Preparation and characterization of sol-gel Li and Al codoped ZnO thin films

Li and Al codoped ZnO (LAZO) thin films have been prepared by a sol-gel method and their structural and optical properties have been investigated. The prepared LAZO films had an average transmittance of over 85% in the visible range. The UV absorption edge was red-shifted with Li-doping, whereas it was blue-shifted with Al-doping. A broad yellowish-white emission was observed from the LAZO films annealed above 600 °C. The visible emission was enhanced with increasing annealing temperature and dopant concentration.     

Nanocrystalline SiC films prepared by direct deposition of carbon and silicon ions

The method of direct deposition of carbon and silicon ions was used for preparation of nanocrystalline silicon carbide films. The deposition energy of carbon and silicon ions was 90 eV. The effect of substrate temperature in the range of 500-1150 °C on the structure of SiC films was studied by means of X-ray photoelectron spectroscopy (XPS) and X-ray diffractometry (XRD). According to XPS data, the films contained heterobonded Si-C atoms and homobonded Si-Si and C-C atoms, the relation between which varied as the function of substrate temperature. The data of XRD showed a noticeable growth of a nanocrystalline phase of cubic silicon carbide in the films at a temperature of about 700 °C. The content of 3C-SiC nanocrystalline phase reached 80 at.% at 950 °C. There was an established change from cubic polytype to rhombohedral polytype of silicon carbide α-SiC-21R at a substrate temperature higher than 1000 °C. The size of SiC crystal grains depended on the substrate temperature and changed from 4-5 up to 8-10 nm over the range of 700-950 °C. Besides, silicon unbonded with carbon also crystallized in nanocrystalline form with similar sizes of crystal grains. A possible model of the change of the polytypic composition of SiC film under the conditions of direct ion deposition was discussed.     

Preparation and character of textured ZnO:Al thin films deposited on flexible substrates by RF magnetron sputtering

ZnO:Al thin films deposited on transparent TPT substrates by magnetron sputtering were etched in acetic acid solution. The effects of etching solution concentration and etching time on the structure and properties of ZnO:Al films were investigated. The obtained films had a hexagonal structure and a highly preferred orientation with the c-axis perpendicular to the substrate. The ZAO film etched in 1% acetic acid solution for 10 s had a pyramidal structure and an enhanced light scattering ability, the average transmittance and reflectance in the visible region were 72% and 26% respectively, the sheet resistance was 260 Ω/□. Both transmittance and reflectance of the films decreased as the etching solution concentration and etching time increasing. Etching had a negative effect on the conductive properties of ZAO films. The lowest sheet resistance was 120 Ω/□ for the ZAO film without etching.     

Structural,electrical and photoluminescence properties of ZnO:Al films grown on MgO(0 0 1) by direct current magnetron sputtering with the oblique target

ZnO:Al films were deposited on MgO(0 0 1) substrates at 300 K and 673 K by direct current magnetron sputtering with the oblique target. The Ar pressure was adjusted to 0.4 Pa and 1.2 Pa, respectively. All the films have a wurtzite structure and a c-axis orientation in the film growth direction. The films deposited at 300 K initially grow with thin columnar grains and subsequently grow with large granular grains on the thin columnar grains. However, the films grown at 673 K consist mainly of dense columnar grains perpendicular to the substrate surface. The ZnO:Al film deposited at 673 K and 0.4 Pa has the lowest resistivity, the highest free electron concentration and Hall's mobility. A temperature dependence of the resistivity within 5–300 K reveals that the films grown at 300 K exhibit a semiconducting behavior and those grown at 673 K show a metal–semiconductor transition. The carrier transport mechanism is Mott's variable range hopping in the temperature range below 90 K for all the films and thermally activated band conduction above 215 K for the films grown at 300 K. Room temperature photoluminescence spectra for wavelengths between 300 nm and 800 nm reveal mainly blue-green emissions centered at 452 nm, 475 nm and 515 nm.     

The properties of aluminum-doped zinc oxide thin films prepared by rf-magnetron sputtering from nanopowder targets

Aluminum-doped zinc oxide (ZnO:Al) films were deposited onto glass substrates by rf-magnetron sputtering at ambient temperature using, for the first time, doped nanocrystalline powder synthesized by the sol–gel method. The effects of aluminum on structural, electrical, morphological and optical properties were investigated. The films showed a hexagonal wurtzite structure and high preferential orientation in the (002) crystallographic direction. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to study the films morphology. The obtained samples have a typical columnar structure and a very smooth surface. The optical transmittance spectra showed transmittance higher than 90% within the visible wavelength region. A minimum resistivity of 5.436 · 10^− 5 Ω cm at room temperature was obtained for the 3.0 at.% Al-doped film.     

