Unraveling the Mechanism of Covalent Organic Frameworks-Based Functional Separators in High-Energy Batteries.

Covalent organic frameworks (COFs) are promising porous materials due to their high specific surface area, adjustable structure, highly ordered nanochannels, and abundant functional groups, which brings about wide applications in the field of gas adsorption, hydrogen storage, optics, and so forth. In recent years, COFs have attracted considerable attention in electrochemical energy storage and conversion. Specifically, COF-based functional separators are ideal candidates for addressing the ionic transport-related issues in high-energy batteries, such as dendritic formation and shuttle effect. Therefore, it is necessary to make a comprehensive understanding of the mechanism of COFs in functional separators. In this review, the advantages, applications as well as synthesis of COFs are firstly presented. Then, the mechanism of COFs in functional separators for high-energy batteries is summarized in detail, including pore channels regulating ionic transport, functional groups regulating ionic transport, adsorption effect, and catalytic effect. Finally, the application prospect of COFs-based separators in high-energy batteries is proposed. This review may provide new insights into the design of functional separators for advanced electrochemical energy storage and conversion systems.

Efficient Broadband Near-Infrared CaMgGe2O6:Cr3+ Phosphor for pc-LED.

Broadband near-infrared (NIR) phosphor-converted light-emitting diodes (pc-LEDs) are essential to integrate near-infrared spectrometers into mobile devices for the rapid and noninvasive detection of biological components. However, efficient broadband NIR phosphors with a peak emission wavelength longer than 800 nm are deficient. In this study, CaMgGe2O6:Cr3+ phosphor was prepared by a high-temperature solid-state reaction. The phosphor doped with 0.02Cr3+ showed an emission band at 845 nm with a broad bandwidth of 160 nm and a high quantum yield of 84% under 450 nm excitation. The broadband NIR pc-LED was fabricated using CaMgGe2O6:0.02Cr3+ phosphor based on a blue light-emitting diode (LED) chip. A photoelectric efficiency of 27.2% @ 10 mA and an NIR output power of 57.98 mW @ 100 mA were achieved, which are the highest values reported yet for broadband NIR pc-LEDs with a peak wavelength longer than 800 nm. Using the fabricated NIR pc-LED as the light source, the characteristic absorption spectra of some substances were obtained. All of the results indicated that the CaMgGe2O6:Cr3+ phosphor has considerable potential in near-infrared spectroscopic applications.

Efficient Visible-to-NIR Spectral Conversion for Polycrystalline Si Solar Cells and Revisiting the Energy Transfer Mechanism from Ce3+ to Yb3+ in Lu3Al5O12 Host.

The so-called Shockley-Queisser converting efficiency limit of Si solar cells is believed to be surpassed by using the spectral converter. However, searching for efficient spectral converting materials is still a challenging task. In this paper, efficient visible-to-NIR spectral conversion for polycrystalline Si solar cells has been demonstrated in Ce3+ and Yb3+ codoped Lu3Al5O12. Moreover, the underlying energy transfermechanism from Ce3+ to Yb3+ is systematically re-investigated by the detailed excitation and emission spectra as well as fluorescent decay curves, and our results demonstrate that fast metal-to-metal charge transfer from Ce3+ to nearby Yb3+ is the dominant energy transfermechanism. Finally, we provide new evidence that Ce4+-Yb2+ charge-transfer state is responsible for the relatively low quantum efficiency of NIR emission in Ce3+ and Yb3+ codoped system.

Highly efficient upconversion emission of Er3+ in δ-Sc4Zr3O12 and broad-range temperature sensing.

