Femtosecond laser induced photoluminescence in poly(methyl methacrylate) and three-dimensional optical storage

We report on a femtosecond-laser induced photoluminescence (PL) in poly(methyl methacrylate) and its potential application to three-dimensional optical storage. Irradiation with a focused 800 nm, 1 kHz, 100 fs pulsed laser induced a strong PL change in UV-visible region. Absorption spectra and Fourier-transform infrared spectra before and after laser irradiation indicate the PL may result from the emissive oxidized products of photo-degradation reaction of PMMA. This makes it possible to read out the stored data by detecting the PL change. The pulse energy threshold of the light-induced PL change of PMMA is found to be at ∼2 μJ/pulse and the optimal recording energy is ∼3 μJ/pulse. A ten-layer pattern inside the bulk sample recorded by tightly focusing a pulsed laser beam was read out by a reflection-type fluorescent confocal microscope, which detected the emission in visible range as the signal. High-contract fluorescent images with a much higher signal-to-noise ratio were obtained without crosstalk in comparison with the ordinary reflection mode.     

IR laser ablation of doped poly(methyl methacrylate)

We investigate the TEA CO₂ laser ablation of films of poly(methyl methacrylate), PMMA, with average M_W 2.5, 120 and 996 kDa doped with photosensitive compounds iodo-naphthalene (NapI) and iodo-phenanthrene (PhenI) by examining the induced morphological and physicochemical modifications. The films casted on CaF₂ substrates were irradiated with a pulsed CO₂ laser (10P(20) line at 10.59 μm) in resonance with vibrational modes of PMMA and of the dopants at fluences up to 6 J/cm². Laser induced fluorescence probing of photoproducts in a pump and probe configuration is carried out at 266 nm. Formation of naphthalene (NapH) and phenanthrene (PhenH) is observed in NapI and PhenI doped PMMA, respectively, with relatively higher yields in high M_W polymer, in similarity with results obtained previously upon irradiation in the UV at 248 nm. Above threshold, formation of photoproducts is nearly complete after 200 ms. As established via optical microscopy, bubbles are formed in the irradiated areas with sizes that depend on polymer M_W and filaments are observed to be ejected out of the irradiated volume in the samples made with high M_W polymer. The implications of these results for the mechanisms of polymer IR laser ablation are discussed and compared with UV range studies.     

High-repetition-rate femtosecond laser micromachining of poly(methyl methacrylate)

Investigations are performed to explore high-repetition-rate femtosecond laser ablation effects on the physical and chemical properties of poly(methyl methacrylate)(PMMA). A scanning electron microscopy(SEM) is used to characterize the morphology change in the laser-ablated regions. The infrared and Raman spectroscopy reveals that the fundamental structure of the PMMA is altered after laser ablation. We demonstrate the cumulative heating is much greater during high-repetition-rate femtosecond laser ablation, supporting a photothermal depolymerization mechanism during the ablation process.     

Femtosecond laser fabrication of phase-shifted Bragg grating waveguides in fused silica

Phase-shifted Bragg grating waveguides (PSBGWs) were formed in bulk fused silica glass by femtosecond laser direct writing to produce narrowband (22±3) pm filters at 1550 nm. Tunable π and other phase shifts generated narrow passbands in controlled positions of the Bragg stopband, while the accurate placement of multiple cascaded phase-shift regions yielded a rectangular-shaped bandpass filter. A waveguide birefringence of (7.5±0.3)×10(-5) is inferred from the polarization-induced spectral shifting of the PSBGW narrowband filters.     

Pulse-duration dependency of femtosecond laser refractive index modification in poly(methyl methacrylate)

Refractive index modification of pure poly(methyl methacrylate) (PMMA) is investigated as a function of pulse duration using femtosecond lasers at 800 and 387 nm wavelength. It is observed that at 800 nm, the refractive index is modified more efficiently as the pulse duration decreases below 100 fs, whereas at 387 nm, efficient index modification is accomplished with longer, 180 fs pulses. Results suggest that three- and two-photon absorption is responsible for modification of pure PMMA at 800 nm and 387 nm, respectively. Repeated irradiation with short pulses of low laser fluence allows control of the photomodification via incubation, thus reducing bulk damage.     

