一种具有二次谐波发生和适中双折射的紫外透过稀土金属甲酸盐

本研究工作报道了一例采用溶液挥发法合成的稀土金属甲酸盐，分子式为(C(NH₂)₃)[Er(HCOO)₄]。该化合物结晶于非中心对称空间群。光学性质研究表明：该化合物具有较大光学带隙(4.76 eV)、适中的双折射率(0.066@546 nm)；在1 064 nm处，其粉末倍频效应为KH₂PO₄(KDP)的0.2倍，并且可实现相位匹配。第一性原理计算和单晶结构分析揭示了线性和非线性光学效应来源于C (NH₂)₃⁺、[ErO₈]和HCOO^-单元的协同作用。     

两种具有二次谐波响应的紫外透过氨基磺酸盐A(NH2SO3)(A=Li、Na)

通过简便的蒸发方法得到了 2种碱金属磺酸盐非线性光学(NLO)晶体, 即 Li(NH₂SO₃)和 Na(NH₂SO₃)。Li(NH₂SO₃)以极性空间群Pca2₁(编号 29)结晶。Li(NH₂SO₃)的结构可以描述为由[LiO₄]7-多面体通过共角连接与 NH₂SO₃^-四面体相互连接而形成的三维网络。Na(NH₂SO₃)以极性空间群 P2₁2₁2₁(编号 19)结晶。Na(NH₂SO₃)的结构可以描述为由扭曲的[NaO₆]^11-八面体通过共角连接与 NH₂SO₃^-四面体相互连接而形成的三维网络。紫外可见近红外光谱表明, Li(NH₂SO₃)和 Na(NH₂SO₃)分别具有 5.25 和 4.81 eV 的大光学带隙。粉末二次谐波发生(SHG)测量显示, Li(NH₂SO₃)和 Na(NH₂SO₃)的 SHG 强度分别为 KH₂PO₄的 0.32 倍和 0.31倍。第一原理计算证实, 非线性光学性能主要来自氨基磺酸阴离子和碱金属氧阴离子多面体的协同作用。     

两种具有二次谐波响应的紫外透过氨基磺酸盐A(NH2SO3)(A=Li、Na)

通过简便的蒸发方法得到了2种碱金属磺酸盐非线性光学(NLO)晶体,即Li(NH₂SO₃)和Na(NH₂SO₃)。Li(NH₂SO₃)以极性空间群Pca2₁(编号29)结晶。Li(NH₂SO₃)的结构可以描述为由[LiO₄]^7-多面体通过共角连接与NH₂SO₃^-四面体相互连接而形成的三维网络。Na(NH₂SO₃)以极性空间群 P2₁2₁2₁(编号 19)结晶。Na(NH₂SO₃)的结构可以描述为由扭曲的[NaO₆]^11-八面体通过共角连接与 NH₂SO₃-四面体相互连接而形成的三维网络。紫外可见近红外光谱表明,Li(NH₂SO₃)和 Na(NH₂SO₃)分别具有 5.25 和 4.81eV 的大光学带隙。粉末二次谐波发生(SHG)测量显示,Li(NH₂SO₃)和 Na(NH₂SO₃)的 SHG 强度分别为 KH₂PO₄的 0.32 倍和 0.31倍。第一原理计算证实,非线性光学性能主要来自氨基磺酸阴离子和碱金属氧阴离子多面体的协同作用。     

银簇化合物Ag3B6O10I的合成、晶体结构和双折射性质

通过高温固相合成技术,成功合成了一种新型含银簇卤化硼酸盐Ag₃B₆O₁₀I。该晶体属正交晶系,空间群为Pnma (No. 62)。结构分析表明,该晶体结构中BO₄四面体和BO₃三角形连接形成[B₆O₁₀]^2-并最终相互连接形成三维孔洞结构,Ag₃I三角锥位于孔洞中。这种基于B₆O₁₀基元的含银簇三维孔洞结构为首次报道。热稳定性分析表明Ag₃B₆O₁₀I为非同成分熔融化合物,熔融分解温度为963 K。紫外-可见-近红外漫反射光谱分析显示该晶体光学带隙约为3.1 eV。值得关注的是,Ag₃B₆O₁₀I晶体具有较大的双折射率(0.031@550 nm)。第一性原理理论计算揭示了该晶体的光学特性来源。     

新型隔层材料LB交替多层膜的二次谐波研究

有机光学非线性材料在光计算和光通讯领域中有着非常广泛的应用前景［1，2］．非中心对称结构是二阶非线性光学器件的基本要求之一，对于有机两亲光学活性分子而言，使用能够在分子尺度上实现有序组装的Langmuir－Blodgett（LB）技术，可以制备具有稳定而非中心对称结构的多层膜．一般说来，Y型结构的多层膜比X型或Z型更稳定．然而，由单一材料组成的Y型LB多层膜只能形成中心对称结构，因而对宏观二阶非线性极化率X（2）没有贡献．为了解决稳定性与非中心对称性的矛盾，我们可以将光学非线性活性材料（如半花菁染料）与非活性隔层材料…     

