Structure and optical properties of carbon films obtained by multipulse pulsed laser deposition

We have obtained carbon thin films on silicon and glass substrates with multipulse pulsed laser irradiation of graphite under vacuum (p ≈ 2.6 Pa) using a high-frequency series of nanosecond laser pulses (τ = 85 ns, λ = 1060 nm) with pulse repetition frequency f ≈ 10–20 kHz and laser power density q ≈ 15–40 MW/cm². We established the optimal laser power density and laser pulse repetition frequency for obtaining amorphous nanostructured diamond-like films.     

Femtosecond-laser-induced-crystallization and simultaneous formation of light trapping microstructures in thin a-Si:H films

We report the observation of crystallization and simultaneous formation of surface microstructures in hydrogenated amorphous silicon (a-Si:H) thin films as one step laser processing. Light trapping microstructures of around 300 nm in height were formed on a-Si:H films of thickness in the range of 1.5 μm to 2 μm deposited on soda lime glass after exposure to femtosecond laser pulses. Scanning electron microscope (SEM) images show the formation of spikes that are around 1 μm part and their heights could be controlled by the laser fluences. Atomic force microscope (AFM) images were taken to study the roughness created on the surface. The mean roughness of the textured surface increases with laser fluence at smaller power densities, and for power densities beyond 0.5 J/cm² the film removal deteriorates the texturing. X-ray diffraction results indicate the formation of a nano-crystalline structure with (111) and (311) crystal orientation after the laser treatment. The observed black color and enhanced optical absorption in the near infrared region in laser treated films may be due to a combined effect of light trapping in the micro-structured silicon surface because of multiple total internal reflections, phase change in the film, possible defect sites induced after laser treatment and formation of SiO_x. Demonstration of light trapping microstructures in thin a-Si:H films and simultaneous crystallization could provide new opportunities for optoelectronic devices. PACS 42.55.Px; 42.62.Cf; 81.05.Ge     

Patterned laser annealing of silicon oxide films

UV-absorbing silicon monoxide (SiO _x , x≈1) thin films on fused silica substrates are irradiated by an ArF excimer laser (wavelength 193 nm) in the sub-ablation threshold regime. Multi-pulse irradiation of films with ∼200-nm thickness at a fluence of about 100 mJ/cm² leads to a significant increase of the UV transmission, indicating the oxidation of SiO _x to SiO₂. The quality of the obtained films after this laser annealing process depends on the oxygen content of the environment. Irradiation in air at atmospheric pressure leads to the formation of sub-micron-sized oxide particles on top of the film. Structured illumination is applied either to form areas of the film with changed transmission and refractive index, or for the formation of regular particle patterns with sub-micron periods. These processes can be utilized for the fabrication of phase masks or for various types of surface functionalization.     

Photothermal laser processing of thin silicon nanoparticle films: on the impact of oxide formation on film morphology

Photothermal laser processing of thin films of H-terminated silicon nanoparticles (Si NPs) is investigated. Ethanolic dispersions of Si NPs with an average diameter of 45 nm are spin-coated on silicon substrates yielding films with thicknesses ≤500 nm. Small-area laser processing is carried out using a microfocused scanning cw-laser setup operating at a wavelength of 532 nm and a 1/e laser spot size of 1.4 μm. In conjunction with microscopic techniques, this provides a highly reproducible and convenient approach in order to study the dependence of the resulting film morphology and composition on the experimental parameters. Processing in air results in strongly oxidized granular structures with sizes between 100 and 200 nm. The formation of these structures is dominated by surface oxidation. In particular, changing the processing parameters (i.e., laser power, writing speed, and/or the background air pressure) has little effect on the morphology. Only in vacuum at pressures <1 mbar, oxygen adsorption, and hence oxide formation, is largely suppressed. Under these conditions, irradiation at low laser powers results in mesoporous surface layers, whereas compact silicon films are formed at high laser powers. In agreement with these results, comparative experiments with films of H-terminated and surface-oxidized Si NPs reveal a strong impact of the surface oxide layer on the film morphology. Mechanistic aspects and implications for photothermal processing techniques, e.g., targeting photovoltaic and thermoelectric applications, are discussed.     

