光退火制备多晶硅薄膜的量子态现象

用PECVD法直接沉积的非晶硅(a-Si:H)薄膜在中温情况下光退火,然后用XRD、Raman光谱和SEM分析,发现晶粒大小随退火温度和退火时间呈现量子态现象.平均晶粒大小为30nm左右.     

New large grain,highly crystalline,transparent glass–ceramics

Two main reasons assure the transparency in the visible of some glass–ceramics (TGC): their crystal sizes are much smaller than the wavelength of light or the difference between the refractive index of glass matrix and crystal phase is small. The majority of traditional TGC have nano-size crystals and small to moderate crystallized volume fraction, usually between 3% and 70%. In this article we present a new type of transparent glass–ceramics having large (micrometric) grain size and very high crystallized volume fraction, which reaches up to 97%. Their high transparency mainly results from simultaneous variations of the glass matrix and crystal compositions during crystallization, which considerably decreases the difference between the respective refractive indexes, and this factor prevails, regardless of crystal size. Preliminary tests of their optical properties indicate that this new family of TGC can be further developed by doping with transition metals and rare-earths.     

Polycrystalline silicon with large disk-shaped grains by Ni-mediated crystallization of doped amorphous silicon

Silicide mediated crystallization (SMC) of p-doped amorphous silicon (a-Si) has been studied. There are the different grain-shapes of crystallization of doped and non-doped a-Si. Non-doped a-Si is crystallized with needle-shaped grains, while it is observed the disk-shaped grains are formed in crystallized doped a-Si. The crystallization of slightly doped a-Si exhibits larger grain size compared with non-doped and heavily doped films. The p-dopant in a-Si suppresses the formation of the NiSi₂ precipitate which act as a crystallization nucleus, causing continuous grain growth and the formation of disk-shaped grains.     

单晶硅外延生长晶化硅薄膜的研究

采用P型单晶硅片为衬底,并经混合酸溶液腐蚀抛光、清洗后,利用射频磁控溅射镀膜系统在其表面制备非晶硅薄膜;再结合快速光热退火工艺,于N2气氛下480℃退火30 min,得到晶化硅薄膜;利用光学金相显微镜、XRD衍射仪和拉曼散射光谱(Raman)仪对单晶硅衬底和晶化硅薄膜进行结构和性能表征.研究了混合酸溶液对单晶硅表面腐蚀效果、籽晶诱导外延生长晶化硅薄膜的物相结构和薄膜带隙.结果表明:采用混合酸溶液腐蚀后得到表面平整、光滑的单晶硅衬底;非晶硅薄膜经过快速退火后受籽晶诱导生成晶化硅薄膜,其晶相沿单晶硅衬底取向择优生长;随着非晶硅薄膜厚度从80 nm增加到280 nm,晶化后硅薄膜的表面粗糙度逐渐减小,晶化率从90.0;逐渐降低到37.0;;晶粒尺寸从6.65 nm逐渐减小到1.71 nm;带隙从1.18 eV逐渐升高到1.52 eV.     

Doping limits in II–VI compounds - Challenges, problems and solutions

Wide-band-gap II–VI semiconductors have a potential for a variety of applications especially in the areas of light-emitting and light-detecting devices, photovoltaic conversion (solar cells), X-ray and γ-ray detection, etc. In all applications, a good bipolar electrical conduction, i.e. efficient doping from both n- and p-side is essential, but due to the reasons which are not yet fully understood, it is still difficult to achieve. In this paper, a number of possible doping-limiting mechanisms in II–VI's are critically analyzed, in particular: self-compensation by spontaneous formation of native defects, amphoteric behavior of several potential dopants, lattice relaxation around some doping atoms, insufficient solubility of the others, and ‘softness’ of the lattice of the IIB-VI compounds. In the third part of the paper, various approaches to overcome doping difficulties have been analyzed, in particular growth and doping under non-equilibrium conditions (low-temperature growth/doping techniques, particularly MBE, MOVPE, MOCVD), doping by ion implantation, co-doping with more than one dopant, non-equilibrium doping using ultra-fast techniques, etc., as well as the reinforcement of crystal lattice by alloying with some IIA-VI compounds. The results of these efforts are overviewed, including the status of maximum p- and n-doping so far achieved in each of II–VI compounds. It is concluded that a much greater range of applications of the II–VI's, in accordance with their extraordinary properties and potential in many fields, can be expected in the foreseeable future.     

