Polyoxometalates (POMs) are a subset of metal oxides that represent a diverse range of molecular clusters with an almost unmatched range of physical properties and the ability to form dynamic structures that can range in size from the nano- to the micrometer scale Herein we present the very latest developments from synthesis to structure and function of POMs We discuss the possibilities of creating highly sophisticated functional hierarchical systems with multiple, interdependent, functionalities along with a critical analysis that allows the non-specialist to learn the salient features We propose and present a "periodic table of polyoxometalate building blocks" We also highlight some of the current issues and challenges that need to be addressed to work towards the design of functional systems based upon POM building blocks and look ahead to possible emerging application areas

Polyoxometalates: Building Blocks for Functional Nanoscale Systems

One-dimensional (1D) ZnO nanostructures have been studied intensively and extensively over the last decade not only for their remarkable chemical and physical properties, but also for their current and future diverse technological applications. This article gives a comprehensive overview of the progress that has been made within the context of 1D ZnO nanostructures synthesized via wet chemical methods. We will cover the synthetic methodologies and corresponding growth mechanisms, different structures, doping and alloying, position-controlled growth on substrates, and finally, their functional properties as catalysts, hydrophobic surfaces, sensors, and in nanoelectronic, optical, optoelectronic, and energy harvesting devices.

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One-dimensional ZnO nanostructures: Solution growth and functional properties

The III-nitrides include the semiconductors AlN, GaN and InN, which have band gaps spanning the entire UV and visible ranges. Thin films of III-nitrides are used to make UV, violet, blue and green light-emitting diodes and lasers, as well as solar cells, high-electron mobility transistors (HEMTs) and other devices. However, the film growth process gives rise to unusually high strain and high defect densities, which can affect the device performance. X-ray diffraction is a popular, non-destructive technique used to characterize films and device structures, allowing improvements in device efficiencies to be made. It provides information on crystalline lattice parameters (from which strain and composition are determined), misorientation (from which defect types and densities may be deduced), crystallite size and microstrain, wafer bowing, residual stress, alloy ordering, phase separation (if present) along with film thicknesses and superlattice (quantum well) thicknesses, compositions and non-uniformities. These topics are reviewed, along with the basic principles of x-ray diffraction of thin films and areas of special current interest, such as analysis of non-polar, semipolar and cubic III-nitrides. A summary of useful values needed in calculations, including elastic constants and lattice parameters, is also given. Such topics are also likely to be relevant to other highly lattice-mismatched wurtzite-structure materials such as heteroepitaxial ZnO and ZnSe.

https://iopscience.iop.org/article/10.1088/0034-4885/72/3/036502/pdf

X-ray diffraction of III-nitrides

Polyoxometalates (POMs) have remarkable properties and a great deal of potential to meet contemporary societal demands regarding health, environment, energy and information technologies. However, implementation of POMs in various functional architectures, devices or materials requires a processing step. Most developments have considered the exchange of POM counterions in an electrostatically driven approach: immobilization of POMs on electrodes and other surfaces including oxides, embedding in polymers, incorporation into Layer-by-Layer assemblies or Langmuir–Blodgett films and hierarchical self-assembly of surfactant-encapsulated POMs have thus been thoroughly investigated. Meanwhile, the field of organic–inorganic POM hybrids has expanded and offers the opportunity to explore the covalent approach for the organization or immobilization of POMs. In this critical review, we focus on the use of POM hybrids in selected fields of applications such as catalysis, energy conversion and molecular nanosciences and we endeavor to discuss the impact of the covalent approach compared to the electrostatic one. The synthesis of organic–inorganic POM hybrids starting from bare POMs, that is the direct functionalization of POMs, is well documented and reliable and efficient synthetic procedures are available. However, as the complexity of the targeted functional system increases a multi-step strategy relying on the post-functionalization of preformed hybrid POM platforms could prove more appealing. In the second part of this review, we thus survey the synthetic methodologies of post-functionalization of POMs and critically discuss the opportunities it offers compared to direct functionalization.

