Laser Floating Zone: General Overview Focusing on the Oxyorthosilicates Growth

This chapter reviews the laser floating zone (LFZ) technique, also known as the laser-heated pedestal growth (LHPG), focusing on the recently produced rare-earth-doped oxyorthosilicate fibers. LFZ has been revealed as a suitable prototyping technique since high-quality crystals can be developed in short time with low consumption of precursor materials in a crucible-free processing that ensures to practically avoid by-products. Moreover, additional advantages are the possibility to treat and melt highly refractory materials together with the easy way for tailoring the final microstructural characteristics and this way the macroscopic physical properties. Thus, refractory rare-earth (RE) doped oxyorthosilicates following the formula RE2SiO5 have been recently produced by the LFZ technique for tuning laser emission parameters. The oxyorthosilicates have high chemical stability and allow incorporation of many rare-earth ions yielding different applications, such as laser host materials, gamma ray detectors or scintillators, environmental barrier coatings (EBCs) and waveguides, among others. Thus, different kinds of oxyorthosilicates were produced by the LFZ technique, and the detailed effects of the main processing parameters on crystal’s characteristics are discussed in this chapter

A review on the laser-assisted flow deposition method: growth of ZnO micro and nanostructures

Zinc oxide (ZnO) is a widely versatile semiconductor with major importance from the technological point of view, presenting the advantage to be grown by a large number of techniques and with one of the richest varieties of morphologies. Due to the special interest of this semiconductor, several methods have been developed to control the production of its nanostructures. Herein, we report the development of a vapour-based method, designated by laser-assisted flow deposition (LAFD), able of producing ZnO micro and nanocrystals with different morphologies, with a high crystalline and optical quality. This new process allows high yield of ZnO production, showing great prospects for scalable applications. In the present work, we review in detail the main growth parameters and their relationship with the produced morphologies, in addition to their influence in the structural and optical properties. Furthermore, an assessment of the possible growth mechanisms that may be involved in this new method is reported. Some potential applications of the ZnO structures produced by LAFD were also evaluated, with focus on the photocatalysis and photovoltaic fields. Additionally, the possibility of synthesizing ZnO composite nanostructures, as well as the growth of other metal oxides using this technique was explored.publishe

Production of graphene in solution by unzipping of carbon nanotubes

Chemical modification of the outer graphene layer of carbon nanotubes is an approach increasingly used, mainly to overcome the problem of interfacial bonding with different materials. The effect of functionalization of CNT under different conditions, using the 1,3-dipolar cycloaddition reaction [1], was studied by Scanning Tunneling Microscopy (STM). STM demonstrated the potential for unzipping of the outer graphene layer of CNT modified by the 1,3-dipolar cycloaddition reaction [2]. The unzipping of graphene ribbons from the functionalized CNT was imaged under STM conditions. The present work reports the formation of graphene in solution by unzipping of functionalized CNT. The solutions prepared were studied by UV-Visible and Raman spectroscopy, and electron microscopy. Solutions of exfoliated graphite prepared under similar conditions were studied for comparison

Laser-induced graphene from paper for non-enzymatic uric acid electrochemical sensing in urine

This work was developed within the scope of project i3N (LA/P/0037/2020. I.P. N. F. Santos thanks i3N for the BPD Grant BPD/UI96/5177/2020. S. O. Pereira thanks i3N for the BPD Grant BPD/UI96/5808/2017. The authors also thank Jonas Deuermeier for the XPS measurements. Publisher Copyright: © 2022 Elsevier LtdLaser-induced graphene from paper (paper-LIG) was applied in non-enzymatic electrochemical sensing of uric acid (UA) in human urine. Paper-LIG was formed by CO2 laser modification of paper into a 3D graphene arrangement. Kinetic analysis of paper-LIG electrodes returned effective heterogeneous electron transfer standard rate constants of 1.4 × 10−3 cm s−1 and 7.8 × 10−4 cm s−1 for [Ru(NH3)6]2+/3+ and [Fe(CN)6]4−/3− redox probes, respectively. These electrodes were able to detect and quantify uric acid in PBS within the 10–300 μM range at pH between 5.6 and 7.4. At pH 7.4, a linear response (R2 = 0.999) from 10 to 250 μM was achieved, with a limit of detection of 3.97 μM and a sensitivity of 0.363 μA cm−2 μM−1. Paper-LIG electrodes denoted adequate selectivity in synthetic urine as well as in ascorbic acid (AA) and dopamine (DA)-containing electrolytes. Determination of urinary UA content in human samples returned a concentration of c.a. 1.8–1.9 mM, within the range for healthy individuals. Recoveries of samples spiked with 50 and 100 μM UA were 100.6% and 95.4%, respectively, with satisfactory reproducibility and stability. These cheap, lightweight, flexible, and eco-friendly paper-LIG biosensors for non-enzymatic quantification of UA in human urine pave the way to widespread application in the detection of other important biomarkers.publishersversionpublishe

Laser floating zone growth: Overview, singular materials, broad applications, and future perspectives