微波辅助水热合成条件对直接合成纳米HZSM-5晶体性质的影响

利用微波辅助水热合成法直接制备了纳米HZSM-5晶体.采用XRD、FT-IR、SEM、BET和NH3-TPD等手段对合成样品进行了分析表征,研究了晶化温度和时间对合成产物晶体性质的影响.结果表明,晶化温度和时间对微波辅助水热直接合成产物微观形貌、晶粒尺寸和分散度影响明显.较低的晶化温度和较短的晶化时间均难以形成形貌规则的HZSM-5晶体.随着晶化温度的升高,合成样品逐渐变为球形晶粒、晶粒尺寸逐渐增大、分散度逐渐提高,继续提高晶化温度达180 ℃时,晶粒长大使比表面积稍有降低;随着晶化时间的延长,样品的微孔和介孔增多,比表面积和孔容逐渐增大,继续延长晶化时间,晶体内微孔可能的收缩和晶粒的长大使得样品孔容和比表面积减小.160 ℃和1.5 h条件下制备的HZSM-5分子筛晶体形貌呈球形,晶粒尺寸约为60 nm,分散程度较好;其比表面积、孔容和平均孔径分别为398.45 m2·g-1、0.63 cm3·g-1和6.27 nm;晶体表面具有弱酸特征.     

Variation of crystallization mechanisms in flash-lamp-irradiated amorphous silicon films

Flash lamp annealing (FLA) can form polycrystalline silicon (poly-Si) films with various microstructures depending on the thickness of precursor amorphous Si (a-Si) films due to the variation of crystallization mechanisms. Intermittent explosive crystallization (EC) takes place in precursor a-Si films thicker than approximately 2 μm, and the periodicity of microstructure formed resulting from the intermittent EC is independent of the thickness of a-Si films if their thickness is 2 μm or greater. In addition to the intermittent EC, continuous EC and homogeneous solid-phase crystallization (SPC) also occur in thinner films. These crystallization mechanisms are governed by the ignition of EC at Si film edges and the homogeneous heating of interior a-Si. The results obtained in this study could be applied to control the microstructures of flash-lamp-crystallized poly-Si films.     

Atomistic examinations of the solid-phase epitaxial growth of silicon

The low-temperature vapor deposition of silicon thin films and the ion implantation of silicon can result in the formation of amorphous silicon layers on a crystalline silicon substrate. These amorphous layers can be crystallized by a thermally activated solid-phase epitaxial (SPE) growth process. The transformations are rapid and initiate at the buried amorphous to crystalline interface within the film. The initial stages of the transformation are investigated here using a molecular dynamics simulation approach based upon a recently proposed bond order potential for silicon. The method is used first to predict an amorphous structure for a rapidly cooled silicon melt. The radial distribution function of this structure is shown to be similar to that observed experimentally. Molecular dynamics simulations of its subsequent crystallization indicate that the early stage, rate limiting mechanism appears to be removal of tetrahedrally coordinated interstitial defects in the nominally crystalline region just behind the advancing amorphous to crystalline transition front. The activation barriers for this interstitials migration within the bulk crystal lattice are calculated and are found to be comparable to the activation energy of the overall solid-phase epitaxial growth process simulated here.     

利用快速热退火法制备多晶硅薄膜

为了制备优质的多晶硅薄膜,该论文研究了非晶硅薄膜的快速热退火(RTA)技术.先利用PECVD设备沉积非晶硅薄膜,然后把其放入快速热退火炉中进行退火.退火前后的薄膜利用X射线衍射(XRD)仪、Raman光谱仪及扫描电子显微镜(SEM)测试其晶体结构及表面形貌,利用电导率测试设备测试其暗电导率.研究表明退火温度、退火时间以及沉积时的衬底温度对非晶硅薄膜的晶化都有很大的影响.     

