A nanoindentation study of the mechanical properties of ZnO thin films on (0 0 0 1) sapphire

The mechanical properties of epitaxial ZnO thin films grown on (0 0 0 1) sapphire substrate were investigated by nanoindentation with a Berkovich tip and compared with that of bulk ZnO single crystal. In all indents on ZnO film a single discontinuity (‘pop-in’) in the load versus indentation depth data was observed at a specific depth of between 13 and 16 nm. In bulk ZnO, however only 65% of indents showed pop-in event at a specific depth of between 12 and 20 nm. The mechanism responsible for the ‘pop-in’ event in the epitaxial ZnO thin films as well as in bulk ZnO was attributed to the sudden propagation of dislocations, which had been pinned down by pre-existing defects, along the pyramidal and basal {0 0 0 1} planes (cross slip). The elastic modulus and hardness of the epitaxial ZnO thin films were determined to be 154 ± 5 and 8.7 ± 0.2 GPa, respectively, at an indentation depth of 30 nm.     

Effect of electrically degenerated layer on the carrier transport property of ZnO epitaxial thin films

ZnO films were prepared on (1 1 1) YSZ and (0 0 0 1) sapphire by pulsed laser deposition method. Effect of lattice mismatch on the carrier transport properties of ZnO epitaxial thin films was investigated. The carrier mobility of the ZnO films on YSZ was larger than that of ZnO/sapphire due to smaller lattice mismatch when the thickness was below 150 nm. The effect of electrically degenerated layer on the carrier transport property increased with decreasing the film thickness of ZnO film. The carrier density and electron mobility of 20 nm-thick-ZnO film on either substrate were regardless of the temperature. We concluded that the dominant carrier scattering mechanism in ZnO ultra thin films is double Schottky barriers at the grain boundary and that their height depends on the carrier concentration.     

Effects of the sputtering time of ZnO buffer layer on the quality of GaN thin films

ZnO thin films with different thickness (the sputtering time of ZnO buffer layers was 10 min, 15 min, 20 min, and 25 min, respectively) were first prepared on Si substrates using radio frequency magnetron sputtering system and then the samples were annealed at 900 °C in oxygen ambient. Subsequently, a GaN epilayer about 500 nm thick was deposited on ZnO buffer layer. The GaN/ZnO films were annealed in NH₃ ambient at 950 °C. X-ray diffraction (XRD), atom force microscopy (AFM), X-ray photoelectron spectroscopy (XPS) and photoluminescence (PL) were used to analyze the structure, morphology, composition and optical properties of GaN films. The results show that their properties are investigated particularly as a function of the sputtering time of ZnO layers. For the better growth of GaN films, the optimal sputtering time is 15 min.     

Harmonic generation in ZnO nanocrystalline laser deposited thin films

ZnO plasma produced by third harmonic 355 nm of Nd:YAG laser at various ambient pressures of oxygen was used for depositing quality nanocrystalline ZnO thin films. Time and space resolved optical emission spectroscopy is used to correlate the plasma properties with that of deposited thin films. The deposited films showed particle size of 8 and 84 nm at ambient oxygen pressure of 100 and 900 mTorr, respectively. Third harmonic generation observed in ZnO thin films deposited under 100 mTorr of ambient oxygen is reported.     

Epitaxial growth of Ba8Ga16Ge30 clathrate film on Si substrate by RF helicon magnetron sputtering with evaluation on thermoelectric properties

Epitaxial Ba₈Ga₁₆Ge₃₀ clathrate thin films were successfully grown on Si substrate by using helicon magnetron sputtering. The (1 0 0) lattice of Ba₈Ga₁₆Ge₃₀ was identified grown on four Si(2 0 0) lattices in small mismatch (0.1%). Both the color of samples and XRD results suggest 600 °C is the optimal substrate temperature for the growth of high quality Ba-Ga-Ge clathrate film on Si substrates. High Seebeck coefficients and electrical resistivities for the deposited clathrate thin films in comparison with those of bulk are obtained. The high crystal quality and thermionic effects in heterostructures may contribute to the larger Seebeck coefficients, while the increasing of interface scattering for electrons probably is the reason for large electrical resistivities. Although the thermoelectric (TE) results are not ideal as designed, our results are significant due to the first successful work on epitaxial growth of Ba₈Ga₁₆Ge₃₀ clathrate thin films on Si substrate with large Seebeck coefficient.     

