Cu,Fe掺杂LiNbO_3晶体电子结构和光学性质的第一性原理研究

利用基于密度泛函理论的第一性原理对Cu,Fe单掺及共掺LiNbO_3晶体的电子结构和光学性质进行了计算.结果显示:Cu,Fe单掺杂LiNbO_3晶体禁带内均产生了杂质能级,主要由Cu3d,Fe3d轨道及O 2p轨道贡献;共掺LiNbO_3晶体禁带内出现了双能级结构,深能级由Cu3d和O2p轨道贡献,浅能级由Fe3d和O2p轨道贡献.Cu,Fe单掺和共掺LiNbO_3晶体带隙依次缩小,在可见光区的光吸收明显增强.共掺LiNbO_3在445和630nm左右分别表现出一个宽吸收峰,比单掺LiNbO_3晶体表现出更好的光吸收性质.研究表明,Fe占Nb位比Fe占Li位的双掺样品在双光存储应用中更有优势;同时,浓度比[Fe2+]/[Fe3+]值的适当降低有助于这种优势的形成.     

激光自倍频晶体研究和应用进展

激光自倍频晶体是一类同时具有激光和非线性效应的复合功能晶体。以激光自倍频晶体制作的全固态激光器具有体积小,调整方便,稳定性高等优点。自1970年代以来,以LiNbO3,YAl3(BO3)4倍频晶体为基质的激光自倍频晶体实现了自倍频激光运转。近年来,以RECa4O(BO3)3(RECOB)为基质的激光自倍频晶体受到重视和广泛研究。本文从对激光晶体、非线性光学晶体及激光自倍频晶体的基本要求出发,在综述激光自倍频晶体研究历史的基础上,讨论了激光自倍频晶体中的基波和倍频光,探讨了NYAB和Nd:GdCOB一类晶体中晶体长度,Nd3+浓度和效率之间的关系。理论估算表明,当浓度适当,晶体长度10mm时,这两类晶体的光–光转换效率可达30%以上。本文总结了NYAB系列晶体的研究历程及RECOB系列激光自倍频研究的思路及取得的成果。在最近10年中,利用山东大学生长的Yb:YAB晶体,获得1.1 W自倍频绿光,光光转换效率为10%;在RECOB体系中,比较了各种晶体的特点,选定Nd:GdCOB为主要研究对象,经过晶体掺钕浓度和长度关系,位相匹配方向、膜系及热工程等多方面研究,获得了1.36 W的545 nm绿光输出,光–光转换效率为17.1%;输出功率为1.03 W时,半小时功率波动不超过1%。这是目前为止,Nd3+离子激光自倍频晶体的最好结果。文章最后介绍了激光自倍频晶体的可能应用。通过理论和实验分析,认为到目前为止Nd:GdCOB是以Nd3+为激活离子最后的激光自倍频晶体,而在Yb3+为激活离子时,Yb:YAB晶体最佳。     

掺Gd3+的LiYF4∶Yb3+/Ho3+微米晶体制备以及在防伪中的应用研究

研究一种具有良好上转换发光性能的稀土掺杂发光材料,对于防伪技术领域具有非常重要的意义。为了改善LiYF₄∶Yb3+/Ho3+微米晶体的上转换发光性能,采用水热合成法成功制备了一系列Gd3+掺杂的LiYF₄∶Yb3+/Ho3+微米晶体,并采用X射线衍射(XRD)和扫描电子显微镜(SEM)对样品的相纯度和晶体形貌尺寸进行表征;在980 nm激光激发下,通过荧光光谱测试对LiGd_xY_1-xF₄∶Yb3+/Ho3+微米晶体的上转换发光性能进行分析。首先,研究了LiGd_xY_1-xF₄∶Yb3+/Ho3+微米晶体的晶体结构、尺寸、形貌和上转换发光性能的影响。结果显示,LiGd_xY_1-xF₄∶Yb3+/Ho3+微米晶体样品的XRD衍射峰与四方相的LiYF₄标准卡（PDF#17-0874）特征峰的位置完全对应且没有其他杂峰,SEM实验结果显示晶体形貌为八面体形状,表明成功合成了纯四方相的LiGd_xY_1-xF₄∶Yb3+/Ho3+微米晶体;荧光光谱测试结果显示,样品的上转换发光强度随着Gd3+掺杂比例的升高呈现出先增强后减弱的趋势,并且在Gd3+掺杂浓度为30 mol%时达到最强。其次,进一步研究了Gd3+掺杂浓度30 mol%样品的上转换发光性能与激发功率之间的关系,激发功率为0.5~1.5 W。LiGd_0.3Y_0.49F₄∶Yb3+/Ho3+微米晶体的红色和绿色上转换发光强度之比(R/G)随着激发功率的增加只发生大约12%的变化,样品的上转换发光并没有因为激发功率的增加而发生明显的变色,仍然可以发出稳定明亮的绿色光。这一现象表明,Gd3+的掺入很好地改善了样品的上转换发光性能,这种稳定高效的发光性能保证了其良好的防伪性能。最后,将Gd3+掺杂浓度为30 mol%的LiYF₄∶Yb3+/Ho3+微米晶体粉末与丝网金属油墨按照一定比例混合制成丝网防伪油墨,通过丝网印刷技术在玻璃基底上印制了“西安”字样的防伪标识图案,经过干燥处理后在980 nm激光的激发下,发出明亮且稳定的绿色可见光,制成的防伪标识图案具有发光强度高、易于识别、不易脱落的特点,可被广泛应用于防伪领域。     

