Highly enhanced solar conversion efficiency of novel layer-by-layer PbS:Hg and CdS quantum dots-sensitized ZnO thin films prepared by sol–gel spin coating

Owing to superior optical properties, ZnO thin films have immense potential in solar cell preparation. ZnO thin films were prepared by sol–gel technology. However, this is prolonged technique and it necessitates a complex precursor solution. In the present work, ZnO thin films are prepared by sol–gel spin coating with simple precursor, zinc acetate. A very remarkable feature of the method is that polycrystalline, non-abrasive and translucent films were obtained. Additionally, novel PbS:Hg quantum dots (QDs) and CdS QDs are successfully synthesized. Moreover, both types of QDs are deposited layer-by-layer over pure ZnO and Ag:ZnO thin films. The films are characterized by X-ray diffraction, and crystallinity continuation is observed even after the addition of QDs layer. Presence of synthesized QDs over thin films is also confirmed. The films were also characterized by scanning electron microscopy (SEM) and UV–Vis spectroscopy. Uniform, dense and porous surface morphology is clearly revealed. Sensitized thin films show a huge decline in band gap and large enhancement in efficiency. Superior current density (\(10.87~\hbox {mA}~\hbox {cm}^{-2})\) is achieved with PbS:Hg/CdS/Ag:ZnO, which leads to enhancement in overall solar conversion efficiency by 6.34 times.     

Dependency of oxygen partial pressure on the characteristics of ZnO films grown by radio frequency magnetron sputtering

The effects of oxygen and argon gas contents on the structural and optical properties of epitaxially grown ZnO thin films on sapphire substrates by radio frequency magnetron sputtering were investigated. The growth rate of ZnO thin film decreases with increase in oxygen gas contents in the gas mixture. The high-resolution x-ray diffraction $ {\left( {10\overline{1} 2} \right)} $ rocking curve and plane-view transmission electron microscopy investigations reveal the presence of a reduced dislocation density in the ZnO thin films with decrease in oxygen/argon flow ratio. However, large density of defects were observed in the boundaries and inside of the micro-hillocks formed on the surface of ZnO thin film grown with pure argon. The increase in oxygen gas ratio resulted in the improvement of optical properties with suppression and red-shift of the deep level emission.     

Effect of ZnO buffer layer on AZO film properties and photovoltaic applications

Aluminum-doped ZnO (AZO) transparent conducting films were deposited on glass substrates with and without intrinsic ZnO (i-ZnO) buffer layers by a home made and low cost radio-frequency (RF) magnetron sputtering system at room temperature in pure argon ambient and under a low vacuum level. The films were examined and characterized for electrical, optical, and structural properties for the application of CIGS solar cells. The influence of sputter power, deposition pressure, film thickness and residual pressure on electrical and optical properties of layered films of AZO, i-ZnO and AZO/i-ZnO was investigated. The optimization of coating process parameters (RF power, sputtering pressure, thickness) was carried out. The effects of i-ZnO buffer layer on AZO films were investigated. By inserting thin i-ZnO layers with a thickness not greater than 125 nm under the AZO layers, both the carrier concentration and Hall mobility were increased. The resistivity of these layered films was lower than that of single layered AZO films. The related mechanisms and plasma physics were discussed. Copper indium gallium selenide (CIGS) thin film solar cells were fabricated by incorporating bi-layer ZnO films on CdS/CIGS/Mo/glass substrates. Efficiencies of the order of 7–8% were achieved for the manufactured CIGS solar cells (4–5 cm² in size) without antireflective films. The results demonstrated that RF sputtered layered AZO/i-ZnO films are suitable for application in low cost CIGS solar cells as transparent conductive electrodes.     

Effect of annealing atmosphere on microstructure,optical and electronic properties of spray-pyrolysed In-doped Zn(O,S) thin films

Spray-pyrolysed zinc oxy-sulphide Zn(O,S) has been doped with varying concentrations of indium (In) to improve its electrical and optical properties for possible application as buffer layer in thin film solar cells. The In-doping in Zn(O,S) is found to change the electron carrier concentration from \(10^{19}\) to \(10^{18}\,\hbox {cm}^{-3}\) and a subsequent annealing in argon atmosphere is found to improve its electrical conductivity. Moreover, annealing in air atmosphere reduces the carrier concentration to a range of \(10^{13}\)–\(10^{15}\,\hbox {cm}^{-3}\) making it useful as a buffer layer. The reduction in degeneracy of In-doped Zn(O,S) is desirable for its application as buffer material, whereas annealing in argon makes it suitable as electron membrane (window layer) in thin film solar cell.     

