Eu‐Doped β‐SiAlON Phosphors: Template‐Assistant Low Temperature Synthesis,Dual Band Emission,and High‐Thermal Stability

A hard template route has been successfully developed for synthesis of β‐SiAlON:Eu phosphors at low temperatures. The synthesis utilizes mesoporous silica (SBA‐15) skeleton as an active Si source, combined with the carbothermal reduction and nitridation method. It has been shown that the additional driving force from high surface area and porosity of SBA‐15 enables β‐SiAlON:Eu (with compositions of Si_6?zAl_z?xO_z+xN_8?z?x: xEu, x = 0.010–0.200 and z = 1.000) phosphors to be formed as a dominant phase at low temperature of 1400°C. The resultant β‐SiAlON:Eu phosphor powders exhibit a typical rod‐like morphology and a well dispersed state. By tailoring the Eu²⁺ concentration in the phosphors, a continuous change in emission band can be realized, that is a blue emission dominated for low Eu²⁺ concentrations and a green emission dominated for high Eu²⁺ doping concentrations. Furthermore, the resultant phosphors exhibit a small thermal quenching up to high temperature of 250°C. Therefore, the developed method is beneficial to synthesize LED phosphors of oxynitride systems at lower temperatures.     

A novel dazzling Eu3+‐doped whitlockite‐type phosphate red‐emitting phosphor for white light‐emitting diodes

A series of novel red‐emitting Ca₈ZnLa_1?xEu_x(PO₄)₇ phosphors were successfully synthesized using the high‐temperature solid‐state reaction method. The crystal structure, photoluminescence spectra, thermal stability, and quantum efficiency of the phosphors were investigated as a function of Eu³⁺ concentration. Detailed analysis of their structural properties revealed that all the phosphors could be assigned as whitlockite‐type β‐Ca₃(PO₄)₂ structures. Both the PL emission spectra and decay curves suggest that emission intensity is largely dependent on Eu³⁺ concentration, with no quenching as the Eu³⁺ concentration approaches 100%. A dominant red emission band centered at 611 nm indicates that Eu³⁺ occupies a low symmetry sites within the Ca₈ZnLa(PO₄)₇ host lattice, which was confirm by Judd‐Ofelt theory. Ca₈ZnLa_1?xEu_x(PO₄)₇ phosphors exhibited good color coordinates (0.6516, 0.3480), high color purity (~96.3%), and high quantum efficiency (~78%). Temperature‐dependent emission spectra showed that the phosphors possessed good thermal stability. A white light‐emitting diode (LED) device were fabricated by integrating a mixture of obtained phosphors, commercial green‐emitting and blue‐emitting phosphors into a near‐ultraviolet LED chip. The fabricated white LED device emits glaring white light with high color rendering index (83.9) and proper correlated color temperature (5570 K). These results demonstrate that the Ca₈ZnLa_1?xEu_x(PO₄)₇ phosphors are a promising candidate for solid‐state lighting.     

Photoluminescence Properties of Heavily Eu3+‐Doped BaCa2In6O12 Phosphor for White‐Light‐Emitting Diodes

Heavily Eu³⁺‐doped BaCa₂In₆O₁₂ phosphors were prepared by conventional solid‐state reaction, and its structural properties were investigated by means of Rietveld refinement method using an X‐ray source. XRD patterns confirm the hexagonal phase of BaCa₂In₆O₁₂: Eu³⁺ phosphors. The obtained spectrum data indicate that the emission spectra of Ba_1?xEu_xCa₂In₆O₁₂ samples excited at 393 nm exhibit a series of shaped peaks assigned to the ⁵D_0,1,2,3 →⁷F_J (J = 0,1,2,3,4) transitions. Luminescence from the higher excited states, such as ⁵D₁, ⁵D₂, and ⁵D₃, were also observed even though the Eu³⁺ concentration was up to x = 0.4. More importantly, the Ba_1?xEu_xCa₂In₆O₁₂ phosphor still emits white luminescence, when the Eu³⁺ ion concentration is up to x = 0.07 before concentration quenching is observed, which shows that the phosphor is a promising single‐phase phosphor for near ultraviolet (NUV) light‐emitting diodes (LED). Furthermore, the temperature's impact on white luminescent properties was studied. Finally, a white‐light‐emitting diodes (W‐LEDs) fabricated with the Ba_0.95Eu_0.05Ca₂In₆O₁₂ phosphor incorporated with an encapsulant in ultraviolet LEDs (λ_max = 395 nm) is discussed.     

