Growth of cubic MgxZn1−xO alloy films by electron beam evaporation

We report the growth of cubic Mg_xZn_1−xO alloy thin films on quartz by electron beam evaporation. It can be found that all the samples have sharp absorption edges by the absorption measurements. X-ray diffraction measurements indicate the Mg_xZn_1−xO films are cubic phase with preferred orientation along the (1 1 1) direction. Energy dispersive spectrometry (EDS) demonstrates that the Mg concentration in Mg_xZn_1−xO films is much higher than the ceramic target used, and the composition can be tuned in a small scope by varying the substrate temperature and the beam electric current. The reasons of this phenomenon are also discussed.     

Cu(In,Ga)Se2 superstrate-type solar cells with Zn1−xMgxO buffer layers

Superstrate-type Cu(In,Ga)Se₂ (CIGS) thin film solar cells were fabricated using Zn_1−xMg_xO buffer layers. Due to the diffusion of Cd into CIGS during the growth of the CIGS layer, the conventional buffer material of CdS is not suitable. ZnO is a good candidate because of higher thermal tolerance but the conduction band offset (CBO) of ZnO/CIGS is not appropriate. In this study, the Zn_1−xMg_xO buffer layers were used to fulfill both the requirements. The superstrate-type solar cells with a soda-lime glass/In₂O₃:Sn/Zn_1−xMg_xO/CIGS/Au structure were fabricated with different band gap energies of the Zn_1−xMg_xO layer. The CIGS layers [Ga/(In + Ga)∼0.25] were deposited by co-evaporation method. The substrate temperature during the CIGS deposition of 450 °C did not cause the intermixing of the Zn_1−xMg_xO and CIGS layers. The conversion efficiency of the cell with Zn_1−xMg_xO was higher than that with ZnO due to the improvement of open-circuit voltage and shunt resistance. The results well corresponded to the behavior of the adjustment of CBO, demonstrating that the usefulness of the Zn_1−xMg_xO layer for the CBO control in the superstrate-type CIGS solar cells.     

Oxygen flux influence on the morphological, structural and optical properties of Zn1−xMgxO thin films grown by plasma-assisted molecular beam epitaxy

The Zn_1−xMg_xO thin films were grown on Al₂O₃ substrate with various O₂ flow rates by plasma-assisted molecular beam epitaxy (P-MBE). The growth conditions were optimized by the characterizations of morphology, structural and optical properties. The Mg content of the Zn_1−xMg_xO thin film increases monotonously with decreasing the oxygen flux. X-ray diffractometer (XRD) measurements show that all the thin films are preferred (0 0 2) orientated. By transmittance and absorption measurements, it was found that the band gap of the film decreases gradually with increasing oxygen flow rate. The surface morphology dependent on the oxygen flow rate was also studied by field emission scanning electron microscopy (FE-SEM). The surface roughness became significant with increasing oxygen flow rate, and the nanostructures were formed at the larger flow rate. The relationship between the morphology and the oxygen flow rate of Zn_1−xMg_xO films was discussed.     

The effect of growth ambient on the structural and optical properties of MgxZn1−xO thin films

Mg_xZn_1−xO (x = 0.0-0.20) thin films have been deposited by sol-gel technique on glass substrates and the effect of growth ambient (air and oxygen) on the structural, and optical properties have been investigated. The films synthesized in both ambient have hexagonal wurtzite structure. The c-axis lattice constant decreases linearly with the Mg content (x) up to x = 0.05, and 0.10 respectively for air- and oxygen-treated films, above which up to x = 0.20, the values vary irregularly with x. The change in the optical band gap values and the ultraviolet (UV) peak positions of Mg_xZn_1−xO films show the similar change with x. These results suggest that the formation of solid solution and thus the structural and optical properties of Mg_xZn_1−xO thin films are affected by the growth ambient.     