非线性光学环氧聚合物的近程结构对二次谐波产生弛豫特性的影响

设计合成了三种具有不同主链化学结构的二阶非线性光学功能化环氧聚合物,并对其化学结构进行了表征,考察了聚合物近程结构对材料极化后二次谐波产生弛豫特性的影响。极化后线型聚合物链节的扭转弹性回复是二次谐波产生弛豫的主要原因,在温度处于Ｔｇ 以下或Ｔｇ 附近时玻璃化转变温度的高低决定了二次谐波产生弛豫的快慢;聚合物交联后有助于提高二次谐波产生的稳定性,但此时聚合物单个链节结构的柔顺性成为影响二次谐波产生弛豫的主要原因,刚性越大,材料将具有更稳定的二次谐波产生性能。极化聚合物的二次谐波产生弛豫过程非常复杂,需要综合考虑聚合物材料的近程和远程结构因素。     

2,4-二硝基苯丙氨酸钠盐·2,4-二硝基苯丙氨酸的合成、分子结构和二次谐波效应

合成了一种新的有非线性光学性能的标题化合物晶体NaAP·HAP,晶体属正交晶系,空间群为P2₁2₁2₁,a=25.773(6),b=12.377(3),c=7.2037(6)Å,z=4,D_c=1.54g·cm^-3。晶体结构由HAP分子(2,4-二硝基苯丙氨酸)、AP^-离子和Na⁺离子组成。Na⁺离子由周围的六个氧原子形成扭曲的八面体配位。这些NaO₆八面体通过共点形成无限链状结构。可用晶体结构的空间因素来解释实验测定的MAP和NaAP·HAP的二次谐波相对强度的顺序。     

中心对称双酞菁铥LB膜二次谐波产生特性

利用二次谐波产生(SHG)方法研究了中心对称分子稀土夹心双酞菁铥(TmPc₂) Langmuir-Blodgett (LB)膜二阶非线性光学特性, 测量了二次谐波强度随入射基频光入射角的关系, 并对其二阶非线性产生机制进行了讨论. 实验结果表明, TmPc₂分子LB膜具有较好的二次谐波信号, 二次谐波信号强度的最大值在基频光入射角为45°的地方, 其二阶非线性极化率χ⁽²⁾和分子超极化率β分别为1.152×10^-8和1.905×10^-30 esu. 通过测量样品二次谐波信号的偏振特性, 并与理论分析相比较, 得出其二阶非线性起源于电四极子作用机制.     

N原子对取代NH_4H_2PO_4盐类晶体的二次谐波发生的影响(英文)

从N—H键在取代NH4H2 PO4盐的 [AH]4 [H2 PO4]类晶体中的突出作用出发 ,作者对几个 [AH]4 [H2 PO4]型晶体的二次谐波发生进行理论上的研究 (这里A =伯、仲、叔胺 )。并对这一类晶体的二次谐波发生和其亚结构单元 [AH]+ 中N原子上的净电荷之间的依赖关系进行了估计。     

钼和稀土的二乙基二硫代甲酸盐配合物的电化学研究

研究了N,N-二乙基二硫代甲酸根(dtc)作配体的双核配位化合物[Mo(dtc)₄][Ln(dtc)₄](Ln=La,Pr,Nd,Sm,Eu,Gd,Tb,Dy,Ho和Er)的氧化还原性质及其在电极过程中的电化学特性.     

类钙钛矿甲酸盐的线性和非线性光学响应

采用原位溶剂热法合成了2种混合有机阳离子杂化甲酸盐(CH(NH₂)₂)[RE (HCOO)₄](RE=Y、Er)。这2种材料是同构的(手性空间群C222₁)，并具有有趣的类钙钛矿结构。进行了包括线性和非线性光学特性在内的光物理研究。(CH(NH₂)₂)[Y(HCOO)₄]和(CH(NH₂)₂)[Er(HCOO)₄]分别表现出5.59和5.61 eV的宽光学带隙，对应于222和221 nm的紫外吸收边缘。粉末倍频测量表明，(CH(NH₂)₂)[Y(HCOO)₄]和(CH(NH₂)₂)[Er(HCOO)₄]的倍频效应分别是基准KH₂PO₄(KDP)的0.32和0.37倍。测量得到(CH(NH₂)₂)[Y(HCOO)₄]和(CH(NH₂)₂)[Er(HCOO)₄]的双折射率分别为0.013和0.015。第一性原理研究表明，2个π共轭的(CH(NH₂)₂)⁺和HCOO^-基团是光学性质的主要贡献者。     