Structure and Luminescence of New Red‐Emitting Materials‐Eu3+‐Doped Triple Orthovanadates NaALa(VO4)2 (A = Ca,Sr, Ba)

The new red‐emitting phosphors of Eu³⁺‐doped triple orthovanadates NaALa(VO₄)₂ (A = Ca, Sr, Ba) were prepared by the high‐temperature solid‐state reaction. The formation of single phase compound with isostructural structure of Ba₃(VO₄)₂ was verified through X‐ray diffraction (XRD) studies. The photoluminescence excitation and emission spectra, the fluorescence decay curves and the dependence of luminescence intensity on doping level were investigated. The phosphor can be efficiently excited by near UV and blue light to realize an intense red luminescence (613 nm) corresponding to the electric dipole transition ⁵D₀→⁷F₂ of Eu³⁺ ions. Their potential applications as red‐emitting phosphors for solid‐state lighting were evaluated in comparison with the Eu³⁺‐doped lanthanum orthovanadate LaVO₄ and other reported references. The luminescence was discussed in detail on the base of the crystal structures. The luminescence thermal stability on temperature was investigated and the thermal activated energy was calculated. The phosphors can be suggested to be a potential red‐emitting phosphor for the application on white LEDs under irradiation of near‐UV or blue chips.     

A Novel Blue‐Emitting Phosphor of Eu2+‐Activated Magnesium Haloborate Mg3B7O13Cl

Eu²⁺‐doped magnesium haloborate Mg₃B₇O₁₃Cl was synthesized by the conventional high‐temperature solid‐state reaction. The phase formation was confirmed by X‐ray powder diffraction (XRD) measurements and structure refinement. The photoluminescence excitation and emission spectra, and decay curves were measured. Under the excitation of near‐UV light, Eu²⁺‐doped Mg₃B₇O₁₃Cl presents a narrow blue‐emitting band centered at 423 nm. The maximum absolute quantum efficiency (QE) of Mg₃B₇O₁₃Cl:Eu²⁺ phosphor was measured to be 80% excited at 385 nm light at 300 K. The thermal stability of the blue luminescence was evaluated by the luminescence decays as a function of temperature. The phosphor shows an excellent thermal stability on temperature quenching effects. Moreover, Mg₃B₇O₁₃Cl:Eu²⁺ phosphor shows scintillation characteristics excited by X‐ray irradiation at room temperature and presents a blue luminescence band with a fast lifetime of 600 ns.     

Far‐Red‐Emitting BiOCl:Eu3+ Phosphor with Excellent Broadband NUV‐Excitation for White‐Light‐Emitting Diodes

Rare‐earth ion‐doped semiconducting phosphor has attracted extensive attention due to the ability to achieve efficient luminescence through the host sensitization. Here, we present a new type red‐emitting Eu³⁺ ‐doped BiOCl phosphors possessing a broad excitation band in the near‐ultraviolet (NUV) region. Experimental measurements and theoretical calculations confirm that Eu³⁺ ion dopants result in forming impurity energy level near valence band, and the excellent broadband NUV‐exciting ability of Eu³⁺ ion is due to the electronic transitions of BiOCl band gap. Moreover, the highest emission intensity of the phosphors is from the ⁵D₀ → ⁷F₄ transition of Eu³⁺ around 699 nm (far‐red) through whether host excitation or direct Eu³⁺ ions excitation, which lie in the particular structure of BiOCl crystals. Our results indicate that the Eu³⁺ ‐doped BiOCl crystals show great potential as red phosphors for white‐light‐emitting diodes.     