Femtosecond laser ablation of DAST

High rate femtosecond (fs) laser ablation of the organic salt 4-N,N-dimethylamino-4-N-methyl-stilbazolium tosylate (DAST), an organic crystal with very high optical nonlinearities has been demonstrated. The threshold fluence and the ideal fluence range for damage free ablation for the wavelengths 550, 600, and 775 nm have been determined and the quality of the produced grooves has been investigated. The threshold fluences are in the order of 10–70 mJ/cm² and the ideal fluence range for damage free ablation is ranging from 30 to 300 mJ/cm², depending on the wavelength. The optimal focussing for ablation has been investigated and first results towards the structuring of a ridge waveguide are presented. We conclude that this method is most promising for waveguide patterning of DAST surfaces for integrated optics applications.     

中远红外非线性光学晶体研究进展

3—5μm和8—12μm波段中远红外激光,在国防和民用领域均具有广泛的应用,作为全固态激光频率转换系统的核心部件,非线性光学晶体需要不断地优化和发展.本文从红外非线性光学晶体材料组成角度出发,总结了几种具有重大应用前景的磷族化合物(ZnGeP_2,CdSiP_2)、硫属化合物(CdSe, GaSe, LiInS_2系列,BaGa_4S_7系列)以及准位相匹配晶体(OP-GaAs, OP-GaP)等中远红外波段非线性光学晶体的研究进展.     

Er3+/Yb3+共掺NaYF4/LiYF4微米晶体的上转换荧光特性

采用水热法成功制备了Er³⁺/Yb³⁺共掺杂的NaYF₄和LiYF₄微米晶体. 通过X射线衍射仪和环境扫描电子显微镜对样品的晶体结构及形貌进行表征. 实验结果表明: 六方相NaYF₄微米晶体为棒状结构, 而四方相LiYF₄微米晶体则为八面体结构. 在近红外光980 nm激发下, NaYF₄:Yb³⁺/Er³⁺和LiYF₄:Yb³⁺/Er³⁺ 微米晶体均展现出很强上转换荧光发射. 且NaYF₄:Yb³⁺/Er³⁺微米晶体的荧光发射强度大约是LiYF₄:Yb³⁺/Er³⁺微米晶体的2倍, 但红绿比明显较低. 根据荧光光谱, 并借助激光光谱学及发光动力学深入探讨基质变化及表面修饰剂乙二胺四乙二酸(EDTA)对荧光特性的影响. 实验结果发现: 影响荧光强度的主要因素是基质环境的局域对称性, 而导致不同红绿比则是由于样品表面较多的EDTA分子所引起. Er³⁺掺杂的NaYF₄和LiYF₄ 微米晶体呈现出很强的绿光发射可被应用于全色显示, 荧光粉和微光电子器件中.     

