the nanometer scale metal precipitatation of Pt or Cu in the oxide or nitride matrix. Thus, isolated metallic clusters with low resistivity coexist with a high resistivity phase, establishing a preferential electrical conduction path and giving the system a lower effective resistivity. The decomposition process is investigated by four-point probe method, X-ray diffraction, spectrophotometry, white light interference, scanning and transmission electron microscopies.     

基于等色干涉的膜分析

基于膜等色干涉原理,将等色干涉条纹与已知线光谱在光谱仪谱面上叠加,通过对干涉条纹宽度及其变化的测量,可计算出膜厚、膜厚突变、膜厚渐变等.对膜进行扫描分析,膜的面积达10-2mm2数量级即可进行测量.     

Al/ZnO/Al薄膜的结构与磁性分析

采用直流磁控溅射的方法制备了Al/ZnO/Al纳米薄膜,并对薄膜分别在真空及空气中进行退火处理.利用X射线衍射仪(XRD)和物理性能测量仪(PPMS)分别对薄膜样品的结构和磁性进行了表征.XRD分析表明,不同的退火氛围对薄膜的微结构有着很大的影响.采用了一种新的修正方法对磁测量结果进行修正,计算了基底拟合误差的最大值,并对修正后样品的磁性进行了分析.结果显示,室温铁磁性可能与Al和ZnO基体之间发生的电荷转移以及在不同退火氛围下Al在ZnO晶格中的地位变化有关. 关键词： Al/ZnO/Al薄膜 铁磁性 磁性表征     

Structural characterization of supported nanocrystalline ZnO thin films prepared by dip-coating

Nanocrystalline ZnO thin films prepared by the sol-gel dip-coating technique were characterized by grazing incidence X-ray diffraction (GIXD), atomic force microscopy (AFM), X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS). The structures of several thin films subjected to (i) isochronous annealing at 350, 450 and 550 °C, and (ii) isothermal annealing at 450 °C during different time periods, were characterized. The studied thin films are composed of ZnO nanocrystals as revealed by analysing several GIXD patterns, from which their average sizes were determined. Thin film thickness and roughness were determined from quantitative analyses of AFM images and XR patterns. The analysis of XR patterns also yielded the average density of the studied films. Our GISAXS study indicates that the studied ZnO thin films contain nanopores with an ellipsoidal shape, and flattened along the direction normal to the substrate surface. The thin film annealed at the highest temperature, T = 550 °C, exhibits higher density and lower thickness and nanoporosity volume fraction, than those annealed at 350 and 450 °C. These results indicate that thermal annealing at the highest temperature (550 °C) induces a noticeable compaction effect on the structure of the studied thin films.     

Semipolar (11\bar 2\bar 2) ZnO thin films grown on LaAlO3‐buffered LSAT (112) single crystals by pulsed laser deposition

Semipolar (11\bar 2 \bar 2) ZnO was successfully grown on (112) LaAlO₃/(LaAlO₃)_0.29(Sr₂AlTaO₆)_0.35 substrate by pulsed laser deposition. The epitaxial relationship is [11\bar 23]_{\rm ZnO} // [11\bar 1]_{\rm LAO/LSAT} with the polar axis of [000\bar 1]_{\rm ZnO} pointing to the surface. For ZnO films with thickness of 1.6 μm, the threading dislocation density is ～1 × 10⁹ cm^–2, and the density of basal stacking faults is below 1 × 10⁴ cm^–1. The (11\bar 2 \bar 2) ZnO exhibits strong D⁰X emissions with a FWHM of 9 meV and very few green–yellow emissions in the low‐temperature (10 K) and room‐temperature photoluminescence spectra, respectively.

     

An investigation on the variations in properties of Ni+ irradiated ZnO thin films

ZnO thin films, irradiated by 80 MeV Ni⁺ ions, were analysed with the help of different characterization techniques like X-ray diffraction, optical absorption, transmission, photoluminescence (PL), electrical resistivity, photosensitivity (PS) and thermally stimulated current (TSC) measurements. Crystallinity and absorption edge were hardly affected by irradiation. PL spectrum of pristine sample showed a broad peak at 517 nm, whereas irradiated film had two emissions at 517 and 590 nm. Intensity ratio between these two emissions (I₅₁₇/I₅₉₀) decreased with the fluence, and finally at a fluence of 3×10¹³ ions/cm², the emission at 517 nm completely disappeared. Electrical resistivity of the sample irradiated with a fluence of 1×10¹³ ions/cm² drastically increased. However, on increasing the fluence to 3×10¹³ ions/cm², resistivity decreased, probably due the onset of hopping conduction through defects. PS also decreased due to irradiation. TSC measurements on pristine sample could reveal only one defect level at 0.6 eV, due to interstitia1 zinc (Zn_I). But, irradiation at a fluence of 1×10¹² ions/cm², resulted in three different defect levels as per TSC studies. Interestingly, the sample irradiated at a fluence of 3×10¹³ ions/cm² had only one defect level corresponding to a deep donor. The possible origin of these defect levels is also discussed in the paper.     

