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深紫外双折射晶体Na3Ba2(B3O6)2F和中红外非线性光学晶体Pb17O8Cl18的设计合成、晶体生长及性质研究
张辉
学位类型硕士
导师潘世烈
2015-05-20
学位授予单位中国科学院大学
学位授予地点北京
学位专业材料工程
关键词双折射晶体 非线性光学晶体 孤对电子 路易斯酸碱 维度减小
摘要

本论文主要探索合成与生长新型光电功能晶体材料,尤其是深紫外双折射晶体和中红外非线性光学晶体,主要通过以下思路和策略:(1)在体系中引入大电负性的卤素,以使化合物具有宽带隙;(2)引入无d-d轨道电子跃迁的碱金属和碱土金属元素,以探索紫外/深紫外光电功能材料;(3)引入含有易产生二级姜泰勒效应的阳离子,具有d0电子的八面体基元或具有孤立电子的阳离子(如Pb2+)来增强化合物的倍频效应;(4)用经典理论如阴离子基团理论、路易斯酸碱理论、维度减小理论来指导新化合物合成,从而提高合成效率。1. 深紫外双折射晶体Na3Ba2(B3O6)2F的设计合成、晶体生长及性质研究成功研发出了一种新型的深紫外双折射晶体NBBF,并生长出尺寸为35 mm × 35 mm × 9 mm的高质量单晶,加工出相关器件,系统测试表征了其光、电、热等性质:NBBF具有理想的双折射率,在透过范围(175 nm-3.35 μm),双折射率Δn = 0.2554-0.0750;紫外截止边为175 nm,比α-BBO蓝移14 nm,有利于其在深紫外波段更有效地利用;避免了α-BBO中存在的高低温相变,大大减小了晶体生长的难度;NBBF的单晶生长温度是目前常用双折射晶体中最低的,既有利于晶体生长的控制,也有利于节能减排、降低成本;同时,NBBF大大减弱了α-BBO的热学各向异性,可以有效避免其在晶体生长和应用过程中的开裂;晶体不吸潮,热学稳定性好,激光损伤阈值较大,有利于实际应用。综上所述,NBBF相比于α-BBO,既保留了优良的光学性质,也克服了阻碍α-BBO晶体高效利用的本征缺陷。NBBF的综合性能优于α-BBO,有可能取代α-BBO成为下一代深紫外双折射晶体材料。2. 开放体系中合成的一种具有大激光损伤阈值的中红外非线性光学晶体材料-Pb17O8Cl18我们将体系中引入电负性较大的卤素来形成较强的离子键以加强阴离子周围价电子的结合作用,从而获得较大的带隙,同时探索含氧化合物作为红外倍频材料的可能性,通过引入重元素Pb来保证其在中红外波段的光透过,经过系统的探索合成,发现了Pb17O8Cl18(POC),利用单晶衍射技术确定了其单晶结构,并成功在开放体系中生长出POC单晶,进一步的性质表征表明POC在红外波段应用具有以下两大优势:(1) POC具有较大的激光损伤阈值(408 MW/cm2),为AgGaS2的12.8倍,可以保证在高功率激光系统中的应用;(2) 在开放体系中成功生长出尺寸为7 mm × 2 mm × 2 mm 的POC透明单晶,降低了传统的坩埚下降法在封闭系统中生长红外倍频晶体的工艺难度。同时,POC在1064 nm和2090 nm处的倍频效应分别为4倍KDP和6倍AgGaS2,并且均能实现一类相位匹配,具有较好的热学稳定性。综上所述,POC是一种有前景的中红外非线性光学晶体材料,进一步生长大尺寸高质量POC单晶的探索尝试正在进行中。3. 单金属复合阴离子磷酸盐Pb5(PO4)2P2O7的设计合成与性质研究以维度减小理论为指导,成功合成出一种结构新颖的单金属复合阴离子磷酸盐Pb5(PO4)2P2O7。Pb5(PO4)2P2O7中同时存在PO4和P2O7两种P-O基团,具有这种结构特点的化合物很罕见,经过系统充分的调研,没有找到单金属体系的此类化合物。我们又分析其结构特点,发现其结构在室温下不稳定,P2O7基团的热振动活性很高,因此利用变温X射线单晶衍射技术分别收集其室温(296 K)和低温(110 K)单晶数据并分别解析其单晶结构,发现在低温下发生了结构相变,进一步用原位XRD确定了其高低温相变的温度范围。从这部分工作得到启发:在设计新化合物的过程中,可以以维度减小理论为指导通过改变阳离子数目而从一定程度上调控阴离子基团的排布以合成新化合物。4. Pb8M(BO3)6(M = Mg,Ca)的设计合成与结构性质研究以路易斯酸碱理论为指导,尝试进行阳离子替换,用碱土金属阳离子替换路易斯酸相近的过渡金属离子,从而合成了两例碱土金属铅硼酸盐新化合物Pb8M(BO3)6(M = Mg,Ca)。Pb8M(BO3)6(M = Mg,Ca)中形成沿c方向排列的[Pb8B6O18]2-双层结构,层与层之间则通过Mg2+(Ca2+)进行连接,形成三维网络结构。以上合成思路简单有效,对于我们进行改性合成具有一定的指导和借鉴作用。

其他摘要
The main purpose of this dissertation is to design, synthesize and grow novel photoelectric functional crystal materials, especially to explore the deep-ultraviolet birefringent crystal and mid-infrared nonlinear optical crystal materials. In this work, we followed the following idea and strategies: (1) introducing the large electronegativity halogen to extend the bandgap; (2) introducing the alkali metal and alkaline earth metal elements which is without the d-d electron transition to explore the UV-DUV materials; (3) employing the cations susceptible to second-order Jahn-Teller (SOJT) effects, octahedrally coordinated d0 transition metals and lone-pair cations (e.g., Pb2+) to enhance the SHG response; (4) follow the anionic group theory, lewis acid theory and dimensional reduction theory to design and synthesize new compounds. 