Nanostructural Features and Optical Performance of RF Magnetron Sputtered ZnO Thin Films

Zinc oxide (ZnO) thin films were grown on silicon substrate by RF (radio frequency) magnetron sputtering.Surface topography of these films exhibited a nanostructured granular appearance with the size of individual grains between 50 to 100 nm.Corresponding cross-sectional electron micrographs revealed columnar grains in the form of aggregated nanorods/wires with length of about 500 nm,similar to the thickness of these thin films of ZnO nucleated and grown vertically on the silicon substrate.High resolution l...     

Influence of working pressure on ZnO:Al films from tube targets for silicon thin film solar cells

Mid-frequency magnetron sputtering of aluminum doped zinc oxide films (ZnO:Al) from tube ceramic targets has been investigated for silicon based thin film solar cell applications. The influence of working pressure on structural, electrical, and optical properties of sputtered ZnO:Al films was studied. ZnO:Al thin films with a minimum resistivity of 3.4 × 10⁻⁴ Ω cm, high mobility of 50 cm²/Vs, and high optical transmission close to 90% in visible spectrum region were achieved. The surface texture of ZnO:Al films after a chemical etching step was investigated. A gradual increase in feature sizes (diameter and depth) was observed with increasing sputter pressure. Silicon based thin film solar cells were prepared using the etched ZnO:Al films as front contacts. Energy conversion efficiencies of up to 10.2% were obtained for amorphous/microcrystalline silicon tandem solar cells.     

Structural characterization of ZnO thin films deposited by dc magnetron sputtering

In this work we present recent results on ZnO thin films grown by dc magnetron sputtering technique at room temperature (RT), focusing on structural and surface characterization using conventional cross-section transmission electron microscopy (XTEM) and high resolution cross section transmission electron microscopy (HRXTEM) in an attempt to understand the thickness influence on film, mechanical and optical properties as well as photoreduction/oxidation conductivity changes. Films were found to be polycrystalline with a columnar mode of growth. For films with thickness over 100 nm, XTEM and HRTEM analysis evidenced the presence of a small grains transition layer near interface with the substrate, feature which plays an important role in ZnO thin films for gas sensing application. The control of such structural parameters is proved to be critical for the improvement of their gas sensing performance.     

Opto-electronic properties of rough LP-CVD ZnO:B for use as TCO in thin-film silicon solar cells

Polycrystalline Boron-doped ZnO films deposited by low pressure chemical vapor deposition technique are developed for their use as transparent contacts for thin-film silicon solar cells. The size of the columnar grains that constitute the ZnO films is related to their light scattering capability, which has a direct influence on the current generation in thin-film silicon solar cells. Furthermore, if the doping level of the ZnO films is kept below 1 × 10²⁰ cm^− 3, the electron mobility can be drastically enhanced by growing large grains, and the free carrier absorption is reduced. All these considerations have been taken in account to develop ZnO films finely optimized for the fabrication of microcrystalline thin-film silicon solar cells. These TCO allow the achievement of solar cell conversion efficiencies close to 10%.     

Microstructural size effects on the hardness of nanocrystalline TiN/amorphous-SiNx coatings prepared by magnetron sputtering

It has been postulated that equiaxed nanocrystalline (<10 nm) TiN grains embedded in a thin amorphous silicon nitride (a-SiN_x) phase are a prerequisite to obtain ultrahard TiN/a-SiN_x coatings. The present study correlates hardness and microstructure of TiN/a-SiN_x coatings with Si contents between 0 and 17 at.%. The coatings have been deposited by magnetron sputtering in industrial-scale physical vapour deposition systems. Transmission electron microscopy studies revealed that increasing the silicon content causes the TiN grain size to decrease. This is accompanied by a change in grain morphology: At Si contents lower than 1 at.% TiN grains become columnar, while at Si contents higher than 6 at.% equiaxed grains with diameters of 6 nm form. For silicon contents between 1 and 6 at.%, a transition region with nanocrystalline columnar grains exists. This nanocrystalline columnar microstructure causes maximum hardness values of more than 45 GPa for TiN/a-SiN_x coatings as determined by nanoindentation. The elongated and equiaxed nanocrystalline TiN grains exhibit almost theoretical strength as dislocation-based deformation mechanisms are constrained.     

