Blue luminescent silicon nanocrystals prepared by short pulsed laser ablation in liquid media

The pulsed laser processing in liquid media is an attractive alternative to produce room temperature luminescent silicon nanocrystals (Si-ncs). We report on a blue luminescent Si-ncs preparation by using nanosecond pulsed laser (Nd:YAG, KrF excimer) processing in transparent polymer and water. The Si-ncs fabrication is assured by ablation of crystalline silicon target immersed in liquids. During the processing and following aging in liquids, oxide based liquid media, induce shell formation around fresh nanocrystals that provides a natural and stable form of surface passivation. The stable room temperature blue-photoluminescent Si-ncs are prepared with maxima located around ∼440 nm with corresponding optical band gap around ∼2.8 eV (∼430 nm). Due to the reduction of surface defects, the Si-ncs preparation in water, leads to a narrowing of full-width-half-maxima of the photoluminescence spectra.     

飞秒脉冲激光辐照对硅发光性能的影响

利用飞秒脉冲激光对单晶硅进行辐照,研究了在不同环境(纯水和空气)和能量密度条件下激光刻蚀过后硅片的光致荧光特性.对于辐照后的硅片,利用了场发射扫描电子显微镜(FESEM)、能谱仪(EDS)、傅里叶红外光谱仪(FT-IR)、光致荧光光谱仪(PL)进行表征.结果显示:在空气中样品表面形成了条纹状微结构,纯水中硅片表面生成了尺寸更小的珊瑚状微结构;激光刻蚀后在硅片表面的生成物主要是SiOx(x2),在纯水中处理后硅片氧元素的含量接近是空气中的4倍;傅里叶变换红外透射谱中主要为Si—Si键(610 cm-1)和Si—O—Si键(1105 cm-1)的振动;在空气和纯水中激发出的荧光均为蓝光(420—470 nm),在各自最佳激发波长下,纯水中荧光强度比空气中强2到3倍,但是在可见光范围内荧光峰的位置和形状都基本没有发生变化.研究表明:氧元素在光致发光增强上起着重要作用,光致发光最主要是由形成的氧缺陷SiOx(x2)导致的,生成低值氧化物SiOx的多少决定了发光的强弱.     

Self-organized silicon microcolumn arrays generated by pulsed laser irradiation

Cumulative nanosecond pulsed excimer laser irradiation of silicon produces an array of high-aspect-ratio microcolumns that protrude well above the initial surface. The growth of these microcolumns is strongly affected by the gas environment, being enhanced in air or in other oxygen-containing atmosphere. An array of very large and complex conical structures that also protrude above the surface is formed if the irradiation is performed in sulfur hexafluoride (SF₆). Kinetics studies of microcolumn growth show that: (i) A certain number of pulses is required to initiate growth of microcolumns; (ii) column nucleation is inhomogeneous, taking place always at the edges of deep grooves or pits; (iii) growth is fast with the earlier pulses but slows down to a halt when the columns reach a certain length. These studies show that columns nucleate and grow by continuous influx of silicon with each laser pulse. It is proposed that the axial growth of microcolumns and cones is due to the deposition of atoms or clusters at their tips. The column/cone tips are melted during irradiation and act as preferred sites for deposition, resulting in a very high axial growth rate. The contribution of etching and ablation to the flux of silicon-rich vapor produced during irradiation is discussed. The mechanism of columnar growth is compared with the vapor-liquid-solid method to grow silicon whiskers.     

Tip-based nanoscale selective growth of discrete silicon nanowires by near-field laser illumination

Growth of discrete silicon nanowires is reported with nanoscale location selectivity by employing near-field laser illumination. An uncoated dielectric atomic force microscope (AFM) tip provides a nanometer-scale light source that is sufficiently localized to induce nucleation and subsequent growth of a single nanowire under its optical near-field. Far-field laser-induced heating is additionally supplied to the substrate to both relieve the required near-field light budget and also assist stable epitaxial growth. Specific catalysts are selected for the nanowire growth by non-contact mode AFM imaging. Through real-time monitoring of the deflection of the AFM cantilever during the growth process, the gap between the tip and the sample and hence truly near-field illumination are maintained throughout the growth process. The study shows that tip-based near-field laser illumination could be an effective tool for the direct integration of semiconductor nanowires.     

