Microstructure of ZnO thin films produced by magnetron sputter oblique deposition

ZnO films deposited at different oblique angles of 40, 60 and 80°, under different Ar pressures 0.27, 0.67, 1.33 and 2.67 Pa, DC currents of 0.15 and 0.25 A, and distances of 10-15 cm from the target were studied. It was found that the film grains grow at an angle to the substrate when deposition angle is above 40°. It was shown that the grains consisted of a number of small crystals growing one on top of the other and shifted towards the target with the crystal orientation not along the grain growth but perpendicular to the substrate. Crystal size decreased with the deposition angle and internal stress disappeared when α = 80°. It was found that 1.33 Pa pressure provided the best balance between the deposition parameters. Growth rate reached maximum, samples had the biggest crystal size and high crystal density. However, crystal spatial alignment changed gradually with pressure and distance.     

Non-uniform deposition in the early stage of hot-wire chemical vapor deposition of silicon: The charge effect approach

The deposition behavior in hot-wire chemical vapor deposition (HWCVD) of silicon was investigated, focusing on the thickness uniformity of films deposited on silicon and glass substrates, and based on the previous suggestion that a major depositing flux in HWCVD should be negatively charged nanoparticles. The deposition was performed using a 20%-SiH₄-80%-H₂ gas mixture at a 450 °C substrate temperature under a working pressure of 66.7 Pa (0.5 Torr). Non-uniform depositions for three hot-wire temperatures, 1590 °C, 1670 °C, and 1800 °C, and on the silicon and glass substrates were compared. The non-uniformity was most pronounced at 1800 °C and more pronounced on the glass substrate. On the glass substrate, the deposition rate was highest at the corner and lowest at the center, which was attributed to the fastest charge removal, to a conducting stainless steel substrate holder, at the corner. Once the entire glass substrate was deposited with silicon, the growth rate tended to become uniform, possibly due to the high charge removal rate of silicon. The observed deposition behavior indicated that the major depositing flux is negatively charged.     

High-rate deposition by microwave RPECVD at atmospheric pressure

The post-discharge of a microwave resonant cavity working at atmospheric pressure is used to enhance deposition of SiO_x thin films from HMDSO by chemical vapor deposition. Maximum static deposition rates are close to 150 μm h^− 1 for low power consumption per unit of coated width (~ 100 W/cm). Dynamic deposition rates are close to 3.5 nm m s^− 1. The distribution of the coating thickness is heterogeneous over an area of 150 × 90 mm². The influence of the main parameters of the process is systematically studied to show how the key reactions, i.e. gas phase synthesis of powders and surface deposition, are correlated.     

Low threading dislocation Ge on Si by combining deposition and etching

Blanket and selective Ge growth on Si is investigated using reduced pressure chemical vapor deposition. To reduce the threading dislocation density (TDD) at low thickness, Ge deposition with cyclic annealing followed by HCl etching is performed. In the case of blanket Ge deposition, a TDD of 1.3 × 10⁶ cm^− 2 is obtained, when the Ge layer is etched back from 4.5 μm thickness to 1.8 μm. The TDD is not increased relative to the situation before etching. The root mean square of roughness of the 1.8 μm thick Ge is about 0.46 nm, which is of the same level as before HCl etching. Further etching shows increased surface roughness caused by non-uniform strain distribution near the interface due to misfit dislocations and threading dislocations. The TDD also becomes higher because the etchfront of Ge reaches areas with high dislocation density near the interface. In the case of selective Ge growth, a slightly lower TDD is observed in smaller windows caused by a weak pattern size dependence on Ge thickness. A significant decrease of TDD of selectively grown Ge is also observed by increasing the Ge thickness. An about 10 times lower TDD at the same Ge thickness is demonstrated by applying a combination of deposition and etching processes during selective Ge growth.     

Plasma dynamics studies during deposition of thin film PbTe on a glass substrate

PbTe thin films were prepared by pulsed laser deposition using a Nd:YAG laser (532 nm) in an argon atmosphere. Dynamic processes in the gas phase induced by Nd:YAG laser ablation of PbTe are investigated by analyzing the light emitted by the plume. Pressure in the chamber varied from 1.0×10⁻⁵ to 1.0 mbar. Space and time-resolved optical spectroscopy measurements indicate the presence of both neutral, Pb(I) and Te(I) and ionized, Pb(II) and Te(II), species. The velocities of the species remain unchanged for argon pressures up to 10⁻¹ mbar, which suggests that expansion of the plume occurs without further collision with the foreign gas in this pressure range. It is found that an addition of 5×10⁻¹ mbar Ar enhances the emission line intensity and leads to a decrease in species velocity observed at large distances from the target surface. Furthermore, a region of maximum emission intensity at distance of 5-10 mm from the target is found when a gas environment is present.     

