Stability and fragmentation of organic silicon functionalizations studied by laser desorption mass spectrometry

A method is introduced to investigate organic functionalizations on silicon by laser-induced thermal desorption (LITD), where well-ordered Si(1 1 1)-(1 × 1):H(D) surfaces are used to determine the desorption temperature as a function of laser fluence. To demonstrate the potential of this technique silicon surfaces with ultrathin oxide layers were functionalized with organic end groups. The species desorbed with focused XeCl laser pulses were monitored at an oblique angle and their time-of-flight (TOF) distributions were measured with a quadrupole mass analyzer after electron impact ionization. By assuming a negligible contribution of the oxide and organic layers to the heating effect, the TOF temperatures measured for Si(1 1 1)-(1 × 1):H(D) could be used to determine the mass of the desorbed species. Detailed results are presented for dimethylsilyl (DMS), bromomethyldimethylsilyl (BMDMS), and chloromethyldimethylsilyl (CMDMS) terminated surfaces which were prepared by silanization with suitable chloro and disilazane compounds. While for the DMS termination dimethylsilanol (76 u) is desorbed as a single species, clearly identifying the terminating group, in the case of BMDMS and CMDMS further fragmentation of the end group occurs at the surface.     

Influence of the photoionization process on the fragmentation of laser desorbed polycyclic aromatic hydrocarbons

Characterization of polycyclic aromatic hydrocarbons (PAHs) samples has been performed by laser desorption combined with multi-photon ionization technique using two different geometries of the ionization laser beam. This comparative study evidences the strong influence of ionization laser fluence on PAH fragmentation. Through a ∼10³ enlargement of the ionization probe volume and 10⁴ reduction of laser fluence over previous studies, fragment free mass spectra are obtained with higher sensitivity and selectivity. The ability to measure fragment free PAH mass spectra is a very important step in the end goal of measuring complex unknown mixtures of PAH desorbed from solid surface such as soot samples.     

Two unstable oscillations in the multimode laser with modulated inversion

We present comprehensive results of numerical studies on the dynamical properties of a multimode ring laser under modulation of the population inversion in the bad-cavity condition. Incoherent properties of unstable oscillations in this system are investigated in detail as a function of two control parameters: the dc component of the population inversion and the modulation amplitude. Two kinds of optical chaos in two limiting regions reported in a previous paper are extensively studied to clarify their different characteristics from deterministic and stochastic points of view. The competition between their different origins is revealed. Statistical properties of their stochasticity are investigated to clarify their non-Gaussian natures. Comparison with analytical results for a single-mode laser with fluctuations is also made.     

Optical characterization and manipulation of alkali metal nanoparticles in porous silica

Rubidium and cesium metal nanoparticles were grown in nanoporous silica samples placed in alkali vapor cells. Their size and shape were investigated by measuring the sample optical transmittance. Spectral changes due to photodesorption processes activated by weak light were also analyzed. Alkali atoms photoejected from the silica walls diffuse through and out of the nanopores, modifying both the nanoparticle distribution in the silica matrix and the atomic vapor pressure in the cell volume. The number of rubidium and cesium atoms burst out of the samples was measured as a function of photon energy and fluence. The optical absorption measurements together with the analysis of the photodesorption yield give a complete picture of the processes triggered by light inside the nanopores. We show that atomic photodesorption, upon proper choice of light frequency and intensity, induces either growth or evaporation of nanosized alkali metal clusters. Cluster size and shape are determined by the host-guest interaction.     

3D atom probe assisted by femtosecond laser pulses

The 3DAP allows to image a material in 3D on a nearly atomic scale. It is based on the field evaporation occurring at the surface of a biased tip like shape specimen with an end radius of 50 nm. Surface atoms are removed one by one from the tip by means of fs laser pulses so that the physical process involved in this laser enhanced field evaporation might correspond to the very early stages of the ablation process. This technique makes possible to distinguish between different regimes of material removal such as thermal evaporation or in the case of metals or semiconductors an evaporation assisted by the rectification of the optical field at the surface. In this paper the principle of the 3DAP is presented and the underlying physics involved in the field evaporation assisted by femtosecond laser pulses is discussed.     

