Bottom-up self-assembly of macroporous ZnO nanostructures for photovoltaic applications

The present study utilized a template-assisted electrodeposition route for the bottom-up epitaxial growth of macroporous zinc oxide nanostructures. To this end, the ZnO seed layer was coated on the p-type silicon substrates using a radio frequency magnetron sputtering technique to form a p-n heterojunction. Then, polymer microspheres were implanted on ZnO/Si substrates to act as a template. Subsequently, ZnO nanostructures were electrodeposited through the interstitial spaces between the microspheres. After the deposition, the microspheres were removed by dissolving in chloroform solvent, forming a porous structure. The planar and cross-sectional electron microscopy analyses exhibited a uniform macroporous morphology with an average pore diameter of ∼1 μm. The pores were homogeneously distributed on the surface of the electrodeposited ZnO layer. The advantage of this technique over the top-down approaches, such as electrochemical etching, is that the porosity and size of pores can be easily adjusted by varying the concentration and diameter of microsphere templates. The optical investigations revealed enhancement in photon absorption and photoluminescence (PL) intensity due to multiple light scattering in the pore walls of the deposited ZnO nanostructures. For the templated sample, a PL blue shift was observed due to the reduction in crystallite size of ZnO nanostructures. A heterojunction thin film solar cell was designed by the metallization of ZnO/p-Si samples to study the power conversion capability of macroporous ZnO nanostructures. The photovoltaic performance of the developed devices was evaluated under a solar light simulator. The device based on the templated sample showed increased shunt resistance and reduced series resistance compared to the flat sample. The optoelectrical results indicated an efficiency improvement for the fabricated solar cells based on the macroporous ZnO sample due to its higher exposed area and increased rate of electron-hole generation.     

Improved optical and structural properties of cadmium sulfide nanostructures for optoelectronic applications

In this study, the effect of ZnO seed layer on the growth of uniform CdS nanostructures was investigated using chemical bath deposition technique. Besides, the influence of molar concentration of reagents on the surface morphology, structural and optoelectrical properties of the deposited CdS thin films were examined. The CdS nanostructures were grown on bare glass and ZnO/glass substrates with different reagent molar concentrations. The results indicated an improvement in the homogeneity and uniformity of the grown CdS nanostructures on ZnO seed layer which can be due to the low lattice mismatch between ZnO and CdS structures. The CdS/ZnO samples were optimized by changing the molar concentration of reagents. A three–dimensional intersecting vertical nanosheet morphology with hexagonal structure was obtained when modified chemical concentration of 0.5 M was applied. The XRD pattern of CdS nanosheets indicated the hexagonal phase of CdS which were strongly orientated along (002) plane. The elevated intensity of dominant peak related to this sample confirmed the improved crystal quality of this CdS nanostructure comparing to the other samples. The UV–Vis spectrum demonstrated a high absorption coefficient for CdS intersecting nanosheets which might be due to the high specific surface area and light trapping behavior of this sample. The photoluminescence study also showed an improvement in optical properties of optimized CdS nanostructures. In order to study the optoelectrical properties of CdS nanostructures, metal–semiconductor–metal photodetectors were fabricated with different CdS samples and their current–voltage characteristics were analyzed. The results indicated an enhancement in photosensitivity, responsivity, and speed of photodetectors based on optimized CdS nanostructures.     

Effect of chlorine ion concentration on morphology and optical properties of Cl-doped ZnO nanostructures

Effect of Cl^?1 concentration on morphology and optical properties of Cl-doped ZnO nanostructures was studied. The Cl-doped ZnO nanostructures and undoped ZnO microstructures were grown on Si(1 1 1) substrates using a physical vapor deposition method. The ZnO nanostructures have been doped with different concentrations of chlorine. The Cl-doped ZnO nanostructures with 6% atom Cl, showed a nanodisk morphology with a hexagonal shape, while the Cl-doped ZnO nanostructures with 9% atom Cl, exhibited a stacked nanoplate morphology with smaller thickness in comparison to the Cl-doped ZnO nanodisks. In addition, with increasing Cl content to 13%, morphology of the products changed to more stacked nanoplates with nanoflakes morphology. X-ray diffraction results clearly showed a hexagonal structure for the all samples. Raman spectroscopy results showed a strong crystalline quality for the undoped ZnO microdisks and Cl-doped ZnO nanodisks; while these results indicated a weak crystalline quality for the Cl-doped ZnO nanoplates and nanoflakes. Photoluminescence (PL) studies also confirmed the Raman results and it exhibited a lower optical property for the Cl-doped ZnO nanoplates and nanoflakes in comparison to the undoped ZnO microdisks and Cl-doped ZnO nanodisks. Furthermore, the UV peak of the Cl-doped ZnO nanostructures was blue-shifted with respect to that of the undoped ZnO.     

