Temperature-dependent Luminescence Research Articles

Delineating Dy3+ and Sm3+ in thermally stable strontium silicate apatites for multifunctional applications

The structural, optical and temperature dependent luminescence properties of a series of Sr2Y8-xREx(SiO4)6O2 (RE=Dy and Sm) silicate phosphors are investigated for their multifunctional applications. The phosphors were synthesized using the solid-state reaction route with varying doping levels and characterized for phase purity. X-ray Diffraction analysis revealed the hexagonal crystal structure of (Sr2RE2)(RE6)(SiO4)6O2, indicating the incorporation of rare earth (RE) ions into two distinct crystallographic sites, thereby augmenting the luminescence properties. Dy3+ doped compounds exhibit intense yellow emission, promising white light generation when paired with InGaN blue LED chips. Sm3+ doped samples show orange-red emission around 601 nm, attributed to multipole-multipole interactions, with rapid decay curves suitable for high-speed response LEDs. Correlated Color Temperature (CCT) values were computed to assess the commercial viability of these phosphors in luminescence applications and the role of lighting in the growth of indoor plants and office spaces is discussed. The Sr2Y7.8Dy0.2(SiO4)6O2 phosphor with remarkable quantum yield of 63.56% demonstrated a thermal stability of 0.27 eV with enhanced sensitivity of about 0.39% K−1 and Sr2Y7.8Sm0.2(SiO4)6O2 with stability around 0.31eV with sensitivity of 1.11% K⁻¹ at 100K reveals them as potential candidates for optical temperature sensing. These results declare the competence of synthesized novel silicate apatites in solid-state lighting and optical thermometry.

Highly efficient and water-resistant BaGa4S7:Eu2+ phosphor prepared by a self-reduction method

The development of eco-friendly luminescent materials is imperative for the advancement of phosphor-based technologies. This study corroborates the self-reduction of Eu3+ to Eu2+ through analyses utilizing photoluminescence (PL), excitation spectroscopy (PLE), and X-ray photoelectron spectroscopy (XPS). Density functional theory (DFT) calculations demonstrate that Eu2+ ions can efficaciously substitute Ba2+ ions within the BaGa4S7 lattice, preserving its structural integrity. Upon blue light excitation, BaGa4S7:Eu2+ manifests a robust green emission attributed to Eu2+ ions, showcasing a peak wavelength near 526 nm. The quantum yield (QY) of BaGa4S7:Eu2+ is remarkably high, registering at 74.8 %. Moreover, the temperature-dependent luminescence properties of BaGa4S7:Eu2+ phosphor were subjected to thorough investigation. Water resistance assays indicate that the sample preserves 76 % of its initial luminous intensity following 40 days of aqueous immersion. Additionally, BaGa4S7:Eu2+ based phosphor-converted white light-emitting diodes (WLEDs) demonstrate emission of high-quality white light. This unique water-resistant green emission sulfide phosphor is expected to have potential applications in lighting fields.

Defect level induced negative thermal quenching of β-Ba3LuAl2O7.5: Yb3+, Er3+ phosphor

Temperature-dependent behavior of phosphors has recently attracted significant research attention. This is due to the widespread applications of phosphors. Unfortunately, the thermal quenching effect in many phosphors greatly limits their performance at high temperatures. Herein, negative thermal quenching phosphor β-Ba3LuAl2O7.5: 0.3Yb3+, 0.03Er3+ is synthesized using the high-temperature solid-state method. X-ray Rietveld refinement and EPR results indicate the defect state of oxygen vacancy. Temperature-dependent upconversion luminescence spectra demonstrate that the green and red emission intensities increase with temperature to reach maximums at 398K and 348K respectively. Diffuse reflectance spectrum and downshifting luminescence spectrum prove that the defect state is near the 4F7/2 state of Er3+ ions. The defect state traps electrons at room temperature and releases them to populate the 4F7/2 state of Er3+ ion at elevated temperatures to cause the observed thermal enhancement of upconversion luminescence. This material's negative thermal quenching effect makes it a suitable candidate for applications in displays and anti-counterfeiting.

