Dual-emitting temperature dependent material based on Bi3+/Eu3+ co-activated Ba2Y2Si4O13 phosphor with multicolor anti-counterfeiting.

Bi3+, Eu3+ co-doped Ba2Y2Si4O13 phosphors with multi-color luminescence properties were prepared by high temperature solid state method. The structure, luminescent properties and temperature characteristics were studied by X-ray diffraction, scanning electron microscope, fluorescence spectrum and temperature-dependence of emission spectrum. Ba2Y2Si4O13: Bi3+, Eu3+ phosphors can emit color from cyan to red when the excitation wavelength was changed from 340 nm to 390 nm, which is attributed to that there are two Bi3+ ion emission centers, and their emission intensity will change with the change of excitation wavelength. Moreover, the emission of the phosphor has good temperature sensing characteristics, based on the fluorescence intensity ratio of the two blue emission bands of Bi3+ and the red emission peak of Eu3+, a multimode thermometer with high temperature sensitivity was constructed. At the same time, based on the dynamic luminescence characteristics of the phosphor, the dynamic anti-counterfeiting experiments are designed. Therefore, the results show that the material has a bright prospect in the field of temperature sensing and anti-counterfeiting.

[Zn2+-Ge4+] co-substitutes [Ga3+-Ga3+] to coordinately broaden the near-infrared emission of Cr3+ in Ga2O3 phosphors.

Here, a "chemical unit co-substitution" method is used to improve the near-infrared (NIR) emission of phosphors, using [Zn2+-Ge4+] to co-substitute [Ga3+-Ga3+] sites to reduce crystal field splitting to affect the structure of gallium oxide. A series of broadband NIR phosphors are synthesized by a high-temperature solid-phase method, and their phase structures, crystal structures, morphologies, diffuse reflectance spectra, and luminescence lifetimes are investigated. The Ga1.68(Zn-Ge)0.3O3:0.02Cr3+ (GZGOC) phosphor exhibits NIR wide-band emission, with a peak wavelength of 766 nm and a half-width of 138 nm. Meanwhile, the quantum yield of photoluminescence can reach 81.2%. The phosphor has good thermal stability. When the temperature reaches 373 K, its emission intensity still remains at 73.4% of that at room temperature. A 460 nm LED chip and this phosphor are used to fabricate a phosphor-converted light emitting diode (pc-LED) device which can be used as a NIR light source. All these results show the application potential of the as-prepared phosphor in NIR imaging.

Manipulation of time-dependent multicolour evolution of X-ray excited afterglow in lanthanide-doped fluoride nanoparticles.

External manipulation of emission colour is of significance for scientific research and applications, however, the general stimulus-responsive colour modulation method requires both stringent control of microstructures and continously adjustment of particular stimuli conditions. Here, we introduce pathways to manipulate the kinetics of time evolution of both intensity and spectral characteristics of X-ray excited afterglow (XEA) by regioselective doping of lanthanide activators in core-shell nanostructures. Our work reported here reveals the following phenomena: 1. The XEA intensities of multiple lanthanide activators are significantly enhanced via incorporating interstitial Na+ ions inside the nanocrystal structure. 2. The XEA intensities of activators exhibit diverse decay rates in the core and the shell and can largely be tuned separately, which enables us to realize a series of core@shell NPs featuring distinct time-dependent afterglow colour evolution. 3. A core/multi-shell NP structure can be designed to simultaneously generate afterglow, upconversion and downshifting to realize multimode time-dependent multicolour evolutions. These findings can promote the development of superior XEA and plentiful spectral manipulation, opening up a broad range of applications ranging from multiplexed biosensing, to high-capacity information encryption, to multidimensional displays and to multifunctional optoelectronic devices.

Improved relative temperature sensitivity of over 10% K-1 in fluoride nanocrystals via engineering the interfacial layer.

Real-time in situ temperature sensing is of significance in the bio-medical field; however, the low relative temperature sensitivity Sr is one of the major obstacles in the development of nanothermometers. Herein, we provide an effective route that engineers the interfacial layer in a core/shell/shell nanostructure to enlarge the temperature-dependent luminescence intensity ratio (LIR) variations followed by an improved Sr. The CaF2 interlayer is employed to inhibit the interaction between the core and outer shell, and increase the interfacial phonon energy to enhance the negative thermal quenching effect (TQE) of Nd3+ ions in the outer shell and positive TQE of Er3+ ions in the core layer. Based on the temperature-dependent LIR variations of Er (650 nm) to Nd (800 nm), the maximum Sr of 10.01% K-1 and minimum Sr of % 2.56% K-1 are achieved.

Designing Optical Thermometers Using Down/Upconversion Ca14Al10Zn6O35: Ti4+, Eu3+/Yb3+, Er3+ Thermosensitive Phosphors.

