Enhanced Efficiency, Broadened Excitation, and Tailored Er3+ Luminescence Triggered by Te4+ Codoping in Cs2NaYbCl6 Crystals for Multifunctional Applications.

The quest for efficient and tunable luminescent materials has been at the forefront of research in the fields of chemistry and materials science. This work delves into the investigation of the luminescence properties of Er3+ ions triggered by 1% Te4+ in the environmentally benign perovskite Cs2NaYbCl6 (CNYC) crystals, aiming to enhance their efficiency and tune the luminescence color. The ratio of the green (2H11/2, 4S3/2-4I15/2) to red (4F9/2-4I15/2) emissions of Er3+ can be freely tunable by varying the concentration of Er3+ and producing the defects induced by codoping Te4+. The calculations reveal that the multiexcitonic excitations of Er3+ stem from f-f (4I15/2-4G11/2, 2H9/2) rather than d-f transitions. The broadened excitation, tuning of color, and enhancement of efficiency achieved in the luminescence perovskite crystals Cs2NaYbCl6:Te4+, Er3+ (CNYC:Te4+,Er3+) presents promising opportunities for the development of advanced optoelectronic devices with superior performance. Moreover, our investigation demonstrates the tunable luminescence response of CNYC:Er3+ to temperature variations, offering potential applications in temperature sensing.

Precise Hue Control in a Single-Component White-Light Emitting Perovskite Cs2 SnCl6 through Defect Engineering Based on La3+ Doping.

Single-component white light emitters based on the all-inorganic perovskites will act as outstanding candidates for applications in solid-state lighting thanks to their abundant energy states for self-trapped excitons (STE) with ultra-high photoluminescence (PL) efficiency. Here, a complementary white light is realized by dual STEs emissions with blue and yellow colors in a single-component perovskite Cs2 SnCl6 :La3+ microcrystal (MC). The dual emission bands centered at 450 and 560 nm are attributed to the intrinsic STE1 emission in host lattice Cs2 SnCl6 and the STE2 emission induced by the heterovalent La3+ doping, respectively. The hue of the white light can be tunable through energy transfer between the two STEs, the variation of excitation wavelength, and the Sn4+ /Cs+ ratios in starting materials. The effects of the doping heterovalent La3+ ions on the electronic structure and photophysical properties of the Cs2 SnCl6 crystals and the created impurity point defect states are investigated by the chemical potentials calculated using density functional theory (DFT) and confirmed by the experimental results. These results provide a facile approach to gaining novel single-component white light emitter and offer fundamental insights into the defect chemistry in the heterovalent ions doped perovskite luminescent crystals.

Spectral Tunability, Luminescence Enhancement, and Temperature Sensitivity of Sb3+-Doped Bismuth-Based Halide Emission Crystals for Anti-Counterfeiting Applications.

The synthesis of sustainable luminescent materials with simplicity, low energy consumption, and nontoxicity is of great importance in the field of chemistry and materials science. In this study, a room temperature evaporation method was employed to synthesize Sb3+-doped bismuth-based halide emission crystals, allowing for investigation of spectral tuning, luminescence enhancement, and temperature sensitivity. By substitution of Rb+ with varying concentrations of Cs+ in Rb3BiCl6 (RBC), the luminescent color of the crystals can be tuned from orange to yellow. The resulting alloyed yellow-emitting crystals were identified as Rb2CsBiCl6 (RCBC). Remarkably, when one-third of the Rb+ ions were replaced by Cs+ in the RBC, the crystals exhibited improved thermal stability and a 20-fold increase in luminescence intensity. The temperature-sensitive behavior was observed for RBC:Sb, with emission shifting from 590 to 574 nm upon heating while the yellow emission of RCBC:Sb exhibited no significant peak shift with temperature. Notably, the yellow emission of RBC:Sb could be reversibly converted back to orange light upon cooling to room temperature. In contrast, RCBC:Sb exhibited no significant peak shift with temperature. The differential temperature sensitivity between RBC:Sb and RCBC:Sb offers potential applications in anti-counterfeiting measures.

Metal Halide Single Crystals RbCdCl3:Sn2+ and Rb3SnCl7 with Blue and White Emission Obtained via a Hydrothermal Process.

