Tm3+/Ho3+掺杂的Gd3Ga5O12～2.0μm波段红外激光晶体的生长和性能研究

采用提拉法生长了最大尺寸为φ25mm×(30～40)mm优质透明的Tm3+:GGG、Yb3+/Tm3+:GGG、Cr3+/Tm3+:GGG、Tm3+/Ho3+:GGG和Cr3+/Tm3+/Ho3+:GGG共五种晶体.在室温下测试了这些晶体的吸收光谱、荧光光谱及荧光衰减曲线等,详细研究了光谱性能,对部分晶体进行了Judd-Ofelt理论计算,得到强度参数等重要的光谱参数.计算了～2.0μm附近荧光峰值波长处相应的能级跃迁的发射截面、量子效率等.研究表明:Yb3+和Cr3+的掺入分别使得Tm:GGG晶体在980nm附近和451 nm、628 nm附近的吸收大大增强,有利于商业激光二极管和闪光灯泵浦.在Tm激活的Tm3+:GGG、Yb3+/Tm3+:GGG、Cr3+/Tm3+:GGG晶体中,～2.0μm波段附近发射强度和发射截面值最大的峰值对应的波长为2000nm;而在Ho激活的Tm3+/Ho3+:GGG和Cr3+/Tm3+/Ho3+:GGG晶体中,发射强度和发射截面最大的峰值对应的波长为2080 nm.用氙灯抽运键合的尺寸为φ5mm×45mm Cr3+/Tm3+/Ho3+:Gd3+ Ga5 O12晶体,在2.086～2.102μm波段实现了平均功率为170 mw的激光输出.     

Cr:iSrAlF6晶体生长及其性能表征

本文报道了布里奇曼法生长的高品质Cr:iSrAlF6 晶体及其激光特性.采用固相氟化反应除去原料中的氧化物和水.在较小的温度梯度和较慢的生长速率下生长出的Cr:iSrAlF6晶体尺寸达到φ20mm×130mm.均匀的Cr3+掺杂浓度为1～15mol;.从XRD谱图计算出的Cr:iSAF晶体点阵参数为a=0.502nm,c=0.967nm.测试了晶体的吸收曲线,并分析了其吸收与能带结构的关系.实现了闪光灯泵浦的Cr:iSAF激光器运转,激光转换斜效率达到5.85;.     

晶体(NH4)2C4H4O6:VO2+的EPR参量及局域结构的研究

采用叠加模型和双旋-轨耦合参量模型,建立了结构参数与EPR参量之间的定量关系;较好地解释了[VO(H2O)5]2+络离子的局域结构和EPR参量;研究结果发现,(NH4)2C4H4O6:VO2+晶体中络离子[VO(H2O)5]2+的键长为R//≈0.130nm,R⊥≈0.195nm;在(NH4)2C4H4O6:VO2+晶体中,局域结构沿C4轴方向呈压缩的八面体结构;所得EPR参量的理论计算与实验测量数据符合很好.     

Cr:LiSrAlF_6 晶体生长及其性能表征(英文)

本文报道了布里奇曼法生长的高品质Cr:LiSrAlF6晶体及其激光特性。采用固相氟化反应除去原料中的氧化物和水。在较小的温度梯度和较慢的生长速率下生长出的Cr:LiSrAlF6晶体尺寸达到2 0mm× 130mm。均匀的Cr3 +掺杂浓度为 1～ 15mol%。从XRD谱图计算出的Cr:LiSAF晶体点阵参数为a =0 .5 0 2nm ,c =0 .96 7nm。测试了晶体的吸收曲线 ,并分析了其吸收与能带结构的关系。实现了闪光灯泵浦的Cr:LiSAF激光器运转 ,激光转换斜效率达到 5 .85 %。     

