Novel Visible Emission and Mechanism Investigation from PbS Nanoclusters‐Doped Borosilicate Glasses

Borosilicate glasses doped with PbO, ZnS, or PbS were fabricated to investigate the visible emissions (one located at 370 nm and another at 550 nm) observed in the PbO and ZnS codoped glass. Several series of glassy systems were designed to investigate the mechanism of above visible emissions. The absorption, photoluminescence (PL), photoluminescence excitation (PLE) spectra, and lifetime measurements were used to characterize all the emissions. The nanosecond level lifetimes for all the samples' 370 nm emissions ascribed the 370 nm emission to the glass defects. Measured lifetimes for the PbS quantum dots (QDs) in the glasses with an emission in the near‐infrared region which was about 8 μs was close to the values for the yellow emission, which confirmed the formation of PbS nanoclusters in the codoped glass was responsible for the yellow emission.     

Quantum Dots in Glasses: Size-Dependent Stokes Shift by Lead Chalcogenide

Size-dependent Stokes shift of PbS quantum dots (QDs) formed in the glasses was investigated. PbS QDs with diameters of 3.5 nm to 13.3 nm were precipitated in silicate glasses with different S/Pb ratios using the conventional thermal treatment method. Absorption and photoluminescence (PL) of PbS QDs were tuned from ~0.9 μm (1.38 eV) to ~2.3 μm (0.54 eV) by adjusting the diameters of PbS QDs from 3.5 nm to 13.3 nm. PL energies of QDs exhibited linear dependence on the absorption energies with a slope of 0.484 for PbS QDs with band gap energies larger than 0.98 eV, and the maximum Stokes shift was found to be 206.2 meV for 3.5 nm-sized PbS QDs. For large PbS QDs with band gap energies smaller than 0.98 eV, Stokes shift was found to be ~20 meV or smaller. The size-dependent Stokes shift indicated that surface defects made the main contribution and relative energy positions of these surface defects were strongly dependent on the size of PbS QDs.     

Structural,optical and temperature dependent photoluminescence properties of Cr3+-activated LaGaO3 persistent phosphor for optical thermometry

Cr³⁺ doped LaGaO₃ phosphor was prepared by hydrothermal reaction method with post-annealing treatment. XRD pattern showed the pure orthorhombic phase of LaGaO₃ at an annealing temperature of 1000 °C. TEM image showed the particles in the range 40-120 nm. The bandgap energy and Urbach tail increased in the doped sample as compared to the undoped sample as estimated from UV–visible diffuse reflectance spectra. PL excitation spectra showed peaks in UV, blue and orange regions. The emission spectra showed broadband with peaks in the NIR region due to emission from ⁴T₂ and ²E states. The intermediate strength of the crystal field has been calculated from the estimated spectroscopic parameter. The average lifetime was found to be in the ms range. Afterglow decay was also recorded. From the low-temperature PL, the zero phonon line, stokes shift energy, vibrational energy and Huang-Rhys parameter were calculated. With rising the temperature, PL emission peak intensity and lifetime values decreased and FWHM increased because of increased numbers of electrons in ⁴T₂ state and increasing non-radiative transition. Temperature-dependent peak intensity ratios and lifetime values were utilized for temperature sensing applications in below room temperature and above room temperature. The results indicate the possibility of present phosphor to be used as optical nanothermometer.     

Quantum-dots-precipitated rare-earth-doped glass for ultra-broadband mid-infrared emissions

Mid-infrared (MIR) fiber lasers have wide application prospects and great commercial value in the fields of medical operation, remote sensing and military weapon, etc. At present, Tm³⁺-doped glass can obtain broadband luminescence at 2 μm, the introduction of Ho³⁺ or Er³⁺ ions also shows a tunable MIR emission but with limited success. Herein, the rare-earth (RE) doped glass with quantum dots (QDs) precipitation is proposed for achieving ultra-broadband MIR emissions. The types and sizes of QDs are determined by the XRD and TEM, and their optical properties are further characterized by the absorption and emission spectra as well as the lifetime decay curves. It is found that the diameter of the QDs is gradually increased from 1.7 to 5.1 nm by increasing the heat-treated temperature from 490°C to 530°C, respectively. Interestingly, an ultra-broadband emission covering 1400-2600 nm is achieved from the heat-treated glass upon the excitation of 808 nm laser diode as a result of an overlapped emission from Tm³⁺ and PbS. All results suggest that these QDs-precipitated RE-doped glasses have important application prospects in ultra-broadband MIR laser glass, glass fiber, and fiber lasers.     

