ZnO纳米管的拉曼光谱学研究

通过对ZnO纳米管样品的拉曼光谱研究,发现ZnO纳米管拉曼频率和体材料拉曼频率相同,在不同波长激发下,ZnO纳米管拉曼谱峰的频率也保持不变,从而得到了极性晶体拉曼谱不同于以往非极性拉曼谱的特性:在纳米体系中没有出现明显的尺寸限制效应。     

氧化锌纳米晶高压下的晶粒演化和性能

用GS-1B型六面顶压机研究了ZnO纳米晶高压下的晶粒演化和性能，用X射线衍射仪和场发射扫描电子显微镜对高压样品的晶粒尺寸、微观形貌进行了表征.结果表明，高压下ZnO纳米晶存在压致晶粒碎化效应.硬度和伏安特性实验表明，高压调制后样品的显微硬度约是常压烧结样品硬度的2.3倍，非线性伏安特性明显优于常压烧结样品. 关键词： 氧化锌纳米晶 高压 压致碎化 非线性伏安特性     

不同晶粒尺寸SnO2纳米粒子的拉曼光谱研究

对晶粒尺寸在4—80nm范围的纯SnO₂纳米颗粒进行了拉曼散射研究.除了SnO₂本征拉曼振动峰外，还有几个新的拉曼振动峰和波长在700nm左右的一个发光很强而且峰宽很大的荧光峰被观察到.结果所示，当纳米颗粒尺寸减小时，纳米SnO₂颗粒的体相 特征拉曼峰变弱，而由缺陷，表面和颗粒尺寸引起的相关效应呈强势.晶粒尺寸在20nm左右是引起体相拉曼光谱变化的临界尺寸.晶粒尺寸在20nm以下，其体相拉曼峰的发生宽化和峰位移动，以及分别出现在位于571cm^-1 的表面振动峰，位于351cm-1 处的界面峰和与表面吸附水分子及氢氧基团的N系列拉曼峰是纳米SnO颗粒的主要特征.这些结果反映了纳米颗粒的微结构变化与颗粒尺寸和表面效应以及它们之间相互作用的信息. 关键词： ２')" href="#">纳米SnO_２ 拉曼光谱 荧光光谱 水分子的吸附     

ZnO纳米块体材料的制备及其性能的研究

采用连续成型方式压制了纳米ZnO素坯，考察了素坯密度、烧结时间、致密化温度等参数与 成型方式的关系.用场发射扫描电镜表征了烧结体微观组织特征.测定了ZnO纳米块体材料中 硬度随烧结温度的变化规律.结果表明，采用连续成型方式可使素坯密度提高56％、烧结时 间缩短了3h、致密化温度降低200℃.场发射扫描电镜显示烧结体内部密度及颗粒尺寸分布 均匀.硬度测定结果显示ZnO纳米块体材料中显微硬度随烧结温度的变化不是单调的，而是随 烧结温度的升高显微硬度先升高后降低，拐点对应的晶粒尺寸为50—60nm. 关键词： ZnO纳米块体 连续成型 硬度     

ZnO纳米棒的拉曼和发光光谱研究(英文)

本文对采用湿化学方法合成的ZnO纳米棒样品的拉曼光谱和发光光谱进行了研究。由扫描电镜结果可知,合成的ZnO纳米棒具有很好的尺寸发布均匀性,直径在30 nm左右,长度大于1微米。采用显微拉曼光谱技术,得到了632.8 nm波长激发的拉曼光谱,并和体相样品的拉曼光谱进行了对比分析;由325 nm激光波长激发得到的荧光光谱可知样品具有很好的紫外发光性质。     

