Nd^(3+):GdScO_(3)晶体场能级及拟合分析

采用提拉法生长出了钕掺杂钪酸钆晶体(Nd^(3+):GdScO_(3)),通过低温吸收光谱和室温发射光谱,对其中Nd^(3+)的实验能级进行分析指认,确定了Nd^(3+):GdScO_(3)的66个实验Stark能级,拟合了其自由离子参数和晶体场参数,拟合均方根误差为13.17 cm^(–1).与Nd^(3+):YAP和Nd^(3+):YAG相比,Nd^(3+):GdScO_(3)的晶场强度较弱.弱的晶体场强度有可能是Nd^(3+):GdScO_(3)晶体具有优良激光特性的原因之一.本文数据集可在https://www.doi.org/10.57760/sciencedb.15702中访问获取.

Nd^(3+)掺杂钙钛锆石(Ca_(1-x)Nd_(x)ZrTi_(2)O_(7+x/2))相变行为的研究

为研究钙钛锆石对放射性元素Am^(3+)的稳定固化作用,以Nd^(3+)为Am^(3+)的模拟元素,系统研究了高温固相法制备Ca_(1-x)Nd_(x)ZrTi_(2)O_(7+x/2)时,Nd^(3+)异价取代钙钛锆石晶格中Ca^(2+)位(0≤x≤1.0)所导致的相态演变行为。合成Ca_(1-x)Nd_(x)ZrTi_(2)O_(7+x/2)的XRD、Raman、BSE和EDS测试结果表明:钙钛锆石(Zirconolite)晶格对Nd^(3+)离子的固溶量可达70%(x=0.7),可有效实现对Am^(3+)模拟元素Nd^(3+)离子的固化。但随着Nd^(3+)掺杂量(x≤0.3)增加,Zirconolite-2M晶格中O^(2-)和Nd^(3+)的无序化程度逐渐增加、(Ca/Nd)-O键长逐渐变小,直至(x=0.4)引起Zr^(2+)、Ti^(4+)附近的O^(2-)配位数发生改变(ZrO7→ZrO8、TiO5→TiO6),Zirconolite-2M晶格结构开始向Zirconolite-4M转变。x=0.5时,陶瓷体完全转变为Zirconolite-4M晶格且O^(2-)和Nd^(3+)有序度重新变高、Ti—O键长增加;直至x=0.6、x=0.7时,陶瓷体仍为单一Zirconolite-4M结构,但晶格中O^(2-)和Nd^(3+)的有序度又逐渐降低,以至于在x=0.7陶瓷体亚晶格中微量Ca^(2+)、Zr^(4+)、Nd^(3+)离子占位转变为烧绿石(Pyrochlore)结构。而在0.8≤x≤0.9范围内,Zirconolite-4M结构完全消失,陶瓷体为多相共存状态(Pyrochlore、ZrTiO_(4)和Nd2(TiZr)_(4)O_(11)物相)。Nd^(3+)完全取代Ca^(2+)位(x=1.0)时,陶瓷体变为单一Nd2(TiZr)_(4)O_(11)固溶体相。陶瓷体晶粒的BSE和EDS分析证实了这种相变规律。

Yb^(3+)/Nd^(3+)掺杂对Sr_(9)Ga(PO_(4))_(7)∶Cr^(3+)发光性能的影响

近红外荧光粉由于其独特的物理特性和广阔的应用前景吸引了人们极大的研究兴趣。本文通过高温固相反应法合成Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+)近红外荧光粉,使用460 nm蓝光激发样品的发射波长位于833 nm,半峰宽为117 nm。随后引入稀土离子合成Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+),Yb^(3+)和Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+),Nd^(3+)近红外荧光粉。相比Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+),460 nm蓝光激发的Sr_(9)Ga(PO_(4))_(7)∶0.8Cr^(3+),Yb^(3+)同时出现Cr^(3+)和Yb^(3+)特征发射峰,经过光谱分析和荧光寿命变化证明Cr^(3+)-Yb^(3+)存在能量传递通道,最高使Cr^(3+)-Yb^(3+)能量传递效率达80.2%,得益于Yb^(3+)卓越的热稳定性促使整体荧光光谱热稳定性提高约3.7倍。设计合成的Sr_(9)Ga(PO_(4))_7∶0.8Cr^(3+),Nd^(3+)样品调制出833,876,1 060 nm的多峰发射,显著拓宽了近红外光谱范围。最终,讨论了荧光粉在温度传感和无损检测领域的应用,证明该系列荧光粉具有广阔的应用前景。