Evaluation of different deposition conditions on thin films deposited by electrostatic spray deposition using a uniformity test

Copper indium disulphide films were produced by electrostatic spray deposition using a water/alcohol solution of copper chloride (CuCl₂), indium chloride (InCl₃) and thiourea (CS(NH₂)₂) sprayed onto SnO₂:F coated glass substrates. The influence of various deposition parameters, namely substrate temperature (380-450 °C), applied voltage (12-18 kV), solution concentration (0.21-0.49 M), flow rate (25-200 μl/min) and needle-substrate distance (40-70 mm) were investigated. particle image velocimetry measurements were made of the spray cone and correlated with the film uniformity. The film uniformity was measured using an optically based test developed in-house. Results show that the highest concentrated spray solution and lowest deposition temperature produce non-uniform films. In contrast, a needle-substrate distance of 50 mm, and the lowest applied voltage and flow rate resulted in the most uniform films.     

Influence of target-substrate distance and composition on the preferential orientation of yttria-stabilized zirconia thin films

The use of yttria-stabilized zirconia (YSZ) thin films calls for a controlled deposition with full understanding on the influence of deposition parameters on the crystallographic properties of YSZ. YSZ thin films were deposited using magnetron sputtering from two sources, enabling to modify the sample composition in a flexible way. The influence of target-substrate (T-S) distance and the Y content on the crystallographic orientation were studied under different chamber pressures. Correlations were found under both conditions. This way, a two-dimensional map was obtained by showing the change in preferential orientation as a function of sample composition. This map shows the existence of two different trends depending on the pressure. At low pressure, the addition of Y and the decrease in T-S distance, change the orientation from [200] to a complete [111] out-of-plane orientation resulting in a competition between the fastest growth direction and the lowest surface energy. However, a different trend was observed at high pressure, where T-S distance and composition do not influence the preferential orientation of the film.     

Pulsed electron beam deposition of transparent conducting Al-doped ZnO films

Good quality transparent conducting Al-doped ZnO films were deposited on quartz substrates from a high purity target using pulsed electron deposition (PED). Two series of films were made, one deposited at room temperature but at four pressures, viz., 0.7, 1.3, 2.0 and 2.7 Pa of oxygen and one deposited at 1.3 Pa oxygen pressure but at the substrate temperature ranged from room temperature to 600 °C. In order to evaluate the effect of substrate temperature and oxygen pressure on the properties of obtained films, various characterization techniques were employed including X-ray diffraction, stylus profiler, scanning electron microscope, optical spectrophotometer and electrical resistivity. For the first series films, the optimal oxygen pressure of 1.3 Pa was found to bring about the appropriate energetic deposition atoms which results in the best crystallinity. For the second series films, the lowest resistivity was obtained in the film grown at 400 °C. An attempt was made to reduce the resistivity by lowering the oxygen pressure to 0.5 Pa which was the lower limit of working pressure of the PED system. The obtained results indicate that PED is a suitable technique for growing transparent conducting ZnO films.     

Improvement of thickness uniformity and crystallinity of AlN films prepared by off-axis sputtering

We improved both the thickness uniformity and crystallinity of Aluminum nitride (AlN) films deposited by off-axis sputtering. The results in thickness uniformity and X-ray rocking curve full-width at half-maximum (FWHM) of AlN (0 0 0 2) are achieved to be ±0.2% and 1.4°, respectively on a 100 mm Si (1 0 0) substrate. The residual stress can be controlled from tensile to compressive by varying sputtering parameters such as gas pressure, RF power and DC bias voltage applied to a substrate without degradation in the crystallinity and thickness uniformity.     

Hot-wire chemical vapor deposition of silicon nanoparticles on fused silica

Silicon nanoparticles on fused silica have potential as recombination centers in infrared detectors due quantum confinement effects that result in a size dependent band gap. Growth on fused silica was realized by etching in HF, annealing under vacuum at 700-750 °C, and cooling to ambient temperature before ramping to the growth temperature of 600 °C. Silicon particles could not be grown in a thermal chemical vapor deposition (CVD) process with adequate size uniformity and density. Seeding fused silica with Si adatoms in a hot-wire chemical vapor deposition (HWCVD) process at a disilane pressure of 1.1 × 10^− 5 Pa followed by thermal CVD at a disilane pressure of 1.3 × 10^− 2 Pa, or direct HWCVD at a disilane pressure of 2.1 × 10^− 5 Pa led to acceptable size uniformity and density. Dangling bonds at the surface of the as-grown nanoparticle were passivated using atomic H formed by cracking H₂ over the HWCVD filament.     

