掺铈Cs_(2)BaBr_(4)晶体的生长和闪烁性能研究

以高纯度BaBr_(2)、CsBr、CeBr_(3)为原料,采用高温固相反应法合成了Cs_(2)BaBr_(4)∶1%Ce^(3+)多晶料,并通过坩埚下降法生长了Cs_(2)BaBr_(4)∶1%Ce^(3+)晶体。将晶体切割研磨抛光后得到不同厚度的Cs_(2)BaBr_(4)∶1%Ce^(3+)晶片。对晶体进行了物相分析,XRD图谱表明晶体为一致熔融物,且无相变。研究了晶体的闪烁性能,测试了光学透射率、光致发光、X射线激发发光、多通道gamma能谱、衰减时间。与LaBr_(3)晶体对比,分析了晶体的吸湿性。结果表明,晶体的光学透过率接近80%,在一定波段的紫外光及X射线的激发下,晶体在349与372 nm波长有发射峰。^(137)Cs源伽马射线的激发下,能量分辨率为11%,在紫外激发下,晶体衰减时间为21.9 ns。晶体的吸湿性比LaBr_(3)晶体有大幅改善。

Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体的光谱分析及中红外发射增强

采用非化学计量配比的提拉法成功生长出Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体、Er^(3+)/Yb^(3+):SrLaGaO_(4)和Er^(3+):SrLaGaO_(4)晶体并进行了详细的光谱分析,同时对纯的SrLaGaO_(4)晶体进行了热学性能分析。与Er^(3+):SrLaGaO_(4)晶体相比,Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体不仅展示了更好的吸收特性,而且还表现出较弱的近红外发射,以及优异的中红外发射;Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体中2.7μm铒激光下能级4I13/2的荧光寿命显著减少,而上能级4I11/2的寿命略微下降,成功抑制了自终止效应。此外,本工作还研究了Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体中Yb^(3+)的敏化作用和Pr^(3+)离子的去激活作用以及能量传递机制。总之,引入Yb^(3+)和Pr^(3+)有利于在Er^(3+)/Yb^(3+)/Pr^(3+):SrLaGaO_(4)晶体中实现增强的2.7μm发射,这使其成为中红外激光有前途的候选材料。

Synthesis of energetic coordination polymers based on 4-nitropyrazole by solid-melt crystallization in non-ionization condition

Based on the theory of crystallization,a solvent-free solid-liquid phase crystallization method called solid-melt crystallization was designed to prepare energetic coordination polymers.Two target compounds[Cu(NPyz)_(4)NO_(3)]·NO_(3)(ECPs-1)and Cu(NPyz)_(4)(ClO_(4))_(2)(ECCs-2)were prepared through programmed heating and cooling by using 4-nitropyrazole(NPyz),(Cu(NO_(3))_(2)·5H_(2)O and Cu(ClO_(4))_(2)·5H_(2)O) as raw materials.In addition,crystallization pre-experiments and annealing experiments also verified the feasibility of the method.Their structures were confirmed by IR,elemental analysis,single-crystal X-ray diffraction and powder X-ray diffraction.The physicochemical properties and sensitivity test results showed that ECCs-2 has better thermal stability(T_(d)=221℃),while ECPs-1 is less sensitive to mechanical stimuli(IS=12 J,FS=240 N).Calculations based on EXPLO5 and the Kamlet-Jacobs equation showed that ECCs-2 has more considerable detonation performance(P=25.2 GPa,D=7.5 km/s).In comparison,the more intuitive results from the HN test,flame test,thermal resistance test and lead plate explosion test revealed that ECCs-2 has an“acceptable”detonation performance.The laser detonation test also showed that ECCs-2 is a promising excellent laser detonation material(E=408 mJ,P=24 W,τ=17 ms).

基于共沉积法的高结晶反蛋白石g-C_(3)N_(4)制备及其产氢性能分析

为获得光催化产氢性能优异的g-C_(3)N_(4),采用共沉积法,通过二氧化硅微球/单氰胺混合溶液制备具有高结晶反蛋白石结构的g-C_(3)N_(4),并通过扫描电镜、X射线衍射仪、红外光谱仪和比表面积及孔径分析仪等表征手段对其结构和形貌进行分析,采用气相色谱仪对其光催化产氢性能进行表征。结果表明:当二氧化硅微球/单氰胺混合溶液的离心速率为5500r/min和单氰胺溶液质量分数为70%时,所制备的高结晶反蛋白石结构的g-C_(3)N_(4)(CN5500-70%)层间距为3.23Å,比表面积为32m^(2)/g,光催化产氢性能显著提升,产氢速率为7217.01μmol/(g·h)。该方法制备的高结晶反蛋白石结构g-C_(3)N_(4)具有良好的结晶性和优异的光催化产氢活性,为g-C_(3)N_(4)基催化材料的实际应用提供参考。