Cation substitution induced blue-shift of optical band gap in nanocrystalline $$\hbox {Zn}_{(1-x)} \hbox {Ca}_{x}\hbox {O}$$ thin films deposited by sol–gel dip coating technique

Transparent nanocrystalline \(\hbox {Zn}_{(1-x)}\hbox {Ca}_{x}\hbox {O }(0 \le x \le 0.20)\) thin films were deposited on glass substrates by sol–gel dip coating method. The X-ray diffraction (XRD) pattern revealed the polycrystalline nature of the films with hexagonal wurtzite structure and confirmed the non-existence of the secondary phase corresponding to CaO indicating the monophasic nature of the deposited films. The crystallinity of the films deteriorated with higher dopant concentration due to the segregation or separation of dopant ions in grain boundaries. The lattice parameters and the unit cell volume increased to a higher Ca-dopant concentration. This was due to the successful incorporation of \(\hbox {Ca}^{2+}\) ions with larger ionic radius in the host zinc oxide (ZnO) lattice. The optical transmittance spectra of the samples showed transmittances above 60% in the visible spectral range and the absorption edge in the near ultra-violet region got blue-shifted with cation substitution. The estimated optical energy gaps confirmed the band gap widening with increase in Ca-dopant concentration. The calculated values increased from 3.30 eV for undoped ZnO to 3.73 eV for \(\hbox {Zn}_{0.8}\hbox {Ca}_{0.2}\hbox {O}\) thin films giving 13.03% enhancement in the energy gap value due to the electronic perturbation caused by cation substitution as well as deterioration in crystallinity.     

Synthesis of ZnO single crystals by the flux method

Zinc oxide (ZnO) single crystals have been grown at temperatures ranging from 450–900 °C and for 1–12 h, using hydrous KOH and NaOH melts as fluxes. For a KOH flux, brown ZnO single crystals with diameter 0.5 mm × 7.5 mm were grown under conditions of 500 °C for 20 h and white crystals of diameter 0.5 mm × 7 mm were grown at 800 °C for 20 h, using a small crucible (average 50 ml). When a large crucible (average 400 ml) was used, ZnO single crystals with diameter 0.5 mm × 8 mm were formed at 900 °C for 30 h. When using a KOH + NaOH (1∶1) flux, light-brown and long crystals with diameter 1.0 mm × 18 mm could be grown. The grown ZnO single crystals were bounded with only both p- and m-faces. It seems that crystal qualities were good under conditions of 900 °C for 30 h. The following mechanisms of dissociation and formation of ZnO single crystal from KOH (or NaOH) + ZnO melt seemed to occur $$KOH(or{\text{ NaOH}}){\text{ }} \to {\rm K}^ + {\text{ (or Na}}^{\text{ + }} {\text{) + OH}}^ - $$ $$ZnO{\text{ + 2 OH}}^ - \to {\text{ ZnO}}_{\text{2}}^{{\text{2}} - } {\text{ + H}}_{\text{2}} {\text{O,}}$$ $${\text{ZnO}}_{\text{2}}^{{\text{2}} - } {\text{ }} \to {\text{ ZnO + O}}^{{\text{2}} - } .$$      

Design and Characterisation of Titanium Nitride Subarrays of Kinetic Inductance Detectors for Passive Terahertz Imaging

We report on the investigation of titanium nitride (TiN) thin films deposited via atomic layer deposition (ALD) for microwave kinetic inductance detectors (MKID). Using our in-house ALD process, we have grown a sequence of TiN thin films (thickness 15, 30, 60 nm). The films have been characterised in terms of superconducting transition temperature \(T_\mathrm{c}\), sheet resistance \(R_\mathrm{s}\) and microstructure. We have fabricated test resonator structures and characterised them at a temperature of 300 mK. At 350 GHz, we report an optical noise equivalent power \(\hbox {NEP}_\mathrm{opt} \approx 2.3\times 10^{-15}~\hbox {W}/\sqrt{\hbox {Hz}}\), which is promising for passive terahertz imaging applications.     

