Search

Typical low-temperature frustrated triangular antiferromagnet CuFeO2 is attracting extensive interest due to its narrow-band-gap semiconductor properties. High-quality and impurity-free CuFeO2 epitaxial thin films would be preferable for fundamental studies on the physical and chemical properties. However, the heteroepitaxial growth of impurity-free CuFeO2 thin films has been a significant challenge due to its narrow formation window in the Cu–Fe–O system as well as the metastable nature of the Cu1+ cations. This work reports for the first time the fabrication and characterization of high-quality and impurity-free (00.1)-oriented CuFeO2 epitaxial thin films grown with relaxed interfaces on (00.1) sapphire substrates by pulsed laser deposition. Below the critical thickness of around 16 nm, the films exhibit a rhombohedral structure with relatively good crystalline quality where all Cu ions appear to be in the 1+ oxidation state, while the rocking curves display a narrow full width at half maximum of about 0.11°. Increasing the thickness, the (111)-oriented γ-Fe2O3 nanograins grow embedded in the CuFeO2 films. Here, an excess Fe3+-assisted growth mechanism is proposed to explain the iron oxide grain formation. This study provides insight into the heteroepitaxial growth of relaxed CuFeO2 thin films with high purity and crystalline quality as an ideal sample design to characterize the fundamental properties of this material in view of potential device applications. [ABSTRACT FROM AUTHOR]

Using N2O as an alternative background gas to O2 when growing oxide thin films by pulsed laser deposition (PLD) was previously expected to result in larger oxygen contents of as-grown thin films. In this work, we investigate the composition and kinetic energy of the pulsed laser induced plasmas that propagated in N2O and O2 by using mass spectrometry and plasma imaging. Two distinguished features were observed when using N2O instead of O2. (1) In N2O background gas as compared to O2, a larger proportion of negative oxygen ions was detected. (2) The alkaline-earth elements were fully oxidized in the N2O background, which is not achievable in O2. These observations are attributed to the smaller dissociation energy of the N2O molecules as compared to O2. The smaller dissociation energy of the background gas molecule is expected to reduce the interaction strength during their central collisions with the plasma species. As a result, the dissociable or electron detachable plasma species can be formed in larger amounts in N2O background, compared to O2. Comparing the composition of the deposited thin films indicates a larger oxygen content of the film grown in N2O background gas, as compared to O2, at pressures of ∼10−1 mbar, which is the most commonly used deposition pressure in PLD. Nevertheless, this was not achieved when performing PLD at ∼10−2 mbar, since the pressure was not high enough to trigger the formation of the shockwave front during the plasma expansion and thereby the lightest oxygen plasma species were preferentially scattered. [ABSTRACT FROM AUTHOR]

The misfit-layered cobalt oxide [Ca2CoO3-δ][CoO2]1.62 is a promising material for high-temperature thermoelectric heat recovery. Here, we show that discrepancies in the numerously reported thermoelectric performances can result from Co3OM4 impurities or a change of the defects, i.e., the relative Co content in the [Ca2CoO3-δ][CoO2]1.62 phase. We observe that increasing the relative Co content in the [Ca2CoO3-δ][CoO2]1.62 phase leads to a larger figure of merit ZT. We attribute this increase of ZT to additional p-type charge carriers introduced by Ca vacancies and the resulting reduction of the electrical resistivity. For Co/Ca ratios above the miscibility limit, the increase in thermal conductivity due to the formation of Co3OM4 impurities leads to a reduction of ZT when the volume fraction of the Co3OM4 phase is increased from 1% to 3%. Hence, the best figure of merit is expected close to the upper phase boundary of the [Ca2CoO3-δ][CoO2]1.62 phase. [ABSTRACT FROM AUTHOR]