Effect of substrate temperature on the morphology, structural and optical properties of Zn1−xCoxO thin films

Zn_1−xCo_xO thin films with c-axis preferred orientation were deposited on sapphire (0 0 0 1) by pulsed laser deposition (PLD) technique at different substrate temperatures in an oxygen-deficient ambient. The effect of substrate temperature on the microstructure, morphology and the optical properties of the Zn_1−xCo_xO thin films was studied by means of X-ray diffraction (XRD), atomic force microscopy (AFM), UV-visible-NIR spectrophotometer, fluorescence spectrophotometer. The results showed that the crystallization of the films was promoted as substrate temperature rose. The structure of the samples was not distorted by the Co incorporating into ZnO lattice. The surface roughness of all samples decreased as substrate temperature increased. The Co concentration in the film was higher than in the target. Emission peak near band edge emission of ZnO from the PL spectra of the all samples was quenched because the dopant complexes acted as non-radiative centers. While three emission bands located at 409 nm (3.03 eV), 496 nm (2.5 eV) and 513 nm (2.4 eV) were, respectively, observed from the PL spectra of the four samples. The three emission bands were in relation to Zn interstitials, Zn vacancies and the complex of V_O and Zn_i (V_OZn_i). The quantity of the Zn interstitials maintained invariable basically, while the quantity of the V_OZn_i slightly decreased as substrate temperature increased.     

Influence of Mg content on optical properties of exciton confinement in wurtzite ZnO/MgxZn1−xO coupled quantum dots

Based on the framework of effective-mass approximation and variational approach, optical properties of exciton are investigated theoretically in ZnO/Mg_xZn_1−xO vertically coupled quantum dots (QDs), with considering the three-dimensional confinement of electron and hole pair and the strong built-in electric field effects. The exciton binding energy, the emission wavelength and the oscillator strength as functions of the structural parameters (the dot height, the barrier thickness between the coupled wurtzite ZnO QDs and Mg content x in the barrier layers) is calculated in detail. The results elucidate that Mg content have a significant influence on the exciton state and optical properties of ZnO coupled QDs. When Mg content x increases, the strong built-in electric field increases and leads to the redshift of the effective band gap of the Mg_xZn_1−xO layer. These theoretical results are useful for design and application of some important photoelectronic devices constructed by using ZnO strained QDs.     

The influence of Mn content on luminescence properties in Mn-doped ZnO films deposited by ultrasonic spray assisted chemical vapor deposition

Mn-doped ZnO (Zn_1−xMn_xO, 0 ≤ x ≤ 0.1) films are prepared by an ultrasonic spray assisted chemical vapor deposition method. X-ray diffraction and Raman scattering show that all the Zn_1−xMn_xO films are good wurtzite structures without any impurity phases. Cathodoluminescence spectra show that ultraviolet emission and green luminescence can be observed. The intensity of ultraviolet emission decreases with the increment of x, while the intensity of green luminescence increases with the increment of x when x ≤ 0.02. However, when x (x > 0.02) is further increased, the intensity of green luminescence decreases gradually, and the green luminescence disappears when x is above 0.075. We consider that the change of the luminescence is related to the competition between the radiative recombination and the non-radiative recombination.     

Structural and photoluminescent properties of Ni doped ZnO nanorod arrays prepared by hydrothermal method

Self-assembled Ni-doped zinc oxide (Zn_1−xNi_xO, x = 0.05, 0.10, 0.15, i.e., ZnNiO, nominal composition) nanorod arrays vertically grown on the ZnO seed layer covered glass along [0 0 1] direction were synthesized by hydrothermal method. Their images and structures have been characterized by scan electron microscope (SEM), X-ray diffraction (XRD) and Raman spectra, showing that Ni doping is beneficial to the formation of ZnO nanorods with hexagonal cross section and the enhancement of ZnO crystal quality. X-ray photoemission spectroscopy (XPS) study further demonstrated that Ni atoms were successfully doped into ZnO lattices. The photoluminescence (PL) spectra of ZnNiO samples show near bandedge emission (NBE) peaks at about 380 nm at a low excitation power and the NBE peak position redshifts while its intensity continuously increases with the increase of Ni doping concentration. With the excitation power increasing, the NBE peak redshifts from 380 nm to about 400 nm for ZnNiO nanorod arrays. The NBE mechanisms for ZnNiO nanorod arrays have been discussed, which is helpful for understanding their room temperature ferromagnetisms.     