Developing optical temperature sensors with a wider range, higher sensitivity and repeatability based on Er3+/Yb3+ doped upconverting phosphors has always been at the forefront of temperature measurement technologies. Here, we report the intense green upconversion luminescence in Er3+/Yb3+ doped δ-Sc4Zr3O12 for the first time and its temperature sensing performance is investigated. The structure of δ-Sc4Zr3O12 is given by Rietveld refinement of XRD data and the site occupancy of Er3+ ions has been determined. Compared with cubic Sc2O3 and ZrO2, under 972 nm excitation, the green emission from Er3+ centers in Sc4Zr3O12 is increased by 59-fold and 264-fold, respectively. By experimental analysis, this enhancement of upconversion luminescence is attributed to the low-symmetrical environment of Er3+, generation of Yb3+ clusters and high internal efficiency of Yb3+ emission in Sc4Zr3O12. In addition, the fluorescence intensity ratio of two green emission bands (2H11/2/4S3/2 → 4I15/2) is studied as a function of temperature ranging from 303 to 793 K in Sc4Zr3O12. The maximum sensitivity observed via calculation is 0.00634 K-1 at 573 K, and the sensitivity is still as high as 0.00534 K-1 at 793 K. The stability of a Sc4Zr3O12 thermometer is also examined via a recycling test. These findings suggest that δ-Sc4Zr3O12 is a promising upconversion host and could achieve high-sensitivity optical temperature sensing with a wide measuring range.

Highly Efficient Green-Emitting Phosphors Ba2Y5B5O17 with Low Thermal Quenching Due to Fast Energy Transfer from Ce3+ to Tb3.

This paper demonstrates a highly thermally stable and efficient green-emitting Ba2Y5B5O17:Ce3+, Tb3+ phosphor prepared by high-temperature solid-state reaction. The phosphor exhibits a blue emission band of Ce3+ and green emission lines of Tb3+ upon Ce3+ excitation in the near-UV spectral region. The effect of Ce3+ to Tb3+ energy transfer on blue to green emission color tuning and on luminescence thermal stability is studied in the samples codoped with 1% Ce3+ and various concentrations (0-40%) of Tb3+. The green emission of Tb3+ upon Ce3+ excitation at 150 °C can keep, on average, 92% of its intensity at room temperature, with the best one showing no intensity decreasing up to 210 °C for 30% Tb3+. Meanwhile, Ce3+ emission intensity only keeps 42% on average at 150 °C. The high thermal stability of the green emission is attributed to suppression of Ce3+ thermal de-excitation through fast energy transfer to Tb3+, which in the green-emitting excited states is highly thermally stable such that no lifetime shortening is observed with raising temperature to 210 °C. The predominant green emission is observed for Tb3+ concentration of at least 10% due to efficient energy transfer with the transfer efficiency approaching 100% for 40% Tb3+. The internal and external quantum yield of the sample with Tb3+ concentration of 20% can be as high as 76% and 55%, respectively. The green phosphor, thus, shows attractive performance for near-UV-based white-light-emitting diodes applications.

The Inductive Effect of Neighboring Cations in Tuning Luminescence Properties of the Solid Solution Phosphors.

Forming solid solutions through cation substitution is an efficient way to improve the luminescence properties of Ce3+ or Eu2+ activated phosphors and even to develop new ones, which is badly needed for phosphor-converted white LEDs. Here, we report new color tunable solid solution phosphors based on Eu2+ activated K2Al2B2O7 as a typical case to demonstrate that, besides crystal field splitting of 5d levels, centroid shift and Stokes shift can be dominant in tuning excitation and emission spectra as well as thermal stability of solid solution phosphors, both of which were previously considered to be negligible. Moreover, a general model involving the inductive effect of neighboring cations is proposed to explain the obvious variations in centroid shift and Stokes shift with cation substitution. Our work is propitious for the construction of more reasonable structure-property relations and thus offers theoretical guidance for designing solid solution phosphors.

Enhanced ∼2 µm Emission of Tm3+ in Lu2O3 by Addition of a Trace Amount of Er3.

Er3+-induced intensity enhancement of ∼2 µm emission is observed in 2 atom % Tm3+ doped Lu2O3 under 782 nm excitation. The maximum enhancement reaches 41.9% with only 0.05 atom % Er3+. Er3+ introduces a new quantum cutting process which is proved to be a Tm3+ → Er3+ → Tm3+ forward-backward energy transfer (FBET) system. The FBET system is observed to work efficiently even at very low Er3+ concentration. Thus, energy loss due to energy migration among Tm3+ ions is suggested to be suppressed by the FBET process. The Tm3+ → Er3+ → Tm3+ FBET system may be a new route to improve the performance of Tm3+ lasers.

Investigation of the Energy-Transfer Mechanism in Ho3+- and Yb3+-Codoped Lu2O3 Phosphor with Efficient Near-Infrared Downconversion.