Ag掺杂氧化锌纳米材料的制备及高压相变拉曼光谱研究

宽禁带直接带隙半导体材料氧化锌（ZnO）,具有优异的光电性能、机械性能和化学特性。ZnO材料的结构对其性能影响较大,元素掺杂可改变ZnO晶体结构和带隙宽度,是提升ZnO材料性能的有效手段,当前常用Ag掺杂ZnO即为提高光催化反应效率。高压独立于温度、成分,是调控材料结构组织性能的重要手段,是产生新材料、发现新调控原理的重要因素。该研究通过对比纯ZnO晶体和Ag掺杂ZnO晶体的高压相变行为,揭示了元素掺杂对ZnO纳米晶体材料结构性能的影响。研究首先采用水热法辅助制备纯ZnO纳米微球和Ag掺杂ZnO纳米微球（1∶150Ag/ZnO）,表征结果显示水热法合成的纯ZnO和1∶150Ag/ZnO均为六角纤锌矿晶体结构,形貌均为几十纳米尺寸小颗粒堆积形成的微球,ZnO晶格常数随着Ag离子掺杂而变大,Ag掺杂导致ZnO晶格膨胀。随后应用金刚石压腔结合原位拉曼光谱技术测定了纯ZnO和Ag掺杂ZnO的高压结构相变行为。相比于纯ZnO拉曼峰,Ag掺杂ZnO的E₂（high）振动模式439 cm-1拉曼峰峰宽变窄,并呈现向低频方向移动的趋势,与无定形ZnO谱峰相近,表明Ag+取代Zn2+影响了Zn-O键,同时也影响了ZnO晶格结构的长程有序性。随体系压力增大,表征六角纤锌矿结构ZnO的拉曼特征峰439 cm-1出现瞬间弱化和宽化。压力增大至9.0 GPa时,纤锌矿结构ZnO拉曼特征峰439 cm-1消失,585 cm-1处出现新峰,ZnO晶体发生由六角纤锌矿向岩盐矿的结构转变。压力继续增大至11.5 GPa,新的拉曼峰显著增强,峰形变窄,同时向高波数方向移动,相变完成,岩盐矿结构ZnO性能稳定。1∶150 Ag/ZnO从六角纤锌矿结构到立方岩盐结构的相变压力为7.2 GPa,低于纯ZnO。相变压力降低表明晶体结构稳定性下降,可能的原因在于掺杂Ag导致ZnO晶格膨胀,晶体结构松弛,两相相对体积变化增加,从而导致相变势垒降低,使样品在较低压力下发生相变。纳米材料的高压研究揭示了元素掺杂对材料结构稳定性的影响,是纳米材料调控原理的潜在研究手段。     

γ-LiAlO2上非极性ZnO薄膜制备及其光谱性质研究

利用激光脉冲沉积(PLD)技术在(302)γ-LiAlO₂衬底上成功生长了非极性的a面(1120) ZnO薄膜. 衬底温度为350℃时，薄膜是混合取向(a向和c向)，以c面ZnO为主，且晶粒尺寸分布很宽；提高温度达500℃，薄膜变为单一的(1120)取向，摇摆曲线半高宽0.65°，晶粒尺寸分布趋窄，利用偏振透射谱可以明显看出其面内的各向异性. 衬底温度650℃下制备的样品晶粒继续长大，虽然摇摆曲线半高宽变大，但光致发光谱(PL)带边发射峰半高宽仅为105meV，比在350℃，500℃下制备的样品小1/5. 关键词： 非极性ZnO 2')" href="#">γ-LiAlO₂ PLD 透射谱     

纳米VO2/ZnO复合薄膜的热致变色特性研究

为提高VO₂薄膜的热致变色性能,采用纳米结构和复合结构二者相结合的方法,通过磁控溅射技术先在玻璃衬底上制备高(002)取向ZnO薄膜,再在ZnO层上室温沉积钒金属薄膜,最后经热氧化处理获得纳米结构VO₂/ZnO复合薄膜.利用变温拉曼光谱观察分析了VO₂/ZnO薄膜相变前后的晶格畸变和键态的演变过程,讨论了薄膜的结构与热致红外开关特性和相变温度的内在关系.结果显示,与相同条件获得的同厚度的单层VO₂薄膜相比,纳米VO关键词： ZnO 2')" href="#">VO₂ 纳米复合薄膜 热致变色 拉曼光谱     