Oxygen vacancy defects engineering on Cu-doped Co_(3)O_(4) for promoting effective COS hydrolysis

The activation of H_(2)O is a key step of the COS hydrolysis,which may be tuned by oxygen vacancy defects in the catalysts.Herein,we have introduced Cu into Co_(3)O_(4) to regulate the oxygen vacancy defect content of the catalysts.In situ DRIFTS and XPS spectra reveal that COS and H_(2)O are adsorbed and activated by oxygen vacancy.The 10 at%Cu doped Co_(3)O_(4) sample(10Cu-Co_(3)O_(4))exhibits the optimal activity,100%of COS conversion at 70℃.The improved oxygen vacancies of CueCo_(3)O_(4) accelerate the activation of H_(2)O to form active -OH.COS binds with hydroxyl to form the intermediate HSCO^(-)_(2),and then the activated-OH on the oxygen vacancy reacts with HSCO^(-)_(2) to form HCO^(-)_(3).Meanwhile,the catalyst exhibits high catalytic stability because copper species(Cu+/Cu^(2+))redox cycle mitigate the sulfation of Co_(3)O_(4)(Co^(2+)/Co^(3+)).Our work offers a promising approach for the rational design of cobalt-related catalysts in the highly efficient hydrolysis COS process.

A ratiometric fluorescent probe for hypoxanthine detection in aquatic products based on the enzyme mimics and fluorescence of cobalt-doped carbon nitride

A ratiometric fluorescent probe for hypoxanthine(Hx)detection was established based on the mimic enzyme and fluorescence characteristics of cobalt-doped graphite-phase carbon nitride(Co doped g-C_(3)N_(4)).In addition to emitting strong fluorescence,the peroxidase activity of Co doped g-C_(3)N_(4)can catalyze the reaction of O-phenylenediamine and H_(2)O_(2)to produce diallyl phthalate which can emit yellow fluorescence at 570 nm.Through the decomposition of Hx by xanthine oxidase,Hx can be indirectly detected by the generating hydrogen peroxide based on the measurement of fluorescent ratio I(F_(570)/F_(370)).The linear range was 1.7-272.2 mg/kg(R^(2)=0.997),and the detection limit was 1.52 mg/kg(3σ/K,n=9).The established method was applied to Hx detection in bass,grass carp,and shrimp,and the data were verified by HPLC.The result shows that the established probe is sensitive,accurate,and reliable,and can be used for Hx detection in aquatic products.

Preparation of Sn-doped Ga_(2)O_(3) thin films and their solar-blind photoelectric detection performance

Sn doping is an effective way to improve the response rate of Ga_(2)O_(3) film based solar-blind detectors. In this paper,Sn-doped Ga_(2)O_(3) films were prepared on a sapphire substrate by radio frequency magnetron sputtering. The films were characterized by X-ray diffraction, scanning electron microscopy, X-ray photoelectron spectroscopy and ultraviolet visible spectroscopy, and the effect of annealing atmosphere on the properties of films was studied. The Ga_(2)O_(3) films changed from amorphous to β-Ga_(2)O_(3) after annealing at 900 °C. The films were composed of micro crystalline particles with a diameter of about 5–20 nm.The β-Ga_(2)O_(3) had high transmittance for wavelengths above 300 nm, and obvious absorption for solar-blind signals at 200–280 nm.The metal semiconductor metal type solar-blind detectors were prepared. The detector based on Sn-doped β-Ga_(2)O_(3) thin film annealed in N_2 has the best response performance to 254 nm light. The photo-current is 10 μA at 20 V, the dark-current is 5.76 pA,the photo dark current ratio is 1.7 × 10~6, the response rate is 12.47 A/W, the external quantum efficiency is 6.09 × 10~3%, the specific detection rate is 2.61 × 10~(12) Jones, the response time and recovery time are 378 and 90 ms, respectively.

