Temperature-dependent Emission Research Articles

Temperature-dependent excitonic emission characteristics of highly crystallized carbon nitride nanosheets

Highly-crystallized carbon nitride (HCCN) nanosheets exhibit significant potential for advancements in the field of photoelectric conversion. However, to fully exploit their potential, a thorough understanding of the fundamental excitonic photophysical processes is crucial. Here, the temperature-dependent excitonic photoluminescence (PL) of HCCN nanosheets and amorphous polymeric carbon nitride (PCN) is investigated using steady-state and time-resolved PL spectroscopy. The exciton binding energy of HCCN is determined to be 109.26 meV, lower than that of PCN (207.39 meV), which is attributed to the ordered stacking structure of HCCN with a weaker Coulomb interaction between electrons and holes. As the temperature increases, a noticeable reduction in PL lifetime is observed on both the HCCN and PCN, which is ascribed to the thermal activation of carrier trapping by the enhanced electron–phonon coupling effect. The thermal activation energy of HCCN is determined to be 102.9 meV, close to the value of PCN, due to their same band structures. Through wavelength-dependent PL dynamics analysis, we have identified the PL emission of HCCN as deriving from the transitions: σ*–LP, π*–π, and π*–LP, where the π*–LP transition dominants the emission because of the high excited state density of the LP state. These results demonstrate the impact of high-crystallinity on the excitonic emission of HCCN materials, thereby expanding their potential applications in the field of photoelectric conversion.

Ultrastable Copper Iodide Hybrid with Intrinsic Greenish White-Light Emission by Incorporating an Anionic Inorganic Functional Unit into an Extended Structure.

Incorporating a functional unit into the multidimensional coordination polymer skeleton is an efficient way to improve the stability of materials and expand their application. In this paper, anionic copper iodide inorganic functional modules are incorporated into one-dimensional extended chains by using a unique bidentate cationic organic ligand. Benefiting from the ionic extended structure, the resulting hybrid possesses a remarkable stability with a decomposition temperature as high as 300 °C. Meanwhile, the hybrid material exhibits intrinsic greenish white-light emission with a high photoluminescent quantum yield of 70%. The emission was investigated by temperature-dependent emission spectra, which proved to be the result of the synergistic effect of two energy states. The novel synthetic strategy provides an efficient route for the development of functional organic metal halides.

Photophysical Studies of a Zr(IV) Complex with Two Pyrrolide-Based Tetradentate Schiff Base Ligands.

The reaction of two equivalents of N,N'-bis(2-pyrrolylmethylidene)-1,2-phenylenediamine (H2bppda) with tetrabenzylzirconium provided the air- and moisture-stable eight-coordinate complex Zr(bppda)2. Temperature-dependent steady-state and time-resolved emission spectroscopy established weak photoluminescence (ΦPL = 0.4% at 293 K) by a combination of prompt fluorescence and thermally activated delayed fluorescence (TADF) upon visible light excitation at and around room temperature. TADF emission is strongly quenched by 3O2 and shows highly temperature-sensitive emission lifetimes of hundreds of microseconds. The lifetime of the lowest energy singlet excited state, S1, was established by transient absorption spectroscopy and shows rapid deactivation (τ = 142 ps) by prompt fluorescence and intersystem crossing to the triplet state, T1. Time-dependent density functional theory (TD-DFT) calculations predict moderate ligand-to-metal charge transfer (LMCT) contributions of 25-30% for the S1 and T1 states. A comparison of Zr(bppda)2 to related zirconium pyridine dipyrrolide complexes, Zr(PDP)2, revealed important electronic structure changes due to the eight-coordinate ligand environment in Zr(bppda)2, which were correlated to differences in the photophysical properties between the two compound classes.

Temperature-dependent self-trapped exciton emission in Cu(I) doped zinc-based metal halides from well-resolved excited state structures

Temperature-dependent self-trapped exciton emission in Cu(I) doped zinc-based metal halides from well-resolved excited state structures

Pt-S Bond-Enabled Temperature-Dependent Phosphorescence in S-Heteroaryl Tetradentate Pt(S^C^N^O) Complexes.