Preparation of γ‐aluminum oxynitride phosphor with Eu doping by direct nitridation in ammonia and postannealing

γ‐aluminum oxynitride (γ‐AlON) with spinel structure has attracted much attention for structural and functional application. γ‐AlON powders were successfully prepared by direct nitridation method of Al/Al(OH)₃ starting mixture in ammonia and then calcined at high temperature. XRD, SEM, TEM, EDX, and photoluminescence were conducted to investigate the detail procedure and the optical properties of AlON: xEu phosphors. Nitrogen was introduced by the nitridation of metallic aluminum, appropriate Al amount and nitridation condition was necessary to obtain phase pure γ‐AlON. The as‐prepared AlON powders exhibited multifaceted grain morphology with fine particle size (1‐5 μm). Eu₂O₃ activator was reduced and transformed to EuAl₁₂O₁₉ by reaction with alumina, which remained in the product when x > 0.25%. Under 331 nm excitation, AlON: xEu phosphors exhibited emission bands of 475 and 410 nm. 475 nm band reached a plateau at x = 0.25% due to the solubility of Eu²⁺ ion in AlON, whereas 410 nm band showed a linear increase in intensity with Eu²⁺ doping amount, which was believed to be the contribution of EuAl₁₂O₁₉. The present approach combination of direct nitridation in ammonia and postcalcination process showed potential application for AlON ceramic and AlON phosphors.     

Synthesis and luminescent properties of Sr4−xSi3O8Cl4: xEu3+ red phosphor by hydrothermal method

Sr_4‐xSi₃O₈Cl₄:xEu³⁺ (SSOC:Eu³⁺) phosphors were successfully synthesized by hydrothermal method. The crystallization of this phosphor was analyzed by means of X‐ray diffraction patterns. The size and morphology were recorded using SEM patterns of samples. And the PLE and PL spectra were characterized by a PL spectrophotometer. Excited by 394 nm UV light, the intense red emission is recognized in SSOC:Eu³⁺ phosphor and the main emission peak located at 620 nm. The influences of Eu³⁺ concentration, pH value of reaction solution, and charge compensator on PL spectra of SSOC:Eu³⁺ phosphors were investigated. The results revealed that this red phosphor had potential applications for white LEDs.     

Phase Transformation in Ca3(PO4)2:Eu2+ via the Controlled Quenching and Increased Eu2+ Content: Identification of New Cyan‐Emitting α‐Ca3(PO4)2:Eu2+ Phosphor

A case of phosphor is reported where the cooling rate parameter significantly influences the luminescence property. By quenching the sample after the high‐temperature solid‐state reaction at 1250°C, we successfully prepared the Eu²⁺‐doped α form Ca₃(PO₄)₂ (α‐TCP:Eu²⁺) as a new kind of bright cyan‐emitting phosphor. The unusual emission color variation (from cyan to blue) depends on the cooling rate after sintering and Eu²⁺ doping level as it was observed in the TCP‐based phosphors. By the Rietveld analysis, it is revealed that the cyan‐ and blue‐emitting phosphors are two different TCP forms crystallizing in the monoclinic (space group P2₁/a, α‐TCP) and the rhombohedral structure (space group R3c, β‐TCP), respectively. Upon 365 nm UV light excitation, α‐TCP:Eu²⁺ exhibits an asymmetric broad‐band cyan emission peaking at 480 nm, while β‐TCP:Eu²⁺ displays a relatively narrow‐band blue emission peaking at 416 nm. The Eu²⁺‐doping in Ca₃(PO₄)₂ shifts the upper temperature limit of the stable structural range of β form from 1125°C to ≥1250°C. Moreover, the crystal structures of α/β‐TCP:Eu²⁺ were compared in the aspects of compactness and cation site sets. The emission thermal stability of α/β‐TCP:Eu²⁺ was comparatively characterized and the difference was related to the specific host structural features.     

