Selective growth of ZnO nanorods for gas sensors using ink-jet printing and hydrothermal processes

Selective growth of ZnO nanorod arrays with well-defined areas was developed to fabricate the NO₂ gas sensor. The seed solution was ink-jet printed on the interdigitated electrodes. Then, vertically aligned ZnO nanorods were grown on the patterned seed layer by the hydrothermal approach. The influences of seed-solution properties and the ink-jet printing parameters on the printing performance and the morphology of the nanorods were studied. Round micropattern (diameter: 650 μm) of ZnO nanorod arrays is demonstrated. The dimensions and positions of the nanorod arrays can be controlled by changing the printed seed pattern. The effects of nanorod structure and nanorod size on the gas-sensing capability of ZnO nanorod gas sensors were demonstrated. Due to the high surface-to-volume ratios of the nanorod-array structure, the ZnO nanorod gas sensor can respond to 750 ppb NO₂ at 100 °C. The sensors without baking treatment exhibit the typical response of a p-type semiconductor. However, only the response of n-type semiconductor oxides was observed after the annealing treatment at 150 °C for 2 h.     

Fabrication of the selective-growth ZnO nanorods with a hole-array pattern on a p-type GaN:Mg layer through a chemical bath deposition process

ZnO nanorod arrays were effectively selective-grown on a p-type GaN:Mg layer through chemical bath deposition (CBD) at a low temperature hydrothermal synthesis (85 °C) with a ZnO seed layer. The 5 μm-diameter hole-array patterns of the ZnO seed layer were grown on a p-type GaN:Mg layer in aqueous solution with a mercury lamp illumination. The diameter and the height of ZnO nanorods were measured as the values of 500 nm and 3 μm, respectively. The growth orientation, surface morphology, and aspect ratio of the ZnO nanorods can be controlled and formed on the hole-array patterned ZnO seed layer. The peak wavelength of the photoluminescence spectrum was measured at 384 nm.     

Compact and vertically-aligned ZnO nanorod thin films by the low-temperature solution method

Highly c-axis-oriented ZnO nanorod thin films were obtained on silica glass substrates by a simple solution-growth technique. The most compact and vertically-aligned ZnO nanorod thin film with the thickness of ∼ 800 nm and average hexagonal grain size of ∼ 200 nm exhibits the average visible transmittance 85%, refractive index 1.74, packing density 0.84, and energy band gap 3.31 eV, and it was fabricated under the optimum parameters: 0.05 M, 75 °C, 6 h, multiple-stepwise, and ZnO seed layer with an average grain size of ∼ 20 nm. The photoluminescence spectrum indicates that the densest ZnO nanorod thin film possesses lots of oxygen vacancies and interstitials. As we demonstrate here, the solution-growth technique was used to produce high-quality and dense ZnO nanorod thin films, and is an easily controlled, low-temperature, low-cost, and large-scale process for the fabrication of optical-grade thin films.     

Effects of Metal-Organic Chemical Vapour Deposition grown seed layer on the fabrication of well aligned ZnO nanorods by Chemical Bath Deposition

Well aligned, long and uniform ZnO nanorods have been reproducibly fabricated adopting a two-steps Metal-Organic Chemical Vapour Deposition (MOCVD) and Chemical Bath Deposition (CBD) fabrication approaches. Thin (< 100 nm) ZnO buffer layers have been seeded on silicon substrates by MOCVD and ZnO layers have been subsequently grown, in form of well textured nanorods, using CBD. It has been found that the structure and thickness of the seed layer strongly influence the final morphology and the crystal texturing of ZnO nanorods as well as the CBD growth rate. There is, in addition, a strong correlation between morphologies of CBD grown ZnO nanorods and those of the seed layer underneath. Thus, nanorods deposited over low temperature MOCVD buffer layers are less homogeneous in lateral dimensions and poorly vertically oriented. On the contrary, higher temperature nano-dimensional ZnO seeds favour the CBD growth of almost mono-dimensional homologue nanorods, with an adequate control of the lateral transport of matter. The nanorod aspect ratio values decrease upon increasing the deposition temperatures of the seed layers. Moreover, the nanorods length can be tailored either by adjusting the CBD growth time or by changing concentration of the N,N,N′,N′-tetramethylethylenediamine ligand used in the CBD process. In particular, at high concentrations, the CBD process is faster with a greater global aspect ratio in agreement with a preferential one-dimensional growth of the ZnO nanostructures. Finally, these ZnO nanorod arrays possess good optical quality in accordance to the photoluminescence properties.     

