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Luminescent Materials 2017

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Energy Materials".

Deadline for manuscript submissions: closed (31 October 2017) | Viewed by 66149

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Dr. Jonathan Kitchen

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Guest Editor

Chemistry, University of Southampton, Southampton SO17 1BJ, UK

Dr. Robert Elmes

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Guest Editor

Department of Chemistry, Maynooth University, National University of Ireland, Maynooth, Ireland

Special Issue Information

Dear Colleagues,

Luminescent materials have continued to attract the interest of researchers over the past decade, and with many important technological applications for everyday life, the field shows no signs of slowing down.

Applications for luminescent materials traverse the traditional chemical and biological sciences where examples include light emitting technology (LEDs/OLEDs), bio-markers for diagnostics, sensor technologies, solar cells, logic gates/molecular electronics, and cellular imaging agents to name just a few. Similarly, the systems used to create luminescent materials have been constructed using a diverse range of luminophores that include those based purely on organic systems, those based on emissive metals (transition metals and lanthanides) and hybrid mixtures of both. Moreover, luminescent materials can take many forms and, over the past few years there have been many excellent examples reported in the literature including soft materials (e.g., micelles and colloids), nano-particles (e.g., surface functionalised AuNPs), polymers (e.g., biodegradable polymeric biomaterials), gels (e.g., supramolecular organo- and hydro-gels), quantum dots, thin films (e.g., Langmuir-Blodgett monolayers), clays, 2D and 3D network materials (e.g., MOFs/COFs, ordered layered materials), as well as others.

With this Special Issue we aim to highlight some new advances in the field of luminescent materials, from fundamentals aspects through to application and future directions for the field. We would like to take this opportunity to invite contributions from experts in the field where we welcome both original research papers, as well as review articles.

Dr. Jonathan A. Kitchen
Dr. Robert Elmes
Guest Editors

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Keywords

Luminescent materials
Supramolecular Materials
Photoluminescence
Electroluminescence
Chemiluminescence
Lanthanides
Bio-markers
Cellular Imaging
Soft-materials
Polymers
Gels
Sensors
Up-conversion
Quantum Dots
Thin Films
Nano-particles

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Published Papers (12 papers)

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18 pages, 4956 KiB

Open AccessArticle

The Preparation and Optical Properties of Novel LiLa(MoO₄)₂:Sm³⁺,Eu³⁺ Red Phosphor

by Jiaxi Wang, Li Luo, Baoyu Huang, Jingqi He, Wei Zhang, Weiren Zhao and Jianqing Wang

Materials 2018, 11(2), 297; https://doi.org/10.3390/ma11020297 - 14 Feb 2018

Cited by 16 | Viewed by 5560

Abstract

Novel LiLa_1−x−y(MoO₄)₂:xSm³⁺,yEu³⁺ (in short: LL_1−x−yM:xSm³⁺,yEu³⁺) double molybdate red phosphors were synthesized by a solid-state [...] Read more.

Novel LiLa_1−x−y(MoO₄)₂:xSm³⁺,yEu³⁺ (in short: LL_1−x−yM:xSm³⁺,yEu³⁺) double molybdate red phosphors were synthesized by a solid-state reaction at as low temperature as 610 °C. The optimal doping concentration of Sm³⁺ in LiLa_1−x(MoO₄)₂:xSm³⁺ (LL_1−xM:xSm³⁺) phosphor is x = 0.05 and higher concentrations lead to emission quenching by the electric dipole—electric dipole mechanism. In the samples co-doped with Eu³⁺ ions, the absorption spectrum in the near ultraviolet and blue regions became broader and stronger than these of the Sm³⁺ single-doped samples. The efficient energy transfer from Sm³⁺ to Eu³⁺ was found and the energy transfer efficiency was calculated. Under the excitation at 403 nm, the chromaticity coordinates of LL_0.95−yM:0.05Sm³⁺,yEu³⁺ approach to the NTSC standard values (0.670, 0.330) continuously with increasing Eu³⁺ doping concentration. The phosphor exhibits high luminous efficiency under near UV or blue light excitation and remarkable thermal stability. At 150 °C, the integrated emission intensity of the Eu³⁺ remained 85% of the initial intensity at room temperature and the activation energy is calculated to be 0.254 eV. The addition of the LL_0.83M:0.05Sm³⁺,0.12Eu³⁺ red phosphors can improve the color purity and reduce the correlated color temperature of WLED lamps. Hence, LL_1−x−yM:xSm³⁺,yEu³⁺ is a promising WLED red phosphor. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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1577 KiB