Structural, optical and electrical properties of Al-doped ZnO microrods prepared by spray pyrolysis

Al-doped ZnO thin films were obtained on glass substrates by spray pyrolysis in air atmosphere. The molar ratio of Al in the spray solution was changed in the range of 0-20 at.% in steps of 5 at.%. X-ray diffraction patterns of the films showed that the undoped and Al-doped ZnO films exhibited hexagonal wurtzite crystal structure with a preferred orientation along (002) direction. Surface morphology of the films obtained by scanning electron microscopy revealed that pure ZnO film grew as quasi-aligned hexagonal shaped microrods with diameters varying between 0.7 and 1.3 μm. However, Al doping resulted in pronounced changes in the morphology of the films such as the reduction in the rod diameter and deterioration in the surface quality of the rods. Nevertheless, the morphology of Al-doped samples still remained rod-like with a hexagonal cross-section. Flower-like structures in the films were observed due to rods slanting to each other when spray solution contained 20 at.% Al. Optical studies indicated that films had a low transmittance and the band gap decreased from 3.15 to 3.10 eV with the increasing Al molar ratio in the spray solution from 0 to 20 at.%.     

Real time spectroscopic ellipsometry of Ag/ZnO and Al/ZnO interfaces for back-reflectors in thin film Si:H photovoltaics

Real time spectroscopic ellipsometry (RTSE) has been applied to analyze the optical characteristics of Ag/ZnO and Al/ZnO interfaces used in back-reflector (BR) structures for thin film silicon photovoltaics. The structures explored here are relevant to the substrate/BR/Si:H(n-i-p) solar cell configuration and consist of opaque Ag or Al films having controllable thicknesses of microscopic surface roughness, followed by a ZnO layer up to ~ 3000 Å thick. The thicknesses of the final surface roughness layers on both Ag and Al have been varied by adjusting magnetron sputtering conditions in order to study the effects of metal film roughness on interface formation and interface optical properties. The primary interface loss mechanisms in reflection are found to be dissipation via absorption through localized plasmon modes for Ag/ZnO and through intraband and interband transitions intrinsic to metallic Al for Al/ZnO.     

Defects in amorphous and solid phase epitaxial silicon

The microstructural morphology of amorphous Si (a-Si) layers deposited in ultrahigh vacuum, as well as crystalline Si grown by solid phase epitaxy (SPE), was studied as a function of Al doping and vapour beam incidence angle. The microstructure of the films was investigated using cross-section transmission electron microscopy. All a-Si layers have a columnar structure, with an average column width of 5 nm. The direction of the columns abruptly changes with the change of deposition direction and shows local column tilts and void formation at substrate surface irregularities. These built-in defects in the a-Si films also influence the defect structure in epitaxial Si films grown by SPE. Voids are initially aligned along the column directions and extra voids form owing to irregularities of the columnar structure. Doping of amorphous Si with Al to 10¹⁸−10²⁰ cm⁻³ does not leave detectable effects in the amorphous structure itself, but will increase the void density of the re-grown SPE Si layers. Furthermore, segregation of Al resulting in metallic inclusions in the amorphous crystalline interface causes metal induced crystallization of Si at temperatures far below the normal SPE regrowth temperature, thus preventing the formation of single crystalline silicon in a single-step process.     

Effect of annealing temperature on ZnO:Al/p-Si heterojunctions

Al-doped, zinc oxide (ZnO:Al) films with a 1.2 at.% Al concentration were deposited on p-type silicon wafers using a sol-gel dip coating technique to produce a ZnO:Al/p-Si heterojunction. Following deposition and subsequent drying processes, the films were annealed in vacuum at five different temperatures between 550 and 900 °C for 1 h. The resistivity of the films decreased with increasing annealing temperature, and an annealing temperature of 700 °C provided controlled current flow through the ZnO:Al/p-Si heterojunction up to 20 V. The ZnO:Al film deposited on a p-type silicon wafer with 1.2 at.% Al concentration was concluded to have the potential for use in electronic devices as a diode after annealing at 700 °C.     

Microstructure evolution of zinc oxide films derived from dip-coating sol-gel technique: formation of nanorods through orientation attachment

ZnO:Al thin films with Al incorporation of 0-20 at.% were deposited through the sol-gel technique. Such a film undergoes a significant microstructure development, from columnar to granular structures and then nanorod arrays with increasing Al content. The important role of Al incorporation level in the microstructure evolution was determined using scanning electron microscopy, x-ray photoelectron spectroscopy and transmission electron microscopy. At low Al level, the transition from columnar to granular grains can be attributed to the coarsening barrier resulting from the introduction of Al into the matrix. However, oriented structures of ZnO nanorod arrays are formed at a high Al level. TEM investigation reveals that a nanorod with smooth morphology at the top and rough morphology at the bottom has a single-crystalline wurtzite structure, which is the aggregation of nanoparticles of a few nanometers in size formed through the orientation attachment mechanism followed by epitaxial growth on the aggregated particles. Finally, the physical properties of the ZnO films with different degrees of Al concentration are discussed. Such detailed microstructure studies may aid the understanding of the doping effect process on the growth of a film, which is essential to altering its physical or chemical properties.     