厚度对未掺杂ZnO薄膜光谱性能的影响

X射线衍射光谱、拉曼光谱和紫外可见透射光谱技术是薄膜材料检测的重要技术手段。通过对薄膜材料光谱性能的分析,可以获得薄膜材料的物相、晶体结构和透光性能等信息。为了解厚度对未掺杂ZnO薄膜的X射线衍射光谱、拉曼光谱和紫外可见透射光谱性能的影响,利用溶胶-凝胶法在石英衬底上旋涂制备了不同厚度的未掺杂ZnO薄膜样品,并对薄膜样品进行了X射线衍射光谱、拉曼光谱和紫外可见透射光谱的检测。首先,通过X射线衍射光谱检测发现,薄膜样品呈现出（002）晶面的衍射峰,ZnO薄膜为六角纤锌矿结构,均沿着C轴择优取向生长,且随着薄膜厚度的增加,衍射峰明显增强,ZnO薄膜的晶粒尺寸随着膜厚的增加而长大。利用扫描电子显微镜对薄膜样品的表面形貌分析显示,薄膜表面致密均匀,具有纳米晶体的结构,其晶粒具有明显的六角形状。通过拉曼光谱检测发现,薄膜样品均出现了437 cm-1的拉曼峰,这是ZnO纤锌矿结构的特征峰,且随着薄膜厚度的增加,其特征拉曼峰强度也增加,进一步说明了随着ZnO薄膜厚度的增加,ZnO薄膜晶化得到了加强。最后,通过紫外可见透射光谱测试发现,随着膜厚的增加,薄膜的吸收边发生一定红移,薄膜样品在可见光区域内的透过率随着膜厚度增加而略有降低,但平均透过率都超过90%。通过对薄膜样品的紫外-可见透射光谱进一步分析,估算了薄膜样品的折射率,定量计算了薄膜样品的光学禁带宽度,计算结果表明：厚度的改变对薄膜样品的折射率影响不大,但其禁带宽度随着薄膜厚度的增加而变窄,且均大于未掺杂ZnO禁带宽度的理论值3.37 eV。进一步分析表明,ZnO薄膜厚度的变化与ZnO晶粒尺寸的变化呈正相关,本质上,吸收边或光学禁带宽度的变化是由于ZnO晶粒尺寸变化引起的。     

Fe、Ni共掺杂ZnO基稀磁半导体光学性能与铁磁性研究

采用水热法成功制备了不同掺杂浓度的Zn_1-2xFe_xNi_xO（x=0,0.025,0.05,0.1）稀磁半导体材料,利用X射线衍射（XRD）、透射电子显微镜（TEM）和X射线能量色散分析仪（XEDS）对样品进行表征,并结合拉曼（Raman）光谱、光致发光光谱（PL）和振动样品磁强计（VSM）研究样品的光学性能和磁学性能。结果表明,水热法制备的样品具有结晶性良好的纤锌矿结构,没有杂峰出现,形貌为纳米棒状结构,分散性良好。Fe²⁺、Ni²⁺是以替代的形式进入ZnO晶格中,Fe和Ni的掺杂使得晶体中的缺陷和应力增加,拉曼光谱峰位发生红移,光致发光光谱发生猝灭现象。另外,共掺杂样品在室温条件下存在明显的铁磁性,饱和磁化强度随着掺杂量的增加而增强。     

Surface-enhanced Raman spectroscopy of semiconductor nanostructures

We review our recent results concerning surface-enhanced Raman scattering (SERS) by confined optical and surface optical phonons in semiconductor nanostructures including CdS, CuS, GaN, and ZnO nanocrystals, GaN and ZnO nanorods, and AlN nanowires. Enhancement of Raman scattering by confined optical phonons as well as appearance of new Raman modes with the frequencies different from those in ZnO bulk attributed to surface optical modes is observed in a series of nanostructures having different morphology located in the vicinity of metal nanoclusters (Ag, Au, and Pt). Assignment of surface optical modes is based on calculations performed in the frame of the dielectric continuum model. It is established that SERS by phonons has a resonant character. A maximal enhancement by optical phonons as high as 730 is achieved for CdS nanocrystals in double resonant conditions at the coincidence of laser energy with that of electronic transitions in semiconductor nanocrystals and localized surface plasmon resonance in metal nanoclusters. Even a higher enhancement is observed for SERS by surface optical modes in ZnO nanocrystals (above 10⁴). Surface enhanced Raman scattering is used for studying phonon spectrum in nanocrystal ensembles with an ultra-low areal density on metal plasmonic nanostructures.     