Open AccessArticle

Tuning the Photoluminescence of Graphene Quantum Dots by Photochemical Doping with Nitrogen

by Xiaofen Xu, Fuhua Gao, Xiaohua Bai, Fuchi Liu, Wenjie Kong and Ming Li

Materials 2017, 10(11), 1328; https://doi.org/10.3390/ma10111328 - 20 Nov 2017

Cited by 42 | Viewed by 7330

Abstract

Nitrogen-doped graphene quantum dots (NGQDs) were synthesized by irradiating graphene quantum dots (GQDs) in an NH₃ atmosphere. The photoluminescence (PL) properties of the GQDs and the NGQDs samples were investigated. Compared with GQDs, a clear PL blue-shift of NGQDs could be achieved by regulating the irradiating time. The NGQDs obtained by irradiation of GQDs for 70 min had a high N content of 15.34 at % and a PL blue-shift of about 47 nm. This may be due to the fact that photochemical doping of GQDs with nitrogen can significantly enhance the contents of pyridine-like nitrogen, and also effectively decrease the contents of oxygen functional groups of NGQDs, thus leading to the observed obvious PL blue-shift. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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6725 KiB

Open AccessArticle

Co-Precipitation Synthesis and Optical Properties of Mn⁴⁺-Doped Hexafluoroaluminate w-LED Phosphors

by Tim Senden, Robin G. Geitenbeek and Andries Meijerink

Materials 2017, 10(11), 1322; https://doi.org/10.3390/ma10111322 - 17 Nov 2017

Cited by 30 | Viewed by 5889

Abstract

Mn⁴⁺-activated hexafluoroaluminates are promising red-emitting phosphors for white light emitting diodes (w-LEDs). Here, we report the synthesis of Na₃AlF₆:Mn⁴⁺, K₃AlF₆:Mn⁴⁺ and K₂NaAlF₆:Mn⁴⁺ phosphors through a simple two-step co-precipitation method. Highly monodisperse large (~20 μm) smoothed-octahedron shaped crystallites are obtained for K₂NaAlF₆:Mn⁴⁺. The large size, regular shape and small size distribution are favorable for application in w-LEDs. All Mn⁴⁺-doped hexafluoroaluminates show bright red Mn⁴⁺ luminescence under blue light excitation. We compare the optical properties of Na₃AlF₆:Mn⁴⁺, K₃AlF₆:Mn⁴⁺ and K₂NaAlF₆:Mn⁴⁺ at room temperature and 4 K. The luminescence measurements reveal that multiple Mn⁴⁺ sites exist in M₃AlF₆:Mn⁴⁺ (M = Na, K), which is explained by the charge compensation that is required for Mn⁴⁺ on Al³⁺ sites. Thermal cycling experiments show that the site distribution changes after annealing. Finally, we investigate thermal quenching and show that the luminescence quenching temperature is high, around 460–490 K, which makes these Mn⁴⁺-doped hexafluoroaluminates interesting red phosphors for w-LEDs. The new insights reported on the synthesis and optical properties of Mn⁴⁺ in the chemically and thermally stable hexafluoroaluminates can contribute to the optimization of red-emitting Mn⁴⁺ phosphors for w-LEDs. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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2204 KiB

Open AccessArticle

Optical Characterization of Nano- and Microcrystals of EuPO₄ Created by One-Step Synthesis of Antimony-Germanate-Silicate Glass Modified by P₂O₅

by Jacek Zmojda, Marcin Kochanowicz, Piotr Miluski, Agata Baranowska, Wojciech A. Pisarski, Joanna Pisarska, Renata Jadach, Maciej Sitarz and Dominik Dorosz

Materials 2017, 10(9), 1059; https://doi.org/10.3390/ma10091059 - 9 Sep 2017

Cited by 13 | Viewed by 4376

Abstract

Technology of active glass-ceramics (GC) is an important part of luminescent materials engineering. The classic method to obtain GC is based on annealing of parent glass in proper temperature and different time periods. Generally, only the bulk materials are investigated as a starting host for further applications. However, the effect of an additional heat-treatment process on emission and structural properties during GC processing is omitted. Here, we focus on the possibility of obtaining transparent glass-ceramic doped with europium ions directly with a melt-quenching method. The influence of phosphate concentration (up to 10 mol %) on the inversion symmetry of local environment of Eu³⁺ ions in antimony-germanate-silicate (SGS) glass has been investigated. The Stark splitting of luminescence spectra and the local asymmetry ratio estimated by relation of (⁵D₀→⁷F₂)/(⁵D₀→⁷F₁) transitions in fabricated glass confirms higher local symmetry around Eu³⁺ ions. Based on XRD and SEM/EDX measurements, the EuPO₄ nano- and microcrystals with monoclinic geometry were determined. Therefore, in our experiment, we confirmed possibility of one-step approach to fabricate crystalline structures (glass-ceramic) in Eu–doped SGS glass without additional annealing process. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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3756 KiB

