Nanohole 3D-size tailoring through polystyrene bead combustion during thin film deposition

A novel approach is presented for nanohole 3D-size tailoring. The process starts with a monolayer of polystyrene (PS) beads spun coat on silicon wafer as a template. The holes can be directly prepared through combustion of PS beads by oxygen plasma during metal or oxide thin film deposition. The incoming particles are prevented from adhering on PS beads by H₂O and CO₂ generated from the combustion of the PS beads. The hole depth generally depends on the film thickness. The hole diameter can be tailored by the PS bead size, film deposition rate, and also the combustion speed of the PS beads. In this work, a series of holes with depth of 4-24 nm and diameter of 10-36 nm has been successfully prepared. The hole wall materials can be selected from metals such as Au or Pt and oxides such as SiO₂ or Al₂O₃. These templates could be suitable for the preparation and characterization of novel nanodevices based on single quantum dots or single molecules, and could be extended to the studies of a wide range of coating materials and substrates with controlled hole depth and diameters.     

Effect of surface modification by thermally oxidization and HF etching on UV photoluminescence emission of porous silicon

Photoluminescence of porous silicon (PS) is instable due perhaps to the nanostructure modification in air. The controllable structure modification processes on the as-prepared PS were conducted by thermal oxidization and/or HF etching. The PL spectra taken from thermally oxidized PS showed a stable photoluminescence emission of 355 nm. The photoluminescence emission taken from both of PS and oxidized porous silicon (OPS) samples etched with HF were instable, which can be reversibly recovered by the HF etching procedure. The mechanism of UV photoluminescence is discussed and attributed to the transformation of luminescence centers from oxygen deficient defects to the oxygen excess defects in the thermal oxidized PS sample and surface absorbed silanol groups on PS samples during the chemical etched procedure.     

场发射冷阴极微栅孔阵列制备技术

实现了一种采用聚苯乙烯纳米球自组装技术和微机械制造技术加工的场发射阴极用亚微米栅极微孔阵列。设计了一套完整的工艺实验方案,首先采用微球自组装技术获得了亚微米级金属网孔掩膜,然后通过反应离子刻蚀技术获得了亚微米栅极孔阵列,从而实现了集成度高、分布均匀的周期性亚微米孔洞阵列的制备,微孔集成度达到108cm-2。实验研究了氧气刻蚀聚苯乙烯微球的规律。采用金属掩膜,四氟化碳干法刻蚀二氧化硅,获得了深度为500 nm的微孔。实验结果证明该工艺方案是一种获得大面积、均匀分布、集成度高的场发射冷阴极栅孔阵列的有效方法。     

Excimer-laser etching on silicon

Studies have been made of poly- and single Si etching induced by excimer-laser irradiation of the silicon surfaces in halogenated gases. Etching was investigated for different conduction types, impurity concentrations and crystallographic planes. Chlorine atoms accept electrons generated in photoexcited, undoped p-type Si, thus becoming negative ions which are pulled into the Si. However, the n⁺-type Si is etched spontaneously by Cl^– as a result of the availability of conduction electrons. Fluorine atoms, with the highest electronegativity, take in electrons independent of whether the material is n- or p-type. And thus, the easy F^– ion penetration into Si causes spontaneous etching in both types. New anisotropic etching for n⁺ poly-Si is investigated because of its importance to microfabrication technology. Methyl methacrylate (MMA) gas, which reacts with Cl atoms, produces a deposition film on the n⁺ poly-Si surface. The surface, from which the film is removed by KrF (5 eV) laser irradiation, is etched by Cl atoms, while the film remains on the side wall to protect undercutting. However, with the higher photon energy for the ArF (6.4 eV) laser, the Si-OH bonds are broken and electron traps are formed. These electrontrapping centers are easily annealed out in comparison to the plasma-induced centers. Pattern transfer etching for n⁺ poly-Si has been realized using reflective optics. The problems involved in obtaining finer resolution etching are discussed.     

