Fabrication and characterizations of Cr3+-doped ZnGa2O4 transparent ceramics with persistent luminescence

0.5 at.% Cr:ZnGa₂O₄ precursor was synthesized by the co-precipitation method with nitrates as raw materials, using ammonium carbonate as the precipitant. Low-agglomerated Cr:ZnGa₂O₄ powders with an average particle size of 43 nm were obtained by calcining the precursor at 900℃ for 4 h. Using the powders as starting materials, 0.5 at.% Cr:ZnGa₂O₄ ceramics with an average grain size of about 515 nm were prepared by presintering at 1150℃ for 5 h in air and HIP post-treatment at 1100℃ for 3 h under 200 MPa Ar. The in-line transmittance of 0.5 at.% Cr:ZnGa₂O₄ ceramics with a thickness of 1.3 mm reaches 59.5% at the wavelength of 700 nm. The Cr:ZnGa₂O₄ ceramics can be effectively excited by visible light and produce persistent luminescence at 700 nm. For Cr:ZnGa₂O₄ transparent ceramics, the brightness of afterglow was larger than 0.32 mcd/m² after 30 min, which is far superior to that of Cr:ZnGa₂O₄ persistent luminescence powders.     

ZnGa2O4纳米晶的制备和结构表征

采用喷射共沉淀法制备了ZnGa2O4 纳米晶，XRD、SEM和TEM结构分析结果表明，喷射共沉淀法制备的ZnGa2O4的纳米晶颗粒细小均匀，形状完整，与化学共沉淀法相比，粒子尺寸明显减小，小于10nm，同时ZnO杂相峰消失，分析了喷射共沉淀法的机理，并对实验结果进行了解释。     

pH值对水热法制备ZnGa2O4粉体的影响

采用水热法制备了ZnGa2O4纳米粉体,使用XRD、SEM、TEM及AFM对不同pH值条件下产物的结构及微观形貌进行了表征.结果表明pH值调节严重影响ZnGa2O4的晶相及粒度:当pH≥7.5时,可得到纯相的ZnGa2O4纳米粉体;随着pH的增加,晶胞参数增加,所得样品的平均粒径不断减小,其粒径范围为6～11nm,发射峰位置在450nm左右.所得样品的晶型很完整,GaO(OH)为细长棒状,ZnGa2O4晶粒为四方形和圆形.     

水热法制备石墨烯-镓酸锌复合物及其气敏性能的研究

通过水热法制备了一系列的石墨烯-镓酸锌复合物。所制备的材料用XRD,SEM,TEM,拉曼和XPS进行表征。同时,探究了复合物的气敏性能。结果表明,石墨烯的含量对复合材料的气敏响应值和选择性有着很大的影响,并且当石墨烯的含量在0.1%时,复合材料的性能最好。当操作温度在203摄氏度时,0.1%石墨烯-镓酸锌复合材料对1000ppm的甲醛的响应值达32.2倍,最低检测限度为1ppm。同时,该材料的选择性也比较优越,对1000ppm甲醛和1000ppm丙酮的响应值的比值为26.8。该材料对1000ppm甲醛的响应和恢复时间分别为11秒和5秒,对1ppm甲醛的响应和恢复时间分别为6秒和5秒.     

ZnGa2O4：Cr3+ 近红外长余辉荧光粉制备与光学性能研究

采用高温固相法制备了ZnGa₂O₄：Cr³⁺ 近红外（660-1300 nm）长余辉荧光粉,并系统地研究了样品的荧光、长余辉、光激励发光及热释光性能.样品的余辉激发谱测试结果显示,ZnGa₂O₄：Cr³⁺ 长余辉材料的余辉主要源自O²-Ga³⁺之间的电荷迁移跃迁激发,而非Cr³⁺离子的本征跃迁激发.光激励发光性能的研究表明,ZnGa₂O₄：Cr³⁺ 在紫外光激发的余辉完全衰减后可以被近红外光再次激发出明亮的余辉,这说明ZnGa₂O₄：Cr³⁺ 在紫外光信息写入后可以用红外光进行信息读出.根据实验测试结果采用导带电子复合发光模型对样品的发光机理进行了详细的阐述.     

