Scientists resolve the long-debated issue of the nature and value of the bandgap in hexagonal boron nitride by providing evidence for an indirect bandgap at 5.955 eV and an exciton binding energy of about 130 meV by means of optical spectroscopy.

Hexagonal boron nitride is an indirect bandgap semiconductor

For more than seven decades, hexagonal boron nitride (hBN) has been employed as an inert, thermally stable engineering ceramic; since 2010, it has also been used as the optimal substrate for graphene in nanoelectronic and optoelectronic devices. Recent research has revealed that hBN exhibits a unique combination of optical properties that enable novel (nano)photonic functionalities. Specifically, hBN is a natural hyperbolic material in the mid-IR range, in which photonic material options are sparse. Furthermore, hBN hosts defects that can be engineered to obtain room-temperature, single-photon emission; exhibits strong second-order nonlinearities with broad implications for practical devices; and is a wide-bandgap semiconductor well suited for deep UV emitters and detectors. Inspired by these promising attributes, research on the properties of hBN and the development of large-area bulk and thin-film growth techniques has dramatically expanded. This Review offers a snapshot of current research exploring the properties underlying the use of hBN for future photonics functionalities and potential applications, and covers some of the remaining obstacles. Hexagonal boron nitride (hBN) is highly sought after for mid-IR nanophotonics, nonlinear and quantum optics, and as an efficient UV emitter. This Review surveys its fundamental physical properties, applications and synthesis.

Photonics with hexagonal boron nitride

A handheld and battery-operated far-ultraviolet plane-emission device is demonstrated. The device has low current consumption and stable operation at an output power of 0.2 mW at 225 nm, and may be useful in photochemical and biotechnological applications such as photo catalysis, sterilization and the modification of chemical substances.

Far-ultraviolet plane-emission handheld device based on hexagonal boron nitride

ZnGa2O4:Cr3+ is shown to be a new bright red UV excited long-lasting phosphor potentially suitable for in vivo imaging due to its 650 nm-750 nm emission range. Photoluminescence and X-ray excited radioluminescence show the 2E → 4A2 emission lines of both ideal Cr3+ and Cr3+ distorted by a neighboring antisite defect while long-lasting phosphorescence (LLP) and thermally stimulated luminescence (TSL) almost exclusively occur via distorted Cr3+. The most intense LLP is obtained with a nominal Zn deficiency and is related to a TSL peak at 335K. A mechanism for LLP and TSL is proposed, whereby the antisite defect responsible for the distortion at Cr3+ acts as a deep trap.

ZnGa2O4:Cr3+: a new red long-lasting phosphor with high brightness

© 2020 The Author(s). We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resourceconsuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown.

Production and processing of graphene and related materials

This paper reports on the ZnCa{sub 2}O{sub 4} phosphor investigated for its application to vacuum fluorescent displays (VFDs) utilizing low-voltage cathodoluminescence. It is expected that this oxide phosphor does not cause damage to filaments in VFD's, while it is a serious problem for conventional sulfide phosphors. This phosphor shows blue luminescence with a spectral peak at with 470 nm and a chromaticity at X = 0.170 and Y = 0.130. A luminous efficiency of 0.7 lm/W has been obtained, when the VFD with this phosphor is operated at 30 V dc. The results of high-temperature operating life test have proven the excellent stability of VFDs utilizing this phosphor.

The ZnGa2 O 4 Phosphor for Low‐Voltage Blue Cathodoluminescence

Planar vacuum-fluorescent-display devices emitting polarized UV-C, blue, and green light are demonstrated using immiscible Al1-x Inx N nanostructures grown in nonpolar m-directions. Despite the presence of high concentration of nonradiative recombination centers, the Al1-x Inx N nanostructures emit polarized light with the luminescence lifetimes of 22-32 ps at 300 K. This defect-resistant radiative performance suggests supernormal localized characteristics of electron-hole pairs.

Defect‐Resistant Radiative Performance of m‐Plane Immiscible Al1−xInxN Epitaxial Nanostructures for Deep‐Ultraviolet and Visible Polarized Light Emitters

Hexagonal boron nitride as a new ultraviolet luminescent material and its application—Fluorescence properties of hBN single-crystal powder ☆☆

— FEDs are one of the attractive flat-panel displays that realize high-quality motion images and low power consumption. FEDs are constructed by using three elemental technologies: micro- or nano-fabrication technology of emitters, opto-electronic semiconductor technology of anode patterns, and vacuum packaging technology. Each of the three elemental technologies is essential to realize FEDs. The present status of each three technologies, especially the improvement of Spindt-type field emitters, the trend of flat vacuum packages, and development of phosphors for FEDs is described in this paper.

Development of field-emission displays

A method for preparing a gallium nitride phosphor which is capable of emitting light at luminance increased to a degree sufficient to permit the phosphor to be practically used. A dopant compound containing elements reacted with H 2 and gasified by heating is arranged on an upstream side in a calcination oven in which NH 3 is flowed and a matrix element compound is arranged on the downstream side therein, resulting in calcination of the compound being carried out. This permits GaN to be surrounded with ammonia and the dopant during the calcination, so that the GaN phosphor may be fully doped with the dopant.

Yoshitaka Sato

Papers

The ZnGa2 O 4 Phosphor for Low‐Voltage Blue Cathodoluminescence

Defect‐Resistant Radiative Performance of m‐Plane Immiscible Al1−xInxN Epitaxial Nanostructures for Deep‐Ultraviolet and Visible Polarized Light Emitters

Hexagonal boron nitride as a new ultraviolet luminescent material and its application—Fluorescence properties of hBN single-crystal powder ☆☆

Development of field-emission displays

Method for preparing gallium nitride phosphor