大尺寸优质Cr^(3+)∶BeAl_(2)O_(4)晶体生长与性能研究

本文采用感应加热提拉法结合上称重自动控径技术,成功生长出大尺寸、高质量的翠绿宝石(Cr^(3+)∶BeAl_(2)O_(4))晶体。晶坯等径圆柱体尺寸达到ϕ70 mm×140 mm,晶坯质量超过2800 g。通过冷光源照射晶坯,发现晶坯中心区域ϕ10~15 mm存在气泡。采用5 mW绿光激光照射ϕ8 mm×130 mm的翠绿宝石晶体棒,晶体内部无散射颗粒。利用Zygo激光平面干涉仪对晶体棒进行测试,波前畸变为0.3λ@632.8 nm。用电感耦合等离子体原子发射光谱法测定了翠绿宝石晶体的铬离子掺杂浓度,并计算出轴向浓度梯度为0.5×10^(-4)~1.9×10^(-4)cm^(-1)(摩尔分数)。用Perkin Elmer Lambda-950紫外可见近红外分光光度计测试了不同掺杂浓度的翠绿宝石晶体在室温下的吸收光谱,并计算了吸收系数。这些研究结果为翠绿宝石晶体的应用提供了重要的基础数据。

6-氟-4-羟基-3-氧代-3,4-二氢喹喔啉-1(2 H)-羧酸叔丁酯的合成、晶体结构及抗肿瘤活性研究

喹喔啉类化合物由于具有显著的生物活性而被广泛应用于医药、化工领域,特别是抗癌药物研发领域。本文通过四步反应法首次合成了6-氟-4-羟基-3-氧代-3,4-二氢喹喔啉-1(2 H)-羧酸叔丁酯,经溶液结晶法获得其单晶体。晶体学分析表明,该化合物属单斜晶系,空间群C2/c,晶胞常数a=1.28663(10)nm,b=2.25249(17)nm,c=1.01564(7)nm,Z=8,ρ_(c)=1.359 g·cm^(-3),R=0.0538,R_(w)=0.1406。在B3LYP/6-311+G(2d,p)模式下使用密度泛函理论(DFT)计算了该化合物的最佳结构,与X射线单晶衍射确定的晶体结构基本一致。抗肿瘤活性研究表明其有良好的抗肿瘤作用。此外,通过DFT计算了分子的静电势和前沿分子轨道。

Analyses of Reaction Mechanisms among Different Sulfonation Reagents and m-Diphenylamine and Crystal Structures of the Formed Compounds

In the traditional process, m-phenylenediamine reacts with fuming sulfuric acid at high temperature to get intermediates, and then after dehydration occurs intramolecular rearrangement to get 2,4-diaminobenzenesulfonic acid. Traditional methods need to consume a lot of fuming sulfuric acid or concentrated sulfuric acid, resulting in high industrial large-scale production cost, more waste, and posing a serious environmental pollution risk. In this thesis, three different sulfonation reagents were used for the sulfonation reaction of m-phenylenediamine, and the reaction mechanisms and crystal structures of the three pathways were investigated. The three routes are: 1) one-step synthesis of monosulfonated compound 1 from raw material and sulfur trioxide (SO3);2) rapid reaction of raw material and chlorosulfonic acid to synthesize bisulfonated compound 2;3) direct eutectic crystallization of raw material and ordinary sulfuric acid to obtain compound 3. The crystal structure of the compounds synthesized by three paths was analyzed by X-ray single crystal diffraction, and compound 1 was characterized by NMR, Fourier infrared spectra, UV-visible spectrum and Mass spectrometry. The one-step synthesis of SO3 as a sulfonation reagent has the advantages of mild reaction conditions, simple operation and low cost.

Growth,defects,and properties of GdCa4O（BO3）3 and Nd：GdCa4O（BO3）3 crystals

Pure and neodymium-doped gadolinium calcium oxoborate crystals of high quality were grown by the Czochralski method.The orientation of crystal was precisely determined,and the samples for measurements were prepared.Through synchrotron x-ray topography and high-resolution x-ray diffractometry,the twin structure was discovered.Some properties such as the figure of merit value,and dielectric,piezoelectric,and elastic constants were meausured along with a discussion of the anisotropy of the laser properties.