溶剂热合成多级ZnO微球及其光催化降解苯酚

以乙二醇为溶剂,KAc为助剂,采用溶剂热法合成多级ZnO微球。通过改变反应温度来调控ZnO微球形貌,并对合成的ZnO微球进行XRD、SEM、PL和UV-Vis DRS等表征分析。结果表明,合成的ZnO为六方纤锌矿晶体结构,由短纳米棒自组装成多级微球。在紫外-可见光照射下,ZnO表现出优异的光催化降解苯酚活性,180℃合成的ZnO样品光催化活性明显优于其他温度合成的样品。用0.1 g的ZnO降解100 mL浓度为5 mg·L^(-1)的苯酚溶液,光照150 min降解率达94.5%。多级ZnO微球光催化性能的提高可推测为较窄的禁带宽度(3.08 eV)有利于吸收光子,较小的晶粒尺寸(25.38 nm)、粗糙的表面以及中空结构有利于反应液与催化剂表面的充分接触。此外,由捕获实验证实光催化降解苯酚的机理是羟基(·OH)为主要的活性自由基,在苯酚降解过程中起主要作用。     

Effect of indium concentration on morphology and optical properties of In-doped ZnO nanostructures

In-doped ZnO nanostructures with different indium concentrations were grown using a thermal evaporation method. The In-doped ZnO nanostructures with a low concentration of indium exhibited a javelin shape, while the In-doped ZnO nanostructures with a high concentration of indium showed a flake shape. In addition, undoped ZnO nanojavelins were grown under the same conditions, but the sizes of these undoped ZnO nanojavelins were larger than the In-doped ZnO nanojavelins. It was shown that the In³⁺ cations played a crucial role in controlling the size. X-ray diffraction and Raman spectroscopy clearly showed hexagonal structures for all of the products. However, the Raman results demonstrated that the In-doped ZnO nanoflakes had a lower crystalline quality than the In-doped ZnO nanojavelins. Furthermore, photoluminescence (PL) measurements confirmed the Raman results. Moreover, the PL results demonstrated a larger band-gap for the In-doped ZnO nanostructures in comparison to the undoped ZnO.     

孔结构可调聚合物微球的制备及贯通性能

具备贯通性能的聚合物微球在微球材料中具有广泛应用。本文采用溶剂挥发法制备孔结构可调的聚甲基丙烯酸甲酯微球并对微球的贯通性能进行研究。通过调控聚合物浓度、致孔剂用量、溶剂组成以及升温速率等实现微球孔结构可调并研究以上参数对微球贯通性能的影响。结果表明：当聚合物的浓度逐渐升高时，微球内部由中空向多孔结构演变，且随着聚合物浓度的增加，微球内部孔数量增多，孔径变小，贯通性能降低；当致孔剂用量逐渐增加时，微球内部结构由多孔向中空演变，且伴随致孔剂用量的减少，微球孔数量增多，孔径变小，贯通性能降低；无论是调控聚合物浓度还是致孔剂用量，微球的贯通性能与结构密切相关，当微球中空或者内部为稀疏的大孔结构时，贯通性较好，在水溶液中沉降率高达80%以上；使用混合溶剂替代单一溶剂以提高多孔聚合物微球的贯通性，发现微球多孔结构的变化趋势并不明显，但是可以较为显著地改变聚合物微球的贯通性，其中当R_TCM/DCM=3∶10时，微球贯通性最佳，相比单一溶剂条件下，在水溶液中沉降率从30%提高到60%。升温速率对微球贯通性影响巨大，升温过快或过慢均对微球贯通性产生不利影响，40℃/25min条件下所制备微球沉降率较高，约60%。     

Controllable electrochemical synthesis of La/ZnO hierarchical nanostructures and their optical and magnetic properties

Here we presented a facile electrochemical deposition route for the controllable preparation of La³⁺/ZnO hierarchical nanostructures, such as flower-like nanostructures consisted of nanorods, flower bundles, and hexagonal nanorods with nests at the top. These prepared La³⁺/ZnO deposits were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, UV-vis spectrophotometer, and photoluminescence spectroscopy. The formation process of La³⁺-doped ZnO and the growth mechanisms of La³⁺/ZnO hierarchical nanostructures were discussed. The UV and PL spectra measurements show that the surface morphologies of La³⁺/ZnO deposits have an obvious effect on their optical properties and we can easily adjust their optical properties as well as La³⁺/ZnO nanostructures by changing electrochemical deposition parameters. In addition, the magnetic properties of La³⁺/ZnO deposits were also investigated.     

