Artifacts in femtosecond transient absorption spectroscopy

The paper discusses three different artifacts related to two-photon absorption (TPA), stimulated Raman amplification (SRA) and cross-phase modulation (XPM), all intrinsic to transient absorption measurements with femtosecond time resolution. Certain properties of these signals are analysed and shown to superimpose onto measured transient absorption spectra. Ways of reducing the influence of the artifacts discussed are suggested. A simple correcting procedure based on the linear intensity dependence of the artifacts discussed is proposed. Received: 29 May 2001 / Final version: 15 October 2001 / Published online: 29 November 2001     

Optical properties of high-density amorphous carbon films grown by nanosecond and femtosecond pulsed laser ablation

High-density tetrahedral amorphous carbon (ta-C) films have been prepared by nanosecond (17 ns) and femtosecond (150 fs) pulsed laser deposition (PLD) using fluences and repetition rates compatible with fast and homogeneous growth over large areas. Their optical properties were measured by spectroscopic ellipsometry from 1.0 to 4.7 eV and analyzed using a multi-layer Tauc-Lorentz model. In spite of very different ablation mechanisms, both PLD techniques produce high density bulk layers as revealed by a refractive index (n at 2 eV) of 2.7±0.1 for both fs-PLD and ns-PLD. Films are covered by a few nm-thick sp²-rich top layer which is denser and thicker in femtosecond PLD as compared to nanosecond PLD. The respective roles of low and high energies in the kinetic energy distribution of the incident carbon species are discussed in terms of densification and sp³↦sp² configurational relaxation predicted by the subplantation growth model. The significantly higher optical gap found in the ns-PLD films is attributed to the larger contribution of energetic species with kinetic energies E_c≥200 eV, as revealed by time-of-flight optical studies. PACS 81.40.Tv; 81.05.Uw; 81.15.Fg     

Nonlinear two-photon absorption properties induced by femtosecond laser with the films of two novel anthracene derivatives

Two novel anthracene derivatives containing 4-vinylpyridine (FPEA) and 2-vinylpyridine (TPEA) poly(methyl methacrylate) films are prepared on quartz glass substrates. Their nonlinear absorption properties are investigated by using a 120-fs, 800-nm Ti:sapphire femtosecond pulsed laser operating at a 1-kHz repetition rate. The unique nonlinear absorption properties of these new compounds are observed by utilizing a Z-scan system. These two-photon absorption (TPA) properties are proven by the two-photon fluorescence excited at 800 nm. The FPEA and TPEA films have nonlinear TPA coefficients of 0.164 and 0.148 cm/GW and the TPA cross sections of 3.345 × 10-48 and 3.081 × 10-48 cm4 ·s/photon, respectively. The influence of the chemical structures on the nonlinear TPA properties of the compounds is also discussed. The highly nonlinear TPA activities of the films implied that the new anthracene derivatives are suitable materials with promising applications in super-high-density three-dimensional data storage and nano- or microstructure fabrication.     

Ag-SiO2复合薄膜形貌和吸收特性的研究

通过分层镀膜的方式制备Ag和SiO2的分层结构,经过快速热退火后,Ag颗粒扩散到复合薄膜的表面附近.通过改变Ag颗粒扩散的距离(SiO2的膜厚),可很好地控制Ag颗粒在复合薄膜表面附近的大小,浓度和形貌,进而对共振吸收特性产生影响.在实验中,根据Ag颗粒扩散的长度来调节退火的时间.发现经过足够长的时间(17.5 min)后,Ag颗粒会形成平行于衬底的平面团簇.由于Ag原子在平面团簇之间容易扩散,使得Ag颗粒的粒径平均值变小并趋于某一特定的半径,且粒径分布范围变小,导致吸收谱发生蓝移,吸收带变窄,且强度增加.     

高度取向的半导体聚合物薄膜的溶液浸涂法生长及其电荷传输特性研究

有效地控制有机半导体分子取向和堆积特性对实现高性能电子器件具有非常重要的意义,而发展简便高效的溶液相成膜技术是实现这一目的的重要途径.本文采用改进的溶液浸涂法,成功地成长出大面积宏观取向的半导体聚合物P(NDI2OD-T2)和PTHBDTP薄膜.偏光显微镜和极化的紫外-可见光吸收谱测量显示,薄膜中聚合物分子主链骨架沿成膜时液面下移方向择优取向.原子力显微镜观察到聚合物薄膜由纳米尺度的取向有序晶畴构成,畴的取向与分子链的取向一致.采用衬底-溶液界面处表面张力和溶剂蒸发诱导的分子自组织过程来解释浸涂法生长聚合物取向薄膜的微观机理.使用取向的P(NDI2OD-T2)薄膜制备场效应晶体管,显著地提高了电子迁移率(可达4倍),并实现高达19的迁移率各向异性度.这可归因于共轭的聚合物主链骨架择优取向引起电荷传导通路的变化.     