A high-temperature solid-state method was used to synthesize the Ho3+- and Yb3+-codoped cubic Lu2O3 powders. The crystal structures of the as-prepared powders were characterized by X-ray diffraction. The energy-transfer (ET) phenomenon between Ho3+ ions and Yb3+ ions was verified by the steady-state spectra including visible and near-infrared (NIR) regions. Beyond that, the decay curves were also measured to certify the existence of the ET process. The downconversion phenomena appeared when the samples were excited by 446 nm wavelength corresponding to the transition of Ho3+: 5I8→5G6/5F1. On the basis of the analysis of the relationship between the initial transfer rate of Ho3+: 5F3 level and the Yb3+ doping concentration, it indicates that the ET from 5F3 state of Ho3+ ions to 2F5/2 state of Yb3+ ions is mainly through a two-step ET process, not the long-accepted cooperative ET process. In addition, a 62% ET efficiency can be achieved in Lu2O3: 1% Ho3+/30% Yb3+. Unlike the common situations in which the NIR photons are all emitted by the acceptors Yb3+, the sensitizers Ho3+ also make contributions to the NIR emission upon 446 nm wavelength excitation. Meanwhile, the 5I5→5I8 transition and 5F4/5S2→5I6 transition of Ho3+ as well as the 2F5/2→2F7/2 transition of Yb3+ match well with the optimal spectral response of crystalline silicon solar cells. The current research indicates that Lu2O3: Ho3+/Yb3+ is a promising material to improve conversion efficiency of crystalline silicon solar cell.

Inhomogeneous-Broadening-Induced Intense Upconversion Luminescence in Tm3+ and Yb3+ Codoped Lu2O3-ZrO2 Disordered Crystals.

Near-infrared (980 nm) to near-infrared (800 nm) and blue (490 nm) upconversion has been studied in 0.2% Tm3+ and 10% Yb3+ codoped Lu2O3-ZrO2 solid solutions as a function of the ZrO2 content in the range of 0-50%, prepared by a high-temperature solid-state reaction. The continuous enhancement of upconversion luminescence is observed with increasing ZrO2 content up to 30%. Analyses of the Yb3+ emission intensity and lifetime indicate enlarged absorption of a 980 nm excitation laser and enhanced energy transfer from Yb3+ to Tm3+ with the addition of ZrO2. The spectrally inhomogeneous broadening of the dopants in this disordered solid solution is considered to play the main role in the enhancement by providing better matches with the excitation laser line and increasing the spectral overlap for efficient energy transfer from Yb3+ to Tm3+. In addition, the inhomogeneous broadening is also validated to improve energy migration among Yb3+ ions and energy back transfer from Tm3+ to Yb3+. Hence, it is understandable that a drop in the upconversion luminescence intensity occurs as the concentration of ZrO2 is further increased from 30% to 50%. This work indicates the possibility of disordered crystals to achieve intense upconversion luminescence for biological and optoelectronic applications.

Low-Concentration Eu2+-Doped SrAlSi4N7: Ce3+ Yellow Phosphor for wLEDs with Improved Color-Rendering Index.

Luminescence property of low-concentration Eu2+-doped SrAlSi4N7:Ce3+ yellow phosphor is reported in this paper. Three optical centers Ce1, Ce2, and Eu2 are observed in the phosphor. Deconvolution of emission spectrum confirms the three centers to be green (530 nm), yellow (580 nm), and red (630 nm), respectively. This property promises considerable improvement of color-rendering property of a white light-emitting diode (wLED). For example, color-rendering index (CRI) of wLED fabricated by combining a blue LED chip and SrAlSi4N7:0.05Ce3+,0.01Eu2+ phosphor reaches 88. A competitive energy transfer process between Ce1-Ce2 and Ce1-Eu2 is confirmed based on Inokuti-Hirayama formula. Ratio of energy transfer rate between Ce1-Ce2 and Ce1-Eu2 (WCe1-Eu2/WCe1-Ce2) is calculated to be 2.0. This result reveals the effect of Eu2+ concentration on quantity of green and red components in SrAlSi4N7:Ce3+,Eu2+ phosphor.

Intense Upconversion Luminescence of CaSc2 O4 :Ho(3+) /Yb(3+) from Large Absorption Cross Section and Energy-Transfer Rate of Yb(3.).

