Luminescent Crystals Research Articles

Mineralogical evolution of the anorogenic granites of Tirmini (Damagaram Southeast, Niger)

The present study focuses on the anorogenic granites of Tirmini. The latter are part of the younger granites of the pan-African province of Damagaram-Mounio, which constitutes a connection between the younger granites of the Aïr in the north and those of the Jos Plateau in the south. The objective of this study is to determine the mineralogical characteristics of the anorogenic granites of Tirmini. The methodological approach used includes X-ray diffraction (XRD) analysis on the one hand, and scanning electron microscope (SEM) and cathodoluminescence munimicroscope observations on the other. Two magmatic lineages form the Tirmini granite complex: one alkaline and the other peralkaline. Qualitative analysis at XRD shows that alkaline rocks include orthose, albite, quartz with little or no arfvedsonite. In addition to these minerals, peralkaline rocks contain aegyrin and arfvedsonite. SEM observation of all the Tirmini rocks shows that ilmenite (FeTiO3) is xenomorphic and luminescent in the yellow-orange range. Fluorapatite Ca5(PO4)F, which is stocky or elongated in shape, is present only in granites. Zircon (ZrSiO4) occurs in an elongated prism or quadratic section. Thus, at cathodoluminescence, monazite appears in luminescent zoned crystals in dark gray. Titanite is luminescent and appears in yellow-oranges. Semi-quantitative analysis of alkaline rocks shows the percentage of orthotics 50-65%, albite 6-8%, arfvedsonite quasi-absent 6%. Quartz is present between 30-34% in all rocks compared to 11% in the quartz alkaline syenite of Tirmini. In the peralkaline line, arfvedsonite and aegyrin account for 13% and 7%, respectively. Orthoclase 40-46%, albite 4% and biotite 2%. Quartz is present at 30%. The high orthotic contents show that the Tirmini rocks are persolvated and that the exsolution dome in the albite-orthotic system was well separated from the solidus.

A Ferroelastic Salt Cocrystal with Ultraviolet Emission.

The coexistence and coupling of photoluminescence and ferroelasticity in a single matter are vitally important for developing multifunctional materials and devices. However, the effective construction of ferroelastics with efficient photoluminescence, especially in the ultraviolet range, is a great challenge. In this work, a salt cocrystal, (DPA)(DPAH)PF6 (DPA = diphenylamine, DPAH = diphenylamine cation), with ultraviolet emission and ferroelasticity was reported by introducing the anion group PF6- in the parent DPA crystal. Besides, the thermally triggered order-disorder transition of PF6- groups leads to a ferroelastic phase transition at ∼340 K with the Aizu notation of 2/mF1̅. In addition, (DPA)(DPAH)PF6 displays a bright ultraviolet emission at 392 nm with a photoluminescence quantum yield of 49.4%. This work presents a strategy to achieve ultraviolet (UV)-emissive ferroelastic based on the luminescent organic crystal, which not only extends the luminescence of ferroelastic to the UV region but also paves a new way for the development of multifunctional ferroelastic materials and devices.

Luminescent anthracene-based elastic mixed molecular crystals for flexible and FRET-assisted optical waveguides

Abstract Optical waveguides based on elastic molecular crystals are of interest as flexible and compact optical communication materials. Low emission efficiency is often a problem in terms of communication signal strength, and an increase in the loss factor α due to fluorescence reabsorption in the crystal reduces the photon transport efficiency. Here, we report the development and improvement of Förster resonance energy transfer (FRET)-assisted optical waveguides using anthracene-based elastic mixed molecular crystals. 9,10-Dicyanoanthracene was selected as the dopant for solution-grown crystallization of 9,10-dibromoanthracene. 1H NMR measurements of the obtained crystals showed that the acceptor doping to be 1% to 5%. Elastic behavior was observed even when doped with a few percent of the acceptor. The quantum efficiency was 0.016, a dramatic improvement over the previous luminescent elastic mixed molecular crystals (0.004). The α value (92 dB/cm) of this crystal containing 1%-doped 9,10-dicyanoanthracene is much lower than that of the crystal consisting of only 9,10-dibromoanthracene (1258 dB/cm) due to the reduced reabsorption in the FRET system. We have demonstrated a practical approach toward developing improved fluorescent, highly efficient, and flexible optical waveguides by constructing the mixed crystal structure by selecting appropriate acceptor molecules and their low doping ratios.