Multi-mode up-conversion emission of Tm@Yb@Er phosphors for color modulation and thermometry

Rare earth doped up-conversion materials play an important role in information security, colorful display and temperature sensing. In this work, the up-conversion luminescence of NaYF4:0.2Tm/20Yb@NaYF4:20Yb@NaYF4:2Er/20Yb phosphors, synthesized by typical co-precipitation method, are investigated under different excitation condition. The emission color of sample can be tuned from yellow to blue-green through changing pump laser from 1550 to 980 nm because the Tm3+ ions in the core cannot be excited by 1550 nm laser. More interesting, the value of red-to-green (R/G) and blue-to-green (B/G) can be finely manipulated by tuning the excitation pulse width and frequency. This phenomenon can be interpreted by different rising processes of the green, red and blue up-conversion emission. In addition, the core-shell structured sample displays a temperature-dependent color change, ranging from blue-green to purple. The green emissions, radiated from thermal coupled levels (2H11/24S3/2), are used in thermometry and the max relatively sensing sensitivity reaches 0.01 K−1 at 303 K. The findings indicate that the core-shell Tm@Yb@Er phosphors, with excitation-dependent and temperature-dependent up-conversion luminescence, have potential applications in information security and temperature sensing.

Enhancement of Interlayer Exciton Emission in a TMDC Heterostructure via a Multi-Resonant Chirped Microresonator Upto Room Temperature.

We report on multi-resonance chirped distributed Bragg reflector (DBR) microcavities. These systems are employed to investigate the light-mater interaction with both intra- and inter-layer excitons of transition metal dichalcogenide (TMDC) bilayer heterostructures. The chirped DBRs consisting of SiO2 and Si3N4 layers of gradually varying thickness exhibit a broad stopband with a width exceeding 600nm. Importantly, the structures provide multiple resonances across a broad spectral range, which can be matched to resonances of the embedded TMDC heterostructures. Studying cavity-coupled emission of both intra- and inter-layer excitons from an integrated WSe2/MoSe2 heterostructure in a chirped microcavity system, an enhanced interlayer exciton emission with a Purcell factor of 6.67 ± 1.02 at 4 K is observed. The cavity-enhanced emission of the interlayer exciton is used to investigate its temperature-dependent luminescence lifetime of 60ps at room temperature. The cavity system modestly suppresses intralayer exciton emission by intentional detuning, thereby promoting a higher IX population and enhancing cavity-coupled interlayer exciton emission. This approach provides an intriguing platform for future studies of energetically distant and confined excitons in different semiconducting materials, which paves the way for various applications such as microlasers and single-photon sources by enabling precise emission control and utilizing multimode resonance light-matter interaction.

Synthesis, characterization, and temperature-dependent luminescence of Tb3+-activated and self-activated Sr10(PO4)6Cl2 phosphors

In this work, a series of new nanosized phosphors based on strontium chlorapatite (Sr10(PO4)6Cl2, abbreviated as SrClAp) with varying terbium concentration were synthesized using a modified microwave-hydrothermal method. This study meticulously investigated the impact of Tb3+ concentration and annealing temperature on factors such as crystal purity, particle morphology, photoluminescence, chromatic properties, and the mechanism of thermal quenching.The synthesized phosphors underwent characterization using X-Ray Diffraction (XRD) and scanning electron microscopy (SEM) to verify their crystal structure purity and examine their morphology. Upon near-ultraviolet (NUV) excitation at the 378 nm line, the obtained nanosized powders emitted green light arising from the characteristic 5D4→7FJ (J = 6, 5, 4, 3) transitions of Tb3+ ions. Notably, a broad host-related emission was discernible at 80 K, with its intensity diminishing as the temperature increased. The mechanism governing this host-related emission and the process of its thermal quenching have been proposed. Moreover, a comprehensive exploration of the influence of ambient temperature on the emission of Tb3+-doped SrClAp was undertaken.

Solvent-Assisted Structural Modifications of Sulfur Dots Followed by Time-Dependent Emergence of a New Emissive State and Long-Lived Afterglow.