机械-化学方法在硅(100)表面制备芳香烃重氮盐单层膜

利用机械-化学方法同时实现硅表面的图形化和功能化. 在芳香烃重氮盐(C₆H₅N₂BF₄)中用金刚石刀具刻划单晶硅(100),使单晶硅表面的Si-O键断裂,形成硅的自由基,进而它们与溶液中含有的有机分子共价结合以形成自组装单层膜. 用原子力显微镜对自组装前后的表面形貌进行表征,用飞行时间二次离子质谱和红外光谱对自组装单层膜进行检测和分析,通过确认C₆H₅离子的存在证明自组装单层     

Ultrafast and nanosecond laser-induced desorption of positive ions from lithium fluoride single crystals

We compare desorption of positive ions from lithium fluoride single crystals following pulsed laser excitation using either femtosecond (180 fs, 265 nm) or nanosecond (3 ns, 266 nm) sources. Following optical excitation, desorbed ions are mass analyzed using standard time-of-flight techniques. Several important differences between nanosecond and femtosecond excitation are revealed. Femtosecond excitation produces higher kinetic energy Li⁺ than does nanosecond excitation (10 eV vs. 5 eV) while nanosecond excitation yields significant quantities of impurity ions Na⁺ and K⁺, in addition to efficient Li⁺ emission. The Li⁺ desorption threshold is similar for both laser sources. This similarity is a surprising result, as sub-bandgap nanosecond pulses are only likely to excite defect states efficiently (via linear excitation), while the ultrahigh peak-power femtosecond pulses could in principle induce multiphoton and avalanche excitation. Femtosecond excitation results in much less complicated time-of-flight spectra, as predominantly Li⁺ is detected with some H⁺ also observed. We have measured the Li⁺ yield as a function of time delay between two sub-threshold femtosecond laser pulses. We find that the majority of the Li⁺ yield decays rapidly, largely within the fs pulse duration. However, a weak but measurable decay component of approximately 2 ps is indicated.     

External-field-controlled laser wet etching of polycrystalline Al2O3TiC

Laser-induced etching of polycrystalline Al₂O₃TiC material by tightly focused CW Ar ion laser has been investigated in both H₃PO₄ and KOH solutions with influence of an external electric field. It is found that a weak external electric field will change the ions distribution in chemical solutions and cause obvious change in etching behavior. The laser etching in a H₃PO₄ solution can be enhanced by both positive and negative biases of the substrate. While etching in a KOH solution, a positive bias can enhance the etching reaction, whereas a negative bias can suppress the etching process. It is also found that the external electric field can always enhance the mass transfer between reaction products and fresh etchant in a H₃PO₄ solution. It is revealed that the supply of H⁺ ions contributes to the etching process in a H₃PO₄ solution, while the supply of OH^– ions contributes to the etching process in a KOH solution. The electric field can be used to control the etching process to achieve fast tuning and higher accuracy.     

Chemical etching of silicon by CO2-laser-induced dissociation of NF3

The pulsed infrared laser dissociation of NF₃ is reported for the first time, and is used to investigate silicon etching. The role played by collision-enhanced multiple-photon absorption and dissociation is considered, with data on the nonlinear decrease of the absorption cross-section with increasing pulse energy and increasing pressure presented. Using an experimental arrangement in which the laser beam is focussed parallel to the surface, the dissociation process induces spontaneous etching of silicon. Fluorinecontaining radicals diffuse from the focal volume to the surface where a heterogeneous chemical reaction occurs. Etching was monitored by use of a quartz-crystal microbalance upon which a thin film of amorphous silicon was deposited. For a surface with no previous exposure to the photolysis products, dissociation causes the formation of a surface layer prior to the onset of etching. X-ray photoelectron spectroscopy demonstrates this to be a fluorosilyl layer possessing a significant concentration of SiF₃ and SiF₄. In contrast, a surface already thickly fluorinated does not form a thicker layer once laser pulsing commences again. In this case, etching starts immediately with the first pulse. The etch yield dependencies on several parameters were obtained using silicon samples possessing a thick fluorosilyl surface layer. These parameters are NF₃ pressure, laser wavenumber, pulse energy, buffer gas pressure, and perpendicular distance from focal volume to surface. Modeling of the etch yield variation with perpendicular distance shows the time-integrated flux of radicals impinging on the surface to be inversely proportional to the distance. Attempts at etching SiO₂ under identical conditions were unsuccessful despite the evidence that thin native oxide films are removed during silicon etching.     

Controlled Evolution of Silicon Nanocone Arrays Induced by Ar+ Sputtering at Room Temperature

Controlled evolution of silicon nanocone arrays induced by Ar^＋ sputtering at room temperature, using the coating carbon as a mask, is demonstrated. The investigation of scanning electron microscopy indicates that the morphology of silicon nanostructures can be controlled by adjusting the thickness of the coating carbon film. Increasing the thickness of the coating carbon film from 50-60 nm, 250-300 nm and 750-800 nm to 1500 nm, the morphologies of silicon nanostructures are transformed from smooth surface ripple, coarse surface ripple and surface ripple with densely distributed nanocones to nanocone arrays with a high density of about 1 × 10^9- 2 × 10^9 cm^-2.     