Radiation effects on poly(methyl methacrylate) induced by pulsed laser irradiations

Poly(methyl methacrylate) (PMMA) was irradiated using a medical UV-ArF excimer laser operating at the fundamental wavelength of 193 nm. Characterized by a beam diameter of 1.8 mm and energy of 180 mJ with a Gaussian energy profile, it operates in a single mode or at 30 Hz repetition rate. Mechanical profilometry was carried out on ablation craters in order to study the rugosity and the ablation yield in the various operative conditions. Optical transmission and reflection measurements at six wavelengths were conducted in order to characterize the optical properties of the irradiated surfaces. Measured crater depths in PMMA were lower with respect to the forecasted ones in corneal tissue, while the lateral crater aperture was maintained. The rugosity produced at the crater bottom after irradiation was about 0.3 μm, and the ablation yield was about 10¹⁵ molecules/laser pulse, while etching depth and diameter show a roughly linear dependence on the number of laser shots. These experiments constitute a base for deeper clinical investigations.     

飞秒激光精密微纳加工的研究进展

飞秒激光由于其超快时间特性和超高峰值功率特性在精密微纳加工领域引起了人们广泛的重视．在与物质的相互作用中它能快速、准确地将能量作用在特定的区域内，从而可以获得极高的分辨率和加工精度。文章综述了飞秒激光精密微纳加工的最新研究进展，分别就飞秒激光烧蚀微加工和飞秒激光双光子聚合产生三维微纳结构进行了介绍，阐述了各自的物理机制．最后对飞秒激光微纳加工的研究前景做了初步探讨。     

Photochemistry of refractive index structures in poly(methyl methacrylate) by femtosecond laser irradiation

Femtosecond, subablation threshold photomodification of poly(methyl methacrylate) (PMMA) at 387 nm is explored to enable fabrication of optical components. Volatile fragment analysis (thermal desorption gas chromatography-mass spectrometry) and molecular weight distribution monitoring (size exclusion chromatography) suggest photochemical modification, involving direct cleavage of the polymer backbone and propagation via chain unzipping under formation of monomers, similar to the pyrolytic degradation of PMMA. Waveguides were produced in undoped, clinical-grade PMMA, showing an increased refractive index in the laser focal region (Dnmax=4x10(-3)).     

Low-energy librational excitations in vitreous poly(methyl methacrylate)

The infrared (IR) and Raman spectra of vitreous poly(methyl methacrylate) (PMMA) are measured and investigated in the frequency range 10–150 cm^?1. A comparison of the results obtained from IR and Raman spectroscopic measurements permits the assignment of the low-frequency anomaly (boson peak) observed in the spectra to librational vibrations occurring in a segment of the main chain that is comparable in length to the statistical chain segment. It is demonstrated that coherent librational excitations are associated with the relaxation processes proceeding in the polymers.     

Laser processing of poly(methyl methacrylate) Lambertian diffusers

Matrix-assisted pulsed laser deposition was used to deposit poly(methyl methacrylate) on silicon wafers and sodium silicate glass slides for the purpose of making optical diffusers. After deposition, the reflectance of the coated substrates was measured as a function of scattering angle. We found that the angular dependence of the reflectance could be described as the sum of two functions. First, a Gaussian describes the specular reflection of the underlying substrate that has been broadened by passage through the film. Second, a cosine function describes the reflectance contribution from the film itself. We found that by increasing the thickness of the deposited film that we could eliminate the specular reflection to obtain Lambertian diffusers. Since we can control the surface roughness by adjusting the ratio of the two matrices in laser processing, this deposition technique offers the possibility of producing a wide range of diffusers of different types.     

