Local Piezoelectricity and Polarity Distribution of Preferred <Emphasis Type="Italic">c</Emphasis>-Axis-Oriented ZnO Film Investigated by Piezoresponse Force Microscopy

The piezoelectric properties and polarity distribution of preferred c-axis-oriented ZnO films have been investigated using piezoresponse force microscopy (PFM). Simultaneous imaging of the morphology, as well as the magnitude and phase of the out-of-plane and in-plane piezoresponse, was performed by PFM on the ZnO films. The out-of-plane piezoresponse with two primary antiparallel spontaneous polarization orientations (upward and downward), which is perpendicular to the surface of the film, has been found, and the spontaneous polarization orientation of most grains is upward. Meanwhile, the in-plane piezoresponse has also been detected in some of the grains. In addition, the polarization orientation of the individual grains is discussed and determined by analyzing phase images of the out-of-plane and in-plane piezoresponse.     

Spontaneous growth of GaN nanowire nuclei on N- and Al-polar AlN: A piezoresponse force microscopy study of crystallographic polarity

The polarity of gallium nitride (GaN) nanowire nuclei grown on AlN layers was studied by piezoresponse force microscopy (PFM). N- or Al-polar AlN layers were grown by molecular beam epitaxy (MBE) on Si (111) substrates by use of Al- or N-rich growth conditions, respectively. Short and low density GaN nanowires were then grown on each AlN polarity type. PFM measurements verified the expected AlN layer polarity and further indicated that predominantly N-polar nanowires are produced for growth on both AlN polarity types. Cross-section scanning transmission electron microscopy (STEM) images further reveal that the nanowires on Al-polar AlN films are nucleated on regions in the AlN layer that contain inversion domains, which propagate into the GaN nanowire nuclei. PFM measurements were found to be a convenient technique for mapping the polarity of a statistically significant number of individual GaN nanowires.     

Growth of Polarity-Controlled ZnO Films on (0001) Al<Subscript>2</Subscript>O<Subscript>3</Subscript>

The polarity control of ZnO films grown on (0001) Al₂O₃ substrates by plasma-assisted molecular-beam epitaxy (P-MBE) was achieved by using a novel CrN buffer layer. Zn-polar ZnO films were obtained by using a Zn-terminated CrN buffer layer, while O-polar ZnO films were achieved by using a Cr₂O₃ layer formed by O-plasma exposure of a CrN layer. The mechanism of polarity control was proposed. Optical and structural quality of ZnO films was characterized by high-resolution X-ray diffraction and photoluminescence (PL) spectroscopy. Low-temperature PL spectra of Zn-polar and O-polar samples show dominant bound exciton (I₈) and strong free exciton emissions. Finally, one-dimensional periodic structures consisting of Zn-polar and O-polar ZnO films were simultaneously grown on the same substrate. The periodic inversion of polarity was confirmed in terms of growth rate, surface morphology, and piezo response microscopy (PRM) measurement.     

Effect of Temperature on Structural and Morphologic Properties of ZnO Films Annealed in Ammonia Ambient

ZnO thin films were prepared on Si(111) substrates by pulsed laser deposition (PLD). Then, the samples were annealed at different temperatures in NH₃ ambient and their properties were investigated particularly as a function of annealing temperature. The structure, morphology, and optical properties of ZnO films were studied by x-ray diffraction (XRD), Fourier transform infrared spectroscope (FTIR), scanning electron microscope (SEM), and photoluminescence (PL). The results show that the increase of annealing temperature makes for the improvement in the crystal quality and surface morphology below the temperature of 650°C. However, when the annealing temperature is above 650°C, the ZnO films will volatilize and, especially at 750°C, ZnO will volatilize completely.     

PLD法制备ZnO薄膜的退火特性和蓝光机制研究

通过脉冲激光沉积(PLD)方法,在O2中和100～500℃衬底温度下,用粉末靶在Si(111)衬底上制备了ZnO薄膜,在300℃温度下生长的薄膜在400～800℃温度和N2氛围中进行了退火处理,用X射线衍射(XRD)谱、原子力显微镜(AFM)和光致发光(PL)谱表征薄膜的结构和光学特性。XRD谱显示,在生长温度300℃时获得较好的复晶薄膜,在退火温度700℃时获得最好的六方结构的结晶薄膜;AFM显示,在此退火条件下,薄膜表面平整、晶粒均匀;PL谱结果显示,在700℃退火时有最好的光学特性。     