Comparison of NH3 laser dynamics with the extended lorenz model

We present a comparison of the intensity and the electric field measured from an optically pumped FIR NH₃ laser showing instabilities with the respective results obtained from numerical integration of the Lorenz model extended to allow for detuning of the laser cavity with respect to emission line center. Good agreement between experimental and numerical results for high gas pressure suggests that this laser is appropriately described by the Lorenz model for higher operating pressure, while in the low pressure domain qualitative differences are found.Dedicated to Prof. Dr. Herbert Welling on the occasion of his 60th birthdayVisiting from Bryn Mawr College, Bryn Mawr, PA 19010, USA     

Effects of nonlinear mode coupling on the chaotic dynamics of multimode lasers

The dynamics of individual modes of a cw multimode dye laser in a 2-mirror configuration has been studied theoretically and experimentally. Numerical solutions of the laser rate equations including nonlinear mode coupling exhibit chaotic and stochastic behavior in the regime of high and low power, respectively. Chaotic behavior due to mode coupling has been observed in the operating regime well above threshold. The mode dynamics in this case is characterized by a chaotic attractor with low dimension between 2 and 3. With decreasing laser power the dimension increases, suggesting stochastic behavior due to quantum noise in the limit of the laser threshold.On leave at 1. Institut für Experimentalphysik, Universität Hamburg, Fed. Rep. Germany     

Self pulsing properties of optically pumped FIR NH3 lasers

We report on measurements of periodic and chaotic self-pulsing beyond the second threshold of far-infrared NH₃ lasers. While the instabilities of the 81 m¹⁴NH₃ laser follow a simple pattern, for the 374 m¹⁵NH₃ laser different pulsing properties are found in different parameter ranges.Pulses under conditions of high pumping power are measured in detail, in view of possible applications of these coherent, high-repetition rate far-infrared pulsed lasers.     

Spatiotemporal instabilities from a transversely excited atmospheric CO2 laser

Local spatiotemporal instabilities in a TEA CO₂ laser have been studied. Their evolution was studied from the beginning of the gain switch peak to the quasistationary state in the collisional transfer tail of the pulse.The dynamics varies when the diameter of an intracavity aperture is changed. In the TEM₀₀ mode an ordered axial mode beating is observed. In transverse multimode regime irregular fluctuations are observed. In this case signals from two different points taken in the near field show a low cross-correlation. The application of the Grassberger-Procaccia algorithm to the irregular signals shows a good slope convergence towards a value of 2.5, pointing to a chaotic deterministic behaviour.     

O<Subscript>2</Subscript> photodesorption from AuO<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack> and Au<Subscript>2</Subscript>O<Stack><Subscript>2</Subscript><Superscript>−</Superscript></Stack>

Using time-resolved photoelectron spectroscopy, the decay channels of AuO₂⁻ and Au₂O₂⁻ following photoexcitation with 3.1-eV photons have been studied. For AuO₂⁻, a state with a rather long lifetime of 30 ps has been identified. Its decay path could not be determined but photodesorption can be excluded. For Au₂O₂⁻, the spectra indicate O₂ desorption after 3.1-eV photoexcitation on a time scale of 1 ps. While comparing these results on Au _n O₂⁻ with analogous data on Ag _n O₂⁻ clusters, a discernible pattern emerges: for dissociatively bound O₂(AuO₂⁻, Ag₃O₂⁻), there are long-living excited states which do not decay by oxygen desorption, while for molecular chemisorption (Au₂O₂⁻, Ag₂O₂⁻, Ag₄O₂⁻, Ag₈O₂⁻), the 3.1-eV photoexcitation triggers fast O₂ desorption with a high quantum yield.