1. Na3Ba2(B3O6)2F: next generation of deep-ultraviolet birefringent materials. We have fully developed a new deep UV birefringent crystal of NBBF. A single crystal of NBBF with dimensions of 35 mm × 35 mm × 9 mm was grown from its stoichiometric melt for the first time in 2 days, a greatly improved crystal growth method. These NBBF crystals achieve desirable optical properties with a large birefringence (Δn = 0.0750?0.2554) from the IR (3.35 μm) to the deep UV (175 nm) range. NBBF melts congruently with no phase transitions and possesses the lowest growth temperature among birefringent materials, which is beneficial for the growth of large, high quality optical single crystals. The good chemical stability and mechanical properties make it easy to process by cutting and polishing. In particular, by comparing its optical, thermal, and mechanical properties with the industrial birefringent materials, we believe that NBBF is an attractive candidate for the next generation of deep UV birefringent materials. 2. Pb17O8Cl18: a promising IR nonlinear optical material with large laser damage threshold synthesized in an open system. We have successfully developed POC as a new promising IR NLO crystal. It is type-I phase matchable with a large powder SHG efficiency of about 4 times that of KDP at 1064 nm and 6 times that of AgGaS2 at 2090 nm. The introduction of the Cl- anion with a large electronegativity and Pb as a relatively heavy element in POC gives rise to the extension of its UV and IR cut-off edge to 0.34 and 13.9 μm, respectively. POC also exhibits high thermal stability. Remarkably, POC could effectively overcome the two main drawbacks of the commercially available IR NLO materials: (a) it shows high LDT of 408 MW/cm2, which is 12.8 times that of the benchmark IR NLO AgGaS2 materials; (b) transparent POC single crystals with sizes up to 7 mm × 2 mm × 2 mm can be obtained in an open system, which can overcome the difficulty to grow high-quality crystals by the conventional Bridgman?Stockbarger technique. Theoretical morphology of POC was studied according to the Bravais–Friedel and Donnay–Harker (BFDH) theory.We therefore believe that POC is a promising IR NLO material and research to grow larger high quality POC single crystals is in progress. 3. Application of dimensional reduction formalism to Pb5(PO4)2P2O7. We have successfully synthesized Pb5(PO4)2P2O7, a novel unitary metal phosphate with two types of discrete P-O groups, which is very rare. We obtained its LT phase and RT phase using the variable-temperature X-ray single crystal diffractions and confirmed the temperature section of phase transition by the the variable-temperature powder X-ray diffractions technique. The synthesis followed the dimensional reduction theory. 4. Synthesis, crystal structure and properties of Pb8M(BO3)6 (M = Mg, Ca). Followed the Lewis acid theory, we have successfully synthesized Pb8M(BO3)6 (M = Mg,Ca) through the substitution of cations with the similar lewis acid strength. Pb8M(BO3)6 (M = Mg,Ca) contain ?[Pb8B6O18]2- double layer, the double layers are connected by Mg2+ (Ca2+) along the c axis. The synthesis of Pb8M(BO3)6 (M = Mg,Ca) is a good example of using the lewis acid theory.
文献类型学位论文
条目标识符http://ir.xjipc.cas.cn/handle/365002/4239
专题材料物理与化学研究室
作者单位中国科学院新疆理化技术研究所
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张辉. 深紫外双折射晶体Na3Ba2(B3O6)2F和中红外非线性光学晶体Pb17O8Cl18的设计合成、晶体生长及性质研究[D]. 北京. 中国科学院大学,2015.
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