Atomic layer deposition of Zr-sandwiched ZnO thin films for transparent thermoelectrics.

Atomic layer deposited (ALD) transparent thermoelectric materials enable the introduction of energy harvesting and sensing devices onto surfaces of various shapes and sizes in imperceptible manner. Amongst these materials, ZnO has shown promising results in terms of both thermoelectric and optical characteristics. The thermoelectric performance of ZnO can be further optimized by introducing extrinsic doping, to the realization of which ALD provides excellent control. Here, we explore the effects of sandwiching of ZrO2layers with ZnO on glass substrates. The room-temperature thermoelectric power factor is maximised at 116µW m-1K-2with samples containing a 2% nominal percentage of ZrO2. The addition of ZrO2layers is further shown to reduce the thermal conductivity, resulting in a 20.2% decrease from the undoped ZnO at 2% doping. Our results contribute to increasing the understanding of the effects of Zr inclusion in structural properties and growth of ALD ZnO, as well as the thermal and thermoelectric properties of Zr-doped ZnO films in general.

Hydrogen induced interface engineering in Fe2O3-TiO2 heterostructures for efficient charge separation for solar-driven water oxidation in photoelectrochemical cells.

Semiconductor heterostructure junctions are known to improve the water oxidation performance in photoelectrochemical (PEC) cells. Depending on the semiconductor materials involved, different kinds of junctions can appear, for instance, type II band alignment where the conduction and valence bands of the semiconductor materials are staggered with respect to each other. This band alignment allows for a charge separation of the photogenerated electron-hole pairs, where the holes will go from low-to-high valance band levels and vice versa for the electrons. For this reason, interface engineering has attracted intensive attention in recent years. In this work, a simplified model of the Fe2O3-TiO2 heterostructure was investigated via first-principles calculations. The results show that Fe2O3-TiO2 produces a type I band alignment in the heterojunction, which is detrimental to the water oxidation reaction. However, the results also show that interstitial hydrogens are energetically allowed in TiO2 and that they introduce states above the valance band, which can assist in the transfer of holes through the TiO2 layer. In response, well-defined planar Fe2O3-TiO2 heterostructures were manufactured, and measurements confirm the formation of a type I band alignment in the case of Fe2O3-TiO2, with very low photocurrent density as a result. However, once TiO2 was subjected to hydrogen treatment, there was a nine times higher photocurrent density at 1.50 V vs. the reversible hydrogen electrode under 1 sun illumination as compared to the original heterostructured photoanode. Via optical absorption, XPS analysis, and (photo)electrochemical measurements, it is clear that hydrogen treated TiO2 results in a type II band alignment in the Fe2O3-H:TiO2 heterostructure. This work is an example of how hydrogen doping in TiO2 can tailor the band alignment in TiO2-Fe2O3 heterostructures. As such, it provides valuable insights for the further development of similar material combinations.

Enhanced Thermoelectric Transport and Stability in Atomic Layer Deposited-HfO2/ZnO and TiO2/ZnO-Sandwiched Multilayer Thin Films.

Herein, enhancements in thermoelectric (TE) performance, both the power factor (PF) and thermal stability, are exhibited by sandwiching HfO2 and TiO2 layers onto atomic layer deposited-ZnO thin films. High-temperature TE measurements from 300 to 450 K revealed an almost two-fold improvement in electrical conductivity for TiO2/ZnO (TZO) samples, primarily owing to an increase in carrier concentration by Ti doping. On the other hand, HfO2/ZnO (HZO) achieved the highest PF values owing to maintaining Seebeck coefficients comparable to pure ZnO. HZO also exhibited excellent stability after multiple thermal cycles, which has not been previously observed for pure or doped ZnO thin films. Such improvement in both TE properties and thermal stability of HZO can be attributed to a shift in crystalline orientation from the a axis to c axis, as well as the high bond dissociation energy of Hf-O, stabilizing the ZnO structure. These unique properties exhibited by HZO and TZO thin films synthesized by atomic layer deposition pave the way for next-generation transparent TE devices.

Large-Area Thermal Distribution Sensor Based on Multilayer Graphene Ink.