Down/upconversion Ca14Al10Zn6O35 inorganic phosphors codoped with Ti4+/Eu3+ or Yb3+/Er3+ were prepared. The crystal structure and downconversion luminescence properties of Ca14Al10Zn6O35:Ti4+, Eu3+ phosphors were studied in detail. Ti4+ and Eu3+ occupied Al3+ and Ca2+ sites in the host lattice, respectively. Under the excitation of 273 nm, the emission peak in the 300-570 nm band originated from the 2T2 → O2- transition of Ti4+. The f-f transition of Eu3+ ions generated multiple peaks in the 570-800 nm range. The emission intensity of Ti4+ and Eu3+ ions can be used as a fluorescence intensity ratio (FIR) signal. Based on the FIR technology, the maximum relative sensitivity (Sr) and the minimum temperature uncertainty (δT) reached 1.41% K-1 and 0.07 K, respectively. Meanwhile, the temperature-sensing behaviors were explored by the temperature-dependent upconversion spectra of Er3+- and Yb3+-codoped Ca14Al10Zn6O35 phosphors. Based on the fluorescence intensity ratio of thermal coupling levels (Er3+:2H11/2/4S3/2), the maximum Sr and minimum δT of upconversion phosphors reached 1.28% K-1 and 0.08 K in the temperature range of 293-473 K, respectively. Ca14Al10Zn6O35:Ti4+/Eu3+ (Yb3+/Er3+) phosphors realize temperature sensors with higher relative sensitivity, and it is a good candidate material for optical temperature measurement.

Narrow-band Rb1-yKyNa3(Li3SiO4)4:Eu2+(0 ≤ y ≤ 1) cyan-blue phosphors for full-spectrum white LEDs.

A series of Rb1-yKyNa3(Li3SiO4)4:Eu2+(0 ≤ y ≤ 1) phosphors were successfully synthesized through a high-temperature solid-state reaction. The introduction of K+ into the RbNa3(Li3SiO4)4:Eu2+ phosphor to partially or completely replace Rb+ allows the emission spectrum to be modulated from blue (λ = 473 nm, FWHM = 22.5 nm) to a narrow cyan band (λ = 485 nm, FWHM = 21.1 nm). As the K+ ion content increases, the space group of the phosphor evolves from I4/M to I41/A. The complete replacement of Rb+ by K+ results in the KNa3(Li3SiO4)4:Eu2+ cyan phosphor, which shows excellent thermal stability (the comprehensive emission loss is only 8% at 150 °C) and can be used to fill the cyan light gap in white LED devices. By adding the KNa3(Li3SiO4)4:Eu2+ cyan phosphor in packaging with yellow and red phosphors, the color rendering index is increased from 90.2 to 97.1 and the correlated color temperature improved to 3658 K. These results indicate that the cyan phosphor has important application value in full-spectrum white LEDs.

Tunable emission of Li4SrCaSi2O4-yN2y/3:Eu2+ phosphors based on anion substitution induction for WLEDs and optical thermometry.

Polychromatic emission can be achieved by controlling the distribution of the rare earth activator in multi-cation lattices, which can be used in the fields of white light LED and fluorescence temperature sensing. However, it is still a challenge to control their distribution and location of the target site in a given host material because the distribution of the rare earth activator is uncertain. In this paper, we have chosen Li4SrCa(SiO4)2 as the multi-cation site host and induced the distribution of Eu2+ ions between different cation sites through anion substitution, for the first time, to regulate the luminescence characteristics of a series of Li4SrCaSi2O8-yN2y/3:Eu2+ phosphors. In Li4SrCa(SiO4)2:Eu2+ phosphors, the substitution of O2- by N3- triggered a distinct ordered to disordered structure transition of the SiO4 tetrahedron and induced the remote distribution of the Eu2+ activator, which was verified through the analysis of the XRD, EPR, FT-IR and fluorescence spectra. Due to the location of Eu2+ ions in different cation sites (Eu2+Sr and Eu2+Ca), two distinguishable emission peaks with tunable color emissions and different responses to temperature were realized. The white LED that utilized blue-orange-emitting Li4SrCaSi2O4N8/3:Eu2+ and green-emitting BaSi2O2N2:Eu2+ (500 nm) displayed an outstanding color rendering index (Ra) of 85.1. Based on the fluorescence intensity ratio (FIR) technique, an optical temperature measurement mechanism was hypothesized and studied in the temperature range of 293-473 K. The highest Sa of the material was 0.086 K-1, and Sr was 1.76% K-1 based on the FIR detection technology, revealing obviously better than most inorganic optical temperature-measuring materials reported before. Our work indicates that Li4SrCaSi2O8-2yN4y/3:Eu2+ is a promising material for application in White LEDs and optical thermometers.

Fabrication of large size individual octahedral tungsten oxide hydrate and Au NPs as SERS platforms for sensitive detection of cytochrome C.