Influence of Co doping content on its valence state in Zn1−xCoxO (0 ≤ x ≤ 0.15) thin films

Zn_1−xCo_xO (0 ≤ x ≤ 0.15) thin films grown on Si (1 0 0) substrates were prepared by a sol-gel technique. The effects of Co doped on the structural, optical properties and surface chemical valence states of the Zn_1−xCo_xO (0 ≤ x ≤ 0.15) films were investigated by X-ray diffraction (XRD), ultraviolet-visible spectrometer and X-ray photoelectron spectroscopy (XPS). XRD results show that the Zn_1−xCo_xO films retained a hexagonal crystal structure of ZnO with better c-axis preferred orientation compared to the undoped ZnO films. The optical absorption spectra suggest that the optical band-gap of the Zn_1−xCo_xO thin films varied from 3.26 to 2.79 eV with increasing Co content from x = 0 to x = 0.15. XPS studies show the possible oxidation states of Co in Zn_1−xCo_xO (0 ≤ x ≤ 0.05), Zn_0.90Co_0.10O and Zn_0.85Co_0.15O are CoO, Co₃O₄ and Co₂O₃, with an increase of Co content, respectively.     

Investigation of carrier dynamics in Zn1−xMgxO by time-resolved photoluminescence

The influence of the Mg concentration and lattice temperature on the carrier recombination dynamics in Zn_1−xMg_xO alloys has been studied by time-resolved photoluminescence for different emission and excitation energies. Carrier localization effects are found to play a significant role, becoming increasingly important for lower temperatures and higher Mg concentrations. Emission energy dependent dynamics were analyzed by the application of the theoretical model, yielding a characteristic localization energy of 60±15 meV for the sample with the highest Mg concentration of x=0.21.     

High-throughput synthesis and characterization of Mg1−xCaxO films as a lattice and valence-matched gate dielectric for ZnO based field effect transistors

Using composition-spread technique, we have grown metastable Mg_1−xCa_xO solid solution films on ZnO layers by pulsed laser deposition. All the films exhibited (1 1 1) oriented cubic phase. Despite a large miscibility gap, no phase separation took place at growth temperatures up to 700 °C, whereas an optimal growth temperature was found at 400 °C in terms of the crystallinity. The composition-spread films were characterized by X-ray diffraction mapping technique. Both lattice parameters and diffraction intensity increased with increasing the CaO composition. The present isovalent heterointerfaces realized the perfect lattice-matching by properly adjusting the CaO composition, leading to particular interest for ZnO based field effect transistors.     

Structural,optical, FTIR and photoluminescence properties of Zn0.96−xCo0.04CuxO (x=0.03, 0.04 and 0.05) nanopowders

Un-hydrogenated and hydrogenated Cu, Co co-doped ZnO (Zn_0.96−xCo_0.04Cu_xO, x=0.03, 0.04 and 0.05) nanopowders have been synthesized by co-precipitation method. The synthesized samples have been characterized by powder X-ray diffraction, energy dispersive X-ray spectra, UV–Visible spectrophotometer and Fourier transform infrared spectroscopy. The calculated average crystalline size increases from 37.3 to 50.6 nm for un-hydrogenated samples from x=0.03 to 0.05 and it changes from 29.4 to 34.9 nm for hydrogenated samples. The change in lattice parameters, micro-strain, a small shift of X-ray diffraction peaks towards lower angles and reduction in energy gap reveal the substitution of Cu²⁺ ions into Zn–Co–O lattice. The hydrogenation effect reduces the particle size and induces the more uniform distribution of particles than the un-hydrogenated samples which is confirmed by SEM micrographs. Photoluminescence spectra of Zn_0.96−xCo_0.04Cu_xO system shows that red shift in near band edge ultraviolet emission from 393 to 403 nm with suppressing intensity and a blue shift in green band emission from 537 to 529 nm with enhancing intensity confirms the substitution of Cu into the Zn–Co–O lattice.     