硅铝共掺杂对TiO2薄膜结构及性能的影响

采用非水解溶胶-凝胶法制备了Si、Al共掺杂的TiO2薄膜.应用X射线衍射、紫外可见分光光度计研究了Si、Al掺杂对TiO2薄膜晶型转变、晶粒尺寸、光吸收性能及光催化性能的影响.结果表明:适量引入Si、Al后,可显著提高1000℃热处理后TiO2薄膜的光催化活性;当Si/Ti物质的量比为0.2时,薄膜由于混晶结构光催化活性最佳;Si、Al共掺杂能抑制TiO2的晶型转变及TiO2的晶粒生长,且Si、Al共掺杂的抑制作用比单一Si掺杂更有效;当Si/Ti物质的量比为0.15、Al/Ti物质的量比为0.05时,TiO2锐钛矿向金红石的转变温度从750℃提高到1200℃.     

玻璃衬底上中温制备多晶硅薄膜的量子态现象

用PECVD法直接沉积的非晶硅(a-Si:H)薄膜用传统炉在中温退火,然后用拉曼光谱、XRD和SEM分析,发现晶粒大小随退火温度和退火时间呈现量子态现象.分析发现在传统炉中850℃下退火三个小时晶粒大小出现极大值,平均晶粒尺寸为30nm左右.     

Cw argon laser crystallization of silicon films: Structural properties

This paper deals with the structural characterization of amorphous silicon films deposited on glass in the amorphous state and then post-crystallized using a continuous wave argon laser. In opposite to the excimer laser crystallization method, the processing window is wider. Due to the low cooling rate induced by the continuous irradiation, very large grains are obtained. With an epitaxial growth induced by an adequate overlapping of the laser traces, grains as large as 100 μm can be reached. Electron back-scattered diffraction analysis highlights the single crystalline character of the large size grains crystallized with this kind of laser. The technique is able to produce large area single crystalline regions, suitable to fabricate high speed circuits.     

离子掺杂对纳米二氧化钛粒径的影响

本研究以工业钛液和尿素为基本原料,采用普通均匀沉淀法制备出单分散的锐钛矿型的球形纳米TiO2,研究了La3+、Fe3+、Co2+、Al3+四种离子不同掺杂量对纳米TiO2粒子粒径的影响,并对其机理进行了分析.研究结果表明,离子掺杂可以显著细化纳米TiO2的粒径,且掺杂后的TiO2仍为锐钛矿型.没有发现掺杂离子的特征峰,可以认为离子掺杂属于替位掺杂.     

Metal contamination detection in nickel induced crystallized silicon by spectroscopic ellipsometry

In this paper a new approach is presented for the simulation of spectroscopic ellipsometry (SE) data to estimate the level of nickel (Ni) contamination in silicon crystallized by metal induced crystallization (MIC). The method employs the addition of Ni as reference for a Bruggemann effective medium approximation (BEMA) to simulate the optical response of the crystallized silicon. This new approach is sensitive to changes in the initial average metal thickness used on the crystallization process to thickness values as low as 0.05 nm. This corresponds to a volume fraction of 0.24%, confirmed by Rutherford backscattering spectrometry (RBS) where it was observed that the Ni volume fraction detected by SE varies linearly with the metal amount inside the crystallized films determined by RBS.     

P型微晶硅氧薄膜光电性能研究

本工作采用甚高频等离子体化学气相沉积(VHF-PECVD)技术制备了P型微晶硅氧窗口层薄膜,讨论了P型微晶硅氧的光电特性随硼烷掺杂率的变化.采用紫外-可见透射光谱,拉曼光谱,傅立叶变换红外吸收光谱(FTIR),暗电导测量对薄膜的光电特性进行了表征.结果表明,P型微晶硅氧材料均表现为微晶态,随着硼烷掺杂率增加,晶化程度逐步降低,暗电导率快速减小,光学带隙持续降低.该结果可归因于硼烷掺杂的增加抑制晶化使得非晶成分增多,有效掺杂率降低导致薄膜电导率下降,另一方面,对硅氧物相分离的阻碍作用导致薄膜带隙下降.硼烷掺杂率为0.4;样品的电导率高达0.158 S/cm且光学带隙为2.2 eV,兼具高透射性和良好电导率,可作为高效硅基太阳电池的窗口层.     

