Achieving Narrowed Bandgaps and Blue-Light Excitability in Zero-Dimensional Hybrid Metal Halide Phosphors via Introducing Cation-Cation Bonding

Zero-dimensional(0D)hybrid metal halides,which consist of organic cations and isolated inorganic metal halide anions,have emerged as phosphors with efficient broadband emissions.However,these materials generally have too wide bandgaps and thus cannot be excited by blue light,which hinders their applications for efficient white light-emitting diodes(WLEDs).The key to achieving a blue-light-excitable 0D hybrid metal halide phosphor is to reduce the fundamental bandgap by rational chemical design.In this work,we report two designed hybrid copper(I)iodides,(Ph_(3)MeP)_(2)Cu_(4)I_(6)and(Cy_(3)MeP)_(2)Cu_(4)I_(6),as blue-light-excitable yellow phosphors with ultrabroadband emission.In these compounds,the[Cu_(4)I_(6)]^(2-)anion forms an I6 octahedron centered on a cationic Cu_(4)tetrahedron.The strong cation-cation bonding within the unique cationic Cu_(4)tetrahedra enables significantly lowered conduction band minimums and thus narrowed bandgaps,as compared to other reported hybrid copper(I)iodides.The ultrabroadband emission is attributed to the coexistence of free and self-trapped excitons.The WLED using the[Cu_(4)I_(6)]^(2-)anion-based single phosphor shows warm white light emission,with a high luminous efficiency of 65 Im W^(-1)and a high color rendering index of 88.This work provides strategies to design narrow-bandgap 0D hybrid metal halides and presents two first examples of blue-light-excitable 0D hybrid metal halide phosphors for efficient WLEDs.

Fabrication of YAG:Ce^(3+) and YAG:Ce^(3+),Sc^(3+) Phosphors by Spark Plasma Sintering Technique

In this study,a single-doped phosphors yttrium aluminum garnet(Y_(3)Al_(5)O_(12),YAG):Ce^(3+),single-doped YAG:Sc^(3+),and double-doped phosphors YAG:Ce^(3+),Sc^(3+) were prepared by spark plasma sintering(SPS)(lower than 1 200℃).The characteristics of synthesized phosphors were determined using scanning electron microscopy(SEM),X-ray diffraction(XRD),and fluorescence spectroscopy.During SPS,the lattice structure of YAG was maintained by the added Ce^(3+) and Sc^(3+).The emission wavelength of YAG:Ce^(3+) prepared from SPS(425-700 nm) was wider compared to that of YAG:Ce^(3+) prepared from high-temperature solid-state reaction(HSSR)(500-700 nm).The incorporation of low-dose Sc^(3+) in YAG:Ce^(3+) moved the emission peak towards the short wavelength.

Synthesis and Luminescence Improvement of CaAlSiN_(3)Phosphors Doped with Eu^(2+)and Mn^(2+)for White LEDs

Eu^(2+)and Mn^(2+)co-activated CaAlSiN_(3)red phosphors were produced using the solid-state reaction tech⁃nique in a N2 environment.Excitation spectra,emission spectra,and diffuse reflection spectra were used to study the luminescence characteristics,energy gap,and thermal stability in detail.CaAlSiN_(3)∶Eu^(2+)exhibits an extended emission band when stimulated with 450 nm blue light,which is caused by the 4f65d to 4f7 transition of Eu^(2+).Similar⁃ly,CaAlSiN_(3)∶Mn^(2+)displays a wide emission band centered at 628 nm,which results from Mn^(2+)’s transition from 4T1(4G)to 6A1(6S).When the ions of Mn^(2+)were combined into CaAlSiN_(3)∶Eu^(2+),the photoluminescence intensity of Eu^(2+)was greatly boosted because there was energy transfer and co-emission between Mn^(2+)and Eu^(2+).Beyond that,CaAlSiN_(3)∶Eu^(2+),Mn^(2+)emerges with splendid thermostability and high quantum efficiency,the quenching temperature surpasses 300℃,and the internal quantum efficiency is determined to be around 84.9%.The white LED was pack⁃aged with a combination of CaAlSiN_(3)∶Eu^(2+),Mn^(2+),LuAG∶Ce3+and a blue chip.At a warm white-light corresponding color temperature(3009 K)with CIE coordinates(0.4223,0.3748),the color rendering index Ra has reached 93.2.CaAlSiN_(3)∶Eu^(2+),Mn^(2+)would have great application potential as a red-emitting phosphor for white LEDs.