Solid phase epitaxy of silicon thin films by diode laser irradiation for photovoltaic applications

High temperature solid phase epitaxial crystallization of amorphous silicon layers prepared by electron beam evaporation is investigated. By using a continuous wave diode laser for heating the films rapidly (in milliseconds to seconds) this method is suitable on glass substrates with low temperature resistance. Therefore, the method is an economically advantageous technique of producing absorber layers for thin film solar cells. For the experiments 500 nm of amorphous silicon was deposited on two different configurations of substrates. In the first one monocrystalline wafers of three different crystallographic orientations were used. In the second one a polycrystalline seed layer prepared on borosilicate glass served as substrate. The crystallization process was monitored in situ by time resolved reflectivity measurements. Depending on the crystal orientation 2 s to 3 s was needed for complete solid phase epitaxial crystallization of the amorphous films. The evolution of temperature during crystallization was simulated numerically.     

Rapid thermal-plasma annealing of ZnO:Al films for silicon thin-film solar cells

Rapid thermal annealing of sputter-deposited ZnO and Al-doped ZnO (AZO) films with and without an amorphous silicon (a-Si) capping layer was investigated using a radio-frequency (rf) argon thermal plasma jet at atmospheric pressure. The resistivity of bare ZnO films on glass decreased drastically from 10⁶ to 10³ Ω·cm at maximum surface temperatures T_max above 650 °C, whereas the resistivity increased from 10^− 4 to 10^− 3-10^− 2 Ω·cm for bare AZO films. On the other hand, the resistivity of AZO films with a 30-nm-thick a-Si capping layer remained below 10^− 4 Ω·cm, even after TPJ annealing at a T_max of 825 °C. X-ray diffraction and X-ray photoemission electron studies revealed that the film crystallization of both AZO and a-Si layers was promoted without the formation of an intermixing layer. Additionally, the crystallization of phosphorous- and boron-doped a-Si layers at the sample surface was promoted, compared to that of intrinsic a-Si under identical plasma annealing conditions. The role of the a-Si capping layer on sputter-deposited AZO and ZnO films during TPJ annealing is demonstrated. The effects of the mixing of phosphorous and boron impurities in a-Si:H during TPJ annealing of flat and textured AZOs are also discussed.     

Effects of pre-annealing conditions on the characteristics of ZnO nanorods and ZnO/p-Si heterojunction diodes grown through hydrothermal method

Pre-annealing of seed layers before the growth of ZnO nanorods (NRs), at various temperatures (non-annealing ~ 800 °C) and in various atmospheres (vacuum, N₂, or O₂), was systematically studied to investigate the effects of pre-annealing on the material properties of ZnO NRs as well as the rectifying behaviour of ZnO NRs/p-Si heterojunction diodes (HJDs). A seed layer was initially prepared on the Si substrate through hydrothermal (HT) method and subsequently pre-annealed; finally, the ZnO NRs were grown through the same HT method. We found that without the annealed seed layer, the ZnO NRs cannot be grown on the Si template and increase in the pre-annealing temperature led to better crystallization and fewer defect-centres in ZnO NRs. However, at a high pre-annealing temperature, the characteristics of ZnO NRs degraded due to the evaporation of oxygen atoms, resulting in more oxygen-vacancy-related defects. The smallest diameter and shortest length of ZnO NRs were observed on the samples pre-annealed at 450 °C. The short length of ZnO NRs implies a slow growth rate, because of which the NRs have sufficient time to align normal to the surface of the substrate. When the seed layer is pre-annealed in an O₂ atmosphere, the oxygen atoms fill the oxygen-vacancy-related defects, which lead to a higher nucleation density and improved characteristics of ZnO NRs. This leads to an extremely high rectification ratio of 1.8 × 10⁵ in ZnO NR/p-Si HJDs. The related mechanisms were explored in this study.     