Effect of $$\hbox {Ar}^{+}$$ ion implantation on the properties of electrodeposited CdTe thin films

Semiconducting nanomaterials of II–VI groups are the key elements of continued technological approaches made in the field of optoelectronic, magnetic and photonic devices due to their size-dependent properties. Ion beams create changes in the material along their track; this not only exhibits excellent properties but also tailors new materials. This article reports the effect of \(\hbox {Ar}^{+}\) ion implantation on the properties of cadmium telluride thin films of about 80 nm thickness. The implantation parameters were adjusted based on computer-aided learning using SRIM (stopping and range of ions in matter) software. The CdTe thin films were deposited by electrodeposition method on ITO substrate. Thin films of CdTe are exposed to \(\hbox {Ar}^{+}\) ions with different fluencies of \(1 \times 10^{15}\), \(5 \times 10^{15}\) and \(1 \times 10^{16} \, \hbox {ions cm}^{-2}\) at Ion Beam Centre, Kurukshetra University, Kurukshetra, India. After implantation, the films were characterized using UV–visible spectroscopy, photoluminescence (PL) and a four-probe set-up with a programmable current–voltage (I–V) source metre. The scanning electron microscopy of pristine film showed smooth and uniform growth of sphere-shaped grains on substrate surface. From optical studies, the values of optical band gap for as-deposited and argon-ion-implanted thin films were calculated. It was found that values of optical band gap decreased with the increase in fluence of ion beam. From PL studies it was found that the intensity got increased with ion fluence. A considerable increase in current was noticed from I–V measurements with ion fluence after implantation. Different properties of pre- and post-implanted thin films are studied.     

Correlation of luminescent properties of ZnO and Eu doped ZnO nanorods

ZnO and ZnO:Eu nanorods were originally synthesized by concussion method. The nanorods present a wurtzite nanostructure with dispersive distribution morphology. The average diameter and length of the nanorods are about 80 nm and 2 μm, respectively. The best concussion time, concussion frequency, the function of HMT and the growth mechanism are presented in this paper. This method is simple, economical, and environmentally mild. We believe other kinds of ZnO nanostructures could be obtained by this method when appropriate agents are added. However, because of the different chemical properties between trivalent RE ions and the cations of ZnO, it is rather difficult to incorporate RE ions into the lattice of semiconductors effectively via a wet chemical method. Based on our experiments, the sample of $ {\text{ZnO}}:{\text{Eu}}^{3 + }_{1\% } $ is single-phase and its PL signal is stronger than other single-phase $ {\text{ZnO}}:{\text{Eu}}^{3 + }_{X} $ samples. So 1% content of Eu³⁺ was chosen as the best doping concentration.     

Conductive and transparent ZnO:Al thin films obtained by chemical spray

Electrical, structural, morphological and optical characteristics of ZnO:Al thin films obtained by chemical spray are presented in this paper. The dependence of the resistivity on the substrate temperature and the film thickness is reported. For the optimized conditions with no post-annealing the lowest resistivity values obtained for ZnO:Al thin films were for films with thicknesses of 1500 and 600 nm, respectively. Preferential growth in the (0 0 2) direction was observed in all cases. The surface morphology was analyzed by using atomic force and scanning electron microscopy (AFM and SEM) techniques. High transmittance, 85%, was obtained in all cases. The band gap was of the order of 3.35 eV.     