Mn^(4+) activated phosphors in photoelectric and energy conversion devices

Owing to their high luminous efficiency and tunable emission in both red light and far-red light regions,Mn^(4+)ion-activated phosphors have appealed significant interest in photoelectric and energy conversion devices such as white light emitting diode(W-LED),plant cultivation LED,and temperature thermometer.Up to now,Mn^(4+)has been widely introduced into the lattices of various inorganic hosts for brightly redemitting phosphors.However,how to correlate the structure-activity relationship between host framework,luminescence property,and photoelectric device is urgently demanded.In this review,we thoroughly summarize the recent advances of Mn^(4+)doped phosphors.Meanwhile,several strategies like co-doping and defect passivation for improving Mn^(4+)emission are also discussed.Most importantly,the relationship between the protocols for tailoring the structures of Mn^(4+)doped phosphors,increased luminescence performance,and the targeted devices with efficient photoelectric and energy conversion efficiency is deeply correlated.Finally,the challenges and perspectives of Mn^(4+)doped phosphors for practical applications are anticipated.We cordially anticipate that this review can deliver a deep comprehension of not only Mn^(4+)luminescence mechanism but also the crystal structure tailoring strategy of phosphors,so as to spur innovative thoughts in designing advanced phosphors and deepening the applications.

Properties of Self-recoverable Mechanoluminescence Phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+) and Its Information Encryption Application

A novel self-recoverable mechanoluminescent phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+) was developed by the high-tem-perature solid-state reaction method,and its luminescence properties were investigated.Ca_(5)Ga_(6)O_(14)∶Eu^(3+)can produce red mechanoluminescence,and importantly,it shows good repeatability.The mechanoluminescence of Ca_(5)Ga_(6)O_(14)∶Eu^(3+) results from the piezoelectric field generated inside the material under stress,rather than the charge carriers stored in the traps,which can be confirmed by the multiple cycles of mechanoluminescence tests and heat treatment tests.The mechanoluminescence color can be turned from red to green by co-doping varied concentrations of Tb^(3+),which may be meaningful for encrypted letter writing.The encryption scheme for secure communication was devised by harnessing mechanoluminescence patterns in diverse shapes and ASCII codes,which shows good encryption performance.The results suggest that the mechanoluminescence phosphor Ca_(5)Ga_(6)O_(14)∶Eu^(3+),Tb^(3+)may be applied to the optical information encryption.

Structural and Luminescent Properties of Mg_(0.25-x)Al_(2.57)O_(3.79)N_(0.21):xMn^(2+)Green-Emitting Transparent Ceramic Phosphor

A series of spinel-type Mg_(0.25-x)Al_(2.57)O_(3.79)N_(0.21):xMn^(2+)(MgAlON:xMn^(2+))phosphors were synthesized by the solid-state reaction route.The transparent ceramic phosphors were fabricated by pressureless sintering followed by hot-isostatic pressing(HIP).The crystal structure,luminescence and mechanical properties of the samples were systematically investigated.The transparent ceramic phosphors with tetrahedrally coordinated Mn^(2+)show strong green emission centered around 515 nm under blue light excitation.As the Mn^(2+)concentration increases,the crystal lattice expands slightly,resulting in a variation of crystal field and a slight red-shift of green emission peak.Six weak absorption peaks in the transmittance spectra originate from the spin-forbidden ^(4)T_(1)(^(4)G)→^(6)A_(1) transition of Mn^(2+).The decay time was found to decrease from 5.66 to 5.16 ms with the Mn^(2+)concentration.The present study contributes to the systematic understanding of crystal structure and properties of MgAlON:xMn^(2+)green-emitting transparent ceramic phosphor which has a potential application in high-power light-emitting diodes.