Preparation of porous polymer membranes using nano- or micro-pillar arrays as templates

ZnO or polystyrene (PS) pillar arrays were formed on solid substrates and used as templates for the formation of porous polymer membranes. The membranes were formed by casting a polymer solution in the inter-pillar space of these templates and evaporating the solvent. Dissolution of the pillars in a selective solvent resulted in thin films containing monodisperse micrometer-sized channels. Membranes produced using the pillar template technique showed high water permeability and high size selectivity.     

Porous ZnO-ZnSe nanocomposites for visible light photocatalysis

We report the synthesis of porous ZnO-ZnSe nanocomposites for use in visible light photocatalysis. Porous ZnO nanostructures were synthesized by a microwave-assisted hydrothermal reaction then converted into porous ZnO-ZnSe nanocomposites by a microwave-assisted dissolution-recrystallization process using an aqueous solution containing selenium ions. ZnO and ZnSe nanocrystallites of the nanocomposites were well-mixed (rather than forming simple core-shell (ZnO-ZnSe) structures), particularly, in the outer regions. Both ZnO and ZnSe were present at the surface and exposed to the environment. The porous ZnO-ZnSe nanocomposites showed absorption bands in the visible region as well as in the UV region. The porous ZnO-ZnSe nanocomposites had much higher activities than the porous ZnO nanostructures. Control experiments using cutoff filters revealed that the main photocatalytic activity of the synthesized nanostructures arose from photo-excitation of the semiconductor (ZnO or ZnSe) via absorption of light of an energy equal to or exceeding the band gap energy.     

One-dimensional ZnO nanostructure growth prepared by thermal evaporation on different substrates: Ultraviolet emission as a function of size and dimensionality

Large-scale uniform one-dimensional ZnO nanostructures were fabricated through thermal evaporation via the vapor solid mechanism on different substrates. The effects of Si (100), Si (111), SiO₂ and sapphire substrates with constant oxygen treatment on the morphology and diameter of ZnO nanostructures were investigated. It is found that the type of substrate has a great effect on the shape and diameter of the synthesized nanowires, nanorods, and nanotubes. It is noticed that the size and dimensionality were the most influential parameters on both structural and optical properties of the grown ZnO nanostructures. X-ray diffraction analysis confirms the stability of the wurtzite crystal structure for all grown ZnO nanostructures and the preferred orientation is substrate dependent. The crystallinity as well as the defects within the crystal lattice of the grown ZnO nanostructures was studied through Raman spectroscopy. The photoluminescence spectra of ZnO nanostructures grown on Si (100), Si (111), SiO₂ and sapphire substrates showed two peaks at a near-band-edge (NBE) emission in the ultraviolet region and a broad deep-level emission (DLE) around the green emission.     

Facile synthesis of different morphologies of Te-doped ZnO nanostructures

Te-doped ZnO nanostructures were synthesized by an annealing (vapor–solid) process under ambient conditions, and characterized in terms of their morphological, structural, compositional and optical properties. The structural and morphological characterizations revealed that the synthesized nanostructures were well-defined multipods, needles and spherical particles, and possessed well-crystalline ZnO wurtzite hexagonal phase. Also, in the X-ray diffraction studies, the presence of a shift in the peak positions towards a lower angle, and a decrease in the intensity, with an increase in the Te concentration, as compared to the undoped ZnO, were observed. The chemical composition confirmed the presence of Te, in the case of multipod and needle morphologies. The effect of doping on the crystalline quality and optical properties was also investigated, by using photoluminescence (PL) and Raman spectrometers. The Raman results demonstrated that the doped ZnO nanostructures had a lower crystalline quality than the undoped ZnO. Moreover, the PL results showed a decrease in the band gap for the doped ZnO nanostructures, in comparison to the undoped ZnO. A possible growth mechanism was also proposed.     