The influence of heat-dissipation and temperature fluctuations on SbSI crystallization in thin layers

Single crystal films of SbSI 5 to 100 μ in thickness have been obtained by crystallization from melts in a close spacing. The films crystallized under conditions under conditions of direct heat -dissipation and periodical fluctuations of temperature near the melting point. The phase transition in the films was revealed by means of capacity measurements at temperatures of ∼ 20 °C.     

非晶锗的低温晶化和光学特性研究

本文采用直流磁控溅射在(100)硅衬底上沉积了单层锗薄膜,分别用拉曼光谱和X射线衍射研究了薄膜的结晶性,通过对结晶性的研究发现,在衬底温度为200℃时溅射功率为150W时结晶性开始变好,功率增至250W的过程,锗薄膜的择优取向发生(220)向(331)的变化.这样在无金属掺杂的情况下得到了结晶性较好的样品.光致发光结果表明,非晶锗在可见光区有较强的发光现象,发光峰位中心分别在648.1nm和713.0nm.发光峰位不随晶粒尺寸变化而变化,但峰强对晶粒大小的依赖性很强,平均晶粒较大的锗薄膜在可见光区发光现象不显著.     

The influence of N2 flow rate and substrate temperature on Ti1‐xAlxN thin films

Titanium aluminium nitride (Ti_1‐xAl_xN) films have been deposited on silicon (111) substrate at a N₂ flow rate of 2 sccm and 20 sccm and at a substrate temperature of 773 K and at a N₂ flow rate of 2 sccm and at a substrate temperature of 873 K by reactive DC magnetron sputtering technique. The effect of N₂ flow rate and substrate temperature on the grain size and surface roughness of the deposited films have been investigated. The films have been analysed by X‐ray diffraction (XRD) and atomic force microscopy (AFM). The films were found to be nanocrystalline. While the grain size of the films decreases with increasing N₂ flow rate and decreases with increasing substrate temperature, the surface roughness of the films decreases with increasing N₂ flow rate and increases with increasing temperature. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Effect of annealing and composition on crystal structure,surface morphology and optical absorption of chemically deposited Cd1‐xSnxS films

Cd_1‐xSn_xS thin films were successfully deposited on suitably cleaned glass substrate by chemical bath deposition method at 74 °C. Hydrated Stannous Chloride (SnCl₂.2H₂O) in aqueous solution was added to the CdS growing solution in different proportions. The experimental results indicate, a successful doping for lower concentration of Sn, saturation for intermediate doping levels, and a degradation of the doping process for higher concentration of Sn. Indirect (X‐ray diffraction) and Direct (Scanning electron microscopy) measurements were performed to characterize the growth and the nature of crystallinity of the different Cd_1‐xSn_xS films. The effect of annealing on the crystal structure and morphology of the deposited films has also been discussed. The X‐ray diffraction spectra show that the thin films are polycrystalline and have both cubic and hexagonal structure. The Interplanar spacing, lattice constant, grain size, strain, and dislocation density were calculated for as‐deposited and annealed films. The grain size was found to decrease from 5 nm to 0.89 nm with doping concentration of Sn. The grain size further decreased due to annealing at 400 °C. SEM studies show layered growth and long needle like structures along with some voids. After annealing the densification and smaller size of the particles was also observed. The optical absorption spectra show shifting of absorption peaks towards lower wavelength side (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The effect of dopants on the microstructure of polycrystalline silicon thin film grown by MILC method

The effect of dopants on the crystal growth and the microstructure of poly-crystalline silicon (poly-Si) thin film grown by metal induced lateral crystallization (MILC) method was intensively investigated. PH₃ and B₂H₆ were used as source gases in ion mass doping (IMD) process to make n-type and p-type semiconductor respectively. It was revealed that the microstructure of MILC region varies significantly as the doping type of the samples varied from intrinsic to n-type and p-type, which was investigated by field emission (FE)-SEM. The microstructure of MILC region of the intrinsic was bi-directional needle network structure whose crystal structure has a (1 1 0) preferred orientation. For p-type doped sample, the microstructure of MILC region was revealed to become unidirectional parallel growth structure more and more as MILC growth proceed, which was led by unidirectional division of needlelike grain at the front of MILC region. And for n-type doped sample, the microstructure was random-directional needlelike growth structure. These phenomena can be explained by an original model of Ni ion and Ni vacancy hopping in the NiSi₂ phase and its interface at the front of MILC region.