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.     

Effect of Ca2+ and Mg2+ ions on the sintering and spectroscopic properties of cr-doped yttrium aluminum garnet ceramics

In this work, we investigated the effects of Ca²⁺ and Mg²⁺ ions and annealing temperature on the spectroscopic parameters of chromium-doped yttrium aluminum garnet ceramics (Cr:YAG). Samples were obtained with either a separate or a simultaneous addition of calcium and magnesium oxides. To achieve this, aqueous suspensions were prepared using Y₂O₃, Al₂O₃, Cr₂O₃, MgO, and CaO high-purity powders as raw materials. The obtained suspensions were freeze-granulated, pressed into pellets, debinded, and subjected to reactive sintering in vacuum at 1715°C for 6 h. Each material was annealed in air with temperatures between 1300 and 1700°C. Samples were also compared to Cr:YAG ceramics with the addition of silica as a sintering aid. All the materials obtained were then exposed to 445 nm excitation, and emission spectra in the visible and infrared wavelengths were recorded. The results showed that the emission spectra of Cr:YAG ceramics varied according to the annealing conditions: as-sintered samples exhibited strong emissions of around 680 nm and, after air annealing, of around 1400 nm. This phenomenon is attributed to the Cr³⁺→Cr⁴⁺ transition. Samples doped solely with MgO exhibited the highest emission intensity in the infrared region. Thus, Mg²⁺ ions provided the best conversion efficiency of chromium ions.     

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.     

Luminescent Dy3+ and Dy3+/Cr3+ doped transparent Al2O3 ceramics: Microstructure and optical properties

Highly transparent Dy³⁺ and Dy³⁺/Cr³⁺ polycrystalline alumina ceramics were prepared with the real in-line transmittance (RIT) up to 55% (at λ = 632 nm), one of the highest values reported for luminescent rare-earth elements doped alumina. The RIT of doped alumina decreased more sharply with increasing mean grain size than predicted by the models for pure alumina. Co-doping with Dy³⁺ and Cr³⁺ resulted in a moderate increase of the RIT, which was independent on grain size. EDX analysis revealed that dysprosium segregated at grain boundaries and chromium was dispersed throughout the alumina matrix. A thermodynamic model for diffusion of multiple species in systems with multiple sorts of traps was proposed. The photoluminescence excitation and emission spectra of Dy³⁺-doped alumina showed peaks characteristic for Dy³⁺-doped materials. In co-doped Dy³⁺/Cr³⁺ alumina, Dy³⁺ emitted in the blue and yellow regions and Cr³⁺ in the red region, creating a suitable combination for obtaining white light.     

Influence of Gd2O3 on the microstructure and properties of transparent MgAl2O4: Cr3+ ceramic

In this work, MgAl₂O₄: Cr³⁺ transparent ceramics have been synthesized by the hot press sintering techniques, and the effect of the sintering aid Gd₂O₃ and its content on the densification, microstructure, and optical, photoluminescence was studied and discussed. The relative density reached 99.29% with 0.8 wt% Gd₂O₃ as a sintering aid, and the optical transmittance at 686 nm and 1446 nm were approximately 76%. As Gd₂O₃ content continued to increase, the grain size of the ceramics became smaller and uniform, accompanied by some pores with the size of ～1 μm. The ceramics with 4.0 wt% Gd₂O₃ showed a higher transmittance, of 82% at 1446 nm. Additionally, Gd₂O₃ was helpful for Cr³⁺ in the sites of octahedral symmetry, which increased the quantum yield. The quantum yield of MgAl₂O₄: Cr³⁺ with 0.8 wt% Gd₂O₃ was about 0.175, which was 36% higher than that of ceramic without Gd₂O₃. In short, the sintering aid Gd₂O₃ not only contributed to improving the densification, homogenizing the grain size, and heightening the optical transmittance but also enhanced the quantum yield of Cr³⁺.     

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.     

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.     

