Accelerated Sequential Deposition Reaction via Crystal Orientation Engineering for Low-Temperature,High-Efficiency Carbon-Electrode CsPbBr_(3) Solar Cells

Low-temperature,ambient processing of high-quality CsPbBr_(3)films is demanded for scalable production of efficient,low-cost carbon-electrode perovskite solar cells(PSCs).Herein,we demonstrate a crystal orientation engineering strategy of PbBr_(2)precursor film to accelerate its reaction with CsBr precursor during two-step sequential deposition of CsPbBr_(3)films.Such a novel strategy is proceeded by adding CsBr species into PbBr_(2)precursor,which can tailor the preferred crystal orientation of PbBr_(2)film from[020]into[031],with CsBr additive staying in the film as CsPb_(2)Br_(5)phase.Theoretical calculations show that the reaction energy barrier of(031)planes of PbBr_(2)with CsBr is lower about 2.28 eV than that of(O2O)planes.Therefore,CsPbBr_(3)films with full coverage,high purity,high crystallinity,micro-sized grains can be obtained at a low temperature of 150℃.Carbon-electrode PSCs with these desired CsPbBr_(3)films yield the record-high efficiency of 10.27%coupled with excellent operation stability.Meanwhile,the 1 cm^(2)area one with the superior efficiency of 8.00%as well as the flexible one with the champion efficiency of 8.27%and excellent mechanical bending characteristics are also achieved.

Controllable Modulation of Morphology and Property of CsPbCl_(3)Perovskite Microcrystals by Vapor Deposition Method

As a direct wide bandgap semiconductor,CsPbCl_(3)has great potential applications in the eld of near-ultraviolet photodetectors,lasers and higher-order multiphoton uores-cent detectors.In this work,we synthesized CsPbCl_(3)micro/nanocrystals by vapor depo-sition method with CsCl and PbCl_(2)powders as the source materials.It was con rmed that the formation of CsPbCl_(3)perovskite through the chemical reaction of CsCl with PbCl_(2)occurred in the quartz boat before the source evaporation,not in vapor or on sub-strate surface.The evaporated CsPbCl_(3)can form micro/nanocrystals on substrate surfaces under appropriate conditions.Various morphologies including irregular polyhedrons,rods and pyramids could be observed at lower temperature,while stable and uniform CsPbCl_(3)single crystal microplatelets were controllably synthesized at 450℃.Prolonging the growth time could modulate the size and density of the microcrystals,but could not change the morphology.Substrate types made little di erence to the morphology of CsPbCl_(3)crystals.The photoluminescence spectra indicated that the crystallinity and morphology of CsPbCl_(3)micro/nanocrystals have signi cant e ects on their optical properties.The work is expected to be helpful to the development of optoelectronic devices based on individual CsPbCl_(3)microcrystal.

Pr,Yb,Ho:GdScO_(3)晶体生长及光谱性能

2.7-3.0μm波段激光在很多领域具有重要应用,为探索和发展该波段新型晶体材料,本文采用提拉法生长出Pr,Yb,Ho:GdScO_(3)晶体,通过共掺入Pr3+离子以达到衰减Ho^(3+):^(5)I_(7)能级寿命的目的.采用X射线衍射测试得到了晶体的粉末衍射数据,测量了拉曼光谱,并对晶体的拉曼振动峰进行指认,对Pr,Yb,Ho:GdScO_(3)晶体的透过光谱、发射光谱和荧光寿命进行表征.Yb^(3+)的最强吸收峰在966 nm,吸收峰半峰宽为90 nm;2.7-3.0μm波段最强发射峰在2850 nm,半峰宽为70 nm;Ho^(3+):^(5)I_(6)和^(5)I_(7)能级寿命分别为1094μs和56μs.与Yb,Ho:GdScO_(3)晶体相比,Yb^(3+)的吸收峰和2.7-3.0μm的发射峰半峰宽明显展宽,同时下能级寿命显著减小,计算表明Ho^(3+):^(5)I_(7)与Pr^(3+):^(3)F_(2)+^(3)H_(6)能级之间能实现高效的能量传递.以上结果表明Pr,Yb,Ho:GdScO_(3)晶体是性能更优异的2.7-3.0μm波段激光材料.