碳化硅薄膜脉冲激光晶化特性研究

采用XeCl准分子激光对非晶碳化硅(a-SiC)薄膜的脉冲激光晶化特性进行了研究.通过原子力显微镜（AFM）和Raman光谱技术对退火前后薄膜样品的形貌、结构及物相特性进行了分析.结果表明，选用合适的激光能量采用激光退火技术能够实现a-SiC薄膜的纳米晶化.退火薄膜中的纳米颗粒大小随着激光能量密度的增加而增大；Raman谱分析结果显示了退火后的薄膜的晶态结构特性并给出了伴随退火过程存在的物相分凝现象.根据以上结果并结合激光退火特性，对a-SiC的脉冲激光晶化机理进行了讨论. 关键词： 激光退火 晶化 碳化硅     

Effects of irradiation conditions on the lateral grain growth during laser crystallization of amorphous silicon films on borosilicate glass substrates

The effects of preheating laser power and pulse laser energy on the size and crystallinity of laterally grown grains by dual-laser crystallization of amorphous silicon (a-Si) films on borosilicate glass substrates were investigated. Plasma-enhanced chemical vapor deposition was adopted for the deposition of the a-Si films in order to reduce the process temperature and thus the diffusion of metal impurities from the glass substrate to the deposited a-Si films. It was found that the preheating laser power is critical in enhancing grain size, whereas the pulse laser energy is closely related to crystal quality. It is demonstrated that by properly adjusting the process conditions, laterally grown grains of 50-μm size could be obtained.     

Crystallization kinetics of amorphous SiC films: Influence of substrate

The crystallization kinetics of amorphous silicon carbide films was studied by means of X-ray diffractometry (XRD) and transmission electron microscopy (TEM). The films were deposited by radio frequency (r.f.) magnetron sputtering on glassy carbon and single crystalline silicon substrates, respectively. TEM micrographs and XRD patterns show the formation of nano-crystalline β-SiC with crystallite sizes in the order of 50 nm during annealing at temperatures between 1200 and 1600 °C. A modified Johnson-Mehl-Avrami-Kolmogorov (JMAK) formalism was used to describe the isothermal transformation of amorphous SiC into β-SiC as an interface controlled, three-dimensional growth processes from pre-existing small crystallites in the order of 10 nm. These pre-existing crystallites are formed in a transient process in the early stages of crystallization. For films deposited on the silicon substrate, the obtained rate constants of crystallite growth obey an Arrhenius behavior with an activation enthalpy of 4.1 ± 0.5 eV in accordance with literature data. Films deposited on glassy carbon show an increased stability of amorphous SiC films, which is reflected in smaller rate constants of crystallite growth of several orders of magnitude at low temperatures and a higher activation enthalpy of 8.9 ± 0.9 eV. A model is proposed, where the faster crystallization of films on silicon substrates can be explained with the presence of superabundant point defects, which diffuse from the substrate into the film and accelerate the incorporation of atoms from the amorphous into the crystalline phase.     

Nickel oxide thin films synthesized by reactive pulsed laser deposition: characterization and application to hydrogen sensing

Transparent nickel oxide thin films were grown by reactive pulsed laser deposition. An ArF* (λ=193 nm, τ=12 ns) excimer laser source was used to ablate the Ni targets in a controlled pressure of ambient oxygen. The substrates were either kept at room temperature or heated to a selected temperature within the 200–400 °C range. Post-deposition heat treatment, which was applied to further promote crystallization and overcome any oxygen deficiency, yielded transparent thin films. The surface morphology and crystalline status of the synthesized thin structures were analyzed in correlation with their optical properties. A significant response to several concentrations of hydrogen was demonstrated when heating the nickel oxide films at 185 °C. PACS 78.66.Hf; 81.15.Fg; 82.47.Rs     

488 nm连续激光晶化本征非晶硅薄膜的喇曼光谱研究

利用等离子增强化学气相沉积系统制备了本征非晶硅薄膜,并选用488 nm波长的连续激光进行晶化.采用喇曼测试技术对本征非晶硅薄膜在不同激光功率密度和扫描时间下的晶化状态进行了表征,并用514 nm波长与488 nm波长对样品的晶化效果进行了比较.测试结果显示:激光照射时间60 s, 激光功率密度在1.57×10⁵ W/cm²时,能实现非晶硅向多晶硅的转变,在功率密度达到2.7 56×10⁵ W/cm²时,有非晶开始向单晶转变,随着激光功率密度的继续增加,晶化结果仍为单晶;在功率密度为2.362×10⁵ W/cm²下,60 s照射时间晶化效果较好;在功率密度为2.756×10⁵ W/cm²和照射时间为60 s的条件下,用488 nm波长比514 nm波长的激光晶化本征非晶硅薄膜效果较好,并均为单晶态.     

