Color-tunable Emission Research Articles

Multiple wavelengths excitation of NaYF4:Tm/Er microcrystals for multicolor anti-counterfeiting and temperature sensing

Multicolor luminescence and optical thermometry hold charming potential applications in many fields, which are likely to be achieved in one rationally designed unit. Herein, a triple-wavelength (980 nm, 1550 nm and 808 nm) responsive upconversion microcrystal, using Er3+ ions as sensitizers, is proposed, which can generate tunable emission color from red to yellow and then to green. The modulated population route and energy transfer process of Er3+ are perceived to be the reason for tunable luminescence color upon excitation-wavelength. In addition, based on thermally coupled energy levels (TCLs), i.e., 2H11/2/4S3/2 and non-thermally coupled energy levels (NTCLs), i.e., 2H11/2/4F9/2 of Er3+ ions, the temperature-dependent upconversion properties were investigated. The maximum relative sensing sensitivity (Sr) of NaYF4:0.5%Tm/20%Er was found to be 1.373 % K−1 at 313 K, outperforming the majority of the same type thermometers. The results indicate that the NaYF4:0.5%Tm/20%Er microcrystals serve as a promising candidate for multicolor anticounterfeiting and optical thermometry applications.

Cooling Condition Effect on Spectral Properties and Smartphone-Based Anticounterfeiting Application of Zn3Ga2Ge2O10/Cr3+ Phosphors.

The influence of cooling history for the Zn3Ga2Ge2O10/Cr3+ phosphors prepared by solid state reaction on the spectral properties was discovered, and an anticounterfeiting scheme based on the identification with smartphone was proposed and experimentally demonstrated using the studied phosphors. A combination of color-tunable visible fluorescence emission and near-infrared (NIR) afterglow emission in Zn3Ga2Ge2O10/x mol % Cr3+(x = 0, 0.05, 1, 2, 3, and 4) phosphors to achieve multimode anticounterfeiting was reported. It is found that with the increasing Cr3+ concentrations, the visible emission can be tuned from green, light pink, and light red to deep red under 254 nm ultraviolet (UV) excitation. This phenomenon is related to the formation of oxygen vacancies in the host during the process of natural cooling and the characteristic emission of Cr3+. In addition, the persistent time of the Cr3+ emission centered at 700 nm can be also tuned by various Cr3+ concentrations. A possible mechanism was deduced to explain the afterglow phenomenon. Lastly, a flower pattern applied in anticounterfeiting was fabricated using the Zn3Ga2Ge2O10/x mol % Cr3+ (x = 0, 0.05, 1, 2, 3, and 4) phosphors to present tunable color and NIR afterglow signals at different excitation modes, and the camera of smartphone was chosen as a detection tool to take the NIR images. The results obtained above suggest that the prepared phosphors at natural cooling condition have great potential in affording advanced optical anticounterfeiting.

Emission color tuning and enhancement of the upconversion emission in NaBiF4:Yb3+,Er3+ phosphors by controlling the Na/F ratio

NaBiF4:Yb3+(20 mol%),Er3+(2mol%) phosphors (NBF:Yb,Er) were synthesized by a simple precipitation method. Several NBF:Yb,Er samples were made with different Na/F ratios (from 2/16 to 6/16 and 6/24). XRD and SEM measurements indicated that all the NBF:Yb,Er phosphors presented an hexagonal phase and morphology of microbars with sizes of 1–2 μm, respectively. According to the photoluminescence measurements, these phosphors emitted red/green emission bands at 541/655 nm and their emission intensity increased ⁓10.5 and 21 times for the green and red bands, respectively, after increasing the Na/F ratio from 2/16 to 4/16. In addition, the emission color was tuned from deep-green to yellow. Moreover, the Na/F ratio was decreased from 6/16 to 6/24, this in turn, changed the color emission from deep-green to orange. This last change of color occurred because the red emission was mainly favored by the following two cross relaxation (CR) processes CR1: 4I11/2 (Er3+)+ 4F7/2 (Er3+)→4F9/2 (Er3+)+ 4F9/2 (Er3+) and CR2: 4S3/2 (Er3+)+ 2F7/2 (Yb3+)→4I13/2 (Er3+)+ 2F5/2 (Yb3+). The second CR2 process also promoted the NIR emission at 1527 nm. Additionally, the lifetimes for the green and red bands increased from 393 to 420 μs and from 428 to 518 μs with the Na/F ratio, respectively. Thus, we presented here a new strategy to enhance the photoluminescence intensity and to control the emission-color/lifetimes without using extra co-dopants (as previously reported in literature).