Emergent applications in wearable electronics require inexpensive sensors suited to scalable manufacturing. This work demonstrates a large-area thermal sensor based on distributed thermocouple architecture and ink-based multilayer graphene film. The proposed device combines the exceptional mechanical properties of multilayer graphene nanocomposite with the reliability and passive sensing performance enabled by thermoelectrics. The Seebeck coefficient of the spray-deposited films revealed an inverse thickness dependence with the largest value of 44.7 µV K-1 at 78 nm, which makes thinner films preferable for sensor applications. Device performance was demonstrated by touch sensing and thermal distribution mapping-based shape detection. Sensor output voltage in the latter application was on the order of 300 µV with a signal-to-noise ratio (SNR) of 35, thus enabling accurate detection of objects of different shapes and sizes. The results imply that films based on multilayer graphene ink are highly suitable to thermoelectric sensing applications, while the ink phase enables facile integration into existing fabrication processes.

Photodeposition of RuO x Nanostructures on TiO2 Films with a Controllable Morphology.

RuO2/TiO2 catalysts have shown broad use in promoting a variety of photocatalytic phenomena, such as water splitting and the photodecomposition of organic dyes and pollutants. Most current methods of photodepositing ruthenium oxide species (RuO x ) onto titanium dioxide (TiO2) films involve precursors that are either difficult to produce and prone to decomposition, such as RuO4, or require high-temperature oxidations, which can reduce the quality of the resulting catalyst and increase the risks and toxicity of the procedure. The present work demonstrates the photodeposition of RuO x onto TiO2 films, using potassium perruthenate (KRuO4) as a precursor, by improving substantially a procedure known to work on TiO2 nanopowders. In addition to demonstrating the applicability of this method of photodeposition to TiO2 films, this work also explores the importance of the material phase of the TiO2 substrate, outlines viable concentrations and photodeposition times at a given optical intensity, and demonstrates that the morphology of the photodeposited nanostructures changes from cauliflower-like spheroids to a matted, porous sponge-like structure with the addition of methanol to the precursor solution. This morphology change has not been documented previously. By providing an explanation for this difference in the morphology, this work provides both newer insights into the photodeposition process and provides an excellent foundation for future procedures, allowing a more targeted and controlled deposition based on the desired morphology.

Synergies of co-doping in ultra-thin hematite photoanodes for solar water oxidation: In and Ti as representative case.

Solar energy induced water splitting in photoelectrochemical (PEC) cells is one of the most sustainable ways of hydrogen production. The challenge is to develop corrosion resistant and chemically stable semiconductors that absorb sunlight in the visible region and, at the same time, have the band edges matching with the redox level of water. In this work, hematite (α-Fe2O3) thin films were prepared onto an indium-doped tin oxide (ITO; In:SnO2) substrate by e-beam evaporation of Fe, followed by air annealing at two different temperatures: 350 and 500 °C. The samples annealed at 500 °C show an in situ diffusion of indium from the ITO substrate to the surface of α-Fe2O3, where it acts as a dopant and enhances the photoelectrochemical properties of hematite. Structural, optical, chemical and photoelectrochemical analysis reveal that the diffusion of In at 500 °C enhances the optical absorption, increases the electrode-electrolyte contact area by changing the surface topology, improves the carrier concentration and shifts the flat band potential in the cathodic direction. Further enhancement in photocurrent density was observed by ex situ diffusion of Ti, deposited in the form of nanodisks, from the top surface to the bulk. The in situ In diffused α-Fe2O3 photoanode exhibits an improved photoelectrochemical performance, with a photocurrent density of 145 µA cm-2 at 1.23 VRHE, compared to 37 µA cm-2 for the photoanode prepared at 350 °C; it also decreases the photocurrent onset potential from 1.13 V to 1.09 V. However, the In/Ti co-doped sample exhibits an even higher photocurrent density of 290 µA cm-2 at 1.23 VRHE and the photocurrent onset potential decreases to 0.93 VRHE, which is attributed to the additional doping and to the surface becoming more favorable to charge separation.

Solar-Powered Carbon Fixation for Food and Feed Production Using Microorganisms-A Comparative Techno-Economic Analysis.