Effect of annealing treatment on optical properties and microstructural variation of $$\hbox {WO}_{3}/\hbox {Ag}/\hbox {WO}_{3}$$ multilayer nano-films

Structural and optical properties of \(\text {WO}_{3}/\text {Ag}/\text {WO}_{3}\) nano-multilayer composites were investigated for heat mirror applications. \(\text {WO}_{3}/\text {Ag}/\text {WO}_{3}\) thin films were fabricated through a physical vapour deposition method by using electron-beam evaporation at the vacuum chamber at 10\(^{-5}\) Torr. \(\text {WO}_{3}\) nano-layer was fabricated at 40 nm. Annealing treatment was carried out at 100, 200, 300 and 400\(^{\circ }\)C for 1 h after the deposition of first layer of \(\text {WO}_{3}\) on the glass. On \(\text {WO}_{3}\) film, Ag nano-layers with 10, 12 or 14 nm thickness were deposited. Individual layers morphology was investigated using atomic force microscopy (AFM) and deduced that a smoother layer can be achieved after the annealing at 300\(^{\circ }\)C. Ellipsometry analysis was executed to determine both layers, Ag film thickness and inter-diffusion between the \(\text {WO}_{3}\)–Ag–\(\text {WO}_{3}\) layers. It was inferred that there was almost no interfering among the \(\text {WO}_{3}\)–\(\text {WO}_{3 }\) layers in the samples with 12 and 14 nm Ag thickness; while silver was deposited on the annealed \(\text {WO}_{3}\) layer at 300\(^{\circ }\)C. UV–visible spectrophotometer showed that the annealing treatment of the first \(\text {WO}_{3}\) layer enhanced the transparency of films in the visible region. The innovations of the present study have been based on the annealing of the films and finding an optimum thickness for the Ag film at 12–14 nm. Heat mirrors efficiency was assessed according to the principle of their optical behaviour and optimum performance obtained for 14 nm of Ag film, deposited on annealed tungsten oxide at 300\(^{\circ }\)C.     

Investigation of physico-chemical properties of conductive Ga-doped ZnO thin films deposited on glass and silicon wafers by RF magnetron sputtering

We report on the physico-chemical properties of Undoped and Ga-doped ZnO films fabricated on glass and p-Silicon wafers at room temperature by RF magnetron sputtering using a ZnO and Ga₂O₃ mixture raw powder target without sintering procedure. X-ray diffraction (XRD) and energy dispersion spectroscopy (EDS), scanning electronic microscopy, Raman scattering, ultraviolet–visible spectroscopy, photoluminescence (PL), Hall effect and impedance spectroscopy technique have been applied for the comparative study of ZnO and ZnO:Ga thin films. XRD and Raman studies have shown that the deposited films have a preferred orientation growth with Ga atoms both in substitutional and interstitial positions. EDS analyses have allowed to show that the metallic Ga atoms have been incorporated in the ZnO films. Doping by gallium resulted in a slight increase in the optical band gap energy of the films while the optical transmittance remains about 80 %. The PL analysis at room temperature revealed violet, blue, green and red emissions. Room temperature Hall measurements show that the lowest resistivity was 3.40 × 10^?4 Ω cm with an electron mobility of 18.56 cm²/V.s for an optimum Ga concentration of 4 wt%. Impedance spectroscopy study showed that σ_ac obeys the relation \(\sigma_{ac} = A\omega^{s}\). The exponent ‘‘s’’ was found to decrease with increasing the temperature. It is found that, the AC conductivity of all samples follow the correlated barrier hopping model. The Nyquist plots showed a single semicircle, indicating an equivalent circuit with a single parallel resistor R and capacitance C network. The values of the activation energy E _a deduced from both DC conductivity and relaxation frequency for all the studied samples ranged from 0.51 to 0.73 eV and the results are explained on the basis of the induced defects due to the addition of Ga into the ZnO films.     

Surface Recombination Velocity Dependence on Morphological Properties of CdTe Thin Films Prepared by Close-Spaced Sublimation

Cadmium telluride (CdTe) thin films were prepared on glass substrates by employing the close-spaced sublimation technique. Different source ( $T_\mathrm{sou}$ ) and substrate temperatures ( $T_\mathrm{sub}$ ) were used in order to change the structural properties of layers. The ranges chosen were: $550\,^{\circ }\hbox {C} \le T_\mathrm{sou} \le 650\,^{\circ }\hbox {C}$ and $400\,^{\circ }\hbox {C} \le T_\mathrm{sub} \le 600\,^{\circ }\hbox {C}$ . The environment in the growing chamber was also changed with the purpose to study its influence on the crystalline properties of the surface and volume of the material. Three different surroundings were used: vacuum, high-purity argon, and high-purity oxygen. The surface recombination velocity (SRV) was calculated from photoacoustic (PA) measurements by employing the open PA cell configuration. The behavior of the experimental results was analyzed as a function of the structural characteristics of the films: texture and grain size. Scanning electron microscopy, optical absorption, X-ray diffraction, and dark resistivity measurements were also employed to analyze the properties of the CdTe films. The minimum value for the SRV was found for $T_\mathrm{sou} = 650\,^{\circ }\hbox {C},\, T_\mathrm{sub} = 600\,^{\circ }\hbox {C}$ in an oxygen ambient.     

