Patterning thin metallic film via laser structured weakly bound template

A weakly bound buffer material is structured on a surface by interfering low power laser beams, as a template for patterning metallic thin films deposited on top. The excess buffer material and metal layer are subsequently removed by a second uniform laser pulse. This laser pre-structured buffer layer assisted patterning procedure is demonstrated for gold layer forming a grating on a single crystal Ru(1 0 0) under UHV conditions, using Xe as the buffer material. Millimeters long, submicron (0.65 μm) wide wires can be obtained using laser wavelength of 1.064 μm with sharp edges of less than 30 nm, as determined by AFM. This method provides an all-in-vacuum metallic film patterning procedure at the submicron range, with the potential to be developed down to the nanometer scale upon decreasing the patterning laser wavelength down to the UV range.     

Growth of b-axis oriented VO2 thin films on glass substrates using ZnO buffer layer

VO₂ thin films are grown on glass substrates by pulsed laser deposition using vanadium metal as a target. In this study, a ZnO thin film was used as a buffer layer for the growth of VO₂ thin films on glass substrates. X-ray diffraction studies showed that the VO₂ thin film had b-axis preferential orientation on a c-axis oriented ZnO buffer layer. The thickness of the ZnO buffer layer and the oxygen pressure during VO₂ deposition were optimized to grow highly b-axis oriented VO₂ thin films. The metal-insulator transition properties of the VO₂ film samples were investigated in terms of infrared reflectance and electrical resistance with varying temperatures.     

In situ study of epitaxial growth of ZnO nanowires at the junctions of nanowall networks on zinc particles

The authors show the real-time growth of ZnO nanowalls and nanowires on zinc particles via in situ observation in an environmental scanning electron microscopy. It was observed that a ZnO polycrystalline film is first deposited on zinc particles. The nanowires started to grow when the nanowalls had just formed and they grew epitaxially on the junctions of the nanowalls. The nanowalls and the nanowires grew together until the source of zinc was exhausted. The vapor–solid mechanism is deemed to be the growth mechanism as it quantitatively accounts for the growth speed of the nanowalls and nanowires observed in the experiment. Cathodoluminescence reveals that the growth at low zinc concentration leads to blue emission from defects, which may be zinc vacancies.     

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)     

ZnO:Ag film growth on Si substrate with ZnO buffer layer by rf sputtering

ZnO buffer layers were deposited on n-Si (1 0 0) substrate by rf magnetron sputtering at a lower power of 40 W. Then Ag-doped ZnO (SZO) films were deposited on buffered and non-buffered Si at a higher sputtering power of 100 W. The effects of buffer layer on the structural, electrical and optical properties of SZO films were investigated. The three-dimensional island growth process of ZnO buffer layer was discussed. The energy band diagram of p-SZO/n-Si heterojunction was constructed based on Anderson's model. Results show the ZnO buffer layer leads to better properties of SZO film, including larger grain size, smoother surface, higher carrier mobility, better rectifying behavior, lower interface state density, and weaker deep-level emission. It is because the ZnO buffer layer effectively relaxes the partial stress induced by the large lattice mismatch between SZO and Si.     

Zn1−x Mg x O (0≤x≤0.05) nanowalls grown on catalyst-free sapphire substrates by high-pressure PLD and their photoluminescence properties

We report the growth of Zn_1?x Mg _x O (x=0, 0.02, 0.05 at.%) nanowalls on sapphire substrates without any metal catalysts by a high-pressure pulsed laser deposition (PLD). The influences of the experimental parameters like growth pressure, temperature, and target-substrate distance on the growth of Zn_1?x Mg _x O nanowalls were systemically studied and the growth mechanism was discussed. It was found that large area and uniform Zn_1?x Mg _x O nanowalls with c-orientation can be grown on sapphire substrates when the growth temperature and pressure were 950 °C and 400 Torr at a target-substrate distance of 2 cm. A thin layer assisted vapor-solid (VS) process was proposed for Zn_1?x Mg _x O nanowalls growth. The photoluminescence spectrum shows the bandgap of Zn_1?x Mg _x O nanowall was effectively expanded together with defect-related levels formation in a forbidden gap, which also induced enhancement of visible emission.     