NdF_(3)-LiF-Nd_(2)O_(3)-NdF_(2)熔盐体系结晶行为的研究

氟化物体系稀土氧化物熔盐电解过程中,熔盐的结晶析出行为显著影响电解过程,为此本文针对NdF_(3)-LiF-Nd_(2)O_(3)、NdF_(3)-LiF-NdF_(2)以及NdF_(3)-LiF-Nd_(2)O_(3)-NdF_(2)三种熔盐体系(NdF_(3)和LiF质量比固定为85∶15),采用降温黏度曲线测定熔盐的结晶温度,通过X射线衍射分析结晶物相。结果表明:NdF_(3)-LiF-Nd_(2)O_(3)和NdF_(3)-LiF-NdF_(2)熔盐体系中,随着熔盐中Nd_(2)O_(3)或NdF_(2)含量的增加,熔盐的结晶温度升高,熔盐的结晶物相分别为NdOF和NdF_(2);NdF_(3)-LiF-Nd_(2)O_(3)-NdF_(2)熔盐体系中,当Nd_(2)O_(3)含量为2%~3%、NdF_(2)含量为1%~3%时,熔盐结晶温度在981~988℃范围内,且NdOF与NdF_(2)共结晶。适当提高电解槽底部温度、改善底部熔盐的流动性,是抑制稀土熔盐电解过程熔盐结晶析出的有效方法。

1英寸CsPbCl_(3)晶体的生长及其发光性能研究

CsPbX_(3)(X=Cl^(-), Br^(-), I^(-))钙钛矿单晶具有优异的光电性能,有望成为下一代光电探测材料。由于CsCl在前驱体中的溶解度过小,通过低温溶液法较难生长得到CsPbCl_(3)晶体。本工作采用坩埚下降法成功生长了1英寸完整的CsPbCl_(3)晶体,并对晶体进行了一系列加工,得到了ϕ10 mm×10 mm和厚度为2 mm的单晶片。测试了晶体的X射线粉末衍射图谱、TG/DTA曲线、X射线激发发射光谱、透过光谱和低温荧光光谱。在X射线的激发下,在430和575 nm观察到两个X射线激发发射峰,晶体的透过率达到75%;光致发光(PL)强度与温度依赖性曲线中可以观察到热猝灭现象,计算得到晶体4个峰的激子结合能分别为12.59、8.21、12.41和21.59 meV。

稀土Er^(3+)离子掺杂的全无机CsPbCl_(3)钙钛矿纳米晶的合成及发光性能

CsPbCl_(3)全无机钙钛矿纳米晶(PNC)的应用受到其弱发光、极低的光致发光量子产率(PLQY)以及长期暴露于氧气和湿气环境中稳定性差等的限制。为了解决这一问题,使用稀土金属元素铒的三价阳离子(Er^(3+))作为B位掺杂元素,制备出了明亮蓝紫光发射的Er^(3+)∶CsPbCl_(3)钙钛矿纳米晶发光材料。掺杂后的纳米晶具有最佳的形貌和发光性能:PLQY为16.7%、平均粒径约为7.98nm、荧光发射峰蓝移至400nm、半峰全宽仅为10.0nm。同时该纳米晶的环境稳定性也显著提升,在测试环境(温度60℃、湿度60%RH)下存放10天后,其发光强度仍能保持初始荧光发射强度的60%以上。此工作较大程度上改善了CsPbCl_(3)钙钛矿纳米晶存在的问题,对于其实际应用存在重大意义。