Photovoltaic properties of black silicon microstructured by femtosecond pulsed laser

Prototype devices based on black silicon have been fabricated by microstructuring 250 μm thick multicrystalline n doped silicon wafers using femtosecond pulsed laser in ambient gas of SF₆ to measure its photovoltaic properties. The enhanced optical absorption of black silicon extends across the visible region and all the black silicons prepared in this work exhibit enhanced optical absorption close to 90% from 300 nm to 800 nm. The highest open-circuit voltage (V_oc) and short-circuit current (I_sc) under the illumination of He–Ne continuous laser at 632.8 nm were measured to be 53.3 mV and 0.11 mA, respectively at a maximum power conversion efficiency of 1.44%. Upon excitation with He–Ne continuous laser at 632.8 nm, external quantum efficiency (EQE) of black silicon as high as 112.9% has also been observed. Development of black silicon for photovoltaic purposes could open up a new perspective in achieving high efficient silicon-based solar cell by means of the enhanced optical absorption in the visible region. The current–voltage characteristic and photo responsivity of these prototype devices fabricated with microstructured silicon were also investigated.     

脉冲激光作用单晶硅的等离子体光谱分析

从激光与物质相互作用理论出发,对脉冲激光作用单晶硅的热特性进行分析。建立一套实验装置,所用激光光源的波长为1 064 nm,脉宽为10 ns,重复频率为1 Hz。得到单晶硅的等离子体谱及热辐射谱,在单晶硅的光电性质基础上对其热表面损伤进行理论分析。提取380~460 nm波段的单晶硅等离子体光谱,分析了谱图中SiⅠ390.52 nm, SiⅡ385.51 nm,SiⅡ413.12 nm三条谱线的相对强度与激光输出功率密度的对应关系。     

Plasma induced by pulsed laser and fabrication of silicon nanostructures

It is interesting that in preparing process of nanosilicon by pulsed laser, the periodic diffraction pattern from plasmonic lattice structure in the Purcell cavity due to interaction between plasmons and photons is observed. This kind of plasmonic lattice structure confined in the cavity may be similar to the Wigner crystal structure. Emission manipulation on Si nanostructures fabricated by the plasmonic wave induced from pulsed laser is studied by using photoluminescence spectroscopy.The electronic localized states and surface bonding are characterized by several emission bands peaked near 600nm and 700nm on samples prepared in oxygen or nitrogen environment. The electroluminescence wavelength is measured in the telecom window on silicon film coated by ytterbium. The enhanced emission originates from surface localized states in band gap due to broken symmetry from some bonds on surface bulges produced by plasmonic wave in the cavity.     

Room temperature fabrication of silicon nanocrystals by pulsed laser deposition

Reaction of 10 nm gold nanoparticles (AuNPs) with a thiol-functionalized bipyridine copper(II) complex, Cu[(N-(6-mercaptohexyl)-2,2′-bipyridinyl-5-carboxamide)]Cl₂ (3), and (1-mercaptohex-6-yl)tri(ethylene glycol) (5) in different ratios resulted in mixed monolayer modified NPs with varying surface coverage of capping agent. The copper complex modified NPs were used for surface plasmon resonance (SPR) promoted homogeneous catalysis applied to the hydrolysis of the nerve agent methyl parathion (MeP) at pH 8.0. Low power green laser (532 nm) irradiation of solutions of modified AuNPs with MeP resulted in significant increase in the rate of phosphate ester hydrolysis which could not be attributed to a thermal process. Ratios of initial rates (laser/dark) at high substrate concentrations of MeP as a function of copper catalyst coverage were determined. A possible mechanism for catalytic enhancement involving dissociation of catalytically inactive hydroxy-bridged Cu(II) dimer is discussed.     

脉冲激光作用单晶硅的等离子体光谱分析

从激光与物质相互作用理论出发,对脉冲激光作用单晶硅的热特性进行分析。建立一套实验装置,所用激光光源的波长为1 064 nm,脉宽为10 ns,重复频率为1 Hz。得到单晶硅的等离子体谱及热辐射谱,在单晶硅的光电性质基础上对其热表面损伤进行理论分析。提取380~460 nm波段的单晶硅等离子体光谱,分析了谱图中SiⅠ390.52 nm,SiⅡ385.51 nm,SiⅡ413.12 nm三条谱线的相对强度与激光输出功率密度的对应关系。     