The Effect of Nd^(3+) Concentration on Upconversion Luminescence in Yb^(3+)/Tm^(3+)/Nd^(3+) Tripledoped b-NaGdF_(4) Nanocrystals

Nd^(3+)-doped NaGdF_(4):Yb,Tm nanocrystals were synthesized by an improved high-temperature thermal decomposition method,and the effects of doping concentrations on the crystal structure,phase composition,and upconverted fluorescence intensity were also investigated.The results reveal that the introduction of Nd^(3+) ions does not cause the transformation of the crystal phase,but induce the change of the unit cell parameters.Meanwhile,the fluorescence intensity of the synthesized nanocrystals when co-doped with 3 mol%Nd^(3+) is the strongest under the excitation of 980 nm laser,which is 3.9 times that of the Nd^(3+)-free doped nanoparticles,and the average size is 62.9 nm.And it is located in the blue area of the CIE coordinate diagram,and the corresponding color purity is 91.81%under the same experimental conditions.The resulting nanocrystals show the potential as excellent fluorescence labeling and in vivo imaging probes.

Spectroscopic Properties of Nd^(3+)-Doped Tellurite Glasses

The Nd^3＋-doped pared. The absorption and tellurite glasses were preemission spectra of Nd^3 ＋- doped tellurite glasses at room temperature were measured. The Judd-Ofelt parameters （Ω2, Ω4, Ω6） of the glasses were calculated from measured absorption spectra. The calculation results of luminescence properties （A, β, τrad, σ） of Nd^3＋ ions in the tellurite were glasses were given. Spectroscopic properties, concentration quenching in these kinds of the glasses were investigated. The results indicate that the tellurite glasses with composition of 70% TeO2, 20% ZnO, （ 10 - x ） % La2O3, x % Nd2O3 （ mol% ） show high emission cross section and low phonon energy. The fluorescent intensity and the emission cross section have a maxi- mum value at x = 0.5, namely, the optimum Nd^3 ＋ ion concentration in the tellurite glass is 0.5% （1.93 × 10^20 ions·cm^-3）. The fluorescence properties of Nd^3＋ measured are basically in accord with the calculated results.

Spectroscopic Properties of Nd^(3+)-Doped High Silica Glass Prepared by Sintering Porous Glass

A new kind of Nd^3＋-doped high silica glass （SiO2 〉 96% （mass fraction）） was obtained by sintering porous glass impregnated with Nd^3 ＋ ions. The absorption and luminescence properties of high silica glass doped with different Nd^3 ＋ concentrations were studied. The intensity parameters Ωt （t = 2, 4, 6）, spontaneous emission probability, fluorescence lifetime, radiative quantum efficiency, fluorescence branching ratio, and stimulated emission cross section were calculated using the Judd-Ofelt theory. The optimal Nd^3＋ concentration in high silica glass was 0.27% （mole fraction） because of its high quantum efficiency and emission intensity. By comparing the spectroscopic parameters with other Nd^3 ＋- doped oxide glasses and commercial silicate glasses, the Nd^3 ＋ -doped high silica glasses are likely to be a promising material used for high power and high repetition rate lasers.