Fabrication and characterization of iron and fluorine co-doped BST thin films for microwave applications

The effects of fluorine co-doping by means of a post-thermal annealing process of iron-doped BST thin films in a fluorine-containing atmosphere have been investigated. XPS and ToF-SIMS sputter depth profiling verified a homogeneous fluorine distribution in the thin films. By employing EPR, it was shown that singly charged ( $ {\text{Fe}}_{\text{Ti}}^{\prime } $ – $ {\text{V}}_{\text{O}}^{ \cdot \cdot } $ )^· defect complexes, as well as ‘isolated’ $ {\text{Fe}}_{\text{Ti}}^{\prime } $ centres with a distribution of $ {\text{F}}_{\text{O}}^{ \cdot } $ sites in remote coordination spheres exist in the fluorinated films. Tunability enhancement due to fluorine co-doping as well as a Q-factor enhancement due to iron doping is demonstrated.     

Mathematical model of Boltzmann’s sigmoidal equation applicable to the set-up of the RF-magnetron co-sputtering in thin films deposition of $$\hbox {Ba}_{{x}}\hbox {Sr}_{1-{x}} \hbox {TiO}_{3}$$

In this work, we present the stoichiometric behaviour of \(\hbox {Ba}^{2+}\) and \(\hbox {Sr}^{2+}\) when they are deposited to make a solid solution of barium strontium titanate. \(\hbox {Ba}_{{x}}\hbox {Sr}_{1-{x}} \hbox {TiO}_{3}\) (BST) thin films of nanometric order on a quartz substrate were obtained by means of in-situ RF-magnetron co-sputtering at 495\({^{\circ }}\)C temperature, applying a total power of 120 W divided into intervals of 15 W that was distributed between two magnetron sputtering cathodes containing targets of \(\hbox {BaTiO}_{3}\) and \(\hbox {SrTiO}_{3}\), as follows: 0–120, 15–105, 30–90, 45–75, 60–60, 75–45, 90–30, 105–15 and 120–0 W. Boltzmann’s sigmoidal modified equation (Boltzmann’s profile) is proposed to explain the behaviour and the deposition ratio Ba/Sr of the BST as a function of the RF-magnetron power. The Boltzmann’s profile proposal shows concordance with experimental data of deposits of BST on substrates of nichrome under the same experimental conditions, showing differences in the ratio Ba/Sr of the BST due to the influence of the substrate.     

Influence of Thermal Annealings in Argon on the Structural and Thermochromic Properties of $$\mathrm{MoO}_{3}$$ Thin Films

The effect of thermal annealing in an inert atmosphere (argon) on the structural and thermochromic properties of \(\hbox {MoO}_{3}\) thin films was investigated. \(\hbox {MoO}_{3}\) thin films were deposited by thermal evaporation in vacuum of \(\hbox {MoO}_{3}\) powders. X-ray diffraction patterns of the films showed the presence of the monoclinic Magneli phase \(\hbox {Mo}_{9}\hbox {O}_{26}\) for annealing temperatures above \(250\,{^{\circ }}\hbox {C}\). Absorbance spectra of the films annealed in argon indicated that their thermochromic response increases with the annealing temperature in the analyzed range (23 \({^{\circ }}\hbox {C}\)–300 \({^{\circ }}\hbox {C}\)), a result opposite to the case of thermal annealings in air, for which case the thermochromic response shows a maximum value around 200 \({^{\circ }}\)C–225 \({^{\circ }}\)C and decreases for higher temperatures. These results are explained in terms of a higher density of oxygen vacancies formed upon thermal treatments in inert atmospheres.     

