Theoretical and experimental study on the photoluminescence in BaTiO3 amorphous thin films prepared by the chemical route

A polymeric precursor method was used to synthesize BaTiO₃ amorphous thin film processed at low temperature. The luminescence spectra of BaTiO₃ amorphous thin films at room temperature revealed an intense single-emission band in the visible region. The visible emission band was found to be dependent of the thermal treatment history. Photoluminescence (PL) properties for different annealing temperatures were investigated. It was concluded that the intensity of PL is strongly dependent on both the heat treatment of the films and the presence of an inorganic disordered phase. Experimental optical absorption measurements showed the presence of a tail. These results are interpreted by the nature of these exponential optical edges and tails, associated with defects promoted by the disordered structure of the amorphous material. We discuss the nature of visible PL at room temperature in amorphous barium titanate in the light of the results of recent experimental and quantum mechanical theoretical studies. Our investigation of the electronic structure involved the use of first-principle molecular calculations to simulate the variation of the electronic structure in the barium titanate crystalline phase, which is known to have a direct band gap, and we also made an in-depth examination of amorphous barium titanate.     

The role of defect states in the creation of photoluminescence in SrTiO<Subscript>3</Subscript>

We discuss the nature of visible photoluminescence at room temperature in amorphous strontium titanate in the light of the results of a recent experimental and quantum mechanical theoretical study. Our calculation of the electronic structure involves the use of first-principles molecular calculations to simulate the variation of the electronic structure in the strontium titanate crystalline phase, which is known to have a direct band gap, and we also make an in-depth examination of amorphous strontium titanate. The results of our simulations of amorphous strontium titanate indicate that the formation of five-fold coordination in the amorphous system may introduce delocalized electronic levels in the highest occupied molecular orbital and the lowest unoccupied molecular orbital. These delocalized electronic levels are ascribed to the formation of a tail in the absorbance-spectrum curve. Optical absorption measurements experimentally showed the presence of a tail. The results are interpreted by the nature of these exponential optical edges and tails associated with defects promoted by the disordered structure of the amorphous material. We associate them with localized states in the band gap. Received: 15 January 2002 / Accepted: 7 August 2002 / Published online: 4 December 2002 RID="*" ID="*"Corresponding author. Fax: +55-16/2615-215, E-mail: derl@power.ufscar.br     

Hydrogen in crystalline and amorphous silicon: A first principles molecular dynamics study

Structural and dynamical properties of hydrogen in crystalline and amorphous silicon are analyzed by ab initio molecular dynamics simulations. In the crystalline case we focus mainly on the diffusion process of an isolated positively charged hydrogen impurity at high temperature, finding important dynamical effects. In the amorphous case we analyze the local order and the dynamical properties corresponding to an atomic hydrogen concentration of 11%, typical of a device quality material. We find that hydrogen atoms form monohydride complexes and show interesting clustering effects. In both crystalline and amorphous cases, our results are in good agreement with available experimental data and give unique insight into the microscopic details of hydrogen incorporation in silicon.     

Diffusion of silicon in Fe-based amorphous and crystalline alloys

The segregation rate of silicon was measured in three different Fe-based amorphous and crystallized alloys with different silicon contents: 3.5, 5 and 9 at%. Analysis of the segregation kinetics yielded the diffusion activation energies E, as well as the frequency factors D₀. A linear dependence was found between In D₀ and E. In general, the D₀ and E values were lower for the amorphous specimens than for the crystalline ones, were independent of silicon content and are explained in terms of an oversaturated concentration of structural defects. In the crystalline specimens, diffusion behaviour was influenced by silicon content near the solubility limit of silicon in iron.     

Modelling amorphous silicon with hydrogenated defects: GW treatment of the ST12 phase

The ST12 phase of silicon is investigated as a possible model for amorphous silicon (a-Si). The structure is studied both with and without hydrogenated hole defects to model the properties of hydrogenated amorphous silicon (a-Si:H) as well as a-Si. A density functional theory model of ST12 Si is structurally relaxed, and the radial correlation function and phonon density of states are used to compare the structural properties of the model to those of a-Si. One-shot GW self-energy corrections are used to generate the band structure, and the corrected electronic structure is found to reproduce the experimental energy gap of a-Si. Introducing hydrogenated defects to the ST12 structure leads to a slight decrease in the band gap and a shift in the density of states, as the breaking of symmetry results in band splitting. The dielectric functions are calculated for both a-Si and a-Si:H, using the GW corrected band structures, with a density functional perturbation theory approach. The model ST12 Si is found to absorb strongly at slightly lower energies than experimental a-Si, whereas the spectrum of the hydrogenated ST12 closely matches that of a-Si:H.     