Surface modification and fabrication of white-light-emitting Tm3+/CdS quantum dots co-doped glass fibers

Due to the widely tunable band gap and broadband excitation, CdS quantum dots (QDs) show great promise for yellow-light luminescence center in white-light-emitting devices. The light intensity of the CdS QD-doped glass was enhanced by doping the Tm³⁺ ions due to the higher absorption rate. The influence of Tm³⁺ ions on the surface structure of CdS QDs was enormous according to the first-principles calculations. Doping Tm³⁺ ions change the surface state of CdS QDs, which will fix the QDs emission peaks and enhance the luminescence of CdS QDs at a lower heat-treatment temperature. White-light emission was obtained by tuning the relative concentration between Tm³⁺/CdS QDs. However, there is a fundamental challenge to fabricate QD-doped glass fibers by rod-in-tube method since uncontrollable QDs crystallization is hard to avoid. Herein, a white-light-emitting borosilicate glass fiber was fabricated by the “melt-in-tube” method using a special designed Tm³⁺/CdS QDs co-doped borosilicate glass with low-melting temperature as fiber core. After heat treatment, ideal white-light emission was observed from the fiber under excitation at single wavelength (359 nm). This finding indicates that Tm³⁺/CdS QDs co-doped glass fiber with white-light-emitting devices has potential application as gain medium of white-light-emitting sources and fiber lasers.     

Lead Chalcogenide Quantum Dot-Doped Glasses for Photonic Devices

Tunable absorption and photoluminescence (PL) of lead chalcogenide quantum dots (QDs) doped in glasses due to the quantum confinements effect have been actively investigated for application as saturable absorbers, laser sources, and fiber-optic amplifiers. Optical properties of QDs have been carefully monitored by controlling their sizes through heat treatment and rare-earth ion doping. Two- and three-dimensional precipitation of lead chalcogenide QDs were also realized using silver ion exchange and femtosecond laser irradiation in combination with thermal treatment. Prototypes of microstructured single-mode fibers and tapered fiber amplifiers containing QDs proved potentials of these materials for fiber-optic amplifiers application. Further research works on QD-doped solid core fibers, surface passivation of quantum dots and their application for the mid-infrared optical devices are necessary.     

Controlled growth and spectroscopy characterization of blue violet perovskite quantum dots in borate glasses

Blue violet light emitting CsPb(Cl/Br)₃ perovskite quantum dots glasses (QDGs) have been successfully fabricated in multi-component borate glass matrix by melt quenching and heat treatment. The spectral characteristics have been evaluated by photoluminescence (PL), PL excitation (PLE), PL decay and absorption spectra. The recipe and preparation conditions have been optimized for controlled growth of QDs. By using raw materials of NH₄Br/NH₄Cl/PbO and crucible cover, optimizing composition of Na₂O/K₂O in matrix, melting temperature and time, heat treatment temperature and time, and NH₄Cl and NH₄Br contents, we have finally realized blue violet exciton emission in target range of 405–440 nm. The PL wavelength adjustment is comprehensive effect of the abovementioned influence factors. The emission in short wavelength of 405–440 nm is due to controlled growth of the QDs. In final CsPb(Cl/Br)₃ QDs, the contents of Cl and Br are suitable and the Cl/Br ratios are large. A little Br is necessary for growth of CsPb(Cl/Br)₃ QDs and then the Br is partially replaced by Cl at suitable treatment condition. Unsymmetrical PL spectrum profile of some samples is explained as reabsorption effect by monitoring PL spectral profile and PL decay. The temperature characteristics of PL spectra show good recoverability after a temperature cycle.     