Europium‐Activated KSrPO4–(Ba,Sr)2SiO4 Solid Solutions as Color‐Tunable Phosphors for Near‐UV Light‐Emitting Diode Applications

This article reports the structural and luminescence characteristics of Eu²⁺‐activated solid solutions of (KSrPO₄)_1?x·((Ba,Sr)₂SiO₄)_x for 0 ≤ x ≤ 1. These phosphors were prepared by a sol‐gel/Pechini method. The lattice parameters of the solid solutions are linearly dependent on x. The reliability factor from Rietveld analysis is nearly constant and independent of x, indicating KSrPO₄·(Ba,Sr)₂SiO₄ forms an ideal solid solution. The emission spectra consist of two distinct broad bands, which depend on x: blue ranging from 430 to 470 nm and green–yellow ranging from 515 to 570 nm. Both emission peaks red‐shift as x increases due to the crystal field effect and an anomalous transition. The emission intensity of these solid solutions is also a function of x and is comparable to that of LiCaPO₄:Eu²⁺ (QE = 81%) at x = 0.1, suggesting that these color‐tunable solid solutions are promising for applications in solid‐state white lighting.     

Tunable full color emission from single-phase LiSr3.99−xDy0.01(BO3)3:xEu3+ phosphors

Tunable full color emissive LiSr_3.99?xDy_0.01(BO₃)₃:xEu³⁺ (0≤x≤0.09) phosphors peaked at 481 nm (blue), 574 nm (yellow), 592 nm (orange), and 617 nm (red) were synthesized in air by high temperature solid-state reaction route. The as-synthesized phosphors were characterized by X-ray powder diffraction (XRD), photoluminescence excitation (PLE) and photoluminescence (PL) spectra. The PLE spectra in the range from 200 to 500 nm include an Eu–O charge transfer band (CTB) and several 4f–4f transition peaks of Dy³⁺ and Eu³⁺, indicating its potential application in white light emitting diodes (LEDs). The effect of Eu³⁺ concentration on the emission intensity of LiSr_3.99?xDy_0.01(BO₃)₃:xEu³⁺ phosphors was investigated in detail and the optical concentration is found to be x=0.005. The CIE chromaticity coordinates for LiSr_3.99?xDy_0.01(BO₃)₃:xEu³⁺ phosphors are simulated. With an increase in Eu³⁺ ion concentration, the chromaticity color coordinates can be tuned efficiently from the border of greenish white region to its equal-energy white light point, and eventually to red region. All the results imply that the studied LiSr_3.99?xDy_0.01(BO₃)₃:xEu³⁺ phosphors could be potentially used as white LEDs.     

Precipitation Synthesis and Color‐Tailorable Luminescence of α‐Zr(HPO4)2: RE3+(RE = Eu,Tb) Nanosheet Phosphors

The rare earth (RE = Eu and Tb) ions‐doped α‐Zr(HPO₄)₂ (ZrP) nanosheet phosphors were synthesized by direct precipitation method, and their structures and photoluminescence properties were investigated. The results of X‐ray diffraction and scanning electron microscopy indicated that the systems of ZrP:RE³⁺ had similar nanosheet structure except with relatively larger interlayer spacing as compared with pure α‐ZrP. Under the excitation of UV light, the ZrP:RE³⁺ nanosheet phosphors showed red and green emission peaks corresponding to the ⁵D₀→⁷F₂ transition of Eu³⁺ and the ⁵D₄→⁷F₅ transition of Tb³⁺, respectively. After Eu³⁺ and Tb³⁺ were co‐doped in ZrP host, not only the red and green emission peaks were simultaneously observed, but also the luminescent intensity and fluorescence lifetimes of Tb³⁺ were gradually decreased with the increase in Eu³⁺‐doping concentration, which implied the energy transfer from Tb³⁺ to Eu³⁺ happened. It was deduced that the energy transfer from Tb³⁺ to Eu³⁺ occurred via exchange interaction. Through optimization to the samples, a nearly white‐light emission with the color coordinate (0.322, 0.263) was achieved under 377 nm excitation. The ZrP:RE³⁺ nanosheet phosphors may be a potential color‐tailorable candidate for fabricating optoelectronic devices such as electroluminescence panels.     