Structural relaxation of amorphous silicon carbide

We have examined amorphous structures of silicon carbide (SiC) using both transmission electron microscopy and a molecular-dynamics approach. Radial distribution functions revealed that amorphous SiC contains not only heteronuclear (Si-C) bonds but also homonuclear (Si-Si and C-C) bonds. The ratio of heteronuclear to homonuclear bonds was found to change upon annealing, suggesting that structural relaxation of the amorphous SiC occurred. Good agreement was obtained between the simulated and experimentally measured radial distribution functions.     

Dynamic nuclear polarization in silicon microparticles

We report record high 29Si spin polarization obtained using dynamic nuclear polarization in microcrystalline silicon powder. Unpaired electrons in this silicon powder are due to dangling bonds in the amorphous region of this intrinsically heterogeneous sample. 29Si nuclei in the amorphous region become polarized by forced electron-nuclear spin flips driven by off-resonant microwave radiation while nuclei in the crystalline region are polarized by spin diffusion across crystalline boundaries. Hyperpolarized silicon microparticles have long T1 relaxation times and could be used as tracers for magnetic resonance imaging.     

过渡区p型氢化硅氧薄膜结构和光电特性的研究

采用射频等离子体增强化学气相沉积技术,利用二氧化碳(CO_2)、氢气(H_2)、硅烷(SiH_4)和乙硼烷(B_2H_6)作为气源,制备出一系列p型氢化硅氧薄膜.利用拉曼光谱、傅里叶变换红外光谱和暗电导测试,研究了不同二氧化碳流量对薄膜材料结构和光电特性的影响,获得了从纳米晶相向非晶相转变的过渡区P层.研究表明:随着二氧化碳流量从0增加到1.2 cm~3·min~(-1),拉曼光谱的峰值位置从520 cm~(-1)逐渐移至480 cm~(-1).材料红外光谱表明,随着二氧化碳流量的增加,薄膜中的氧含量逐渐增加,氢键配置逐渐由硅单氢键转换为硅双氢键.P层SiO:H薄膜电导率从3S/cm降为8.3×10~(-6)S/cm.所有p型SiO:H薄膜的光学带隙(Eopt)都在1.82—2.13 eV之间变化.在不加背反射电极的条件下,利用从纳米晶相向非晶相转变的过渡区P层作为电池的窗口层,且在P层和I层之间插入一定厚度的缓冲层,制备出效率为8.27%的非晶硅薄膜电池.     

Silicon dioxide and the chalcogenide semiconductors; similarities and differences

The purpose of this article is to examine current hypotheses about the optical and electrical properties of the amorphous chalcogenide semiconductors, and to examine whether they can be extended to explain some of the properties of amorphous silicon dioxide. For the selenides and tellurides we assume the validity of the model of ‘charged dangling bonds’ introduced by Street and Mott. Absorption of light by these defects leads to photoluminescence with a large Stokes shift; formation of an electron-hole pair far from a defect, on the other hand, leads to radiationless recombination. In enquiring why this is so, we examine the nature of excitons in non-crystalline systems, and the mechanism of self-trapping both of excitons and of free carriers in crystalline and non-crystalline materials. Self-trapping by the V _K-type mechanism, if it occurs, takes place after a certain delay for a free hole or exciton, but not for one bound at a defect, so that free-exciton absorption bands are narrower than those from bound excitons at defects. The radiationless recombination of a free or bound exciton normally occurs through the mechanism first considered by Dexter et al., if more energy than ～1 eV is emitted.

In SiO₂ electrons are exceptionally mobile, but on the basis of work by Hughes, we think that holes are self-trapped after a delay, and can then move by polaron-type hopping. We propose that the first absorption peak (at 10.2 eV) in the optical spectrum is due to an optically allowed exciton, which recombines by the Dexter mechanism, but only after a delay of a type proposed here. The delay allows a comparatively narrow absorption peak, of width given by that of the exciton band. The absorption peak due to a Na⁺ ion linked to a non-bridging oxygen atom is considerably broader because it is due to a bound exciton. We estimate the band-gap in SiO₂ to be about 10.6 eV and also the position of the centre of gravity of the level due to a Na⁺ ion with a non-bridging oxygen atom to be ～1.5 eV above the valence band of SiO₂, less than usually supposed.