Electrochemical deposition and superhydrophobic behavior of ZnO nanorod arrays

Vertically aligned ZnO nanorod arrays with different heights are grown on the ZnO seeded indium tin oxide substrate by cathodic electrochemical deposition from zinc nitrate at two temperatures of 60 °C and 80 °C. As-grown ZnO nanorods exhibit wurzite crystal structure and their heights can be well controlled by different deposition times. The fluorination coating tends to induce a superhydrophobicity of ZnO nanorods, i.e., the maximal value of contact angle: 166.9°. The super water repellency can be attributed to the fact that an air layer is confined in the nanorod arrays, and thus leads to water droplets sitting on the ZnO surfaces, referring as Cassie state. Interestingly, their water contact angles are found to vary with the heights of ZnO nanorods, ranged from 99.8 to 746 nm. The superhydrophobicity of ZnO surfaces can be well predicted by a proposed model that is capable of determining the wetted fraction of ZnO pillars. This satisfactory result would shed one light on how the variation of rod height would induce the superhydrophobic behavior of ZnO nanorod arrays.     

Low-temperature synthesis of ZnO nanorods using a seed layer of zinc acetate/sodium dodecyle sulfate nanocomposite

Aligned ZnO nanorods were synthesized by a simple hydrothermal method without calcination. A seed layer of zinc acetate (ZnAc₂)/sodium dodecyle sulfate (SDS) nanocomposite was used for nucleation of ZnO nanorods. First, a ZnAc₂/SDS composite was deposited on a Si substrate by spin-coating. And then, ZnO nanorods were grown under hydrothermal conditions at 90 °C. ZnO crystals were grown in the direction of c-axis perpendicular to the surface of the Si substrate. However, nucleation did not occur on the substrate of a ZnAc₂ seed layer without SDS, indicating that the presence of the ZnAc₂/SDS seed enhanced the nucleation of ZnO crystals. These results show that high dispersion of ZnAc₂ in the nanocomposite effectively assists a nucleation of ZnO crystals.     

Growth specificity of vertical ZnO nanorods on patterned seeded substrates through integrated chemical process

A simple and cost effective method has been employed for the random growth and oriented ZnO nanorod arrays over as-prepared and patterned seeded glass substrates by low temperature two step growth process and growth specificity by direct laser writing (DLW) process. Scanning electron microscopy (SEM) images and X-ray diffraction analysis confirm the growth of vertical ZnO nanorods with perfect (0 0 2) orientation along c-axis which is in conjunction with optimizing the parameters at different reaction times and temperatures. Transmission electron microscopy (TEM) images show the formation of vertical ZnO nanorods with diameter and length of ∼120 nm and ∼400 nm respectively. Photoluminescence (PL) spectroscopic studies show a narrow emission at ∼385 nm and a broad visible emission from 450 to 600 nm. Further, site-selective ZnO nanorod growth is demonstrated for its high degree of control over size, orientation, uniformity, and periodicity on a positive photoresist ZnO seed layer by simple geometrical (line, circle and ring) patterns of 10 μm and 5 μm dimensions. The demonstrated control over size, orientation and periodicity of ZnO nanorods process opens up an opportunity to develop multifunctional properties which promises their potential applications in sensor, piezoelectric, and optoelectronic devices.     

The effect of growth conditions on the properties of ZnO nanorod dye-sensitized solar cells

In this article, we report ZnO nanorod samples grown on transparent conductive SnO₂:F (FTO) glass substrates by two different growth routes through hydrothermal method in a closed autoclave. One route is one-step continuous growth for 10 h. The other route is discrete multi-step growth for total 48 h. In this process, fresh solution was repeatedly introduced in every step. The structural, photoluminescence (PL) and photovoltaic properties of the as-prepared nanorod arrays were investigated. The nanorod arrays obtained through multi-step growth show longer rods, higher aspect ratio, larger spacing, better crystalline quality. The PL spectrum of nanorod arrays obtained through multi-step growth shows a strong and sharp near-band-gap emission (UV) peak and a weak green-yellow emission (GY) peak (I_UV/I_GY = 7.7), which also implies its good crystallinity and high optical quality. Dye-sensitized solar cells based on ZnO nanorod arrays were fabricated, and those grown with discrete multi-step procedure present better photovoltaic properties duo to its special morphology and better crystal quality.     