Laser-ablated plasma for deposition of ZnO thin films on various substrates

We report optical and structural properties of ZnO films deposited by pulsed laser deposition technique on (100) n-type silicon and quartz substrates at various pressures of back ground gas. ZnO plasma was created using KrF laser (248 nm) at various pressures of the ambient gas, oxygen. Laser induced plasma at varying fluence on the target was investigated using optical emission spectroscopy and 2-D images of the expanding plumes. X-ray diffraction, atomic force microscopy, and spectro-photometry were used to characterize as grown films.     

Study of ZnO layers growth by pulsed laser deposition from Zn and ZnO targets

The article deals with structural properties of ZnO thin layers prepared on Si (111) by pulsed laser deposition at different pressures (1-35 Pa) of ambient oxygen in the deposition chamber. The growth temperature was 400 °C and a pulsed Nd:YAG laser was used at a wavelength of 355 nm. Two parallel sets of samples deposited by ablation of different targets (a sintered ceramic pellet of ZnO and a pure metallic Zn target) were examined. The samples were characterized by different analytical methods: scanning electron microscope (SEM), secondary ion mass spectroscopy (SIMS), and X-ray diffraction (XRD). The prepared layers exhibited columnar structure and uniform preferred c-axis orientation. The results showed that deposition of the high quality of ZnO films fabricated from both targets is comparable, except for those obtained at low (1 Pa) pressures.     

Scratch resistant optical coatings on polymers by magnetron-plasma-enhanced chemical vapor deposition

The magnetron-plasma-enhanced chemical vapor deposition (magPECVD) provides silicon-organic thin films for optical, electrically insulating or diffusion barrier coating applications. With process pressures of ≤ 1 Pa this technology is well adapted to the sputtering process of optical interference coatings and also facilitates an inline-process implementation. This paper describes the deposition process for scratch resistant coatings on polycarbonate (PC) and allyl diglycol carbonate substrates. Based on the optical, chemical and mechanical characterization of single magPECVD thin films of varied chemical composition, several types of layer stacks (e.g. of gradient or alternating hardness distribution) were deposited with varied total thickness on PC substrates. Abrasion test results indicate two main effects: the resistance against scratches of high load abrasion (50 N) mainly depends on the total coating thickness. The durability against scratches of low load abrasion (5 N) shows a clear advantage for the multilayer design in contrast to homogeneous single layers even of higher thickness. Finally a 5-layer antireflective system was reactively sputtered onto the magPECVD coating and successfully passed adhesion and environmental tests.     

AFM surface analysis of ZnO layers prepared by pulsed laser deposition at different oxygen pressures

Polycrystalline thin films of zinc oxide were deposited by pulsed laser deposition onto silicon substrates at different oxygen partial pressures in the range of 1-35 Pa. For ablation of the sintered zinc oxide target a pulsed Nd:YAG laser was used. Other processing parameters such as laser pulse energy, pulse repetition rate, substrate temperature and deposition pressure were identical. The effect of oxygen pressure on the structural properties of the films was systematically studied by using atomic force microscopy. The surface morphology, average roughness S_a, root mean square S_q, and mean size of grains on selected places with 2 × 2 μm² area of prepared samples were evaluated. Detailed structural analysis confirmed that partial oxygen pressure leads to the modification of surface morphology. Mean grain size in height and lateral direction decreases with raising oxygen pressure from 1 to 5 Pa while the further increase of oxygen pressure from 5 to 35 Pa results in grain size enlargement. The zinc oxide film formed at oxygen partial pressure 5 Pa shows smallest values of evaluated parameters (S_a = 0.6 nm, S_q = 0.7 nm and mean size of grains 50 nm).     

Uniformity of gallium doped zinc oxide thin film prepared by pulsed laser deposition

Recently, transparent conducting oxide thin films have attracted attention for the application to transparent conducting electrodes. In this work, we evaluated the uniformity of electrical, optical and structural properties for gallium doped zinc oxide thin films prepared on the 10 × 10 cm² silica glass substrate by pulsed laser deposition. The resistivity, carrier concentration, mobility, bonding state and atomic composition of the film were uniform along in-plane and depth direction over the 10 × 10 cm² area of the substrate. The film showed the average transmittance of 81-87%, resistivity of 1.4 × 10^− 3 Ω cm, carrier concentration of 9.7 × 10²⁰/cm³ and mobility of 5 cm²/Vs in spite of the amorphous X-ray diffraction pattern. The gradual thickness distribution was found, however, the potential for large-area and low temperature deposition of transparent conducting oxide thin film using pulsed laser deposition method was confirmed.     