The effects of the type of background gas and pressure on the spatial distributions of plume species have been investigated by time and space resolved imaging in vacuum, 1×10-2 mbar and 1×10-1 mbar O2 and Ar. The ablation of La0.4Ca0.6MnO3 in vacuum shows dissimilar arrival times for the different neutral species and a backscattering of the impinging species from the substrate. At 1×10-2 mbar, a species-dependent plume splitting appears and preferential scattering of the lighter elements is detected generating a cation off-stoichiometry along the plume axis. In addition at 1×10-1 mbar the plume expansion in this relatively high pressure traps a portion of the background gas against the substrate holder, thereby creating a transient high local pressure with remarkable effects once the plume reaches the substrate. In an Ar background, a rebound wave is seen, which travels backwards and recoats/contaminates the target with a different composition than the original target. In O2, in addition to the rebound, a long-lived volume of excited species is created, which consists mainly of LaO I. The rebound has important effects on the film composition and is background gas dependent. The same effects are also detected during Ag ablation and are probably valid for most target materials. [ABSTRACT FROM AUTHOR]

Pulsed reactive crossed-beam laser ablation is an effective technique to govern the chemical activity of plasma species and background molecules during pulsed laser deposition. Instead of using a constant background pressure, a gas pulse with a reactive gas, synchronized with the laser beam, is injected into vacuum or a low background pressure near the ablated area of the target. It intercepts the initially generated plasma plume, thereby enhancing the physicochemical interactions between the gaseous environment and the plasma species. For this study, kinetic energy resolved mass-spectrometry and time-resolved plasma imaging were used to study the physicochemical processes occurring during the reactive crossed beam laser ablation of a partially 18O substituted La0.6Sr0.4MnO3 target using oxygen as gas pulse. The characteristics of the ablated plasma are compared with those observed during pulsed laser deposition in different oxygen background pressures. [ABSTRACT FROM AUTHOR]

High mobility hydrogenated indium oxide is investigated as a transparent contact for thin film Cu(In,Ga)Se2 (CIGS) solar cells. Hydrogen doping of In2O3 thin films is achieved by injection of H2O water vapor or H2 gas during the sputter process. As-deposited amorphous In2O3:H films exhibit a high electron mobility of ~50 cm²/Vs at room temperature. A bulk hydrogen concentration of ~4 at. % was measured for both optimized H2O and H2-processed films, although the H2O-derived film exhibits a doping gradient as detected by elastic recoil detection analysis. Amorphous IOH films are implemented as front contacts in CIGS based solar cells, and their performance is compared with the reference ZnO:Al electrodes. The most significant feature of IOH containing devices is an enhanced open circuit voltage (VOC) of ~20 mV regardless of the doping approach, whereas the short circuit current and fill factor remain the same for the H2O case or slightly decrease for H2. The overall power conversion efficiency is improved from 15.7% to 16.2% by substituting ZnO:Al with IOH (H2O) as front contacts. Finally, stability tests of non-encapsulated solar cells in dry air at 80 °C and constant illumination for 500 h demonstrate a higher stability for IOH-containing devices. [ABSTRACT FROM AUTHOR]

Polycrystalline tungsten-substituted CaMn1-xWxO3-δ (0.00 ≤ x ≤ 0.05) powders were synthesized from a polymeric precursor, pressed and sintered to high density. The impact of tungsten substitution on the crystal structure, thermal stability, phase transition, electronic and thermal transport properties is assessed. Tungsten acts as an electron donator and strongly affects high-temperature oxygen stoichiometry. Oxygen vacancies form in the high figure-of-merit (ZT)-region starting from about T = 1000 K and dominate the carrier concentration and electronic transport far more than the tungsten substitution. The analysis of the transport properties yields that in the investigated regime the band filling is sufficiently high to overcome barriers of polaron transport. Therefore, the Cutler-Mott approach describes the electrical transport more accurately than the Mott approach for small polaron transport. The lattice thermal conductivity near room temperature is strongly suppressed with increasing tungsten concentration due to mass-difference impurity scattering. A ZT of 0.25 was found for x = 0.04 at 1225 K. [ABSTRACT FROM AUTHOR]