Until now, effective blue light-emitting materials are essentially needed for the creation of white light and precise color renderings in real-world applications, but the efficiency of blue light-emitting materials has lagged far behind. Here, we present a hydrothermal method to synthesize tin-based metal halide single crystals (RbCdCl3:Sn2+ and Rb3SnCl7). Two single crystal materials with different shapes and phases can simultaneously be synthesized in the same stoichiometric ratio. Rb3SnCl7 has a bulk shape, while RbCdCl3:Sn2+ has a needle shape. The deep blue emission (436 nm) of RbCdCl3:Sn2+ can be obtained under the optimal excitation wavelength irradiation. However, pure blue emission (460 nm) to white light can be obtained by changing the excitation wavelength in Rb3SnCl7. The refinement spectra of the electronic structures of RbCdCl3:Sn2+ and Rb3SnCl7 are investigated by density functional theory. It is concluded that the difference in the distribution of Cl energy states leads to the existence of Cl local defect states, which is the reason for the rich luminescence of the two single crystals. These findings provide a path for realizing single-phase broadband white-emitting materials.

Multimode Luminescence Tailoring and Improvement of Cs2 NaHoCl6 Cryolite Crystals via Sb3+ /Yb3+ Alloying for Versatile Photoelectric Applications.

Lead-free halide double perovskites are currently gaining significant attention owing to their exceptional environmental friendliness, structural adjustability as well as self-trapped exciton emission. However, stable and efficient double perovskite with multimode luminescence and tunable spectra are still urgently needed for multifunctional photoelectric application. Herein, holmium based cryolite materials (Cs2 NaHoCl6 ) with anti-thermal quenching and multimode photoluminescence were successfully synthesized. By the further alloying of Sb3+ (s-p transitions) and Yb3+ (f-f transitions) ions, its luminescence properties can be well modulated, originating from tailoring band gap structure and enriching electron transition channels. Upon Sb3+ substitution in Cs2 NaHoCl6 , additional absorption peaking at 334 nm results in the tremendous increase of photoluminescence quantum yield (PLQY). Meanwhile, not only the typical NIR emission around 980 nm of Ho3+ is enhanced, but also the red and NIR emissions show a diverse range of anti-thermal quenching photoluminescence behaviors. Furthermore, through designing Yb3+ doping, the up-conversion photoluminescence can be triggered by changing excitation laser power density (yellow-to-orange) and Yb3+ doping concentration (red-to-green). Through a combined experimental-theoretical approach, the related luminescence mechanism is revealed. In general, by alloying Sb3+ /Yb3+ in Cs2 NaHoCl6 , abundant energy level ladders are constructed and more luminescence modes are derived, demonstrating great potential in multifunctional photoelectric applications.

Large Spectral Shift of Mn2+ Emission Due to the Shrinkage of the Crystalline Host Lattice of the Hexagonal CsCdCl3 Crystals and Phase Transition.

All-inorganic halide perovskite crystals are considered excellent optical host lattices for various dopants to obtain wavelength-tunable emissions with ultra-broad bands even over a wide spectral range. Here, a series of Mn2+-doped bulk ligand-free CsCdCl3 (CCC) perovskite crystals with a hexagonal shape and size of about 1 millimeter (mm) have been prepared by a facile hydrothermal method. These CCC:Mn2+ (CCC:Mn) crystals emit the representative orange-red photoluminescence (PL) of Mn2+ (4T1(G)-6A1(S)) in the centers of hexagonal octahedrons coordinated with six Cl- ions. A fine-tuning of the Mn2+ concentration from 1 to 50 mol % Cd2+ induces a substantial red shift of emission spectra from 570 to 630 nm due to the shrinkage of the crystalline host lattice, and the maximum intensity of emission is achieved at 20 mol % Mn2+ doping. A further increase in the Mn2+ concentration causes a decrease of the PL intensity due to the phase transition from CCC to CsMnCl3·2H2O (CMCH). The strong excitation bands at 360, 370, 420, and 440 nm can make the excitation of the emissive CCC:Mn crystals possible with ultraviolet (UV) and blue chips for application in white light-emitting diodes (WLEDs). The similarity of the Mn2+-concentration-dependent emission spectra excited by various wavelengths indicates that there is only one type of site for Mn2+ occupation in CCC.