Band Gap and Diameter Modulation of Quantum Dots in Glasses

Modulation of the band gap energy and diameter of quantum dots (QDs) formed in glasses is important to achieve the optimized performance for applications as infrared light sources, lasers, saturable absorbers, etc. Absorption and photoluminescence of PbS QDs were extended into mid-infrared wavelength range in glasses containing small amount of lead but oversaturated with sulfur. Dual-band photoluminescence of PbSe QDs was prepared in oxyfluoride glass-ceramics containing BaF₂ nanocrystals. By introducing SnO in the glasses, alloyed Pb_1-xSn_xSe QDs with smaller band gap energies were formed in glasses, and mid-infrared photoluminescence of Pb_1-xSn_xSe QDs at ~2570 nm in wavelength was achieved.     

Role of Nd3+ ions on the nucleation and growth of PbS quantum dots (QDs) in silicate glasses

The influence of Nd₂O₃ addition on the precipitation kinetics of lead chalcogenide (PbS) quantum dots (QDs) in silicate glasses was investigated. Energy dispersive X‐ray spectroscopy (EDS) indicated that the Nd³⁺ ions are preferentially located inside the PbS QDs rather than in the glass matrix. Changes in diameter (D) of PbS QDs exhibited smaller time dependencies (i.e., D≈t^{0.270‐0.286}) than that predicted by the classical Lifshitz–Slyozov–Wagner (LSW) theory. This is due to the limited concentrations of Pb²⁺ and S^2? ions and the large diffusion distance inside the glass matrix. In addition, extended X‐ray absorption fine structure (EXAFS) results indicated that the formation of PbS QDs was retarded due to the presence of Nd₂O₃ in the glasses, as the large NdO_x polyhedra interrupt the diffusion of Pb²⁺ and S^2? ions. We believe that these Nd³⁺ ions are primarily located in PbS QDs in the form of Nd–O clusters, and that the PbS QDs are built on top of these clusters.     

Effect of ZnO on the crystallization and photoluminescence of CsPbI3 perovskite quantum dots in borosilicate glasses

CsPbI₃ perovskite quantum dots (QDs) doped borosilicate glass was prepared by the process of melt-quenching and subsequent annealing. With the introduction of ZnO to the parent glass as the glass network intermediate, the optical properties of the resultant samples are dramatically enhanced. Both the photoluminescence (PL) intensity and photoluminescence quantum yield (PLQY) shows a strong dependence on ZnO concentration as ZnO is found to facilitate the precipitated of the QDs by reducing the connectivity of three-dimensional glass network built from SiO₄ tetrahedrons. The tunable visible-band PL emission of the CsPbI₃ QD-doped glass could find potential applications in white LEDs and lasers.     

Plasmon‐Assisted Precipitation of PbS Quantum Dots in Glasses Containing Ag Nanoparticles

PbS QDs of ~ 5nm diameter were precipitated in glasses containing Ag nanoparticles after 3 min of 1.5‐W continuous‐wave laser illumination at λ = 532 nm. Photoluminescence spectra of the PbS QDs recorded in the 1.3~1.6 μm wavelength region revealed conversion of photon energy to thermal energy by surface plasmon resonance. Laser‐assisted local heating around Ag NPs can provide a new method to control the spatial distribution of QDs in glasses.     