Functionalization and post-functionalization: a step towards polyoxometalate-based materials

Polyoxometalates (POMs) are a subset of metal oxides with unique physical and chemical properties, which can be reliably modified through various techniques and methods to develop sophisticated materials and devices. In parallel with the large number of new crystal structures reported in the literature, the application of these POMs towards multifunctional materials has attracted considerable attention. This critical review summarizes recent progress on POM-based molecular and composite materials, and particularly highlights the emerging areas that are closely related to surface, electronic, energy, environment, life science, etc. (171 references).

Recent advances on polyoxometalate-based molecular and composite materials

In situ stress monitoring has been employed during metalorganic chemical vapor deposition of AlGaN/GaN distributed Bragg reflectors (DBRs). It was found that the insertion of multiple AlN interlayers is effective in converting the tensile growth stress typically observed in this system into compression, thus alleviating the problem of crack generation. Crack-free growth of a 60 pair Al0.20Ga0.80N/GaN quarter-wavelength DBR was obtained over the entire 2 in. wafer; an accompanying reflectivity of at least 99% was observed near the peak wavelength around 380 nm.

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Stress Engineering During Metalorganic Chemical Vapor Deposition of AlGaN/GaN Distributed Bragg Reflectors

We have designed and implemented a monolithic, dual-wavelength blue/green light emitting diode (LED) consisting of two active indium gallium nitride/gallium nitride (InGaN/GaN) multiple-quantum-well segments. The segments are part of a single vertical epitaxial structure in which a p++/n++ InGaN/GaN tunnel junction is inserted between the LEDs, emitting in this proof-of-concept device at 470 nm and 535 nm, respectively. The device has been operated as a three-terminal device with independent electrical control of each LEDs to a nanosecond time scale.

A dual-wavelength indium gallium nitride quantum well light emitting diode

Hybrid organic–inorganic films consisted of molecular layers of a Keggin-structure polyoxometalate (POM: 12-tungstophosphoric acid, H3PW12O40) and 1,12-diaminododecane (DD) on 3-aminopropyl triethoxysilane (APTES)-modified silicon surface, fabricated via the layer-by-layer (LBL) self-assembly method are evaluated as molecular materials for electronic devices. The effect of the fabrication process parameters, including primarily compositions of deposition solutions, on the structural characteristics of the POM-based multilayers was studied extensively with a combination of spectroscopic methods (UV, FTIR, and XPS). Well-characterized POM-based films (both single-layers and multilayers) in a controlled and reproducible way were obtained. The conduction mechanisms in single-layered and multilayered structures were elucidated by the electrical characterization of the produced films supported by the appropriate theoretical analysis. Fowler−Nordheim (FN) tunneling and percolation mechanisms were encountered in ...

Polyoxometalate-based layered structures for charge transport control in molecular devices.

We have designed and implemented a vertical cavity violet light emitting diode which features an optical resonator composed of an in situ grown GaN/AlGaN DBR and a high reflectivity dielectric mirror. The active InGaN MQW medium is grown directly atop the AlGaN DBR and the structure includes an intracavity lateral current spreading layer based on a p++/n++ InGaN/GaN tunnel junction. Electroluminescence shows directional emission, with modal linewidths as narrow as 0.6 nm.

Vertical cavity violet light emitting diode incorporating an aluminum gallium nitride distributed Bragg mirror and a tunnel junction

We report on the development of UV light-emitting diodes in the 340nm wavelength range, based on quaternary AlGaInN quantum-well active media. Output powers up to 1mW from small area devices (<100μm diameter) directly off a planar chip have been achieved. The devices have been operated as subnanosecond pulsed sources to demonstrate their applicability to compact time-resolved fluorescence spectroscopy.

Eleni Makarona

Papers

Stress Engineering During Metalorganic Chemical Vapor Deposition of AlGaN/GaN Distributed Bragg Reflectors

A dual-wavelength indium gallium nitride quantum well light emitting diode

Polyoxometalate-based layered structures for charge transport control in molecular devices.

Vertical cavity violet light emitting diode incorporating an aluminum gallium nitride distributed Bragg mirror and a tunnel junction

Ultraviolet light-emitting diodes operating in the 340 nm wavelength range and application to time-resolved fluorescence spectroscopy