Synthesis and characterization of ZnO nanorod films for photocatalytic disinfection of contaminated water

The growth of ZnO nanorods on a flat substrate was studied as a function of the main parameters used in their preparation and their ability to photocatalytically eliminate bacteria in water.The seed layer was obtained, by a spray pyrolysis technique, from a zinc acetate solution. Subsequently, to grow the rods, the seeds were immersed in a basic solution of zinc nitrate maintained at 90 °C. The growth parameters, thickness of the seed layer, acidity of the precursor solution used to obtain the seed layer, and the rate of crystal growth on the seed layer during the thermal bath treatment, were studied.The resulting materials were characterized morphologically by scanning electron microscopy and transmission electron microscopy (TEM); X-ray diffraction and TEM were used to study their structure and ultraviolet-visible spectroscopy to determine their absorbance. Most of the obtained materials were textured in the (002) direction perpendicular to the substrate. The rods have a hexagonal cross section between 60 and 150 nm. Using these rods, the photocatalytic degradation of Escherichia coli bacteria in water was studied; a positive influence of the surface area and crystalline growth on the degradation rate was observed.     

小晶粒TS-1分子筛膜的制备及表征

以椭球形小晶粒TS-1分子筛为晶种, 采用超声法在多孔α-Al₂O₃载体上获得紧密、均匀、连续的晶种层, 经二次生长形成小晶粒的TS-1分子筛膜. 通过改变合成液碱度(OH^-/Si)和晶化时间等合成参数, 调变分子筛膜的微结构. SEM和XRD检测结果表明, 当OH^-/Si＝0.09, 水热合成24h时, 晶种没有交联成膜, 延长晶化时间至48h, 可得到致密交联的TS-1分子筛膜, 晶体的大小约为500nm, 进一步延长晶化时间至72h时, 膜的结晶度降低, 表面覆盖一层无定形物质. 提高碱度, OH^-/Si＝0.21, 水热反应24h, 得到的膜结构不对称, 上层是高度交联的致密分子筛膜, 晶粒大小约为400nm, 致密膜与载体之间没有交联生长的晶种.     

Seed layer-free electrodeposition of well-aligned ZnO submicron rod arrays via a simple aqueous electrolyte

A potentiostatic electrodeposition technique was used to directly fabricate large-scale, well-aligned, and single-crystalline submicron ZnO rod arrays on tin doped indium oxide glass substrate without a pre-prepared seed layer of ZnO from an aqueous solution only containing zinc nitrate. The effects of electrochemical parameters, such as electrodeposition potential, electrodeposition duration, solution temperature, and precursor concentration, on the orientation, morphology, aspect ratio, and growth rate of ZnO rod arrays were systematically investigated. Results show that submicron ZnO rod arrays with (0 0 0 2) preferred orientation and perfect crystallization were obtained when electrodeposition potential was in the range from −0.6 to −1.1 V and solution temperature was controlled above 60 °C. Both high solution temperature and low precursor concentration resulted in the decrease in rod diameters. Photoluminescence measures showed that small diameter and nanotips of ZnO rod arrays should be responsible for strong and sharp ultraviolet emission in the room temperature photoluminescence spectra.     

Low-temperature synthesis of ZnO nanorods using organic-inorganic composite as a seed layer

Well-aligned zinc oxide (ZnO) nanorods were synthesized using a low-temperature hydrothermal method employing a zinc/sodium dodecyl sulfate (Zn/SDS) composite as a seed layer. The results of X-ray diffraction measurements indicate that the Zn/SDS composite has a lamellar structure with an interlayer distance of 3.12 nm, which is shorter than that of the lamellar structure of SDS (3.82 nm) due to ion exchange between Zn and Na. The results of X-ray absorption fine structure analyses suggest that ZnO crystals start to grow after an induction period of 20-30 min. The length of nanorods and the aspect ratio of ZnO nanorods could be controlled by altering the molarity of ammonium and zinc nitrate in the growth solutions.     

