近化学计量比LiNbO3晶体电畴结构观察和机理探讨

采用双坩埚提拉法(DCCZ)生长了各种不同成分的近化学计量比LiNbO3晶体,并用腐蚀法观察了其电畴结构.结果表明,化学成分对未经极化处理晶体的电畴结构起决定性作用,当Li2O含量处于49.4mol%附近时,晶体z面电畴呈现特殊的三次对称反畴;当晶体中Li2O含量为49.7mol%时,晶体为完全单畴.本文对其形成机理进行了探讨,认为在由顺电相向铁电相转变时,局部铁电畴的极性方向与该处沿z轴方向的温度梯度正负密切相关,z轴生长晶体时,由于相变发生所处位置离生长界面的距离受LiNbO3晶体计量比影响,所处温场固有温梯也随之不同,在此基础上解释了不同成分晶体的电畴结构形成原因.最后讨论了控制铁电畴结构的工艺措施.     

外加电场法制备LiNbO3周期畴的工艺研究

研究了LiNbO₃单晶周期极化畴结构的制备工艺, 讨论了外电场的特性对周期极化过程的影响. 在对周期畴制备各工艺步骤进行实验研究的基础上, 提出解决LiNbO₃单晶周期畴制备中一直存在的边缘击穿问题, 必须选择合适的周期电极形式并对脉冲波形进行优化. 采用所提出的工艺, LiNbO₃周期极化畴的成品率提高到了90%. 为解决周期极化过程中反转畴的侧向扩展, 在对周期极化物理过程进行分析的基础上, 采取了对周期电极宽度进行优化设计和在样品上包覆聚酰亚胺绝缘胶的方法, 有效克服了这一问题, 制备了占空比符合预期的高质量的周期畴结构.     

激光非线性复合功能晶体的研究和发展

简要回顾了激光非线性复合功能晶体(即自倍频晶体)的发展过程,从结构、生长和性能等方面对现已研制发展的Nd:Mg:LiNbO₃(NMLN)、Nd_xY_1-xAl₃(BO₃)₄(NYAB)、Cr:KTP、LaBGe_^O5:Nd³⁺、β’-Gd₂(MoO₄)₃:Nd³⁺(GMO:Nd³⁺)、掺Nd³⁺或Yb³⁺的ReCa₄O(BO₃)₃(ReCOB;Re=Gd、Y)(即 Nd:GdCOB、Yb:GdCOB、Nd:YCOB、Yb:YCOB)、Yb:BaCaBO₃F 等几种主要类型的自倍频晶体的研究现状进行了总结,并对该类晶体的发展做了展望.     

Pb(Mg1/3Nb2/3)O3-PbTiO3晶体组分对结构与性能的影响

用熔体Modified Brdgman法生长出尺寸直径40 mm长度80 mm的弛豫铁电单晶PMNT90/10,表明该方法不仅适合在准同型相界(MPB)附近生长PMNT单晶,也适合生长PT含量很低的PMNT单晶.在生长出的PMNT90/10晶体中,铁电相与顺电相两相共存,并呈现亚微畴结构特征.随着晶体组分由PMN组元变化到MPB组分附近,PMNT的电畴结构呈现微畴-亚微畴-不规则宏畴-规则宏畴演化系列,而介电弛豫特性则逐步弱化.PMNT固熔体的电学性能依赖于晶体组分,(001)切型PMNT90/10晶体的压电常数d33约80 pC/N,显著低于MPB附近组分,但其介电常数ε达到12600,明显高于后者.     

掺Mn近化学计量比铌酸锂晶体生长及其性质

采取中频加热和TSSG的方法,从掺入了6%(质量分数)K2O的同成分Li2O-Nb2O5熔体中生长出了近化学计量比铌酸锂单晶,其铁电畴结构为单畴结构,居里温度为1191.5℃.在此基础上,分别掺入0.05%(质量分数),0.16%(质量分数)和0.32%(质量分数)的氧化锰,生长了掺Mn近化学计量比的铌酸锂晶体,其铁电畴结构也均为单畴结构,居里温度分别为1195.3、1201.5和1219℃.对这4个晶体进行的红外光谱测试的结果表明均在3466cm-1有一吸收峰.通过二波耦合实验,我们对不同掺杂浓度的4种晶体进行了光折变性能测试.     