Pillar effect induced by ultrahigh phosphorous/nitrogen doping enables graphene/MXene film with excellent cycling stability for alkali metal ion storage

Graphene's large theoretical surface area and high conductivity make it an attractive anode material for potassium-ion batteries(PIBs).However,its practical application is hindered by small interlayer distance and long ion transfer distance.Herein,this paper aims to address the issue by introducing MXene through a simple and scalable method for assembling graphene and realizing ultrahigh P doping content.The findings reveal that MXene and P-C bonds have a "pillar effect" on the structure of graphene,and the P-C bond plays a primary role.In addition,N/P co-doping introduces abundant defects,providing more active sites for K^(+) storage and facilitating K^(+) adsorption.As expected,the developed ultrahigh phosphorous/nitrogen co-doped flexible reduced graphene oxide/MXene(NPrGM) electrode exhibits remarkable reversible discharge capacity(554 mA hg^(-1) at 0.05 A g^(-1)),impressive rate capability(178 mA h g^(-1) at 2 A g^(-1)),and robust cyclic stability(0.0005% decay per cycle after 10,000 cycles at 2 A g^(-1)).Furthermore,the assembled activated carbon‖NPrGM potassium-ion hybrid capacitor(PIHC) can deliver an impressive energy density of 131 W h kg^(-1) and stable cycling performance with 98.1% capacitance retention after5000 cycles at 1 A g^(-1).Such a new strategy will effectively promote the practical application of graphene materials in PIBs/PIHCs and open new avenues for the scalable development of flexible films based on two-dimensional materials for potential applications in energy storage,thermal interface,and electromagnetic shielding.

Durable hierarchical phosphorus‐doped biphase MoS_(2)electrocatalysts with enhanced H^(*)adsorption

Phase engineering is an efficient strategy for enhancing the kinetics of electrocatalytic reactions.Herein,phase engineering was employed to prepare high‐performance phosphorous‐doped biphase(1T/2H)MoS_(2)(P‐BMS)nanoflakes for hydrogen evolution reaction(HER).The doping of MoS_(2)with P atoms modifies its electronic structure and optimizes its electrocatalytic reaction kinetics,which significantly enhances its electrical conductivity and structural stability,which are verified by various characterization tools,including X‐ray photoelectron spectroscopy,high‐resolution transmission electron microscopy,X‐ray absorption near‐edge spectroscopy,and extended X‐ray absorption fine structure.Moreover,the hierarchically formed flakes of P‐BMS provide numerous catalytic surface‐active sites,which remarkably enhance its HER activity.The optimized P‐BMS electrocatalysts exhibit low overpotentials(60 and 72 mV at 10 mA cm^(−2))in H_(2)SO_(4)(0.5 M)and KOH(1.0 M),respectively.The mechanism of improving the HER activity of the material was systematically studied using density functional theory calculations and various electrochemical characterization techniques.This study has shown that phase engineering is a promising strategy for enhancing the H*adsorption of metal sulfides.

YAG∶Ce Phosphors for WLED via Nano-Pesudoboehmite Sol-Gel Route

The sub-micron sized YAG ： Ce phosphors were synthesized via a modified sol-gel method by peptizing nano-pesudoboehmite particulate. It is found that YAG phase from the dried gel powders appears at 1000 ℃ then the pure YAG phase exists at a relatively lower sintering temperature of 1400 ℃. The smaller sizes of phosphors in the ranges of 1 - 3 μm are obtained due to the contribution of seeding effects of nano-sized alumina particles to strengthen each step of the processes. Both the excitation and emission spectra of photoluminescence of the phosphor obtained at 1400 ℃ meet well with the spectroscopic requirements of the WLED phosphors.