Guiding properties of proton-implanted Nd^(3+)-doped phosphate glass waveguides

We report on the fabrication and properties of an optical waveguide in Nd^(3+)-doped phosphate glass.The planar waveguide was obtained by 550-ke V proton implantation with a dose of 8.0×10^(16)ions/cm^(2).The proton–glass interaction was simulated by the stopping and range of ions in matter(SRIM software).The characteristics of the waveguide including the refractive index profile and the near-field intensity distribution were studied by the reflectivity calculation method and the end-face coupling technique.The optical waveguide demonstrated multi-mode behavior at the wavelength of 632.8 nm.The propagation features of the proton-implanted Nd^(3+)-doped phosphate glass waveguide shows its potential to operate as an integrated photonic device.

Growth and Spectral Properties of Nd^(3+) Doped KLa(MoO_4)_2 Crystal

Nd^3＋ doped KLa（MoO4）2 single crystal with the size up to Ф25 × 40 mm^3 was grown by the Czochralski technique. The absorption and luminescence spectra of trivalent neodymium in KLa（MoO4）2 crystal were investigated at room temperature. The absorption and emission cross 10-20 sections are 3.02 ×10^-20 cm^2 at 808 nm and 20.01 × 10^-2 cm^2 at 1061 nm, respectively. The fluorescence lifetime is 164μs at room temperature.

B掺杂对单层g-C_(3)N_(4)光催化性能调控机制的第一性原理研究

光催化技术以太阳能为驱动,在环境治理、氢能制备等领域具有十分广阔的应用前景。g-C_(3)N_(4)是一种极具潜力的绿色光催化剂,但其有限的可见光响应范围以及较宽的能隙限制了其光催化性能的进一步提高。非金属元素掺杂是一种有效提升g-C_(3)N_(4)光催化活性的方法,采用第一性原理计算的方法研究了B元素掺杂对g-C_(3)N_(4)光催化活性的影响机理,考察了掺杂前后的电子结构以及光学性能。结果表明,g-C_(3)N_(4)(001)表面的H位点是B原子掺杂的最稳定位点,掺杂能为-7.81 eV,B元素的加入使g-C_(3)N_(4)(001)表面的能隙从未掺杂的1.468 eV降低到了0.732 eV,功函数从4.055 eV降低到3.108 eV,并提高了表面C原子的反应活性,从而使得g-C_(3)N_(4)(001)表面的光催化活性得到了有效地提高。光学性质研究表明,B元素的加入使得g-C_(3)N_(4)(001)表面发生了明显的“红移”现象,使表面的光响应能力得到了提高,从而获得了更高的光催化能力。

Ce^(3+)掺杂一维多孔SnO_(2)纳米材料的模板合成及光致发光性能

以四氯化锡为金属源,P123为造孔剂,尿素为沉淀剂,无水乙醇为溶剂制备前躯体,以多孔阳极氧化铝(AAO)为模板合成了一维多孔SnO_(2)纳米材料,并采用多种手段进行表征。结果表明:所合成的一维SnO_(2)纳米材料直径大小均匀,具有多孔和四方晶相结构,Ce^(3+)离子通过掺杂的方式使其具备良好的光致发光性能。

CuO掺杂C_(3)N对C_(5)F_(10)O分解组分吸附性能的第一性原理研究

全氟五碳酮(C_(5)F_(10)O)作为可替代SF_(6)的新型环保绝缘气体已被投入到实际应用中.当绝缘设备内部发生局部放电等故障时,C_(5)F_(10)O会分解产生弱绝缘性的CF_(4)、C_(2)F_(6)以及剧毒的CF_(2)O、HF等有害组分,为保证绝缘设备的安全运行,需有选择地通过吸附去除这些分解组分.新型类石墨烯C_(3)N材料在气体吸附领域具有良好的应用前景,文中基于第一性原理计算了CuO分子掺杂C_(3)N对主要分解组分CF_(4)、C_(2)F_(6)及剧毒产物CF_(2)O、HF的吸附过程,计算并分析了各分解组分吸附时的吸附能、态密度、电荷转移量、差分电荷密度以及不同环境温度下的恢复时间.结果表明,CuO-C_(3)N对HF表现出良好的吸附性,CF_(2)O次之,但其无法吸附CF_(4)与C_(2)F_(6),因此CuO-C_(3)N可以作为一种高性能的气体吸附剂对C_(5)F_(10)O绝缘设备内的剧毒分解组分HF进行吸附去除.