Push-pull biphenyl and tolane derivatives as novel luminescent liquid crystals: synthesis and properties

ABSTRACT Addressing the current challenge of high melting points and long π-conjugated skeletons in luminescent nematic liquid crystals (LCs), this study explores the incorporation of push-pull dyes with biphenyl and tolane skeletons to extend fluorescence emission wavelengths into the visible light region. We synthesised push-pull-type biphenyl and tolane derivatives incorporating alkylamino groups as donors and cyano groups as acceptors. The thermal behaviour was investigated using optical polarisation microscopy, differential scanning calorimetry and X-ray diffraction. Notably, some molecules exhibited a nematic phase. The photophysical properties of the solution and solid states were also investigated. Furthermore, we formulated a room-temperature luminescent LC by blending several LCs. Importantly, the fluorescence in the nematic phase exhibited a red-shift compared to that observed in the solution and solid states. This study demonstrates the efficacy of the push-pull structure in the design of luminescent LCs. The findings of this study hold considerable implications for the development of advanced optoelectronic devices, particularly those requiring luminescent materials with tailored properties.

Dual-Stimuli-Responsive Turn-On Luminescence of Chiral Bisimidazolyl BINOL Dimethyl Ether Crystals.

Stimuli-responsive organic luminescent crystals have attracted significant attention in recent years for their potential in sensor and memory applications. While turn-on luminescence is superior in detection sensitivity compared with turn-off luminescence, the development of organic crystals that exhibit turn-on luminescence in response to multiple stimuli remains a significant challenge. Herein, the crystals of chiral bisimidazolyl 1,1'-bi-2-naphthol (BINOL) dimethyl ether have exhibited a dual-stimuli-responsive turn-on luminescence based on two distinct mechanisms. In the crystalline state, luminescence was substantially quenched by the intermolecular hydrogen bonds between the imidazole rings. Mechanical stimulation induced a transition to a blue-violet-emissive amorphous state. In contrast, thermal stimulation produced an orange luminescence, attributed to excited-state intramolecular proton transfer (ESIPT) luminescence from thermally demethylated products. Furthermore, the thermally induced state exhibited circularly polarized luminescence (CPL), marking a rare instance of stimuli-responsive turn-on CPL in a solid-state system. This study provides new insights into environmental and structural factors for solid-state luminescent properties and advances the design guidelines for multifunctional luminescent sensors.

Na5Y9F32:Yb3+/Ho3+/Tm3+ up-conversion luminescent single crystals for highly sensitive optical temperature sensor

A novel non-contact optical temperature sensor with excellent performance of its adequate temperature resolution (δ(T) = 0.017 K) and exceptional relative thermal sensitivity (Sr = 1.97% K−1) was developed based on the up-conversion fluorescence intensity ratio (FIR) of Ho3+/Tm3+/Yb3+ triply incorporated Na5Y9F32 single crystal grown by Bridgman method. The up-conversion (UC) emission bands at 482 nm/669 nm/700 nm of Tm3+ and 522 nm/542 nm/653 nm of Ho3+ ions were observed upon excitation of 980 nm. The effects of Yb3+ concentration from 0.5 to 4 mol% on the UC emission of the Ho3+/ Tm3+ fixed doped Na5Y9F32 single crystal were also carried out. It has been demonstrated through the calculation of the steady-state rate equation that the intensity of UC emission is linearly heightened with the pump power, confirming the conversion mechanism. The temperature sensing performance of the Ho3+/Tm3+/Yb3+ incorporated Na5Y9F32 single crystals was explored by analyzing the FIR employing thermally coupled energy levels (TCLs) and non-thermally coupled energy levels (NTCLs). The maximum values of absolute sensitivity (Sa) and relative sensitivity (Sr) of the material are estimated to be 19.1% K−1 (323 K) and 1.97% K−1 (398 K), separately, which are far higher than those of previously reported RE3+-doped UC optical temperature sensor materials. This study shows that the transparent single crystal has the great potential as a non-contact optical thermometer, and provides a new idea for studying other highly optical sensing materials.