Mid-frequency deposition of a-C:H films using five different precursors

The plasma-enhanced chemical vapour deposition (PECVD) of amorphous hydrogenated carbon films from pulsed discharges with frequencies in the range from 50 kHz to 250 kHz was investigated. Five different hydrocarbons (acetylene C₂H₂, isobutene C₄H₈, cyclopentene C₅H₈, toluene C₇H₈ and cycloheptatriene C₇H₈) were probed as film growth precursors. In addition, two types of pulse-generators with somewhat different waveforms were used to power the discharges in the so called mid-frequency range. The a-C:H films deposited in a parallel-plate reactor were characterised for their thickness/deposition rate, hardness and hydrogen content. The hydrogen concentration in the films varied between 19 at.-% and 37 at.-%. With the substrate temperature held constant, it is roughly in inverse proportion to the hardness. The film with the highest hardness of 25 GPa was formed at a deposition rate of 0.8 μm/h in the C₂H₂ discharge at the lowest investigated pressure of 2 Pa. With increasing molecular mass of the precursor mostly weaker films were deposited. Relatively high values of both deposition rate and hardness were achieved using the precursor isobutene: a hardness of 21 GPa combined with a deposition rate of 4.1 μm/h. From the probed precursors, isobutene is also most advantageous for a-C:H deposition at higher pressures (up to 50 Pa investigated). But, as an over-all trend, the a-C:H hardness decreases with increasing deposition rate.     

Mid-frequency deposition of a-C:H films using five different precursors

The plasma-enhanced chemical vapour deposition (PECVD) of amorphous hydrogenated carbon films from pulsed discharges with frequencies in the range from 50 kHz to 250 kHz was investigated. Five different hydrocarbons (acetylene C₂H₂, isobutene C₄H₈, cyclopentene C₅H₈, toluene C₇H₈ and cycloheptatriene C₇H₈) were probed as film growth precursors. In addition, two types of pulse-generators with somewhat different waveforms were used to power the discharges in the so called mid-frequency range. The a-C:H films deposited in a parallel-plate reactor were characterised for their thickness/deposition rate, hardness and hydrogen content. The hydrogen concentration in the films varied between 19 at.-% and 37 at.-%. With the substrate temperature held constant, it is roughly in inverse proportion to the hardness. The film with the highest hardness of 25 GPa was formed at a deposition rate of 0.8 μm/h in the C₂H₂ discharge at the lowest investigated pressure of 2 Pa. With increasing molecular mass of the precursor mostly weaker films were deposited. Relatively high values of both deposition rate and hardness were achieved using the precursor isobutene: a hardness of 21 GPa combined with a deposition rate of 4.1 μm/h. From the probed precursors, isobutene is also most advantageous for a-C:H deposition at higher pressures (up to 50 Pa investigated). But, as an over-all trend, the a-C:H hardness decreases with increasing deposition rate.     

Electrophoretic deposition of siderite thin layers: Influence of electrode potential and deposition time

Siderite thin layers have been obtained by electrophoretic deposition on an inert substrate (gold). Scanning electron microscopy image exhibits a compact and homogeneous film composed of round grains which diameter is about 1-2 µm. The influence of two parameters, namely the electrode potential and the deposition time, on its thickness and its microstructure was investigated. The thickness was shown to be slightly dependent of the electrode potential (1.2 µm for − 0.70 V and 1.7 µm for − 0.95 V after 17 h). The crystallite size, estimated by X-ray diffraction patterns, was about 5 nm, depending on both electrode potential and deposition time. Despite its high sensitivity to oxygen, X-ray photoelectron spectroscopy spectra prove that the siderite surface has been kept out from oxidation. These siderite thin layers could be used as modified electrodes for further interaction studies.     

Laser-ablated plasma for deposition of ZnO thin films on various substrates

We report optical and structural properties of ZnO films deposited by pulsed laser deposition technique on 1100) n-typesilicon and quartz substrates at various pressures of back ground gas. ZnO plasma was created using KrF laser 1248 nm) atvarious pressures of the ambient gas, oxygen. Laser induced plasma at varying fluence on the target was investigated using optical emission spectroscopy and 2-D images of the expanding plumes. X-ray diffraction, atomic force microscopy, and spectro-photometry were used to characterize as grown films.     

A critical comparison of silicide film deposition techniques

Three different film deposition techniques are compared. WSi₂ was chosen as a test sample. Fabrication of films with the desired composition and lowest electrical resistivities are emphasized. Rutherford backscattering analysis was found to be a very useful tool to perform rapid non-destructive examination of in-depth composition variation and determination of relative thickness. Co-evaporation of tungsten and silicon was found to provide films with the lowest resistivity but was the most difficult method of film deposition. Co-sputtering is slightly simpler than co-evaporation but it is preferable to sputter from a compound or composite target of high purity if available. Low pressure chemical vapor deposition is the simplest method for tungsten silicide film deposition with uniformity and high throughput. However, these films contain more impurities, and thus the resulting resistivities are higher than those of purer films deposited by other techniques.