Effect of laser treatment on the optical properties of poly(methyl methacrylate) thin films

In this work, the effect of laser pulse treatment on the optical properties of poly(methyl methacrylate) (PMMA) films has been studied experimentally. The second harmonic of a pulsed Nd:YAG laser at 532 nm and 6 ns pulse width with 10 Hz repetition rate was used to modify the surface of red-BS-dye-doped PMMA films. Samples were ablated with 50 and 100 laser pulses. Optical reflectance and transmittance spectra were obtained in the range of 200–2000 nm. The optical properties of the films were influenced by the pulse number significantly. The oscillator and dispersion energies of the films were determined using the Wemple-Didomenico model. The optical band gap energy was extracted using the Tauc method. Results show that the optical parameters of the films were changed significantly after laser treatment.     

Configurational-conformational statistics of stereoirregular poly(methyl methacrylate)s

The mean-square radius of gyration of poly(methyl methacrylate) (PMMA) with Bemoullian statistics was theoretically investigated utilizing the method of periodic condition. The dependent curve of the characteristic ratio of mean-square end-to-end distance on periodic microstructure length increases monotonously with the length and goes gradually to its asymptotic value for atactic PMMA chains (P _m = 0.5). Conformational energies E _α ～1.3 kcal mol^?1 and E _β ～-0.6 kcal mol^?1 of the two-state scheme are acceptable, from which the derived meansquare end-to-end distance and mean-square radius of gyration conform to the experimental data. The ratio ?S²?/χ of atactic PMMA (P _m = 0.2) as a function of the degree of polymerization χ first increases with increasing chain length, then passes through a maximum at χ = 30, and finally decreases to its asymptotic value, which is in reasonable agreement with the experimental measurements reported elsewhere. The ratio ?S²?/χ as a function of stereochemical composition indicates that theoretical and experimental data are in accord for isotactic and atactic PMMA, but small-angle neutron scattering (SANS) measurements are higher than the calculated values for syndiotactic PMMA.     

Cobalt iron-oxide nanoparticle modified poly(methyl methacrylate) nanodielectrics

In this paper, we report the dielectric properties of composite systems (nanodielectrics) made of small amounts of mono dispersed magnetic nanoparticles embedded in a polymer matrix. It is observed from the transmission electron microscope images that the matrix polymeric material is confined in approximately 100 nm size cages between particle clusters. The particle clusters are composed of separated spherical particles which comprise unconnected networks in the matrix. The dielectric relaxation and breakdown characteristics of the matrix polymeric material are altered with the addition of nanometer size cobalt iron-oxide particles. The dielectric breakdown measurements performed at 77 K showed that these nanodielectrics are potentially useful as an electrical insulation material for cryogenic high voltage applications. Finally, structural and dielectric properties of nanocomposite dielectrics are discussed to present plausible reasons for the observed low effective dielectric permittivity values in the present and similar nanodielectric systems. It is concluded that polymeric nanoparticle composites would have low dielectric permittivity regardless of the permittivity of nanoparticles are when the particles are coordinated with a low dielectric permittivity surfactant.     

飞秒激光精密微纳加工的研究进展

飞秒激光由于其超快时间特性和超高峰值功率特性在精密微纳加工领域引起了人们广泛的重视.在与物质的相互作用中它能快速、准确地将能量作用在特定的区域内,从而可以获得极高的分辨率和加工精度.文章综述了飞秒激光精密微纳加工的最新研究进展,分别就飞秒激光烧蚀微加工和飞秒激光双光子聚合产生三维微纳结构进行了介绍,阐述了各自的物理机制.最后对飞秒激光微纳加工的研究前景做了初步探讨.     