Nanosecond pulsed laser ablation of silicon in liquids

Laser fluence and laser shot number are important parameters for pulse laser based micromachining of silicon in liquids. This paper presents laser-induced ablation of silicon in liquids of the dimethyl sulfoxide (DMSO) and the water at different applied laser fluence levels and laser shot numbers. The experimental results are conducted using 15 ns pulsed laser irradiation at 532 nm. The silicon surface morphology of the irradiated spots has an appearance as one can see in porous formation. The surface morphology exhibits a large number of cavities which indicates as bubble nucleation sites. The observed surface morphology shows that the explosive melt expulsion could be a dominant process for the laser ablation of silicon in liquids using nanosecond pulsed laser irradiation at 532 nm. Silicon surface’s ablated diameter growth was measured at different applied laser fluences and shot numbers in both liquid interfaces. A theoretical analysis suggested investigating silicon surface etching in liquid by intense multiple nanosecond laser pulses. It has been assumed that the nanosecond pulsed laser-induced silicon surface modification is due to the process of explosive melt expulsion under the action of the confined plasma-induced pressure or shock wave trapped between the silicon target and the overlying liquid. This analysis allows us to determine the effective lateral interaction zone of ablated solid target related to nanosecond pulsed laser illumination. The theoretical analysis is found in excellent agreement with the experimental measurements of silicon ablated diameter growth in the DMSO and the water interfaces. Multiple-shot laser ablation threshold of silicon is determined. Pulsed energy accumulation model is used to obtain the single-shot ablation threshold of silicon. The smaller ablation threshold value is found in the DMSO, and the incubation effect is also found to be absent.     

Optical properties of silicon microcolumn grown by nanosecond pulsed laser irradiation

We have investigated the optical properties of silicon pillars formed by cumulative nanosecond pulsed excimer laser irradiation of single-crystal silicon in vacuum created under different repetition rates. The changes in optical characteristics of silicon pillar were systematically determined and compared as the number of KrF laser shots was increased from 1 to 15,000.The results show that silicon pillar PL curves exhibit a blue band around 430 nm and an ultraviolet band peaking at 370 nm with the vanishing of the green emission at 530 nm. A correlation between the intensity of the blue PL band and the intensity of the Si-O absorption bands has been exploited to explain such emission, whereas, the origin of the ultraviolet band may be attributed to different types of defects in silicon oxide.     

Hyperdoping of silicon with deep-level impurities by pulsed YAG laser melting

Hyperdoping with deep-level impurity is a promising method to prepare intermediate band semiconductors. We prepared silicon hyperdoped with deep-level impurities, sulfur and titanium, by ion implantation followed by pulsed YAG laser melting. The processes of sulfur and titanium hyperdoping are comparatively studied. The amorphous sulfur and titanium ion-implanted layers changed to monocrystal by following pulsed laser melting. The depth profile of sulfur impurity after pulsed laser melting is similar to that of ion-implanted sample, while large segregation is observed for titanium hyperdoping. The crystallinity and degree of segregation depend on the laser shot number and initially implanted titanium dose. There is a trade-off between crystallinity and depth profile of impurity for titanium hyperdoping. From a viewpoint material processing, formation of high-quality silicon monocrystal hyperdoped with sulfur is easier than that with titanium. Correlation between the mid-infrared optical absorption and photoconductivity is also discussed for sulfur-hyperdoped sample.     

激光干涉结晶法制备一维周期结构的纳米硅阵列

利用激光干涉结晶方法,采用周期为400 nm的一维(1D)移相光栅掩模调制KrF准分子激光器的脉冲激光束斑的能量分布,在不同厚度的超薄氢化非晶硅(a-Si:H)膜内直接制备1D有序纳米硅(nc-Si)阵列.拉曼散射谱表明,样品上呈条状分布的受辐照区域发生晶化.原子力显微镜和透射电子显微镜测试结果表明：1D的nc-Si阵列的周期和移相光栅掩模一样.随着a-Si:H膜厚度从10nm降至4nm,通过控制激光的能量密度,每个周期中nc-Si条状分布区宽度可达到30nm.nc-Si条状分布区的高分辨电子显微镜照片显 关键词： 纳米硅 激光干涉结晶 移相光栅 定域晶化     

Nanostructuring of silicon surface by femtosecond laser pulse mediated with enhanced near-field of gold nanoparticles

High-energy synchrotron X-ray diffraction and imaging experiments were performed at the Advanced Photon Source on two ancient Chinese bronzes from the Art Institute of Chicago with the goal to nondestructively study their microstructure. The first object, a bronze fragment from an early Western Zhou dynasty vessel (Hu, 11th/10th century B.C.), was investigated with spatially-resolved diffraction to reveal the depth and composition of the surface corrosion layer as well as the composition and grain size of the underlying bronze core. The second object, a bronze dagger-axe (Ge, 3rd/2nd century B.C.) with a silver-inlaid sheath, was studied under both diffraction and imaging conditions. It was found to have been cast as a single object, answering longstanding scholars’ questions on whether the ceremonial object concealed an interior blade. PACS 81.00; 01.75.+m     