Structural, electrical, optical and magnetic properties of Co0.2AlxZn0.8−xO films

Co_0.2Al_xZn_0.8−xO films prepared with different molar ratio of aluminum nitrate to zinc acetate were deposited on substrates by the sol-gel technique. X-ray diffraction, photoluminescence and ferromagnetism measurements were used to characterize the Co_0.2Al_xZn_0.8−xO diluted magnetic semiconductors. The authors found that the intensity of the acceptor-related photoluminescence increased with increasing aluminum concentration and an increase in the number of the acceptor-like defects (zinc vacancies especially) in the Co_0.2Al_xZn_0.8−xO film might lead to the enhancement of the magnetic properties. This implies that controls of the aluminum concentration and the number of the acceptor-like defects are important factors to produce strong ferromagnetism Co_0.2Al_xZn_0.8−xO films prepared by the sol-gel method.     

Optical properties of MgxZn1−xO thin films deposited on silicon and sapphire substrate by rf magnetron sputtering

The index dispersion at UV–VIS range for polycrystalline Mg_xZn_1−xO films on silicon with different Mg concentration was obtained by spectroscopic ellipsometry (SE) method. It decreases with the increase of the Mg content. Above the relative peak wavelength, they are well fitted by the first-order Sellmeier relation. The band gap of films on sapphire of different Mg content was determined from transmission measurements. Photoluminescence (PL) illustrated that for Mg_xZn_1−xO films every PL peak corresponded to a special excitation wavelength. The wavelength of the PL peak was proportional to the special excitation wavelength. A strong peak was obtained in the blue band for the films due to the large amount of oxygen vacancies caused by excess Zn and Mg atoms, while weak peak at ultraviolet band.     

BiFeO3/Zn1−xMnxO bilayered thin films

BiFeO₃/Zn_1−xMn_xO (x = 0-0.08) bilayered thin films were deposited on the SrRuO₃/Pt/TiO₂/SiO₂/Si(1 0 0) substrates by radio frequency sputtering. A highly (1 1 0) orientation was induced for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO thin films demonstrate diode-like and resistive hysteresis behavior. A remanent polarization in the range of 2P_r ∼ 121.0-130.6 μC/cm² was measured for BiFeO₃/Zn_1−xMn_xO. BiFeO₃/Zn_1−xMn_xO (x = 0.04) bilayer exhibits a highest M_s value of ∼15.2 emu/cm³, owing to the presence of the magnetic Zn_0.96Mn_0.04O layer with an enhanced M_s value.     

Zn1−xMgxO/ZnO heterostructures studied by Kelvin probe force microscopy conjunction with probe characterizer

The surface potential of Zn_1−xMg_xO/ZnO heterostructure grown by radical source molecular beam epitaxy was measured by Kelvin force microscopy (KFM). A clear correlation was observed between the topographic image and the surface potential of Zn_0.56Mg_0.44O/ZnO heterostructure. The potential area around the surface pits was about 60 mV lower than that of the surrounding region, which suggests the effects of the pits on the electrical properties of the potential layer. In order to guarantee the accuracy of measurement, the probe shape was analyzed by probe characterizer and using Au thin films as a potential standard.     