Molecular dynamics in thin films of isotactic poly(methyl methacrylate)

The molecular dynamics in thin films (18 nm-137 nm) of isotactic poly(methyl methacrylate) (i-PMMA) of two molecular weights embedded between aluminium electrodes are measured by means of dielectric spectroscopy in the frequency range from 50 mHz to 10 MHz at temperatures between 273 K and 392 K. The observed dynamics is characterized by two relaxation processes: the dynamic glass transition (α-relaxation) and a (local) secondary β-relaxation. While the latter does not depend on the dimensions of the sample, the dynamic glass transition becomes faster (≤2 decades) with decreasing film thickness. This results in a shift of the glass transition temperature T _g to lower values compared to the bulk. With decreasing film thickness a broadening of the relaxation time distribution and a decrease of the dielectric strength is observed for the α-relaxation. This enables to deduce a model based on immobilized boundary layers and on a region displaying a dynamics faster than in the bulk. Additionally, T _g was determined by temperature-dependent ellipsometric measurements of the thickness of films prepared on silica. These measurements yield a gradual increase of T _g with decreasing film thickness. The findings concerning the different thickness dependences of T _g are explained by changes of the interaction between the polymer and the substrates. A quantitative analysis of the T _g shifts incorporates recently developed models to describe the glass transition in thin polymer films. Received 12 August 2001 and Received in final form 16 November 2001     

Structural modification of poly(methyl methacrylate) by proton irradiation

A general survey is presented on the structural modification of poly(methyl methacrylate) (PMMA) by proton implantation. The implanted PMMA films were characterized by FT-IR attenuated total reflection (FT-IR ATR), Raman, Rutherford backscattering spectroscopy (RBS), gel permeation chromatography (GPC) and surface profiling. The ion fluence of 350 keV protons ranged from 2×10¹⁴ to 1×10¹⁵ ions/cm². The IR and Raman spectra showed the reduction of peaks from the pendant group of PMMA. The change of absorption and composition was observed by UV–VIS and RBS, respectively. These results showed that the pendant group is readily decomposed and eliminated by proton irradiation. The change of molecular weight distribution was also measured by GPC and G-value of scission was estimated to be 0.67.     

Generation of microcellular poly(methyl methacrylate) by compressed gases

Abstract

Generation of microcellular poly(methy1 methacrylate) (PMMA) was studied in CO₂ and N₂O at pressures from 2 to 15MPa at three temperatures, 293.2K, 308.2K, and 323.2 K. The average diameter d and average number density N of voids generated by a rapid expansion of compressed gases in PMMA were measured by use of an optical microscope. Effects of gases, temperature, and pressure on the d and N values were examined. Even at pressure below glass transition pressure of PMMA with both gases, voids of diameter being as small as those found at high pressure, 15MPa, were obtained at each temperature. However, the void density of PMMA at lower pressure by both gases was not so good as those obtained at high pressures.     

Characterization of phenanthrenequinone-doped poly(methyl methacrylate) for holographic memory

The holographic recording characteristics of phenanthrenequinone- (PQ-) doped poly(methyl methacrylate) are investigated. The exposure sensitivity is characterized for single-hologram recording, and the M/# is measured for samples as thick as 3 mm. Optically induced birefringence is observed in this material.     

Femtosecond laser fabrication of nanostructures in silica glass

A femtosecond laser beam focused inside fused silica and other glasses can modify the refractive index of the glass. Chemical etching and atomic-force microscope studies show that the modified region can have a sharp-tipped cone-shaped structure with a tip diameter as small as 100 nm. Placing the structure near the bottom surface of a silica glass sample and applying a selective chemical etch to the bottom surface produces clean, circular, submicrometer-diameter holes. Holes spaced as close to one another as 1.4 microm are demonstrated.     

Cracking of poly(methyl methacrylate) caused by plane stress waves

Tiny spalls of various growth stages were produced in poly(methyl metacrylate) (PMMA) plates at temperatures ranging from ?48 to 80° by the flying plate method using a foil explosion technique. Optical inspections revealed that the spalls consist of many small, disk-shaped cracks; the cracks may be morphologically classified into three types. Some speculations on the growing and healing processes of these cracks are presented. The density of crack nuclei in PMMA is estimated to be 10⁴ to 10⁶ cm³, depending on the specimen properties and the amplitude of the applied stress waves. Specimen temperatures and annealing were found to have no appreciable effects on the pattern of spall cracks or on the density of crack nuclei. In the light of the observed results it is suggested that the spall patterns characteristic to PMMA are, besides the properties of the polymer itself, principally due to internal nuclei, such as flaws, which are rather randomly located.