Finally, we examine the nature of the positive and negative charges which occur in SiO₂ grown thermally on silicon; these are responsible for Anderson localization of electrons in the inversion layer, and for the ‘slow states’ of silicon technology. We tentatively conclude that they are non-bridging oxygen atoms and that these, like dangling bonds in chalcogenides, are normally positively and negatively charged. We examine their positions in the gap and the activation energies of charging and discharging.     

溅射制备非晶氮化镓薄膜的光学性能

采用直流磁控溅射方法在不同的氩气-氮气（Ar-N₂）气氛中制备了非晶氮化镓（a-GaN）薄膜. X射线衍射分析（XRD）和拉曼光谱（Raman）表明薄膜具有非晶结构. 通过椭偏光谱（SE）得到薄膜的折射率和厚度都随着氩气分量的增多而增大. 紫外—可见光谱（UV-Vis）的测量得到,当氩气分量R,即Ar/（Ar+N₂）,为0%时,薄膜的光学带隙为3.90eV,比晶体GaN （c-GaN） 的较大,这主要是由非晶结构中原子无序性造成的;而当R关键词： 非晶氮化镓 溅射 光学带隙 带尾态     

Electronic structure and band alignment of 9,10-phenanthrenequinone passivated silicon surfaces

In this work we demonstrate that the room-temperature deposition of the organic molecule 9,10-phenanthrenequinone (PQ) reduces the surface defect density of the silicon (100) surface by chemically bonding to the surface dangling bonds. Using various spectroscopic measurements we have investigated the electronic structure and band alignment properties of the PQ/Si interface. The band-bending at the PQ-passivated silicon surface is negligible for both n- and p-type substrates, demonstrating a low density of surface defects. Finally we show that PQ forms a semiconducting wide-bandgap type-I heterojunction with silicon.     

Generation of single-crystalline domain in nano-scale silicon pillars by near-field short pulsed laser

We observe laser-induced grain morphology change in silicon nanopillars under a transmission electron microscopy (TEM) environment. We couple the TEM with a near-field scanning optical microscopy pulsed laser processing system. This novel combination enables immediate scrutiny on the grain morphologies that the pulsed laser irradiation produces. We find unusual transformation of the tip of the amorphous or polycrystalline silicon pillar into a single crystalline domain via melt-mediated crystallization. On the basis of the three-dimensional finite difference simulation result and the dark field TEM data, we propose that the creation of the distinct single crystalline tip originates from the dominant grain growth initiated at the apex of the non-planar liquid–solid interface. Our microscopic observation provides a fundamental basis for laser-induced conversion of amorphous nanostructures into coarse-grained crystals.     

Luminescence and ESR studies of defects in hydrogenated amorphous silicon

New experimental information on luminescence and light induced ESR (LESR) in hydrogenated amorphous silicon is described. We demonstrate that the two experiments involve identical recombination transitions, and identify two separate processes. One process involves defect states, and from the doping dependence of LESR we deduce that the electronically active defects are dangling bonds with positive electronic correlation energy.     

The influence of boron concentrations on structural properties in disorder silicon films

In this work we present a detailed structural of a series of B-doped hydrogenated microcrystalline silicon (μc-Si:H) films deposited by plasma-enhanced chemical vapor deposition (PECVD) and B-doped polycrystalline silicon (poly-Si) films produced by step-by-step laser crystallization process from amorphous silicon. The influence of doping on the structural properties and structural changes during the sequential crystallization processes were monitored by Raman spectroscopy. Unlike μc-Si:H films, that consist of a two-phase mixture of amorphous and ordered Si, partially crystallized sample shows a stratified structure with polycrystalline silicon layer at the top of an amorphous layer. With increasing doping concentration the LO-TO phonon line in poly-Si shift to smaller wave numbers and broadens asymmetrically. The results are discussed in terms of resonant interaction between optical phonons and direct intraband transitions known as a Fano resonance. In μc-Si:H films, on the other hand, the Fano effect is not observed. The increase of doping in μc-Si:H films suppressed the crystalline volume fraction, which leads to an amorphization in the film structure. The structural variation in both μc-Si:H and poly-Si films leads to a change in hydrogen bonding configuration.     