Tunable Dual Emission in Bi3+/Te4+-Doped Cs2HfCl6 Double Perovskites for White Light-Emitting Diode Applications.

Multicolor-emission-based single-phase white light derived from different luminescence centers is an effective way to manipulate the optical properties of halide perovskites. In this work, we developed a codoping strategy to incorporate Bi3+ and Te4+ emission centers into all-inorganic lead-free Cs2HfCl6 perovskite by a hydrothermal method. The as-prepared Bi3+/Te4+-doped Cs2HfCl6 microcrystals show bright blue (Bi3+), yellow (Te4+), and warm-white emissions (Bi3+/Te4+), respectively. The broad efficient dual emission in Bi3+/Te4+ co-doped Cs2HfCl6 is assigned to the typical 3P1 → 1S0 transition emission from Bi3+ originating from [BiHf + VCl] and self-trapped excitons (STEs) from Te4+. Moreover, the concentration-optimized Cs2HfCl6:Te4+ shows excellent antiwater stability and high photoluminescence quantum yield (PLQY) of ∼70%. Meanwhile, a white light-emitting diode (WLED) fabricated using Bi3+/Te4+ co-doped Cs2HfCl6 is close to warm white with a color rendering index (CRI) of 75.4, CIE color coordinate of (0.370, 0.393), and a correlated color temperature (CCT) of 4380 K. These results suggest that Bi3+/Te4+ co-doped all-inorganic lead-free Cs2HfCl6 is a potential single-phase white light-emitting phosphor candidate for solid-state lightings.

Growth of SnX2 (X = Br, I) Single Crystals with Self-Trapped Exciton Emission.

Broadband emission with a large Stokes shift is important to obtain an excellent color rendering index of the solid-state lighting device. Among low-dimensional material and perovskite-like phosphors with broadband self-trapped emission, Sn-based phosphors have attracted much attention due to their high photoluminescence quantum yield (PLQY). However, the disadvantage is that the synthesis of Sn-based phosphors needs to be performed in a glovebox. Upon photoexcitation, the broadband emission of self-trapped excitons results from exciton-phonon coupling induced by the transient distortion of the lattice. Low-dimensional material structures often promote self-trapped emission because of more vibrational degrees of freedom and easier polarization under photoexcitation. Here, zero-dimensional (0D) SnX2 (X = Br, I) single crystals are synthesized by the solvent evaporation method in the air. SnX2 emits blue light, broadband yellow light, and deep red light, among which SnBr2 has the best luminescence performance. The photoluminescence quantum yield (PLQY) of SnBr2 reaches 85% and the Stokes shift reaches 265 nm. The PL intensity of SnX2 is linearly related to excitation power, which preliminarily indicates that the origin of SnX2 luminescence is attributed to self-trapped emission (STE). The white light-emitting diodes (WLEDs) were fabricated using yellow-emitting SnBr2 and blue-emitting BaMgAl10O17:Eu2+, which has a low correlated color temperature (3160 K) and a relatively common color rendering index (79).

4-Bromo-Butyric Acid-Assisted In Situ Passivation Strategy for Superstable All-Inorganic Halide Perovskite CsPbX3 Quantum Dots in Polar Media.

A crucial challenge is to develop an in situ passivation treatment strategy for CsPbX3 (CPX, X=Cl, Br, and I) quantum dots (QDs) and simultaneously retain their luminous efficiency and wavelength. Here, a facile method to significantly improve the stability of the CPX QDs via in situ crystallization with the synergistic effect of 4-bromo-butyric acid (BBA) and oleylamine (OLA) in polar solvents including aqueous solution and a possible fundamental mechanism are proposed. Monodispersed CsPbBr3 (CPB) QDs obtained in water show high photoluminescence quantum yields (PLQYs) of 86.4 % and their PL features of CPB QDs have no significant change after being dispersed in aqueous solution for 96 h, which implies the structure of CPB QDs is unchanged. The results provide a viable design strategy to synthesize all-inorganic perovskite CPX QDs with strong stability against the attack of polar solvents and shed more light on their surface chemistry.