Structure and optical properties of ZnO nanowires fabricated by pulsed laser deposition on GaN/Si(111) films with the use of Au and NiO catalysts

The growth of ZnO nanowires on a Si(111) substrate with a GaN buffer layer by pulsed laser deposition at a high argon pressure and with the use of Au and NiO catalysts has been investigated. Application of the low-temperature NiO catalyst makes it possible to reduce the optimal growth temperature from 900°C (in the case of the Au catalyst) to T = 570°C and grow ZnO nanowires 20 nm in diameter, which are highly-oriented in the direction of the c lattice axis and completely free of dislocations.     

Pulsed laser deposition of high-quality ZnO films using a high temperature deposited ZnO buffer layer

High-quality ZnO film growth on sapphire was achieved by pulsed laser deposition using a high temperature deposited ZnO buffer layer. This high temperature deposited buffer layer remarkably improves crystallinity of subsequent films. In particular, the full width at half-maximum of X-ray diffraction ω-rocking curves for ZnO films grown with the buffer layer is 0.0076° (27.36 arcsec) and 0.1242° (447.12 arcsec) for the out-of-plane (002) and in-plane (102) reflections, respectively. In addition, ZnO films grown with this buffer layer showed a carrier mobility of 88 cm²/V s, which is three times higher than that realized for ZnO films grown without the buffer layer. The room temperature photoluminescence spectra showed strong band edge emission with little or no defect-related visible emission. PACS 78.55.Et; 81.05.Dz     

Characteristics of ZnO epilayer on the post-annealed buffer layer on GaN/sapphire substrate by pulsed laser deposition

We employed epi-GaN substrates for ZnO film growth, and studied the deposition and post-annealing effects. ZnO films were grown by pulsed laser deposition (PLD) method. The as-grown films were annealed for one hour under atmospheric pressure air. ZnO morphologies after annealing were investigated and the post-annealed ZnO films grown at T _g =700^oC have very smooth surfaces and the rms with roughness is about 0.5 nm. Finally, ZnO post-annealed buffer layer was inserted between ZnO epilayer and GaN/sapphire substrates. It is confirmed by AFM that growth temperature of 700^oC helps the films grow in step-flow growth mode. It is observed by cathode luminescence spectrum that the ZnO film grown at 700^oC has very low visible luminescence, indicating the decrease of the deep level defects. It is also revealed by Hall measurements that carrier concentration is decreased by increasing the growth temperatures. It is suggested that low temperature buffer layer growth and post-annealing technique can be used to fabricate ZnO hetero-epitaxy.     

Si(001)基片上反应射频磁控溅射ZnO薄膜的两步生长方法

利用反应射频磁控溅射技术，采用两步生长方法制备了ZnO薄膜，探讨了基片刻蚀时间和低温过渡层沉积时间对ZnO薄膜生长行为的影响.研究结果表明，低温ZnO过渡层的沉积时间所导致的薄膜表面形貌的变化与过渡层在Si(001)表面的覆盖度有关.当低温过渡层尚未完全覆盖基片表面时，ZnO薄膜的表面岛尺度较小、表面粗糙度较大，薄膜应力较大；当低温过渡层完全覆盖Si(001)基片后，ZnO薄膜的表面岛尺度较大、表面粗糙度较小，薄膜应力较小.基片刻蚀时间对薄膜表面形貌的影响与低温过渡层的成核密度有关.随着刻蚀时间的增加，ZnO薄膜的表面粗糙度逐渐下降，表面形貌自仿射结构的关联长度逐渐减小. 关键词： ZnO薄膜 反应射频磁控溅射 两步生长 形貌分析     

Growth mechanism studies of ZnO nanowire arrays via hydrothermal method

Well-controlled ZnO nanowire arrays have been synthesized using the hydrothermal method, a low temperature and low cost synthesis method. The process consists of two steps: the ZnO buffer layer deposition on the substrate by spin-coating and the growth of the ZnO nanowire array on the seed layer. We demonstrated that the microstructure and the morphology of the ZnO nanowire arrays can be significantly influenced by the main parameters of the hydrothermal method, such as pH value of the aqueous solution, growth time, and solution temperature during the ZnO nanowire growth. Scanning electron microscopy observations showed that the well oriented and homogeneous ZnO nanowire arrays can be obtained with the optimized synthesis parameters. Both x-ray diffraction spectra and high-resolution transmission electron microscopy (HRTEM) observations revealed a preferred orientation of ZnO nanowires toward the c-axis of the hexagonal Wurtzite structure, and HRTEM images also showed an excellent monocrystallinity of the as-grown ZnO nanowires. For a deposition temperature of 90 °C, two growth stages have been identified during the growth process with the rates of 10 and 3 nm/min, respectively, at the beginning and the end of the nanowire growth. The ZnO nanowires obtained with the optimized growth parameters owning a high aspect ratio about 20. We noticed that the starting temperature of seed layer can seriously influence the nanowire growth morphology; two possible growth mechanisms have been proposed for the seed layer dipped in the solution at room temperature and at a high temperature, respectively.     

