Atomic layer deposition of nickel-cobalt spinel thin films.

We report the atomic layer deposition (ALD) of high-quality crystalline thin films of the spinel-oxide system (Co1-xNix)3O4. These spinel oxides are ferrimagnetic p-type semiconductors, and promising material candidates for several applications ranging from photovoltaics and spintronics to thermoelectrics. The spinel phase is obtained for Ni contents exceeding the x = 0.33 limit for bulk samples. It is observed that the electrical resistivity decreases continuously with x while the magnetic moment increases up to x = 0.5. This is in contrast to bulk samples where a decrease of resistivity is not observed for x > 0.33 due to the formation of a rock-salt phase. From UV-VIS-NIR absorption measurements, a change from distinct absorption edges for the parent oxide Co3O4 to a continuous absorption band ranging deep into the near infrared for 0 < x ≤ 0.5 was observed. The conformal deposition of dense films on high-aspect-ratio patterns is demonstrated.

Anomalous thickness-dependent optical energy gap of ALD-grown ultra-thin CuO films.

Usually an inverse square relation between the optical energy gap and the size of crystallites is observed for semiconducting materials due to the strong quantum localization effect. Coulomb attraction that may lead to a proportional dependence is often ignored or considered less important to the optical energy gap when the crystallite size or the thickness of a thin film changes. Here we report a proportional dependence between the optical energy gap and the thickness of ALD-grown CuO thin films due to a strong Coulomb attraction. The ultrathin films deposited in the thickness range of 9-81 nm show a p-type semiconducting behavior when analyzed by Seebeck coefficient and electrical resistivity measurements. The indirect optical energy gap nature of the films is verified from UV-vis spectrophotometric measurements. A progressive increase in the indirect optical energy gap from 1.06 to 1.24 eV is observed with the increase in the thickness of the films. The data are analyzed in the presence of Coulomb attractions using the Brus model. The optical energy gap when plotted against the cubic root of the thickness of the films shows a linear dependence.

Isovalent Ca and Ba substitutions in thermoelectric layer-structured oxyselenide Sr2CoO2Cu2Se2.

Multilayered compounds typically present exotic functionalities, and some of them have been suggested as potential materials for thermoelectric conversion owing to their unique capability to decouple electronic and heat transport. Here we report new [CoO2] and [Cu2Se2] layered A2CoO2Cu2Se2 compounds in which Sr at the intervening alkaline-earth A site is partially replaced with Ca or Ba. The parent Sr2CoO2Cu2Se2 phase is a direct gap p-type semiconductor, and density functional theory (DFT) calculations indicate its topmost valence band consists of Cu 3d-Se 4p states. Upon the isovalent cation substitution the lattice modification in the ab plane is constrained by the stiff [CoO2] layer such that the lattice shrinkage/expansion mainly happens along the c axis. Substitution of Sr with the heavier and larger Ba significantly enhances the thermopower but more hole states would be required to optimize the thermoelectric performance. Thermal stability is related to the inter-oxide-selenide-layer interaction, and our thermogravimetric measurement data reveal that the A2CoO2Cu2Se2 materials could operate in the intermediate temperature region.

An experimental setup for the simultaneous measurement of thermoelectric power of two samples from 77 K to 500 K.

We report on an experimental setup for the simultaneous measurement of the thermoelectric power (TEP) of two samples in the temperature range from 77 K to 500 K using optimum electronic instruments. The setup consists of two rectangular copper bars in a bridge arrangement for sample mounting, two surface mount (SM) chip resistors for creating alternate temperature gradient, and a type E thermocouple in differential geometry for gradient temperature (ΔT) measurement across the samples. In addition, a diode arrangement has been made for the alternate heating of SM resistors using only one DC current source. The measurement accuracy of ΔT increases with the differential thermocouple arrangement. For the calibration of the setup, measurements of TEP on a high purity (99.99%) platinum wire and type K thermocouple wires Chromel and Alumel have been performed from 77 K to 500 K with respect to copper lead wires. Additionally, this setup can be utilized to calibrate an unknown sample against a sample of known absolute TEP.