Concentration-optimized CaSc2 O4 :0.2 % Ho(3+) /10 % Yb(3+) shows stronger upconversion luminescence (UCL) than a typical concentration-optimized upconverting phosphor Y2 O3 :0.2 % Ho(3+) /10 % b(3+) upon excitation with a 980 nm laser diode pump. The (5) F4 +(5) S2 →(5) I8 green UCL around 545 nm and (5) F5 →(5) I8 red UCL around 660 nm of Ho(3+) are enhanced by factors of 2.6 and 1.6, respectively. On analyzing the emission spectra and decay curves of Yb(3+) : (2) F5/2 →(2) F7/2 and Ho(3+) : (5) I6 →(5) I8 , respectively, in the two hosts, we reveal that Yb(3+) in CaSc2 O4 exhibits a larger absorption cross section at 980 nm and subsequent larger Yb(3+) : (2) F5/2 →Ho(3+) : (5) I6 energy-transfer coefficient (8.55×10(-17) cm(3) s(-1) ) compared to that (4.63×10(-17) cm(3) s(-1) ) in Y2 O3 , indicating that CaSc2 O4 :Ho(3+) /Yb(3+) is an excellent oxide upconverting material for achieving intense UCL.

Efficient near-infrared downconversion and energy transfer mechanism of ce(3+)/yb(3+) codoped calcium scandate phosphor.

An efficient near-infrared (NIR) downconversion has been demonstrated in CaSc2O4: Ce(3+)/Yb(3+) phosphor. Doping concentration optimized CaSc2O4: 1%Ce(3+)/5%Yb(3+) shows stronger NIR emission than doping concentration also optimized typical YAG: 1%Ce(3+)/5%Yb(3+) under 470 nm excitation. The NIR emission from 900 to 1100 nm is enhanced by a factor of 2.4. In addition, the main emission peak of Yb(3+) in the CaSc2O4 around 976 nm matches better with the optimal spectral response of the c-Si solar cell. The visible and NIR spectra and the decay curves of Ce(3+): 5d → 4f emission were used to demonstrate the energy transfer from Ce(3+) ions to Yb(3+) ions. The downconversion phenomenon has been observed under the direct excitation of Ce(3+) ions. On analyzing the dependence of energy transfer rate on Yb(3+) ion concentration, we reveal that the energy transfer (ET) from Ce(3+) ions to Yb(3+) ions in CaSc2O4 occurs mainly by the single-step ET process. Considering that the luminescence efficiency of CaSc2O4: Ce(3+) is comparable to that of commercial phosphor YAG: Ce(3+), the estimated maximum energy transfer efficiency reaches 58% in the CaSc2O4: 1%Ce(3+)/15%Yb(3+) sample, indicating that CaSc2O4: Ce(3+)/Yb(3+) sample has the potential in improving the conversion efficiency of c-Si solar cells.

Blue-emitting K2Al2B2O7:Eu(2+) phosphor with high thermal stability and high color purity for near-UV-pumped white light-emitting diodes.

Novel blue-emitting K2Al2B2O7:Eu(2+) (KAB:Eu(2+)) phosphor was synthesized by solid state reaction. The crystal structural and photoluminescence (PL) properties of KAB:Eu(2+) phosphor, as well as its thermal properties of the photoluminescence, were investigated. The KAB:Eu(2+) phosphor exhibits broad excitation spectra ranging from 230 to 420 nm, and an intense asymmetric blue emission band centered at 450 nm under λex = 325 nm. Two different Eu(2+) emission centers in KAB:Eu(2+) phosphor were confirmed via their fluorescence decay lifetimes. The optimal concentration of Eu(2+) ions in K2-xEuxAl2B2O7 was determined to be x = 0.04 (2 mol %), and the corresponding concentration quenching mechanism was verified to be the electric dipole-dipole interactions. The PL intensity of the nonoptimized KAB:0.04Eu(2+) phosphor was measured to be ∼58% that of the commercial blue-emitting BaMgAl10O17:Eu(2+) phosphor, and this phosphor has high color purity with the CIE coordinate (0.147, 0.051). When heated up to 150 °C, the KAB:0.04Eu(2+) phosphor still has 82% of the initial PL intensity at room temperature, indicating its high thermal stability. These results suggest that the KAB:Eu(2+) is a promising candidate as a blue-emitting n-UV convertible phosphor for application in white light emitting diodes.