The Laser Floating Zone (LFZ) technique, also known as Laser-Heated Pedestal Growth (LHPG), has been developed throughout the last several decades as a simple, fast, and crucible-free method for growing high-crystalline-quality materials, particularly when compared to the more conventional Verneuil, Bridgman-Stockbarger, and Czochralski methods. Multiple worldwide efforts have, over the years, enabled the growth of highly oriented polycrystalline and single-crystal high-melting materials. This work attempted to critically review the most representative advancements in LFZ apparatus and experimental parameters that enable the growth of high-quality polycrystalline materials and single crystals, along with the most commonly produced materials and their relevant physical properties. Emphasis will be given to materials for photonics and optics, as well as for electrical applications, particularly superconducting and thermoelectric materials, and to the growth of metastable phases. Concomitantly, an analysis was carried out on how LFZ may contribute to further understanding equilibrium vs. non-equilibrium phase selectivity, as well as its potential to achieve or contribute to future developments in the growth of crystals for emerging applications

Nd:YAG laser scribed zinc oxide on semi-flexible copper foils

In this work, a novel approach to synthesise zinc oxide (ZnO) directly on flexible copper substrates is proposed. The produced samples show a foam-like morphology made of agglomerates of small ZnO particles when processed at laser energy density of 18.0 J/cm2. On the other hand, the samples processed at higher beam energy density, i.e. 33.2 J/cm2, resulted in a more granular morphology, with some ZnO particles dispersed over the sample’s surface. Raman spectroscopy measurements demonstrated that this method resulted in the formation of wurtzite-ZnO crystalline phase in all samples. Room temperature photoluminescence spectroscopy analysis revealed the presence of a broad visible band in the orange-red region dominating the spectra, with a small contribution from the near band edge emission in the UV spectral region. Decreasing the beam energy fluence from 33.2 to 18.0 J/cm2 resulted in samples with higher overall visible band intensity, in line with what was observed for their crystalline quality. Moreover, the shift of the broad band maxima towards longer wavelengths could be an indication of the possibility of tuning the visible emission according to the chosen laser processing conditions.publishe

Formation of graphene nanoribbons in solution

Recently, the formation of graphene by exfoliation of carbon nanotubes (CNT) has shown increasing interest. This process originates graphene nanoribbons (GNR) that are expected to present excellent electrical properties, depending on their width and on their edge shape [1]. Several methods for the unzipping of graphene from CNT were proposed along the past few years [2-6]. These methods often present some limitation, such as low yield of GNR, or extensively oxidized GNR without electrical conductivity. Recently, the formation of GNR was observed “in situ” by unzipping of carbon nanotubes under ultra-high vacuum scanning tunneling microscopy (UHV STM) [7]. The CNT under observation were functionalized by the 1,3-dipolar cycloaddition reaction [8]. This particular functionalization route seems to be responsible for the unzipping of the CNT under STM imaging conditions. The present work demonstrates the formation of GNR in solution by unzipping of functionalized CNT, in different solvents. The GNR thus formed were analyzed by UV-vis and Raman spectroscopy, and by transmission electron spectroscopy. GNR bundles were deposited from an ethanol solution and observed by TEM.Institute for Nanostructures, Nanomodelling and Nanofabrication (I3N

Graphene nanoribbons from carbon nanotubes

Chemical functionalization of the outer graphene layer of carbon nanotubes (CNT) has been increasingly studied, aiming at the application of CNT in different areas. The functionalization of CNT using the 1,3-dipolar cycloaddition reaction, leading to the formation of cyclic amine groups on the CNT surface [1], was observed to induce the unzipping of the CNT under specific conditions. The CNTs thus functionalized were imaged by Scanning Tunneling Microscopy (STM) and the unzipping was observed under STM conditions. The unzipping process was also observed to occur in solution, in different solvents. The graphene nanoribbons thus formed were analyzed by UV-vis and Raman spectroscopy, and by transmission electron spectroscopy. A theoretical interpretation of the unzipping process is under studyInstitute for Nanostructures, Nanomodelling and Nanofabrication (I3N

Thermoelectric oxides: challenges and selected approaches for materials design

Sem resumo disponível.publishe

Optical Studies in Red/NIR Persistent Luminescent Cr‐Doped Zinc Gallogermanate (ZGGO:Cr)

Zn1+xGa2‐2xGexO4 (ZGGO:Cr)‐persistent phosphor, with a molar fraction, x, of x = 0.1, doped with a 0.5% molar of chromium, was synthesised via solid‐state reaction at 1350 °C for 36 h. X‐ray diffraction measurements and Raman spectroscopy evidence a single crystalline phase corresponding to the cubic spinel structure. Room temperature (RT) photoluminescence (PL) and afterglow decay profiles were investigated using above and below bandgap excitation. In both cases, persistent PL was observed for almost 8 h, mainly originating from a Cr3+ defect, the so‐called N2 optical centre. RT PL excitation and diffuse reflectance allow identification of the best pathways of Cr3+ red/NIR emission, as well as estimation of the ZGGO bandgap energy at 4.82 eV. An in‐depth investigation of the observed luminescence at 15 K and temperature‐dependent PL under site‐selective excitation reveals the spectral complexity of the presence of several optically active Cr3+ centres in the ZGGO host that emit in almost the same spectral region. Furthermore, the temperature dependence of the R‐lines’ intensity indicates the existence of thermal populating processes between the different optical centres. Such observations well account for a wide distribution of defect trap levels available for carrier capture/release, as measured by the persistent luminescence decay, from which the carriers are released preferentially to the N2 Cr3+‐related optical centre.publishersversionpublishe