This study presents the rare examples of S-heteroaryl tetradentate Pt(S^C^N^O) luminescent complexes (PtSZ and PtSZtBu) containing a Pt-S bond. The presence of the Pt-S bond allows the novel Pt(S^C^N^O) complexes to exhibit temperature-dependent phosphorescent emission behavior. The PtSZtBu exhibits dual-emission phenomena and biexponential transient decay spectra above 250 K, indicating the presence of two minimal excited states in the potential energy surface (PES) of the T1 state. Through complementary experimental and computational studies, we have identified changes in orbital composition between Pt(dxy)-S(px) and Pt(dyz)-S(pz) in excited states with increasing temperature. This results in two energy minima, enabling the excited states to decay selectively and radiatively at different temperatures. Consequently, this leads to remarkable steady-state and transient emission spectra changes. Our work not only provides valuable insights for the development of novel Pt-S bond-based tetradentate Pt(II) complexes but also enhances our understanding of the distinctive properties governed by the Pt-S bond.

The Autoxidation of Polyether-Polyurethane Open Cell Soft Foam: An analytical aging method to reproducibly determine VOC emissions caused by thermo-oxidative degradation

We present a new method for investigating the oxidation and emission behavior of air-permeable materials. Employing this method, a differentiated statement can be made about the extent to which critical volatile organic compounds (VOCs) such as formaldehyde, acetaldehyde, and acrolein are contained in the material as impurities or formed by thermo-oxidative degradation of the polymer matrix in the use phase. The parameters affecting methods of VOC analysis are reviewed and considered for the developed method. The molecular mechanisms of VOC formation are discussed. Toxicological implications of the reaction kinetics are put into context with international guidelines and threshold levels. This new method enables manufacturers of cellular materials not only to determine the oxidative stability of their products but also to optimize them specifically for higher durability. Environmental ImplicationCellular materials are ubiquitous in the technosphere. They play a crucial role in various microenvironments such as automotive interiors, building insulation, and cushioning. These materials are susceptible to oxidative breakdown, leading to the release of formaldehyde, acetaldehyde, and acrolein. The ecotoxicological profiles of these compounds necessitate monitoring and regulation. The absence of reproducible and reliable analytical methods restricts research and development aimed at risk assessment and mitigation. This work significantly enhances the toolbox for optimizing the oxidative stability of any open-cell cellular material and evaluating these materials in terms of their temperature-dependent oxidation and emission behavior.

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.

Optical and photoluminescence properties of trivalent rare earth ions doped LiMgPO4

Trivalent rare-earth-activated luminescent materials have attracted a lot of attention due to their fascinating optical properties and broad range of applications. In this study, polycrystalline Sm and Eu-doped LiMgPO4 luminescent materials were synthesized using a solid-state reaction technique. The crystalline structures, morphological features, and optical characteristics of the synthesized materials were thoroughly investigated using x-ray diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Field-Emission Scanning Electron Microscopy (FE-SEM) and UV–vis spectroscopy. The Rietveld refinement analysis confirmed the phase purity of synthesized phosphors. In addition, the strain induced owing to the incorporation of trivalent rare-earth ions and crystallite sizes of each synthesized material was estimated using the Williamsons-Hall (W-H) and modified Debye-Sherrer equations. The estimated results of the microstrain were reported to be 0.0010, 0.0023 and 0.0020. Subsequently, as a consequence of distinct peak profile options, the projected average crystallite size by both approaches was distinct. The UV–vis spectroscopy analysis reveals that Sm and Eu doped materials exhibit absorption bands around 402 nm and 396 nm and depicts the declining band gap values. The Photoluminescence (PL) spectra at 402 nm and 395 nm excitation wavelengths exhibited the distinctive emissions of both Sm3+ (4G5/2 → 6H7/2) and Eu3+ (5D0 → 7F2) ions emanating due to the intra-configurational f - f and 4 f − 4 f transitions. Finally, the CIE diagram explicitly demonstrates that the Sm and Eu-modified materials reveal their exceptional color purity. McCamy’s approach was used to determine various parameters of trivalent rare-earth doped materials. The correlated color temperature ( TCCT ) and their coordinates TCCT (ζ, β) was found to be 2287 K, 1900 K, 0.281, 0.632, and 0.302, 0.681 respectively. Temperature-dependent emission spectra exhibit excellent color and thermal stability at high temperatures. The obtained results in this study indicate that the synthesized luminescent materials can potentially be used in white light-emitting diode applications.

Confinement of Sustainable Carbon Dots Results in Long Afterglow Emitters and Photocatalyst for Radical Photopolymerization.