Open AccessArticle

The Effect of Heat Treatment on the Emission Color of P-Doped Ca₂SiO₄ Phosphor

by Hiromi Nakano, Konatsu Kamimoto, Nobuyuki Yokoyama and Koichiro Fukuda

Materials 2017, 10(9), 1000; https://doi.org/10.3390/ma10091000 - 26 Aug 2017

Cited by 7 | Viewed by 4292

Abstract

In a series of (Ca_2–x/2–yEu_y□_x_/2)(Si_1–xP_x)O₄ (x = 0.06, 0.02 ≤ y ≤0.5), various color-emitting phosphors were successfully synthesized by a solid-state reaction. These phosphors were characterized by photoluminescence (PL) spectroscopy, X-ray powder diffractometry, transmission electron microscopy, and X-ray absorption fine structure spectroscopy. We evaluated the effect of heat treatment on PL properties with various annealing temperatures at 1373–1773 K for 4 h before/after reduction treatment from Eu³⁺ to Eu²⁺. In the red-emitting (Ca_1.95Eu³⁺_0.02□_0.03)(Si_0.94P_0.06)O_4+δ phosphor, the highest PL intensity exhibited when it was annealed at 1773 K. On the other hand, in the green-emitting (Ca_1.95Eu²⁺_0.02□_0.03)(Si_0.94P_0.06)O₄ phosphor, the highest PL intensity was realized when it was annealed at 1473 K and consequently treated under a reductive atmosphere. With increasing annealing temperature, the emission peak wavelength steadily decreased. Furthermore, with increasing Eu²⁺ content, the emission peak wavelength increased, with the color of emitting light becoming yellowish. Thus, the PL properties of the phosphors were affected by both the structural change from β to α’_L, which occurred by heat treatment, and the amount of doped Eu ions. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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5045 KiB

Open AccessArticle

Preparation of Luminescent Metal-Organic Framework Films by Soft-Imprinting for 2,4-Dinitrotoluene Sensing

by Javier Roales, Francisco G. Moscoso, Francisco Gámez, Tânia Lopes-Costa, Ahmad Sousaraei, Santiago Casado, Jose R. Castro-Smirnov, Juan Cabanillas-Gonzalez, José Almeida, Carla Queirós, Luís Cunha-Silva, Ana M. G. Silva and José M. Pedrosa

Materials 2017, 10(9), 992; https://doi.org/10.3390/ma10090992 - 25 Aug 2017

Cited by 29 | Viewed by 6104

Abstract

A novel technique for the creation of metal-organic framework (MOF) films based on soft-imprinting and their use as gas sensors was developed. The microporous MOF material [Zn₂(bpdc)₂(bpee)] (bpdc = 4,4′-biphenyldicarboxylate; bpee = 1,2-bipyridylethene) was synthesized solvothermally and activated by removing the occluded solvent molecules from its inner channels. MOF particles were characterized by powder X-ray diffraction and fluorescence spectroscopy, showing high crystallinity and intense photoluminescence. Scanning electron microscope images revealed that MOF crystals were mainly in the form of microneedles with a high surface-to-volume ratio, which together with the high porosity of the material enhances its interaction with gas molecules. MOF crystals were soft-imprinted into cellulose acetate (CA) films on quartz at different pressures. Atomic force microscope images of soft-imprinted films showed that MOF crystals were partially embedded into the CA. With this procedure, mechanically stable films were created, with crystals protruding from the CA surface and therefore available for incoming gas molecules. The sensing properties of the films were assessed by exposing them to saturated atmospheres of 2,4-dinitrotoluene, which resulted in a substantial quenching of the fluorescence after few seconds. The soft-imprinted MOF films on CA/quartz exhibit good sensing capabilities for the detection of nitroaromatics, which was attributed to the MOF sensitivity and to the novel and more efficient film processing method based on soft-imprinting. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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2549 KiB

Open AccessArticle

Insight the Luminescence Properties of AlON: Eu, Mg Phosphor under VUV Excitation

by Xian Jian, Hui Wang, Ming-Hsien Lee, Wei Tian, Guo-Zhang Chen, Wen-Qiao Chen, Wei-Wei Ji, Xin Xu and Liang-Jun Yin