Core-Shell Structured Upconversion/Lead-Free Perovskite Nanoparticles for Anticounterfeiting Applications.

In view of their excellent luminescence properties, nanocrystalline metal halide perovskites have diverse optoelectronic applications, including those related to anticounterfeiting. However, high-quality optical anticounterfeiting typically requires multiple encryptions relying on several optical modes to ensure information security. Herein, an efficient anticounterfeiting strategy based on dual optical encryption is realized by combining up- and downconversion luminescence in a nanocomposite with NaYF4 : Er3+ ,Yb3+ as core and a CsMnCl3 as shell. The emission color of this nanocomposite depends on the penetration depth of incident radiation and can be changed by varying the excitation source (980 nm laser or UV light) to produce different luminescent patterns. This feature allows one to effectively improve the anticounterfeiting index and fabricate professional anticounterfeiting materials.

Improved Moisture-Resistant and Luminescence Properties of a Red Phosphor Based on Dodec-fluoride K3RbGe2F12:Mn4+ through Surface Modification.

Mn4+-activated red-emitting fluoride phosphors are essential for white light-emitting diodes (WLEDs) with desirable color rendition index (CRI) because of their unique and efficient luminescence characteristics. Herein, we synthesized a novel Mn4+-activated dodec-fluoride phosphor K3RbGe2F12:Mn4+ (KRGF:Mn) through a facile ionic exchange method at room temperature. A surface-modified strategy using weak reducing agents such as oxalic acid and citric acid is proposed to improve the moisture-resistance ability of KRGF:Mn phosphor dramatically, and the possible mechanism of surface modification has been investigated. A shell formed on the surface of the KRGF:Mn phosphor reduces the concentration of Mn4+ on the surface, which can prevent the internal KRGF:Mn group hydrolysis by the external moisture and effectively decreased the probability of energy migration to surface defects, thereby increasing both the emission efficiency and the moisture-resistance ability of KRGF:Mn. More interestingly, the KRGF:Mn phosphor is quenched after soaking in water for 72 h but recovered to the initial brightness after soaking in the modifier solutions for 2 min. This work fabricates a new efficient red phosphor KRGF:Mn for application in warm WLEDs and provides insight into the mechanism of the strategy to improve the moisture resistance of the stability of Mn4+ through surface modification.

Simultaneous Broadening and Enhancement of Cr3+ Photoluminescence in LiIn2 SbO6 by Chemical Unit Cosubstitution: Night-Vision and Near-Infrared Spectroscopy Detection Applications.

Near-infrared (NIR)-emitting phosphor materials have been extensively developed for optoelectronic and biomedical applications. Although Cr3+ -activated phosphors have been widely reported, it is challenging to achieve ultra-broad and tunable NIR emission. Here, a new ultra-broadband NIR-emitting LiIn2 SbO6 :Cr3+ phosphor with emission peak at 965 nm and a full-width at half maximum of 217 nm is reported. Controllable emission tuning from 965 to 892 nm is achieved by chemical unit cosubstitution of [Zn2+ -Zn2+ ] for [Li+ -In3+ ], which can be ascribed to the upshift of 4 T2g energy level due to the strengthened crystal field. Moreover, the emission is greatly enhanced, and the FWHM reaches 235 nm. The as-prepared luminescent tunable NIR-emitting phosphors have demonstrated the potential in night-vision and NIR spectroscopy techniques. This work proves the feasibility of chemical unit cosubstitution strategy in emission tuning of Cr3+ -doped phosphors, which can stimulate further studies on the emission-tunable NIR-emitting phosphor materials.

Broadband Near-Infrared Emitting Ca2LuScGa2Ge2O12:Cr3+ Phosphors: Luminescence Properties and Application in Light-Emitting Diodes.