CsPbX_(3)钙钛矿纳米晶中Mn(Ⅱ)离子的可控掺杂及其发光性能研究

Mn离子掺杂策略被广泛用于提高CsPbX3钙钛矿纳米晶(Nanocrystals,NCs)的稳定性和调控Pb的含量,但离子掺杂反应速率极快,不易控制。本文分别采用一步和两步热注射法对Mn^(2+)的掺杂含量进行大范围和精确调控,制备出具有不同Mn^(2+)掺杂含量的CsPbCl_(3)∶Mn^(2+)NCs。通过对其结构及发光性能的研究,将其区分为合金结构和掺杂结构,并进一步揭示了一步法和两步法进行Mn^(2+)调控时的不同机制,明确了在相同Pb∶Mn投料比的情况下,一步法合成的合金结构纳米晶具有更高的Mn^(2+)掺杂量,使得纳米晶在610nm左右与Mn相关的发射峰更为强烈,最高光致发光量子产为77%,而两步法合成的掺杂结构纳米晶在较少的Mn^(2+)情况下同样具有较高的光致发光量子产率。同时,Mn^(2+)的可控掺杂使得钙钛矿纳米晶的稳定性有效提升,放置四周后形貌和发光性能仍稳定。值得注意的是,合金结构对于本征激子发光稳定性的提升比掺杂结构更加有利。此外,还合成了具有优异发光性能的CsPb(Cl_(x)Br_(3-x))∶Mn^(2+)钙钛矿纳米晶,其荧光光谱可在404~640nm之间调控;但当Br-含量较高时,与Mn相关的发射峰消失,这是由于CsPbBr_(3)的能带与Mn^(2+)的^(4)T_(1-)^(6)A_(1)能级不匹配所致。本文强调了在CsPbCl_(3)∶Mn^(2+)钙钛矿制备过程中Mn^(2+)可控掺杂的重要性,对于实现纳米晶的可控合成具有重要意义。

Centimeter-sized Cs_(3)Cu_(2)I_(5)single crystals grown by oleic acid assisted inverse temperature crystallization strategy and their films for high-quality X-ray imaging

Low-dimensional halide perovskites have become the most promising candidates for X-ray imaging,yet the issues of the poor chemical stability of hybrid halide perovskite,the high poisonousness of lead halides and the relatively low detectivity of the lead-free halide perovskites which seriously restrain its commercialization.Here,we developed a solution inverse temperature crystal growth(ITCG)method to bring-up high quality Cs_(3)Cu_(2)I_(5)crystals with large size of centimeter order,in which the oleic acid(OA)is introduced as an antioxidative ligand to inhibit the oxidation of cuprous ions effieiently,as well as to decelerate the crystallization rate remarkalby.Based on these fine crystals,the vapor deposition technique is empolyed to prepare high quality Cs_(3)Cu_(2)I_(5)films for efficient X-ray imaging.Smooth surface morphology,high light yields and short decay time endow the Cs_(3)Cu_(2)I_(5)films with strong radioluminescence,high resolution(12 lp/mm),low detection limits(53 nGyair/s)and desirable stability.Subsequently,the Cs_(3)Cu_(2)I_(5)films have been applied to the practical radiography which exhibit superior X-ray imaging performance.Our work provides a paradigm to fabricate nonpoisonous and chemically stable inorganic halide perovskite for X-ray imaging.

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。

Eu^(3+)掺杂CsPbCl_(3)钙钛矿纳米晶柔性发光薄膜的制备及其稳定性提升

柔性发光薄膜在柔性电子和可穿戴智能器件中具有巨大的发展潜力,因此研究柔性发光薄膜是近年来的研究热点.铯卤化铅钙钛矿由于优异的光学性能迅速成为明星材料,但是它在稳定性、毒性等方面仍然面临很多问题.将Eu^(3+)离子作为掺杂剂,通过一步热注入法制备了CsPbCl_(3)∶Eu^(3+)钙钛矿纳米晶体,对其结构、性能进行分析,实现了对CsPbCl_(3)纳米晶重元素铅的有效替代,同时增加了其发光稳定性能;进而,在合成CsPbCl_(3)∶Eu^(3+)钙钛矿纳米晶体表面包覆一层TPU,成功地实现了薄膜的柔性化.该薄膜具有优异的拉伸性能和防水性能,在紫外灯的照射下能够呈现出明亮的紫色,给柔性发光薄膜的发展提供了一个新的思路.

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.