Control of a- and c-plane preferential orientations of ZnO thin films

We report orientation-controllable growth of ZnO thin films and their orientation-dependent electrical characteristics. ZnO thin films were deposited on single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃ substrates using pulsed laser deposition (PLD) at different substrate temperatures (400-800 °C). It was found that the orientation of ZnO films could be controlled by using different substrates of single-crystalline (1 0 0) LaAlO₃ and (1 0 0) SrTiO₃. The a-plane () and c-plane (0 0 0 2) oriented ZnO films are formed on LaAlO₃ and SrTiO₃, respectively. In both cases, the degree orientation increased with increasing deposition temperature T_s. Both the surface free energy and the degree of lattice mismatch are ascribed to play an important role for the orientation-controllable growth. Further characterization show that the grain size of the films with both orientations increases for a substrate temperature increase (i.e. from T_s = 400 °C to T_s = 800 °C), whereas the electrical properties of ZnO thin films depend upon their crystalline orientation, showing lower electrical resistivity values for a-plane oriented ZnO films.     

Nanoindentation characterization of GaN epilayers on A-plane sapphire substrates

Gallium nitride (GaN) epilayers was deposited on a-axis sapphire substrate by means of metal-organic chemical vapor deposition (MOCVD) method. The GaN epilayers has been investigated in their repetition pressure-induced impairment events from nanoindentation technique and, the relative deformation effect was observed from atomic force microscopy (AFM). From the morphological studies, it is revealed that none of crack and particle was found even after the indentation beyond the critical depth on the residual indentation impression. The ‘pop-in’ event was explained by the interaction of the deformed region, produced by the indenter tip, with the inner threading dislocations in the GaN films. Pop-in events indicate the generation and motion of individual dislocation, which is measured under critical depth and, no residual deformation of the GaN films is observed.     

Epitaxial structures of self-organized, standing-up pentacene thin films studied by LEEM and STM

Growth of pentacene (Pn) thin films has been studied in situ by means of low-energy electron microscopy (LEEM) and scanning tunneling microscopy (STM). A very low nucleation density of Pn grains has been observed on Bi(0 0 0 1)/Si(1 1 1) template, resulting in formation of large, monolayer-high Pn grains with diameter exceeding several hundreds of micrometers. We determined that formation of self-organized, standing-up Pn epitaxial layers was stabilized by a weak interaction between the substrate and Pn molecules and by the presence of the commensurate structure between the oblique Pn lattice and trigonal substrate surface lattice. The ‘point-on-line’ commensurability has been found along a-axis of Pn and one of the primitive vectors of substrate surface lattice. Strong ‘point-on-line’ commensurability in Pn/Bi(0 0 0 1)/Si(1 1 1) system resulted in a bulk-like epitaxial thin film growth, starting from the first layer. The presence of twins, often having a mirror line parallel to the direction of the ‘point-on-line’ matching, has been also detected using an asymmetric dark-field imaging mode in LEEM experiments, which, we believe, is the first LEEM demonstration of molecular tilt imaging.     

Local environment of nitrogen in GaNyAs1−y epilayers on GaAs (0 0 1) studied using X-ray absorption near edge spectroscopy

X-ray absorption near-edge spectroscopy (XANES) is used to study the N environment in bulk GaN and in GaN_yAs_1−y epilayers on GaAs (0 0 1), for y∼5%. Density-functional optimized structures were used to predict XANES via multiple-scattering theory. We obtain striking agreement for pure GaN. An alloy model with nitrogen pairs on Ga accurately predicts the threshold energy, the width of the XANES ‘white line’, and features above threshold, for the given X-ray polarization. The presence of large quantitities of N-pairs may point to a role for molecular N₂ in epitaxial growth kinetics.     