ZnO缓冲层上低温生长Al掺杂的ZnO薄膜

采用射频磁控溅射法在ZnO缓冲层上制备了不同Al掺杂量的ZnO（AZO）薄膜。利用X射线衍射（XRD）、扫描电子显微镜（SEM）和光致发光（PL）等表征技术,研究了AZO薄膜的微观结构、表面形貌和发光特性。结果表明,随着Al掺杂量的增加,ZnO薄膜的择优取向性发生了改变,且当Al的掺杂量为0.81%（原子分数）时,（002）衍射峰与其它衍射峰强度的比值达到最大,表明适合的Al掺杂使ZnO薄膜的择优取向性得到了改善。在可见光范围内薄膜的平均透过率超过70%。通过对样品光致发光（PL）谱的研究,发现所有样品出现了3个发光峰,分别对应于以444nm（2.80eV）、483nm（2.57eV）为中心的蓝光发光峰和以521nm（2.38eV）为中心较弱的绿光峰。并对样品的发光机理进行了详细的探讨。     

Ultrasonic-assisted fabrication of superhydrophobic ZnO nanowall films

Zinc oxide-based superhydrophobic surfaces were fabricated on aluminium oxide-seeded glass substrates via sonochemical approach by varying the parameter, the sonication time duration. The fabricated structures have nanowall-like morphology with an average long axis length and thickness of \({\sim }300\) and \({\sim }40~\hbox {nm}\), respectively.  The surface roughness created by surface-modified ZnO nanowalls and the air pockets trapped within the dense nanowalls, transformed the hydrophobic glass substrates into superhydrophobic surfaces with water contact angle of \(156{^{\circ }}\) during 20 min of sonication. An independent analysis was carried out to study the growth of ZnO nanowalls over glass substrates in the absence of the aluminium oxide seed layer and sonication process. The results suggested that the synergistic effect of the aluminium oxide seed layer and sonochemical process can enable the formation of ZnO nanowall structures favourable for superhydrophobic property. A possible growth mechanism of ZnO nanowalls formation during sonication process has been discussed in detail.     

Hydrothermal growth of wheatear-shaped ZnO microstructures and their photocatalytic activity

A facile hydrothermal process was developed to synthesize novel wheatear-shaped ZnO microstructures at a low temperature (\(85^{\circ }\hbox {C}\)) without the assistance of any template agent. X-ray diffraction and field emission scanning electron microscopy were used to characterize the structure and morphology of the samples. Results showed that the length of the ‘wheatear’ was about \(5.8~\upmu \!\hbox {m}\) and the section width was \(1.2~\upmu \!\hbox {m}\). The particles consisted of closely packed nanorods with average diameter of 100 nm. The growth of wheatear-shaped ZnO is very rapid and can be achieved in only 5 min. \(\hbox {OH}^{-}\)-driven oriented aggregation and multistep nucleation resulted in the formation of wheatear-shaped ZnO microstructures. The product had assembled open structures and it exhibited excellent photocatalytic activity in the degradation of methyl orange under UV-light irradiation.     

Microstructure of ZnO films synthesized on MgAl2O4 from low-temperature aqueous solution: growth and post-annealing

The microstructure of ZnO films synthesized from low-temperature (90 °C) aqueous solution on (111) MgAl₂O₄ single crystal substrates was characterized by X-ray diffraction, high-resolution scanning electron microscopy, conventional and high-resolution transmission electron microscopy. To examine the thermally activated microstructural evolution of the ZnO, both as-deposited and annealed films were characterized. The ZnO films were confirmed to have a ZnO $ [10\bar{1}0](0001)\left\| {{\text{MgAl}}_{ 2} {\text{O}}_{4} [011](1\bar{1}1)} \right. $ orientation relationship, with Zn polarity normal to the surface. Despite their highly oriented nature, the ZnO films have a columnar grain structure with low-angle (<2.5°) grain boundaries. In addition to lattice dislocations forming low-angle grain boundaries, threading dislocations were observed, emanating from the interface with the substrate. In annealed films, thermally generated voids were observed and appeared to preferentially form at grain boundaries and dislocations. Based on these characterization results, mechanisms are proposed for film growth and microstructural evolution. Finally, the diffusion coefficient of vacancies via dislocations at grain boundaries in the produced ZnO films was estimated.