Fabrication and Characterization of Transparent (Y0.98−xTb0.02Eux)2O3 Ceramics with Color‐Tailorable Emission

Transparent (Y_0.98?xTb_0.02Eu_x)₂O₃ (x = 0–0.04) ceramics with color‐tailorable emission have been successfully fabricated by vacuum sintering at the relatively low temperature of 1700°C for 4 h. These ceramics have the in‐line transmittances of ~73%–76% at 613 nm, the wavelength of Eu³⁺ emission (the ⁵D₀→⁷F₂ transition). Thermodynamic calculation indicates that the Tb⁴⁺ ions in the starting oxide powder can essentially be reduced to Tb³⁺ under ~10^?3 Pa (the pressure for vacuum sintering) when the temperature is above ~394°C. The photoluminescence excitation (PLE) spectra of the transparent (Y_0.98?xTb_0.02Eu_x)₂O₃ ceramics exhibit one spin‐forbidden (high‐spin, HS) band at ~323 nm and two spin‐allowed (low‐spin, LS) bands at ~303 and 281 nm. Improved emissions were observed for both Eu³⁺ and Tb³⁺ by varying the excitation wavelength from 270 to 323 nm, without notably changing the color coordinates of the whole emission. The transparent (Y_0.98Tb_0.02)₂O₃ ceramic exhibits the typical green emission of Tb³⁺ at 544 nm (the ⁵D₄→⁷F₅ transition). With increasing Eu³⁺ incorporation, the emission color of the (Y_0.98?xTb_0.02Eu_x)₂O₃ ceramics can be precisely tailored from yellowish‐green to reddish‐orange via the effective energy transfer from Tb³⁺ to Eu³⁺ under the excitation with the peak wavelength of the HS band. At the maximum Eu³⁺ emission intensity (x = 0.02), the ceramic shows a high energy‐transfer efficiency of ~85.3%. The fluorescence lifetimes of both the 544 nm Tb³⁺ and 613 nm Eu³⁺ emissions were found to decrease with increasing Eu³⁺ concentration.     

Microstructure of Eu3+‐Doped Perovskites‐Type Niobate Ceramic La3Mg2NbO9

Eu³⁺‐doped red‐emitting ceramics of Eu³⁺‐doped La₃Mg₂NbO₉ were prepared via typical solid state. X‐ray diffraction and scanning electron microscope were utilized to characterize the ceramics. The photoluminescence excitation and emission spectra, the fluorescence decay curves, and color coordinates were investigated. The concentration quenching of the samples were discussed as well. The microstructures of the ceramics were discussed according to the spectral properties of probe ions of Eu³⁺, for example, substitution sites for Eu³⁺, inhomogeneous broadening and splitting of the emission bands, nonexponential decay, ⁵D₀→⁷F₀ emission transition, distorted symmetry sites, etc. The crystal structure of La₃Mg₂NbO₉ is heavily distorted due to the mixed occupation of Mg and Nb on B sites. Eu³⁺ ions only substitute La³⁺ sites and Eu³⁺ ions (or rare‐earth ions) are arranged in the heavily disordered environments over the whole structure in La₃Mg₂NbO₉.     