Analysis of amorphous-nano-crystalline multilayer structures by optical, photo-deflection and photo-current spectroscopy

Thin film structures consisting of nano-crystalline and amorphous silicon layers deposited on glass by plasma enhanced chemical vapour deposition have been studied by optical spectroscopy methods (transmittance, photo-thermal deflection spectroscopy and photo-current spectroscopy) while structure was examined by Raman spectroscopy. The nano-crystalline layers were grown on the same amorphous layers, using different radio-frequency (RF) discharge powers, leading to different structural and optical properties. The energy dependence of the absorption coefficient above the band gap agrees well to the bimodal size distribution of crystals and crystal fraction estimated by Raman spectroscopy. For energies below the band gap, the comparison of the absorption of the bi-layer systems with respect to single amorphous layer reveals that the samples produced at higher RF discharge present a higher disorder degree (Urbach edge increases) and higher number of structural defects (absorption related to the defects increases).     

Enhanced multiple exciton generation in amorphous silicon nanowires and films

ABSTRACT

Multiple exciton generation (MEG) in nanometer-sized hydrogen-passivated silicon nanowires (NWs), and quasi two-dimensional nanofilms depends strongly on the degree of the core structural disorder as shown by the perturbative many-body quantum mechanics calculations based on the density functional theory simulations. Working to the second order in the electron–photon coupling and in the screened Coulomb interaction, we calculate quantum efficiency (QE), the average number of excitons created by a single absorbed photon, in the Si₂₉H₃₆ quantum dots (QDs) with crystalline and amorphous core structures, simple cubic three-dimensional arrays constructed from these QDs, crystalline and amorphous NWs, and quasi two-dimensional silicon nanofilms, also both crystalline and amorphous. Efficient MEG with QE ranging from 1.3 up to 1.8 at the photon energy of about 3E_g, where E_g is the electronic gap, is predicted in these nanoparticles except for the crystalline NW and crystalline film where QE ? 1. MEG in the amorphous nanoparticles is enhanced by the electron localisation due to structural disorder. Combined with the lower gaps, the nanometer-sized amorphous silicon NWs and films are predicted to have effective carrier multiplication within the solar spectrum range.     

Intrinsic stability of quasicrystals under the generation of Frenkel pairs

Under irradiation metastable quasicrystals undergo a phase transition to an amorphous state. This transition can be reversed by annealing. As in normal crystalline materials the phase transition is considered to be triggered by generation and recombination of vacancies and interstitial atoms (Frenkel pairs). We have classified the possible Frenkel defects in a metastable monatomic quasicrystal with respect to geometric and energetic properties. With numerical simulation we have studied the behaviour of the quasicrystal under a load of Frenkel defects for various defect concentrations. We find three ranges of behaviour: up to 5% defects per atom the structure remains icosahedral, in a middle range it stays disordered icosahedral or it becomes either disordered or perfect crystalline, depending on the implementation of the defects. If there are more than 10% defects the structure becomes irreversibly amorphous. We finally compare our results with experimental data.     

富硅氮化硅薄膜的制备及其光学带隙研究

采用双极脉冲磁控反应溅射法在不同参数条件下制备了一系列氮化硅薄膜。利用数字式显微镜和紫外-可见光光谱仪研究了沉积薄膜的表面形貌及其光学带隙,利用共焦显微拉曼光谱仪比较了硅衬底、氮化硅薄膜退火前后的拉曼光谱。结果表明,氮气流量对薄膜的光学带隙影响较大,制备的薄膜主要为富硅氮化硅薄膜。原沉积薄膜的拉曼光谱存在明显的非晶硅和单晶硅峰,退火处理后非晶硅峰减弱或消失,表明薄膜出现明显的结晶化;单晶硅峰出现频移现象,表明薄膜中出现硅纳米颗粒,平均尺寸约为6.6 nm。     

Growth kinetics and polysilicon formation by aluminium-induced crystallization on glass-ceramic substrates

In this work, we present extended structural properties of poly-Si thin films fabricated by aluminium-induced crystallization (AIC) of amorphous silicon (a-Si) on high-temperature glass-ceramic substrates. The silicon nucleation kinetics on glass-ceramic substrates was investigated by optical microscopy. The crystalline quality of the films was studied by micro-Raman spectroscopy as a function of exchange annealing conditions. By means of electron backscattering diffraction (EBSD), we have analyzed the effect of thermal annealing on silicon grain size and its distribution, intra- and inter-grains defects, and on the grains preferential crystallographic orientation. The optimal thermal annealing condition, allowing 100% crystallized polysilicon large grains with an average grain size of 26 μm and 〈100〉 oriented, acquired a thermal budget of 475°C and 8 h.