Young’s modulus and density of nanocrystalline cubic boron nitride films determined by dispersion of surface acoustic waves

Cubic boron nitride (c-BN) films of 200–420 nm thickness and high phase purity were deposited on silicon (100) substrates by ion-assisted pulsed laser deposition (IA PLD)from a boron nitride target using a KrF-excimer laser, and by plasma-enhanced physical vapor deposition (PE PVD)with a hollow-cathode arc evaporation device. In order to improve the c-BNfilm adhesion, hexagonal boron nitride (h-BN) films with 25–50 nm thickness were used as buffer layers. The density and Young’s modulus of the c-BNfilms were obtained by investigating the dispersion of surface acoustic waves. In data analysis a two-layer model was applied in order to take the influence of the h-BNlayer into consideration. The values for the density vary from 2.95±0.25 g/cm³to 3.35±0.3 g/cm³, and those for the Young’s modulus from 420±40 GPa to 505±30 GPa. The results are compared with literature values reported for nanocrystalline films, polycrystalline disks and single crystal c-BN. Received: 26 March 2001 / Accepted: 29 March 2001 / Published online: 25 July 2001     

Aerosol deposition of detonation nanodiamonds used as nucleation centers for the growth of nanocrystalline diamond films and isolated particles

The aerosol deposition of detonation nanodiamonds (DNDs) on a silicon substrate is comprehensively studied, and the possibility of subsequent growth of nanocrystalline diamond films and isolated particles on substrates coated with DNDs is demonstrated. It is shown that a change in the deposition time and the weight concentration of DNDs in a suspension in the range 0.001–1% results in a change in the shape of DND agglomerates and their number per unit substrate surface area N _s from 10⁸ to 10¹¹ cm⁻². Submicron isolated diamond particles are grown on a substrate coated with DND agglomerates at N _s ≈ 108 cm⁻² using microwave plasma-enhanced chemical vapor deposition. At N _s ≈ 10¹⁰ cm⁻², thin (∼100 nm) nanodiamond films with a root-mean-square surface roughness less than 15 nm are grown.     

Formation of SERS-active silver structures on the surface of mesoporous silicon

We have optimized the procedure for preparation of nanostructured silver films on the surface of mesoporous silicon (PSi) to use them as active substrates in surface-enhanced Raman scattering (SERS) spectroscopy. The greatest enhancement of the SERS signal was observed for samples obtained when the silver was deposited on PSi from an aqueous AgNO₃ solution with concentration 1⋅10^–2 M over a 10–15 minute period. The detection limit for rhodamine 6G on SERS-active substrates prepared by the optimized procedure was 1⋅10^–10 M. The enhancement factor for the SERS signal on these surfaces was estimated as ≈2⋅10⁸. We have shown that SERS-active substrates based on mesoporous silicon are promising for detection and study of complex organic compounds, in particular tetrapyrrole molecules. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 2, pp. 298–306, March–April, 2009.     

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.     

Nanosecond laser ablation and deposition of silicon

Nanosecond-pulsed KrF (248 nm, 25 ns) and Nd:YAG (1064 nm, 532 nm, 355 nm, 5 ns) lasers were used to ablate a polycrystalline Si target in a background pressure of <10⁻⁴ Pa. Si films were deposited on Si and GaAs substrates at room temperature. The surface morphology of the films was characterized using scanning electron microscopy (SEM) and atomic force microscopy (AFM). Round droplets from 20 nm to 5 μm were detected on the deposited films. Raman Spectroscopy indicated that the micron-sized droplets were crystalline and the films were amorphous. The dependence of the properties of the films on laser wavelengths and fluence is discussed.     

Characterization of particulates accompanying laser ablation of pressed polytetrafluorethylene (PTFE) targets

We present observations of sub-micron- to micron-sized particles generated by high fluence (≈2 J/cm²) 248-nm laser ablation of pressed polytetrafluorethylene (PTFE) targets in air at atmospheric pressure. The original target material was hydrostatically compressed ≈7 μm PTFE powder, sintered at 275 °C. Collected ejecta due to laser irradiation consists of four basic particle morphologies ranging from small particles 50–200 nm in diameter to larger particles ≈10 μm in diameter. Many particles formed in air carry electric charge. Using charged electrodes we are able to collect charged particles to determine relative numbers of ± charge. We observe roughly equal numbers of positively and negatively charged particles except for the largest particles which were predominantly negative. For a range of particle sizes we are able to measure the sign and magnitude of this charge with a Millikan-oil-drop technique and determine surface charge densities. The implications of these observations with respect to pulsed laser deposition of PTFE thin films and coatings are discussed. Received: 15 January 1999 / Accepted: 18 January 1999 / Published online: 7 April 1999     

Corrugated neat thin-film conjugated polymer distributed-feedback lasers

Wave-guided thin-film distributed-feedback (DFB) polymer lasers are fabricated by spin coating a PPV-derived semiconducting polymer, thianthrene-DOO-PPV, onto oxidised silicon wafers with corrugated second-order periodic gratings. The gratings are written by reactive ion beam etching. Laser action is achieved by transverse pumping with picosecond laser pulses (wavelength 347.15 nm, duration 35 ps). The DFB-laser surface emission and edge emission are analysed. Outside the grating region the polymer film is used for comparative wave-guided travelling wave laser (amplified spontaneous emission (ASE)) studies. The pump pulse threshold energy density for wave-guided DFB-laser action (4–9 μJ cm^-2) is found to be approximately a factor of two lower than the threshold for wave-guided travelling wave laser action. The spectral width of the DFB laser (down to Δλ_DFB≈0.07 nm) is considerably narrower than that of the travelling wave laser (Δλ_TWL≈14 nm). The DFB-laser emission is highly linearly polarised transverse to the grating axis (TE mode). Only at high pump pulse energy densities does an additional weak TM mode build up. The surface-emitted DFB-laser radiation has a low divergence along the grating direction. For both the DFB lasers and the travelling wave lasers, gain saturation occurs at high excitation energy densities. Received: 7 January 2002 / Revised version: 15 February 2002 / Published online: 14 March 2002     