Mesomorphism, high-contrast negative fluorosolvatochromism and photoinduced fluorescence conversion of thienylcyanostyrene-pyridinium salts

Novel thienylcyanostyrene and pyridinium-based luminescent ionic liquid crystals (ILCs) characterized with different length of N-alkyl chains (N–C3H7 and N–C8H17) and different size of counter anions (Br−, BF4−, PF6− and Tf2N−) on pyridinium moiety have been synthesized. The chemical modifications of N-alkyl chains and counter anions are easily achieved via pyridine alkylation followed with further ion exchanges, which played a key role in tuning supramolecular self-assembly of these ILCs. The compounds with shorter N–C3 alkyl chain (E-CTPC3X, X = Br−, BF4−, PF6− and Tf2N−) can self-assemble into 3D cubic phase or 2D hexagonal columnar phase depending on the size of counter anion, while the analogues with longer N–C8 alkyl chain (E-CTPC8X, X = BF4− and Tf2N−) only result smectic A phases. Moreover, the prolongation of the N-alkyl chain or enlargement of counter anion could significantly decrease the clear points of LC phases avoiding the thermal decomposition at high temperature, whereas introducing counter anions such as BF4−, PF6− that can form hydrogen bonds have stabilized the LC phases. The notable negative fluorosolvatochromism and the photoinduced fluorescence conversion with high-contrast of these ILCs were observed using UV–vis absorption and photoluminescence (PL) spectra, and was further analyzed by dynamic 1H NMR. These ILCs had been used as dopant to modify the n-Si/PEDOT:PSS heterojunction solar cells (HSCs) with 2 fold hole mobility (μhole) enhancement of the PEDOT:PSS layer.

Tunable Multicolor Emission and High Thermal Stability in Single‐Matrix Luminescent Crystals Based on Calcium Perovskites for Advanced Solid‐State Lighting Applications

AbstractThe development of environmentally friendly full‐inorganic luminescent materials with tunable emission properties and exceptional thermal stability is of paramount importance for applications in optoelectronic devices, solid‐state lighting, and anti‐counterfeiting technologies. In this study, a novel luminescent crystal based on calcium perovskites Cs2CaCl4·2H2O (CCCH) are explored using a hydrothermal method. Simultaneous co‐doping of CCCH with Sn2+ and Mn2+ yields the s‐p transition‐induced cyan light from Sn2+ and d‐d transition‐induced yellow light from Mn2+. It demonstrates effective energy transfer from self‐trapped exciton (STE) of matrix CCCH and s‐p transition of Sn2+ to Mn2+, synergizing composite white lights with tunable colors. Furthermore, the incorporation of Sn2+ into CCCH introduces a red shift from blue to cyan emission with a remarkable enhancement in luminescent intensity by a factor of 12 times. The crystal orbital Hamiltonian populations (─COHP) calculations revealed the crucial role of Mn2+ in lattice stability, as evidenced by the decomposition temperature exceeding 305 °C for CCCH:Sn2+,Mn2+ whereas 210 °C for undoped CCCH matrix. This research provides a comprehensive investigation of the luminescent properties of CCCH:Sn2+,Mn2+ crystal, holding significant promise for practical technological advancements in lighting and anti‐counterfeiting technologies.

Mechanically Tunable Circularly Polarized Luminescence of Liquid Crystal-Templated Chiral Perovskite Quantum Dots.