Sulfur dots are a new class of recently developed nonmetallic luminescent nanomaterials with various potential applications. Herein, we synthesized sulfur dots using a mild chemical etching method and then modified the structural features of the as-synthesized sulfur dots using a slow and defined solvent-assisted aggregation process. This increases the particle size and overall crystallinity along with the modifications of the surface functional groups, which eventually show a new emission band at longer wavelengths. Detailed photophysical and temperature-dependent luminescence studies confirmed that the new emissive state evolves due to interparticle interactions in the excited state. Furthermore, the occurrence of a new emissive state in a longer-wavelength region helped reduce the energy gap between the lowest excited singlet state and the lowest excited triplet state in modified sulfur dots, resulting in an aqueous stable room-temperature phosphorescence/afterglow emission through efficient intersystem crossing. This typical efficacious afterglow emission directly shows the potential applicability of structurally modified sulfur dots in encryption devices and can also be potentially effective in light emitting diodes (LED) and sensing devices.

Unveiling highly sensitive Dy3+ doped BaMgAl10O17 phosphor’s thermoluminescence trap features and temperature dependent luminescence for solid state lighting applications

This article explores the structural, morphological, thermoluminescence, and temperature-dependent emission properties of novel Dy3+ doped BaMgAl10O17(BAM-Dy) phosphors. Structural studies reveal that the phosphor has a similar structure to β-alumina. Rod-shaped interlinked surface morphology is a notable characteristic of the BAM-Dy samples. Incorporation of Dy3+ ions lead to the formation of distinct emission peaks (485 nm, 577 nm, and 635 nm) in the PL emission spectra. The effect of dopant concentration on the light output is crucial, and the highest PL intensity is observed for 1.5 mol% of Dy3+ concentration. The potential use of BAM-Dy phosphors for Gamma radiation detection and measurement is tested through thermoluminescence studies, which reveal high sensitivity, low threshold dose values, and exceptional response to low gamma doses, making them suitable for dosimetry applications. The investigation of trap parameters provides useful information about the number of traps, trapping mechanism, and trap energies, which is essential for in-depth study of synthesized phosphors for γ dosimetry application. The study of the effect of temperature on the luminescence behaviour is crucial for the application of phosphors in the light-emitting field. The BAM-Dy samples exhibit excellent thermal stability even at 210 °C, making them suitable for use in the field of White LEDs.

Effect of Ca co-doping on gamma-stimulated luminescence of Lu2SiO5:Ce

In order to estimate the stability of the light output of the scintillation detector, the Lu2SiO5:Ce scintillation crystals, additionally doped with Ca2+ ions at concentrations of 0 ÷ 0.4 at%, were studied. The spectra of optical absorption, gamma-luminescence, thermal luminescence, dose and temperature dependences of luminescence were measured. Gamma-luminescence in the dose range 10 - 5·107 Gy was recorded using 60Co gamma-source at the temperature range of 310–460 K. In contrast to the initial sample (non-doped with Ca), in the sample doped with 0.1 at% of Ca, an increase in the luminescence intensity was observed in the range of 390–425 nm, but further with an increase in the concentration of Ca (0.3–0.4 at%), the intensity of this band decreased to the initial level (undoped). At Ca concentrations of 0.3 and 0.4 at%, the intensity of the Ce1 center band remains practically unchanged up to a dose of 5·107 Gy. LSO crystals doped with Ce 0.1 at% and co-doped with Ca 0.1 at% can be recommended as a scintillation detector up to a gamma-dose of 105 Gy at room temperature.

Mn4+-activated NaSr10Y5W4O30 far-red emitting luminescent material for plant growth lighting

A series of Mn4+-doped NaSr10Y5W4O30 (NSYWO) phosphors have been successfully synthesized and further characterized to estimate their potentials for application as a far-red emitting component of pc-LED. An XRD analysis and crystal structure refinement have been carried out to characterize its quality. The doping concentration and temperature (80–500 K) dependent luminescence properties as well as decay kinetics have been studied and analyzed. It has been found that Mn4+ substitutes for W6+ sites resulting in far-red emission at 688 nm. The temperature quenching is attributed to thermal activation of an electron from Mn4+ 2Eg to 4A2g state via crossover, yielding an activation energy of 0.35 eV. Furthermore, to assess practical application of the novel phosphor, a blue-emitting LED chip combined with NSYWO: 0.8 mol% Mn4+has been packaged. The light from both the blue-emitting LED chip and NSYWO: Mn4+ phosphor was shown to be effectively utilized, revealing a good promise for application of the phosphor in the field of plant growth lighting.