掺杂对PMN-10PT铁电陶瓷介电性能的影响

铌镁酸铅与钛酸铅组成比为9:1(PMN-10PT)的固溶体陶瓷是典型的弛豫铁电体,其介电行为与偶极玻璃的介电行为极为相似.本文使用常用的Swartz两步法,研究了基体掺杂不同物质对PMN-10PT铁电陶瓷的介电性能的影响.经研究发现,当掺入Li₂O时,材料的峰值介电常数为28640,大于纯PMN-10PT,而频率色散和弥散相变的程度都变小.当掺杂CaO和Yb₂O₃时,材料的峰值介电常数下降,分别为19300和18850,它们的频率色散和弥散相变的程度都变大了.同时通过拉曼光谱研究了PMN-10PT陶瓷的B位离子有序度的变化.     

钡过量非化学计量M型铁氧体的合成与表征

采用并加共沉淀工艺在900℃热处理2h的条件下合成了单相钡过量非化学计量M型铁氧体Ba_1+xCoTiFe₁₀O_19+x(x=0.00、0.05、0.10、0.15、0.20), 并用XRD、SEM、TEM和VSM表征了这种新的非化学计量M型铁氧体的结构和磁学特性. 结果表明: 当0c和剩余磁化强度σ_r均随x增大而显著增大(Δσ_r=5.36A·m^2·kg^-1, ΔH_c=16.99 kA·m^-1, 但比饱和磁化强度σ_s基本不变; 0.053+离子被稀释导致σ_s、H_c和σ_r均随x增大而持续降低. 同时证实钡过量并不会导致晶体对称性破坏, 02+离子分布于平行于a轴方向的大孔隙位?置, 不仅具有助熔剂作用, 而且对磁畴壁产生了钉扎效应.     

PZT铁电薄膜Sol-Gel技术制备和电性能研究

以乙酸铅(Pb(CH₃COO)₂·3H₂O)、钛酸四丁酯(Ti(OC₄H₉)₄)、硝酸锆(Zr(NO₃)₄·5H₂O)替代锆醇盐为原料,通过在Pt/Ti/SiO₂/si基片与PZT薄膜之间引入PT种子层,采用改进的sol-gel工艺制备出无裂纹,致密性好,晶粒尺寸小且分布均匀的单一钙钛矿结构的Pb(Zr_0.53Ti_0.47)O₃铁电薄膜.实验结果表明,具有PT种子层的PZT铁电薄膜电性能较好.经600℃热处理的具有PT种子层的PZT薄膜,在1kHz测试频率下,其剩余极化强度和矫顽场分别为20μC/cm²和59kV/cm,介电常数和介电损耗分别为385和0.030.     

Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3压电单晶的弛豫反常

对用改进的Bridgman法生长的Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3(PZNT91/9)单晶用Laue衍射法和XRD衍射曲线定向,取(001)晶片研究材料的电学性能.结果表明,材料的介电性能呈现出明显的频率色散现象,随着测试频率的升高,介电常数的峰值温度出现反常,峰的位置向低温方向移动.用扫描电子显微镜和正交偏光显微镜研究了PZNT91/9单晶的电畴结构,发现规则排列的带状畴与杂乱分布的细畴并存.X射线荧光分析结果表明,在PZNT91/9单晶中存在着由成分分凝引起的组分变化.成分分凝引起的组分波动和电畴结构的复杂性导致了材料性能的不均匀性,并与材料铁电相变的弥散性特征相关.     

Bridgman法生长的MnxCd1-xIn2Te4晶体相形成规律和物理性能研究

采用Bridgman法生长了x为0.1,0.22和0.4的四元稀磁半导体化合物Mn_xCd_1-xIn₂Te₄晶体.研究了三根晶体中相的形貌、结构、成分和Mn_0.1Cd_0.9In₂Te₄晶体中各组元沿轴向和径向的成分分布.晶体生长初始端的组织为α+β+β₁,随着生长的进行,形成β相的单相区.在晶锭末端,形成In₂Te₃类面心立方结构化合物.组分x增大后,Mn_xCd_1-xIn₂Te₄晶体的吸收边向短波方向移动,禁带宽度则线性增大.磁化率测量结果表明:晶体在高温区的x^-1-T曲线服从居里-外斯定律,在低温区(<50K)则表现出顺磁增强现象.     