In situ deposition of poly(1,8-diaminonaphthalene): from thin films to nanometer-sized structures

Chemical in situ deposition of poly(1,8-diaminonaphthalene) (p(1,8-DAN)) on conductive supports in aqueous and acetonitrile solutions was investigated using electrochemical quartz crystal microbalance (EQCM) and UV-vis spectroscopy. The resulting deposits were examined by the means of cyclic voltammetry (CV), FT-IR and Raman spectroscopy. P(1,8-DAN) was also deposited via chemical polymerization onto a porous polycarbonate membrane (PC) which served as a template for synthesis of nanometer-sized structures. The deposits of p(1,8-DAN) on PC substrate were imaged by atomic force microscopy (AFM) and the nanostructures obtained by dissolution of the template were visualized by scanning electron microscopy (SEM). The EQCM and UV-vis studies indicated that the polymer is formed both on the surface of the substrate and in the bulk of the polymerization solution. However, polymerization of 1,8-DAN in solution is delayed in comparison with deposition on the substrate. Electrochemical and spectroscopic properties of p(1,8-DAN) formed chemically closely resemble the properties of the electrosynthesized polymer. Furthermore, SEM images of p(1,8-DAN) nanostructures revealed that the polymer nanowires are formed in aqueous solutions, whereas two types of structures: nanowires and round shaped structures, not fitting to the pore size, can be obtained by chemical polymerization in the acetonitrile medium.     

Electron field emission from semiconducting nanowires

In this paper we report on investigations of field emission (FE) properties of semiconducting (SiC, ZnO) one-dimensional (1D) nanostructures – nanowire/nanorod arrays, and fabrication of low-voltage field emission display (FED) devices based on these 1D nanomaterials. SiC nanowires were grown on Ni-coated Si substrates using a thermal metal-organic chemical vapor deposition (MOCVD) technique, and ZnO nanostructures were grown on gold-coated Si substrates by a thermal CVD method. Electron field emission properties of SiC and ZnO nanostructures were examined in plane geometry using a flat phosphor screen. The interrelation between the FE characteristics (emission thresholds, current density, surface uniformity, etc.) and microstructure and surface morphology of the produced 1D nanostructures was established. Diode-type FED devices (flat vacuum lamps) with SiC-nanowire-based cathodes were developed and fabricated. The FEDs are characterized by low threshold and operating electric fields – lower 2 V/μm and 5 V/μm, respectively, high current density and brightness, and stable performance of the nanowire-based cathodes.     

Partially ordered porous structures on layer-by-layer polyaniline/poly(vinyl sulfate sodium) ultrathin films: Easy fabrication of robust submicroscopic patterning

The use of polyaniline (PANI) as a conductive material has steadily increased in recent years due to its interesting physicochemical properties, low manufacturing cost, and easy processing. This conductive material, associated with the diffraction properties of organized nanostructures in thin films, has excellent application potential in microelectronics and photonic devices. Initially, this work presents improvement routes for the breath figure method (a nanopatterning technique) in polystyrene (PS) films through the control of film deposition parameters and the presence of water in the polymer solution. Such improvements are then extended to the production of PANI nanostructures, in the form of pores, from patterned porous PS films. Consequently, PANI films with a partially ordered pore structure (mean pore diameter of ~100 nm) are produced in a facile and easily scalable method. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48597.     

Effects of substrate annealing on the gold-catalyzed growth of ZnO nanostructures

The effects of thermal substrate pretreatment on the growth of Au-catalyzed ZnO nanostructures by pulsed laser deposition are investigated. C-plane sapphire substrates are annealed prior to deposition of a thin Au layer. Subsequent ZnO growths on substrates annealed above 1,200°C resulted in a high density of nanosheets and nanowires, whereas lower temperatures led to low nanostructure densities. Separate Au film annealing experiments at 700°C showed little variation in the size and density of the Au catalyst droplets with substrate annealing temperature. The observed variation in the density of nanostructures is attributed to the number of surface nucleation sites on the substrate, leading to a competition between nucleation promoted by the Au catalyst and surface nucleation sites on the rougher surfaces annealed below 1,200°C.     