Importance of suppression of Yb(3+) de-excitation to upconversion enhancement in ß-NaYF4: Yb(3+)/Er(3+)@ß-NaYF4 sandwiched structure nanocrystals.

Nanosized Yb(3+) and Er(3+) co-doped ß-NaYF4 cores coated with multiple ß-NaYF4 shell layers were synthesized by a solvothermal process. X-ray diffraction and scanning electron microscopy were used to characterize the crystal structure and morphology of the materials. The visible and near-infrared spectra as well as the decay curves were also measured. A 40-fold intensity increase for the green upconversion and a 34-fold intensity increase for the red upconversion were observed as the cores are coated with three shell layers. The origin of the upconversion enhancement was studied on the basis of photoluminescence spectra and decay times. Our results indicate that the upconversion enhancement in the sandwiched structure mainly originates from the suppression of de-excitation of Yb(3+) ions. We also explored the population of the Er(3+4)F9/2 level. The results reveal that energy transfer from the lower intermediate Er(3+4)I13/2 level is dominant for populating the Er(3+4)F9/2 level when the nanocrystal size is relatively small; however, with increasing nanocrystal size, the contribution of the green emitting Er(3+4)S3/2 level for populating the Er(3+4)F9/2 level, which mainly comes from the cross relaxation energy transfer from Er(3+) ions to Yb(3+) ions followed by energy back transfer within the same Er(3+)-Yb(3+) pair, becomes more and more important. Moreover, this mechanism takes place only in the nearest Er(3+)-Yb(3+) pairs. This population route is in good agreement with that in nanomaterials and bulk materials.

Red emission of additional Pr³âº and adjusting effect of additional Mg²âº in Ca3Sc2Si3O12:Ce³âº, Mn²âº phosphor.

In this Letter, we report the addition of Pr3+ and Mg2+ in CSS:Ce3+, Mn2+ phosphor for improving the performances of white light-emitting diodes (LEDs). The additional trivalent Pr3+ will occupy the Ca2+ site in this host like the situation of Ce3+, its concentration can be enhanced by the addition of Mg2+ in Sc3+ site due to the substitution of Mg2+ for Sc3+ can compensate the charge mismatch between Pr3+ and Ca2+. Based on the efficient Ce3+→Pr3+ and Mn2+→Pr3+ energy transfers (ETs) and the compensation effect of Mg2+, the additional Pr3+ in our present phosphors exhibits an intense red-emission around 610 nm, which is significant for enhancing the color rendering property. In addition, we also find that the additional Mg2+ in Sc3+ site can markedly adjust the photoluminescence (PL) spectrum shape of our phosphor by controlling the distribution of Mn2+ at Ca2+ and Sc3+ sites. A new tunable full-color emission is obtained via the ETs (Ce3+→Mn2+, Ce3+→Pr3+ and Mn2+→Pr3+) and the adjusting effect of Mg2+ in our present phosphors. Finally, a white LED with higher color rendering index of 90, lower correlated color temperature of 4980 K, and chromaticity coordinates of (0.34, 0.31) was obtained by combining the single CSS:0.08Ce3+, 0.01Pr3+, 0.3Mn2+, 0.2Mg2+ phosphor with a blue-emitting InGaN LED chip.

The energy transfer mechanism in Pr(3+) and Yb(3+) codoped ß-NaLuF(4) nanocrystals.

The Pr(3+) and Yb(3+) codoped ß-NaLuF4 hexagonal nanoplates with a size of 250 nm × 110 nm were synthesized by a solvothermal process. X-Ray diffraction and scanning electron microscopy were used to characterize the crystal structure and morphology of the materials. The visible and near infrared spectra as well as the decay curves of Pr(3+):(3)P0 level were used to demonstrate the energy transfer from Pr(3+) ions to Yb(3+) ions. The downconversion phenomenon has been observed under the direct excitation of the (3)P2 level of Pr(3+). According to the analysis of the dependence of the initial transfer rate upon Yb(3+) ion concentration, it indicates that the ET from Pr(3+) ions to Yb(3+) ions is only by a two-step ET process when the Yb(3+) concentration is very low; however, with the increase of the Yb(3+) concentration, a cooperative ET process occurs and gradually increases; when the Yb(3+) ion concentration increases to 20 mol%, the ET from Pr(3+) ions to Yb(3+) ions occurs only by the cooperative ET process. When the doping concentration of Yb(3+) ions reaches 20 mol% at a fixed concentration of Pr(3+) ions (1 mol%), the theoretical quantum efficiency is 192.2%, close to the limit of 200%. The current research has great potential in improving the conversion efficiency of silicon solar cells.