Layer by layer growth of ZnO on (0001) sapphire substrates by radical-source molecular beam epitaxy

Layer by layer growth of ZnO epilayers on (0001) Al₂O₃ substrates is achieved by radical-source molecular beam epitaxy. A thin MgO buffer, followed by a low-temperature ZnO buffer was used in order to accommodate the lattice mismatch between ZnO and sapphire. Reflection high-energy electron diffraction intensity was employed for the optimization of the ZnO growth. The surface morphology of the samples was studied with atomic force microscopy. Investigation of the nature of the influence of the MgO buffer layer on the formation of ZnO on sapphire substrate was carried out using Transmission Electron Microscopy. For the first time it was shown that a thin spinel (magnesium aluminum oxide) layer is formed on the interface of the sapphire substrate and MgO buffer layer leading to the crystalline quality improvement of the ZnO main layer. X-Ray diffractometry measurements of the obtained ZnO layers show excellent quality of the single crystalline ZnO heteroepitaxially grown on sapphire. The crystalline quality of the ZnO layers is even better than that of our previously reported layers grown employing hydrogen peroxide as an oxidant. The full width at half maximum of the XRD (0002) rocking curve is as low as 25 arc s. The influence of growth parameters (Zn/O flux ratio, temperature, etc.) on the structural properties as well as on the surface morphology of the zinc oxide layers on sapphire is investigated and discussed.     

Control growth of catalyst-free high-quality ZnO nanowire arrays on transparent quartz glass substrate by chemical vapor deposition

ZnO nanowire arrays have been successfully synthesized on transparent quartz glass substrate by chemical vapor deposition technique. Our work demonstrates the critical role of the growth temperature and the buffer layer on the effective control of the morphology of ZnO nanowires. A proper growth temperature and the thicker buffer layer could promise the good alignment and high density of the nanowires. The room-temperature photoluminescence spectrum shows that the buffer layer has also great effects on optical properties of ZnO nanowire arrays. The integrated intensity ratio [I_UV/I_{Visible band}] of the ZnO UV emission peak to visible band emission decreases with the increase of the thickness of the buffer layers. The obtained nanowire arrays have transmittance of above 50% in the visible region.     

Excimer laser accelerated hydrothermal synthesis of ZnO nanocrystals & their electrical properties

The synthesis of ZnO nanocrystals is reported using a hydrothermal chemical growth technique combined with 248 nm nanosecond excimer laser heating at fluences in the range 0-390 mJ cm⁻². The effect of laser heating in controlling the morphology of the nanocrystals is investigated using optical spectroscopy and electron microscopy characterization. Laser heating is shown to allow control of the crystal morphology from nanoparticles to nanorods as well as to modify the size distributions. The results indicate that not only does the laser accelerate the growth of nanocrystals, but can also produce crystals with a narrow size distribution possibly via photothermal size selection. An initial study of electrical conduction properties of ZnO nanocrystal thin films is also discussed.     

Selective growth of ZnO nanowires on substrates patterned by photolithography and inkjet printing

Zinc oxide nanowires (ZnO NWs) were grown by a two-step growth method, involving the deposition of a patterned ZnO thin seeding layer and the chemical vapor deposition (CVD) of ZnO NWs. Two ways of patterning the seed layer were performed. The seeding solution containing ZnO precursors was deposited by sol–gel/spin-coating technique and patterned by photolithography. In the other case, the seeding solution was directly printed by inkjet printing only on selected portion of the substrate areas. In both cases, crystallization of the seed layer was achieved by thermal annealing in ambient air. Vertically aligned ZnO NWs were then grown by CVD on patterned, seeded substrates. The structure and morphology of ZnO NWs was analyzed by means of X-ray diffraction and field emission scanning electron microscopy measurements, respectively, while the vibrational properties were evaluated through Raman spectroscopy. Results showed that less-defective, vertically aligned, c-axis oriented ZnO NWs were grown on substrates patterned by photolithography while more defective nanostructures were grown on printed seed layer. A feature size of 30 µm was transferred into the patterned seed layer, and a good selectivity in growing ZnO NWs was obtained.     