Improved photoluminescence quantum yield of CsPbBr3 quantum dots glass ceramics

We have fabricated CsPbBr₃ perovskite quantum dots (QDs) in a multi-component borate glass by melt-quenching technique. Transmission electron microscopy (TEM) reveals a cubic phase CsPbBr₃ crystal for QDs. As the treatment temperature or the treatment time duration increases, the photoluminescence (PL) peak shifts to long wavelength in the range of 510 to 525 nm, and the full width at half-maximum varies in the range of 24 to 18 nm. The absorption edge shifts to low energy side in the range of 2.54 to 2.41 eV. The different photoluminescence excitation spectra (PLE) reflect the change of microstructure for different samples. The PL peak wavelength and line-shape are independent of excitation wavelength. These results of spectra show typical exciton emission characteristics. As treatment conditions strengthens, photoluminescence quantum yield (PLQY) first increases and then decreases, having the best PLQY 86.9%. Bi-exponential fitting curves show that short lifetime τ₁ continuously decreases. Long lifetime τ₂, weight for long lifetime component, and average lifetime τ_avg first increase and then decrease. The PLQY values are affected by both τ₁ and τ₂, which are relative to the crystal quality in the interior and the surface of QDs, respectively. The high PLQY value corresponds to medium treatment condition, which is attributed to a balanced effect of crystal quality in interior and the surface of QDs.     

Surface plasmon enhanced energy transfer in metal-semiconductor hybrid nanostructures

We report a type of hybrid nanostructures composed of ZnO nanoparticles, CdSe/ZnS core/shell quantum dots (QDs), and Ag nanoprisms. With ultraviolet light illumination, the energy absorbed by ZnO nanoparticles was transferred to the CdSe/ZnS core/shell QDs inducing a photoluminescence (PL) emission. To enhance the PL emission, Ag nanoprisms were doped in the ZnO nanoparticles and the QDs. Enhanced energy transfer from the ZnO nanoparticles to the QDs via the surface plasmon effect of the Ag nanoprisms was also demonstrated. The PL emission dependence was investigated as a function of the doped Ag nanoprism concentration and a 7.4 times PL enhancement was obtained at an Ag nanoprism concentration of 5 × 10(-8) M.     

Strong localization effect and carrier relaxation dynamics in self-assembled InGaN quantum dots emitting in the green

Strong localization effect in self-assembled InGaN quantum dots (QDs) grown by metalorganic chemical vapor deposition has been evidenced by temperature-dependent photoluminescence (PL) at different excitation power. The integrated emission intensity increases gradually in the range from 30 to 160 K and then decreases with a further increase in temperature at high excitation intensity, while this phenomenon disappeared at low excitation intensity. Under high excitation, about 40% emission enhancement at 160 K compared to that at low temperature, as well as a higher internal quantum efficiency (IQE) of 41.1%, was observed. A strong localization model is proposed to describe the possible processes of carrier transport, relaxation, and recombination. Using this model, the evolution of excitation-power-dependent emission intensity, shift of peak energy, and linewidth variation with elevating temperature is well explained. Finally, two-component decays of time-resolved PL (TRPL) with various excitation intensities are observed and analyzed with the biexponential model, which enables us to further understand the carrier relaxation dynamics in the InGaN QDs.     

CdS Quantum Dots in Glass: “Modification of Photoluminescence by Silver Doping”

Silicate glasses containing CdS and Ag₂O were made by the melt-quenching method. CdS quantum dots (QDs) were precipitated inside the glass matrix by heat treatment at 570–590 °C for 10 h, and the influence of Ag on photoluminescence (PL) of CdS QDs was investigated. The emission located at 478–493 nm in wavelength originated from the direct recombination of electron/hole pairs was quenched due to charger transfer between Ag and CdS QDs. Modification of PL from CdS QDs by Ag provides potentials toward developing the color changing materials for light-emitting diodes (LEDs).     

Direct Imaging of the Distribution of Nd3+ Ions in Glasses Containing PbS Quantum Dots

The influence of Nd³⁺ ions was investigated on the precipitation and optical properties of PbS quantum dots (QDs) inside silicate glasses. The diameters of the PbS QDs decreased as the concentration of Nd³⁺ in the glass increased as evidenced by blue shifts in the absorption and photoluminescence spectra. Electron energy loss spectroscopy shows that Nd³⁺ ions exist preferentially inside the PbS nanocrystals rather than in the glass matrix. We postulate that Nd–O clusters are preserved during heat treatment and serve as nucleation sites for PbS crystals. No change in the local bonding scheme of the Nd³⁺ ions was observed following heat treatment.     

