Effects of Sintering Aids on the Transparency and Conversion Efficiency of Cr4+ Ions in Cr: YAG Transparent Ceramics

Tetravalent chromium‐doped Y₃Al₅O₁₂ ceramics were fabricated by solid‐state reactive sintering method using high‐purity Y₂O₃, α‐ Al₂O₃, and Cr₂O₃ powders as the starting materials. CaO and MgO were co‐doped as the sintering aids. The effects of TEOS and divalent dopants (CaO and MgO) on the optical qualities, the conversion efficiency of Cr⁴⁺ ions, and the microstructure evolutions of 0.1 at.% Cr⁴⁺: YAG ceramics were investigated. Fully dense, dark brown colored Cr⁴⁺: YAG ceramics with an average grain size of 3.1 μm were achieved. The in‐line transmittance of the as‐prepared ceramic at 2000 nm was 85.3% (4 mm thick), and the absorption coefficient at 1030 nm (the characteristic absorption peak of Cr⁴⁺ ions) was as high as 3.7 cm^?1, which was higher than that of corresponding single crystals fabricated by Czochralski method.     

Effect of complex Si4++Mg2+ additive on sintering and properties of undoped YAG ceramics

The paper is devoted to studying of Si⁴⁺+Mg²⁺ complex additive for obtaining transparent YAG ceramics for laser applications. Ceramics were fabricated by reactive vacuum sintering of commercial Y₂O₃, Al₂O₃ powders taken in a stoichiometric mixture with TEOS and MgO as sintering aids. Microstructure and optical properties of YAG:Si⁴⁺,Mg²⁺ ceramics were investigated as a function of the Si⁴⁺/Mg²⁺ ratio. It was found that the influence of complex additive does not correspond to the direct superposition of known Si⁴⁺- and Mg²⁺-induced sintering mechanisms and involves interaction between Si⁴⁺ and Mg²⁺ ions during sintering. It was shown that C_Si/C_Mg> 1 provides more effective pore elimination and uniform microstructure when C_Si/C_Mg< 1 gives more intense inhibition of grain grown which may be important for scaling the size of ceramics.     

Sintering additives regulated Cr ion charge state in Cr doped YAG transparent ceramics

Cr: YAG and Cr, Nd: YAG transparent ceramics have significant application prospects in solid state lasers, therefore a controllable charge state of Cr ion in Cr doped YAG transparent ceramics is necessary. In this study, a successful regulation of Cr charge state in both Cr, Nd: YAG and Cr: YAG transparent ceramics was achieved, by a simple optimizing the sintering additives. Both ceramics with the Cr doping concentration of 0.3?at% reached to the theoretical transmittance, after the vacuum sintering and the subsequent annealing process. It was found that by adopting silica additive, divalent charged Cr²⁺ ions could be detected from the vacuum sintered samples, and they were transferred into trivalent state after further annealing in air. Meanwhile, by vacuum sintering ceramics with divalent additives (CaO and MgO), a stable trivalent charged Cr ion could be obtained, and the subsequent air annealing process indicated a significant conversion from Cr³⁺ to Cr⁴⁺. Further increasing the Cr concentration was not benefit to the optical quality as well as the conversion of Cr³⁺ ion in Cr, Nd: YAG transparent ceramics.     

Assessment of conversion efficiency of Cr4+ ions by aliovalent cation additives in Cr:YAG ceramic for edge cladding

0.25at.% Cr:YAG ceramics were successfully fabricated as the edge cladding of Yb:YAG transparent ceramic slabs through vacuum sintering of co‐precipitated powders, using oxide additives to introduce different cations. The effects of various cation additives (Si⁴⁺, Ca²⁺, and Si⁴⁺ + Ca²⁺) on the conversion efficiency of Cr⁴⁺ ions and optical characteristics of the Cr:YAG edge cladding were investigated. Measurements of the absorption spectra of the Cr:YAG ceramics without any additives revealed 2 absorption bands centered at 430 nm and 600 nm, which imparted the sample with a green color. The introduction of only Si⁴⁺‐bearing additive did not promote the transition of Cr ions from the 3+ to 4+ state. Theoretical analysis and experimentation revealed that the addition of CaO not only enhanced the microstructure and improved the transmittance of the Cr:YAG ceramic, but also introduced vacancies that assisted in the formation of Cr⁴⁺ ions. It was determined that CaO has the same effect on the conversion efficiency of Cr⁴⁺ ions whether it is added as a single additive or in combination with SiO₂. The underlying mechanisms by which these aliovalent cation additives influence the formation of Cr⁴⁺ ions and affect optical properties are discussed in detail. High quality composite ceramics with Yb:YAG transparent ceramic slabs and dark brown‐colored Cr⁴⁺: YAG ceramic edge cladding were achieved through the addition of 0.05 wt.% CaO to the edge cladding, with no interfacial effects between the 2 regions being observed.     