Dielectric behavior dependence on temperature and Cr-doping contents of Aurivillius Bi5Ti3FeO15 ceramics

The dielectric behavior of Cr-doped Bi₅Ti₃FeO₁₅ (BTFCO) ceramics was systemically studied by temperature-dependent dielectric/impedance spectroscopy from 200 K to 400 K. Two dielectric relaxation processes were found in grain interiors of the BTFCO ceramics. Both of them showed similar activation energy. This usually brings a great challenge to discern the different mechanisms of the conductivity and/or dielectric responses in Fe–Cr-based materials; nevertheless the origins of the two relaxations were unambiguously determined by adjusting the Cr doping contents. One relaxation at high temperature region was proposed to be associated with the localized electron hopping between Fe³⁺ and Fe²⁺, whereas another one at lower temperatures was assigned to the localized hole transfer between Cr³⁺ and Cr⁶⁺ inside the grains. Moreover, the transition temperature between the two relaxations showed a nearly linear reducing trend with the Cr-doping content.     

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.     

The ultra-wideband near-infrared luminescence properties and applications of K2SrGe8O18:Cr3+ phosphor

The near-infrared (NIR) light sources are fascinating in real-time nondestructive examination applications. Given that chemical bonds in organic substances (such as C–H, O–H and N–H) have extensive absorption and reflection of light in the NIR region, the emission spectrum of the NIR light sources should be as broad as possible. In this work, ultra-wideband K₂SrGe₈O₁₈ (KSGO):Cr³⁺ NIR-emitting phosphors with a 650–1200 nm emission span are developed. Structural analysis combined with electron paramagnetic resonance (EPR), photoluminescence (PL) spectra, time-resolved spectrum (TRES) and temperature-dependent PL spectra confirm that the super broadband emission with full width at half-maximum (FWHM) of 214 nm originates from the double Cr³⁺ luminescence centers occupying different [GeO₆] octahedra. Li⁺ ion as charge compensator is introduced to balance the negative charge induced by the un-equivalent replacement of Cr³⁺ for Ge⁴⁺, and the PL intensity and thermal stability are greatly enhanced. The NIR phosphor-converted luminescent diodes (pc-LEDs) prepared by combining optimized KSGO:0.10Cr³⁺, 0.07Li⁺ samples with 460 nm LED chips demonstrate their application in night vision. The measured absorption spectra of hemoglobin, water, ethyl alcohol and peanut oil illuminated by the as-prepared KSGO:0.10Cr³⁺, 0.07Li⁺ phosphors indicate nondestructive analysis in the areas of food safety.     

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.     

Structural,electrical, and magnetic transport properties of La0.72Ca0.28Mn1−xCrxO3 (0 ≤ x ≤ 0.06) ceramics

To obtain comprehensive materials with both high temperature coefficient of resistivity (TCR) and magnetoresistance (MR) at low magnetic fields, polycrystalline La_0.72Ca_0.28Mn_1?xCr_xO₃ (x = 0, 0.02, 0.04, 0.06) ceramics were prepared herein by sol–gel method. Electronic configuration of Cr³⁺ ions is similar to that of Mn⁴⁺ ions, therefore, successive substitution of Mn with Cr increases electrical resistivity and decreases metal–insulator transition temperature of ceramics, even yielding hump-like feature for Cr-rich (x = 0.06) samples. The best TCR (28.50%·K^?1) and MR (72.37%) values were obtained simultaneously at Cr dopant content of 0.02 (La_0.72Ca_0.28Mn_0.98Cr_0.02O₃). Strong response of the material to temperature and magnetic field was caused by minimal symmetry of orthorhombic structure and the most robust Jahn–Teller distortion. With increasing Cr content, Mn³⁺/Mn⁴⁺ or Mn³⁺/Cr³⁺ double exchange was diluted, and Cr³⁺/Cr³⁺ or Cr³⁺/Mn⁴⁺ superexchange was promoted. However, the internal competition effect was not conducive to the improvement of material properties.     