CsPbBr_(3)晶体生长及变温霍尔效应研究

以定向凝固法提纯的CsPbBr_(3)多晶为原料,采用垂直布里奇曼法生长出尺寸为∅30 mm×70 mm的CsPbBr_(3)单晶。采用ICP-OES对提纯后的多晶测试表明,提纯后的CsPbBr_(3)多晶中杂质含量减少了28.7%。经XRD和EDS对切割得到的晶片分析发现,晶片的晶面方向属{210}晶面族,晶体中Cs、Pb、Br_(3)种元素分布均匀,原子百分含量符合化学计量比。采用傅里叶红外光谱仪和紫外-可见分光光度计对晶体的透过率测试显示,生长晶体在500~4000 cm^(-1)波数范围内的红外透过率超过75%,紫外短波截止边为552 nm,拟合计算出对应的禁带宽度为2.246 eV。选取7个不同温度点对CsPbBr_(3)单晶进行变温霍尔效应测试发现,生长晶体为P型导电,在250~300 K和300~350 K之间晶体中主要的载流子散射机制分别为声学波散射和电离杂质散射,在150~250 K温度范围内,更符合多种散射机构共同作用的散射机制。进一步拟合载流子浓度p与1/T的关系,计算获得晶体中杂质电离能ΔE_(A)=0.3042 eV。

Li(Sc,M)Si_(2)O_(6)∶Cr^(3+)(M=Ga^(3+)/Lu^(3+)/Y^(3+)/Gd^(3+))的近红外发光性能

荧光转换型近红外发光二极管(NIR pc-LED)具有体积小、谱带宽、峰位易调谐等优点,是新一代NIR光源发展的前沿,其关键在于研发可被蓝光有效激发的高效率宽带近红外荧光粉。LiScSi_(2)O_(6)∶Cr^(3+)荧光材料的激发波长为460 nm,发射峰位在845 nm,光谱带宽为156 nm,内量子效率为64.4%。基于该体系,本文通过M离子(M=Ga^(3+),Lu^(3+),Y^(3+),Gd^(3+))取代Sc^(3+)的方式对其性能进行调控。结果表明,引入M离子易生成杂相或发生相变,降低了材料的发光性能。本文从晶体结构出发对其调控过程进行了分析。

Lu^(3+)掺杂Na_(5)Y_(9)F_(32)∶Ho^(3+)/Yb^(3+)/Ce^(3+)单晶体的增强红色上转换发光与光学温度传感性能

采用密封的坩埚下降法技术生长了一系列Lu^(3+)(摩尔分数0、0.6%、1.2%、1.8%)掺杂Na_(5)Y_(9)F_(32)∶Ho^(3+)/Yb^(3+)/Ce^(3+)单晶体。在980 nm LD激发下,观察到单晶体的绿光543 nm(^(5)S_(2)/^(5)F_(4)→^(5)I_(8))、红光656 nm(^(5)F_(5)→^(5)I_(8))以及近红外750 nm(^(5)S_(2)/^(5)F4→^(5)I_(7))上转换发光。从上转换发光强度随激发光强度的变化情况,确定了543 nm、656 nm与750 nm的发光为双光子跃迁过程。研究了Lu^(3+)离子掺杂浓度对其发光强度与荧光寿命的影响情况,随着Lu^(3+)掺杂浓度从0增加到1.8%,单晶体中的656 nm红光逐步增强,543 nm绿光与750 nm近红外光随之减弱,红绿光强度比从0.01增加到了1.55,而543 nm荧光寿命从1.29 ms降低至0.99 ms。Lu^(3+)离子的掺入取代Y^(3+)晶格位,改变了单晶体的局域场环境,导致上转换发光强度的变化。基于随温度变化的上转换红光656 nm(^(5)F5→^(5)I8)与绿光543 nm(^(5)S_(2)/^(5)F4→^(5)I8)的发光强度变化,研究了1.8%Lu^(3+)掺杂Na_(5)Y_(9)F_(32)∶Ho^(3+)/Yb^(3+)/Ce^(3+)单晶体在298~448 K范围内的绝对灵敏度和相对灵敏度最大值分别为0.242%·K^(-1)和0.217%·K^(-1)。