Grain-size effect on Cr3+ and F-centres photoluminescence in nanophase MgAl2O4 ceramics

Photoluminescence (PL) spectroscopy of transparent MgAl₂O₄ spinel ceramics with grain size between 100 and 300 nm was studied at 7 K temperature in the near-IR-VUV range of spectrum with synchrotron radiation excitation. The PL spectra were composed of optical transitions from spatially different regions of the ceramics, which analysis evidenced grain size effect on the emission line-shapes and intensities. In particular, emission of impurity Cr³⁺ ions, being structured in the crystalline bulk, became broad-band in the grain boundary regions, which was associated with respectively strong and weak local crystalline fields. It was observed that (i) excitons and F centres transfer energy to Cr³⁺ and (ii) Cr(²E_g)/Cr(⁴T_2g) and F-centres/Cr³⁺ PL intensity ratios underwent a linear dependence on the grain size.     

The role of Ca2+ ions in the formation of high optical quality Cr4+,Ca:YAG ceramics

The distribution of Ca²⁺ ions in high optical quality Cr⁴⁺,Ca:YAG ceramics after vacuum sintering followed by air annealing was successfully investigated by HRTEM, STEM, EDX, XPS and optical absorption spectroscopy. The HRTEM microscopy reveals the formation of clear grain boundaries without any impurity phase. A highly-doped thin Ca-rich layer was detected at the grain boundary with Ca²⁺ concentration up to 4.9% RTM, while the concentration of Ca²⁺ ions in the grain volume is less than 0.25%. The layer suppressed grain growth allowing the production of high optical quality ceramics with the average grain size of 1.95 ± 0.27 μm, which is five times smaller than in calcium-free ceramics.The air annealing of Cr⁴⁺,Ca:YAG ceramics results in a 10-fold decrease in Ca²⁺ ion concentration at the grain boundaries, practically removing the Ca-rich layer, moreover, the procedure generates Cr⁴⁺ ions within the grains. Most of the calcium originated from the Ca-rich layer diffuses outside the ceramics or dissolves into Al₂O₃ impurities without interfering with the generation of Cr⁴⁺.     

Improving the luminescence and afterglow properties of Mg3Y2Ge3O12:Cr3+ by co-doping Bi3+

Generally, the emission intensity and afterglow of the near infrared phosphors can be improved by co-doping the sensitizer. In this work, Bi³⁺ ions as sensitizer are introduced into the near infrared phosphor Mg₃Y₂Ge₃O₁₂:Cr³⁺, and the luminescence properties are investigated. According to the principle of radius adaptation, Bi³⁺ ions would occupy eight coordinates in the host instead of Y³⁺ and Mg²⁺. Through structural refinement, theoretical calculation and experimental phenomena, there are two kinds of luminescent sources for Bi³⁺ ions, which come from ³P₁ → ¹S₀ (441 nm) and MMCT (330 nm), respectively. In addition, the substitution of Bi³⁺ for Mg²⁺ will result in inequivalent substitution forming defects (Bi_Mg·), and the trap depth is 0.55 eV. For Bi³⁺ and Cr³⁺ co-doped Mg₃Y₂Ge₃O₁₂, there are two factors can that can affect the luminescent properties of Cr, which are energy transfer and defects. The samples are obtained with three times the original emission intensity with the introduction of defects. At the same time, Bi³⁺ ions capture electrons to form new electron traps Bi²⁺ (Bi³⁺ + e^-) and the trap depth is 0.81 eV. Therefore, under the action of two traps Bi_Mg· and Bi²⁺ (Bi³⁺ + e^-), the afterglow characteristics of the samples are improved and the time can reach 1.5 h.     