Studies on the complex behavior of optical phonon modes in wurtzite (ZnO)1−x (Cr2O3) x

This paper reports on the use of phonon spectra obtained with laser Raman spectroscopy for the uncertainty concerned to the optical phonon modes in pure and composite ZnO_1?x (Cr₂O₃) _x . Particularly, in previous literature, the two modes at 514 and 640 cm^?1 have been assigned to ZnO are not found for pure ZnO in our present study. The systems investigated for the typical behavior of phonon modes with 442 nm as excitation wavelength are the representative semiconductor (ZnO)_1?x (Cr₂O₃) _x (x = 0, 5, 10 and 15 %). Room temperature Raman spectroscopy has been demonstrated polycrystalline wurtzite structure of ZnO with no structural transition from wurtzite to cubic with Cr₂O₃. The incorporation of Cr³⁺ at most likely on the Zn sub-lattice sites is confirmed. The uncertainty of complex phonon bands is explained by disorder-activated Raman scattering due to the relaxation of Raman selection rules produced by the breakdown of translational symmetry of the crystal lattice and dopant material. The energy of the E ₂ (high) peak located at energy 53.90 meV (435 cm^?1) due to phonon–phonon anharmonic interaction increases to 54.55 meV (441 cm^?1). A clear picture of the dopant-induced phonon modes along with the B ₁ silent mode of ZnO is presented and has been explained explicitly. Moreover, anharmonic line width and effect of dislocation density on these phonon modes have also been illustrated for the system. The study will have a significant impact on the application where thermal conductivity and electrical properties of the materials are more pronounced.     

Effect of changing incident wavelength on Raman features of optical phonons in SiC nanorods and TaC nanowires

Novel Raman scattering in polar semiconductor SiC and TaC one-dimensional materials have been carried out. With increasing incident laser wavelength from 488 to 633 nm there is a huge difference in Raman intensity enhancement for the LO/IF peaks and the TO peak. This has been interpreted as due to Fröhlich interaction and abundant defects in polar nano-scale semiconductor materials.     

Amplification of raman scattering by localized plasmons in silver nanoparticles on the surface of zinc oxide nanorods

The magnetron sputtering of Ag nanoparticles onto ZnO nanorod arrays is studied. The lateral faces of the nanorods are coated with nanoparticles at a much lower density as compared to the flat faces at comparable sputtering times. The silver density is high on the edges of the lateral faces of the nanorods. The plasmon absorption in the synthesized arrays of nanorods coated with individual Ag nanoparticles is maximal at 450?C500 nm. The appearance of local plasmon excitations increases the intensity of the multiphonon processes with the participation of ZnO polar modes in Raman spectra. The cross section of resonance Raman scattering for A ₁(LO) phonon overtones increases with the equivalent Ag film thickness.     

Optical Analysis of Nanocrystalline ZnO Films Coated on Porous Silicon by Radio Frequency (RF) Magnetron Sputtering

Zinc oxide thin films have been deposited onto porous silicon (PSi) substrates at high growth rates by radio frequency (RF) sputtering using a ZnO target. The advantages of the porous Si template are economical and it provides a rigid structural material. Porous silicon is applied as an intermediate layer between silicon and ZnO films and it contributed a large area composed of an array of voids. The nanoporous silicon samples were adapted by photo electrochemical (PEC) etching technique on n-type silicon wafer with (111) and (100) orientation. Micro-Raman and photoluminescence (PL) spectroscopy are powerful and non-destructive optical tools to study vibrational and optical properties of ZnO nanostructures. Both the Raman and PL measurements were also operated at room temperature. Micro-Raman results showed that the A₁(LO) of hexagonal ZnO/Si(111) and ZnO/Si(100) have been observed at around 522 and 530 cm^–1, re- spectively. PL spectra peaks are distinctly apparent at 366 and 368 cm^–1 for ZnO film grown on porous Si(111) and Si(100) substrates, respectively. The peak luminescence energy in nanocrystalline ZnO on porous silicon is blue-shifted with regard to that in bulk ZnO (381 nm). The Raman and PL spectra pointed to oxygen vacancies or Zn interstitials which are responsible for the green emission in the nanocrystalline ZnO.     