A simple growth route towards ZnO thin films and nanorods

Highly orientated ZnO thin films and the self-organized ZnO nanorods can be easily prepared by a simple chemical vapor deposition method using zinc acetate as a source material at the growth temperature of 180 and 320 °C, respectively. The ZnO thin films deposited on Si (100) substrate have good crystallite quality with the thickness of 490 nm after annealing in oxygen at 800 °C. The ZnO nanorods grown along the [0001] direction have average diameter of 40 nm with length up to 700 nm. The growth mechanism for ZnO nanorods can be explained by a vapor-solid (VS) mechanism. Photoluminescence (PL) properties of ZnO thin films and self-organized nanorods were investigated. The luminescence mechanism for green band emission was attributed to oxygen vacancies and the surface states related to oxygen vacancy played a significant role in PL spectra of ZnO nanorods.     

Quenching of surface traps in Mn doped ZnO thin films for enhanced optical transparency

The structural and photoluminescence analyses were performed on un-doped and Mn doped ZnO thin films grown on Si (1 0 0) substrate by pulsed laser deposition (PLD) and annealed at different post-deposition temperatures (500-800 °C). X-ray diffraction (XRD), employed to study the structural properties, showed an improved crystallinity at elevated temperatures with a consistent decrease in the lattice parameter ‘c’. The peak broadening in XRD spectra and the presence of Mn 2p3/2 peak at ∼640 eV in X-ray Photoelectron Spectroscopic (XPS) spectra of the doped thin films confirmed the successful incorporation of Mn in ZnO host matrix. Extended near band edge emission (NBE) spectra indicated the reduction in the concentration of the intrinsic surface traps in comparison to the doped ones resulting in improved optical transparency. Reduced deep level emission (DLE) spectra in doped thin films with declined PL ratio validated the quenching of the intrinsic surface traps thereby improving the optical transparency and the band gap, essential for optoelectronic and spintronic applications. Furthermore, the formation and uniform distribution of nano-sized grains with improved surface features of Mn-doped ZnO thin films were observed in Field Emission Scanning Electron Microscopy (FESEM) images.     

Epitaxial growth of InN on nearly lattice-matched (Mn,Zn)Fe2O4

We have grown InN films on nearly lattice-matched (Mn,Zn)Fe₂O₄ (111) substrates at low temperatures by pulsed laser deposition (PLD) and investigated their structural properties. InN films grown at substrate temperatures above 400 °C show poor crystallinity, and their in-plane epitaxial relationship is [10-10]InN//[11-2](Mn,Zn)Fe₂O₄, which means that their lattice mismatch is quite large (11%). By contrast, high quality InN films with flat surfaces can be grown at growth temperatures lower than 150 °C with the ideal in-plane epitaxial relationship of [11-20]InN//[11-2](Mn,Zn)Fe₂O₄, which produces lattice mismatches of as low as 2.0%. X-ray reflectivity measurements have revealed that the thickness of the interfacial layer between the InN and the substrates is reduced from 14 to 8.4 nm when the growth temperature is decreased from 400 °C to room temperature. This suppression of the interface reactions by reducing the growth temperature is probably responsible for the improvement in crystalline quality. These results indicate that the use of (Mn,Zn)Fe₂O₄ (111) substrates at low growth temperatures allows us to achieve nearly lattice matched epitaxial growth of InN.     