Growht and defects in YbxY1—xAl3（BO3）4 crystals

YbxY1-xAl3(BO3)4(x=0.1,0.07 and 0)crystals have been grown by the flux method.The growth defects of YbxY1-xAl3(BO3)4 crystals were detected by X-ray topography.It is found that the perfcetion of YbYAB crystal with low Yb dopant is better than that with high Yb dopant.In Yb0.1Y0.9Al3(BO3)4 crystal,growht bands,growth boundaries,grown-in dislocations and inclusions were observed.Howver,the densities of growth defects for Yb0.07Y0.93Al3(BO3)4 and YAl3(BO3)4 are low and no obvious inclusions are observed in these crytals.In addition,growth twins wrer detected in YbxY1-xAl3(BO3)4 crystal by using the chemical etching method.It is found that the growth twins occur frequently in Yb0.01Y0.9Al3(BO3)4 crystal whereas no growth twin appears in YAl3(BO3)4 crystal. Based on the experimental observations,the formation mechanism of growth twins is discussed.In the meantime,the effective measures for reducing the growth twins and defects are proposed.2001 Elsevier Science B.V.All rights reserved.

Characterization of Growth Defects in Nd:YCa4O(BO3)3 Crystals by Transmission Synchrotron Topography

The growth detects in Nd:YCa4O(BO3)3(Nd:YCOB) crystals were investigated by transmission synchrotron topography.It was found that growth striations were the primary defects in Nd:YCOB crystals.Grown-in dislocations.mosaic blocks and inclusions were also obsered in the crystals.The effect of temperature field on the formation of growth defects in the crystals was discussed.

Image shifts resulting from the misorientation of two individuals in GdCa4O（BO3）3 crystal

Large GdCa4O(BO3)3 crystal has been grown by the Czochralski method.The quality of GdCa4(BO3)3 crystal was assessed by white-beam synchrotron radiation topography.It has been found that there is a sub-grain boundary in the GdCa4O(BO3)3 crystal.The boundary divides the large GdCa4O(BO3)3 crystal into two individuals.Due to the misorientation between the two individuals,the image shifts can be observed in the synchrotron topopraphs.Based on the misorientation determined by high resolution X-ray diffractometer,the image shifts were calculated for several reflections.The calculations are in agreement with the measurements from the topogrphs very Well.In addition,the formation mechanism of sub-grain boundary is discussed.2001 Elsevier science B.V.All rights reserved.

GdAl3(BO3)4及其Yb^3＋激活激光晶体的研究

采用顶部籽晶法从K2Mo3O10-B2O3助熔剂体系中生长出尺寸达到20mm的GdAl3(BO3)4(简称GAB)和Yb3+激活的晶体。测试了GAB晶体的〈100〉和〈001〉轴向热膨胀系数,确定了透光波长范围,计算了有效倍频系数和相位匹配角随波长的变化,结果表明GAB晶体在整个透光范围内均可实现相位匹配。测定了Yb3+:GAB晶体在室温下的偏振吸收和荧光光谱,进行了光谱计算,测试了晶体的激光性能,在1046nm处实现了2.1W激光输出,斜率效率达到58%。

GdAl3（BO3）4和Nd离子掺杂的倍频与自变频激光晶体研究

采用熔盐顶部籽晶法从K 2 Mo 3 O 10-B 2 O 3助熔剂中生长出尺寸为20 mm的优质GdAl 3(BO 3)4(简称GAB)和Nd^3+激活的自变频激光晶体。确定了GAB晶体的透光波长范围、折射率和倍频系数随波长的变化,结果表明其在整个透光范围内均可实现相位匹配。测定了Nd^3+∶GAB晶体在室温下的偏振吸收、荧光光谱和荧光寿命,进行了光谱计算,测试了晶体的自变频激光性能,实现了紫外-可见光-红外-中红外多波段激光输出。

N^＋(N=Li,Na,K)对发光材料M3(M=Ca,Sr,Ba)Y2(BO3)4：Eu^3＋光谱的影响

采用高温固相反应方法在空气中制备了M3(M=Ca,Sr,Ba)Y2(BO3)4∶Eu3+红色发光材料,测量结果显示,材料的主发射峰均位于613 nm处,监测613 nm发射峰时,所得材料的激发光谱相同。研究了Li+,Na+和K+对M3(M=Ca,Sr,Ba)Y2(BO3)4∶Eu3+材料激发与发射光谱的影响,结果显示,加入Li+,Na+和K+后,M3(M=Ca,Sr,Ba)Y2(BO3)4∶Eu3+材料的激发与发射光谱的峰值位置并不发生变化,但材料的激发与发射光谱的峰值强度均得到了不同程度的增强。在Li+,Na+和K+掺入浓度相同的条件下,研究发现,与加入Na+和K+时相比,加入Li+时,M3(M=Ca,Sr,Ba)Y2(BO3)4∶Eu3+材料的激发与发射光谱的峰值增强效果最明显。进而研究了Sr3Y2(BO3)4∶Eu3+材料发射峰强度随Li+掺杂浓度的变化情况,结果表明,随着Li+掺杂浓度的增大,Sr3Y2(BO3)4∶Eu3+材料发射峰强度先增大后减小,在Li+浓度为5 mol%时到达峰值,约为未掺杂时的两倍。