Investigations on Valence-Change Behaviors of Europium Ions in Eu-Doped Aluminate and Silicate Phosphors

Compounds of Sr3Al2O6 ： Eu, SrgAl14O25 ： Eu, and BaZnSiO4 ： Eu were synthesized by high-temperature solid state reactions. The doping Eu^3 ＋ ions were partially reduced to Eu^2＋ in Sr4Al14O25：Eu and BaZnSiOg：Eu prepared in an oxidizing atmosphere, N^2 ＋ O2. However, such an abnormal reduction process could not be performed in Sr3Al2O6：Eu, which was also prepared in an atmosphere of N^2 ＋ O2. Moreover, even though Sr3A1EO6：Eu was synthesized in a reducing condition CO, only part of the Eu^3 ＋ ions was reduced to Eu^2 ＋ . The existence of trivalent and divalent europium ions was confirmed by photoluminescent spectra. The different valence-change behaviors of europium ions in the hosts were attributed to the difference in host crystal structures. The higher the crystal structure stiffness, the easier the reduction process from Eu^3 ＋ to Eu^2 ＋ .

Preparation and luminescent properties of CaAl_2O_4:Eu^(3+),R^+(R=Li,Na,K) phosphors

CaAl2O4:Eu3+,R+(R=Li+,Na+,K+) red phosphors were synthesized by solid state reaction method.X-ray diffraction(XRD) and photoluminescence(PL) were employed to characterize their structural and luminescent properties.It was found that the optimal sintering temperature and sintering time were 1200 °C and 4 h,respectively.The optimal concentration of doped Eu3+ was 3 mol.%.Furthermore,under ultraviolet excitation with a wavelength of 254 nm,these samples showed red luminescence which were probably attributed to...

Separation of Red (Y_2O_3: Eu^(3+)), Blue (Sr,Ca,Ba)_(10)(PO_4)_6Cl_2: Eu^(2+) and Green (LaPO_4:Tb^(3+),Ce^(3+)) Rare Earth Phosphors by Liquid/Liquid Extraction

A novel process for separation of red （Y2O3： Eu^3＋）, blue （Sr, Ca, Ba）10（PO4）6Cl2： Eu^2＋ and green （LaPO4： Tb^3＋, Ce^3＋） fine tricolor phosphor powders was established. First, the green phosphor was extracted and separated from three phosphor mixtures in heptane/DMF（N, N-Dimethylformamide） system using stearylamine or laurylamine （DDA） as the cationic surfactant. Then, after being treated with 99.5% ethanol, the blue and red phosphors could be separated in Heptane/DMF system in presence of 1-octanesulfonic acid sodium salt as the anionic surfactant. Satisfactory separation results have been achieved through two steps extractions with their artificial mixtures. The grades and recovery of separated products reached respectively as follows： red product was 95.3% and 90.9%, blue product was 90.0% and 95.2%, and green product was 92.2% and 91.8%.

Effect of Yb^(3+) concentration on the structures and upconversion luminescence properties of Y_2O_3:Er^(3+) ultrafine phosphors

Y2O3：Er^3＋ ultrafine phosphors with a varying Yb^3＋ ion concentration were prepared by a urea homogeneous precipitation method. The results of XRD show that all the samples are of a pure cubic structure and the average crystallite sizes can be calculated as 45, 34, and 28 nm for Y2O3：Er^3＋ ultrafine phosphors with Yb^3＋ ion concentrations of 0, 10%, and 20%, respectively. The lattice constant and cell volume of the ultrafine phosphors decrease with enhancing Yb^3＋ ion concentration. The upconversion luminescence spectra of all the samples were studied under 980 nm laser excitation. The strong green and red upconversion emission were observed, and attributed to the ^2H11/2→^4I15/2, ^4S3/2 → ^4I15/2 and ^4F9/2 →^4I15/2 transitions of Er^3＋, respectively. The intensity of red emission increases with increasing Yb^3＋ ion concentration. The effect of Yb^3＋ ion concentration on the structures and upconversion luminescence mechanism were discussed.