CsPbBr3 Perovskite Crack Platelet Nanocrystals and Their Biexciton Generation.

Lead halide perovskite nanocrystals have been extensively studied in recent years as efficient optical materials for their bright and color-tunable emissions. However, these are mostly confined to their 3D nanocrystals and limited to the anisotropic nanostructures. By exploring the Cs-sublattice-induced metal(II) ion exchange with Pb(II), crack CsPbBr3 perovskite platelet nanocrystals having polar surfaces in all three directions are reported here, which remained different than reported standard square platelets. The crack platelets are also passivated with halides to enhance their brightness. Further, as these crack and passivated crack platelets have defects and polar surfaces, the exciton and biexciton generation in these platelets is investigated using femtosecond photoluminescence and transient absorption measurement at ambient as well as cryogenic temperatures, correlated with time-resolved single-particle photoluminescence spectroscopy, and compared with standard square platelets having nonpolar facets. These investigations revealed that the crack platelets and passivated crack platelets possess enhanced biexciton emission compared to square platelets due to the presence of polar surfaces in all three directions. These results provide insights into not only the design of the anisotropic nanostructures of ionic nanocrystals but also the possibility of tuning the single exciton to biexciton generation efficiency, which has potential applications in optoelectronic systems.

Efficient photo-induced RTP materials based on phenothiazine and polycyclic aromatic hydrocarbons: Tunable emission color and thermal stimulus response

Efficient photo-induced RTP materials based on phenothiazine and polycyclic aromatic hydrocarbons: Tunable emission color and thermal stimulus response

Covalent Bond Torsion-Enabled Unique Crystal-Phase Transformation of an Organic Semiconductor for Multicolor Light-Emitting Transistors.

High-mobility and color-tunable highly emissive organic semiconductors (OSCs) are highly promising for various optoelectronic device applications and novel structure-property relationship investigations. However, such OSCs have never been reported because of the great trade-off between mobility, emission color, and emission efficiency. Here, we report a novel strategy of molecular conformation-induced unique crystalline polymorphism to realize the high mobility and color-tunable high emission in a novel OSC, 2,7-di(anthracen-2-yl) naphthalene (2,7-DAN). Interestingly, 2,7-DAN has unique crystalline polymorphism, which has an almost identical packing motif but slightly different molecular conformation enabled by the small bond rotation angle variation between anthracene and naphthalene units. More remarkably, the subtle covalent bond rotation angle change leads to a big change in color emission (from blue to green) but does not significantly modify the mobility and emission efficiency. The carrier mobility of 2,7-DAN crystals can reach up to a reliable 17 cm2 V-1 s-1, which is rare for the reported high-mobility OSCs. Based on the unique phenomenon, high-performance light-emitting transistors with blue to green emission are simultaneously demonstrated in an OSC crystal. These results open a new way for designing emerging multifunctional organic semiconductors toward next-generation advanced molecular (atomic)-scale optoelectronics devices.

Blue-emitting perovskite nanocrystals with enhanced optical properties through using NaBH4

APbX3-type [A = CH3NH3 + (MA+), NH2CH=NH2 + (FA+), X = Cl–, Br–, I–] organic–inorganic perovskite nanocrystals (PeNCs) have superior optical properties, such as emission with a narrow full width at half maximum and emission color tunability over the entire visible range. However, blue-emitting PeNCs [APb(Br/Cl)3] exhibit low photoluminescence quantum yields owing to Cl defects, hindering their practical applications. The Cl defects induce nonradiative recombination caused by the trap levels formed deep in the band gap. Herein, we report the preparation of blue-emitting PeNCs that exhibit excellent optical properties by using NaBH4 to decrease the number of Cl defects.