Materials 2017, 10(7), 723; https://doi.org/10.3390/ma10070723 - 29 Jun 2017

Cited by 11 | Viewed by 4544

Abstract

Owing to high quantum efficiency, adjustable composition and antioxidation properties of oxynitride phosphors, extensive investigations have focused on their photoluminescence properties under low-energy light excitation (UV or blue light). However, the vacuum ultraviolet (VUV) luminescence properties of oxynitride phosphors are rarely researched. Present work studies the structure and VUV luminescence properties of an oxynitride phosphor: AlON: Eu, Mg, which is synthesized by solid-state reaction. Under 147 nm excitation, it was found that AlON: Eu, Mg phosphor shows a blue emission band centered at about 470 nm. The first principle calculation is used to analyze the origin of the VUV absorption. Compared with BaMgAl₁₀O₁₇: Eu²⁺ phosphor, AlON: Eu, Mg phosphor shows better thermal stability. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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2154 KiB

Open AccessArticle

Warm White Light-Emitting Diodes Based on a Novel Orange Cationic Iridium(III) Complex

by Huaijun Tang, Guoyun Meng, Zeyu Chen, Kaimin Wang, Qiang Zhou and Zhengliang Wang

Materials 2017, 10(6), 657; https://doi.org/10.3390/ma10060657 - 16 Jun 2017

Cited by 12 | Viewed by 5210

Abstract

A novel orange cationic iridium(III) complex [(TPTA)₂Ir(dPPOA)]PF₆ (TPTA: 3,4,5-triphenyl-4H-1,2,4-triazole, dPPOA: N,N-diphenyl-4-(5-(pyridin-2-yl)-1,3,4-oxadiazol-2-yl)aniline) was synthesized and used as a phosphor in light-emitting diodes (LEDs). [(TPTA)₂Ir(dPPOA)]PF₆ has high thermal stability with a decomposition temperature (T_d) of 375 °C, and its relative emission intensity at 100 °C is 88.8% of that at 25°C. When only [(TPTA)₂Ir(dPPOA)]PF₆ was used as a phosphor at 6.0 wt % in silicone and excited by a blue GaN (GaN: gallium nitride) chip (450 nm), an orange LED was obtained. A white LED fabricated by a blue GaN chip (450 nm) and only yellow phosphor Y₃Al₅O₁₂:Ce³⁺ (YAG:Ce) (1.0 wt % in silicone) emitted cold white light, its CIE (CIE: Commission International de I’Eclairage) value was (0.32, 0.33), color rendering index (CRI) was 72.2, correlated color temperature (CCT) was 6877 K, and luminous efficiency (η_L) was 128.5 lm∙W⁻¹. Such a cold white LED became a neutral white LED when [(TPTA)₂Ir(dPPOA)]PF₆ was added at 0.5 wt %; its corresponding CIE value was (0.35, 0.33), CRI was 78.4, CCT was 4896 K, and η_L was 85.2 lm∙W⁻¹. It further became a warm white LED when [(TPTA)₂Ir(dPPOA)]PF₆ was added at 1.0 wt %; its corresponding CIE value was (0.39, 0.36), CRI was 80.2, CCT was 3473 K, and η_L was 46.1 lm∙W⁻¹. The results show that [(TPTA)₂Ir(dPPOA)]PF₆ is a promising phosphor candidate for fabricating warm white LEDs. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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2298 KiB

Open AccessArticle

AC Electroluminescent Processes in Pr³⁺-Activated (Ba_0.4Ca_0.6)TiO₃ Diphase Polycrystals

by Nan Gao, Min Zhang and Jun-Cheng Zhang

Materials 2017, 10(5), 565; https://doi.org/10.3390/ma10050565 - 21 May 2017

Cited by 5 | Viewed by 4652

Abstract

We investigated the properties of alternating current (AC)-driven electroluminescence from (Ba_0.4Ca_0.6)TiO₃:Pr³⁺ diphase polycrystal-based device. The results of crystal phases and micrographs, and the symmetrical dual emissions in one AC cycle, indicate the spontaneous formation of a dielectric/phosphor/dielectric sandwich microstructure in (Ba_0.4Ca_0.6)TiO₃:Pr³⁺. The electroluminescent device emits a red light of 617 nm, which is attributed to the ¹D₂-³H₄ transition of Pr³⁺ in the phosphor phase. At a fixed AC frequency, the intensity of electroluminescence exhibits a steep enhancement when applying an increased driving electric field that is beyond a threshold. In a fixed driving electric field, the intensity of electroluminescence shows a rapid rise at low frequencies, but reaches saturation at high frequencies. Based on a double-injection model, we discussed systematically the electroluminescent processes in a whole cycle of AC electric field, which matched well with the experimental data. Our investigation is expected to expand our understanding of such a diphase electroluminescent device, thereby promoting their applications in lighting and displays. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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25309 KiB