Luminescent properties of Li(Ga1-xCrx)5O8 (LGCO) phosphors

In this work, we investigate the synthesis of LiGa₅O₈ ceramic powders through a polyvinyl alcohol-based sol-gel technique and their optical properties when doped with high Cr³⁺ concentrations (5, 25 and 50 mol% with respect to the Ga³⁺ sites). The results indicate that the main crystalline phase, LiGa₅O₈, is obtained after calcining the samples at 1000 °C/2 h in a static air atmosphere. Via X-ray photoelectron spectroscopy, Cr is confirmed to exist in its trivalent oxidation state and the evaluation of the optical properties is performed via photoluminescence excited from visible to vacuum ultraviolet energy range and with X-ray excited optical luminescence, indicating the typical Cr³⁺ emission at the near-infrared energy range. The crystal field and Racah parameters are calculated and the influence of Cr³⁺ concentration in the host material indicates luminescence suppression/quenching and a redshift for a higher amount of these ions.     

High-entropy transparent fluoride laser ceramics

For the first time, a transparent high-entropy fluoride laser ceramic has been prepared and characterized. X-ray diffraction (XRD) analysis of a CeNdCaSrBaF₁₂ (CNCSBF) transparent ceramic consolidated by vacuum hot pressing (VHP) reveals that Ce³⁺, Nd³⁺, Ca²⁺, Sr²⁺, and Ba²⁺ have formed a single-phased fluorite solid solution, with a lattice constant of 5.826 Å. Bulk density measurements produced a value of 6.15 g/cm³. Scanning electron microscopy (SEM) analysis of the ceramic revealed a uniform distribution of grain sizes in the material, with the average grain size being approximately 20 μm. The material exhibits a maximum in-line transmittance of approximately 60% at 1000 nm. A near-infrared range photoluminescence (PL) emission band was observed at 1057 nm, with a visible-range PL emission band being located at 440 nm.     

Instant precipitation of KMgF3:Ni2+ nanocrystals with broad emission (1.3‐2.2 μm) for potential combustion gas sensors

Optical gas sensors present fundamental and industrial importance considering their broad applications. Challenges remain to obtain new photonic materials with broadband emission covering the absorption spectrum of typical combustion gases. Here, broadband near‐infrared (NIR) photoluminescence (PL) spanning the wide absorption spectrum of typical combustion products is realized through instant precipitation of stable cubic perovskite KMgF₃:Ni²⁺ nanocrystals inside an aluminosilicate glass matrix after melt‐quenching. Excited by an 808 nm laser diode, NIR luminescence with a peak centered at ~1624 nm and a bandwidth (FWHM) greater than 315 nm is observed, originating from ³T_2g(³F) → ³A_2g(³F) electronic transition of octahedral coordinated Ni²⁺ in KMgF₃ GC. Controlled precipitation of these perovskite crystals from a supercooled aluminosilicate melt enables immediate encapsulation and, hence, stabilization in an inorganic glass phase. While the precipitation temperature has only a small effect on crystallite size, it controls the redox state of the melt and the degree of dopant incorporation into the crystalline phase so that PL performance can be optimized. Spontaneous crystallization of perovskite nanocrystals inside glass may offer a new way to stabilize these novel nanocrystals. Moreover, spontaneous crystallization can be attractive in the control of activator partitioning and in the fabrication of composite fiber devices with high transparency and emission gain. In the present case, this offers a potential platform for broadly tunable gain media, for example, for combustion gas sensing.     

Broadband near-infrared double-perovskite phosphor Sr2ScTaO6:Cr3+, Yb3+ for NIR pc-LED applications