Investigation of the luminescence properties and temperature dependent luminescence properties of Sm3+ doped NaPbBi2(PO4)3 orthophosphate phosphor: A promising candidate for light and light sensing applications

The red phosphor for light application is in high demand. In this regard, a series of orange-red phosphors, NaPbBi2(PO4)3: Sm3+, with a single phase were obtained by the conventional solid state reaction method. The X-ray diffraction (XRD) confirms that the phosphor belongs to the cubic structure with a space group I-43d (220). The optical property of the phosphor was studied through the diffuse reflectance spectroscopy measurements and the characteristic peaks of the Sm3+ ions were identified. Exciting the phosphors at 404 nm, produced a strong orange-red emission at 601 nm. The optimum concentration of the phosphor was found to be 0.03 mol. In all emission transitions of the Sm3+ ions within the host lattice, the energy transfer (ET) occurs among the nearest neighbour ions. The lifetime values were in the order of milliseconds. The photometric parameters revealed that the emission lies in the orange-red region with color coordinates (0.5863, 0.4129) and a color purity of 99.4 %. The temperature dependent luminescence properties of the phosphor were also investigated and all these results showed that the phosphor could serve as a good candidate for light/light sensing applications.

Construction of a Zn(II)-Eu(III) Nanoring with Temperature-Dependent Luminescence for the Qualitative and Quantitative Detection of Neopterin as an Inflammatory Marker.

A nine-metal Zn(II)-Eu(III) nanoring 1 with a diameter of about 2.3 nm was constructed by the use of a long-chain Schiff base ligand. It shows a luminescence response to neopterin (Neo) through the enhancement of lanthanide emission with high selectivity and sensitivity, which can be used to quantitatively analyze the concentrations of Neo in fetal calf serum and urine. The luminescence sensing of 1 to Neo is temperature-dependent, and it displays more obvious response behavior at lower temperatures. Filter paper strips bearing 1 can be used to qualitatively detect Neo by the color change from chartreuse to red under a UV lamp. The limit of detection is as low as 3.77 × 10-2 nM.

Trivalent dysprosium activated LaSr2AlO5 nanophosphors for NUV-excited wLEDs: Insights into structural, optical, Judd-Ofelt parameters and temperature dependent photoluminescence

Gel-combustion (GC) methodology was implemented in the present research to produce a series of single phase Dy3+ doped LaSr2AlO5 nanophosphors for the usage in wLEDs. X-ray powder diffraction patterns verified the phase purity and crystal structure of the produced materials. The XRD inspection supported the successful fabrication of tetragonal structured (I4/mcm space group) phosphors and revealed good accordance with card number 70–2197 on the JCPDS database. We collected diffuse reflectance spectra (DRS) to examine how doping affects the band gap. Furthermore, energy-dispersive X-ray (EDX) spectroscopy and transmission electron microscopy (TEM) have been employed for assessing elemental composition and surface morphology. On 349 nm excitation, LaSr2AlO5:Dy3+ phosphors produce the distinctive yellow PL emissions causedby 4F9/2→6H13/2 transition. Using excitation spectra, the Judd-Ofelt (J-O) characteristic (Ω = 2, 4, 6) have been determined. The Dy3+ transition's features show that the J-O parameters followed the trend which suggested an asymmetric environment around the ligand. The electric dipole transition predominated in the luminescence spectrum, causing the LaSr2AlO5:Dy3+ phosphor to emit a yellowish whitecolor. The fundamental mechanism for the energy transfer and concentration quenching instances among activator ions was discovered to be dipole-quadrupole interactions. Temperature dependent luminescence showed that the synthesized phosphors had thermal stability up to 523 K with activation energy of 0.1312 eV. The future prospects of the synthesized phosphor as an effective choice for near-ultraviolet-activated wLEDs are substantially supported by current comprehensive research.

