两种新型芴衍生物的合成、晶体结构及光谱性能

合成了两种新型芴衍生物:2,7-二（3,5-二（三氟甲基）苯基）-9,9-二乙基芴（1）和2,7-二（4-氟苯基）-9,9-二乙基芴（2）。通过元素分析、红外光谱（IR）、核磁共振氢谱（¹H NMR）以及单晶X射线衍射对其结构进行了表征。化合物1属于单斜晶系,P2₁/c空间群;化合物2属于三斜晶系,P-1空间群。通过紫外-可见吸收和荧光光谱研究了化合物的发光性能。结果表明:在CH₂Cl₂溶液和固态薄膜中,化合物1、2在350～400 nm波段有吸收峰,归属于π-π^*电荷跃迁;化合物1、2的光学带隙E_g分别为3.31 eV和3.30 eV,并且均有强烈的蓝色荧光发射现象（激发波长为330 nm）,在二氯甲烷中的荧光量子效率分别为0.62和0.61,固态荧光寿命分别为6.39 ns和9.00 ns。     

柔性Pb(Zr_(0.53)Ti_(0.47))O_3薄膜的高温铁电特性

随着柔性电子产品的迅速发展,具有优异铁电和压电性的Pb(Zr_(0.53)Ti_(0.47))O_3 (PZT)薄膜在柔性的非易失性存储器、传感器和制动器等器件中有广泛的应用前景.同时,由于外部环境越来越复杂,具有高温稳定特性的材料和器件受到越来越多的关注.本文在耐高温的二维层状氟晶云母衬底上,用脉冲激光沉积技术制备出外延的PZT薄膜,并通过机械剥离的方法,得到柔性的外延PZT薄膜.研究了Pt/PZT/SRO异质结的铁电和压电性及其高温特性,发现样品表现出优越的铁电性,剩余极化强度(P_r)高达65μC/cm~2,在弯曲104次后其铁电性基本保持不变,且样品在275℃高温时仍然保持良好的铁电性.本文为柔性PZT薄膜在航空航天器件中的应用提供了实验基础.     

RAMAN STUDIES ON THE PHASE TRANSITIONS OF (NH4)2SnBr6 CRYSTALS

We report here the structural phase transitions of the crystal (NH₄)₂SnBr₆ investigated by Raman scattering at temperatures ranging from 10K to room temperature. Two phase transitions occurring at 150 and ll0K are found. Based on the group theory, it is proposed that the crystal undergoes a second-order phase transition at 150 K, resulting from a ferro-distortion with symmetry Γ⁴⁺. The change of structure is confirmed to be O⁵_h to C⁵_4h, which is assigned to the rotary of [SnBr₆]^2- ion groups around the axis of <001>. Furthermore the crystal undergoes an order-disorder phase transition at ll0K which is related with the reorientation of the ammonium ion group. It is noticed that the change of the vibrational modes at 77K does not show any phase transition.     

Excited state biexcitons in monolayer WSe2 driven by vertically grown graphene nanosheets with high-density electron trapping edges

Interface engineering in atomically thin transition metal dichalcogenides (TMDs) is becoming an important and powerful technique to alter their properties, enabling new optoelectronic applications and quantum devices. Interface engineering in a monolayer WSe₂ sample via introduction of high-density edges of standing structured graphene nanosheets (GNs) is realized. A strong photoluminescence (PL) emission peak from intravalley and intervalley trions at about 750 nm is observed at the room temperature, which indicated the heavily p-type doping of the monolayer WSe₂/thin graphene nanosheet-embedded carbon (TGNEC) film heterostructure. We also successfully triggered the emission of biexcitons (excited state biexciton) in a monolayer WSe₂, via the electron trapping centers of edge quantum wells of a TGNEC film. The PL emission of a monolayer WSe₂/GNEC film is quenched by capturing the photoexcited electrons to reduce the electron-hole recombination rate. This study can be an important benchmark for the extensive understanding of light–matter interaction in TMDs, and their dynamics.     