Structural, optical and electrical properties of Zn1−xCdxO thin films prepared by PLD

Ternary polycrystalline Zn_1−xCd_xO semiconductor films with cadmium content x ranging from 0 to 0.23 were obtained on quartz substrate by pulse laser deposited (PLD) technique. X-ray diffraction measurement revealed that all the films were single phase of wurtzite structure grown on c-axis orientation with its c-axis lattice constant increasing as the Cd content x increasing. Atomic force microscopy observation revealed that the grain size of Zn_1−xCd_xO films decreases continuously as the Cd content x increases. Both photoluminescence and optical measurements showed that the band gap decreases from 3.27 to 2.78 eV with increasing the Cd content x. The increase in Cd content x also leads to the broadening of the emission peak. The resistivity of Zn_1−xCd_xO films decreases evidently for higher values of Cd content x. The shift of PL emission to visible light as well as the decrease of resistivity makes the Zn_1−xCd_xO films potential candidate for optoelectronic device.     

Electronic structure and ferromagnetism of polycrystalline Zn1−xCoxO (0≤x≤0.15)

The electronic structure of polycrystalline ferromagnetic Zn_1−xCo_xO (0.05≤x≤0.15) and the oxidation state of Co in it, have been investigated. The Co-doped polycrystalline samples are synthesized by a combustion method and are ferromagnetic at room temperature. XPS and optical absorption studies show evidence for Co²⁺ ions in the tetrahedral symmetry, indicating substitution of Co²⁺ in the ZnO lattice. However, powder XRD and electron diffraction data show the presence of Co metal in the samples. This give evidence to the fact that some Co²⁺ ion are incorporated in the ZnO lattice which gives changes in the electronic structure whereas ferromagnetism comes from the Co metal impurities present in the samples.     

Effects of oxygen partial pressure and substrate temperature on the structure and optical properties of MgxZn1−xO thin films prepared by magnetron sputtering

Deposited with different oxygen partial pressures and substrate temperatures, Mg_xZn_1−xO thin films were prepared using a Mg_0.6Zn_0.4O ceramic target by magnetron sputtering. The structural and optical properties of the prepared thin films were investigated. The X-ray diffraction spectra reveal that all the films on quartz substrate are grown along (2 0 0) orientation with cubic structure. The lattice constant decreases and the crystallite size increases with the increase of substrate temperature. Both energy dispersive X-ray spectroscopy and calculated results suggest the ratio of Mg/Zn increases with increasing substrate temperature. The thin film deposited with T_s = 500 °C has a minimal rms roughness of 7.37 nm. The transmittance of all the films is higher than 85% in the visual region. The optical band gap is not sensitive to the oxygen partial pressure, while it increases from 5.63 eV for T_s = 100 °C to 5.95 eV for T_s = 700 °C. In addition, the refractive indices calculated from transmission spectra are sensitive to the substrate temperature. The photoluminescence spectra of Mg_xZn_1−xO thin films excited by 330 nm ultraviolet light indicate that the peak intensity of the spectra is influenced by the oxygen partial pressure and substrate temperature.     

Structural and optical properties of a-Si1−xCx:H films synthesized by dc magnetron sputtering technique

Hydrogenated amorphous SiC films (a-Si_1−xC_x:H) were prepared by dc magnetron sputtering technique on p-type Si(1 0 0) and corning 9075 substrates at low temperature, by using 32 sprigs of silicon carbide (6H-SiC). The deposited a-Si_1−xC_x:H film was realized under a mixture of argon and hydrogen gases. The a-Si_1−xC_x:H films have been investigated by scanning electronic microscopy equipped with an EDS system (SEM-EDS), X-ray diffraction (XRD), secondary ions mass spectrometry (SIMS), Fourier transform infrared spectroscopy (FTIR), UV-vis-IR spectrophotometry, and photoluminescence (PL). XRD results showed that the deposited film was amorphous with a structure as a-Si_0.80C_0.20:H corresponding to 20 at.% carbon. The photoluminescence response of the samples was observed in the visible range at room temperature with two peaks centred at 463 nm (2.68 eV) and 542 nm (2.29 eV). In addition, the dependence of photoluminescence behaviour on film thickness for a certain carbon composition in hydrogenated amorphous SiC films (a-Si_1−xC_x:H) has been investigated.