Effects of Er3+ and/or Cr3+ doping on crystallization activation energy and fluorescence properties of transparent ZnGa2O4 glass-ceramics

Er³⁺ and/or Cr³⁺ doped transparent ZnGa₂O₄ glass-ceramics were successfully obtained by one-step heat treatment. The results showed that Er³⁺ ions can enrich around ZnGa₂O₄ crystal to reduce the crystallization activation energy and promote the growth of ZnGa₂O₄ crystal. Cr³⁺ ions may successfully occupy the Ga³⁺ sites in the ZnGa₂O₄ lattice but will increase crystallization activation energy and inhibit the growth of the ZnGa₂O₄ crystal. Before and after crystallization, the coordination-field intensity of Cr³⁺ ions increased from 2.17 to 2.86, resulting in the peak position of its emission spectra moving from 850 to 688 nm. By excitation at 378 nm, the precursor glass co-doped with Er³⁺ and Cr³⁺ ions only showed the characteristic emission peaks belonging to Er³⁺ ions. After heat treatment, the characteristic emission peaks belonging to Er³⁺ and Cr³⁺ ions existed simultaneously, and the emission color changed from green to yellow. By excitation at 980 nm, there were only characteristic emission peaks belonging to Er³⁺ ions of the Er³⁺/Cr³⁺ co-doped glasses before and after heat treatment. The results showed that the Er³⁺ and/or Cr³⁺ doped ZnGa₂O₄ glass-ceramics have adjustable luminescence ability and show potential application value in the field of luminescence display.     

Broadband near-infrared emission enhancement in K2Ga2Sn6O16:Cr3+ phosphor by electron-lattice coupling regulation

Cr³⁺-doped phosphors have recently gained attention for their application in broadband near-infrared phosphor-converted light-emitting diodes (pc-LEDs), but generally exhibit low efficiency. In this work, K₂Ga₂Sn₆O₁₆:Cr³⁺ (KGSO:Cr) phosphor was designed and synthesized. The experimental results show that the Cr³⁺-doped phosphor exhibited broadband emissivity in the range 650-1300 nm, with a full width at half maximum (FWHM) of approximately 220-230 nm excited by a wavelength of 450 nm. With the co-doping of Gd³⁺ ions, the internal quantum efficiency (IQE) of the KGSO:Cr phosphor increased from 34% to 48%. The Gd³⁺ ions acted neither as activators nor sensitizers, but to justify the crystal field environment for efficient Cr³⁺ ions broad emission. The Huang-Rhys factor decreased as the co-doping of Gd³⁺ ions increased, demonstrating that the nonradiative transitions were suppressed. An efficient strategy for enhancing the luminescence properties of Cr³⁺ ions is proposed for the first time. The Gd³⁺–co-doped KGSO:Cr phosphor is a promising candidate for broadband NIR pc-LEDs.     

Influence of Cr doping on the phase composition of Cr,Ca:YAG ceramics by solid state reaction sintering

In the present work, the influence of Cr and Ca co-additives on the phase formation under conditions emulated the real sintering process of Cr⁴⁺:YAG ceramics is studied. The XRD analysis of the treated samples revealed the difference in formation rates of intermediate phases between the samples with and without the Cr₂O₃ additive. The formation of intermediate phases in the solid-state reaction between Y₂O₃ and Al₂O₃ is observed to shift toward higher temperatures (ie, toward the stage of fast shrinkage) if the mixture of Cr₂O₃ and CaO is added. The reason for such shift is the appearance of new intermediate, which contains Cr⁴⁺ ions in perovskite structure, as has been established by optical absorption and luminescent investigations. It is found that the Cr,Ca:YAG ceramics prepared by vacuum solid state reaction sintering at 1750°C, 10 hours possesses better optical transparency than Ca:YAG ceramics prepared under the same conditions.     