Regulating room temperature phosphorescence of carbazole quaternization pyridine in polymer through Hofmeister effect

AbstractHofmeister effect is a famous physical chemistry phenomenon that was reported a hundred years ago, which firstly refers to the action of certain salts to decrease the solubility of proteins while others increase. The Hofmeister effect on the luminescent properties of cationic organic fluorophore is still obscure, especially for their room temperature phosphorescence (RTP). Herein, hydrophilic groups (quaternization pyridine) were introduced into carbazole molecules to obtain a series of carbazole derivatives (named CZ‐Py+) with different counter anions in the Hofmeister series. These carbazole derivatives displayed tunable fluorescent color from cyan to yellow in the solid state following the Hofmeister sequence and anti‐Hofmeister behavior in an aqueous solution. Moreover, RTP material with tunable emission color and lifetime was achieved by doping CZ‐Py+ with Hofmeister series anion in polymethyl methacrylate and polyvinyl alcohol, which displayed good performance in time getting information encryption and anti‐counterfeiting.

Tunable emission color of novel Y3NbO7:xDy3+ phosphor

Powders of Y3NbO7:xDy3+ (x = 0.5, 1, 1.5, 3 and 5 mol%) were produced through a solid-state process. X-ray diffraction investigations confirm the fluorite-type structure (space group 𝐹𝑚3̅𝑚) of powders with crystallite size in the range of 19–60 nm. Both the photoluminescence excitation and emission spectra revealed the presence of defects within the material. With different excitation wavelengths, the emission spectra exhibited distinct emission patterns. At each excitation wavelength, the emission was quenched at Dy3+ concentration higher than 1 mol%. The decay time measurements of the highest intensity emission revealed a progressive decrease from 0.472 milliseconds for x = 0.5 mol% to 0.246 milliseconds for x = 5 mol%. The CIE chromaticity coordinates investigation revealed that the emission color may be altered by varying the excitation wavelength, ranging from blue (excitation at 333 nm) and near-white (excitation at 353 nm and 390 nm) to orange (excitation at 457 nm). The chromaticity of emission under 353 nm and 390 nm excitation validated the material's suitability as an almost-white phosphor.

Optical Property Control by the Interligand Charge Transfer Excited State in Brominated Homoleptic and Heteroleptic Aluminum Dinuclear Triple-Stranded Helicates.

The utilization of aluminum, an abundant and inexpensive element, for the synthesis of novel functional complexes is extremely important, but the design and control of photofunctionality are still unexplored. In this study, we focused on our previously developed dinuclear triple-stranded helicates incorporating two aluminum ions (ALPHY) to synthesize both homoleptic and heteroleptic complexes with bromine atoms at the 3-position of the pyrrole moiety in the Schiff base ligands. The brominated Schiff base ligands were reacted with AlCl3 to synthesize homoleptic complexes, while different ligands were mixed to prepare heteroleptic complexes. Single-crystal X-ray structural analysis revealed the structures of these novel complexes. We found that increasing the degree of bromination resulted in a tunable emission color, shifting progressively from 550 (yellow) to 566 nm (orange). Optical resolution of the complexes facilitated the observation of mirror-image circular dichroism and circularly polarized luminescence. Furthermore, employing ultrafast spectroscopy techniques, we have elucidated that the optical properties are governed by the interligand charge transfer (ILCT) among the three ligands. The formation of heteroleptic complexes induces the ILCT state even in nonpolar environments, thereby accelerating nonradiative decay and intersystem crossing. These findings mark significant advancements in photofunctional materials based on multinuclear complexes.

Rational Design of Pyrido[3,2-b]indolizine as a Tunable Fluorescent Scaffold for Fluorogenic Bioimaging.