应力作用下EuTiO3铁电薄膜电热效应的唯象理论研究

基于Laudau-Devonshire的热动力学模型, 计算了EuTiO₃铁电薄膜材料的电热效应. 结果显示在外加应力的调控下, 电极化、电热系数以及绝热温差都会随之变化. 外加垂直于表面的张应力加大, 薄膜的相变温度升高, 绝热温差增加, 最大绝热温差所对应的工作温度向高温区移动. 对于二维平面失配应变u_m =-0.005的薄膜, 当外加张应力σ₃ = 5 GPa时, 其最大电热系数为1.75×10^-3 C/m²·K, 电场变化200 MV/m 时室温下绝热温差ΔT 的最大值可达到14 K 以上, 绝热温差ΔT ≥13 K 的工作温区超过120 K, 表明可以通过调控外部应力来获取室温时较大的绝热温差. 此结果预示着铁电EuTiO₃ 薄膜在室温固态制冷方面可能具有较好的应用前景.     

MAGNETIC AND ELECTRICAL PROPERTIES OF TWO POLYANILINE FAMILIES:PANI-H3PO4 and PANI-C4H6O6

We report a comparative study between two kinds of polyaniline, PANI-H₃PO₄ and PANI-C₄H₆O₆. We have measured the temperature dependence of the dc-conductivity σ_dc(T) and magnetic susceptibility χ_T(T). The structure of polyaniline was characterized by F ourier transform infrared technique, electron-spin-resonance and X-ray diffraction. Polyanil ine synthesized with phosphoric and tartaric acids leads to high magnetic suscep tibility χ_T(at T=295 K)≈10^-4 emu/mol.2rings. The dc-conductivity of both kinds of PANI shows a semiconductor behavior and follows the quasi one-dimensional variable-range-hopping model. A compa rison of the magnetic susceptibility shows greater electron localization in PANI-C₄H₆O₆, which is in agreement with the lower conductivity at room temper ature for PANI-C₄H₆O₆.     

反应前驱物中n(S)∶n(Cd)对CdS薄膜结构及发光特性的影响

采用化学水浴以CdCl2·H2O、CS( NH2)2、NH4Cl、NH3·H2O和去离子水作为反应前驱物制备CdS纳米晶薄膜.采用扫描电镜( SEM)、X射线衍射(XRD)、透射光谱和稳态荧光光谱,研究了反应前驱物中不同的n(S)∶n(Cd)对所制备的CdS薄膜的形貌、结构和光学性能的影响.结果表明:反应前驱物中n(S...     

钙钛矿薄膜气相制备的晶粒尺寸优化及高效光伏转换

钙钛矿薄膜的气相制备是一种极具潜力的工业化生产工艺,但薄膜的质量控制目前远落后于溶液制备法.本文通过建立PbI_2薄膜向钙钛矿薄膜完全转化过程中反应时间、晶粒尺寸与温度的关系,实现了薄膜的质量优化及大面积钙钛矿薄膜的制备,将薄膜的平均晶粒粒径从0.42μm优化到0.81μm.基于空间电荷限制电流模型对缺陷密度的研究显示,钙钛矿薄膜的缺陷密度由5.90×10~(16)cm~(–3)降低到2.66×10~(16)cm~(–3).光伏器件(FTO/TiO_2/C_(60)/MAPbI_3/spiro-OMeTAD/Au结构)测试显示,面积为0.045cm~2器件的平均光电转换效率从14.00%提升到17.42%,最佳光电转换效率达到17.80%,迟滞因子减小至4.04%.同时,基于180℃制备的1cm~2器件的光电转换效率达到13.17%.     

An ingenious approach of determining hydrogen isotope solubilities, diffusivities and permeabilities in GWHER-1 stainless steel

In this paper, by using an ingenious method, the hydrogen isotope solubilities and diffusivities in GWHER-1 stainless steel have been determined by a vacuum heating degassing approach at the temperature range of 597-1022 K on a set of specimens with different sizes previously charged for 24 h under a hydrogen isotope pressure of 105 Pa in the temperature range of 800-1000 K. The permeabilities are then derived from the relation Φ = DKs. It is found D = 1.52 ×10^-6exp（-54100/RT）, Ks = 2.2×10^-exp（-5400/RT） and Φ = 3.3 ×10^-12exp（-59500/RT） for hydrogen, where Ks （Sieverts＇ constant） is given in Pa^-1/2, D in m2.s^-1.Pa^-1/2, T in K and R=8.31 J.mol^-1.K^-1. By taking isotope effects into account, the corresponding Arrhenius relations for deuterium and tritium are also deduced.     