Elastic Energy of Grain Boundaries in Nanocrystalline Films Consisting of Columnar Grains

The elastic characteristics of low-angle grain boundaries in nanocrystalline films consisting of columnar grains are analyzed. A model describing low-angle boundaries between columnar nanocrystallites as an ensemble of rectangular dislocation half-loops is used to calculate the stress field and energy of such boundaries. The energy of elastic distortions in a nanocrystalline film consisting of periodically ordered columnar grains was determined as a function of the misorientation angles of the grains.     

Low wet etching rates of ZnO films prepared by sputtering of mixed ZnO and AlN powder targets

ZnO films codoped with Al and N have been prepared by radio frequency magnetron sputtering in an Ar atmosphere, using targets of mixtures of ZnO and AlN powders. The Al-doped ZnO films are transparent, whereas the films codoped with Al and N are colored. The Al- and N-concentrations in the colored films are estimated to be 4–7 at.% and 1–2 at.%, respectively. No enhancement of the carrier density is seen in the colored ZnO films, whereas the colored films exhibit lower etching rates of 3–5 nm/s in a 0.1 M HCl solution, in comparison with the Al-doped ZnO films. For the colored film, the anisotropic grain growth occurs, and cubic grains are produced after etching. The low etching rates of the colored films are ascribed to the epitaxial growth of AlN films on the surfaces of ZnO grains, rather than the incorporation of Al–N and Al–O bonds into the ZnO lattice.     

IBAD钼膜与Al_2O_3(0001)单晶界面的HREM研究

采用中等能量离子束辅助沉积（IBAD）技术在单晶Al2O3（0001）基片上沉积钼膜，通过HREM等分析手段，在原子尺度上，对于钼膜及其与Al2O3单晶基体界面的显微结构进行了研究。结果表明：钼膜的晶粒呈细小柱状或纤维状，平均晶粒尺寸约为8nm，钼膜的致密度较高，膜内存在非晶组织。在钼膜与Al2O3单晶基片之间存在厚约10～15nm的非晶过渡层，在界面处未发现原子的长程扩散。非晶过渡层与钼膜界面处存在台阶，增加了钼膜的形核点。     

Reaction zone formed during diffusion bonding of TiNi to Ti6Al4V using Ni/Ti nanolayers

This study investigated the interfacial structure of solid state diffusion bonding of TiNi to Ti6Al4V using reactive Ni/Ti multilayer thin films. The TiNi and Ti6Al4V surfaces were modified by sputtering, by deposition of alternated Ni and Ti nanolayers, to increase the diffusivity at the interface. Bonding experiments were performed at 750, 800 and 900 °C at a pressure of 10 MPa with a dwell time of 60 min. The reaction zone was characterized by high-resolution scanning and transmission electron microscopy. Joints free from porosity and cracks were produced with Ni/Ti reactive multilayer thin films. Several phases formed at the interface, ensuring the bonding of these alloys. The reaction zone was constituted by columnar grains of Ti₂Ni and AlNi₂Ti, close to the Ti6Al4V base material, and by alternate layers of Ti₂Ni and TiNi equiaxed grains. The grain size decreased from Ti6Al4V to TiNi base materials. Nanometric grains were observed in the layers closest to the TiNi base material.     

Natively textured surface aluminum-doped zinc oxide transparent conductive layers for thin film solar cells via pulsed direct-current reactive magnetron sputtering

Natively textured surface aluminum-doped zinc oxide (ZnO:Al) layers for thin film solar cells were directly deposited without any surface treatments via pulsed direct-current reactive magnetron sputtering on glass substrates. Such an in-situ texturing method for sputtered ZnO:Al thin films has the advantages of efficiently reducing production costs and dramatically saving time in photovoltaic industrial processing. High purity metallic Zn-Al (purity: 99.999%, Al 2.0 wt.%) target and oxygen (purity: 99.999%) were used as source materials. During the reactive sputtering process, the oxygen gas flow rate was controlled using plasma emission monitoring. The performance of the textured surface ZnO:Al transparent conductive oxides (TCOs) thin films can be modified by changing the number of deposition rounds (i.e. thin-film thicknesses). The initially milky ZnO:Al TCO thin films deposited at a substrate temperature of ~ 553 K exhibit rough crater-like surface morphology with high transparencies (T ~ 80-85% in visible range) and excellent electrical properties (ρ ~ 3.4 × 10^− 4 Ω cm). Finally, the textured-surface ZnO:Al TCO thin films were preliminarily applied in pin-type silicon thin film solar cells.