Evaluation of mass-produced commercial LiTaO3 single crystals using the LFB ultrasonic material characterization system

A mass-production line of lithium tantalate (LiTaO3) crystals with a maximum charge number of 60 for surface acoustic wave (SAW) devices was evaluated with the line-focus-beam (LFB) ultrasonic material characterization system. Some serious problems associated with chemical compositions were observed and resolved by measuring the velocities of Rayleigh-type leaky surface acoustic waves (LSAWs), VLSAW, for two groups of LiTaO3 wafers: 21 36 degrees Y X-LiTaO3 wafers selected randomly from crystal ingots grown with different charge numbers in different furnaces, and 14 42 degrees Y X-LiTaO3 wafers obtained at the top, middle, and bottom parts from 5 crystals selected from 39 crystals grown successively in the same furnace and crucible. Using the measured VLSAW and the predetermined relationship between VLSAW and Li2O concentrations, M(Li2O), we estimated the average M(Li2O) controlled in the current mass-production line to be about 48.77 mol% with a maximum difference of 0.75 mol%. The composition for each crystal ingot increased linearly about 0.04 mol% from the top to the bottom, and no dependence on the charge number was observed, as the melt composition used for the mass production was controlled through Curie temperature (TC) measurements. A nearly true congruent composition of 48.49 Li2O-mol% was obtained through the precise VLSAW data for the 42 degrees Y X-LiTaO3 wafers, that was about 0.3 mol% less than the melt composition in the production line. It was also pointed out that the TC measurement conditions, including room temperatures surrounding the measurement systems, should be re-examined for reliable production control. A guideline for more efficient mass production of the crystals has been established concerning the true congruent composition as the starting material.     

Pb[（Zn1／3Nb2／3）0.91Ti0.09]O3压电单晶的驰豫反常

对用改进的Bridgman法生长的Pb[(Zn1/3Nb2/3)0.91Ti0.09]O3（PZNT91／9）单晶用Laue衍射法和XRD衍射曲线定向，取（001）晶片研究材料的电学性能，结果表明，材料的介电性能呈现出明显的频率色散现象，随着测试频率的升高，介电常数的峰值温度出现反常，峰的位置向低温方向移动。用扫描电子显微镜和正交偏光显微镜研究了PZNT91／9单晶的电畴结构，发现规则排列的带状畴与杂乱分布的细畴并存，X射线荧光分析结果表明，在PZNT91／9单晶中存在着由成分分凝引起的组分变化。成分发凝引起的组分波动和电畴结构的复杂性导致了材料性能的不均匀性，并与材料铁电相变的弥散性特征相关。     

Effect of amino acid doping on the growth and ferroelectric properties of triglycine sulphate single crystals

Effect of amino acids (l-leucine and isoleucine) doping on the growth aspects and ferroelectric properties of triglycine sulphate crystals has been studied. Pure and doped crystals were grown from aqueous solution by low temperature solution growth technique. The cell parameter values were found to significantly vary for doped crystals. Fourier transform infrared analysis confirmed the presence of functional groups in the grown crystal. Morphology study reveals that amino acid doping induces faster growth rate along b-direction leading to a wide b-plane and hence suitable for pyroelectric detector applications. Ferroelectric domain structure has been studied by atomic force microscopy and hysteresis measurements reveal an increase of coercive field due to the formation of single domain pattern.     

Evaluation and improvement of optical-grade LiTaO3 single crystals by the LFB ultrasonic material characterization system

This paper describes the first demonstration for feeding back the results obtained by the line-focus-beam ultrasonic material characterization (LFB-UMC) system to the crystal growth conditions for optical-grade LiTaO₃ crystals and for achieving much improved homogeneity of chemical composition. We evaluated a commercially available optical-grade LiTaO₃ single crystal with a nominally congruent composition in detail, by measuring distributions of the velocities of leaky surface acoustic waves (LSAW) along the Y-axis direction for a Z-cut specimen plate prepared from the crystal grown in the Y-axis direction. We detected an increment of 0.66 m/s in LSAW velocity along the pulling axis direction corresponding to 0.024 mol% in Li₂O content, and the compositional gradient was +0.346×10^-3 (Li₂O-mol%)/mm. By experimentally obtaining the starting material composition dependence of the gradients, we developed a method of estimating the proper composition ratio that would lead to a more homogeneous crystal. We grew a new crystal with a Li₂O content of 48.47 mol%, resulting in a very small compositional gradient of +0.046×10^-3 (Li ₂O-mol%)/mm and a compositional homogeneity of less than 0.012 Li₂O-mol% in a Z-cut area of 50 mm×50 mm used for device substrates     

