Mass spectrometric analysis of elemental and isotopic compositions of several NIST standards is performed by a miniature laser ablation/ionisation reflectron-type time-of-flight mass spectrometer (LMS) using a fslaser ablation ion source (775 nm, 190 fs, 1 kHz). The results of the mass spectrometric studies indicate that in a defined range of laser irradiance (fluence) and for a certain number of accumulations of single laser shot spectra, the measurements of isotope abundances can be conducted with a measurement accuracy at the per mill level and at the per cent level for isotope concentrations higher and lower than 100 ppm, respectively. Also the elemental analysis can be performed with a good accuracy. The LMS instrument combined with a fs-laser ablation ion source exhibits similar detection efficiency for both metallic and non-metallic elements. Relative sensitivity coefficients were determined and found to be close to one, which is of considerable importance for the development of standard-less instruments. Negligible thermal effects, sample damage and excellent characteristics of the fs-laser beam are thought to be the main reason for substantial improvement of the instrumental performance compared to other laser ablation mass spectrometers.

The performance of a laser ablation mass analyser designed for in-situ exploration of the chemical composition of planetary surfaces has been investigated. The instrument measures the elemental and isotopic composition of raw solid materials with high spatial resolution. The initial studies were performed on NIST standard materials using IR laser irradiance (< 1 GW cm(-2)) at which a high temporal stability of ion formation and sufficiently low sample consumption was achieved. Measurements of highly averaged spectra could be performed with typical mass resolution of m/Δm ≈ 600 in an effective dynamic range spanning seven decades. Sensitive detection of several trace elements can be achieved at the ~ ppm level and lower. The isotopic composition is usually reproduced with 1% accuracy, implying good performance of the instrument for quantitative analysis of the isotopic fractionation effects caused by natural processes. Using the IR laser, significant elemental fractionation effects were observed for light elements and elements with a high ionization potential. Several diatomic clusters of major and minor elements could also be measured, and sometimes these interfere with the detection of trace elements at the same nominal mass. The potential of the mass analyser for application to sensitive detection of elements and their isotopes in realistic samples is exemplified by measurements of minerals. The high resolution and large dynamic range of the spectra makes detection limits of ~100 ppb possible.

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High-resolution chemical depth profiling measurements of copper films are presented. The 10 μm thick copper test samples were electrodeposited on a Si-supported Cu seed under galvanostatic conditions in the presence of particular plating additives (SPS, Imep, PEI, and PAG) used in the semiconductor industry for the on-chip metallization of interconnects. To probe the trend of these plating additives toward inclusion into the deposit upon growth, quantitative elemental mass spectrometric measurements at trace level concentration were conducted by using a sensitive miniature laser ablation ionization mass spectrometer (LIMS), originally designed and developed for in situ space exploration. An ultrashort pulsed laser system (τ ∼ 190 fs, λ = 775 nm) was used for ablation and ionization of sample material. We show that with our LIMS system, quantitative chemical mass spectrometric analysis with an ablation rate at the subnanometer level per single laser shot can be conducted. The measurement capabilities of our instrument, including the high vertical depth resolution coupled with high detection sensitivity of ∼10 ppb, high dynamic range ≥10(8), measurement accuracy and precision, is of considerable interest in various fields of application, where investigations with high lateral and vertical resolution of the chemical composition of solid materials are required, these include, e.g., wafers from semiconductor industry or studies on space weathered samples in space research.