类钙钛矿甲酸盐的线性和非线性光学响应

采用原位溶剂热法合成了2种混合有机阳离子杂化甲酸盐(CH (NH₂)₂)[RE (HCOO)₄](RE=Y、Er)。这2种材料是同构的(手性空间群C222₁),并具有有趣的类钙钛矿结构。进行了包括线性和非线性光学特性在内的光物理研究。(CH (NH₂)₂)[Y (HCOO)4]和(CH (NH₂)₂)[Er (HCOO)₄]分别表现出5.59和5.61 eV的宽光学带隙,对应于222和221 nm的紫外吸收边缘。粉末倍频测量表明,(CH (NH₂)₂)[Y (HCOO)₄]和(CH (NH₂)₂)[Er (HCOO)₄]的倍频效应分别是基准KH₂PO₄(KDP)的0.32和0.37倍。测量得到(CH (NH₂)₂)[Y (HCOO)₄]和(CH (NH₂)₂)[Er (HCOO)₄]的双折射率分别为0.013和0.015。第一性原理研究表明,2个π共轭的(CH (NH₂)₂)⁺和HCOO^-基团是光学性质的主要贡献者。     

Phase transition of lipid-like monolayer characterized by second harmonic generation

Phase transition of a lipid-like hemicyanine compound characterized by second harmonic generation is studied carefully. The phase transition is assigned as the first order transition between solid state and liquid state. The transition temperature increases with an increase in the surface molecular concentration. A monolayer structure parameter a which is very sensitive to the phase transition is introduced.     

Pump–probe second harmonic generation study of ultrafast spin dynamics in semiconductor multilayers

We report the first application of pump–probe second harmonic generation (SHG) measurements to characterize optically induced magnetization in non‐magnetic multilayer semiconductors. In the experiment, spin‐polarized electrons are excited selectively by a pump beam in the GaAs layer of GaAs/GaSb/InAs structures. However, the resulting net magnetization manifests itself through the induced SHG probe signal from the GaSb/InAs interface, thus indicating a spin‐polarized electron transport across the heterostructure. We find that the magnetization dynamics are governed by an interplay between the spin density evolution at the interfaces and the spin relaxation. Copyright © 2003 John Wiley & Sons, Ltd.     

In-situ poling and synthesis of NLO chromophore-bearing polyurethanes for second harmonic generation

The preparation of six diol and one triol monomers bearing donor–acceptor chromophores is described. The monomers contain the N,N′-bis(2-hydroxyethyl)aniline unit with various acceptor groups attached in some cases via azo or olefin linkages, at the para position. Acceptors studied include nitro, tricyanovinyl, cyclobutene-1,2-dione, and imidazolidine-2,4-dione. Poled polymer films were prepared by thermal polymerization of these with 2,4-toluenediisocyanate (TDI) in the presence of an electric field generated by a corona tip. The resulting thin (ca. 1 μm), glassy polymer films were shown to exhibit reasonably good second harmonic generation efficiencies. Preliminary results show that the polymers with higher T_g's have the best temporal stability. The polymer derived from the diol bearing an imidazolidine-2,4-dione acceptor shows only a ca. 30% decrease in its second harmonic generation (SHG) signal over 200 days at room temperature, even though it is not crosslinked. We attribute this to hydrogen bonding interactions from the urethane and imidazolidine-2,4-dione groups. A crosslinked film derived from the triol and TDI has an exceedingly stable SHG response at room temperature, and no decrease in the SHG response is observed at 100°C for a few hours. © 1993 John Wiley & Sons, Inc.     

“Small-particle limit” in the second harmonic generation from noble metal nanoparticles

In this paper, we have probed the origin of SHG in copper nanoparticles by polarization-resolved hyper-Rayleigh scattering (HRS). Results obtained with various sizes of copper nanoparticles at four different wavelengths covering the wavelength range 738–1907 nm reveal that the origin of second harmonic generation (SHG) in these particles is purely dipolar in nature as long as the size (d) of the particles remains smaller compared to the wavelength (λ) of light (“small-particle limit”). However, contribution of the higher order multipoles coupled with retardation effect becomes apparent with an increase in the d/λ ratio. We have identified the “small-particle limit” in the second harmonic generation from noble metal nanoparticles by evaluating the critical d/λ ratio at which the retardation effect sets in the noble metal nanoparticles. We have found that the second-order nonlinear optical property of copper nanoparticles closely resembles that of gold, but not that of silver.     

Investigation of dipolar reorientation dynamics of pure bulk polymers using second harmonic generation

Second harmonic generation (SHG) in three corona-poled, pure, bulk polymers is studied as a function of temperature. It is found that this technique readily yields dynamical information that is complementary to that obtained from the technique of dielectric relaxation (DR). The SHG results are compared to those from DR in the same temperature ranges above T_g. It is found that in the temperature ranges examined, the relaxation times obtained from SHG are several orders fo magnitude longer than those measured by dielectric relaxation. This is explained as being due to the strong correlation between oriented dipoles and to trapped charges injected by the poling process. Fitting measured data to the Williams-Landau-Ferry (WLF) equation indicates that more free volume is needed in SHG for dipolar reorientation than is needed in DR. An SHG relaxation elongation phenomenon at constant temperature is found to occur in the pure bulk polymers and is similar to that found in chromophore-doped polymers previously studied. The SHG technique is developed as a new tool to directly study the reorientational dynamics of polar polymer segments. © 1994 John Wiley & Sons, Inc.