Spectroscopic studies of TeO2-based glasses doped with Sm3+ and its use as an optical temperature sensor

This study reports the synthesis and characterization of glasses in the (100-x)65TeO2-15Li2O-20ZnO + xSm2O3 system doped with Sm2O3, denoted as Sm3+: TLZ glasses, with varying doping concentrations from 0.1, 0.15, 0.2, 0.35, 0.5, and 1 mol%. The structural and optical properties, as well as the temperature dependence of luminescence, were investigated. Excitation at 405nm resulted in strong orange-red luminescence at 566, 600, and 646 nm. The local environment surrounding Sm3+ ions was explored using the intensity ratio of electric and magnetic dipole transitions. The non-radiative energy transfer between neighboring Sm3+ ions was evaluated using the Inokuti-Hirayama model, allowing for the determination of the critical transfer distance. The temperature dependence of luminescence, displayed by Commission Internationale de L’Eclairage (CIE) chromaticity coordinates, exhibited a monotonic change from (0.611, 0.387) at 295 K to (0.605, 0.393) at 479 K. The Sm3+:TLZ glasses doped with 0.15 mol% showed the highest relative thermal sensitivity of 0.10%K-1 at 479 K, suggesting their potential as luminescent thermometers.

Interrupting the long-range energy migration among Eu3+ by the introduction of unequivalent [NaO8] units to achieve both high quenching concentration and quantum yield in NaY2Ga2InGe2O12

In the pursuit of optimizing white light-emitting diodes (WLEDs), Eu3+-doped phosphors have emerged as a key component in strategies that combine ultraviolet (UV) LED chips with red, green, and blue (RGB) tricolor phosphors. However, their application has been notably constrained by concentration quenching and thermal quenching. To address this challenge, we have developed a series of novel red phosphors, NaY2-xGa2InGe2O12:xEu3+. The powder X-ray diffraction (XRD) indicates that the NaY2Ga2InGe2O12(NYGIG) belongs to the garnet family. The [NaO8] unit replaces one-third of the eight-coordinated sites of garnet and leaves the other two-thirds for the [YO8], which helps to prevent long-range energy migration among Eu3+ especially when the eight-coordinated sites were highly substituted. Such a structure feature allowed the NaY2-xGa2InGe2O12:xEu3+ phosphor to achieve an optimal quantum yield of 95.6% at an extremely high Eu3+ doping x value up to 1.2. Moreover, further studies on the temperature-dependent luminescence spectra confirm that an anomalous thermal quenching phenomenon will occur when the NaY2-xGa2InGe2O12:1.2Eu3+ phosphor is properly excited. In application, the combination of the red-emitting NaY2-xGa2InGe2O12:1.2Eu3+, blue-emitting BaMgAl10O17:Eu2+, and green-emitting Zn2SiO4:Mn2+ phosphors can realize high color rendering (CRI∼93) white light with the with CIE coordinates of (0.353,0.350), indicating that the NYGIG:Eu3+ phosphor own a promising potential for WLEDs.

Giant thermal enhancement of upconversion photoluminescence in Y2W3O12:Nd phosphor under 808 nm excitation

Luminescent materials usually suffer from thermal quenching at high temperature due to the aggravation of nonradiation relaxations. Herein, a giant enhancement of up conversion (UC) luminescence is observed in negative thermal expansion (NTE) Y2W3O12:Nd phosphor upon increasing the temperature from 310 to 790 K. In addition, the temperature-dependent UC emission is reversible. To penetrate into the mechanisms, the temperature-dependent luminescence intensity and lifetime are investigated for Nd doped negative and positive thermal expansion (PTE) phosphors. Based these investigation, we infer that the underlying mechanism of the giant enhancement for Y2W3O12:Nd phosphor are due to combined effects of phonon assisted absorptions and contraction of NTE crystals. Moreover, the observation of temperature-dependent near-infrared spectra (NIR) can support the mechanism from the other side. The present findings pave the way to overcome thermal quenching of Nd3+ ions and explore new thermal enhancement materials sensitized by Nd3+ ions.

Unlocking the luminescent potential of Pr3+/Yb3+ Co-doped Y2Mo4O15 for advanced thermometry applications