This study evaluates the techno-economic feasibility of five solar-powered concepts for the production of autotrophic microorganisms for food and feed production; the main focus is on three concepts based on hydrogen-oxidizing bacteria (HOB), which are further compared to two microalgae-related concepts. Two locations with markedly different solar conditions are considered (Finland and Morocco), in which Morocco was found to be the most economically competitive for the cultivation of microalgae in open ponds and closed systems (1.4 and 1.9 € kg-1, respectively). Biomass production by combined water electrolysis and HOB cultivation results in higher costs for all three considered concepts. Among these, the lowest production cost of 5.3 € kg-1 is associated with grid-assisted electricity use in Finland, while the highest production cost of >9.1 € kg-1 is determined for concepts using solely photovoltaics and/or photoelectrochemical technology for on-site electricity production and solar-energy conversion to H2 by water electrolysis. All assessed concepts are capital intensive. Furthermore, a sensitivity analysis suggests that the production costs of HOB biomass can be lowered down to 2.1 € kg-1 by optimization of the process parameters among which volumetric productivity, electricity strategy, and electricity costs have the highest cost-saving potentials. The study reveals that continuously available electricity and H2 supply are essential for the development of a viable HOB concept due to the capital intensity of the needed technologies. In addition, volumetric productivity is the key parameter that needs to be optimized to increase the economic competitiveness of HOB production.

Thermal conductivity suppression in GaAs-AlAs core-shell nanowire arrays.

Semiconductor nanowire heterostructures have been shown to provide appealing properties for optoelectronics and solid-state energy harvesting by thermoelectrics. Among these nanoarchitectures, coaxial core-shell nanowires have been of primary interest due to their electrical functionality, as well as intriguing phonon localization effects in the surface-dominated regime predicted via atomic simulations. However, experimental studies on the thermophysical properties of III-V semiconductor core-shell nanowires remain scarce regardless of the ubiquitous nature of these compounds in solid-state applications. Here, we present thermal conductivity measurements of the arrays of GaAs nanowires coated with AlAs shells. We unveil a strong suppression in thermal transport facilitated by the AlAs shells, up to ∼60%, producing a non-monotonous dependence of thermal conductivity on the shell thickness. Such translation of the novel heat transport phenomena to macroscopic nanowire arrays paves the way for rational thermal design in nanoscale applications.

Anderson Localization Quenches Thermal Transport in Aperiodic Superlattices.

We show that aperiodic superlattices exhibit intriguing interplay between phononic coherent wave interference effects and incoherent transport. In particular, broadband Anderson localization results in a drastic thermal conductivity reduction of 98% at room temperature, providing an ultralow value of 1.3 W m^{-1} K^{-1}, and further yields an anomalously large thermal anisotropy ratio of ∼10^{2} in aperiodic Si/Ge superlattices. A maximum in the thermal conductivity emerges as an unambiguous consequence of phonon Anderson localization at a system length scale bridging the extended and localized transport regimes. The frequency-resolved picture, combined with our lattice dynamical description of Anderson localization, elucidates the rich transport characteristics in these systems and the potential of correlated disorder for sub- to few-THz phononic engineering of heat transport in thermoelectric applications.

CuI p-type thin films for highly transparent thermoelectric p-n modules.

Developments in thermoelectric (TE) transparent p-type materials are scarce and do not follow the trend of the corresponding n-type materials - a limitation of the current transparent thermoelectric devices. P-type thermoelectric thin films of CuI have been developed by three different methods in order to maximise optical transparency (>70% in the visible range), electrical (σ = 1.1 × 104 Sm-1) and thermoelectric properties (ZT = 0.22 at 300 K). These have been applied in the first planar fully transparent p-n type TE modules where gallium-doped zinc oxide (GZO) thin films were used as the n-type element and indium thin oxide (ITO) thin films as electrodes. A thorough study of power output in single elements and p-n modules electrically connected in series and thermally connected in parallel is inclosed. This configuration allows for a whole range of highly transparent thermoelectric applications.

Excitation-dependent fluorescence from atomic/molecular layer deposited sodium-uracil thin films.

Atomic/molecular layer deposition (ALD/MLD) offers unique possibilities in the fabrication of inorganic-organic thin films with novel functionalities. Especially, incorporating nucleobases in the thin-film structures could open new avenues in the development of bio-electronic and photonic devices. Here we report an intense blue and widely excitation-dependent fluorescence in the visible region for ALD/MLD fabricated sodium-uracil thin films, where the crystalline network is formed from hydrogen-bonded uracil molecules linked via Na atoms. The excitation-dependent fluorescence is caused by the red-edge excitation shift (REES) effect taking place in the red-edge of the absorption spectrum, where the spectral relaxation occurs in continuous manner as demonstrated by the time-resolved measurements.

Optimization of Cuprous Oxides Thin Films to be used as Thermoelectric Touch Detectors.