In recent years, the demand for near-infrared phosphor-converted light-emitting diodes (NIR pc-LEDs) has increased rapidly, leading to more and more attention being paid to the research of broad-band near-infrared phosphors. In this work, Cr3+-doped Ca2LuScGa2Ge2O12 (CLSGG:Cr3+) phosphors with broad-band NIR emission were prepared through traditional high-temperature solid-state reactions. The crystal structures of the phosphors were analyzed by X-ray diffraction (XRD) and Rietveld refinement. The photoluminescence excitation (PLE) spectra of the synthesized CLSGG:Cr3+ phosphors exhibit a strong absorption band in the 400-500 nm region, which matches well with a blue-light-emitting chip. The photoluminescence (PL) spectra of the phosphors show broad-band emission ranging from 650 to 1100 nm with a full width at half-maximum (fwhm) of about 150 nm. At 423 K, the integrated emission intensity of CLSGG:0.02Cr3+ is about 59% of that at room temperature. A NIR pc-LED device was fabricated by combining a mixture of as-synthesized CLSGG:0.02Cr3+ phosphor and silicone with a 460 nm blue-light-emitting chip. Under a driving current of 100 mA, the output power of the device can achieve 1.213 mW, indicating that the as-prepared phosphors are promising for NIR pc-LED applications.

Highly Efficient Cyan-Green Emission in Self-Activated Rb3RV2O8 (R = Y, Lu) Vanadate Phosphors for Full-Spectrum White Light-Emitting Diodes (LEDs).

Phosphor-converted white-light-emitting diodes (pc-WLEDs) rely on combining a near-ultraviolet (n-UV) or blue chip with trichromatic and yellow-emitting phosphors. It is challenging to discover cyan-green-emitting (480-520 nm) phosphors for compensating the spectral gap and producing full-spectrum white light. In this work, we successfully discovered two unprecedented bright cyan-green emitting Rb3RV2O8 (R = Y, Lu) phosphors that gives emission bands centered at 500 nm upon 362 nm n-UV light excitation. Interestingly, the both self-activated compounds exhibit high internal quantum efficiencies (IQEs) of 71% for Rb3YV2O8 and 85% for Rb3LuV2O8, respectively. Moreover, controllable emission color can be successfully tuned from cyan-green to orange-red across the warm white light region by design strategy of VO43- → Eu3+ energy transfer. The thermal quenching of as-prepared phosphors could be effectively mitigated by this design strategy. Finally, the as-fabricated n-UV (λex = 370 nm) pumped phosphor-converted (pc) W-LED devices utilizing Rb3RV2O8 (R = Y, Lu) along with commercial phosphors demonstrate well-distributed warm white light with high color-rendering index (CRI) of 91.9 and 93.5, and a low correlated color temperature (CCT) of 5095 and 4946 K. It suggests that the both vanadate phosphors have potential applications in full-spectrum pc-WLEDs.

Luminescence and Energy-Transfer Properties in Bi3+/Mn4+-Codoped Ba2GdNbO6 Double-Perovskite Phosphors for White-Light-Emitting Diodes.

Currently, the study of Mn4+-doped oxide red phosphor is a hot research topic to solve the lack of red component in phosphor-converted white-light-emitting diodes (pc-WLEDs). In this Article, we designed Gd3+/Nb5+ cation substitution by Bi3+/Mn4+ in Ba2GdNbO6 with double-perovskite structure based on the radius and coordination of the cations through high-temperature solid-state reaction. The phase purity and microstructure of double-perovskite Ba2GdNbO6:Bi3+,Mn4+ phosphors were characterized by X-ray diffraction and scanning electron microscopy examination. The crystal structures were also determined by the Rietveld refinement, and the photoluminescence (PL) properties were systematically studied. Bi3+ and Mn4+ ions can be effectively doped in the Ba2GdNbO6 matrix with an optical band gap of 3.94 eV. Upon 315 nm UV excitation, the Ba2GdNbO6:Bi3+,Mn4+ phosphor shows two emission bands at 464 nm from Bi3+ and 689 nm from Mn4+, respectively. By the design of Bi3+ → Mn4+ energy transfer, systematic luminescence tuning from blue to red could be achieved because of spectral overlap between the emission spectrum of Bi3+ and the excitation spectrum of Mn4+. The corresponding mechanism of the Bi3+ → Mn4+ energy-transfer process was investigated in detail by the fluorescence decays and PL spectra. The red emission intensity of Mn4+ has been greatly improved by Bi3+ → Mn4+ energy transfer. Moreover, the phonon vibration and zero phonon line of Mn4+ were studied through temperature-dependent PL. Finally, a WLED was fabricated using a 460 nm blue chip with a yellow YAG:Ce3+ phosphor and a red Ba2GdNbO6:0.01Bi3+,0.01Mn4+ phosphor, which has a low correlated color temperature (3550 K) and a high color rendering index (89.6). The above results imply that the improved red emission phosphors have a potential application in warm pc-WLED lighting.