Annealing induced discoloration of transparent YAG ceramics using divalent additives in solid-state reaction sintering

Tetraethyl orthosilicate (TEOS) was commonly served as a sintering additive to promote the densification of transparent Y₃Al₅O₁₂ (YAG) ceramics. However, Si⁴⁺ that decomposed from TEOS would restrain the conversion of dopants into a higher valence state (e.g., Cr³⁺ → Cr⁴⁺). In this study, by using divalent sintering additives (CaO and MgO), the colorless and highly transparent YAG ceramics (T = 84.6%, at 1064 nm) were obtained after vacuum sintering at 1840 °C for 8 h and without subsequent annealing in air. An absorption peak centered at ∼320 nm was observed before annealing, and it extended to ∼550 nm after annealing at 1450 °C for 10 h in air. A discoloration phenomenon occurred and more scattering centers were observed with the formation of new [Mg/Ca²⁺F⁺] color centers. Air annealing did not improve the optical quality of the as-fabricated YAG ceramics with divalent dopants as sintering additives, owing to the formation of scattering centers.     

Luminescence of MgAl2O4 and ZnAl2O4 spinel ceramics containing some 3d ions

The luminescence properties of ceramic phosphors based on two spinel hosts MgAl₂O₄ and ZnAl₂O₄ doped with manganese ions have been studied. It has been found that the spectral properties of these phosphors can be strongly varied by changing synthesis conditions. Both types of doped ceramic spinel can serve as efficient Mn²⁺ green-emitting phosphors having peak emissions at 525 and 510 nm, respectively. Mn-doped MgAl₂O₄ spinel can also be prepared as an efficient Mn⁴⁺ red-emitting phosphor having peak emission at ~651 nm by using specific temperatures of heat treatment in air. It has also been shown that the conversion of Mn²⁺ to Mn⁴⁺ and viсe versa, as well as the coexistence of Mn²⁺ green and Mn⁴⁺ red emissions, can be accomplished by properly chosen annealing conditions of the same initially synthesized MgAl₂O₄:Mn sample. Manganese doped MgAl₂O₄ spinel with an optimal intensity ratio of green and red emissions can be a promising single-phase bicolor phosphor suitable for the development of warm white phosphor-converted LED lamps. On the other hand, it has been determined that perfectly normal ZnAl₂O₄ spinel cannot be doped with Mn⁴⁺ ions in contrast to partially inverse MgAl₂O₄ spinel. However, ZnAl₂O₄ samples unintentionally doped with impurity Cr³⁺ ions show emission spectra in the far-red region with well pronounced R, N and vibronic lines of Cr³⁺ luminescence due to the perfect normal spinel structure of synthesized ZnAl₂O₄ ceramics. Also, by partially substituting Al³⁺ cations for Mg²⁺ in ZnAl₂O₄ there is an opportunity to obtain Mn⁴⁺ doped or Mn⁴⁺/Cr³⁺ codoped far-red emitting phosphors which can be suitable for indoor plant growth lighting sources.     

Near-infrared long-lasting phosphorescence in transparent glass ceramics embedding Cr3+-doped LiGa5O8 nanocrystals

Cr³⁺ doped transparent glass ceramics of SiO₂–Ga₂O₃–Li₂O were fabricated by melt-quenching and subsequent crystallization. X-ray diffraction and transmission electron microscopy analyses evidenced that cubic LiGa₅O₈ nanocrystals were homogeneously precipitated among the silicate glass matrix. The incorporation of Cr³⁺ ions into LiGa₅O₈ nanocrystals was evidenced by absorption, emission and time-resolved luminescence spectra. Impressively, the present Cr³⁺ doped glass ceramics were demonstrated to be a new near-infrared (∼720 nm) long-lasting bulk phosphor whose luminescence can last for more than 2 h after stoppage of UV (250–350 nm) irradiation. The occurring of Cr³⁺ long-lasting phosphorescence in the glass ceramics was confirmed to be mainly due to the precipitation of Cr³⁺:LiGa₅O₈ nanocrystals from glass matrix. The filling/releasing of electrons into/from the intrinsic traps of LiGa₅O₈ nanocrystals through the conduction band of host were proposed to be responsible for the realization of the long-lasting phosphorescence of the investigated Cr³⁺ doped glass ceramics.     