Er^3＋／Yb^3＋：Sr3Y2(BO3)4晶体的光谱和激光性质

采用提拉法生长了双掺Yb3+和Er3+离子浓度分别为18.63%和0.87%(原子分数)的Sr3Y2(BO3)4晶体。利用测量的偏振吸收谱结合Judd-Ofelt理论,拟合得到了该晶体中Er3+离子的偏振和有效J-O参数。测量了Er3+离子4I13/2能级和Yb3+离子2F5/2能级的荧光衰减曲线,并计算了4I13/2能级的荧光量子效率和Yb3+到Er3+的能量传递效率。利用Fuchtbauer-Ladenberg公式计算了Er3+离子4I13/2→4I15/2跃迁的偏振受激发射截面。在平-凹谐振腔中,利用970 nm波长光纤耦合准连续半导体激光端面泵浦1.12 mm厚的该晶体,当输出镜透过率为1.5%时,获得了最大输出功率为1.3 W和斜率效率为20%的1560 nm附近的激光输出。结果表明,Er3+/Yb3+:Sr3Y2(BO3)4晶体是一种优良的1.5～1.6μm波段激光的增益介质。

Er^(3+),Yb^(3+)∶Ba_(3)Gd(PO_(4))_(3)晶体的生长、光谱和1.5μm激光性能

采用提拉法生长了1.85%Er,23.95%Yb∶Ba_(3)Gd(PO_(4))_(3)和1.95%Er,55.73%Yb∶Ba_(3)Gd(PO_(4))_(3)两种晶体(式中Er、Yb浓度为原子数分数)。测量并分析了晶体在室温下的吸收系数谱、上转换荧光谱、发射截面谱、增益截面谱和荧光衰减曲线。1.85%Er,23.95%Yb∶Ba_(3)Gd(PO_(4))_(3)晶体在峰值荧光波长1537 nm处的发射截面、Er^(3+)的4 I 13/2多重态荧光寿命和Yb^(3+)→Er^(3+)的能量传递效率分别为0.54×10^(-20)cm^(2)、9.9 ms和90%;1.95%Er,55.73%Yb∶Ba_(3)Gd(PO_(4))_(3)晶体在峰值荧光波长1537 nm处的发射截面、Er^(3+)的4 I 13/2多重态荧光寿命和Yb^(3+)→Er^(3+)的能量传递效率则分别为0.58×10^(-20)cm^(2)、9.7 ms和93%。基于975 nm半导体激光端面泵浦,在1.85%Er,23.95%Yb∶Ba_(3)Gd(PO_(4))_(3)晶体中实现了97 mW最高功率和27.1%斜效率的1567 nm连续激光输出,在1.95%Er,55.73%Yb∶Ba_(3)Gd(PO_(4))_(3)晶体中实现了93 mW最高功率和17.1%斜效率的1567 nm连续激光输出。

Efficient Near-Infrared Quantum Cutting in Tm3＋/yb3＋ Codoped LiYF4 Single Crystals for Solar Photovoltaic

Downconversion （DC） with emission of two near-infrared photons about 1000 nm for each blue photon absorbed was obtained in thulium （Tm3＋） and ytterbium （Yb3＋） codoped yt- trium lithium fluoride （LiYF4） single crystals grown by an improved Bridgman method. The luminescent properties of the crystals were measured through photoluminescence excitation, emission spectra and decay curves. Luminescence between 960 and 1050 nm from yb3＋： 2Fs/2--＋2FT/2 transition, which was originated from the DC from Tm3＋ ions to Yb3＋ ions, was observed under the excitation of blue photon at 465 nm. Moreover, the energy transfer processes were studied based on the Inokuti-Hirayama model, and the results indicated that the energy transfer from Tm3＋ to Yb3＋ was an electric dipole-dipole interaction. The max- imum quantum cutting efficiency approached with 0.49mo1% Tm3＋ and 5.99mo1% Yb3＋. increasing the energy efficiency of crystalline energy part of the solar spectrum. up to 167.5% in LiYF4 single crystal codoped Application of this crystal has prospects for Si solar cells by photon doubling of the high

NdxY1—xAl3（BO3）4（NYAB）系列晶体中的生长缺陷

采用同步辐射白光形貌术结合化学腐蚀法研究了TNAB系列晶体NdxGd1-xAl3(BO3)4(NGAB)和YbxY1-xAl3(BO3)4(YbYAB）晶体中的生长缺陷。发现生长孪晶是该系列晶体中普遍存在的缺陷。NGAB晶体中的孪晶为180°旋转孪晶，操作轴为[0001]轴，即结构的三次对称轴，该孪晶以结构因子的衬度出现在X射线形貌像中：而YbYAB晶体中的孪晶则为反演孪晶，主晶与孪晶的结构互为中心对称。该孪晶在X射线形貌像中不出现畸的衬底，而仅出现界面的运动学衬度。