Rotational Bands of Some Neutron Deficient Odd-A Pt Isotopes in Particle-Triaxial-Rotor Model

Theoretical calculations are performed for neutron deficient Pt isotopes ^177pt and ^175,173,171 Pt in the particletriaxial-rotor model with variable moment of inertia. The obtained energy spectra agree with experimental data quite well. The calculated results indicate that all these nuclei are in triaxial rotation with ^177pt; being in prolate and ^175,173,171pt in oblate. Several levels are predicted for the 13/2^＋ band in ^169pt.     

Femtosecond time-resolved laser-induced desorption of positive ions from MgO

We have used the pump-probe technique to measure the photostimulated positive ion yield as a function of time delay between two sub-threshold femtosecond laser pulses. We find that the ion yield from UV femtosecond irradiated MgO depends critically on the laser pulse delay, (t, in two-pulse experiments. In single-pulse experiments, excitation of MgO produces a variety of ions including Mg⁺, MgO⁺, and a significant yield of H⁺. In contrast, if the femtosecond laser pulse is split into two sub-threshold beams and then recombined with a variable time delay, the ion yield may be drastically altered depending on the delay between pulses. The Mg⁺ desorption yield displays three distinct lifetimes and persists for laser delays of over 100 ps. A pulse delay of only (t=500 fs nearly eliminates ion desorption except for Mg⁺. The use of a pair of delayed femtosecond laser pulses can thus control the species of the desorbed ion. The mechanism for femtosecond laser desorption is clearly different from nanosecond laser desorption. We hypothesize that the creation of electron-hole pairs by nonresonant two-photon excitation contributes to the ultrafast desorption mechanism.     

Discrete tunneling of holes in porous silicon

It is pointed out that in the partial oxidation of porous silicon (PS) formed on heavily doped crystals, the topology of the pores can result in the formation of an anisotropic material with strings of nanometersized silicon granules embedded in insulating silicon dioxide SiO₂. In this range of granule sizes the correlation effects in the tunneling of electrons (holes) are strong on account of their Coulomb interaction. This should be manifested as discrete electron and hole tunneling at temperatures comparable to room temperature. The room-temperature current-voltage characteristics of n ⁺-PSp ⁺-p ⁺ diode structures with a PS interlayer on p ⁺-Si, which exhibit current steps on the forward and reverse branches, are presented. The current steps are attributed to discrete hole tunneling along the silicon strings in SiO₂. Pis’ma Zh. éksp. Teor. Fiz. 67, No. 10, 794–797 (25 May 1998)     

Au-assisted electroless etching of silicon in aqueous HF/H2O2 solution

The Au-assisted electroless etching of p-type silicon substrate in HF/H₂O₂ solution at 50 °C was investigated. The dependence of the crystallographic orientation, the concentration of etching solution and the silicon resistivity on morphology of etched layer was studied. The layers formed on silicon were investigated by scanning electron microscopy (SEM). It was demonstrated that although the deposited Au on silicon is a continuous film, it can produce a layer of silicon nanowires or macropores depending on the used solution concentration.     

Ordered magnetic multilayer nanobowl array by nanosphere template method

Ordered magnetic multilayer [Co/Pt]_n nanobowls have been fabricated over a silicon substrate based on a polystyrene (PS) monolayer film. The ordered PS monolayer was first prepared by the self-assembly technique, which was used as the template for the multilayer film [Co/Pt]_n deposition. The ordered magnetic multilayer [Co/Pt]_n nanobowl array was obtained after the transferring and the selective etching process. The nanobowls show a uniform size and smooth surfaces. The nanobowls stuck to the neighbors and notches were observed in the bowl brims because of the contact points between the closed-packed PS beads. The nanobowls could be separated from their neighbors by thinning the PS beads before the film deposition and no notches were observed anymore. Compared to the chemical method, this method showed more flexible choices of the material to fabricate the nanobowls, which extended the application scope of the nanobowls greatly.     