Weakly bound buffer layer as a template for metallic nano-clusters growth and film laser-patterning

Growth of metallic nano-clusters and control over their size are critically important for catalysis. Development of film patterning procedures at the nanometer scale has significant impact on future lithography. In this work, we present an approach to grow metallic nano-clusters and control their size using a weakly bound buffer layer as an intermediate substance and a template to control the clusters size at the range 1-15 nm.The buffer layer was further employed to create a pattern based on a selective laser ablation procedure. A thicker metallic film deposited on top of pre-patterned buffer layer has been demonstrated as a novel patterning technique at the sub-micron to nanometer scale employing a single laser pulse. The thermal stability of metallic structures prepared this way has been studied at temperature up to 1000 K.     

低温缓冲层对氧化锌薄膜质量的影响

利用金属有机化学气相沉积(MOCVD)法,在Si衬底上外延生长ZnO薄膜。为了改善氧化锌薄膜的质量,首先在Si衬底上生长低温ZnO缓冲层,然后再生长高质量的ZnO薄膜。通过XRD、SEM、光致发光(PL)光谱的实验研究,发现低温ZnO缓冲层可有效降低ZnO薄膜和Si衬底之间的晶格失配以及因热膨胀系数不同引起的晶格畸变。利用低温缓冲层生长的ZnO薄膜的(002)面衍射峰的强度要比直接在Si上生长的ZnO薄膜样品的高,并且衍射峰的半高宽也由0.21°减小到0.18°,同时有低温缓冲层的样品室温下的光致发光峰也有了明显的增高。这说明利用低温缓冲层生长的ZnO薄膜的结晶质量和光学性质都得到了明显改善。     

Radiation-induced formation of ZnO nanoparticles on the ZnSe single-crystal surface

The possible formation of ZnO nanocrystals was studied as a result of radiolysis of a ZnSe crystal surface exposed to zinc vapor and irradiated with gamma rays and in producing ZnSe-ZnO heterostructures. Under ⁶⁰Co gamma radiation in air, nanocrystals ～27 nm in size are formed from nanoscopic ZnO nuclei. Under a mixed flux of gamma rays and thermal-neutron radiation, a twin structure is formed in the host ZnSe lattice and ZnO is removed. The oxide layer is also destroyed under proton irradiation in vacuum. It is found that the growth of ZnO nanocrystallites causes a manyfold increase in the luminescence intensity in the ～600-nm band and in microhardness and also a decrease in the resistance and blocking and threshold voltages irrespective of polarity. Thus, gamma irradiation brings about the formation of light-emitting ZnSe-ZnO: Zn semiconductor structures with a p-n junction.     

Post-fabrication annealing effects on the performance of P3HT:PCBM solar cells with/without ZnO nanoparticles

In this study, P3HT:PCBM organic photovoltaic (OPV) devices, with or without ZnO nanoparticles buffer layer between the photoactive layer (P3HT:PCBM) and the cathode (Al top electrode), were fabricated. The devices were annealed at 145 °C either before or after depositing the top electrode. The objective of this study was to investigate the effects of the ZnO buffer layer and pre-/post-fabrication annealing on the general performance of these devices. The short-circuit current density (J_SC), open-circuit voltage (V_OC) and the external quantum efficiency (EQE) of the OPV devices were improved by the insertion of the ZnO layer and post-fabrication annealing. The post-fabrication annealed devices, with or without the ZnO layer, exhibited higher values of J_SC, V_OC and EQE than those of similar devices annealed before depositing the Al metal. This can be attributed to, among other things, improved charge transport across the interface between the photoactive layer and the Al top electrode as a result of post-annealing induced modification of the interface morphology.     

Synthesis and characterization of Al-N codoped p-type ZnO epitaxial films using high-temperature homo-buffer layer

Al-N codoped p-type ZnO thin films have been prepared by DC magnetron reactive sputtering reproducibly using a high-temperature (HT) homo-buffer layer. The influence of HT buffer layer deposition time (T_ht) on film properties was investigated by X-ray diffraction (XRD), scanning electron micro-spectra (SEM) and Hall measurement. The Al-N codoped ZnO film was improved evidently in its crystal quality by varying the value of T_ht. Results of Hall effect showed that all of the Al-N codoped ZnO thin films were p-type conduction and had resistivity mainly below 50 Ω cm. The optimum deposition time of HT buffer layer is around 3 min from the comprehensive consideration of structural, electrical, and optical properties. The obtained ZnO thin film can meet the need of application in optoelectronic devices based on ZnO.