Surface-enhanced Raman scattering (SERS) has attracted much attention with its powerful trace detection and analysis capabilities, especially biological and environmental molecules. However, building a protein SERS detection platform based on semiconductor devices is a huge challenge. Herein, through the synergy of NH3 and nickel foam, a large-sized semiconductor tungsten oxide hydrate platform (WOHP) was synthesized. The crystal plane of a single WOHP particle is larger than the excitation spot. As a SERS substrate, WOHP can make full use of the excitation light without destroying the structure during the protein molecules detection process. Through the synergy of WOHP and Au NPs, the enhancement factor is 1.5 × 104. Raman peaks of WOHP can be used as references for the detection of typical protein cytochrome C (Cyt C). As the Cyt C concentration decreases, the ICyt C/IWOHP ratio decreases, and the signal can still be obtained when the concentration is as low as 5 × 10-9 mol L-1. More importantly, the method does not affect the catalytic activity of Cyt C and can be applied to the detection of Cyt C concentration in serum.

Integrating Positive and Negative Thermal Quenching Effect for Ultrasensitive Ratiometric Temperature Sensing and Anti-counterfeiting.

Fluorescence intensity ratio-based temperature sensing with a self-referencing characteristic is highly demanded for reliable and accurate sensing. Although enormous efforts have been devoted to explore high-performance luminescent temperature probes, it remains a daunting challenge to achieve highly relative sensitivity which determines temperature resolution. Herein, we employ a novel strategy to achieve temperature probes with ultrahigh relative sensitivity through integrating both positive and negative thermal quenching effect into a hydrogel. Specifically, Er3+ ions show evidently a positive thermal quenching effect in Yb/Er:NaYF4@NaYF4 nanocrystals while Nd3+ and Tm3+ ions in a Yb2W3O12 bulk exhibit prominently a negative thermal quenching effect. With elevating temperature from 313 to 553 K, the fluorescence intensity ratio of Er (540 nm) to Nd (799 nm) and Tm (796 nm) to Er (540 nm) is significantly decreased about 1654 times and increased about 14,422 times, respectively. The maximum relative sensitivity of 15.3% K-1 at 553 K and 23.84% K-1 at 380 K are achieved. The strategy developed in this work sheds light on highly sensitive probes using lanthanide ion-doped materials.

Ultrabroadband Tuning and Fine Structure of Emission Spectra in Lanthanide Er-Doped ZnSe Nanosheets for Display and Temperature Sensing.

Realizing multicolored luminescence in two-dimensional (2D) nanomaterials would afford potential for a range of next-generation nanoscale optoelectronic devices. Moreover, combining fine structured spectral line emission and detection may further enrich the studies and applications of functional nanomaterials. Herein, a lanthanide doping strategy has been utilized for the synthesis of 2D ZnSe:Er3+ nanosheets to achieve fine-structured, multicolor luminescence spectra. Simultaneous upconversion and downconversion emission is realized, which can cover an ultrabroadband optical range, from ultraviolet through visible to the near-infrared region. By investigating the low-temperature fine structure of emission spectra at 4 K, we have observed an abundance of sublevel electronic energy transitions, elucidating the electronic structure of Er3+ ions in the 2D ZnSe nanosheet. As the temperature is varied, these nanosheets exhibit tunable multicolored luminescence under 980 and 365 nm excitation. Utilizing the distinct sublevel transitions of Er3+ ions, the developed 2D ZnSe:Er3+ optical temperature sensor shows high absolute (15.23% K-1) and relative sensitivity (8.61% K-1), which is superior to conventional Er3+-activated upconversion luminescent nanothermometers. These findings imply that Er3+-doped ZnSe nanomaterials with direct and wide band gap have the potential for applications in future low-dimensional photonic and sensing devices at the 2D limit.

Enhancing the luminescence performance in germanosilicate glasses controlled by ZnF2.

Rare-earth-doped optical functional glasses have attracted great interest for their excellent luminous performance in the applications of optical communications and biomedical systems. To the best of our knowledge, it is demonstrated for the first time that more than seven times' enhancement of luminescence performance in the mid-infrared region (MIR) has been obtained in germanosilicate glasses controlled by ZnF2. Larger absorption and emission cross sections of the Ho3+: I65→I75 transition indicate that this kind of germanosilicate-zinc glass may provide high gain as a good medium for an efficient 2.85 µm laser system.

Enhanced 3 µm luminescence properties based on effective energy transfer Yb3+ : 2F5/2→Dy3+ : 6H5/2 in fluoaluminate glass modified by TeO2.

Enhanced 3 µm luminescence of Dy3+ based on the effective process of Yb3+:F5/22→Dy3+:H5/26 with a higher energy transfer coefficient of 7.36×10-39 cm6/s in fluoaluminate glass modified by TeO2 was obtained. The energy transfer efficiency from Yb3+ to Dy3+ in Dy3+/Yb3+ codoped glass was as high as 80%, indicating the effective energy transfer of Yb3+. The higher temperature of the glass transition (Tg) and larger characteristic temperatures (ΔT,Kgl) revealed better thermal properties of the prepared glasses compared with the traditional fluoaluminate glasses, which is of great benefit to fiber drawing. The lower hydroxyl content (15.7 ppm) indicated better fluorescence properties of the glass. It was noted that the longer lifetime of 572 µs and higher emission cross section of 5.22×10-21 cm2 along with the bandwidth of 245 nm around 3 µm proved potential applications in mid-IR laser materials of the present glass.