Projection-patterned etching of silicon in chlorine atmosphere with a KrF excimer laser

The formation of relief features in silicon by a one-step process that avoids resist patterning has been achieved by laser-projection-patterned etching in a chlorine atmosphere. Etching is performed with a pulsed KrF excimer laser (λ=248 nm, τ=15 ns) and deep UV projection optics having an optical resolution of 2 μm. Etching takes place in two steps. Between laser pulses, the silicon surface is covered with a monolayer of chemisorbed chlorine atoms (one Cl per Si). During the laser pulse, surface transient heating at temperatures in excess of 1250 K results in the desorption of the reaction products (mainly SiCl₂). At laser energy densities that induce surface melting, this desorption results in a saturated etch. rate of 0.06 nm per pulse, corresponding to the removal of about 0.5 Si monolayer per pulse. At densities below the melting threshold, reduced thermal and possibly a small amount of photochemical etching result in lower etch rates. Projection of a resolution test photomask onto the silicon surface shows that the size of etched features differs from the size of the projected features and strongly depends on the laser energy density. As a result of the heat spread in silicon and of the highly nonlinear character of the etching reaction, etched features smaller than the irradiated area are obtained at all fluences in the range 350–700 mJ/cm². Etched lines having a width down to about 1.3 μm were produced. Proximity effects due to heat spread were also evidenced for small projected features (<4 μm). The characteristics of the etched patterns are compared with those obtained for GaAs etching in chlorinated gases with the same experimental set-up. Significant differences in pattern resolution for Si and GaAs etching are observed. This variation in resolution is believed to result from the fact that Si has a greater thermal diffusivity than GaAs.     

Structural Deformation of CO22+ in Intense Femtosecond Laser Fields

The angular distributions of CO^＋ from the dissociation of CO2^2＋ and CO2^＋ in intense femtosecond laser fields （45 fs, about 5 × 10^15 W/cm^2） are studied at a laser wavelength of 800nm based on the time-of-flight mass spectra of CO^＋ fragment ions. The experimental results show that structural deformation occurs in the charge state of CO2^2＋ and the CO^＋ maintains linear geometrical structure.     

多孔硅的微结构与发光特性研究

利用原子力显微镜（AFM）和光致荧光（PL）光谱对一系列直流腐蚀和脉冲腐蚀的多孔硅的微结构及发光特性进行了对比研究．表面和侧面的AFM结果表明，多孔硅表面呈“小山”状，有许多小的、突出的硅颗粒．在相同的腐蚀条件（等效）下，脉冲腐蚀的样品表面Si颗粒更加尖锐、突出，侧面的线状结构更明显，多孔硅层更厚．对应的PL谱，脉冲腐蚀的样品发光更强．量子限制效应的理论可以比较成功地解释这个结果 关键词：     

Photoluminescence enhancement and stabilisation of porous silicon passivated by iron

Iron is incorporated in porous silicon (PS) by impregnation method using Fe(NO₃)₃ aqueous solution. The presence of iron in PS matrix is shown from energy-dispersive X-ray (EDX) analysis and Fourier transform infrared (FTIR) measurements. The optical properties of PS and PS-doped iron are studied by photoluminescence (PL). The iron deposited in PS quenched the silicon dangling bonds then increased the PL intensity. The PL peak intensity of impregnated PS is seven times stronger than that in normal PS. Upon exposing iron-PS sample to ambient air, there is no significant change in peak position but the PL intensity increases during the first 3 weeks and then stabilises. The stability is attributed to passivation of the Si nanocrystallites by iron.     

A novel method of fabricating porous silicon material: ultrasonically enhanced anodic electrochemical etching

Ultrasonically enhanced anodic electrochemical etching is developed to fabricate luminescent porous silicon (PS) material. The samples prepared by the new etching method exhibit superior characteristics to those prepared by conventional direct current etching. By applying ultrasonically enhanced etching, PS microcavities with much higher quality factors can be fabricated. The improved quality induced by ultrasonic etching can be ascribed to increased rates of escape of hydrogen bubbles and other etched chemical species from the porous silicon pillars' surface. This process will cause the reaction between the etchant and the silicon wafer to proceed more rapidly along the vertical direction in the silicon pores than laterally.     

Spectral Hole-Burning of Eu^3＋：Y2SiO5 Crystal at 16 K

By using an Ar^＋ ion laser, a tunable Rh 6G dye laser （linewidth 0.5cm^-1） pumped by the second harmonic of a YAG：Nd laser and a Coherent 899-21 dye laser as light sources and using a monochromator, a phase-locking amplifier and a computer as the data detecting system, we detect the optical properties of Eu^3＋-doped Y2SiO5 crystal. Persistent ,spectral hole burning （PSHB） are observed in the Eu^3＋ ions spectral lines （^5 Do-T Fo transition） in the crystal at the temperature of 16K. For 15mW dye laser burning the crystal for 0.1 s spectral holes with hole width about 80 MHz both at 579.62nm and at 579.82nm are detected and the holes can remain for a long time, more than 10h.