Endowing perovskite quantum dots (PQDs) with circularly polarized luminescence (CPL) offers great promise for innovative chiroptical applications, but the existing strategies are inefficient in acquiring stimuli-responsive flexible chiral perovskite films with large, tunable dissymmetry factor (glum) and long-term stability. Here, we report a strategy for the design and synthesis of luminescent cholesteric liquid crystal elastomer (Lumin-CLCE) films with mechanically tunable CPL, which is enabled by liquid crystal-templated chiral self-assembly and in situ covalent cross-linking of judiciously designed photopolymerizable CsPbX3 (X=Cl, Br, I) PQD nanomonomers into the elastic polymer networks. The resulting Lumin-CLCE films showcase circularly polarized structural color in natural light and noticeable CPL with a maximum glum value of up to 1.5 under UV light. The manipulation of CPL intensity and rotation direction is achieved by controlling the self-assembled helicoidal nanostructure and the handedness of soft helices. A significant breakthrough lies in the achievement of a reversible, mechanically tunable perovskite-based CPL switch activated by biaxial stretching, which enables flexible, dynamic anti-counterfeiting labels capable of decrypting preset information in specific polarization states. This work can provide new insights for the development of advanced chiral perovskite materials and their emerging applications in information encryption, flexible 3D displays, and beyond.

Mechanically Tunable Circularly Polarized Luminescence of Liquid Crystal‐Templated Chiral Perovskite Quantum Dots

AbstractEndowing perovskite quantum dots (PQDs) with circularly polarized luminescence (CPL) offers great promise for innovative chiroptical applications, but the existing strategies are inefficient in acquiring stimuli‐responsive flexible chiral perovskite films with large, tunable dissymmetry factor (glum) and long‐term stability. Here, we report a strategy for the design and synthesis of luminescent cholesteric liquid crystal elastomer (Lumin‐CLCE) films with mechanically tunable CPL, which is enabled by liquid crystal‐templated chiral self‐assembly and in situ covalent cross‐linking of judiciously designed photopolymerizable CsPbX3 (X=Cl, Br, I) PQD nanomonomers into the elastic polymer networks. The resulting Lumin‐CLCE films showcase circularly polarized structural color in natural light and noticeable CPL with a maximum glum value of up to 1.5 under UV light. The manipulation of CPL intensity and rotation direction is achieved by controlling the self‐assembled helicoidal nanostructure and the handedness of soft helices. A significant breakthrough lies in the achievement of a reversible, mechanically tunable perovskite‐based CPL switch activated by biaxial stretching, which enables flexible, dynamic anti‐counterfeiting labels capable of decrypting preset information in specific polarization states. This work can provide new insights for the development of advanced chiral perovskite materials and their emerging applications in information encryption, flexible 3D displays, and beyond.

Dual-Emissive γ-[Cu4I8]4- Enables Luminescent Thermochromism in an Organic-Inorganic Hybrid Copper(I) Halide.

A highly luminescent (C13H28N2)2Cu4I8 single crystal containing isolated γ-[Cu4I8]4- anionic cluster was synthesized without the use of unsaturated cations. To the best of our knowledge, compounds bearing such like anions are not dual-emitting under UV excitation. However, dual emission does occur in (C13H28N2)2Cu4I8. Moreover, the emission bands were found to be temperature-sensitive, allowing tuning of the emission colors from blue (0.19, 0.20) to green (0.33, 0.47) in the Commission International de L' Eclairage (CIE) chromaticity coordinates. Remarkably, the color could be restored on returning to the initial temperature, confirming an efficient and reversible luminescent thermochromic effect in (C13H28N2)2Cu4I8. The origin of this excellent optical performance is discussed, and the difference in the mechanism with the dual-emissive Cu(I) halide complexes is also elucidated. Overall, our work provides a promising way to achieve efficient luminescent thermochromism. The developed (C13H28N2)2Cu4I8 represents one of the viable alternatives for eco-friendly luminescent thermochromic materials.