Novel fluorescent scaffolds are highly demanding for a wide range of applications in biomedical investigation. To meet this demand, the pyrido[3,2-b]indolizine scaffold was designed as a versatile organic fluorophore. With the aid of computational modeling, fluorophores offering tunable emission colors (blue to red) were constructed. Notably, constructed fluorophores absorb lights in the visible range (>400 nm) despite their small sizes (<300 g/mol). Among the fluorophores was discovered a highly fluorogenic fluorophore with a unique turn-on property, 1, and it was developed into a washing-free bioprobe for visualizing cellular lipid droplets in living cells. Furthermore, motivated by the core's compact size and structural analogy to indole, unprecedented tryptophan-analogous fluorogenic unnatural amino acids were constructed and incorporated into fluorogenic peptide probes for monitoring peptide-protein interactions.

Electrochemical and photoluminescence properties of Zinc vanadate nanoparticles synthesized via chemical and green mediated route

Zinc vanadate (Zn2V2O7) nanoparticles (NPs) are successfully synthesized through a solution combustion method, employing Menthaspicata leaves extract as a reducing agent (ZVP) and urea as a chemical fuel (ZVU). Subsequently, the resulting NPs undergo calcination at 600 °C for a duration of 3 h. The pure orthorhombic crystal structure with Cmce space group Bragg reflections are observed in ZVP NPs. However, along with pure orthorhombic phase, few planes corresponding to V2O5 are observed. Green extract helps to retain the single orthorhombic phase. Irregular shaped and bigger sized NPs are observed in ZVU whereas in ZVP, few hexagonal and irregular sized NPs gets decorated on the bigger sized NPs. Better crystalline structure and shape are observed in ZVP compared to ZVU. Transmission electron microscopy analysis matches well with the XRD results. The selected area electron diffraction pattern of ZVP confirms the formation of purity of the sample. The direct energy band gap estimated from the Wood and Tauc’s plot was found to be 3 and 3.04 eV for ZVU and ZVP NPs respectively. The photoluminescence experiment was carried out at 290 and 310 nm excitation wavelengths. As excitation wavelength changes, tuning of emission color is observed from blue to red region. This tuning of color is observed in CIE plot. The CCT value clearly indicates that the samples excited under 290 nm can be utilized for cool LEDs whereas, the sample excited under 310 nm can be utilized for warm LEDs. Thus, the synthesized Zinc vanadate NPs might be the promising candidates for warm/cool display technologies as a nanophosphor based on the excitation wavelength. The electrochemical studies and the capacitance process was evaluated in a 1.0 M Na2SO4 solution utilizing a specific three-electrode setup. The calculated specific capacitance values exhibited variability within the range of 56.8 to 89.7 F/g at scan rates ranging from 10 to 100 mV.

Photoluminescence of Platinum(II) Complexes with Diazine-Based Ligands.

In the last past twenty years, research on luminescent platinum (II) complexes has been intensively developed for useful application such as organic light emitting diodes (OLEDs). More recently, new photoluminescent complexes based on diazine ligands (pyrimidine, pyrazine, pyridazine, quinazoline and quinoxaline) have been developed in this context. This review will summarize the photophysical properties of most of the phosphorescent diazine Pt(II) complexes described in the literature and compare the results to pyridine analogues whenever possible. Based on the emission color, and the photoluminescence quantum yield (PLQY) values, the relationship between structure modification, and photophysical properties are highlighted. Tuning of emission color, quantum yields in solution and solid state and, for some complexes, aggregation induced emission (AIE) or thermally activated delayed fluorescence (TADF) properties are described. When emitting OLEDs have been built from diazine Pt(II) complexes, the external quantum efficiency (EQE) values and luminance for different emission wavelengths and in some cases, chromaticity coordinates obtained from devices, are given. Finally, this review highlights the growing interest in studies of new luminescent diazine Pt(II) complexes for OLED applications.

Glass Disorder Modulated Luminescence in Zero-Dimensional Antimony-Chloride Coplanar Dimers for Optical Anti-counterfeiting.