Effect of topological structure on photoluminescence of PbSe quantum dot‐doped borosilicate glasses

Borosilicate glasses doped with PbSe quantum dots (QDs) were prepared by a conventional melt‐quenching process followed by heat treatment, which exhibit good thermal, chemical, and mechanical stabilities, and are amenable to fiber‐drawing. A broad near infrared (NIR) photoluminescence (PL) emission (1070‐1330 nm) band with large full‐width at half‐maximum (FWHM) values (189‐266 nm) and notable Stokes shift (100‐210 nm) was observed, which depended on the B₂O₃ concentration. The PL lifetime was about 1.42‐2.44 μs, and it showed a clear decrease with increasing the QDs size. The planar [BO₃] triangle units forming the two‐dimensional (2D) glass network structure clearly increased with increasing B₂O₃ concentration, which could accelerate the movement of Pb²⁺ and Se^2? ions and facilitate the growth of PbSe QDs. The tunable broadband NIR PL emission of the PbSe QD‐doped borosilicate glass may find potential application in ultra‐wideband fiber amplifiers.     

Luminescent Characteristics of Silicate Glasses Doped with Rare Earths Under Monochromatic Excitation

Measurements of emission spectra and decay times of Eu³⁺, Sm³⁺ Tb³⁺, Dy³⁺ and Gd³⁺ and their concentration dependence were taken in silicate glasses, in the concentration range 0.05–1.00 weight percent, under monochromatic excitation. The results are compared with those obtained in borate glasses. The lower intensities of the main emission lines for all the five R. E., the longer decay times for Tb³⁺ and Sm³⁺ and the shift to shorter wavelengths for Eu³⁺ and Sm³⁺ are explained in terms of the lower field strength seen by the R. E. in silicate glasses and smaller energy transfer probabilities.     

Long-lasting photoluminescence quantum yield of cesium lead halide perovskite-type quantum dots

Cesium lead halide perovskite(CsPbX₃,X=Cl,Br,I)quantum dots(QDs)and their partly Mn²⁺-substituted QDs(CsPb1–xMnxX3)attract considerable attention owing to their unique photoluminescence(PL)efficiencies.The two types of QDs,having different PL decay dynamics,needed to be further investigated in a form of aggregates to understand their solid-state-induced exciton dynamics in conjunction with their behaviors upon degradation to achieve practical applications of those promising QDs.However,thus far,these QDs have not been sufficiently investigated to obtain deep insights related to the long-term stability of their PL properties as aggregated solid-states.Therefore,in this study,we comparatively examined CsPbX₃-and CsPb1–xMnxX₃-type QDs stocked for>50 d under dark ambient conditions by using excitation wavelength-dependent PL quantum yield and time-resolved PL spectroscopy.These investigations were performed with powder samples in addition to solutions to determine the influence of the inter-QD interaction of the aged QD aggregates on their radiative decays.It turns out that the Mn²⁺-substituted QDs exhibited long-lasting PL quantum efficiencies,while the unsubstituted CsPbX₃-type QDs exhibited a drastic reduction of their PL efficiencies.And the obtained PL traces were clearly sensitive to the sample status.This is discussed with the possible interaction depending on the size and distance of the QD aggregates.     

Optical properties of Cu ions‐doped ZnSe quantum dots in silicate glasses

In order to alleviate the effect of the surface defects on the emission properties of quantum dots, copper ions‐doped ZnSe quantum dots (QDs) in the glasses are prepared using melt‐quenching and subsequent thermal annealing methods. For glasses without copper doping, tunable band‐edge emission from ZnSe QDs is achieved. For glasses with copper doping, efficient energy transfer from ZnSe QDs to copper ions is observed, and efficient broad band emission from copper ions is realized at the expense of the band‐edge emission of ZnSe QDs. Absorption spectra, size‐dependent broad‐band emission spectra and electron spin resonance spectra show the cupric ions are doped into the ZnSe QDs. Results reported here shows that doping of transition‐metal ions into semiconductor QDs in glasses is promising for development of high efficient luminescent glasses.