Open AccessArticle

Effect of Partial Crystallization on the Structural and Luminescence Properties of Er³⁺-Doped Phosphate Glasses

by Pablo Lopez-Iscoa, Turkka Salminen, Teemu Hakkarainen, Laeticia Petit, Davide Janner, Nadia G. Boetti, Mika Lastusaari, Diego Pugliese, Petriina Paturi and Daniel Milanese

Materials 2017, 10(5), 473; https://doi.org/10.3390/ma10050473 - 28 Apr 2017

Cited by 20 | Viewed by 4631

Abstract

Er-doped phosphate glass ceramics were fabricated by melt-quenching technique followed by a heat treatment. The effect of the crystallization on the structural and luminescence properties of phosphate glasses containing Al₂O₃, TiO₂, and ZnO was investigated. The morphological and structural properties of the glass ceramics were characterized by Field Emission-Scanning Electron Microscopy (FE-SEM), X-ray Diffraction (XRD), and micro-Raman spectroscopy. Additionally, the luminescence spectra and the lifetime values were measured in order to study the influence of the crystallization on the spectroscopic properties of the glasses. The volume ratio between the crystal and the glassy phases increased along with the duration of the heat treatment. The crystallization of the glass ceramics was confirmed by the presence of sharp peaks in the XRD patterns and different crystal phases were identified depending on the glass composition. Sr(PO₃)₂ crystals were found to precipitate in all the investigated glasses. As evidenced by the spectroscopic properties, the site of the Er³⁺ ions was not strongly affected by the heat treatment except for the fully crystallized glass ceramic which does not contain Al₂O₃, TiO₂, and ZnO. An increase of the lifetime was also observed after the heat treatment of this glass. Therefore, we suspect that the Er³⁺ ions are incorporated in the precipitated crystals only in this glass ceramic. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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4166 KiB

Open AccessArticle

Tunable Luminescence in Sr2MgSi2O7:Tb3+, Eu3+Phosphors Based on Energy Transfer

by Minhong Li, Lili Wang, Weiguang Ran, Zhihan Deng, Jinsheng Shi and Chunyan Ren

Materials 2017, 10(3), 227; https://doi.org/10.3390/ma10030227 - 24 Feb 2017

Cited by 29 | Viewed by 6740

Abstract

A series of Tb3+, Eu3+-doped Sr2MgSi2O7 (SMSO) phosphors were synthesized by high temperature solid-state reaction. X-ray diffraction (XRD) patterns, Rietveld refinement, photoluminescence spectra (PL), and luminescence decay curves were utilized to characterize each sample’s properties. Intense green emission due to Tb3+ 5D4→7F5 transition was observed in the Tb3+ single-doped SMSO sample, and the corresponding concentration quenching mechanism was demonstrated to be a diople-diople interaction. A wide overlap between Tb3+ emission and Eu3+ excitationspectraresults in energy transfer from Tb3+ to Eu3+. This has been demonstrated by the emission spectra and decay curves of Tb3+ in SMSO:Tb3+, Eu3+ phosphors. Energy transfer mechanism was determined to be a quadrupole-quadrupole interaction. And critical distance of energy transfer from Tb3+ to Eu3+ ions is calculated to be 6.7 Å on the basis of concentration quenching method. Moreover, white light emission was generated via adjusting concentration ratio of Tb3+ and Eu3+ in SMSO:Tb3+, Eu3+ phosphors. All the results indicate that SMSO:Tb3+, Eu3+ is a promising single-component white light emitting phosphor. Full article

(This article belongs to the Special Issue Luminescent Materials 2017)

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3054 KiB

Open AccessFeature PaperReview

Luminescent Lanthanoid Calixarene Complexes and Materials

by Massimiliano Massi and Mark I. Ogden

Materials 2017, 10(12), 1369; https://doi.org/10.3390/ma10121369 - 28 Nov 2017

Cited by 34 | Viewed by 5794

Abstract

This review aims to provide an overview of recent examples of lanthanoid-calixarene complexes incorporated into light-emitting materials. Background information on the antenna effect and early work on lanthanoid complexes on calixarenes is provided to set the context. Classes of materials discussed include polymers, [...] Read more.

(This article belongs to the Special Issue Luminescent Materials 2017)

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