Zero-dimensional metal halides have received wide attention due to their structural diversity, strong quantum confinement, and associated excellent photoluminescence properties. A reversible and tunable luminescence would be desirable for applications such as anti-counterfeiting, information encryption, and artificial intelligence. Yet, these materials are underexplored, with little known about their luminescence tuning mechanisms. Here we report a pyramidal coplanar dimer, (TBA)Sb2Cl7 (TBA = tetrabutylammonium), showing broadband emission wavelength tuning (585-650 nm) by simple thermal treatment. We attribute the broad color change to structural disorder induced by varying the heat treatment temperatures. Increasing the heating temperature transitions the material from long-range ordered crystalline phase to highly disordered glassy phase. The latter exhibits stronger electron-phonon coupling, enhancing the self-trapped exciton emission efficiency. The work provides a new material platform for manifold optical anti-counterfeiting applications and sheds light on the emission color tuning mechanisms for further design of stimuli-responsive materials.

Tunable emission color from lead-free zero-dimensional Mn2+-doped Cs3InCl6 single crystals

In recent years, the magneto-optical properties of zero-dimensional metal halides have attracted widespread interest. In this study, we employed a vacuum solid-state reaction method to synthesize zero-dimensional, lead-free, and all-inorganic Cs3InCl6 single crystals (SCs). In addition to the blue emission of self-trapped excitons (STEs) inherent to pristine Cs3InCl6, the strategic doping with Mn2+ ions not only facilitates multicolor emissions but also significantly boosts the photoluminescence quantum yield (PLQY) from a modest 1.21 % to an impressive 32.18 %. We carried out an exhaustive investigation into the fundamental mechanisms responsible for these multicolor emissions and the intricate compositional transitions that ensue. Furthermore, the pronounced correlation between temperature-dependent photoluminescence (PL) and magnetic characteristics unveiled the genesis of ferromagnetism within both the pristine and Cs3InCl6: xMn2+ samples. The doping-induced modifications in magnetic behavior furnish a coherent explanation for the anomalous inverse temperature dependence emission wavelength shift. Our research highlights the adjustable PL and magnetic attributes of Mn2+ doped Cs3InCl6, yielding invaluable insights that are poised to advance its application in the next wave of optoelectronic and magnetic technologies.

Intrinsic defective long-persistent luminescence from organic-inorganic hybrid halide perovskite for multiple information encryption

As result of spin-forbidden transition for triplet exciton, the afterglow lifetime of OIHPs was limited to a few seconds. Herein, color-tunable emissions and LPL at room temperature are successfully achieved in (C4H6N3O)2InCl5·H2O OIHP. The prepared (C4H6N3O)2InCl5·H2O exhibit three distinct emissions peaks at 400 nm, 450 nm, and 480 nm, which are revealed from the dynamic transformation from the keto form to the enol from through the ESIPT process. Notably, the (C4H6N3O)2InCl5·H2O singe crystals perform green LPL with a long duration of 15000 s at room temperature. In-depth theoretical calculations and experimental studies suggest that intrinsic defects of (C4H6N3O)2InCl5·H2O introduce trap states that store the charge carrier and release them to the triplet state of organic components of (C4H6N3O)2InCl5·H2O to achieve LPL. This work offers a valuable method for increasing LPL duration for its triplet exciton in OIHPs by introducing intrinsic defective. Finally, the good stability and optical information encryption application of (C4H6N3O)2InCl5·H2O are demonstrated.