Sustainable carbon dots based on cellulose, particularly carboxymethyl cellulose carbon dots (CMCCDs), were confined in an inorganic network resulting in CMCCDs@SiO2. This resulted in a material exhibiting long afterglow covering a time frame of several seconds also under air. Temperature-dependent emission spectra gave information on thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP) while photocurrent experiments provided a deeper understanding of charge availability in the dark period, and therefore, its availability on the photocatalyst surface. The photo-ATRP initiator, ethyl α-bromophenylacetate (EBPA), quenched the emission from the millisecond to the nanosecond time frame indicating participation of the triplet state in photoinduced electron transfer (PET). Both free radical and controlled radical polymerization based on photo-ATRP protocol worked successfully. Metal-free photo-ATRP resulted in chain extendable macroinitiators based on a reductive mechanism with either MMA or in combination with styrene. Addition of 9 ppm Cu2+ resulted in Mw/Mn of 1.4 while an increase to 72 ppm improved uniformity of the polymers; that is Mw/Mn=1.03. Complementary experiments with kerria laca carbon dots confined materials, namely KCDs@SiO2, provided similar results. Deposition of Cu2+ (9 ppm) on the photocatalyst surface explains better uniformity of the polymers formed in the ATRP protocol.

Temperature sensing of novel Tb3+/Ho3+/Bi3+ co-doped lead-free double perovskite Cs2AgInCl6 nanocrystals

Up to now, the research field of application of lanthanide ions doped lead-free double perovskite Cs2AgInCl6 nanocrystals (NCs) was relatively limited, even less in temperature sensing. Here, Tb3+/Ho3+/Bi3+ ions were successfully doped into Cs2AgInCl6 NCs by hot-injection. The temperature sensing performance of co-doped NCs by using the fluorescence intensity ratio (FIR) was studied through the temperature-dependent emission spectra. By analyzing the influence of ions' doping concentration on temperature sensing performance, the optimal doping concentration of co-doped Cs2AgInCl6 NCs was determined to be 7 % Tb3+, 20 % Ho3+ and 1 % Bi3+. The highest absolute and relative sensitivities reach 1.48 K−1 and 2.48 %/K, respectively. We provide a new doping scheme of lead-free double perovskite NCs which have good temperature sensing performance. This co-doped NCs have great potential application value in non-contact temperature sensing in nanoscale.

Temperature-Dependent Evaporative Anthropogenic VOC Emissions Significantly Exacerbate Regional Ozone Pollution.

The evaporative emissions of anthropogenic volatile organic compounds (AVOCs) are sensitive to ambient temperature. This sensitivity forms an air pollution-meteorology connection that has not been assessed on a regional scale. We parametrized the temperature dependence of evaporative AVOC fluxes in a regional air quality model and evaluated the impacts on surface ozone in the Beijing-Tianjin-Hebei (BTH) area of China during the summer of 2017. The temperature dependency of AVOC emissions drove an enhanced simulated ozone-temperature sensitivity of 1.0 to 1.8 μg m-3 K-1, comparable to the simulated ozone-temperature sensitivity driven by the temperature dependency of biogenic VOC emissions (1.7 to 2.4 μg m-3 K-1). Ozone enhancements driven by temperature-induced AVOC increases were localized to their point of emission and were relatively more important in urban areas than in rural regions. The inclusion of the temperature-dependent AVOC emissions in our model improved the simulated ozone-temperature sensitivities on days of ozone exceedance. Our results demonstrated the importance of temperature-dependent AVOC emissions on surface ozone pollution and its heretofore unrepresented role in air pollution-meteorology interactions.

Quantitative Fluorescent Lateral Flow Strip Sensor for Myocardial Infarction Using Purity-Color Upconversion Nanoparticles.

Acute myocardial infarction is a serious cardiovascular disease and poses significant risks to human health. Its early diagnosis and real-time detection are of great importance. Herein, we design a low-cost device that has a high sensitivity of cTnT and cTnI detection. Dual-color upconversion nanoparticles (UCNPs) are prepared as probes, which not only have high-purity red upconversion luminescence (UCL) under 980 or 808 nm excitation but also achieve good temperature sensing. Temperature-dependent multicolor emission excitation is obtained, and the color turns from white to orange and red with increasing temperature. In particular, the maximum SR and SA values based on nonthermally coupled levels are 4.76% K-1 and 8.6% K-1, which are higher than those based on thermally coupled levels. With the UCNPs-based lateral flow strip (LFS), the specific detection of cTnI and cTnT antigens in samples is achieved with a detection limit of 0.001 ng/mL, which is 1 order of magnitude lower than that of their clinical cutoff. The UCNPs-LFS device has a low-cost laser diode and a simplified laser and permits a mobile-phone camera to collect the results, which has an important influence on the field of biomarker sensing.