Full Color Luminescence Tuning in Bi3+/Eu3+-Doped LiCa3MgV3O12 Garnet Phosphors Based on Local Lattice Distortion and Multiple Energy Transfers.

In the pursuit of high-quality W-LED lighting, the precise control of emission color of phosphor materials is indispensable. Herein we report a series of single-composition Bi3+-doped LiCa3MgV3O12 garnet-structure phosphors, whose emission colors under n-UV excitation could be tuned from bluish green (480 nm) to yellow (562 nm) on the basis of local lattice distortion and VO43- → Bi3+ energy transfer. Furthermore, full-color luminescence tuning from bluish green to orangish red across the warm white light region was successfully achieved by designing VO43- → Bi3+ → Eu3+ energy transfers. More interestingly, the thermal stabilities of as-prepared samples were gradually enhanced through designing VO43-/Bi3+ → Eu3+ energy transfers. This work provides a new perspective for color tuning originating from simultaneous local lattice distortion and multiple energy transfers.

Luminescence Properties of Ca19Ce(PO4)14:A (A = Eu3+/Tb3+/Mn2+) Phosphors with Abundant Colors: Abnormal Coexistence of Ce4+/3+-Eu3+ and Energy Transfer of Ce3+ → Tb3+/Mn2+ and Tb3+-Mn2.

A series of Eu3+/Tb3+/Mn2+-ion-doped Ca19Ce(PO4)14 (CCPO) phosphors have been prepared via the conventional high-temperature solid-state reaction process. Under UV radiation, the CCPO host presents a broad blue emission band from Ce3+ ions, which are generated during the preparation process because of the formation of deficiency. The Eu3+-doped CCPO phosphors can exhibit magenta to red-orange emission as a result of the abnormal coexistence of Ce3+/Ce4+/Eu3+ and the metal-metal charge-transfer (MMCT) effect between Ce3+ and Eu3+. When Tb3+/Mn2+ are doped into the hosts, the samples excited with 300 nm UV light present multicolor emissions due to energy transfer (ET) from the host (Ce3+) to the activators with increasing activator concentrations. The emitting colors of CCPO:Tb3+ phosphors can be tuned from blue to green, and the CCPO:Mn2+ phosphors can emit red light. The ET mechanism from the host (Ce3+) to Tb3+/Mn2+ is demonstrated to be a dipole-quadrapole interaction for Ce3+ → Tb3+ and an exchange interaction for Ce3+ → Mn2+ in CCPO:Tb3+/Mn2+. Abundant emission colors containing white emission were obtained in the Tb3+- and Mn2+-codoped CCPO phosphors through control of the levels of doped Tb3+ and Mn2+ ions. The white-emitted CCPO:Tb3+/Mn2+ phosphor exhibited excellent thermal stability. The photoluminescence properties have shown that these materials might have potential for UV-pumped white-light-emitting diodes.

Resonance Emission Enhancement (REE) for Narrow Band Red-Emitting A2GeF6:Mn4+ (A = Na, K, Rb, Cs) Phosphors Synthesized via a Precipitation-Cation Exchange Route.