Modification of Local Site Preference for Achieving Tunable Color Emission from Blue to Near-White in Sr3(PO4)2:Dy3+ Phosphor

The color tunability of Sr3(PO4)2:1%Dy3+ phosphor from blue to near white is studied at various annealing conditions. Higher temperature annealing promotes agglomerated rhombohedral (α) phase formation. Experimental and theoretical analysis reveal dopant preference at the low-symmetry Sr(II) site, altering electric (4F9/2→6H13/2) and magnetic (4F9/2→6H15/2) dipole transitions, thereby affecting the yellow-to-blue (Y/B) ratio. The luminescence intensity variation and color tunability are explained based on the local site symmetry and occupation probability of the dopant in the host lattice. An increase in the luminescence intensity up to an annealing temperature of 1200 °C, followed by quenching is observed due to the oxygen vacancies. Commission Internationale d'Eclairage (CIE) color coordinates of (0.31, 0.38), Correlated Color Temperature (CCT) of 6341 K, and color purity of 22.57% confirm the potential of Sr3(PO4)2:1%Dy3+ phosphor annealed at (1200 °C, 6 hrs) for white light generation. A probable photoluminescence mechanism involving 4f→5d→4f transitions in Sr3(PO4)2:1%Dy3+ is proposed.

Color-tunable fluorescence and ultralong organic room temperature phosphorescence from multicomponent copolymers

Materials with color-tunable photoluminescence (PL) have attracted dramatically increasing interest in recent years, especially the tuning of both fluorescence (FL) and ultra-long organic room temperature phosphorescence (UOP). Herein, a series of polymer films are successfully fabricated by in situ copolymerization of carbazole derivatives, lanthanide complex, and acrylamide (AM). With a long lifetime of 2.82 s and a high quantum yield of 21.40%, these copolymers exhibit not only color-tunable FL from violet-red to blue, but also multicolor UOP scope from blue to chartreuse when the excitation wavelength is changed. Moreover, a nearly-white phosphorescence can also be observed by adjusting the excitation wavelength. Multiple information patterns with color-tunable FL and UOP emissions are captured, exhibiting promising potential in the information encryption and anti-counterfeiting fields.

Near-unity quantum yield and long-term emission stability in halide perovskite nanocrystal glass composite

Metal halide perovskites are promising optoelectronic materials due to their outstanding luminescent properties. However, the instability of perovskites has long been the bottleneck to their practical applications. Here Cs4PbBr6 nanocrystals based glass composite (Cs4PbBr6 NCs@glass) are successfully prepared, which displays green emission color (520 nm), narrow bandwidth (23 nm) and a near-unity photoluminescence quantum yield (PLQY). The H2O molecules permeating in the lattice of Cs4PbBr6 were found to be a crucial role in the subband energy emission. The Cs4PbBr6 NCs@glass has excellent emission stability; maintains 93 % of initial PL intensity after ultraviolet light irradiation for over 5000 h. In addition, by adjusting the halogen content, we have achieved tunable emission color from blue (450 nm) to green (520 nm) and red (670 nm) on Cs4PbX6 NCs@glass (X = Cl, Br, I), which covers up to 127 % of the National Television Systems Board (NTSC) standard system. Our finding indicates the commercial applications of perovskite materials in lighting and display.

The crystal structure, energy transfer and tunable luminescence properties of NaLaMgWO6:Tm3+, Eu3+ phosphors

A series of NaLaMgWO6:Tm3+, Eu3+ phosphors with color-tunable emission were successfully synthesized by the solid-state reaction method. The crystal structure, luminescence characteristics and energy transfer of NaLaMgWO6:Tm3+, Eu3+ phosphors have been studied. It is observed that Tm3+ singly doped phosphors exhibit intense blue emission at 484 nm, and Eu3+ singly doped phosphors emit red light at 621 nm. The phosphors co-doped with Tm3+, Eu3+ exhibit fluorescence spectra composed by the characteristic emission peaks of Tm3+ ions and Eu3+ ions. A tunable emission color from blue to red can be obtained by adjusting the ratio of the doping concentration of Tm3+/Eu3+, indicating a significant energy transfer from Tm3+ to Eu3+. The energy transfer mechanism between Tm3+→Eu3+ in the NaLaMgWO6:Tm3+, Eu3+ phosphors is proved to be a quadrupole-quadrupole interaction. These results show that NaLaMgWO6:Tm3+, Eu3+ phosphors may have a potential application in white light emitting diodes.