Unveiling surface and bulk contributions in temperature dependent THz emission from Bi2Te3

We report evolution of the pulsed terahertz (THz) emission from Bi2Te3 topological insulator in a wide temperature range, where an interplay between the topological surface and bulk contributions can be addressed in a distinguishable manner. A circular photogalvanic effect-induced topological surface current contribution to THz generation can be clearly identified in the signal, otherwise, overwhelmed by the hot carrier decoherence in the bulk states. With the decreasing temperature, an initial sharp increase in the topological surface THz signal is observed before it attains a constant value below ∼200 K. The scattering channels between topological surface and bulk regions via carrier-phonon scattering are dominantly active only above the bulk-Debye temperature of ∼180 K, and the temperature-independent behavior of it at lower temperatures is indicative of robust nature of topological surface states. THz emission due to ultrafast photon-drag current in the bulk states is almost independent of temperature in the entire range, while the combined photo-Dember and band-bending effects induced photocurrent is doubled at 10 K.

Luminescence properties and thermal stability of Dy2O3/Sm2O3 doped glass ceramics containing NaBi(WO4)2

Dy2O3–Sm2O3 co-doped transparent glass ceramics (GCs) containing NaBi(WO4)2 crystalline phase were prepared by melt-curing-crystallization method. The optimal heat treatment condition is 580 °C/2 h. The optimum incorporation concentration of Dy2O3 is 0.4%, exceeding which a quenching phenomenon dominated by quadrupole-quadrupole interactions emerges. Meanwhile, when the concentration of Dy2O3 was fixed, the chromaticity coordinate of the sample moved the cool white light region to the warm white light region as the concentration of Sm2O3 increased. The temperature-dependent emission spectra of the 0.4% Dy2O3-0.7% Sm2O3 co-doped GC samples show that emission intensity at 575 nm at 185 °C still reaches 80% of the room temperature. The thermal quenching activation energy was 0.1537 eV and the activation energy after the addition of Mo6+ was 0.1957 eV. This study indicates that Dy2O3–Sm2O3 co-doped GCs containing NaBi(WO4)2 crystalline phase can achieve light-color tunable emission, which is potentially valuable for solid-state color rendering and illumination applications.

Synthesis Design and Properties of Ca5(BO3)3F: Bi3+/Eu3+: Insight into Luminescence, Temperature, and Pressure Sensing.

Nowadays, the utilization of noncontact temperature and pressure sensing is experiencing growing popularity. In this work, Bi3+, Eu3+-doped Ca5(BO3)3F (CBOF) phosphors were synthesized via an ionic liquid-assisted electrospinning approach. The effect of molecular weight of polyvinylpyrrolidone on the morphology of CBOF was investigated, and a comprehensive analysis of its formation mechanism was presented. The luminescence properties of CBOF: Bi3+, Eu3+ were studied systematically. The temperature-dependent emission of CBOF: Bi3+, Eu3+ phosphor was discussed, and it displayed thermal sensitivity, which can be attributed to the distinct thermal response emission behaviors of Bi3+ and Eu3+. The investigation of the pressure-dependent emission behavior of the CBOF: Bi3+ phosphor revealed an anomalous phenomenon: with the increase of pressure, the emission peak showed a trend of first a blue shift and then a red shift. This anomaly was discussed in detail. The phosphor exhibits visual color change (blue to cyan), remarkable pressure sensitivity (4.76 nm/GPa), and a high upper pressure limit (24.2 GPa), indicating its potential use as an optical pressure sensor. Consequently, this study presents an innovative synthetic approach for fabricating CBOF, presenting a bifunctional material with promising prospects in the fields of temperature and pressure sensing.

Optical properties and Judd-Ofelt analysis of a novel Red-Emitting monoclinic Li3Ba2Gd3(WO4)8: Eu3+ phosphor

Red-emitting Li3Ba2Gd3(WO4)8: x at.% Eu3+ (0.5 ≤ x ≤ 10) phosphors were effectively produced using a conventional solid-state reaction method at high temperature in air atmosphere. The phosphors exhibited monoclinic crystalline structure with the C2/c space group and 2/m point group. The unit cell parameters determined from the Rietveld refinement for 3 at.% doped sample are a = 5.2149(4) Å, b = 12.7447(1) Å, c = 19.2058(3) Å, α = γ = 90°, β = a^c = 91.9315(1)° and Vcalc = 1275.748(2) Å3. Photoluminescence spectra, lifetimes, colour coordinates and purity, and temperature-dependent emission spectra have been systematically studied. Upon excitation at 395 nm, the phosphors displayed red emission with a peak centered at 614 nm, which was associated with the 5D0→7F2 electrical dipolar transition of Eu3+. At the same time, the influence of different Eu3+ ion concentration on the photoluminescence intensity is also discussed. The optimal concentration of Eu3+ ions in Li3Ba2Gd3(WO4)8 was found to be 3 at.%. The mechanism behind concentration quenching was ascribed to dipole–dipole interactions, and the critical distance for energy transfer among Eu3+ ions was determined to be 7.409 Å. The Judd–Ofelt theory was utilized to assess the intensity parameters and radiative properties. The fluorescence decay times were also determined for the different concentration levels of Eu3+ cations. The chromatic coordinates of Li3Ba2Gd3(WO4)8: Eu3+ were found to be (0.653, 0.345), closely resembling the standard red light (0.670, 0.330) and demonstrated high colour purity (98.42 %) under excitation at 395 nm. Moreover, the phosphors Li3Ba2Gd3(WO4)8: Eu3+ exhibited favorable thermal stability, characterized by an activation energy of 0.219 eV. The aforementioned findings indicate that the phosphors Li3Ba2Gd3(WO4)8 doped with Eu3+ have the potential to function as a red-emitting phosphor in near-ultraviolet-driven white light-emitting diodes.