掺杂的Bi4Ge3O12晶体的近红外发光性能

生长了Mg、Ca离子掺杂(提拉法)和Cl离子掺杂(坩埚下降法)的Bi₄Ge₃O₁₂(BGO)晶体,测试了晶体样品的吸收谱、光致发光谱和发光衰减时间等。这些掺杂的BGO晶体的可见光发光比纯BGO有所减弱,但在808 nm和980 nm激光二极管(LD)激发下出现了纯BGO几乎没有的近红外发光,归因于改变了能级的Bi离子或可能出现的低价态Bi离子。掺杂对近红外发光的影响跟掺杂离子价态有关,同价态的掺杂离子对近红外发光的影响相差不大。     

Super deformability and thermoelectricity of bulk γ-InSe single crystals

Indium selenide, a III–V group semiconductor with layered structure, attracts intense attention in various photoelectric applications, due to its outstanding properties. Here, we report super deformability and thermoelectricity of γ-In Se single crystals grown by modified Bridgeman method. The crystal structure of In Se is studied systematically by transmission electron microscopy methods combined with x-ray diffraction and Raman spectroscopy. The predominate phase of γ-In Se with dense stacking faults and local multiphases is directly demonstrated at atomic scale. The bulk γ-In Se crystals demonstrate surprisingly high intrinsic super deformative ability which is highly pliable with bending strains exceeding12.5% and 264% extension by rolling. At the meantime, In Se also possesses graphite-like features which is printable,writable, and erasable. Finally, the thermoelectric properties of γ-In Se bulk single crystals are preliminary studied and thermal conductivity can be further reduced via bending-induced defects. These findings will enrich the knowledge of structural and mechanical properties' flexibility of In Se and shed lights on the intrinsic and unique mechanical properties of In Se polytypes.     

High-power efficient diode-pumped Nd:YVO4/LiB3O5 457 nm blue laser with 4.6 W of output power

Continuous-wave 457 blue laser emission at powers as high as 4.6 W is achieved by using a fiber-coupled laser diode array with a power of 30 W to pump 0.1 at. % low-doped bulk Nd:YVO4 crystal, with intracavity frequency doubling in a 15 mm long type I critical phase-matched LiB3O5 (LBO) crystal in a compact three-fold cavity with a length of less than 100 mm. The optical-optical conversion efficiency is greater than 15.3%, and the stability of the output power is better than 3% for an hour.     

Study of TL properties of LaAlO3:Ce,Dy crystals for UV dosimetry

Thermoluminescence properties of lanthanum aluminum oxide (LaAlO₃) crystals doped with optically active rare earth ions have been investigated for ultraviolet dosimetry purposes. Single crystals co-doped with 5.0 at.% of Ce³⁺ and 1.0 at.% of Dy³⁺ ions have two thermoluminescent (TL) peaks at 151 °C and 213 °C which can be sensitized after 1 h of UV exposure. The material shows very high TL output and linear response for UV spectral irradiance ranging from 0.04 to 1.20 mJ cm⁻², that corresponds to 10 times the TL response of the Al₂O₃:C oxides. From 0.62 to 148.0 mJ cm⁻² the dependence is linear with the logarithm of the spectral irradiance. The investigation demonstrates that LaAlO₃:Ce,Dy crystals are very attractive to be investigated as UV dosimeters.     

Structure and optical damage resistance of near-stoichiometric Zn:Fe:LiNbO3 crystals

A series of near-stoichiometric Zn:Fe:LiNbO₃ crystals were grown by the high-temperature top-seed solution growth (HTTSSG) method from stoichiometric melts doped with 6 mol% K₂O. Infrared (IR) transmission spectra were measured and discussed in terms of the defect structure of the near-stoichiometric Zn:Fe:LiNbO₃ crystals. The results of the transmitted beam pattern distortion method show that the optical damage resistance of the near-stoichiometric Zn:Fe:LiNbO₃ crystals increases rapidly when the ZnO concentration exceeds a threshold value. The threshold value concentration of ZnO of the near-stoichiometric Zn:Fe:LiNbO₃ crystals is much lower than that of the congruent LiNbO₃ crystals. The dependence of the optical damage resistance on the defect structure of the near-stoichiometric Zn:Fe:LiNbO₃ crystals are discussed, and the holographic recording properties of the near-stoichiometric Zn:Fe:LiNbO₃ crystals are investigated.     