Luminescence properties of Tb3+, Eu3+, Tm3+ co-doped Na5La(MoO4)4 for white light-emitting diode.

Tb3+, Eu3+, Tm3+ co-doped Na5La(MoO4)4 phosphors were prepared by the conventional solid-state reaction. Under the excitation of UV light, Na5La(MoO4)4:Tm3+, Na5La(MoO4)4:Tb3+, and Na5La(MoO4)4:Eu3+ exhibit the characteristic emissions of Tm3+ (1D2 --> 3F4, blue), Tb3+ (5D4 --> 7F5, green), and Eu3+ (5D0 --> 7F2, red), respectively. By adjusting the doping concentration of rare earth ions in Na5La(MoO4)4:a Tm3+, b Tb3+, c Eu3+, a white emission in a single composition was obtained under the excitation of 362 nm. It might be a promising phosphor for the future applications.

Strongly enhancing photostimulated luminescence by doping Tm3+ in Sr3SiO5: Eu2+.

We report a large enhancement of yellow photostimulated luminescence (PSL) by codoping Tm3+ in Sr3SiO5:Eu2+ upon infrared stimulation at 980 nm after pre-exposure in Ultraviolet light. The initial PSL intensity and light storage capacity are enhanced by a factor of 33 and 2, respectively, for Tm3+ concentration at 0.0004. The thermoluminescence spectra indicate that codoping Tm3+ generates a trap peaking at 385 K. The trap is much more sensitive to infrared light than the original one, so that the light storage period of the material is beyond tens of days with the minimum detectable infrared power density only 54 µW/cm2.

Formation condition of red Ce3+ in Ca3Sc2Si3O12:Ce3+, N3- as a full-color-emitting light-emitting diode phosphor.

In this Letter, we study diffuse reflectance and photoluminescence spectra for O(2-) fully coordinated green-emitting Ce(3+) and N(3-) partially coordinated red Ce(3+) in Ca(3)Sc(2)Si(3)O(12)(CSS):Ce(3+), N(3-) as a function of CeO(2) and Si(3)N(4) contents in the raw material. Our results indicate that the presence of N(3-) can enhance Ce(3+) solubility in the form of red centers in CSS. At low Ce(3+) concentration, green Ce(3+) forms preferentially while red Ce(3+) hardly forms even if N(3-) content in the raw material is sufficient. There exists a threshold concentration of green Ce(3+); only beyond that can color tunable luminescence with enriched red emission be achieved. Energy transfer from green Ce(3+) to red Ce(3+) is also studied, as only the green Ce(3+) is excited by blue light.

Spectroscopic properties and upconversion studies in Ho(3+) /Yb(3+) Co-doped calcium scandate with spectrally pure green emission.

The optical properties of a Ho(3+) /Yb(3+) co-doped CaSc2 O4 oxide material are investigated in detail. The spectral properties are described as a function of doping concentrations. The efficient Yb(3+) →Ho(3+) energy transfer is observed. The transfer efficiency approaches 50 % before concentration quenching. The concentration-optimized sample exhibits a strong green emission accompanied with a weak red emission, showing perfect green monochromaticity. The results of the spectral distribution, power dependence, and lifetime measurements are presented. The green, red, and near-infrared (NIR) emissions around 545, 660, and 759 nm are assigned to the (5) F4 +(5) S2 →(5) I8 , (5) F5 →(5) I8 , and (5) F4 +(5) S2 →(5) I7 transitions of Ho(3+) , respectively. The detailed study reveals the upconversion luminescence mechanism involved in a novel Ho(3+) /Yb(3+) co-doped CaSc2 O4 oxide material.