Synthesis and Photoluminescence of a New Chlorogermanate Phosphor Ca8Mg(GeO4)4Cl2:Eu2+

A new chlorogermanate compound Ca₈Mg(GeO₄)₄Cl₂ (CMGC) was synthesized via high‐temperature solid‐state reaction for the first time. The crystal structure of CMGC had been refined and determined from the XRD profiles by Rietveld refinement method, which belong to space group Fd‐3m with the lattice constants a = b = c = 15.1760(25) Å. Photoluminescence properties of CMGC:Eu²⁺ phosphors were investigated by absorption spectra, excitation, and emission spectra. The occupy situation and energy transfer were investigated by decay lifetimes and emission spectra under different excitation wavelengths. Thermal stability was also measured. The results show that the absorption spectra of CMGC:Eu²⁺ phosphors cover from 250 to 500 nm. Under 365 and 435 nm excitation, the emission spectra of CMGC:Eu²⁺ phosphors show blue‐green (centered at 425 and 510 nm) and green (centered at 510 nm) emission, respectively, which attributed to Eu²⁺ ions occupying different crystal sites. Our results indicated that CMGC:Eu²⁺ phosphors had a potential application use for white light‐emitting diodes.     

Investigation of luminescence properties of Pb2+‐doped Sr2B2O5 phosphor

A near‐UV emitting phosphor, Pb²⁺‐doped Sr₂B₂O₅ was synthesized by the solid‐state reaction method at 900°C for 3 hours in air. The structure of the phosphor was verified by X‐ray diffraction study which shows monoclinic phase. Fourier transform infrared (FTIR) analysis confirmed the formation of Sr₂B₂O₅. The excitation and emission spectra of the synthesized phosphors were investigated at room temperature with photoluminescence spectrophotometer. The emission and excitation bands of Pb²⁺‐doped Sr₂B₂O₅ were observed at 370 and 289 nm, respectively. The dependence of the PL intensities on the Pb²⁺ concentration for the Sr_2?xPb_xB₂O₅ (0.01 ≤ x ≤ 0.03) phosphors was studied and it was observed that the concentration quenching of Pb²⁺ in Sr₂B₂O₅ is 0.025 mol.     

Structure and Luminescence Characteristics of Eu3+‐Activated Trigonal Layered Perovskite Ba2La2ZnW2O12

Eu³⁺‐doped tungstate Ba₂La₂ZnW₂O₁₂ phosphors with perovskite‐structure were prepared by the high temperature solid‐state reaction. The X‐ray powder diffraction (XRD) patterns and structure refinements indicate that the phosphors crystalized in the trigonal layer‐perovskite. The luminescence properties of the phosphors were investigated such as photoluminescence (PL) excitation and emission spectra, decay lifetimes, and color coordinates. It was found that the pure host shows self‐activated emission excited by the UV light. Moreover, Ba₂La₂ZnW₂O₁₂ also shows scintillation characteristics under the X‐ray irradiation. The near‐UV and blue light can efficiently excite Eu³⁺‐doped Ba₂La₂ZnW₂O₁₂ phosphors inducing the strong orange–red luminescence. The optimal Eu³⁺ doping concentration in this host is 40 mol%. The luminescence spectra and the luminescence color of the phosphors strongly depend on the doping levels and excitation wavelength. The different luminescence features were discussed on the base of crystal structure. Eu³⁺ ions have two possible substitutions on A or B sites in this trigonal layered perovskite. The phosphor could act as a candidate for the potential application in near‐UV excited white‐LEDs lighting.     