Crystal growth and dielectric, mechanical, electrical and ferroelectric characterization of n-bromo succinimide doped triglycine sulphate crystals

Single crystals of triglycine sulphate (TGS) doped with n-bromo succinimide (NBS) were grown at ambient temperature by the slow evaporation technique. An aqueous solution containing 1-20 mol% of n-bromo succinimide as dopant was used for the growth of NBSTGS crystals. The incorporation of NBS in TGS crystals has been qualitatively confirmed by FTIR spectral data. The effect of the dopant on morphology and crystal properties was investigated. The cell parameters of the doped crystal were determined by the powder X-ray diffraction technique. The dielectric constant of NBS doped TGS crystal was calculated along the ferroelectric direction over the temperature range of 30-60 °C. The dielectric constant of NBSTGS crystals decrease with the increase in NBS concentration and considerable shift in the phase transition temperature (T_C) towards the higher temperature observed. Pyroelectric studies on doped TGS were carried out to determine the pyroelectric coefficient. The emergence of internal bias field due to doping was studied by collecting P-E hysteresis data. Temperature dependence of DC conductivity of the doped crystals was studied and gradual increase in the conductivity with the increase of dopant concentration was observed. The activation energy (ΔE) calculated was found to be lower in both the ferroelectric and the paraelectric phases for doped crystals compared to that of pure TGS. The micro-hardness studies were carried out at room temperature on thin plates cut perpendicular to the b-axis. Less doped TGS crystals show higher hardness values compared to pure TGS. Piezoelectric measurements were also carried out on 010 plates of doped TGS crystals at room temperature.     

Emission properties of Ta-centres in KCl

Electrolytic colouration at about 600°C and 350 V/cm, for KCl crystal containing Pb²⁺ and for KCl:Pb²⁺ crystals co-doped with Li⁺, Na⁺ and Rb⁺ has been undertaken. Several absorption bands were observed in both doped and co-doped crystals in the visible-UV region. Excitation into these bands gives rise to the same 0.86 eV emission band except for the Li⁺-co-doped crystal which gives rise to a 0.80 eV emission band. These absorption bands are due to the same T_a-centre related to Pb⁻. The observed infrared emission intensity of the crystal with F-centres is higher than of without F-centres.     

Large energy 1341.4 nm Nd: YALO3 pulse laser

On the basis of a measured stimulated emission cross-section for the ⁴F_3/2-⁴I_13/2 transition of the Nd³⁺ ion in a YAP crystal, it is shown that the Nd:YALO₃ crystal is a useful kind of laser crystal to operate in a pulsed laser at 1341.4 nm. Output energy of 5.31 J with an overall efficiency of 1.84% at 1341.4 nm has been achieved by using a 6 mm diameter and 101 mm long A-axis YALO₃ rod with 1 at.% Nd³⁺ ion.     

Red emission of PbWO4 crystals

Luminescence characteristics of a large number of undoped and doped PbWO₄ crystals, grown by the Czochralski or Bridgman method, as-grown or annealed in the nitrogen atmosphere or in air, were studied in the 4.2–300 K temperature range. Two types of red emission centres were found. The centres with the emission band, peaking at 4.2 K at 1.57 eV, were observed in most of the crystals studied. The centres with the emission band, peaking at 4.2 K at 1.48 eV, were observed only in the PbWO₄ : Mo⁶⁺, Y³⁺ crystal. It is suggested that incompletely compensated lead vacancies are responsible for the appearance of the red emission.     

(Tl, Pb, Cu)Sr2(Tl, Pb, Cu)2Cu2O8−δ: a nonsuperconducting Tl-1222 cuprate with both heavy atom single and oxygen depleted double layer motifs

An account is given of the synthesis and structural investigation of a newly discovered tetragonal (Tl, Pb, Cu)Sr₂(Tl, Pb, Cu)₂Cu₂O_8−δ compound (Tl-1222^* phase) with both (Tl, Pb, Cu)O single and oxygen depleted (Tl, Pb, Cu)₂O_x double layer motifs, space group I4/mmm, lattice parameters a=3.8405(2), c=29.2536(5) Å, and D_x=7.46 g cm⁻³. Micaceous and highly reflecting black single crystals of 1 mm×1 mm×3–5 μm size were obtained from a Tl₂O₃- and CuO-rich partial melt. The as-grown compound is nonsuperconducting. The very thin crystals are extremely liable to bend out of shape. Deterioration could not be observed within the period of a year under ambient conditions. The complex crystal structure has been solved using single crystals. We take note of the similarity of the unit cell dimensions to superconducting (Tl, Cu)₂Ba₂(Ca, Tl)Cu₂O₈ (Tl-2212 phase) with TlO double rocksalt layers, and compare crystal-chemical details of similar compounds. Apart from the possibility of obtaining superconducting properties by suitable doping, the mechanical properties of the new material are very attractive from the point of view of its use as highly scattering composite layers of an X-ray monochromator.     