An Ion‐Exchange Phase Transformation to ZnGa2O4 Nanocube Towards Efficient Solar Fuel Synthesis

To realize practical applications of the photocatalysis technique, it is necessary to synthesize semiconductor photocatalysts with specific facets that induce high reactive activities and high reactive selectivity. However, a challenge lies in the synthesis of metal oxides containing more than one type of metal with specific facets. Usually, surfactants are used to control the crystal morphology, which induces surface contamination for the final products. Here, using the GaOOH nanoplate as precursor, ZnGa₂O₄ nanocubes with exposed {100} facets are synthesized by an hydrothermal ion‐exchange route without requiring the introduction of morphology controlling agents. These ZnGa₂O₄ nanocubes exhibit improved performance in the photoreduction of CO₂ into CH₄ or water splitting into hydrogen. Theoretical calculations indicates that the light‐hole effective mass on the {100} facets of ZnGa₂O₄ corresponds to the high hole mobility, which contributes to the efficient water oxidation to offer the protons for promoting CO₂ photoreduction into hydrocarbon fuels.     

The preparation of ZnGa2O4 doped with Mn‐Mg and Tm for green and blue phosphors

Phosphor powders of zinc gallate (ZnGa₂O₄) with Mg and Mn for green and Tm‐Mg for blue luminescence were prepared by solid state reaction method for their improved luminescent properties. Green‐luminescence emitting ZnMnGa₂O₄ reached maximum intensity at Mn = 0.005 mol% and further improvement was achieved by the addition of Mg²⁺. Tm‐Mg based zinc gallate phosphor exhibited a strong blue emission, centered at ∼420 nm with the maximum intensity achieved for 0.003 mol% of Mg and 0.015 mol% of Tm. This study established the possibilities of controlling the luminescent characteristics of zinc gallate by adding various elements. © 2006 Institute of Electrical Engineers of Japan. Published by John Wiley & Sons, Inc.     

Cr^3+掺杂对ZnGa2O4光催化性能影响的研究

试验以Ga(NO3)3·9H2O、Zn(NO3)2·6H2O、Cr(NO3)3·9H2O、Na3C6H5O7·2H2O为原料,采用水热法制备Cr^3+掺杂ZnGa2O4。通过XRD、TEM对样品的结构和形貌进行表征,通过UV-vis DRS、PL对样品进行光学性能表征,利用紫外-可见光分度计测试罗丹明B的吸光度变化情况对样品进行光催化性能检测。研究掺杂量、煅烧温度、保温时间对ZnGa2O4的影响,试验结果表明,最佳制备条件为:Cr^3+掺杂量1.0%、煅烧温度700℃、保温时间8 h。最佳条件下ZnGa1.99Cr0.01O4降解罗丹明B在60 min降解率可达97%;ZnGa1.99Cr0.01O4产氢量为446.4μmol/g,对比Zn Ga2O4产氢量为184.7μmol/g,产氢量增加。     

Low Dose of X‐Ray‐Excited Long‐Lasting Luminescent Concave Nanocubes in Highly Passive Targeting Deep‐Seated Hepatic Tumors

Chromium‐doped zinc gallate, ZnGa₂O₄:Cr³⁺ (ZGC), is viewed as a long‐lasting luminescence (LLL) phosphor that can avoid tissue autofluorescence interference for in vivo imaging detection. ZGC is a cubic spinel structure, a typical agglomerative or clustered morphology lacking a defined cubic shape, but a sphere‐like feature is commonly obtained for the nanometric ZGC. The substantial challenge remains achieving a well‐defined cubic feature in nanoscale. The process by which dispersed and well‐defined concave cubic ZGC is obtained is described, exhibiting much stronger LLL in UV and X‐ray excitation for the dispersed cubic ZGC compared with the agglomerative form that cannot be excited using X‐rays with a low dose of 0.5 Gy. The cubic ZGC reveals a specific accumulation in liver and 0.5 Gy used at the end of X‐ray excitation is sufficient for imaging of deep‐seated hepatic tumors. The ZGC nanocubes show highly passive targeting of orthotopic hepatic tumors.     

Optical transmission,dispersion, and transition behavior of ZnGa2O4 transparent ceramic

As an emerging transparent ceramic with extremely wide transmission range, the unique optical properties of ZnGa₂O₄ are of particular interest. In this work, ZnGa₂O₄ transparent ceramic with high optical quality was prepared by pressureless sintering and hot isostatic pressing. Its optical behavior was then comprehensively studied. The critical optical data, including refractive index, extinction coefficient, Abbé number, absorption coefficient in infrared region, and phonon frequency, were investigated. The indirect band gap and the phonon energy assisting indirect transition were determined as 4.10 and 0.17 eV, respectively. The modified Sellmeier equation and single-oscillator dispersion relation were derived to describe the optical dispersion. Benefitting from the weaker tetrahedral Zn–O bond and heavier cationic masses, the infrared transmission range of ZnGa₂O₄ transparent ceramic was broadened significantly. Oxygen vacancies were suggested to induce the absorption in lower photon energy region of ZnGa₂O₄ transparent ceramic, which may enrich its functionalization. This work is meaningful for gaining overall insight into optical properties of transparent materials.