Ultrasound-switchable fluorescence thermometry with dual detection channels using temperature-sensitive liposomes.

Temperature measurements in biological tissues play a crucial role in studying metabolic activities. In this study, we introduce a noninvasive thermometry technique based on two-color ultrasound-switchable fluorescence (USF). This innovative method allows for a local temperature mapping within a microtube filled with temperature-sensitive liposomes as nano imaging agents. By measuring the temperature-dependent fluorescence emission of the liposomes using a spectrometer, we identify four characteristic temperatures. The local background temperature can be estimated by analyzing the corresponding appearance time of these four characteristic temperatures in the dynamic USF signals captured by a camera-based USF system with two detection channels. Simultaneous measurements with an infrared (IR) camera showed a 0.38°C ± 0.27°C difference between USF thermometry and IR thermography in a physiological temperature range of 36.48°C-40.14°C. This shows that the two-color USF thermometry technique is a reliable, noninvasive tool with excellent spatial and thermal resolution.

Impact of dopant concentration on the structural, morphological, and spectroscopic characteristics of Eu3+-doped Sr10(PO4)6F2 nanomaterials, including temperature-dependent emission

Luminescent materials with desirable properties are in constant demand for lighting applications and as probes in bioimaging. In this study, we successfully synthesized nanosized strontium fluorapatite (SrFAp) powders doped with varying concentrations of Eu3+ ions via the hydrothermal method, targeting applications in lighting and bioimaging probes. Our focus was on understanding the impact of annealing temperature and dopant concentration on structural purity, particle morphology, photoluminescence, dopant ion occupancy, and temperature-dependent emission characteristics. The materials emit red light, with the most intense transition being 5D0→7F2. The asymmetry parameter (R) determination and CIE color coordinates provided insights into the spectroscopic attributes. Emission spectra were measured and discussed at four distinct excitation lines. Lower-energy excitation wavelengths, deemed favorable for organisms, make these materials particularly suitable for bioimaging applications. While the most intense emission occurred under 393 nm excitation, emissions were also detected at 464.5 nm and 525 nm, suggesting alternative excitation wavelengths better suited for bioimaging. Additionally, we conducted extensive studies to assess the effect of ambient temperature on the emission intensity of SrFAp materials doped with 1 mol% Eu3+ ions. Thermal quenching of luminescence was observed in both as prepared and annealed materials, providing insights into the temperature-dependent behaviour of the emission properties.

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.

Li4 Zn(PO4 )2 :Mn2+ thermosensitive phosphor with dual luminescent centres for optical thermometry.

An optical thermometry strategy based on Mn2+ -doped dual-wavelength emission phosphor has been reported. Samples with different doping content were synthesized through a high-temperature solid-phase method under an air atmosphere. The electronic structure of Li4 Zn(PO4 )2 was calculated using density functional theory, revealing it to be a direct band gap material with an energy gap of 4.708 eV. Moreover, the emitting bands of Mn2+ at 530 and 640 nm can be simultaneously observed when using 417 nm as the exciting wavelength. This is due to the occupation of Mn2+ at the Zn2+ site and the interstitial site. Further analysis was conducted on the temperature-dependent emission characteristics of the sample in the range 293-483 K. Mn2+ has different responses to temperature at different doping sites in Li4 Zn(PO4 )2 . Based on the calculations using the fluorescence intensity ratio technique, the maximum relative sensitivity at a temperature of 483 K was determined to be 1.69% K-1 , while the absolute sensitivity was found to be 0.12% K-1 . The results showed that the Li4 Zn(PO4 )2 :Mn2+ phosphor has potential application in optical thermometry.