Chemical analysis of a-CNx thin films synthesized by nanosecond and femtosecond pulsed laser deposition

An ArF excimer laser (22 ns, 193 nm) and a hybrid dye/excimer laser system (500 fs, 248 nm) are used to deposit amorphous carbon nitride films at room temperature by ablation of a graphite target in nitrogen atmosphere. The chemical composition and structure of the films is characterized by X-ray photoelectron spectroscopy. In the nanosecond case, the nitrogen content increases with reactive gas pressure up to 45 atomic %, while in the subpicosecond case it remains below 7 at. %. When processed with nanosecond pulses, the films' nitrogen content steeply increases with fluence up to a maximum. The target-to-substrate distance has only minor influence on the amount of nitrogen incorporated into the films. The dependence of the carbon-carbon and carbon-nitrogen bond configurations on the processing parameters is also given.     

Magnetization dynamics in epitaxial films induced by femtosecond optical pulses near the absorption edge

Peculiarities of the magnetization dynamics induced in iron garnet films by laser pulses with a frequency detuning near the absorption edge have been studied experimentally. It has been found that the dependence of the observed signal amplitude on the pumping energy becomes nonmonotonic with an increase in the pumping frequency. At the same time, the pumping energy corresponding to the maximum amplitude of the signal and this maximum signal amplitude decrease. Moreover, the signal amplitude starts to decrease with an increase in the pumping energy at frequencies within the absorption band. The observed phenomena are possibly caused by generation of magnetostatic spin waves and the effect of ultrafast optically induced demagnetization.     

Temperature and electric field dependences of transient photocurrents in a-Si:H

Temperature and electric field dependences of photocurrents measured at fixed times after pulsed-light excitation in hydrogenated amorphous silicon have been investigated. The photocurrents plotted against inverse absolute temperature for undoped samples exhibit activated behaviours. It is found that the activation energies for all different fixed times after photo-excitation and for all applied electric fields are the same. The results indicate the existence of quasi-equilibrium trapping level during the transit of excess electrons in undoped samples. However, in boron-doped samples the excess holes communicate with the effective trapping levels which move away from E_v (valence band mobility edge) during the transit within the time scale of measurement, which is consistent with the data that the width of valence band tail is wider than that of conduction band tail.     

Effects of solvent on nonlinear absorption properties of tetraphenylporphyrin compounds in the nanosecond regime

The nonlinear absorption properties of tetraphenylporphyrins (TPP) in different solvents and excitation intensities are investigated with nanosecond pulses by the Z-scan technique. The nonlinear absorption behaviour observed presents a distinct difference between in solvent mixtures and in pure solvents. A crossover from reverse saturable absorption (RSA) to saturable absorption (SA) and then again to RSA is observed with the increases of excitation intensity in chloroform and pyridine mixed solvents. However, porphyrin molecules in pure solvents show good RSA behaviour under the studied intensity range, no saturation absorption is observed with nanosecond excitation. Excited state absorption parameters and two-photon absorption coefficients are obtained by theoretical fit using rate equations for population densities in a seven-level energy scheme.     

Water-related charge carrier traps in thermal silicon dioxide films prepared in dry oxygen

The parameters of electron and hole traps in thermal silicon dioxide films prepared in dry oxygen have been investigated using avalanche injection of electrons and holes from silicon in combination with measurements of capacitance-voltage and current-voltage characteristics of photoinjection of electrons from junctions with variations in the conditions of oxidation, annealing, and storage of Si-SiO₂ structures. The model concepts proposed by the author for water-related charge carrier traps in such films have been confirmed. It has been found that the transport characteristics of the traps depend on the time of contact between Si-SiO₂ structures and atmospheric air of natural humidity. The results obtained can be used for the suppression of degradation processes in devices based on Si-SiO₂ structures, in the design of electroluminescent instruments based on Si-SiO₂ structures, and in the study of the transport characteristics of some molecules (for example, water), atoms, and ions in pores (structural channels) whose sizes are comparable to the sizes of water molecules.     