Enhanced hardness in B-doped ZnO thin films on fused quartz substrates by pulsed-laser deposition

B-doped ZnO thin films have been fabricated on fused quartz substrates using boron-ZnO mosaic target by pulsed-laser deposition technique, and the mechanical properties have been studied by nanoindentation continuous stiffness measurement technique and transmission electron microscope (TEM). Nanoindentation measurement revealed that the hardness of B-doped ZnO films, 9.32 ± 0.90 to 12.10 ± 1.00 GPa, is much greater than that of undoped ZnO films and very close to that of traditional semiconductor Si. The mean transmittance (%) is larger than 81% in the visible range (380-780 nm) for all the films, and the Hall effect measurement showed that the carrier density is around 2 × 10²⁰ cm⁻³ and the resistivity lower than 3 × 10⁻³ Ω cm. TEM characteristics show undoped thin films have more amorphous area between grains while the B-doped ZnO films have thin grain boundaries. We suggest that the grain boundaries act as the strain compensation sites and the decrease in thickness of grain boundaries enhances the hardness of the B-doped ZnO films.     

Photosensitivity of nanocrystalline ZnO films grown by PLD

We have studied the properties of ZnO thin films grown by laser ablation of ZnO targets on (0 0 0 1) sapphire (Al₂O₃), under substrate temperatures around 400 °C. The films were characterized by different methods including X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD) and atomic force microscopy (AFM). XPS analysis revealed that the films are oxygen deficient, and XRD analysis with θ-2θ scans and rocking curves indicate that the ZnO thin films are highly c-axis oriented. All the films are ultraviolet (UV) sensitive. Sensitivity is maximum for the films deposited at lower temperature. The films deposited at higher temperatures show crystallite sizes of typically 500 nm, a high dark current and minimum photoresponse. In all films we observe persistent photoconductivity decay. More densely packed crystallites and a faster decay in photocurrent is observed for films deposited at lower temperature.     

Microstructure of epitaxial SrRuO3 thin films on MgO substrates

SrRuO₃ thin films have been grown on singular (1 0 0) MgO substrates using pulsed laser deposition (PLD) in 30 Pa oxygen ambient and at a temperature of 400-700 °C. Ex situ reflection high-energy electron diffraction (RHEED) as well as X-ray diffraction (XRD) θ/2θ scan indicated that the films deposited above 650 °C were well crystallized though they had a rough surface as shown by atom force microscopy (AFM). XRD Φ scans revealed that these films were composed of all three different types of orientation domains, which was further confirmed by the RHEED patterns. The heteroepitaxial relationship between SrRuO₃ and MgO was found to be [1 1 0] SRO//[1 0 0] MgO and 45°-rotated cube-on-cube [0 0 1] SRO//[1 0 0] MgO. These domain structures and surface morphology are similar to that of ever-reported SrRuO₃ thin films deposited on the (0 0 1) LaAlO₃ substrates, and different from those deposited on (0 0 1) SrTiO₃ substrates that have an atomically flat surface and are composed of only the [1 1 0]-type domains. The reason for this difference was ascribed to the effect of lattice mismatch across the film/substrate interface. The room temperature resistivity of SrRuO₃ films fabricated at 700 °C was 300 μΩ cm. Therefore, epitaxial SrRuO₃ films on MgO substrate could serve as a promising candidate of electrode materials for the fabrication of ferroelectric or dielectric films.     

Structural and optical properties of sputtered ZnO thin films

Zinc oxide (ZnO) and aluminium-doped zinc oxide (ZnO:Al) thin films were prepared by RF diode sputtering at varying deposition conditions. The effects of negative bias voltage and RF power on structural and optical properties were investigated. X-ray diffraction measurements (XRD) confirmed that both un-doped and Al-doped ZnO films are polycrystalline and have hexagonal wurtzite structure. The preferential 〈0 0 1〉 orientation and surface roughness evaluated by AFM measurements showed dependence on applied bias voltage and RF power. The sputtered ZnO and ZnO:Al films had high optical transmittance (>90%) in the wavelength range of 400-800 nm, which was not influenced by bias voltage and RF power. ZnO:Al were conductive and highly transparent. Optical band gap of un-doped and Al-doped ZnO thin films depended on negative bias and RF power and in both cases showed tendency to narrowing.     