Synthesis and Characterization of Cerium-Doped Lutetium Aluminum Garnet Phosphors by Nitrate-citrate Sol-Gel Combustion Process

Nanosized cerium-doped lutetium aluminum garnet （LuAG：Ce） phosphors were prepared by nitrate-citrate solgel combustion process using 1：1 ratio of the citrate：nitrate. The prepared LuAG：Ce phosphors were characterized by XRD, TEM, photoluminescence and radioluminescence spectra excited by UV and X-ray, respectively. The purified crystalline phase of LuAG：Ce was obtained at 900 ℃ by directly crystallizing from amorphous materials. The resultant Lu- AG：Ce phosphors were uniform and had good dispersivity with an average particle size of about 30 urn. Both photoluminescence and radioluminescence were well-known Ce^3＋ emissions located in the range of 470 -600 nm consisting of two emission bands because of the transition from the lowest 5d excited state （2D） to the 4f ground state of Ce^3＋, which matched well with the sensitivity curve of the Si-photodiode. There was a little red shift for the emission components from the UV-excited emission spectrum to the X-ray-excited emission spectrum. The fast scintillation decay component of 26 ns satisfies the requirements of fast scintillators.

Effect of fluxes on structure and luminescence properties of Y_3Al_5O_(12):Ce^(3+) phosphors

Ce3＋-activated yttrium aluminum garnet （YAG） was prepared by the solid-state reaction, in which H3BO3, LiF, NaF, KF and BaF2 were used as the fluxes. The effect of fluxes on optical properties of phosphors was studied in detail, especially the fluxes of alkali fluorides, which could enhance the emission intensity and change the wavelength of emission peaks. Among these YAG：Ce phosphors, the phosphor sintered with H3BO3 and NaF exhibited the strongest emission. The emission peaks of phosphors prepared with fluxes from LiF to KF were shifted to long wavelength. The effect of NaF concentration on the emission intensity of YAG：Ce was also investigated. The value of emission intensity reached the maximum when the concentration of NaF was 0.5%.

Controlled Synthesis and Application of α-Al_2O_3 for Lu_3Al_5O_(12): Ce^(3+) Green Spherical Phosphors

Al2O3 powders with different morphologies,namely fibrous,sheet-like,and spherical,were prepared by the hydrothermal-thermolysis method.Subsequently,polycrystalline,transparent cerium doped lutetium aluminum garnet（Lu3Al5O（12）：Ce^3＋）green phosphors were synthesized by high temperature solidstate method using commercial lutetium（III）oxide,cerium（III）oxide,and as-prepared Al2O3 powders with different morphologies.The phases,morphologies,and photoluminescent properties of the prepared phosphors were investigated by X-ray diffraction（XRD）,scanning electron microscopy（SEM）,and photoluminescence spectroscopy（PL）.Moreover,the influences of the morphologies ofα-Al2O3 on the types of crystal structure,morphologies,and photoluminescent properties of LuAG：Ce^3＋green phosphors were investigated.The results indicated that the morphologies and particle sizes of theα-Al2O3 powders could be controlled by the additives and parameters.Notably,the sphericalα-Al2O3 powders with good dispersibility were found to be the excellent base materials of LuAG：Ce^3＋green phosphors for white light emitting diodes.

Synthesis and Luminescence Properties of Red Phosphors:Mn^(2+) Doped MgSiO_3 and Mg_2SiO_4 Prepared by Sol-Gel Method

Sol-gel method was utilized to synthesize two different series of red silicate phosphors : MgSiO3 and Mg2SiO4 powder samples doped with Mn2+, conducted the investigation of red long-lasting phosphor: MgSiO3 : Eu2 + , Dy3+, Mn2+ . TGA curves of the gel precursor for two series depicted that the loss of residual organic groups and NO3 groups occurs below 450℃. According to the XRD patterns, the major diffraction peaks of the MgSiO3 and Mg2SiO4 series are consistent with a proto-enstatite structure (JCPDS No.11-0273) and a forsterite structure (JCPDS No.85-1364) respectively. With the excitation at 415 nm, the red emission band of Mn2+ ions is peaked at 661 nm for MgSiO3:1%(atom fraction) Mn2+ or 644 nm for MgiSiO4: 1 %(atom fraction) Mn2+ . Compared with Mg2SiO4:Mn2+ samples, MgSiO3:Mn2+ samples exhibit higher luminescence intensity and higher quenching concentration. In addition, the two series co-doped with Eu2+ , Dy3+ , Mn2+ were also prepared. Photo-luminescence and afterglow properties of the two co-doped series were analyzed, which show that MgSiO3: Eu2 + , Dy3+ , Mn2+ is more suitable for a red long-lasting phosphor.