Production and characterization of Nd,Cr:GSGG thin films on Si(001) grown by pulsed laser ablation

Nd,Cr:Gd₃Sc₂Ga₃O₁₂ (GSGG) thin films have been produced for the first time. They were grown on Si(001) substrates at 650 °C by pulsed laser ablation at 248 nm of a crystalline Nd,Cr:GSGG target rod. The laser plume was analyzed using time-of-flight quadrupole mass spectroscopy, and consisted of elemental and metal oxide fragments with kinetic energies typically in the range 10 to 40 eV, though extending up to 100 eV. Although films deposited in vacuum using laser fluences of 0.8±0.1 J cm⁻² reproduced the Nd,Cr:GSGG bulk stoichiometry, those deposited using fluences above ≈3 J cm⁻² resulted in noncongruent material transfer and were deficient in Ga and Cr. Attempts to grow films using synchronized oxygen or oxygen/argon pulses yielded mixed oxide phases. Under optimal growth conditions, the films were heteroepitaxial, with GSGG(001)[100]∥Si(001)[100], and exhibited Volmer–Weber-type growth. Room-temperature emission spectra of the films suggest efficient non-radiative energy transfer between Cr³⁺ and Nd³⁺ ions, similar to that of the bulk crystal. Received: 1 October 1999 / Accepted: 15 October 1999 / Published online: 23 February 2000     

Laser-induced local dehydroxylation on surface-oxidized silicon substrates: mechanistic aspects and prospects in nanofabrication

Processing of silicon oxide surfaces with a focused laser beam at a wavelength of 514 nm has been investigated. Laser processing of native silicon samples (d _ox=1–2 nm) allows the fabrication of reactive templates with laterally varying hydroxyl group density. Very similar results were also obtained on thermally oxidized silicon samples (d _ox≈100 nm), whereas respective experiments on quartz plates have failed. These results support a photothermal mechanism where laser irradiation causes a local temperature rise and initiates dehydroxylation. In agreement with a photothermally induced dehydroxylation reaction, a thermokinetic analysis of the experimental data points to a highly activated process. In conjunction with site-selective functionalization routines this opens up an avenue towards functional surface structures with lateral dimensions significantly below the optical diffraction limit.     

Determination and analysis of the optical constants of thin films of nickel(II) and copper(II) hydrazone complexes by spectroscopic ellipsometry

Thin films of four nickel(II) and copper(II) hydrazone complexes, which will hopefully be used as recording layers for the next-generation of high-density recordable disks, were prepared by using the spin-coating method. Absorption spectra of the thin films on K9 optical glass substrates in the 300–700 nm wavelength region were measured. Optical constants (complex refractive indices N) and thickness d of the thin films prepared on single-crystal silicon substrates in the 275–675 nm wavelength region were investigated on a rotating analyzer-polarizer scanning ellipsometer by fitting the measured ellipsometric angles (Ψ(λ) and Δ(λ)) with a 3-layer model (Si/dye film/air). The dielectric functions ε and absorption coefficients α as a function of the wavelength were then calculated. Additionally, a design to achieve high reflectivity and optimum dye film thickness with an appropriate reflective layer was performed with the Film Wizard software using a multilayered model (PC substrate/reflective layer/dye film/air) at 405 nm wavelength. PACS 81.05.L; 78.20.Ci; 78.20.-e     

Silicon grain arrays prepared using a pattern crystallization technique of pulsed-excimer laser irradiation

Silicon grain arrays were prepared using a pattern crystallization technique of pulsed KrF excimer laser irradiation. The precursor material was hydrogenated amorphous silicon (a-Si:H) thin films deposited on single crystal Si wafers by plasma-enhanced chemical vapor deposition. It was shown that Si grains with a uniform size and a well-defined periodicity embedded in the a-Si:H matrix were obtained by this simple technique. The grain size was less than 2 μm. Relativly strong photo-luminescence with two peaks at 720 and 750 nm was observed at room temperature. We expect to reduce Si grain sizes by optimizing the growth conditions of a-Si:H thin films and controlling the temperature distribution in the film during laser irradiation. Received: 21 November 2000 / Accepted: 12 December 2000 / Published online: 9 February 2001