The electronic and optical properties of p-type copper oxides (CO) strongly depend on the production technique as it influences the obtained phases: cuprous oxide (Cu2O) or cupric oxide (CuO), the most common ones. Cu films deposited by thermal evaporation have been annealed in air atmosphere, with temperature between 225 and 375 °C and time between 1 and 4 h. The resultant CO films have been studied to understand the influence of processing parameters in the thermoelectric, electrical, optical, morphological, and structural properties. Films with a Cu2O single phase are formed when annealing at 225 °C, while CuO single phase films can be obtained at 375 °C. In between, both phases are obtained in proportions that depend on the film thickness and annealing time. The positive sign of the Seebeck coefficient (S), measured at room temperature (RT), confirms the p-type behavior of both oxides, showing values up to 1.2 mV·°C-1 and conductivity up to 2.9 (Ω·m)-1. A simple detector using Cu2O have been fabricated and tested with fast finger touch events.

Silicon dioxide mask by plasma enhanced atomic layer deposition in focused ion beam lithography.

In this work, focused ion beam (FIB) lithography was developed for plasma enhanced atomic layer deposited (PEALD) silicon dioxide SiO2 hard mask. The PEALD process greatly decreases the deposition temperature of the SiO2 hard mask. FIB Ga+ ion implantation on the deposited SiO2 layer increases the wet etch resistivity of the irradiated region. A programmed exposure in FIB followed by development in a wet etchant enables the precisely defined nanoscale patterning. The combination of FIB exposure parameters and the development time provides greater freedom for optimization. The developed process provides high pattern dimension accuracy over the tested range of 90-210 nm. Utilizing the SiO2 mask developed in this work, silicon nanopillars with 40 nm diameter were successfully fabricated with cryogenic deep reactive ion etching and the aspect ratio reached 16:1. The fabricated mask is suitable for sub-100 nm high aspect ratio silicon structure fabrication.

Thermal conductivity of amorphous Al2O3/TiO2 nanolaminates deposited by atomic layer deposition.

The thermophysical properties of Al2O3/TiO2 nanolaminates deposited by atomic layer deposition (ALD) are studied as a function of bilayer thickness and relative TiO2 content (0%-100%) while the total nominal thickness of the nanolaminates was kept at 100 nm. Cross-plane thermal conductivity of the nanolaminates is measured at room temperature using the nanosecond transient thermoreflectance method. Based on the measurements, the nanolaminates have reduced thermal conductivity as compared to the pure amorphous thin films, suggesting that interfaces have a non-negligible effect on thermal transport in amorphous nanolaminates. For a fixed number of interfaces, we find that approximately equal material content of Al2O3 and TiO2 produces the lowest value of thermal conductivity. The thermal conductivity reduces with increasing interface density up to 0.4 nm(-1), above which the thermal conductivity is found to be constant. The value of thermal interface resistance approximated by the use of diffuse mismatch model was found to be 0.45 m(2) K GW(-1), and a comparative study employing this value supports the interpretation of non-negligible interface resistance affecting the overall thermal conductivity also in the amorphous limit. Finally, no clear trend in thermal conductivity values was found for nanolaminates grown at different deposition temperatures, suggesting that the temperature in the ALD process has a non-trivial while modest effect on the overall thermal conductivity in amorphous nanolaminates.

Large-area thermoelectric high-aspect-ratio nanostructures by atomic layer deposition.

We report on the thermoelectric properties of large-area high-aspect-ratio nanostructures. We fabricate the structures by atomic layer deposition of conformal ZnO thin films on track-etched polycarbonate substrate. The resulting structure consists of ZnO tubules which continue through the full thickness of the substrate. The electrical and thermal properties of the structures are studied both in-plane and out-of-plane. They exhibit very low out-of-plane thermal conductivity down to 0.15 W m(-1) K(-1) while the in-plane sheet resistance of the films was found to be half that of the same film on glass substrate, allowing material-independent doubling of output power of any planar thin-film thermoelectric generator. The wall thickness of the fabricated nanotubes was varied within a range of up to 100 nm. The samples show polycrystalline nature with (002) preferred crystal orientation.

Broadband laser polarization control with aligned carbon nanotubes.