Multiphonon resonant Raman scattering in N‐doped ZnO

Multiphonon resonant Raman scattering in N‐doped ZnO films was studied, and an enhancement of the resonant Raman scattering process as well as longitudinal optical (LO) phonon overtones up to the sixth order were observed at room temperature. The resonant Raman scattering intensity of the 1LO phonon in N‐doped ZnO appears three times as strong as that of undoped ZnO, which mainly arises from the defect‐induced Raman scattering caused by N‐doping. The nature of the 1LO phonon at 578 cm⁻¹ is interpreted as a quasimode with mixed A₁ and E₁ symmetry because of the defects formed in the ZnO lattice. In addition, the previously neglected impurity‐induced two‐LO‐phonon scattering process was clearly observed in N‐doped ZnO. Copyright © 2009 John Wiley & Sons, Ltd.     

A Semiconductor Laser of the Visible Range as an Exciting Source of Raman Scattering

A possibility of application of semiconductor lasers of the visible range as exciting sources for Raman spectroscopy is studied. An experimental set-up for measuring Raman spectra of polycrystalline dielectrics and broad-gap semiconductors excited by a semiconductor laser with a wavelength of 640 nm was created. The conditions under which the spectral width of the lasing line of a semiconductor laser was within 10^-3 cm^-1 in the continuous mode with a power of 10 mW are realized. The characteristics of various types of exciting sources used in Raman spectroscopy are compared. The results of studies of the characteristic Raman spectra excited with a semiconductor laser in polycrystalline sulfur are presented.     

Al和Sb共掺对ZnO有序阵列薄膜的结构和光学性能的影响

采用水热合成法在预先生长的ZnO种子层的玻璃衬底上制备出Al和Sb共掺ZnO纳米棒有序阵列薄膜. 通过X射线衍射、扫描电镜、透射电镜和选区电子衍射分析表明:所制备的薄膜由垂直于ZnO种子层的纳米棒组成, 呈单晶六角纤锌矿ZnO结构, 且沿[001]方向择优生长, 纳米棒的平均直径和长度分别为27.8 nm和1.02 μm. Al和Sb共掺ZnO纳米棒有序阵列薄膜的拉曼散射分析表明:相对于未掺杂ZnO薄膜的拉曼振动峰(580 cm^-1), Al和Sb共掺ZnO阵列薄膜的E₁(LO)振动模式存在拉曼位移. 当Al和Sb的掺杂量为3.0at%,4.0at%,5.0at%,6.0at%时, Al和Sb共掺ZnO阵列薄膜的拉曼振动峰的位移量分别为3,10,14,12 cm^-1. E₁ (LO) 振动模式位移是由Al和Sb掺杂ZnO产生的缺陷引起的. 室温光致发光结果表明:掺杂Al和Sb后, ZnO薄膜在545 nm处的发光强度减小,在414 nm处的发光强度增加. 这是由于掺杂Al和Sb后, ZnO薄膜中Zn_i缺陷增加, O_i缺陷减少引起的. 关键词： Al和Sb共掺ZnO薄膜 纳米棒有序阵列 结构表征 拉曼散射     

Origin of the Raman mode at 379 cm−1 observed in ZnO thin films grown on sapphire

In this work, we present a detailed Raman scattering study to clarify the origin of the mode at 379 cm⁻¹ which is observed in Raman spectra of the ZnO films grown on c‐sapphire substrates and generally attributed to the A₁‐transverse optical (A₁‐TO) mode of ZnO. The studied ZnO films were deposited by metal‐organic chemical vapor deposition on c‐sapphire and (0001) ZnO substrates. In the z(−,−)z̄ backscattering configuration, the A₁‐TO mode is forbidden, while the 379 cm⁻¹ peak is still observed in the as‐deposited film grown on sapphire substrate. However, this mode is not observed in Raman spectra of the as deposited film grown on ZnO substrate. We suggest that the peak at 379 cm⁻¹ is the E_1g mode of the sapphire substrate which is allowed in z(−,−)z̄ backscattering configuration. The effects of annealing, the substrate and the collection cross‐section on Raman active modes were analyzed. Copyright © 2011 John Wiley & Sons, Ltd.