Effect of Lattice Mismatch on Luminescence of ZnO/Si Hetero-Structure

研究了ZnO薄膜中应力对发光的影响.实验样品为ZnO体单晶、在Si基片上直接生长的ZnO薄膜以及通过SiC过渡层在Si基片上生长的ZnO薄膜.测量了这三种样品的X射线衍射图形、喇曼光谱和光致发光光谱.由X射线衍射图形可以看出,由于SiC过渡层缓解了ZnO与Si之间的晶格失配,使得通过SiC过渡层在Si上生长的ZnO薄膜的结晶质量好于直接在Si上生长的ZnO薄膜的质量.进一步通过喇曼谱测量发现,与ZnO体单晶相比,直接在Si上生长的ZnO薄膜的E2(high)峰红移1.9cm-1,根据喇曼谱峰位移与应力的关系可以推出薄膜中存在0.4GPa的张应力;而通过SiC过渡层在Si上生长的ZnO薄膜的E2(high)峰红移0.9cm-1,对应着0.2GPa的张应力.对照X射线衍射图形的结果可以看出,薄膜中张应力的大小与薄膜的结晶质量密切相关,表明张应力来源于外延层和基片间的晶格失配,晶格失配越大,外延层中产生的张应力越大.有无SiC过渡层的两种薄膜样品的PL光谱中都存在紫外和绿光两种谱带,随样品热处理时氧气分压增加,两种样品都出现绿光增强的相似的变化规律,但有SiC过渡层的样品的变化幅度较小.这一结果说明,绿色发光中心与薄膜的质量,也就是与薄膜中存在的张应力大小有关.在以往研究中得出的非故意掺杂ZnO薄膜的绿色发光中心来源于氧反位缺陷(Ozn),文中研究的结果正好可以解释氧反位缺陷形成的原因.由于薄膜中存在张应力,使得样品的能量升高,其结果必然会产生缺陷来释放张应力,以便降低系统能量.而氧离子半径大于锌离子半径,氧替位锌有利于释放张应力,也就是说,在存在张应力的情况下,Ozn的形成能降低.这一结果进一步证明Si上生长的ZnO薄膜中的绿色发光中心与氧反位缺陷有关.     

Interesting Evidence for Template‐Induced Ferroelectric Behavior in Ultra‐Thin Titanium Dioxide Films Grown on (110) Neodymium Gallium Oxide Substrates

The first evidence for room‐temperature ferroelectric behavior in anatase‐phase titanium dioxide (a‐TiO₂) is reported. Behavior strongly indicative of ferroelectric characteristics is induced in ultra‐thin (20 nm to 80 nm) biaxially‐strained epitaxial films of a‐TiO₂ deposited by liquid injection chemical vapor deposition onto (110) neodymium gallium oxide (NGO) substrates. The films exhibit significant orthorhombic strain, as analyzed by X‐ray diffraction and high‐resolution transmission electron microscopy. The films on NGO show a switchable dielectric spontaneous polarization when probed by piezoresponse force microscopy (PFM), the ability to retain polarization information written into the film using the PFM tip for extended periods (several hours) and at elevated temperatures (up to 100 °C) without significant loss, and the disappearance of the polarization at a temperature between 180 and 200 °C, indicative of a Curie temperature within this range. This combination of effects constitutes strong experimental evidence for ferroelectric behavior, which has not hitherto been reported in a‐TiO₂ and opens up the possibility for a range of new applications. A model is presented for the effects of large in‐plane strains on the crystal structure of anatase which provides a possible explanation for the experimental observations.     

Initiation of a polarized state in thin lithium niobate films synthesized on isolated silicon substrates

The distributions of induced state and surface potential in thin lithium niobate films obtained via the deposition onto a (100)-oriented Si-oxidized substrate by the method of high-frequency magnetron sputtering were mapped using piezoresponse force microscopy (PFM) and Kelvin probe force microscopy (KPFM). Using an electrical field applied with a conducting cantilever, the possibility of the formation of an induced polarization state and of its subsequent visualization was shown. The induced state in KPFM measurements was shown to be retained for a much longer time than for PFM.     

低压高温退火对Ag掺杂ZnO薄膜性质的影响

采用电子束蒸发在n-Si(100)衬底上沉积Ag掺ZnO(ZnO:Ag)薄膜,随后在200 Pa的O<,2>气氛下分别在500、600、700和800℃退火4 h.用X射线衍射(XRD)仪、荧光光谱仪以及Van der Pauw方法测量ZnO:Ag薄膜的结构和光电学性质.结果表明,ZnO:Ag薄膜为多晶结构,且随着退火...     