A novel far-red phosphors Li2ZnTi3O8:Cr3+ for indoor plant cultivation:Synthesis and luminescence properties

A novel far-red phosphors Li₂ZnTi₃O₈:Cr³⁺ were successfully synthesized via the conventional solid-state method. The structural characteristics, luminescence properties and concentration quenching of the Li₂ZnTi₃O₈:Cr³⁺ phosphors were investigated systematically. Under the excitation at 360 nm and 468 nm, the Li₂ZnTi₃O₈:Cr³⁺ phosphors displays the emission spectra in the range from 600 nm to 850 nm. The far-red emission centered at 735 nm was attributed to the spin-forbidden ²E→⁴A₂ transition of Cr³⁺ ions. The research results of this paper indicate that the phosphors Li₂ZnTi₃O₈:Cr³⁺ has prospective applications in indoor plant cultivation.     

Effect of MgO doping on the structure and optical properties of YAG transparent ceramics

The paper studies the features of Mg²⁺ ions as sintering aid for reactive solid-state sintering of YAG transparent ceramics. Phase composition, microstructure and optical properties of YAG ceramics, doped by 0 ÷ 0.15 wt.% MgO, were investigated. Solubility limit of Mg²⁺ ions in YAG crystal lattice was found to be in the range of 0.06 ÷ 0.1 wt.% of MgO additive. Substitution mechanism of Mg²⁺ in ceramic YAG was identified by comparison of XRD data and ab initio calculation. It was shown that within the solubility limit Mg²⁺ ions most likely substitute Al³⁺ sites. Doping by MgO above solubility limit led to precipitation of spinel secondary phases. It was found that doping by Mg²⁺ ions increases concentration of oxygen vacancies in YAG lattice that effectively promote sintering. The optimal concentration range of MgO sintering aid that allow to achieve YAG transparent ceramics was defined as 0.03 ÷ 0.06 wt.%.     

Ce/Mn/Cr: Y3Al5O12 phosphor ceramics for white LED and LD lighting with a high color rendering index

Ce/Mn/Cr: Y₃Al₅O₁₂ transparent ceramics with a pure garnet structure and a high color rendering index were prepared by a solid-state reaction method. Mn²⁺ and Cr³⁺ enhance the emission between 500 and 700 nm and expand the conventional Ce: YAG phosphors spectrum. The Ce³⁺ can work both, as activators and sensitizers, and the intense energy transfer from Ce³⁺ to Mn²⁺/Cr³⁺ is realized through the non-radiative and radiative processes. In the sample with the optimized doping concentration the high color rendering index (CRI) value of 75.3 can be achieved under a 450 nm laser diode excitation. The chromaticity coordinates can be tuned from (0.3125, 0.3232) to (0.2917,0.2851) by varying the doping concentration. With the increasing Mn²⁺/Cr³⁺ doping concentration, the lifetime of Ce³⁺, quantum efficiency and luminous efficiency are all gradually decreased. This work effectively offers a scheme for realizing the high color rendering performance of phosphor-converted transparent ceramics in white LEDs/LDs.     

Fabrication and properties of transparent Tb:YAG fluorescent ceramics with different doping concentrations

Terbium doped yttrium aluminum garnet (Tb:YAG) transparent ceramics with different doping concentrations were fabricated by the solid-state reaction method using commercial Y₂O₃, α-Al₂O₃ and Tb₄O₇ powders as raw materials. Samples sintered at 1750 °C for 20 h were utilized to observe the optical transmittance, microstructure and fluorescence characteristics. It is found that all the Tb: YAG ceramics with different doping concentrations exhibit homogeneous structures with grain size distributions around 22–29 µm. For the 5 at% Tb:YAG transparent ceramics, the grain boundaries are clean with no secondary phases. The photoluminescence spectra show that Tb:YAG ceramics emit predominantly at 544 nm originated from the energy levels transition of ⁵D₄→⁷F₅ of Tb³⁺ ions, and the intensity of the emission peak reaches a maximum value when the Tb³⁺ concentration is 5 at%. The in-line transmittance of the 5 at% Tb:YAG ceramics is 73.4% at the wavelength of 544 nm, which needs to be further enhanced by optimizing the fabrication process. We think that Tb:YAG transparent ceramics may have potential applications in the high-power white LEDs.     