可调谐激光晶体Cr:GSGG的光谱分析及晶场参数计算

用提拉法成功生长出了优质的Cr3+:Gd3Sc2Ga3O12晶体,测定了室温下的吸收光谱和不同温度下的荧光光谱,计算了晶场参数,发现荧光峰值及晶场参数与以前文献报道的均不相同.吸收光谱中,在458.5nm和642.5nm出现了较强的宽带吸收峰,分别对应于Cr3+的4A2→4T1和4A2→4T2的吸收跃迁,在678nm处又叠加了一个非常弱的吸收峰,对应于4A2→2T1的吸收跃迁.测试了晶体从7K到室温的荧光光谱和荧光寿命,在650～850nm范围内出现了宽带荧光,对应于Cr3+的4T2→4A2的发射跃迁.随着温度的升高,荧光峰向长波方向移动,荧光峰半高宽增大,室温下其荧光峰值在732nm,半高宽约为80nm.低温(7K)下的荧光谱中,在694nm处观察到了尖而锐的R线(零声子线),对应于Cr3+的2E→4A2的发射跃迁.由于温度猝灭效应,随着温度升高,晶体的荧光寿命降低,室温下荧光寿命约为114μs.计算了晶场强度参数Dq/B=2.49,4T2零声子能级与2E能级的间距△E为204cm-1,这些参数表明Cr3+处在较弱的晶场中,有利于4T2→4A2的宽带跃迁,Cr:GSGG晶体是较为理想的可调谐激光工作物质.     

Cr,Nd:GSAG晶体生长、光谱及LD泵浦激光性能研究

Cr,Nd:GSAG是一种性能优良的激光晶体,但是关于它的LD泵浦激光性能的研究很少.用提拉法生长了Cr,Nd:GSAG晶体,测定了它的化学成分、结构,初步测试了它的激光性能.晶体的(111)面X射线摇摆曲线半高全宽为0.055°.采用Rietveld方法精修X射线粉末衍射谱得到了Cr,Nd:GSAG晶体的原子结构参数、温度因子等.Cr,Nd:GSAG的最强吸收峰位于808.6nm处,吸收截面为3.38×10-20cm2.808nm光激发下,Cr,Nd:GSAG的最强发射峰位于1060nm,发射截面为6.04×10-20cm2,并测得激光上能级4F3/2的荧光寿命为274μs.利用808nm连续波LD泵浦实现了1060nm的激光输出,在输入功率为8.88W时,最大输出功率为0.513W,斜效率为6.73;,光-光转换效率为5.78;.此外还讨论了Cr,Nd:GSAG晶体中的Cr3+与Nd3+之间的能量传递机理.     

坩埚下降法生长近化学计量比Cr∶LiNbO_3晶体及光谱研究

以K2O为助熔剂,在较大的温度梯度(60～80℃/cm)条件下进行引种和晶体生长,应用坩埚下降法技术生长了Cr3+掺杂的近化学计量比的LiNbO3晶体。采用电感耦合等离子体原子发射光谱法(ICP-AES)分析了晶体的主要成分,其中Cr3+、Li2O、Nb2O3的含量分别为0.62mol%、49.23mol%和50.15mol%,并在FT-IR谱中观察到了因组分变化引起的OH-伸缩振动的变化。测定了晶体的吸收与发射光谱,观测到Cr3+在晶体中有两个宽且强的吸收带及两个微弱的吸收线,两宽带中心波长分别为480nm与658nm,对应于Cr3+的4A2→4T1与4A2→4T2两个具有相同的总自旋能级之间的跃迁,并观测到了微弱的684nm和728nm的R线吸收。同时测定了Cr3+∶LiNbO3晶体在670nm激发下的荧光光谱,是由4T2→4A2跃起所产生的850～1150nm的宽带荧光发射发光带,此发光带是由于取代Li+与Nb5+格位的Cr3+的4T2→4A2能级跃起的复合发光所致,并计算了该晶体的晶场强度以及Racah参数等。     

Cr4+,Yb3+:YAG晶体的生长及其吸收特性

用提拉法生长了Cr,Yb:YAG晶体,研究了在室温的吸收光谱特性以及氧化性气氛退火对其吸收特性的影响.在室温吸收光谱中存在着五大吸收带:在440nm和605nm存在着Cr3+离子的两个吸收带,而且退火使其发生了明显的"红移";在937nm和968nm处存在Yb3+离子的两个吸收带,能与InGaAs激光二极管(LD)有效耦合,适合激光二极管泵浦;而且在1.03μm处有一Cr4+离子的吸收峰,可用作可饱和吸收体,从而可以实现对Yb3+的自调Q激光输出.在氧化性气氛下退火对晶体吸收特性及缺陷的影响是:退火使晶体的缺陷明显减少而且使Cr4+浓度得到进一步的增加;Cr4+离子浓度的增加主要是由于二价阳离子Ca2+进入相应的Y3+晶格所造成.并且从晶格场的角度讨论了退火使Cr3+离子的吸收带发生"红移"的原因.     