微通道内表面上分布密度可控的ZnO纳米棒阵列的生长

在微流控器件的微通道内表面制备了分布可控的ZnO纳米棒阵列。先利用单分散的反相胶束借助非传统的去乳化作用在玻璃毛细管通道内壁上得到了分散很好的ZnO晶种,随后得到了ZnO纳米棒的花状簇阵列。通过调控微乳体系中的W值（水与表面活性剂的摩尔比值）得到了分散密度不同的晶种,从而在毛细管内壁上制备出了分布密度可控的ZnO纳米棒阵列,为密封的长微通道功能化改性提出了一种新的方法,经该方法改善后,可在微通道内得到纳米尺度下的一维纳米材料的特殊结构,用来设计和构筑功能化、集成化的微流控器件。     

Growth of compact arrays of optical quality single crystalline ZnO nanorods by low temperature method

We report the synthesis and optical properties of compact and aligned ZnO nanorod arrays (dia, ∼ 50–200 nm) grown on a glass substrate with varying seed particle density. The suspension of ZnO nanoparticles (size, ∼ 15 nm) of various concentrations are used as seed layer for the growth of nanorod arrays via selfassembly of ZnO from solution. We studied the effect of various growth parameters (such as seeding density, microstructure of the seed layer) as well as the growth time on the growth and alignment of the nanorods. We find that the growth, areal density and alignment of the nanorods depend on the density of seed particles which can be controlled. It is observed that there is a critical density of the seed particles at which nanorod arrays show maximum preferred orientation along [002] direction. The minimum and maximum radius of the aligned nanorods synthesized by this method lie in the range 50–220 nm which depend on the seeding density and time of growth. These nanorods have a bandgap of 3.3 eV as in the case of bulk crystals and show emission in the UV region of the spectrum (∼ 400 nm) due to excitonic recombination and defect related emission in the visible region.     

Influence of seed layers on the vertical growth of ZnO nanowires

We synthesized vertically aligned ZnO nanowires on SiO₂ wafer <100> using the Au, ZnO and Au/ZnO seed layers through the physical vapor deposition process. The growth direction of ZnO nanowire was controlled by using the three different seed layers. From the XRD results, we observed the highest intensity of the (002) peak on the Au/ZnO seed layer among the three seed layers. The SEM images show that all of the ZnO nanowires have an average diameter of about 100 ~ 200 nm and a length of about 5 μm, and the nanowires grown on the Au/ZnO seed layer are oriented the most perpendicularly to the substrate surface. From the PL analysis, we observed that the intensity of broad emissions at 400-600 nm relating the green emission for the ZnO nanowires on the Au/ZnO seed layer was much weaker than that for the ZnO nanowires on the ZnO seed layer. The experiment results indicate that the selection of seed layers is important to grow nanowires vertically for the application of nanoscale devices.     

A novel, substrate independent three-step process for the growth of uniform ZnO nanorod arrays

We report a three-step deposition process for uniform arrays of ZnO nanorods, involving chemical bath deposition of aligned seed layers followed by nanorod nucleation sites and subsequent vapour phase transport growth of nanorods. This combines chemical bath deposition techniques, which enable substrate independent seeding and nucleation site generation with vapour phase transport growth of high crystalline and optical quality ZnO nanorod arrays. Our data indicate that the three-step process produces uniform nanorod arrays with narrow and rather monodisperse rod diameters (∼ 70 nm) across substrates of centimetre dimensions. X-ray photoelectron spectroscopy, scanning electron microscopy and X-ray diffraction were used to study the growth mechanism and characterise the nanostructures.     

Effect of AZO seed layer on electrochemical growth and optical properties of ZnO nanorod arrays on ITO glass

We report the structural and optical properties of ZnO nanorod arrays (NRAs) grown by an electrochemical deposition process. The ZnO NRAs were grown on indium tin oxide (ITO) coated glass substrates with a thin sputtered Al-doped ZnO (AZO) seed layer and compared with ones directly grown without the seed layer. The growth condition dependence of ZnO NRAs was investigated for various synthetic parameters. The morphology and density of the ZnO NRAs were accordingly controlled by means of zinc nitrate concentration and growth time. From photoluminescence results, the ultraviolet emission was significantly enhanced after thermal treatment. For ZnO NRAs grown on ITO glass without the seed layer, the diffuse transmittance was enhanced despite the reduction in the total transmittance, indicating a high haze value. By using a thin AZO seed layer, the well-aligned ZnO NRAs on AZO/ITO glass are controllably and reproducibly synthesized by varying the growth parameters, exhibiting a total transmittance higher than 91% in the visible wavelength range as well as good optical and crystal quality.