Synthesis and luminescence properties of single‐component Ca5(PO4)3F:Dy3+, Eu3+ white‐emitting phosphors

A series of Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors was synthesized by a solid‐state reaction method. The XRD results show that all as‐prepared Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ samples match well with the standard Ca₅(PO₄)₃F structure and the doped Dy³⁺ and Eu³⁺ ions have no effect on the crystal structure. Under near‐ultraviolet excitation, Dy³⁺ doped Ca₅(PO₄)₃F phosphor shows blue (486 nm) and yellow (579 nm) emissions, which correspond to ⁴F_9/2→⁶H_15/2 and ⁴F_9/2→⁶H_13/2 transitions respectively. Eu³⁺ co‐doped Ca₅(PO₄)₃F:Dy³⁺ phosphor shows the additional red emission of Eu³⁺ at 631 nm, and an improved color rendering index. The chromaticity coordinates of Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors also indicate the excellent warm white emission characteristics and low correlated color temperature. Overall, these results suggest that the Ca₅(PO₄)₃F:Dy³⁺, Eu³⁺ phosphors have potential applications in warm white light‐emitting diodes as single‐component phosphor.     

Light‐induced electrons suppressed by Eu3+ ions doped in Ca11.94−xSrxAl14O33 caged phosphors for LED and FEDs

Control of light‐induced electron generation is of vital importance for the application of caged phosphors. For Eu‐doped Ca_11.94?xSr_xAl₁₄O₃₃ caged phosphors, the suppressed effect of strontium doping on the light‐induced electrons is observed compared to the europium‐free Ca_11.94?xSr_xAl₁₄O₃₃ phosphors. In the presence of europium ions, Sr doping will promote the reduction of Eu³⁺ to Eu²⁺. The Rietveld refinement suggests that unit cell volumes of the Ca_11.94?xSr_xAl₁₄O₃₃:Eu_0.06 samples are expanded when Ca²⁺ ions are replaced by Sr²⁺ ions. The absorption and FTIR transmittance spectra confirm that the competitive reaction of encaged O^2? anions with H₂ is suppressed. For the sample (x=0.48), the higher thermal activation energy (~0.40 eV) for luminescence quenching can be attributed to the more rigid framework structure after Sr doping. For Ca_11.94?xSr_xAl₁₄O₃₃:Eu_0.06 phosphors, their emission colours are tuned from red to purple upon 254 nm excitation and from pink to blue under electron beam excitation through Sr substitution. The insight gained from this work may have a significant guiding to design new phosphors for LED and FEDs and novel nanocaged mutifunctional materials.     

Thermal,Structural, and Enhanced Photoluminescence Properties of Eu3+‐doped Transparent Willemite Glass–Ceramic Nanocomposites

The precursor glass in the ZnO–Al₂O₃–B₂O₃–SiO₂ (ZABS) system doped with Eu₂O₃ was prepared by the melt‐quench technique. The transparent willemite, Zn₂SiO₄ (ZS) glass–ceramic nanocomposites were derived from this precursor glass by a controlled crystallization process. The formation of willemite crystal phase, size, and morphology with increase in heat‐treatment time was examined by X‐ray diffraction (XRD) and field‐emission scanning electron microscopy (FESEM) techniques. The average calculated crystallite size obtained from XRD is found to be in the range 18–70 nm whereas the grain size observed in FESEM is 50–250 nm. The refractive index value is decreased with increase in heat‐treatment time which is caused by the partial replacement of ZnO₄ units of ZS nanocrystals by AlO₄ units due to generation of vacancies. Fourier transform infrared (FTIR) reflection spectroscopy was used to evaluate its structural evolution. Vickers hardness study indicates marked improvement of hardness in the resultant glass‐ceramics compared with its precursor glass. The photoluminescence spectra of Eu³⁺ ions exhibit emission transitions of ⁵D₀→⁷F_j (j = 0, 1, 2, 3, and 4) and its excitation spectra show an intense absorption band at 395 nm. These spectra reveal that the luminescence performance of the glass–ceramic nanocomposites is enhanced up to 17‐fold with the process of heat treatment. This enhancement is caused by partitioning of Eu³⁺ ions into glassy phase instead of into the willemite crystals with progress of heat treatment. Such luminescent glass–ceramic nanocomposites are expected to find potential applications in solid‐state red lasers, phosphors, and optical display systems.