Light deflection from ferroelectric domain structures in congruent lithium tantalate crystals

Congruently grown lithium tantalate crystals containing ferroelectric domain structures have been illuminated with ultraviolet light along the crystallographic c axis with simultaneous application of an external electric field. This gives rise to a star-shaped light diffraction pattern in the transmitted beam. The characteristics of this phenomenon are investigated and compared with those observed in lithium niobate crystals.     

Pyroelectric performances of rhombohedral 0.42Pb(In₁/₂)Nb₁/₂)O₃-0.3Pb(Mg₁/₃Nb₂/₃)O₃-0.28PbTiO₃ single crystals

Relaxor-based ferroelectric single crystals xPb(In?/?)Nb?/?)O?-yPb(Mg?/?Nb?/?)O?-(1-x-y)PbTiO? {PIMNT [100x/100y/100(1-x-y)]} have been grown by a modified Bridgman technique. The as-grown PIMNT (42/30/28) crystal with rhombohedral perovskite-type structure shows higher Curie temperature TC ~ 187 °C, and higher ferroelectric rhombohedral-to-tetragonal phase transition temperature TRT ~ 152 °C, both about 50 °C higher than those found for 0.71Pb(In?/?)Nb?/?)O?-0.3Pb(Mg?/?Nb?/?)O?-0.29PbTiO? crystals. Moreover, as a core parameter of pyroelectric material, the detectivity figures-of-merit of PIMNT (42/30/28) crystal are higher than other typical relaxor-based ferroelectric crystals, which primarily stems from the lower dielectric loss, making it promising candidate for infrared detector applications.     

Growth of TGS single crystal by conventional and SR method and its analysis on the basis of mechanical, thermal, optical and etching studies

Unidirectional <001> bulk ferroelectric Tri glycine sulphate (TGS) single crystal of diameter 18 mm and length 150 mm was successfully grown by SR method. The grown TGS single crystal was characterized using etching, Vicker's microhardness, TG-DTA and UV-Vis analysis. The TGS crystals grown by SR method have higher hardness than conventional method grown crystals. Dislocation density (DD) is less in SR grown crystal compared to conventional method grown TGS crystals. The transmittance of SR grown TGS is 8% higher than that of the conventional grown crystal.     

Electromechanical properties and anisotropy of single- and multi-domain 0.72Pb(Mg(1∕3)Nb(2∕3))O(3)-0.28PbTiO(3) single crystals

Complete sets of elastic, piezoelectric, and dielectric constants of 0.72Pb(Mg(1∕3)Nb(2∕3))O(3)-0.28PbTiO(3) single crystal poled along [111](c) (single domain) as well as non-polar axes [001](c) and [011](c) (multidomain) have been measured under natural conditions. These data allowed us to evaluate accurately the extrinsic contributions to the superior piezoelectric properties. Very large extrinsic contributions to the unusual anisotropies in multidomain crystals are confirmed. We found that the instability of domain structures is the origin of the low mechanical quality factor Q for the multidomain relaxor-based ferroelectric single crystals. Our results can provide useful guidance in future design of domain engineered materials.     

升温对[100]cub弛豫铁电PMN-32PT单晶电畴组态演变的影响

采用热台偏光显微镜观察以ACRT+ Bridgman法获得、经过金相抛光处理的弛豫铁电PMN-32PT单晶[100]cub切型电畴组态,考察了未退火状态下[100]cub切型单晶的消光行为及连续升温对本征电畴与由抛光机械应力诱导非本征电畴组态的影响.结果表明,在升温过程中,PMN-32PT单晶非本征电畴在三方-四方铁电相变后消失;本征电畴组态的变化表现为两个阶段,第一阶段畴先细化后宽化,第二阶段进行铁电-顺电相变,相变过程缓慢,持续范围为168～177℃,且与三方-四方相变出现次序相反.