The broadband near-infrared (NIR) phosphor converted light emitting diode (NIR pc-LED) has garnered unprecedented attention due to its crucial role in NIR applications. However, there remains a scarcity of efficient broadband NIR luminescence materials capable of emitting NIR light with wavelengths greater than 800 nm. This study reports the synthesis, crystal structure and photoluminescence (PL) properties for double perovskite Sr₂ScTaO₆:Cr³⁺ phosphors which exhibit a broadband NIR emission in the 650–1250 nm range, peaking at∼815 nm with the full width at half maximum (FWHM) of 161 nm. The observed broadband emission arises from two distinct Cr³⁺ centers, namely Sc³⁺ and Ta⁵⁺ octahedral sites within the Sr₂ScTaO₆ structure, as demonstrated by luminescence and decay kinetic analysis. A significant enhancement of the thermal stability and a remarkable broadening of the FWHM (from 161 to 275 nm) are achieved by employing Yb³⁺ co-doping strategy. The efficient energy transfer from Cr³⁺ to Yb³⁺ was confirmed through emission and excitation spectra, as well as luminescence decay measurements. Finally, Sr₂ScTaO₆:Cr³⁺-Yb³⁺ phosphor was integrated with a 470 nm blue LED chip to fabricate a NIR pc-LED device, and its potential application in night vision was evaluated.     

Far-red-emitting YAl3(BO3)4:Cr3+ phosphors with excellent thermal stability and high luminescent yield for plant growth LEDs

Phosphors-converted LEDs (pc-LEDs) are excellent artificial light sources for indoor plant cultivation, in which the far-red-emitting component (700−780 nm) plays an important role in regulating the photomorphogenesis of plants. Accordingly, highly efficient and thermally stable far-red-emitting phosphors are indispensable for developing high-performance plant cultivation pc-LEDs. Herein, far-red-emitting YAl₃(BO₃)₄:Cr³⁺ (YAB:Cr³⁺) phosphors were synthesized by solid-state reaction, and their photoluminescence characteristics, thermal quenching, quantum yield (QY), and application in pc-LEDs were systematically investigated. The YAB:Cr³⁺ phosphor has an intense broadband absorption to the blue light, simultaneously exhibiting the sharp-line ²E emission and the broadband ⁴ T₂ emission of Cr³⁺ with a QY of ~86.7%. The far-red broadband emissions of YAB:Cr³⁺ centered at ~735 nm show a high resemblance to the active-state (P_FR) absorption of plant phytochrome. Moreover, the YAB:Cr³⁺ phosphor shows the thermally enhanced luminescence at temperatures of 303−393 K and the near-zero thermal quenching up to 423 K. The anomalous thermal enhancement is attributed to the temperature-dependent repopulation between ²E and ⁴ T₂ states. Finally, a pc-LED device was fabricated with the YAB:Cr³⁺ phosphor and blue chip, exhibiting the light out power of ~50.6 mW and energy conversion efficiency of ~17.4% at 100 mA drive current, respectively. The exceptional PL features including suitable excitation/emission wavelengths, suppressed thermal quenching and high QY make YAB:Cr³⁺ phosphors very promising for applications in plant growth pc-LEDs.     

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.     

Luminescence enhancement of Cr3+ doped garnet phosphor for high-performance LED towards smart NIR light source

Cr³⁺ doped phosphor shows great potential for near-infrared (NIR) light-emitting diodes (LED), but it suffers from low quantum efficiency and poor thermal stability. Herein, a novel Cr³⁺ doped broadband NIR garnet Ca₃Sc₂Ge₃O₁₂ phosphor was developed. The multisite structure of the emission band is investigated by site-selective spectroscopy and is attributed to the octahedral Cr³⁺ perturbed by defects. Moreover, we propose different strategies to enhance the luminescence of the phosphor, including enhancement of crystallinity and elimination of defects. Compared with the initial sample, the emission intensity of the optimized phosphor is improved for 8.6 times. The optimal Ca₃Sc₂Ge₃O₁₂: 0.06Cr³⁺ phosphor exhibits excellent thermal stability. At 423 K, the integral emission intensity of the optimal sample remains 94.7% of that at room temperature. Finally, high-performance NIR LED was fabricated using a blue LED and the title phosphor. The packaged LED lamp has high radiance (109.3 mW@300 mA) and photoelectric efficiency (15.96%@40 mA). Our study not only provides a boulevard for enhancing the luminescence of Cr doped NIR phosphor, but also gives a new perspective for understanding the multisite luminescence of Cr³⁺ in garnet host.     

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.