Circularly Polarized Luminescence Switching of Chiral Perylene Diimide‐Doped Nematic Liquid Crystal Using DC Electric Field

AbstractTo obtain chiral luminescent nematic liquid crystals (N*‐LCs), two sets of chiral perylene luminescent materials (R,R)/(S,S)‐N,N′‐bis(1‐cyclohexylethyl)perylene‐3,4,9,10‐tetracarboxylic diimide [(R,R)/(S,S)‐CPDI] and (R,R)/(S,S)‐N,N′‐bis(1‐phenylethyl)perylene‐3,4,9,10‐tetracarboxylic diimide [(R,R)/(S,S)‐BPP] were prepared and doped into a nematic liquid crystal (N‐LC), 5CB. The obtained liquid crystals N*‐LC‐CPDI and N*‐LC‐BPP emitted stronger circularly polarized luminescence (CPL) signals than the CPDI‐ and BPP‐containing chiral poly(methyl methacrylate) (PMMA) luminescent films owing to higher helical twist power. When a direct current (DC) electric field was applied to N*‐LC, a reversible CPL response was obtained due to the field‐induced phase transition from the chiral nematic phase to the nematic phase. This demonstrated the successful construction of an ′′on‐off‐on′′ CPL system based on a DC electric field and was attributed to the change in the liquid crystalline organization from a uniformly lying helical structure to a planar one. This work can provide an effective strategy for the development of functional CPL devices in which the CPL can be regulated by applying a DC electric field to the N*‐LC.

Luminescent Porous Organic Crystals for Adsorptive Separation of Toluene and Methylcyclohexane.

A butterfly-shaped phenothiazine derivative, PTTCN, was synthesized to obtain pure organic porous crystals for the highly efficient absorptive separation of toluene (Tol) and methylcyclohexane (Mcy). Due to the presence of three polar cyano groups and nonplanar conformation, these molecules self-assembled into a hydrogen-bonded organic framework (X-HOF-5) with distinct cavities capable of accommodating Tol molecules through multiple hydrogen-bonding interactions. Upon solvent removal via heating, the activated X-HOF-5 retained its cavity structure albeit with altered stacking arrangements, accompanied by a remarkable fluorescent color change from cyan to green. X-HOF-5a can undergo a phase transformation into X-HOF-5 upon reabsorption of Tol, while exhibiting no accommodation of Mcy due to the weak intermolecular interaction between PTTCN and Mcy. This suggests that the activated HOF material prefers Tol over Mcy. Moreover, X-HOF-5a may selectively accommodate Tol in a Tol/Mcy equimolar mixture, and the purity of Tol can reach 97% after release from the framework. Additionally, it is noteworthy that the HOF material exhibits recyclability without any discernible loss in performance.

DNA hybrid florescent chrominance sensor: Drug sensing through direct gradient florescent color transformation of hybrid DNA crystals loaded lanthanide (Eu3+/Tb3+) complexes

In this study, a highly sensitive anticancer drug sensor was synthesized using DNA crystals loaded with luminescent Ln3+(Eu3+/Tb3+) complexes. The sensors exhibited a pronounced color transformation property due to the differential quenching of Eu3+ and Tb3+ emissions upon drug interactions. These luminescent hybrid DNA crystals present a significant advancement in sensing anticancer drugs like curcumin, transitioning from monitoring fluorescence intensity changes to a visually discernable color change. This new approach eliminates the need for specialized instrumentation. Owing to the intrinsic biocompatibility of materials composed of DNA, this hybrid sensor has the potential to sense drugs within the human body. Hybrid crystals loaded with a single complex will lose their fluorescence properties due to drug quenching; however, crystals loaded with mixed complexes emit distinct fluorescent colors, such as yellow-green and orange-red, at different drug concentrations. This color transformation allows for the direct determination of drug concentration based on crystal color, making the sensing process more simple and easily observable.

Elimination of surface defects in luminescent crystals through solid-liquid interface friction.

In this work, we report a simple yet robust strategy for eliminating surface defects in red-emitting fluorides through solid-liquid interface friction under elevated temperature and high pressure. This method is minimally dependent on the solvent type and especially excels at stripping away the abundant surface defects caused by mechanical crushing.