高压与掺杂对KDP晶体能带结构的影响

构建了高压条件下KDP晶体的原子结构模型和掺杂有Li+、Na+、Rb+、Cs+、Be2、Mg2+、Ca2+、Cr3+、Co2+、Cu2+、Al3+、La3+等12种阳离子的KDP晶体超级原胞结构模型,采用第一性原理计算了高压下的KDP晶体的能带结构和态密度,研究了替位式掺杂的形成能以及不同掺杂离子对电子结构的影响.结果表明:KDP晶体的带隙宽度随着压强的增加呈线性增长趋势;Co2+、Cu2+、La3+等重金属离子具有较低的掺杂形成能而易于形成替位式掺杂;碱金属离子掺杂后其带隙比二价离子和三价离子替位掺杂情形大得多,且随原子序数增大而增大.文章还依据能带理论构建了材料的电导率和热导率与带隙的关联式,分析讨论了高压和掺杂对KDP晶体热导率和激光损伤的影响.     

晶体zinc 1-malate trihydrate∶Cu~(2+)的自旋哈密顿参量及局部结构的理论研究

在晶体场理论的基础上,利用四角对称3d9离子自旋哈密顿参量高阶微扰公式计算了Zinc 1-malate trihydrate:Cu2+的g因子(g//,g⊥)和超精细结构常数(A//,A⊥)。结果表明,由于Jahn-Teller效应,Zinc 1-malate trihydrate:Cu2+晶体中配体氧八面体沿C4轴方向伸长约0.0033 nm,络离子[CuO6]10-的键长R//≈0.2157 nm,R⊥≈0.2058 nm;局域结构沿C4轴方向呈伸长八面体结构。所得EPR参量理论计算与实验符合较好,并对上述结果进行了讨论。     

Crystal structure analyses of bis(triphenyl- phosphoranyliden)ammonium bis(pentafluoroethyl) argentate, [Ph3P=N=PPh3][Ag(C2F5)2] and bis[bis(triphenylphosphoranyliden)ammonium] tetrachloro-diargentate, [Ph3P=N=PPh3]2[ClAg(μ-Cl)2AgCl]

Bis(triphenylphosphoranyliden)ammonium bis(pentafluoroethyl)argentate, [Ph₃P=N= PPh₃][Ag(C₂F₅)₂] (1) and bis[bis(triphenylphosphoranyliden)ammonium]tetrachloro-diargentate, [Ph₃P=N=PPh₃]₂[ClAg(μ-Cl)₂AgCl] (2) were crystallized from the reaction mixture of pentafluoroethylsilver(I) and bis(triphenylphosphoranyliden)ammonium chlo-ride. Crystallization of 1 occurs in the centrosymmetric monoclinic space group P2₁/c (No. 14) with a = 17.083(2) Å, b = 11.600(2) Å, c = 19.833(2) Å, β = 109.66(1)°, V = 3700.8(7) ų, Z = 4. 2 crystallizes in the centrosymmetric orthorhombic space group Pbca (No. 61) with a = 19.540(1) Å, b = 15.926(1) Å, c = 20.160(1) Å, V = 6273.6(3) ų, Z = 8.     

Selective area laser deposition of FCC beta silicon carbide

Silicon Carbide (SiC) has been deposited onto an alumina substrate by the thermal decomposition of the gaseous precursor tetramethylsilane (TMS). A 500 W ytterbium fibre laser was used to heat the surface of an alumina substrate locally, resulting in deposition of SiC at the sample surface. The SiC deposit was analysed using energy dispersive X‐ray spectroscopy and X‐ray diffraction (XRD). The deposit was confirmed to be silicon carbide and found to be face centre cubic (FCC) crystal structure. Raman spectroscopy was used to measure the stoichiometry of the deposit which initially was found to be carbon rich. Further analysis by Raman spectroscopy suggests the deposit may be more stoichiometric following a two hour thermal treatment of the sample at 600 degrees celcius in an atmosphere of air.     

Structural characterization of a zinc(II) complex of a tris(oxime)amine ligand

The ligand tris(1-propan-2-onyl oxime)amine (TRISOXH₃) binds to zinc(II) acetate as a tridentate N₃ donor, with a third oxime group remaining unbound and extending into the crystal lattice. The crystal structure shows a distorted trigonal bipyramidal geometry around the zinc center. An intramolecular hydrogen bonding interaction between a coordinated oxime donor and an oxygen of a bound acetate is observed. This structure is similar to that of a previously reported zinc(II) complex of a related bis(oxime)amine ligand. However, the structure of Zn(TRISOXH₃)(OAc)₂ is different in ligand coordination mode and metal coordination number from those of the previously reported complexes Ni(TRISOXH₃)Cl₂ or [Ni(TRISOXH₃)(NO₃)(H₂O)]NO₃.     