Effects of Annealing Temperature on Properties of ZnO Thin Films Grown by Pulsed Laser Deposition

ZnO thin films are deposited on n-Si（111） substrates by pulsed laser deposition（PLD） system. Then the samples are annealed at different temperatures in air ambient and their properties are investigated particularly as a function of annealing temperature. The microstructure, morphology and optical properties of the as-grown ZnO films are studied by X-ray diffraetion（XRD）. atomic force mieroseope（AFM）, Fourier transform infrared spectroscopy（FTIR） and photoluminescence（PL） spectra. The results show that the as- grown ZnO films have a hexagonal wurtzite structure with a preferred c-axis orientation. Moreover, the diameters of the ZnO crystallites become larger and the crystal quality of the ZnO fihns is improved with the increase of annealing temperature.     

Synthesis and characterization of phosphorus-doped ZnO and (Zn,Mg)O thin films via pulsed laser deposition

The transport and optical properties of phosphorus-doped (Zn,Mg)O thin films grown via pulsed laser deposition (PLD) are studied. The carrier type of as-deposited (Zn,Mg)O:P films converts from n-type to p-type with increasing oxygen partial pressure. All the films exhibit good crystallinity with c-axis orientation. This result indicates the importance of oxidation conditions in realizing p-type (Zn,Mg)O:P films. The as-deposited ZnO:P film properties show a strong dependence on the deposition ambient at different growth temperatures. The resistivity of the samples deposited in O₃/O₂ mixture is two orders of magnitude higher than the films grown in oxygen and O₂/Ar/H₂ mixture. The room-temperature photoluminescence (PL) of the as-deposited films has been shown that growing in the O₂/Ar/H₂ mixture ambient significantly increases the band edge emission while inhibiting the visible emission. The enhanced ultraviolet (UV) emission in the films grown in O₂/Ar/H₂ mixture may result from hydrogen passivation of the deep level emission centers. The annealed ZnO:P films are n-type with nonlinear dependence of resistivity on annealing temperature. The resistivity increases in the films with annealing at 800°C while decreasing with further increasing annealing temperature. Strong visible light emission is observed from the ZnO:P films annealed in oxygen.     

退火对用PLD法制备ZnO薄膜的发光影响

用脉冲激光沉积(PLD)方法在Si(111)和蓝宝石衬底上制备的氧化锌薄膜,在不同的退火温度和不同的退火氛围中进行了退火处理.退火温度及退火氛围对ZnO薄膜的结构和发光特性的影响用X射线衍射(XRD)谱和光致发光谱进行了表征.实验结果表明,随着退火温度的提高,ZnO薄膜的压应力减小,并向张应力转化.在不同的退火温度退火...     

Synthesis of PbS:ZnO nanotrees by thermal evaporation:morphological, structural and optical properties

Nanotrees ZnO films are synthesized by thermal evaporation method on silicon and glass substrates. PbS powder (5 wt%) is used to obtain the nanostructure and growth modifications. ZnO films are compared with non-doped ones (ZnO film was dense structure without nanotrees). The deposited PbS:ZnO films exhibit polycrystalline orientation using X-ray diffraction (XRD), but the films without doping was less crystalline quality. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) were used to characterize the morphology. SEM images (surface and cross section) was confirmed the nanotrees form for doped ZnO film. Energy dispersive X-ray detector (EDX) was used to verify the composition of prepared films. Ultraviolet-visible (UV-Vis), photoluminescence (PL) and micro Raman techniques were used to investigate the optical properties. The PL spectra intensities were found to increase for PbS:ZnO nanotrees. Up to our knowledge, no work has been published regarding the obtained ZnO nanotrees using PbS as dopant via simple thermal evaporation method.     

ZnO growth on Si with low-temperature CdO and ZnO buffer layers by molecular-beam epitaxy

Low-temperature (LT) buffer-layer techniques were employed to improve the crystalline quality of ZnO films grown by molecular-beam epitaxy (MBE). Photoluminescence (PL) spectra show that CdO, as a hetero-buffer layer with a rock-salt structure, does not improve the quality of ZnO film grown on top. However, by using ZnO as a homo-buffer layer, the crystalline quality can be greatly enhanced, as indicated by PL, atomic force microscopy (AFM), x-ray diffraction (XRD), and Raman scattering. Moreover, the buffer layer grown at 450°C is found to be the best template to further improve the quality of top ZnO film. The mechanisms behind this result are the strong interactions between point defects and threading dislocations in the ZnO buffer layer.     

