Transparent conductors as solar energy materials: A panoramic review

Hydrogen sensors are of increasing importance in connection with the development and expanded use of hydrogen gas as an energy carrier and as a chemical reactant. There are an immense number of sensors reported in the literature for hydrogen detection and in this work these sensors are classified into eight different operating principles. Characteristic performance parameters of these sensor types, such as measuring range, sensitivity, selectivity and response time are reviewed and the latest technology developments are reported. Testing and validation of sensor performance are described in relation to standardisation and use in potentially explosive atmospheres so as to identify the requirements on hydrogen sensors for practical applications.

Hydrogen Sensors - A review

Electrochromic (EC) materials are able to change their optical properties, reversibly and persistently, by the application of an electrical voltage. These materials can be integrated in multilayer devices capable of modulating the optical transmittance between widely separated extrema. We first review the recent literature on inorganic EC materials and point out that today's research is focused on tungsten oxide (colouring under charge insertion) and nickel oxide (colouring under charge extraction). The properties of thin films of these materials are then discussed in detail with foci on recent results from two comprehensive investigations in the authors' laboratory. A logical exposition is obtained by covering, in sequence, structural features, thin film deposition (by sputtering), electronic band structure, and ion diffusion. A novel conceptual model is given for structural characteristics of amorphous W oxide films, based on notions of defects in the ideal amorphous state. It is also shown that the conduction band density of states is obtainable from simple electrochemical chronopotentiometry. Ion intercalation causes the charge-compensating electrons to enter localized states, implying that the optical absorption underlying the electrochromism can be described as ensuing from transitions between occupied and empty localized conduction band states. A fully quantitative theory of such transitions is not available, but the optical absorption can be modeled more phenomenologically as due to a superposition of transitions between different charge states of the W ions (6+, 5+, and 4+). The Ni oxide films were found to have a porous structure comprised of small grains. The data are consistent with EC coloration being a surface phenomenon, most likely confined to the outer parts of the grains. Initial electrochemical cycling was found to transform hydrated Ni oxide into hydroxide and oxy-hydroxide phases on the grain surfaces. Electrochromism in thus stabilized films is consistent with reversible changes between Ni hydroxide and oxy-hydroxide, in accordance with the Bode reaction scheme. An extension of this model is put forward to account for changes of NiO to Ni2O3. It was demonstrated that electrochromism is associated solely with proton transfer. Data on chemical diffusion coefficients are interpreted for polycrystalline W oxide and Ni oxide in terms of the lattice gas model with interaction. The later part of this review is of a more technological and applications oriented character and is based on the fact that EC devices with large optical modulation can be accomplished essentially by connecting W-oxide-based and Ni-oxide-based films through a layer serving as a pure ion conductor. Specifically, we treat methods to enhance the bleached-state transmittance by mixing the Ni oxide with other oxides characterized by wide band gaps, and we also discuss pre-assembly charge insertion and extraction by facile gas treatments of the films, as well as practical device manufacturing and device testing. Here the emphasis is on novel flexible polyester-foil-based devices. The final part deals with applications with emphasis on architectural “smart” windows capable of achieving improved indoor comfort jointly with significant energy savings due to lowered demands for space cooling. Eyewear applications are touched upon as well.

/pdf/electrochromics-for-smart-windows-thin-films-of-tungsten-aw0rai8h60.pdf

Electrochromics for smart windows: thin films of tungsten oxide and nickel oxide, and devices based on these

http://nathan.instras.com/MyDocsDB/doc-617.pdf

Electrochromic organic and polymeric materials for display applications

Magnetic flux can penetrate a type-II superconductor in the form of Abrikosov vortices (also called flux lines, flux tubes, or fluxons) each carrying a quantum of magnetic flux phi 0=h/2e. These tiny vortices of supercurrent tend to arrange themselves in a triangular flux-line lattice (FLL), which is more or less perturbed by material inhomogeneities that pin the flux lines, and in high-Tc superconductors (HTSCs) also by thermal fluctuations. Many properties of the FLL are well described by the phenomenological Ginzburg-Landau theory or by the electromagnetic London theory, which treats the vortex core as a singularity. In Nb alloys and HTSCs the FLL is very soft mainly because of the large magnetic penetration depth lambda . The shear modulus of the FLL is c66~1/ lambda 2, and the tilt modulus c44(k)~(1+k2 lambda 2)-1 is dispersive and becomes very small for short distortion wavelengths 2 pi /k<< lambda . This softness is enhanced further by the pronounced anisotropy and layered structure of HTSCs, which strongly increases the penetration depth for currents along the c axis of these (nearly uniaxial) crystals and may even cause a decoupling of two-dimensional vortex lattices in the Cu-O layers. Thermal fluctuations and softening may `melt` the FLL and cause thermally activated depinning of the flux lines or ofthe two-dimensional `pancake vortices` in the layers. Various phase transitions are predicted for the FLL in layered HTSCs. Although large pinning forces and high critical currents have been achieved, the small depinning energy so far prevents the application of HTSCs as conductors at high temperatures except in cases when the applied current and the surrounding magnetic field are small.