Synthesis and characterization of ternary L-histidine complexes. Crystal structure of (2,2′-dipyridyl)-(L-histidinato-N,N′,O)copper(II) perchlorate 1.5 hydrate

A series of ternary complexes of copper(II), cobalt(II) and zinc(II) with L-histidine, 1,10-phenanthroline, 2,2-dipyridyl or imidazole having perchlorate or acetate as counterions were synthesized and characterized by conventional methods and for [Cu(bipy)(L-hist)]ClO₄·1.5H₂O and X-ray crystal structure was determined. The crystals belong to the monoclinic space groupC2 witha=18.843(3),b=10.582(2),c=11.020(2), =115.20(10)°,Z=4,R=0.0535. The structure is consistent of [Cu(bipy)(L-hist)]⁺ cations, perchlorate ions and water molecules. The geometry around copper is trigonal bipyramidal with one N,N,O tridentate L-histidine molecule and one 2,2-dipyridyl ligand, the apical sites are occupied by the -amino nitrogen [Cu–N(71) 1.995(8)] and by N(11) of 2,2-dipyridyl [Cu–N(11) 1.983(7)], the equatorial plane is formed by the N(3) imidazole -nitrogen [Cu–N(3) 2.140(6)], O(82) carboxylic oxygen [Cu–O(82) 2.009(5)] and N(22) [Cu–N(22) 2.010(7)].     

Palladium(II) and platinum(II) tetrakisthiourea dichloride bis(7-hydroxy-5-methyl[1,2,4]triazolo[1,5a]pyrimidine) dihydrate solvates

The title compounds palladium(II) and platinum(II) tetrakisthiourea dichloride bis(7-hydroxy-5-methyl[1,2,4]triazolo[1,5a]pyrimidine (Hmtpo)) dihydrate solvates, have been synthesized by reacting thecis-[MCl₂(Hmtpo)₂] (where M=Pt(II), Pd(II)) complexes with an excess of thiourea (tu) and the structure of the palladium compound was solved by X-ray diffraction. Crystals of [Pd(tu)₄]Cl₂·2Hmtpo·2H₂O are triclinic with space groupP and unit cell dimensionsa=7.972(1),b=9.049(1),c=11.808(2)Å, =88.20(1), =75.15(1), =76.54(1)^o. The cation [Pd(tu)₄]²⁺ is centrosymmetric involving four sulfur thiourea atoms in a near square planar environment. The triazolopyrimidine molecules, chloride anions and water molecules do not take part in the metal center coordination but interact by hydrogen bonding between them and the thiourea moieties. A comparison between powder diffraction data of palladium(II) and platinum(II) compounds clearly indicates that both compounds are isomorphous.     

Crystal structures of the cobalt(III), nickel(II), copper(II), and zinc(II) complexes of 2-thio-6-picoline N-oxide

Structures of the following compounds have been solved: tris(2-thio-6-picoline N-oxide)cobalt(III), [Co(6MOS)₃], orthorhombic, Pca2₁, a = 17.871(3), b = 14.061(2), c = 15.964(2) Å, V = 4011(1) ų, Z = 8, and = 1.193 mm^–1; bis (2-thio-6-picoline N-oxide)nickel(II), [Ni(6MOS)₂], orthorhombic, Pbca, a = 15.602(8), b = 13.606(4), c = 13.348(8) Å, V = 2833(4) ų, Z = 8, and = 1.655 mm^–1; bis(2-thio-6-picoline N-oxide)copper(II), [Cu(6MOS)₂], orthorhombic, Pbca, a = 13.914(5), b = 12.984(5), c = 15.663(6) Å, V = 2830(2) ų, Z = 8, and = 1.836 mm^–1; and bis(2-thio-6-picoline N-oxide)zinc(II), [Zn(6MOS)₂], triclinic, P – 1, a = 7.9737(8), b = 11.7786(9), c = 7.9206(8) Å, = 104.502(7), = 104.495(8), = 93.445(8)°, V = 691.3(1) ų, Z = 2, and = 2.106 mm^–1. The steric effect of the methyl group in the six-position of the N-oxide ring is considered in comparing these structures to complexes of 2-thiopyridine N-oxide.     