高质量ZnO及BeZnO薄膜的发光性质

用分子束外延设备插入缓冲层在c面蓝宝石上生长得到高质量ZnO和BeZnO薄膜。XRD测试显示薄膜具有六方结构和c轴取向,并具有良好的晶体质量,其中ZnO薄膜的半高宽仅为108 arcsec,Be_xZn_1-xO薄膜的半高宽小于600 arcsec。对ZnO和BeZnO薄膜的拉曼光谱进行对比研究发现,随着Be元素的掺入,A₁(LO)、A₁(2LO)声子模频率往大波数方向移动,并且首次发现了与Be元素掺杂有关的局域振动模。利用变温光致发光光谱研究了薄膜的发光性质,结果显示ZnO薄膜室温光致发光只出现一个紫外发发光峰(378 nm),而低温光谱(80 K)则出现了很强的自由激子发光峰。随着温度的升高,束缚激子发光逐渐湮灭向自由激子发光转变,并且峰值位置红移。相对于ZnO薄膜,BeZnO薄膜的紫外发光主峰位置蓝移,并且由于Be元素的掺入导致薄膜晶体质量下降,在低温(80 K)光致发光光谱中没有出现强的自由激子发光峰。另外,在低温光致发光及拉曼光谱中,主峰位置在100~200 K之间有局部最大值,推测为由于合金晶格热膨胀系数失配而引起的应力效应。     

过渡金属与F共掺杂ZnO薄膜结构及磁、光特性

采用溶胶-凝胶法在玻璃衬底上制备了过渡金属元素与F共掺杂Zn_0.98-xTM_xF_0.02O (TM_x=Cu_0.02, Ni_0.01, Mn_0.05, Fe_0.02, Co_0.05)薄膜, 进而利用X射线衍射仪、扫描电子显微镜、紫外-可见透过谱、光致发光及振动样品磁强计等研究了薄膜的表面形貌、微结构、禁带宽度及光致发光(PL)和室温磁学特性. 研究表明: 掺杂离子都以替位的方式进入了ZnO晶格, 掺杂不会破坏ZnO的纤锌矿结构. 其中Zn_0.93Co_0.05F_0.02O薄膜样品的颗粒尺寸最大, 薄膜的结晶度最好且c轴择优取向明显; Zn_0.93Mn_0.05F_0.02O薄膜样品的颗粒尺寸最小, 薄膜结晶度最差且无明显的c轴择优取; Cu, Ni, Fe与F共掺杂样品的颗粒尺寸大小几乎相同. TM掺杂样品均表现出很高的透过率, 同时掺杂后的薄膜样品的禁带宽度都有不同程度的红移. PL谱观察到Zn_0.98-xTM_xF_0.02O薄膜的发射峰主要由较强的紫外发射峰和较弱的蓝光发射峰组成. Zn_0.93Mn_0.05F_0.02O薄膜样品的紫外发光峰最弱, 蓝光发射最强, 饱和磁化强度最大; 与之相反的是Zn_0.96Cu_0.02F_0.02O薄膜, 其紫外发光峰最强, 蓝光发射最弱, 饱和磁化强度最小. 结合微结构和光学性质对Zn_0.98-xTM_xF_0.02O薄膜的磁学性质进行了讨论.     

铒铥共掺氧化锌薄膜近红外宽带发射及变温行为的研究

采用磁控共溅射技术制备了铒铥共掺杂氧化锌发光薄膜. 通过优化退火温度, 实现了薄膜的近红外 平坦宽带发射, 总带宽可达到~ 500 nm, 覆盖了光通信S+C+L+U 区波段. 此发射带由Er³⁺ 的1535 nm (⁴I_13/2 → ⁴I_15/2) 发射峰及Tm³⁺ 的1460 nm (³H₄ → ³F₄), 1640 nm (¹G₄ → ³F₂), 1740 nm (³F₄ → ³H₆) 发射峰组成. 研究表明: 退火温度低于800 ℃ 时, 没有观察到薄膜样品明显的光致发光现象; 随着退火温度 从800 ℃ 升高到1000 ℃, I₁₆₄₀/I₁₅₃₅ 发射峰强度比从0.2 升高到0.3, I₁₇₄₀/I₁₅₃₅ 发射峰强度比从0.5 降低 到0.4, 发射峰强度比均基本保持稳定; 当退火温度高于1000 ℃ 时, I₁₆₄₀/I₁₅₃₅ 发射峰强度比从0.3 升高到 0.6, I₁₇₄₀/I₁₅₃₅ 发射峰强度比从0.4 升高到0.8, 发射峰强度比均急剧增加. 变温行为表明: 随着温度从10 K 逐渐升高到300 K, 谱线的总带宽基本不变, 在340—360 nm 之间; Tm³⁺ 在1640 和1740 nm 处的发射峰强度 分别降低了2/3 和1/2, Er³⁺ 在1535 nm 的发射峰强度增大了1.2 倍. 这是因为随着温度的升高, 声子数目增 多, Er³⁺ 与Tm³⁺ 离子之间发生能量传递的概率不断变大, 并且在Tm³⁺ 离子之间没有发生交叉弛豫现象.     