We introduce a simple approach to fabricate an aligned carbon nanotube (ACNT) device for broadband polarization control in fiber laser systems. The ACNT device was fabricated by pulling from as-fabricated vertically-aligned carbon nanotube arrays. Their anisotropic properties are confirmed with various microscopy techniques. The device was then integrated into fiber laser systems (at two technologically important wavelengths of 1 and 1.5 µm) for polarization control. We obtained a linearly-polarized light output with the maximum extinction ratio of ∼12 dB. The output polarization direction could be fully controlled by the ACNT alignment direction in both lasers. To the best of our knowledge, this is the first time that the ACNT device is applied to polarization control in laser systems. Our results exhibit that the ACNT device is a simple, low-cost, and broadband polarizer to control laser polarization dynamics, for various photonic applications (such as material processing, polarization diversity detection in communications etc.), where linear polarization control is necessary.

Measurement of thin film thermal conductivity using the laser flash method.

We present a method to measure the in-plane thermal conductivity of thin films by the laser flash technique. The method uses a well-defined structure for the analysis. We have realized the structure by conformal deposition of ZnO films of different thicknesses using atomic layer deposition onto a 20 µm thick ion track etched polycarbonate membrane as substrate. By using this procedure we could determine the thermal conductivity of the deposited thin film from the total thermal diffusivity of the nanocomposite structures. The method has been used to obtain the in-plane thermal conductivity of the deposited ZnO layers within the thickness range of less than 100 nm.

High-quality crystallinity controlled ALD TiO2 for waveguiding applications.

We demonstrate a novel atomic layer deposition (ALD) process to make high-quality nanocrystalline titanium dioxide (TiO(2)) with intermediate Al(2)O(3) layers to limit the crystal size. The process is based on titanium chloride (TiCl(4))+water and trimethyl aluminum (TMA)+ozone processes at 250°C deposition temperature. The waveguide losses measured using a prism coupling method for 633 and 1551 nm wavelengths are as low as 0.2±0.1 dB/mm with the smallest crystal size, with losses increasing with crystal size. In comparison, plain TiO(2) deposited at 250°C without the intermediate Al(2)O(3) layers shows high scattering losses and is not viable as waveguide material. The third-order optical nonlinearity decreases with smaller crystal size as verified by third-harmonic generation microscopy but still remains high for all samples. Crystallinity controlled ALD-grown TiO(2) is an excellent candidate for various optical applications, where good thermal stability and high third-order optical nonlinearity are needed.

Aluminum oxide mask fabrication by focused ion beam implantation combined with wet etching.

A novel aluminum oxide (Al2O3) hard mask fabrication process with nanoscale resolution is introduced. The Al2O3 mask can be used for various purposes, but in this work it was utilized for silicon patterning using cryogenic deep reactive ion etching (DRIE). The patterning of Al2O3 is a two-step process utilizing focused ion beam (FIB) irradiation combined with wet chemical etching. Gallium (Ga(+)) FIB maskless patterning confers wet etch selectivity between the irradiated region and the non-irradiated one on the Al2O3 layer, and mask patterns can easily be revealed by wet etching. This method is a modification of Ga(+) FIB mask patterning for the silicon etch stop, which eliminates the detrimental lattice damage and doping of the silicon substrate in critical devices. The shallow surface gallium FIB irradiated Al2O3 mask protects the underlying silicon from Ga(+) ions. The performance of the masking capacity was tested by drawing pairs consisting of a line and an empty space with varying width. The best result was seven such pairs for 1 µm. The smallest half pitch was 59 nm. This method is capable of arbitrary pattern generation. The fabrication of a freestanding single-ended tuning fork resonator utilizing the introduced masking method is demonstrated.

The fabrication of silicon nanostructures by focused-ion-beam implantation and TMAH wet etching.

Local gallium implantation of silicon by a focused ion beam (FIB) has been used to create a mask for anisotropic tetramethylammonium hydroxide (TMAH) wet etching. The dependence of the etch stop properties of gallium-doped silicon on the implanted dose has been investigated and a dose of 4 x 10(13) ions cm(- 2) has been determined to be the threshold value for achieving observable etching resistance. Only a thin, approx. 50 nm, surface layer is found to be durable enough to serve as a mask with a high selectivity of at least 2000:1 between implanted and non-implanted areas. The combined FIB-TMAH process has been used to generate various types of 3D nanostructures including nanochannels separated by thin vertical sidewalls with aspect ratios up to 1:30, ultra-narrow (approx. 25 nm) freestanding bridges and cantilevers, and gratings with a resolution of 20 lines microm(- 1).