Structures of Bis(1-ethylbenzimidazol-2-yl)alkyl Copper(II) Dichlorides: An Unusual Cocrystallization

Abstract  Two structures containing pseudo-tetrahedral Cu(II)N₂Cl₂ coordination complexes are reported. The first molecular structure (A) of the compound, 1,1′bis(1-ethylbenzimidazol-2-yl)propane copper(II) dichloride (triEtBBIM)Cu(II)Cl₂, 1, is reported. The complex crystallized in the triclinic space group P-1 with a = 8.616(3) ?, b = 9.302(3) ?, c = 14.314(4) ?, α = 85.613(6)°, β = 85.170(6)°, γ = 66.117(6)° and V = 1044.1(5) ?³ with Z = 2. The second structure (B) contains 1 and (3,3′bis(1-ethylbenzimidazol-2-yl)pentane) copper(II) dichloride (tetEtBBIM)Cu(II)Cl₂, 2, both of which, cocrystallize in an equal molar ratio with a nitromethane solvate molecule. The complex crystallized in the monoclinic space group P2₁/c with a = 18.876(4) ?, b = 14.975(3) ?, c = 18.344(4) ?, β = 116.75(3)°, and V = 4630.3(16) ?³ with Z = 4. The cocrystallization of such discrete complexes has been coined a chemical Janus. Graphical Abstract  The title complexes contain pseudo-tetrahedral Cu(II)N₂Cl₂ coordination. One of the structures is the result of an unusual cocrystallization, in which two different discrete Cu(II) molecules cocrystallize in an equimolar ratio with a nitromethane solvate molecule.      

稀土焦硅酸盐Re2Si2O7闪烁晶体的研究进展

铈掺杂稀土焦硅酸盐系列晶体Re2Si2O7(其中Re=Lu3+、Y3+、Gd3+等)作为新型无机闪烁晶体材料,近来引起科研人员的关注.本文阐述了稀土焦硅酸盐系列晶体Re2Si2O7的结构、晶体生长方法、闪烁性能和有待进一步研究的问题.     

凝胶浇注法制备中温固体氧化物燃料电池Sm_(0.5)Sr_(0.5)Co_(1-x)Fe_xO_(3-δ)多孔阴极材料的研究

以碳酸盐和氧化物为原料,通过凝胶浇注法制得了Sm_(0.5)Sr_(0.5)Co_(1-x)Fe_xO_(3-δ)(SSCF, x=0～1.0)粉体,对不同温度煅烧所得粉体的相组成和微观形貌进行了测定.制备的Sm_(0.5)Sr_(0.5)Co_(1-x)Fe_xO_(3-δ)粉体模压成形后烧结得到SSCF烧结体.测定了烧结体的密度和孔隙率并对烧结体的微观结构进行了观测,用直流四端子法测定了烧结样品的电导率并对其热膨胀系数及电化学性能等进行了测定.结果表明:干凝胶在1000 ℃煅烧可以得到粒度均匀细小的SSCF粉体,其晶体结构随Fe含量发生变化;一定温度烧结的Sm_(0.5)Sr_(0.5)Co_(1-x)Fe_xO_(3-δ)材料具有多孔结构,随烧结温度的增加,烧结体的密度增大,孔隙率减小;Fe的掺杂降低了Sm_(0.5)Sr_(0.5)CoO_(3-δ)材料的热膨胀系数,Sm_(0.5)Sr_(0.5)Co_(0.2)Fe_(0.8)O_(3-δ)材料在800 ℃时的热膨胀系数为16.4×10~(-6) K~(-1);SSCF材料的电导率随Fe含量的增加而减小,但在500～800 ℃,其电导率均大于100 S·cm~(-1).此外,Sm_(0.5)Sr_(0.5)Co_(1-x)Fe_xO_(3-δ)材料均表现出良好的催化活性.     

Er~(3+)/Yb~(3+): KY(WO_4)_2晶体光谱的各向异性分析

在室温下测量和分析Er~(3+)/Yb~(3+): KY(WO_4)_2晶体三个折射率主轴方向上的吸收光谱和荧光光谱,其吸收光谱和荧光光谱谱带强度明显呈现各向异性;用修正的Judd-Ofelt理论计算Er~(3+)/Yb~(3+): KY(WO_4)_2晶体中Er~(3+)在三个折射率主轴方向上的强度参量Ω_t (t=2,4,6)和各吸收谱带的电偶极跃迁振子强度,同时计算了Yb~(3+)在三个轴向上980 nm波长处的积分吸收截面.结果表明:Er~(3+)/Yb~(3+): KY(WO_4)_2晶体吸收光谱和荧光光谱存在各向异性,N_p轴为Er~(3+)/Yb~(3+): KY(WO_4)_2激光晶体的最佳泵浦轴向.