Narrow band red-emitting A2GeF6:Mn4+ (A = Na, K, Rb, Cs) phosphors were prepared through a two-step precipitation-cation exchange route using a K2MnF6 precursor as the Mn4+ source. The phase purity, morphology, and constituent were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), X-ray photoelectric spectroscopy (XPS), and electron paramagnetic resonance (EPR) examination. Optical properties were investigated by photoluminescence spectra (PL and PLE) and high-resolution PL. A temperature-dependent PL examination was performed to investigate the electron-phonon coupling emission mechanism of Mn4+ in these alkali fluorogermanates. The PL data show that both ordered distribution and appropriate distance between Mn4+ ions are propitious for enhancement of the emission intensity. A resonance emission enhancement (REE) mechanism has been proposed to explain the intensity increment among these products. These phosphors present bright red emission under blue light (467 nm) illumination, among which Cs2GeF6:0.03Mn4+ exhibits the most excellent optical properties with a quantum yield (QY) of 93%. A WLED (white light-emitting diode) fabricated with blend of commercial YAG:Ce3+ and this phosphor emits intense warm white light with low color temperature (CCT = 3385 K) and high color rendering index (Ra = 90.5), implying its potential application as red phosphor in WLEDs.

Photoluminescence and Energy Transfer Properties with Y+SiO4 Substituting Ba+PO4 in Ba3Y(PO4)3:Ce(3+)/Tb(3+), Tb(3+)/Eu(3+) Phosphors for w-LEDs.

A series of Ce(3+), Tb(3+), Eu(3+) doped Ba2Y2(PO4)2(SiO4) (BYSPO) phosphors were synthesized via the high-temperature solid-state reaction route. X-ray diffraction, high-resolution transmission electron microscopy, Fourier transform infrared, solid-state NMR, photoluminescence (PL) including temperature-dependent PL, and fluorescent decay measurements were conducted to characterize and analyze as-prepared samples. BYSPO was obtained by the substitution of Y+SiO4 for Ba+PO4 in Ba3Y(PO4)3 (BYPO). The red shift of PL emission from 375 to 401 nm occurs by comparing BYSPO:0.14Ce(3+) with BYPO:0.14Ce(3+) under 323 nm UV excitation. More importantly, the excitation edge can be extended from 350 to 400 nm, which makes it be excited by UV/n-UV chips (330-410 nm). Tunable emission color from blue to green can be observed under 365 nm UV excitation based on the energy transfer from Ce(3+) to Tb(3+) ions after codoping Tb(3+) into BYSPO:0.14Ce(3+). Moreover, energy transfer from Tb(3+) to Eu(3+) ions also can be found in BYSPO:Tb(3+),Eu(3+) phosphors, resulting in the tunable color from green to orange red upon 377 nm UV excitation. Energy transfer properties were demonstrated by overlap of excitation spectra, variations of emission spectra, and decay times. In addition, energy transfer mechanisms from Ce(3+) to Tb(3+) and Tb(3+) to Eu(3+) in BYSPO were also discussed in detail. Quantum yields and CIE chromatic coordinates were also presented. Generally, the results suggest their potential applications in UV/n-UV pumped LEDs.

Photoluminescence Properties of Efficient Blue-Emitting Phosphor α-Ca1.65Sr0.35SiO4:Ce(3+): Color Tuning via the Substitutions of Si by Al/Ga/B.

A series of Ce(3+)-doped α-Ca1.65Sr0.35SiO4 (CSSO) phosphors without and with the substitutions of Si by Al/Ga/B were synthesized via the high-temperature solid-state reaction process. X-ray diffraction patterns and Rietveld refinements were used to demonstrate the successful incorporations of Al/Ga/B into CSSO:Ce(3+). Without Al/Ga/B, the Ce(3+) singly doped CSSO phosphors present intense blue emission, which correspond to the broad emission bands in visible region with the wavelength range from 360 to 580 nm upon 350 nm excitation. The optimal emission intensity occurs in CSSO:0.05Ce(3+) sample with the emission peak wavelength at 436 nm. With the introduction of Al/Ga/B into the CSSO:0.05Ce(3+), the emission peak shifts from 436 to 457/465/446 nm under 365 nm excitation, respectively. The red shift of Ce(3+) emission is attributed to the polyhedral distortion of the cations, resulting in the enhancement of crystal field spitting due to the variations of the adjacent (Al/Ga/B,Si)O4 polyhedron. Moreover, the temperature-dependent photoluminescence was determined to be of light impact to CSSO:Ce(3+) with the introduction of Al/Ga/B. This research is useful for enriching the emission colors of Ce(3+)-activated phosphors.