Light trapping for a‐Si:H/µc‐Si:H tandem solar cells using direct pulsed laser interference texturing

We present a‐Si:H/µc‐Si:H tandem solar cells on laser textured ZnO:Al front contact layers. Direct pulsed laser interference patterning (DLIP) was used for writing arrays of one‐dimensional micro gratings of submicron period into ZnO:Al films. The laser texture provides good light trapping which is indicated by an increase in short‐circuit current density of 20% of the bottom cell limited device compared to cells on planar ZnO:Al. The open‐circuit voltage of the cells on laser textured ZnO:Al is almost the same as for cells on planar substrates, indicating excellent growth conditions for amorphous and microcrystalline silicon on the U‐shaped grating grooves. DLIP is a simple, single step and industrially applicable method for large area periodic texturing of ZnO:Al thin films. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Quenching of surface traps in Mn doped ZnO thin films for enhanced optical transparency

The structural and photoluminescence analyses were performed on un-doped and Mn doped ZnO thin films grown on Si (1 0 0) substrate by pulsed laser deposition (PLD) and annealed at different post-deposition temperatures (500-800 °C). X-ray diffraction (XRD), employed to study the structural properties, showed an improved crystallinity at elevated temperatures with a consistent decrease in the lattice parameter ‘c’. The peak broadening in XRD spectra and the presence of Mn 2p3/2 peak at ∼640 eV in X-ray Photoelectron Spectroscopic (XPS) spectra of the doped thin films confirmed the successful incorporation of Mn in ZnO host matrix. Extended near band edge emission (NBE) spectra indicated the reduction in the concentration of the intrinsic surface traps in comparison to the doped ones resulting in improved optical transparency. Reduced deep level emission (DLE) spectra in doped thin films with declined PL ratio validated the quenching of the intrinsic surface traps thereby improving the optical transparency and the band gap, essential for optoelectronic and spintronic applications. Furthermore, the formation and uniform distribution of nano-sized grains with improved surface features of Mn-doped ZnO thin films were observed in Field Emission Scanning Electron Microscopy (FESEM) images.     

Effect of mesh patterning with UV pulsed-laser on optical and electrical properties of ZnO/Ag-Ti thin films

In this study, the ZnO/Ag-Ti structure for transparence conducting oxide (TCO) is investigated by optimizing the thickness of the Ag-Ti alloy and ZnO layers. The Ag-Ti thin film is deposited by DC magnetron sputtering and its thicknesses is well controlled. The ZnO thin film is prepared by sol-gel method using zinc acetate as cation source, 2-methoxiethanol as solvent and monoethanolamine as solution stabilizer. The ZnO film deposition is performed by spin-coating technique and dried at 150 °C on Corning 1737 glass. Due to the conductivity of ZnO/Ag-Ti is dominated by Ag-Ti, the sheet resistance of ZnO/Ag-Ti decrease dramatically as the thickness of Ag-Ti layer increases. However, the transmittances of ZnO/Ag-Ti become unacceptable for TCO application after the thickness of Ag-Ti layer beyond 6 nm. The as-deposited ZnO/Ag-Ti structure has the optical transmittance of 83% @ 500 nm and the low resistivity of 1.2 × 10⁻⁵ Ω-cm. Furthermore, for improving the optical and electrical properties of ZnO/Ag-Ti, the thermal treatment using laser is adopted. Experimental results indicate that the transmittance of ZnO/Ag-Ti is improved from 83% to 89% @ 500 nm with resistivity of 1.02 × 10⁻⁵ Ω-cm after laser drilling. The optical spectrum, the resistance, and the morphology of the ZnO/Ag-Ti will be reported in the study.     

Enhanced photo-induced hydrophilicity of the sol-gel-derived ZnO thin films by Na-doping

Na-doped ZnO thin films with different Na/Zn ratio were prepared by sol-gel method. The microstructure, chemical composition, surface morphology, and wettability of the thin films were investigated by X-ray diffraction, X-ray photoelectron spectroscopy (XPS), scanning electron microscopy, and water contact angle apparatus. The relation of wettability and Na/Zn ratio has been studied in detail. The wetting behavior of the thin films can be reversibly switched from hydrophobic to hydrophilic, through alternation of UV illumination and dark storage (or thermal treatment). Photo-induced hydrophilicity of the thin films increases with increasing Na/Zn ratio up to 0.08 and then decreases. The mechanism can be attributed to surface nanostructure and the concentration of Na doping.