Annealing Studies on Zinc Oxide Thin Films Deposited by Magnetron Sputtering

Three annealing techniques for ZnO thin films were studied for modifying electrical properties. The stoichiometry of ZnO has a ratio of ∼1:1 at a depth of 100 ?, independent of the annealing method applied. Laser-annealed samples exhibited a larger grain size compared to the other annealing methods and showed an increase in photoluminescence (PL) and a decrease in defects in the ZnO for laser power above 200 mJ/cm². Metal-semiconductor-metal photodetectors (MSM-PDs) gave the best responsivity of 606.8 A/W. An SiO₂ insulator layer (10 to 20 ?) was added between the ZnO and Si to study potential solar cell applications.     

热氧化磁控溅射金属锌膜制备ZnO纳米棒

利用射频磁控溅射技术在Si(111)衬底上制备金属锌膜 ,在空气中退火热氧化合成了一维ZnO纳米棒。用X射线衍射 (XRD) ,扫描电子显微镜 (SEM) ,透射电子显微镜 (TEM)和光致发光谱 (PL)对样品进行了结构、形貌及光学特性分析。结果表明 :ZnO纳米棒为六方纤锌矿结构单晶相 ,直径在 30～ 6 0nm左右 ,其长度可达5～ 8μm左右。在 2 80nm波长光激发下 ,有很强的 372nm带边紫外光发射和较微弱的 5 16nm深能级绿光发射 ,说明合成的单晶ZnO纳米棒的质量较高     

Studies of the optoelectronic properties of ZnO thin films

ZnO thin films have been deposited on quartz glass, sapphire, and glass substrates by the sol-gel technique and subjected to different annealing ambients. X-ray diffraction measurements show that all the films are hexagonal wurtzite type. The variations in photoluminescence (PL) and photoconductivity (PC) properties have been correlated to the structural and microstructural changes due to different substrates and annealing ambients. The maximum photoresponse has been observed for the films on quartz substrates. The violet emission in the PL spectra is enhanced for vacuum and nitrogen annealed films. The maximum ultraviolet (UV) photoresponse and photo-to-dark current ratio is observed for ZnO films annealed in air.     

Influence of N2 and O2 annealing treatment on the optical bandgap of polycrystalline Ga2O3:Cu films

Cu-doped Ga₂O₃ thin films were deposited by electron beam evaporation with subsequent annealing at 1000 °C in N₂ and O₂ for 1 h. The influence of the annealing atmosphere on the crystal structure, surface morphology and optical properties of Ga₂O₃:Cu films was investigated by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), atomic force microscopy (AFM), and transmittance and photoluminescence (PL) spectroscopy. The optical bandgap deduced from the absorption spectrum was greater for the O₂ annealed than for N₂ annealed samples. In both cases the bandgap was wider than for bulk β-Ga₂O₃. The grain size and surface roughness were sensitive to the annealing atmosphere. Results confirmed that the annealed samples were polycrystalline β-Ga₂O₃ with some amorphous phase. We hypothesize that annealing in oxygen led to recrystallization of the Ga₂O₃:Cu film. Annealing treatment improved the crystal quality of Ga₂O₃:Cu films and the PL intensity of the samples increased.     

基于PLD法制备ZnO:Eu3+,Li+薄膜的发光性质研究

采用脉冲激光沉积(PLD)技术在Si(111)衬底上生长了Eu3+、Li+共掺杂的ZnO薄膜。分别对样品进行了X射线衍射(XRD)谱测试和光致发光(PL)谱分析,重点研究了退火处理对样品结构和发射光谱的影响。XRD谱测试表明,样品具有很好的C轴择优取向。PL谱研究表明,当用325nm光激发样品时,样品的发射光谱仅由ZnO基质的紫外发射和蓝光发射组成,并没有发现稀土Eu3+的特征发光峰;样品的蓝光发射源于电子从Zn填隙形成的浅施主能级到Zn空位形成的浅受主能级跃迁;和真空中退火的样品相比,O2中制备的样品的蓝光发射减弱,紫外发光增强。用395nm的光激发时,退火前样品分别在594nm和613nm处存在两个明显的Eu3+特征发光峰,退火后的样品仅发现Eu3+位于594nm的特征发光峰,这表明,退火处理不利于稀土离子的特征发射,但O2中退火的样品ZnO基质红绿波段发射光谱明显增强。     

超声喷雾热解法制备ZnO：Eu薄膜

以醋酸锌（Zn（CH3COO）2）、氯化铕（EuCl3）水溶液为前驱体,采用超声喷雾热解（USP）方法在ITO导电玻璃衬底上沉积Eu掺杂ZnO（ZnO：Eu）薄膜。通过扫描电镜（SEM）、X射线衍射（XRD）和光致发光（PL）谱对ZnO：Eu薄膜的形貌、结构和光学性质进行了研究。SEM测试结果表明,超声喷雾热解法制备的...