Ag-SiO2复合薄膜形貌和吸收特性的研究

通过分层镀膜的方式制备Ag和SiO₂的分层结构，经过快速热退火后，Ag颗粒扩散到复合薄膜的表面附近. 通过改变Ag颗粒扩散的距离(SiO₂的膜厚)，可很好地控制Ag颗粒在复合薄膜表面附近的大小，浓度和形貌，进而对共振吸收特性产生影响. 在实验中，根据Ag颗粒扩散的长度来调节退火的时间. 发现经过足够长的时间(17.5min)后，Ag颗粒会形成平行于衬底的平面团簇. 由于Ag原子在平面团簇之间容易扩散，使得Ag颗粒的粒径平均值变小并趋于某一特定的半径，且粒径分布范围变小，导致吸收谱发生蓝移，吸收带变窄，且强度增加. 关键词： 复合薄膜 共振吸收 平面团簇     

Chemometric analysis of femtosecond transient absorption spectroscopy data:Study of the photochromism of anils

Chemometric methods are applied for the purpose of extracting relevant information from transient absorption spectroscopy data probing the photochromism of molecules from the family of salicylidene aniline. The process consists of an ultrafast excited state intramolecular proton transfer occurring from an enol form which is then followed by a cis-trans isomerization to finally reach a trans-keto photo-product. This work focuses on the potential of combining multivariate curve resolution for modeling pure profiles and two dimensional correlation spectroscopy data analysis for providing information on the dynamics of spectral features. The results obtained for one derivative of salicylidene aniline provide information regarding the number of species created after the proton transfer and characterization of their absorption spectra and their kinetics in the picosecond time scale. The spectral resolution of two cis-keto* forms is proposed for the first time. It is also found that both cis-keto* species are involved in the formation of the trans-keto photo-product. The main precursor of the trans-keto photo-product is the cis-keto* form which has the shortest characteristic time.     

Photochemistry of tetrasulphonated magnesium phthalocyanine in water and DMSO solutions by Raman, femtosecond transient absorption, and stationary absorption spectroscopies

Photochemical and photophysical behavior of the tetrasulphonated magnesium phthalocyanine MgPcS₄ has been studied by Raman spectroscopy, femtosecond transient absorption, and stationary UV–VIS absorption spectroscopies. It has been shown also that the dimerization equilibrium constant K for the tetrasulfonated magnesium phthalocyanine is strongly shifted towards monomeric form in DMSO solutions compared to aqueous systems. The Raman and emission spectra recorded in the range of 294–77 K combined with the femtosecond transient absorption reveal spectral features that provide unique information about the primary photochemical and photophysical events of magnesium phthalocyanines in liquid solutions as well as in the crystal frozen matrices.     

Submicron foaming in gelatine by nanosecond and femtosecond pulsed laser irradiation

We compare the foaming characteristics induced by irradiation with single ns and fs laser pulses of UV, VIS and IR wavelengths on gelatines differing in gel strength (bloom values 75 and 225) and in crosslinking degree. We have observed that while laser irradiation with nanoseconds leads to the formation of a microfoam layer at 266 nm, and melting and crater formation at longer wavelengths (532 and 1064 nm), fs pulse irradiation leads to submicron foaming at all wavelengths studied (266, 400 and 800 nm). These results show the possibility of controlling the submicrometric foam structure in this biomaterial and can shed light into the working mechanisms of fs laser nanoprocessing in biomaterials, where increase of temperature, thermoelastic stress generation, and stress-induced bubble formation are mediated by the generated plasma.     

Laser ablation of silicon in water with nanosecond and femtosecond pulses

We describe laser ablation of Si under water by 5 ns, 355 nm and 100 fs, 800 nm pulses. Compared to that in air, an approximately twofold improvement in the ablation rate is found in water for femtosecond and nanosecond pulses. For higher laser irradiances, the plasma that forms at the water-air interface hampers further improvement of the ablation rate. We investigated the enhanced ablation process in water and found that the cavity-confinement geometry that increases the laser energy coupling to the target and allows more energy to be transferred to the cavity sidewalls plays an important role in the escalated material removal process. In addition, we show that the water layer that effectively reduces the oxidation and redeposition of the ablated debris is also responsible for improvements in the ablation process.