SUPERCONDUCTING TRANSITION TEMPERATURES AND NORMAL-STATE ELECTRICAL RESISTIVITIES OF Tm1-xPrxBa2Cu3O7-δ

Superconducting transition temperature T_c and normal-state electrical resistivities ρ of the Tm_1-xPr_xBa₂Cu₃O_7-δ system have been measured. The results indicate that T_c remains constant for x = 0 to 0.08 before it drops steadily with higher x. Following the Abrikosov-Gor'kov model, a total suppression of superconductivity occurs at a critical Pr concentration x_cr≈0.56. It is found for the first time, as far as we know, that the logarithmic resistivity at 270 K increases linearly with increasing x, yielding ρ= ρ₀e^ax. Judging from the relation between dρ/dT and x, a metal to insulator transition occurs just beyond x_cr.     

钛酸锶钡薄膜的室温光学性能研究

采用溶胶-凝胶法制备了(Ba0.75Sr0.25)TiO3薄膜,研究了不同退火温度下样品的物相结构、薄膜的光致发光性能和光学透过率。结果表明:室温下非晶钛酸锶钡薄膜在蓝光激发下具有明显的发光现象,发光波长范围是500～650 nm,峰值在525 nm附近。延长非晶态薄膜的退火时间能够显著提高样品的发光强度,且发光强度随薄膜厚度增加而增大。晶态薄膜有微弱的发光现象。透射谱测试结果表明,钛酸锶钡薄膜在可见光范围内具有良好的光学透过率。     

Scintillation properties of the Yb-doped YAlO3 crystals

Yb³⁺-doped YAlO₃ single crystals were grown by the Czochralski method with a radio frequency heating system. The starting melt compositions of Y_1−xYb_xAlO₃ were varied as x=0.02, 0.1, 0.2, 0.3 and 0.45. Photo- and thermo-luminescence characteristics including emission decays were measured within 4–300 K. Very fast charge transfer luminescence of Yb³⁺ was found, with the typical double peak spectrum at 345 and 525 nm. At room temperature the photoluminescence and scintillation decay curves show a leading subnanosecond decay component without any additional slower processes. The high density of Yb-rich YAlO₃ makes this material a promising candidate for fast scintillators.     

Effect of high-temperature annealing on AlN thin film grown by metalorganic chemical vapor deposition

The effect of high-temperature annealing on AlN thin film grown by metalorganic chemical vapor deposition was investigated using atomic force microscopy, Raman spectroscopy, and deep ultra-violet photoluminescence(PL) with the excitation wavelength as short as ～ 177 nm. Annealing experiments were carried out in either N2 or vacuum atmosphere with the annealing temperature ranging from 1200℃ to 1600℃. It is found that surface roughness reduced and compressive strain increased with the annealing temperature increasing in both annealing atmospheres. As to optical properties,a band-edge emission peak at 6.036 eV and a very broad emission band peaking at about 4.7 eV were observed in the photoluminescence spectrum of the as-grown sample. After annealing, the intensity of the band-edge emission peak varied with the annealing temperature and atmosphere. It is also found that a much stronger emission band ranging from 2.5 eV to 4.2 eV is superimposed on the original spectra by annealing in either N2 or vacuum atmosphere. We attribute these deep-level emission peaks to the VAL–ONcomplex in the AlN material.     