https://iopscience.iop.org/article/10.1088/0034-4885/58/11/003/pdf

The flux-line lattice in superconductors

IN many substances, changes in chemical composition, pressure or temperature can induce metal-to-insulator transitions1. Although dramatic changes in optical and electrical properties accompany such transitions, their interpretation is often complicated by attendant changes in crystallographic structure2. Yttrium, lanthanum and the trivalent rare-earth elements form hydrides that also exhibit metal–insulator transitions3–5, but the extreme reactivity and fragility of these materials hinder experimental studies5,6. To overcome these difficulties, we have coated thin films of yttrium and lanthanum with a layer of palladium through which hydrogen can diffuse. Real-time transitions from metallic (YH2 or LaH2) to semiconducting (YH3 or LaH3) behaviour occur in these films during continuous absorption of hydrogen, accompanied by pronounced changes in their optical properties. Although the timescale on which this transition occurs is at present rather slow (a few seconds), there appears to be considerable scope for improvement through the choice of rare-earth element and by adopting electrochemical means for driving the transition. In view of the spectacular changes in optical properties—yttrium hydride, for example, changes from a shiny mirror to a yellow, transparent window—metal hydrides might find important technological applications.

Yttrium and lanthanum hydride films with switchable optical properties

Switchable mirrors1,2,3 made of thin films of the hydrides of yttrium (YHx), lanthanum (LaHx) or rare-earth metals exhibit spectacular changes in their optical properties as x is varied from 0 to 3. For example, α-YHx 2.85 is a yellowish transparent semiconductor. Here we show that this concentration dependence of the optical properties, coupled with the high mobility of hydrogen in metals, offers the possibility of real-time visual observation of hydrogen migration in solids. We explore changes in the optical properties of yttrium films in which hydrogen diffuses laterally owing to a large concentration gradient. The optical transmission profiles along the length of the film vary in such a way as to show that the formation of the various hydride phases is diffusion-controlled. We can also induce electromigration of hydrogen, which diffuses towards the anode when a current flows through the film. Consequently, hydrogen in insulating YH3−δ behaves as a negative ion, in agreement with recent strong-electron-correlation theories4,5. This ability to manipulate the hydrogen distribution (and thus the optical properties) electrically might be useful for practical applications of these switchable mirrors.

Visualization of hydrogen migration in solids using switchable mirrors

Synthesis of yttriumtrihydride films for ex-situ measurements

Thin La1-zYzHx films, in the composition range 0<z<1 and 0<x<3, are studied using x-ray diffraction, dc resistivity measurements, reflectance-transmittance measurements, and ellipsometry in the visible and near-infrared spectral range. For x=0 the structural phase diagram is similar to that of the bulk system. Upon hydrogen absorption and desorption, the La1-zYzHx films do not disproportionate. All dihydrides have a fcc structure with a continuous shift of the lattice parameter, whereas the trihydrides undergo a transition from a fcc lattice structure for 0<z<0.67 to a hexagonal lattice structure for 0.81<z<1. No significant thin-film effects occur in the structural, electrical, and optical properties, whereas disorder effects are observed in the x-ray coherence length, the electron relaxation time at both zero and optical frequencies, and in the optical properties of the trihydrides. In LaH2 a similar dihydride transmission window is observed as in YH2. The suppression of this window upon alloying is a disorder effect. As in the case of their parent materials, all La1-zYzHx alloys (both cubic and hexagonal) exhibit a metal-insulator transition for 2<x<3, which is a clear demonstration of the robustness of the metal-insulator transition in switchable mirrors. The optical band-gap shifts from 1.87±0.03 eV for LaH3 to 2.63±0.03 eV for YH3. The optical properties suggest that the fundamental band gap is 1–1.8 eV lower.

/pdf/structural-electrical-and-optical-properties-of-la1-zyzhx-k2mwmcs1w5.pdf

N.J. Koeman

Papers

Yttrium and lanthanum hydride films with switchable optical properties

Yttrium and lanthanum hydride films with switchable optical properties

Visualization of hydrogen migration in solids using switchable mirrors

Synthesis of yttriumtrihydride films for ex-situ measurements

Structural, electrical and optical properties of La1-zYzHx switchable mirrors.