Synthesis and luminescence properties of Ca_2SiO_4-based red phosphors with Sm^(3+) doping for white LEDs

Sm3＋-activated Ca2SiO4 red phosphors were prepared by the conventional high-temperature solid-state reaction method, and the effects of sodium （Na＋） and samarium （Sm3＋） ions doping concentrations on their crystal structure and luminescent properties were investigated by X-ray diffraction （XRD） and fluorescent spectrofluorometer. XRD patterns demonstrate that a well-crystalline structure forms in the phosphors when they are treated by calcination at 1200~C for 4 h, and the excitation spectra exhibit good absorption in the range between 350 and 420 nm. Under the irradiation of 405 nm near-ultraviolet （NUV） light, the spectra of the phosphors show a main emission peak at 601 nm attributed to the 4G5/2→6H7/2 transition of Sm3＋ ions, and its intensity is greatly influenced by the concentrations of Sm3＋ and Na2CO3. When the concentrations of Sm3＋ ions and Na2CO3 are 2mol% and 6mol%, respectively, the optimal emission intensity can be obtained. From strong absorption in the near ultraviolet zone, the Na0.06Sm0.02Ca1.92SiO4 phosphor is a promising red-emitting phosphor for white light emitting diodes （W-LEDs）.

Sol-gel processed Ce^(3+), Tb^(3+) codoped white emitting phosphors in Sr_2Al_2SiO_7

Sr2Al2SiO7：Ce^3＋, Tb^3＋ white emitting phosphors were fabricated using the sol-gel method. X-Ray Powder Diffraction （XRD） analysis confirmed the formation of Sr2Al2SiO7：Ce^3＋, Tb^3＋. Scanning Electron Microscopy （SEM） observation indicated that the microstructure of the phosphor consisted of regular fine grains with an average size of about 0.5-1 μm. Luminescence properties were analyzed by measuring the photoluminescence spectra. The Ce^3＋, Tb^3＋-codoped Sr2Al2SiO7 phosphors showed four main emission peaks： one at 414 nm for Ce^3＋ and three at 482, 543, and 588 nm for Tb^3＋. The emission spectra of the samples with different doping concentrations showed that the Tb^3＋ emission was dominant because of the persistent energy transfer from Ce^3＋. The decay characteristic was better than that prepared by the solid-state process in the comparable condition. The codoped phosphor displayed long persistent white phosphorescence.

Synthesis of SrAl_2O_4:Eu^(2+),Dy^(3+) phosphors by the coupling route of microemulsion with coprecipitation method

Nano-sized SrAl2O4：Eu^2＋,Dy^3＋ phosphors with good monodispersity and narrow size distribution were synthesized by the coupling of water-in-oil （W/O） microemulsion with coprecipitation method. The phase composition, morphology, crystallinity, excitation spectra, emission spectra, and afterglow decay of SrAl2O4：Eu^2＋,Dy^3＋ nanophosphors were measured. It was found that the amount of surfactant that was used had an important effect on the shape and average size of the phosphor particles. SrAl204 phase of the phosphors showed an increase with the increase in calcination temperature. When the calcination temperature reached 1150℃, the fine crystal of SrAl2O4 was formed and the long afterglow luminescence could be obviously observed. In comparison with the samples prepared by the high-temperature solid-state method, the calcination temperature showed an obvious decrease and a dear blue shift occurred in the excitation and emission spectra of the sample. The afterglow time could be more than 8 h.