Pressure- and temperature-dependent luminescence from Tm3+ ions doped in GdYTaO4

Luminescent properties of Tm³⁺-doped GdYTaO₄ are studied for exploring their potential applications in temperature and pressure sensing.Two main emission peaks from ³H₄→³H₆ transition of Tm³⁺are investigated.Intensity ratio between the two peaks evolves exponentially with temperature and has a highest sensitivity of 0.014 K^?1 at 32 K.The energy difference between the two peaks increases linearly with pressure increasing at a rate of 0.38 meV/GPa.Intensity ratio between the two peaks and their emission lifetimes are also analyzed for discussing the pressure-induced variation of the sample structure.Moreover,Raman spectra recorded under high pressures indicate an isostructural phase transition of GdYTaO₄ occurring at 4.46 GPa.     

EFFECT OF THE SUBSTITUTION OF Ga ON THE STRUCTURE AND MAGNETIC PROPERTIES OF Dy2Fe17 COMPOUND

Dy₂Fe_17-xGa_x (x = 0,1,2,3,4, 5 and 6) compounds were prepared by arc melting. These compounds are of single phase, having a hexagonal Th₂Ni₁₇-type structure fox x=0 and rhombohedral Th₂Zn₁₇-type structure for x≥1. The substitution of Ga for Fe in the Dy₂Fe₁₇ leads to a linear increase of unit-cell volumes. The saturation magnetization M_s at 1.5K is found to decrease linearly with increasing Ga concentration, from 65emu/g for x= 0 to 5emu/g for x = 6; and the Fe magnetic moment μ_Fe is almost independent of Ga concentration. The Curie temperature T_C is found first to increase with increasing Ga content x, and goes through a maximum value of 559 K at about x = 3, then decreases. The sharp increase of T_C at lower Ga content may result from the increase of unit cell volumes. Dy₂Fe_17-xGa_x compounds with x≤5 exhibit easy plane anisotropy at room temperature, and those with x = 6 possess easy-axis.     

MgB2超导薄膜的变温拉曼光谱研究

MgB₂作为迄今为止超导转变温度最高的合金超导体,由于其具有结构简单、相干长度长、晶界间不存在弱连接、上临界场很高、电-声散射时间短等特点,MgB₂超导薄膜在电子学领域有着广阔的的应用前景。拉曼光谱是研究电-声子相互作用和超导能带的一种有效方法,且已广泛用于分析MgB₂材料的电子、声子特征以及超导体能带结构,研究表明,样品质量、晶粒尺寸以及测试条件对MgB₂拉曼峰的峰位和峰形影响很大,其中拉曼光谱随温度的变化也是一个研究重点,但目前关于MgB₂变温拉曼光谱的研究,测试的温度范围相对较小,局限在83 K到室温区域或是转变温度附近。研究了大范围温度区间内MgB₂薄膜的拉曼光谱变化,采用混合物理化学沉积法在(0001)SiC衬底上制备了MgB₂多晶薄膜,薄膜的晶粒尺寸约为300 nm,超导转变温度为39.3 K,对其在10～293 K之间的拉曼光谱进行了测试,测量的波数范围为20～1 200 cm-1。变温拉曼光谱的测试结果显示,在高频620 cm-1附近以及低频80和110 cm-1附近存在MgB₂的拉曼峰。经分析,低频区域出现的两个拉曼峰的频率与超导能隙宽度相对应,表明MgB₂的双能隙特性。考虑到MgB₂中四种声子模式的拉曼活性,高频620 cm-1附近的拉曼峰应是由E_2g振动模所贡献的,且随着测试温度的降低,该拉曼峰的峰位未发生明显的偏移,但半高宽显著变小,从293 K时的380.7 cm-1减小到10 K时的155 .7 cm-1,分析表明E_2g声子与电子系统的非线性耦合所引起的非简谐效应可能是拉曼峰半高宽线性变小的主要原因。     

热退火对SiO2：Er薄膜发光特性的影响

利用离子注入法制备SiO₂:Er样品,并在不同温度下进行退火处理。通过微区拉曼光谱、吸收光谱、X射线光电子能谱等手段对其进行结构表征,并进行了室温和变温的光致发光特性研究,得到了可见区和红外区的光致发光。其中,⁴S_3/2→⁴I_15/2的发光强度随温度的升高,先增强后减弱,呈现出反常的温度淬灭效应,此现象是由Er³⁺与SiO₂的缺陷之间的能量传递造成的。