Crystal orientation control of polycrystalline TiN thin films using ZnO under layers deposited by magnetron sputtering

The effect of ZnO under layers on crystal growth of TiN thin films was investigated. TiN single layers and double-layered ZnO/TiN thin films were deposited on soda-lime-silicate glass substrates by magnetron sputtering. XRD analysis indicated that TiN single layers exhibited {1 1 1} preferred orientation on glass substrates; on the other hand, the TiN thin films with {1 0 0} preferred orientation were obtained using ZnO under layers and crystallized better than the TiN single layers. This crystal orientation change of TiN thin films should come from heteroepitaxial-like growth because the TiN{1 0 0} and ZnO{0 0 1} crystal lattice planes have similar atomic arrangements. Besides, the possible mismatch between TiN and ZnO atomic arrangements was estimated to be 7.8%. Furthermore, the resistivity and optical absorbance of TiN thin films decreased when they were deposited on ZnO under layers. It can be considered that electrical and optical properties should be improved due to the well-crystallization of TiN thin films using ZnO under layers.     

Effect of thickness on structural, optical and electrical properties of nanostructured ZnO thin films by spray pyrolysis

Transparent conducting zinc oxide thin films were prepared by spray pyrolytic decomposition of zinc acetate onto glass substrates with different thickness. The crystallographic structure of the films was studied by X-ray diffraction (XRD). XRD measurement showed that the films were crystallized in the wurtzite phase type. The grain size, lattice constants and strain in films were calculated. The grain size increases with thickness. The studies on the optical properties show that the direct band gap value increases from 3.15 to 3.24 eV when the thickness varies from 600 to 2350 nm. The temperature dependence of the electrical conductivity during the heat treatment was studied. It was observed that heat treatment improve the electrical conductivity of the ZnO thin films. The conductivity was found to increase with film thickness.     

Berkovich nanoindentation and deformation mechanisms in GaN thin films

The deformation mechanisms of GaN thin films obtained by metal-organic chemical vapor deposition (MOCVD) method were studied using nanoindentation with a Berkovich diamond indenter, micro-Raman spectroscopy and the cross-sectional transmission electron microscopy (XTEM) techniques. Due to the sharpness of the tip of Berkovich indenter, the nanoindentation-induced deformation behaviors can be investigated at relatively lower load and, hence, may cover wider range of deformation-related phenomena over the same loading range. The load-displacement curves show the multiple “pop-ins” during nanoindentation loading. No evidence of nanoindentation-induced phase transformation and cracking patterns were found up to the maximum load of 300 mN, as revealed from the micro-Raman spectra and the scanning electron microscopy (SEM) observations within the mechanically deformed regions. In addition, XTEM observation performed near the cross-section of the indented area revealed that the primary deformation mechanism in GaN thin film is via propagation of dislocations on both basal and pyramidal planes. The continuous stiffness measurement (CSM) technique was used to determine the hardness and Young's modulus of GaN thin films. In addition, analysis of the load-displacement data reveals that the values of hardness and Young's modulus of GaN thin films are 19 ± 1 and 286 ± 25 GPa, respectively.     

Structure and properties of ZnO films grown on Si substrates with low temperature buffer layers

Zinc oxide (ZnO) thin films were grown on Si (1 0 0) substrates by pulsed laser deposition (PLD) using two-step epitaxial growth method. Low temperature buffer layer (LTBL) was initially deposited in order to obtain high quality ZnO thin film; the as-deposited films were then annealed in air at 700 °C. The effects of LTBL and annealing treatment on the structural and luminescent properties of ZnO thin film were investigated. It was found that tensile strain was remarkably relaxed by employing LTBL and the band-gap redshifted, correspondingly. The shift value was larger than that calculated from band-gap theories. After annealing treatment, it was found that the annealing temperature with 700 °C has little influence on strains of ZnO films with LTBLs other than directly deposited film in our experiments. Interestingly, the different behaviors in terms of the shift of ultraviolet (UV) emission after annealing between films with and without buffer were observed, and a tentative explanation was given in this paper.