双程放大740 mJ TEC冷却LD泵浦Nd:YAG激光器

报道了一种实现高能量输出的激光二极管（LD）泵浦无水冷全固态Nd：YAG双程放大器结构。整个放大系统采用了泵浦与晶体棒集成的模块以及半导体制冷器（TEC）,从而实现了激光系统的小型化。总腔长为730 mm。在10 Hz重复频率下,主振荡器得到了最大脉冲能量为350 mJ的激光输出。脉宽为9.7 ns,光束质量M²在两个方向分别为7.7和12.3。并进行了双程放大的研究,双程放大后得到了740 mJ、10 ns的激光输出。     

Co,Zn共掺铌酸锂电子结构和吸收光谱的第一性原理研究

利用基于密度泛函的第一性原理的计算方法,研究了Co单掺及Co和Zn共掺LiNbO_3晶体的电子结构和吸收光谱.研究显示,各掺杂体系铌酸锂晶体的带隙均较纯铌酸锂晶体变窄. Co:LiNbO_3晶体禁带宽度为3.32 eV; Co:Zn:LiNbO_3晶体, Zn的浓度低于阈值或达到阈值时,禁带宽度分别为2.87或2.75 eV. Co:LiNbO_3晶体在可见-近红外光波段2.40, 1.58, 1.10 eV处形成吸收峰,这些峰归结于Co 3d分裂轨道的跃迁;加入抗光折变离子Zn~(2+),在1.58, 1.10 eV处的吸收峰增强,可以认为Zn~(2+)与Co~(2+)之间存在电荷转移,使e_g轨道电子减少,但并不影响t_(2g)轨道电子.结果表明,晶体中的Co离子在不同共掺离子下可充当深能级中心(2.40 eV),或可充当浅能级中心(1.58 eV),两种情况下,掺入近阈值的Zn离子均有助于实现优化存储.     

波长锁定878.9nm激光二极管抽运内腔式YVO_4/BaWO_4连续波拉曼激光器

采用波长锁定878.9 nm激光二极管共振抽运复合Nd:YV04激光晶体,改善热效应的同时提高抽运吸收率,分别以YVO_4和BaWO_4晶体作为拉曼介质,实验和理论研究了晶体性能、谐振腔结构和稳定性对内腔分体式连续波拉曼激光器性能的影响.结果表明:由于内腔分体式拉曼激光器腔长较长,谐振腔稳定性对激光器性能影响较大,选择高增益的拉曼晶体,不仅可获得高拉曼转换效率,还能一定程度上减轻热效应.而平凹腔结构中输出镜的曲率半径越小,拉曼晶体中基频光的功率密度越大,腔的动态稳定区越宽,获得的拉曼激光输出功率更高.最终以30 mm的BaWO_4晶体作为拉曼介质,在抽运功率25.1 W时,获得了3.02 W的连续拉曼激光输出,光-光转换效率达到12%.     

Magnetic properties of oxides and silicon single crystals

The magnetic properties of single crystals Si, SrTiO₃, LaAlO₃, MgO, and (La,Sr)(Al,Ta)O₃ were investigated systematically. Three origins of the magnetizations of these crystals, namely, an intrinsic diamagnetic, a paramagnetic, and a ferromagnetic contribution, have been found to influence the magnetic signals measured on the crystals, in some important application scenarios such crystals being served as substrates with the magnetic thin film epitaxially grown on. Quantitative analyses methodologies were developed and thorough investigations were performed on the crystals with the intrinsic materials parameters thus revealed, especially that the intrinsic diamagnetic susceptibility differential dχ_dia/dT were identified quantitatively for the first time in SrTiO₃, LaAlO₃, MgO, and (La,Sr)(Al,Ta)O₃. The paramagnetic contribution is found to be the key in terms of the magnetic properties of the crystals, which in turn is in fact a consequence of the 3d impurities doping inside the crystal. All the intrinsic materials parameters are given in this paper as datasets, the datasets are openly available at https://www.doi.org/10.57760/sciencedb.j00113.00028.