Experimental evidence of the vacancy-mediated silicon self-diffusion in single-crystalline silicon

We have determined silicon self-diffusivity at temperatures 735-875 degrees C based on the Raman shift of longitudinal optical phonon frequencies of diffusion annealed 28Si/30Si isotope superlattices. The activation enthalpy of 3.6 eV is obtained in such low temperature diffusion annealing. This value is significantly smaller than the previously reported 4.95 eV of the self-interstitial mechanism dominating the high temperature region T>855 degrees C and is in good agreement with the theoretical prediction for the vacancy-mediated diffusion. We present a model, containing both the self-interstitial and the vacancy terms, that quantitatively describes the experimentally obtained self-diffusivity between 735 and 1388 degrees C, with the clear crossover of the two diffusion mechanisms occurring around 900 degrees C.     

Optical characterization of thin silicon films deposited by CVD and annealed by pulsed laser

Polycrystalline Si layers 100 to 800 nm thick have been deposited on Si single crystal substrates by CVD and annealed with a Q-switched ruby laser at energies up to 1.5 J/cm². The optical characteristics of these layers have been measured by SEM and ellipsometry. The results can be attributed to a change in surface roughness with film thickness and laser energy.     

Surface morphology of He-implanted single-crystalline silicon

Single-crystalline Si (100) samples were implanted with 30 keV He²⁺ ions to doses ranging from 2.0×10¹⁶ to 2.0×10¹⁷ions /cm² and subsequently thermally annealed at 800℃ for 30min. The morphological change of the samples with the increase of implantation dose was investigated using atomic force microscopy (AFM). It was found that oblate-shaped blisters with an average height around 4.0nm were found on the 2.0×10¹⁶ ions /cm² implanted sample surface; spherical-shaped blisters with an average height around 10.0nm were found on the 5.0×10¹⁶ ions /cm² implanted sample surface; strip-shaped and conical cracks were observed on the sample He-implanted to a dose of 1.0×10¹⁷ ions /cm². Exfoliations occurred on the sample surface to a dose of 2.0×10¹⁷ ions /cm². Mechanisms underlying the surface change were discussed.     

Defects in pulsed laser and thermal processed ion implanted silicon

The evolution of the nature and concentration of the defects produced by 100 or 300 keV As ions at fluences 1 to 4×10^–12 cm^–2 inn-type, Fz Silicon doped with 10¹⁵ to 10¹⁶ cm^–3 has been studied as function of thermal treatments (in the range 500°–900 °C) and of the energy density (in the range 0.3–0.6 J cm^–2) of a light pulse from a ruby laser (15 ns, 0.69 m). Deep-level transient spectroscopy (DLTS) combined with capacitance — voltage (C-V) measurements were used to get the characteristics (energy level, crosssection for the capture of majority carriers) of the defects and theirs profiles. The difficulties encountered in the analysis of the results, due to the large compensation of free carriers in the implanted region and to the abrupt defect and free carrier profiles, are discussed in detail and the corrections to apply on the C-V characteristics and the DLTS spectra are described. The defects resulting from the two types of treatments are found to be essentially the same. Only, for laser energies higher than 0.5 J cm^–2, the laser treatment appears to introduced new defects (atE0.32 eV) which should result from a quenching process. The fact that a laser energy smaller than the threshold energy for melting and recrystallization is able to anneal, at least partially, the defects produced by the implantation, demonstrates that the annealing process induced by the laser pulse is not a purely thermal process but is enhanced by a mechanism involving ionization.     

Generation of multiply charged silicon and germanium ions by excimer laser pulses

Plasma bursts were produced by focusing excimer-laser (XeCl, 308 nm) pulses on Ge and Si targets. At moderate laser fluences (30 MW/cm²) high-intensity Ge³⁺ and Si³⁺ ion pulses were extracted from the laser-produced plasma. A peculiar electrical circuit allows a self-bunching of the beam. By time-of-flight method, the currents produced by the ions of different charge number were measured. Peak currents of 620 mA and 800 mA were recorded for Ge³⁺ and Si³⁺ ions, respectively, with an extraction voltage of only 400 V.