Thermal decomposition synthesis of single-crystalline porous ZnO nanoplates self-assembled by tiny nanocrystals and their pore-dependent magnetic properties

High quality porous ZnO nanoplates with a pure crystal phase of hexagonal wurtzite structure were fabricated by thermal decomposition route for the first time. Electron microscopy investigations show that each porous ZnO nanoplates has a single-crystalline nature, which is self-assembled by tiny nanocrystals. The size and pore density of the ZnO nanoplates can be tuned by only changing the amount of zinc source. Magnetic investigations show that the magnetic phase can be converted from paramagnetism to ferromagnetism at room temperature, by increasing the pore density of ZnO nanoplates. The ZnO nanoplates with highest pore density show a d° room-temperature ferromagnetic characteristic, and the saturation magnetization reaches 26 memu/g. Several experimental evidences, including XPS, PL and ESR spectra, demonstrate that the defects of singly charged oxygen vacancies related to the pore density contribute to the long-range ferromagnetic ordering in the dopant-free porous ZnO nanoplates. This finding suggests that the pore-dependent ferromagnetism can be manipulated by tuning the surface-volume ratio, which is significant for the understanding and exploration of diluted magnetic semiconductors.     

Growth and formation mechanism of sea urchin-like ZnO nanostructures on Si

Sea urchin-like nanostructures of ZnO consisting of ZnO nanowires with blunt faceted ends were grown on Si (100) substrates by oxidation of metallic Zn at 600 °C. ZnO nanowires having a diameter of 30–60 nm and length of 2–4 Μm were in similar shape with uniform diameter along its entire length with well faceted blunt ends. X-ray diffraction and transmission electron microscope analysis showed that the as-grown nanostructures were highly crystalline with wurtzite hexagonal structure having lattice constants of a=b=3.25 å and c=5.21 å. Room temperature photoluminescence (PL) measurements showed a weak near band-edge emission at 380 nm, but a strong green emission at 500–530 nm. A model for vapor-solid (VS) growth mechanism of ZnO nanowires was presented, in which nucleation of ZnO is crucial for the growth of the nanostructures.     

One-step solution synthesis and formation mechanism of flower-like ZnO and its structural and optical characterization

The regular hierarchical flower-like ZnO nanostructures assembled by nanosheets were successfully synthesized by one-step solution route with citrate assistance at room temperature. It was demonstrated that the concentration of citrate and the molar ratio of Zn²⁺/OH⁻ had strong effect on the formation of nanosheets and self-assembly flower-like nanostructures. A reasonable formation mechanism of the flower-like nanostructures was proposed. According to UV–vis spectrum, the flower-like ZnO nanostructures exhibited strong light absorption, and the value of band gap of the obtained ZnO was estimated to be 3.26 eV. Moreover, the room-temperature photoluminescence (PL) spectrum of the sample presented only a near-band edge emission at 382 nm.     

Solid-state thermal dewetted silver nanoparticles onto electrochemically grown self-standing vertically aligned ZnO nanorods for three-dimensional plasmonic nanostructures

Three dimensional (3D) plasmonic nanostructures composed of silver nanoparticles decorated ZnO NRs arrays, have been fabricated by a process combining the electrochemical growth of ZnO NRs and further formation of Ag nanoparticles by the solid-state thermal dewetting (SSD) process. The effect of SSD parameters on the morphological, structural and optical properties of the Ag NPs decorated ZnO NRs arrays has been investigated. It is possible to tune the bandgap of the Ag NPs@ZnO nanorods array 3D plasmonic nanostructure by tailoring the Ag nanoparticle sizes, allowing light manipulation at the nanoscale. The silver nanoparticles attached to the ZnO NRs arrays experienced surface plasmonic coupling effect, causing enhancement in the room temperature photoluminescence (PL) UV emission and quenching the corresponding visible light one. An enhancement in the near band edge emission PL intensity of ZnO to the deep level emission PL intensity ratio after Ag NPs decoration of the ZnO nanostructures corresponding to ca. 11 folds has been observed, indicating that the defect emission is obviously suppressed.     

Pore Narrowing and Formation of Ultrathin Yttria-Stabilized Zirconia Layers in Ceramic Membranes by Chemical Vapor Deposition/Electrochemical Vapor Deposition

Chemical vapor deposition (CVD) and electrochemical vapor deposition (EVD) have been applied to deposit yttria-stabilized-zirconia (YSZ) on porous ceramic media. The experimental results indicate that the location of YSZ deposition can be varied from the surface of the substrates to the inside of the substrates by changing the CVD/EVD experimental conditions, i.e., the concentration ratio of the reactant vapors. The deposition width is strongly dependent on the deposition temperature used. The deposition of YSZ inside the pores resulted in pore narrowing and eventually pore closure, which was measured by using permpor-ometry. However, deposition of YSZ on top of porous ceramic substrates (outside the pores) did not result in a reduction of the average pore size. Ultrathin, dense YSZ layers on porous ceramic substrates can be obtained by suppressing the EVD layer growth process after pore closure.