LD脉冲泵浦Er^(3+)/Yb^(3+):Lu_(2)Si_(2)O_(7)晶体百kHz激光器

目前1.5μm激光二极管(Laser Diode,LD)泵浦的铒镱共掺玻璃/晶体被动调Q微型激光器广泛应用于激光测距、激光雷达等领域。随着激光器输出重频的增加,玻璃面临突出的热效应问题,晶体的热导率是玻璃的10倍以上,有望能够实现比玻璃基质更高重频的激光输出。报道了一种通过LD脉冲端面泵浦Er^(3+)/Yb^(3+):Lu_(2)Si_(2)O_(7)晶体的百kHz人眼安全激光器。通过实验优化增益介质掺杂浓度和长度、泵浦光斑尺寸和调Q晶体初始透过率等实验参数,同时适当缩短脉宽,优化泵浦占空比,提高了输出重频的稳定性。最终获得了重频为100 kHz、单脉冲能量0.7μJ、脉冲宽度240 ns、光束质量M^(2)=1.61的1537 nm脉冲激光输出。实现了输出脉冲频率与泵浦的一致,保证了输出重频的稳定性,有效解决了输出重频具有随机性、不稳定、不可控等问题。

Hydrogen-bond mediated and concentrate-dependent NaHCO_(3) crystal morphology in NaHCO3–Na2CO3 aqueous solution: Experiments and computer simulations

Adding Na_(2)CO_(3) to the NaHCO_(3) cooling crystallizer, using the common ion effect to promote crystallization and improve product morphology, is a new process recently proposed in the literature. However, the mechanism of the impact of Na_(2)CO_(3)on the crystal morphology is still indeterminate. In this work, the crystallization of NaHCO_(3)in water and Na_(2)CO_(3)–NaHCO_(3) aqueous solution was investigated by experiments and molecular dynamics simulations(MD). The crystallization results demonstrate that the morphology of NaHCO_(3) crystal changed gradually from needle-like to flake structure with the addition of Na_(2)CO_(3). The simulation results indicate that the layer docking model and the modified attachment energy formula without considering the roughness of crystal surface can obtain the crystal morphology in agreement with the experimental results, but the lower molecules of the crystal layer have to be fixed during MD. Thermodynamic calculation of the NaHCO_(3) crystallization process verifies that the common ion effect from Na^(+)and the ionization equilibrium transformation from CO_(3)^(2-) jointly promote the precipitation of NaHCO_(3) crystal. The radial distribution function analysis indicates that the oxygen atoms of Na_(2)CO_(3) formed strong hydrogen bonds with the hydrogen atoms of the(0 1 1) face, which weakened the hydration of water molecules at the crystal surface, resulting in a significant change in the attachment energy of this crystal surface. In addition, Na+and CO_(3)^(2-) are more likely to accumulate on the(011) face,resulting in the fastest growth rate on this crystal surface, which eventually leads to a change in crystal morphology from needle-like to flake-like.

Effect of ZnO,La_(2)O_(3),and YF_(3)on Crystallization and Rehological Behavior of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)Glass

The effect of substitution La_(2)O_(3)and YF_(3)as network modifiers respectively for Y_(2)O_(3),and ZnO as intermediate oxide for Al_(2)O_(3)on crystallization and viscous behavior of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)glass was studied.La_(2)O_(3)and YF_(3)substitution for Y_(2)O_(3)decreases the melting temperature of studied glass from 1402 to 1346 and 1379℃,and the activation energy of viscous flow decreases from 340 to 250 and 265 kJ/mol.Meanwhile,ZnO substitution for Al_(2)O_(3)decreases the melting temperature to 1379℃while increases the activation energy of viscous flow to 542 kJ/mol,due to their different role in glass structure.Substitution ZnO for Al_(2)O_(3)refines and homogenizes the crystals size and lowers crystallinity because the nucleation and crystal growth are depressed by higher activation energy of crystallization and change of crystallization mechanism from bulk crystallization to surface crystallization.Replacement of Y_(2)O_(3)by La_(2)O_(3)and YF_(3)respectively also decreases the crystallinity of Y_(2)O_(3)-Al_(2)O_(3)-SiO_(2)glass ceramic due to competitive and hindering effect on the rearranged atoms,structural units and groups required by precipitated two crystals.Besides,y-Y2Si2O7,precipitation of Y4.67(SiO4)3O,ZnAl_(2)O_(4),and Y3Si3O10F were observed respectively due to incorporation of La_(2)O_(3),ZnO,and YF_(3).