Millimeter-Sized K2MnF6:Si4+, NH4+ Red-Luminescent Crystals with High Absorption Efficiency (AEmax of 93.5%) and External Quantum Efficiency (EQEmax of 68.9%) Grown by Cooling-Induced Crystallization.

Luminescent bulk crystals exhibit fewer grain boundaries and defects compared with conventional microsized powdery ones. Herein, targeting Mn4+-activated fluoride crystals with a sharp line-type red luminescence spectrum, we propose a new cooling-induced crystallization method to grow the fluoride crystals. By this new method, we successfully grew millimeter-sized K2MnF6:Si4+, NH4+ crystals, featuring an AEmax (absorption efficiency) of 93.5% and an EQEmax (external quantum efficiency) of 68.9%, which are among the best values for Mn4+-activated fluoride red phosphors. The influence of doping Si4+ and/or NH4+ in K2MnF6 on the local coordination structure and luminescence properties was studied. The anomalous thermal quenching behaviors were discussed, the luminescence decay from the excited state was compared, and the origin for the high quantum efficiencies was analyzed.

Self-assembly of thiophene-based luminescent thin films on flexible substrates.

Luminescent organic thin films are widely used in optoelectronic devices for sensing, imaging and data processing. Herein, the transition to a flexible form is accompanied by a number of challenges associated with a limited endurance and bending-dependent properties. Here we report a study on the growth of thin films based on thiophene-based luminescent molecular crystals (MC) on a flexible polypropylene (PP) substrate of a various thicknesses (400 μm to 50 μm). The resulting flexible thin films demonstrate the stability of their luminescent properties under mechanical bending (up to 100 times) at ambient conditions, which pave the way for large scale production of planar optoelectronic components.

Electrochemiluminescence Properties and Sensing Application of Zn(II)-Metal-Organic Frameworks Constructed by Mixed Ligands of Para Dicarboxylic Acids and 1,10-Phenanthroline.

Four metal-organic frameworks (MOFs) were designed and prepared through a mixed-ligand strategy by controlling the combination of various dicarboxylic acid ligands with invariant center metal and o-phenanthroline heterocyclic ligand. The regulatory effects of ligand electronic band and crystal structure on the electrochemiluminescence (ECL) characteristics of MOFs were verified by experimental results and density functional theory (DFT) calculations. The flexible chain structure of MOF-2 promotes electron transfer between MOF electroactive free radicals and the co-reactant, making it show outstanding ECL characteristics among all of the four MOFs with the luminescence quantum efficiency 8.37 times that of tris(bipyridine)-ruthenium(II) ([Ru(bpy)3]2+). Meanwhile, a new ECL mechanism for MOF luminescent crystal materials with reactive oxygen species in solvents as a co-reactant in the aqueous aerobic environment has been proposed. MOF-2 was selected to construct an ECL sensor for the determination of glucose in human urine samples. This study provides a useful idea for the development and design of new luminescent molecular crystal materials.

Strontium Aluminate Persistent Luminescent Single Crystals: Linear Scaling of Emission Intensity with Size Is Affected by Reabsorption

Strontium Aluminate Persistent Luminescent Single Crystals: Linear Scaling of Emission Intensity with Size Is Affected by Reabsorption

Circularly Polarized Luminescence from Chiral Photonic Crystals of Caesium Lead Halide Perovskites

AbstractThe generation and detection of circularly polarized light (CPL) are of importance in many modern technologies such as digital communications, machine vision, bio‐imaging, and 3D displays. In this study, inspired by the fact that various species of plants and animals can efficiently produce and/or perceive CPL with chiral photonic crystal structures, efforts are made to fabricate luminescent chiral photonic crystals with caesium lead halide perovskites, a class of solution‐processable semiconductors that have excellent luminescence properties and readily tunable electronic band gaps. Coupling between the emission frequency of the perovskite and the cavity resonance frequency of the photonic crystal structure can be established at any desired point in the visible region, giving rise to CPL output with a dissymmetry factor up to −0.34. These results suggest a new approach to chiral light‐emitting materials and may contribute to the development of semiconductors with ordered microstructures.