Effect of Er substituting sites on upconversion luminescence of Er^(3+)-doped BaTiO_3 films

Erbium-doped BaTiO3 films on LaNiO3/Si substrates were fabricated by sol-gel method. The crystalline structure, morphologies and upconversion （UC） luminescence properties of films were respectively investigated by X-ray diffraction （XRD）, atomic force microcopy （AFM） and photoluminescence （PL）. The results indicate that both of the microstructure and luminescence are found to be dependent on Er^3＋ substituting sites. The samples with A-site substitution have smaller lattice constants, larger grains and smoother surface than those with B-site substitution. The photoluminescence spectra show that both of the samples have two stronger green emission bands centered at 528 and 548 nm and a weak red emission band centered at 673 nm, which correspond to the relaxation of Er^3＋ from ^2H11/2, ^4S3/2, and ^4F9/2 levels to the ground level ^4I15/2, respectively. Compared with B-site doped films, A-site doped films have a stronger integrated intensity of green emissions and a weaker relative intensity of red emissions. The differences could be explained by the crystalline quality and cross relaxation （CR） process.

Preparation of Zr-doped CaTiO_3 with enhanced charge separation efficiency and photocatalytic activity

A series of Zr-doped CaTiO3 powders were prepared with the mild co-precipitation method and calcined at 850℃ for 3 h. The as-prepared Zr-doped CaTiO3 samples were characterized by scanning electron microscopy （SEM）, X-ray diffraction （XRD）, UV-Vis diffuse reflectance spectra （DRS） and X-ray photoelectron spectra （XPS）. XRD result revealed the presence of single perovskite phase of CaTiO3. UV-Vis diffusive reflection spectra of Zr-doped CaTiO3 indicated that the absorbance obviously increased in the visible light irradiation. XPS analysis showed that two types of oxygen existed on the photocatalyst surface, including lattice oxygen and absorbed oxygen. Their photocatalytic activity in the case of the degradation of methyl orange in water and photoelectrochemical activity were also tested. The 5%Zr-doped （mole fraction） CaTiO3 sample showed the highest photocatalytic activity. The enhanced photocatalytic activity was ascribed to the change of the lattice structure, existence of oxygen vacancies and increase of the photogenerated charge separation efficiency.

溶液燃烧法制备Nd^(3+)掺杂LaBO_(3)荧光粉

以La(NO_(3))_(3)·6H_(2)O、H_(3)BO_(3)为原料、C_(2)H_(5)NO_(2)为燃烧剂、Nd(NO_(3))_(3)·6H_(2)O为改性剂,通过溶液燃烧法合成Nd^(3+)掺杂LaBO_(3)荧光粉。通过X射线衍射(XRD)、扫描电子显微镜(SEM)、紫外-可见漫反射光谱(UV-Vis DRS)以及荧光光谱(PL)对产物进行表征分析。结果表明,制备的粉体均为正交晶系硼酸镧,在煅烧温度875℃、Nd^(3+)掺杂量3%的优化条件下制备的硼酸镧荧光粉发光性能最好,且其在紫外光区和可见光区均表现出良好的光吸收性能,发蓝绿色光,可广泛应用于激光照明和LED照明等领域。