大尺寸CH_(3)NH_(3)PbBr_(3)晶体生长和光电性能表征

卤化物钙钛矿材料作为一种新型的半导体材料,具有材料廉价和光电转换性能优异的优点,基于该材料的各类光电器件已经开始逐步应用。虽然多晶薄膜仍然是主要的研究方向,但其具有形态无序、杂质较多的缺点,而单晶具有无晶界、低缺陷的特点,因此基于大尺寸单晶的研究开始被广泛关注。本文设计了一套内外反控温循环过滤生长装置,采用逆温结晶和籽晶相结合的方法制备了直径大于60 mm的CH_(3)NH_(3)PbBr_(3)单晶,对晶体样品进行了物相、微观形貌、光学和电学性能的研究。该晶体属于立方晶系,空间群为Pm3m;紫外-可见吸收光谱显示吸收截止边约为576 nm,荧光发射谱峰值552 nm;摇摆曲线显示晶体(100)晶面半峰全宽为91.42″。切割抛光后的晶片光响应灵敏,开关比为2.4×10^(3)。

溶液法生长大尺寸CsCu_(2)I_(3)钙钛矿单晶及其光学性能研究

近年来,铜基钙钛矿因其出色的稳定性和环境友好性在发光和闪烁等领域受到了广泛关注。然而,目前对CsCu_(2)I_(3)晶体材料的研究主要集中在0维和1维领域,这限制了人们对材料本征性质和各向异性的深入理解,也限制了其在闪烁体中的实际应用。本文通过溶液降温法开展了CsCu_(2)I_(3)体块单晶的生长工艺研究,成功得到了长度达5 mm的高质量CsCu_(2)I_(3)单晶,该晶体无色透明、棱角分明、显露面完整。XRD测试结果表明,CsCu_(2)I_(3)晶体在经过6个月后依然保持了良好的稳定性;吸收光谱显示该晶体在310 nm波段具有明显的吸收峰,计算得到其禁带宽度为3.42 eV,表明CsCu_(2)I_(3)晶体属于宽禁带半导体;发射光谱显示该晶体发射波长位于580 nm处,半峰全宽为75 nm,绘制CIE色度图得到其发光色度坐标为(0.47,0.50),位于黄光区域,属于暖白色调(色温3000 K),这与该晶体在紫外灯照射下发出黄色荧光的现象一致;CsCu_(2)I_(3)晶体的荧光寿命测得为51.6和215.5 ns。

含类B_(3)O_(6)型有机平面π共轭基团的紫外非线性光学晶体的研究进展

非线性光学(NLO)晶体材料作为激光科学的重要组成部分,因其在信息存储等领域的广泛应用而越来越受到研究人员的关注.从阴离子基团理论可知,具有π共轭电子结构的平面六元环(B_(3)O_(6))基团是“中国牌”晶体β-Ba_(2)B_(2)O_(4)(BBO)具有优异光学性能的决定性化学组分.因此,利用具有共轭大π键的平面基团进行紫外NLO晶体的分子构筑,已成为探索新型具有良好NLO性能材料的一种非常有效的方式.近年来,为了拓宽紫外NLO晶体的研究范围,具有与(B_(3)O_(6))基团相似构型的一系列有机平面π共轭基团逐渐引起了研究人员的兴趣.目前,研究人员已经发现了许多具有优异光学性能的含类B_(3)O_(6)型有机平面π共轭基团的紫外NLO晶体,这些B_(3)O_(6)型有机共轭基团可以根据构成六元环的原子分为不同的类别:(HxC_(3)N_(3)O_(3))^(x-3)(x=0~3)(氰尿酸离子)、(HxC_(4)N_(2)O_(3))^(x-4)(x=2,3)(巴比妥酸离子)、(C_(3)H_(7)N_(6))^(+)(三聚氰胺离子)、(C_(5)H_(6)ON)+(4-羟基吡啶阳离子)和(C_(4)H_(6)N_(3))+(2-氨基嘧啶阳离子).重点介绍含类B_(3)O_(6)型有机平面π共轭基团的紫外NLO晶体的研究进展,并总结它们的晶体结构、合成方法、光学性能以及结构和性质之间的关系,为了解类B_(3)O_(6)型有机平面π共轭基团及其光学功能性质提供一个清晰的视角,并促进新型紫外NLO晶体的研究.