Processing and properties of luminescent Cr3+ doped transparent alumina ceramics

Transparent Cr₂O₃-doped alumina ceramics were prepared by slip casting, followed by pre-sintering in ambient atmosphere and hot isostatic pressing. The effect of dopant concentration on material properties, including microstructure and optical properties was evaluated. Real in-line transmittance in the range of 20–44 % was measured for the ceramics with the mean grain size <520 nm: the transmittance decreased with increasing grain size and Cr content. The excitation spectra consisted of two broad bands with maxima at 404 nm and 558 nm, corresponding to ⁴A_2g → ⁴T_1g and ⁴A_2g → ⁴T_2g transitions of Cr³⁺ ions in octahedral sites of α-Al₂O₃. The intensive deep red narrow emissions under violet/green light excitation, R-lines (²E_g → ⁴A_2g transition), were observed at 692.5 nm and 693.8 nm, that are very close to ruby single crystal. The highest emission was achieved at the Cr³⁺ concentration of 0.4 at.%. The luminescence decay curves exhibited single-exponential behaviour with decay times of ∼3.6 ms.     

Synthesis,Crystal Structure,and Enhanced Luminescence of Garnet‐Type Ca3Ga2Ge3O12:Cr3+ by Codoping Bi3+

Garnet‐type compound Ca₃Ga₂Ge₃O₁₂ and Cr³⁺‐doped or Cr³⁺/Bi³⁺ codped Ca₃Ga₂Ge₃O₁₂ phosphors were prepared by a solid‐state reaction. The crystal structure of Ca₃Ga₂Ge₃O₁₂ host was studied by X‐ray diffraction (XRD) analysis and further determined by the Rietveld refinement. Near‐infrared (NIR) photoluminescence (PL) and long‐lasting phosphorescence (LLP) emission can be observed from the Cr³⁺‐doped Ca₃Ga₂Ge₃O₁₂ sample, and the enhanced NIR PL emission intensity and LLP decay time can be realized in Cr³⁺/Bi³⁺ codped samples. The optimum concentration of Cr³⁺ in Ca₃Ga₂Ge₃O₁₂ phosphor was about 6 mol%, and optimum Bi³⁺ concentration induced the energy‐transfer (ET) process between Bi³⁺ and Cr³⁺ ions was about 30 mol%. Under different excitation wavelength from 280 to 453 nm, all the samples exhibit a broadband emission peaking at 739 nm and the intensity of NIR emission increases owing to the ET behavior from Bi³⁺ to Cr³⁺ ions. The critical ET distance has been calculated by the concentration‐quenching method. The thermally stable luminescence properties were also studied and the introduction of Bi³⁺ can also improve the thermal stability of the NIR emission.     

Luminescent properties and LED Application of Broadband Near-Infrared Emitting NaInGe2O6: Cr3+ phosphors

A NIR-emitting Cr³⁺-activated phosphors (NaInGe₂O₆: Cr³⁺) covering whole NIR-I region (700–1200 nm) were successfully designed and prepared via solid-state reaction. XRD and Rietveld refinement verified that the octahedral In³⁺ site is the preferred site of Cr³⁺ substitution in NaInGe₂O₆ structure. The synthesized NaInGe₂O₆: Cr³⁺ phosphors exhibit two strong absorption bands at 480 and 700 nm, and show a mountain-like single-band emission at 900 nm with FWHM = 175 nm. The crystal field parameters are calculated using steady-state spectral data, in which a low Dq/B value of 1.89 is obtained and results in this broadband NIR emission. NaInGe₂O₆: Cr³⁺ exhibits good emission thermal stability, i.e. 55 % of room temperature intensity at 373 K. Besides, an efficient NIR pc-LED is fabricated and shows NIR output of 25.2 mW@120 mA. This broadband NaInGe₂O₆: Cr³⁺ NIR phosphor could be merged into pc-LED package for hand-held spectrometers, security cameras and vivo biomarkers.