Nd^(3+)、Sm^(3+)和Eu^(3+)单掺杂NiTiO_(3)的光电磁性能

采用溶胶−凝胶法合成纳米Ni_(1−x)R_(x)TiO_(3)(R=Nd、Sm和Eu,x=0、0.05和0.1)粉末,结合X射线衍射、扫描电子显微镜、X射线光电子能谱、拉曼光谱及综合物性测量系统等表征技术,系统研究了Nd、Sm和Eu掺杂对钛酸镍(NiTiO_(3))微观结构和光电磁性能的影响。结果表明:所有样品均出现O—Ti键和O—Ni键的电荷转移(200~365 nm),Ni^(2+)的^(3)A_(2g)(^(3)F)→^(3)T_(1g)(^(3)P)自旋容许跃迁(450 nm),^(1)T_(2g)(^(1)D)、^(1)A_(1g)(^(1)G)的自旋禁阻跃迁(490~520 nm)以及^(1)E_(g)(^(1)D)的自旋禁阻跃迁(743 nm)。Nd掺杂样品的吸收光谱在588 nm附近出现与八面体位置Nd^(3+)电子跃迁有关的吸收峰,样品从黄色变为绿色。所有样品均在室温下表现出反铁磁性和铁电性,且Ni位掺杂Nd、Sm和Eu能显著增强NiTiO_(3)的铁电性。掺杂离子半径较大的元素导致晶格畸变,促进铁电畴的转动,增强铁电性。

非贵金属掺杂改性g-C_(3)N_(4)光催化分解水制氢的研究进展

光催化裂解水产氢是缓解能源危机和环境污染两大难题最有前景的技术之一。石墨相氮化碳(g-C_(3)N_(4))以其合适的带隙宽度、丰富的活性位点和成本低廉等优点,近年已成为极具有应用前景的光催化材料。然而,单一g-C_(3)N_(4)的可见光响应范围窄、电子-空穴复合严重、光催化产氢效率低等问题制约了其在光催化领域的应用。对g-C_(3)N_(4)进行形貌调控、表面改性、元素掺杂、构建异质结是改善其光催化性能的有效策略。介绍了目前金属掺杂改性g-C_(3)N_(4)复合材料常见的制备方法,归纳了碱金属、过渡金属及稀土金属等非贵金属掺杂改性g-C_(3)N_(4)基复合材料的光催化水解制氢相关研究进展,旨在为光催化分解水制氢方面提供参考。

Mn^(2+)掺杂对YAG∶Ce^(3+)荧光陶瓷发光性能的影响

过渡族金属Mn^(2+)掺杂的石榴石荧光陶瓷被认为是实现高显色激光照明的候选材料。然而,由于Mn^(2+)在不同配位环境下离子半径的多样性,Mn^(2+)掺杂石榴石陶瓷体系设计方案尚不明确。本文采用真空烧结技术制备得到不同浓度Mn^(2+)掺杂的YAG∶Ce^(3+)荧光陶瓷,并将Mn^(2+)分别设计进入八面体(OC)和十二面体(DO)格位。通过表征样品物相和显微结构、光致发光、荧光寿命、量子效率等,并通过LD激光器激发对荧光陶瓷的发光性能进行研究。实验结果表明,在添加电荷与体积补偿剂SiO_(2)的前提下,相比Mn^(2+)进入十二面体格位,Mn^(2+)进入八面体后石榴石的晶体结构更加稳定。因此,当Mn^(2+)的浓度控制在0.5%^(6)%(at)范围内,OC系列样品的量子效率高于DO系列样品。此外,OC系列样品的PL谱中位于588 nm和725 nm处的发射峰分别对应于Mn^(2+)占据八面体和十二面体格位的^(4)T_(1)→^(6)A_(1)电子跃迁,而DO系列样品中位于572 nm处的发射峰则源于Mn^(2+)占据扭曲的十二面体格位产生的电子跃迁。得益于Ce^(3+)→Mn^(2+)间高效的能量传递,将浓度为6%(at)的Mn^(2+)设计进入YAG∶Ce^(3+)中八面体格位制得荧光陶瓷,封装得到的激光白光光源的显色指数为70.8,相对色温为5117 K。本文对于Mn^(2+)掺杂的石榴石发光材料的开发研究是有力补充,也为提升YAG∶Ce^(3+)荧光陶瓷光谱中的红光成分,进而提高医疗、显示等领域的激光光源的显色性能提供借鉴。