In this study, Pr3+/Yb3+ co-doped Y2Mo4O15 phosphor was successfully synthesized using the traditional citric acid-assisted sol-gel method, with the aim of exploring its potential for optical thermometry applications. The structural and morphological characteristics of the synthesized sample were comprehensively analyzed through X-ray powder diffraction (XRD) and scanning electron microscopy (SEM). Photoluminescence and temperature-dependent luminescence properties were systematically investigated within a temperature range of 298 K to 508 K, employing 473 nm excitation. To assess the temperature sensing capabilities of the phosphors, we utilized both the fluorescence intensity ratio (FIR) and fluorescence lifetime (FL) techniques. Optical temperature measurements were conducted through both thermal and non-thermal coupling methods. Our findings revealed that the FIR (I547/I490) exhibited an outstanding maximum sensitivity of 1.27% K−1, accompanied by remarkably low-temperature uncertainty (δT) values ranging from 0.04 to 0.83 K. This outstanding performance makes it the optimal choice for temperature sensing. Additionally, when employing FL thermometry, the maximum sensitivity (Sr) was determined to be 0.21% K−1 at 538 K. These results strongly indicate the significant potential of Y2Mo4O15: Pr3+/Yb3+ in the realm of optical thermometry, offering promising opportunities for precise and reliable temperature measurements.

White light-emitting ZnO:Dy3+ nanophosphors: delving into the spectroscopic parameters via Judd-Ofelt analysis.

Developing a single-phase white emitting nanophosphor with high quantum efficiency has become a hotspot for scientific world. Herein, single-phase white-light emitting Zn1-xO:xDy3+ nanophosphors have been synthesized via a sonochemical method. X-ray diffraction analysis and Raman spectroscopy-based investigations confirmed the hexagonal wurtzite phase for Zn1-xO:xDy3+ nanophosphors with preferential growth along the (101) plane. Scanning electron microscopy images showed the formation of a ribbon-shaped morphology with a diameter of ∼25 nm. The emission spectra of the Dy3+-activated ZnO nanophosphors exhibited three distinct peaks, namely blue (480 nm), yellow (572 nm), and red (635 nm) emissions, under near-UV excitations related to the 4F9/2 → 6HJ (J = 15/2, 13/2, and 11/2) transitions of Dy3+ ions. The values of CIE chromaticity coordinates for the optimized phosphor (x = 0.329, y = 0.334) with correlated color temperature (CCT) of 5657 K indicated cool white-light emission from the phosphor. The thermal stability of ZnO:Dy3+ nanophosphors was probed by temperature-dependent luminescence. Quantitative evaluation of Judd-Ofelt intensity parameters, radiative parameters, luminescence decay, and quantum efficiency of Zn1-xO:xDy3+ using the J-O theory suggests that these nanophosphors are promising luminescent media for commercial white LEDs and other display devices.

Temperature and pressure dependent luminescence mechanism of a zinc blende structured ZnS:Mn nanophosphor under UV excitation

Presenting a novel insight into Mn2+ luminescence processes in the ZnS nanophosphor and revealing its unique high-pressure luminescence decay behaviour and self-powered mechanoluminescence.

Strong green upconversion emission from submicron spindle-shaped SrMoO4:Yb3+,Er3.

Upconversion luminescence (UCL) is a fluorescence process where two or more lower-energy photons convert into a higher-energy photon. Lanthanide (Ln3+)-doped UCL materials often suffer from weak luminescence, especially when directly synthesized by a hydrothermal (HT) process due to the existing hydroxyl group and undesirable arrangement of dopants within host lattices which quench luminescence and limit energy transfer. Therefore, additional heat treatment processes are required to enhance their UCL emission, even though direct hydrothermal synthesis without further heat treatment has the advantages of low energy consumption, fast synthesis, and wide applicability to generate UCL materials. In this study, via a HT process without annealing, we have produced Yb3+ and Er3+ co-doped SrMoO4 submicron spindles with a strong green UCL emission which can be seen with the naked eye, which HT produced oxide-based UCL materials often fail to demonstrate. We have investigated different HT synthesis conditions, such as temperature, time, pH and dopant composition, which control the nucleation, growth, lattice structure arrangement, and ultimately their UCL properties through XRD, SEM, EDS and UCL measurements. The bright green UCL from the SrMoO4:Yb,Er submicron spindles is further enhanced by post-synthesis annealing within a molten NaNO3/KNO3 system to prevent particle size growth. The green UCL intensity from the annealed SrMoO4:Yb,Er submicron spindles surpasses samples produced by the solid-state method and is comparable to that from the commercial NaYF4:Yb,Er sample. We have further studied the temperature-dependent luminescence of both the HT-prepared and molten-salt annealed SrMoO4:Yb,Er submicron spindle samples. The strong UCL from our SrMoO4:Yb,Er submicron spindles could warrant their candidacy for bioimaging and anticounterfeiting applications.