Spectrochimica Acta Part B: Atomic Spectroscopy Volume 136, 1 October 207, Pages 56-5 Femtosecond laser-induced breakdown spectroscopy: Elemental imaging of thin films with high spatial resolution Christoph M. Ahamer 9 p3, Kevin M. Riepl, Norbert Huber, Johannes D.Pedamnig 9 03 @ Show more «@ Share 98 Cite httpsfdoi.org/10.1016j.sab.2017.08.005 7 Get rights and content > Abstract We investigate femtosecond laser-induced breakdown spectroscopy (fs-L1BS) for the spectrochemical imaging of thin films with high spatial resolution, Chemical images are obtained by recording LIBS spectra at each site of 2D raster-scans across the samples employing one fs-laser pulse per site. The diffraction images of the Echelle spectrometer are binned to reduce the read-out time of the intensified CCD detector and to increase the stability of the emission signals against peak drifts in the echellograms. For copper thin films on glass the intensities of Cu | emission lines and the size of ablation craters vary non-monotonously with the film thickness they=5-S0Onm. The emission efficiency, defined as the Cu I line intensity per ablated volume, strongly decreases for films thicker than the optical penetration depth, The Na [line intensity from glass increases exponentially with decreasing Cu film thickness. For yttrium barium copper oxide (YBCO) thin films on MgO various atomic and molecular emission lines of the laser-induced plasma are measured (film thickness hygco=200-1000nm). The obtained element (¥, Ba, Cu, Mg) and molecular (Y-0) fs-LIBS images match the structure of the micro-patterned YBCO films very well. The achieved lateral resolution ‘r=Gum is among the best values reported for spectrochemical LIBS imaging, Graphical abstract 7 ‘oon Download : Download high-res image (225K8)Download : Download full-size image Introduction Laser-induced breakdown spectroscopy (LIBS) is a well-known technique for chemical element analysis of solid, liquid, gaseous, and particulate matter that is applied in a wide range of fields. LIBS offers several advantages due to its simplicity and versatility, little or negligible sample preparation, the possibility to analyze material in gas or liquid background (e.g, in air, vacuum, sea water, etc.) the feasibility of stand-off measurements, and its robustness which enables field applications in harsh environment. Sampling of the target material to be analyzed is performed by pulsed-laser ablation which produces craters on the surface of solid samples. The size of ablation craters can be reduced by using nanosecond (ns) laser pulses of low energy (<1 mj) that are focused to small spots on the sample surface (diameter @s10um) [1]. With femtosecond (fs) laser pulses much smaller ablation craters can be produced [2], [3] and the LIBS analysis. can be performed on sub-micrometer spots (<1 um) [4], [5]. The crater depth reduces due to the smaller thermal penetration depth of fs-pulses as compared to ns-pulses [6], [7]. f5-LIBS depth profiling with depth resolution in the nanometer range has been demonstrated for different materials [8], [9], [10] (Chemical imaging with element-specific spatial contrast (“element imaging’) is used in many applications ranging from materials science to industrial quality control. Various techniques like scanning electron microscopy with energy dispersive X-ray analysis (SEM/EDX) [11], X-ray fluorescence (XRF) [12], particle- induced X-ray emission (PIXE) [13], and mass spectrometry [14] are used for spatially resolved element analysis. Restrictions on sample properties (e.g., conductivity), sample preparation (e.g., time-consuming pre-treatment), measurement conditions (e.g., vacuum), and large operating costs are drawbacks of some of the techniques. LIBS has been applied to element imaging and mapping of various materials [15] including biological samples [16], [17], ceramics {18}, metal coatings [19], metals [20], [21], [22]. [23], [24], nanoparticles [25], [26], and paper [27]. Other related analytical techniques like laset-ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) (e.g., [28], [29], [30]), matrix-assisted laser desorption ionization (MALDI) [31], and some combination of LA-ICP-MS, Raman spectroscopy, and LIBS have been applied for element imaging also [32], (33), [34] In most studies on LIBS imaging, nanosecond laser pulses are employed for material sampling. However, femtosecond laser pulses offer several advantages for LIBS imaging compared to conventional nanosecond laser pulses. The much smaller heat affected zone reduces thermal loading of the target material and produces ablation craters of well-defined size and geometry which is essential for imaging with high spatial resolution, Another advantage is the very low thermal background radiation at early stages of the fs-LIBS plasma which allows for non-gated optical detection. Furthermore, non-linear optical effects (e.g,, multi- photon absorption) can be exploited to investigate optically transparent materials and to reduce the matrix effect in LIBS. ‘The LIBS imaging of thin film materials is challenging and rarely investigated. Larger spots may be required to increase the mass of ablated material and to attain sufficient optical emission intensities thus ‘compromising the achievable spatial resolution. Signal accumulation by oversampling to improve signal/noise ratios becomes impossible if the single pulse ablation depth exceeds the thickness of film samples. Furthermore, the ablation process may be modified if the excitation energy spreads from the thin film into the supporting substrate. In this work we report on femtosecond laser ablation and laser-induced breakdown spectroscopy of thin films employing one, two, or three fs-pulses per site on the sample, We investigate the size of ablation craters and the intensity of emission lines for Cu thin films on glass and determine the emission efficiency.Micro-patterned YBazCu;07 thin films on MgO and YSZ substrates are fs-LIBS imaged by measuring several atomic and molecular emission lines. Binning of diffraction images is employed to increase the scan speed and the stability of the LIBS signals. Section snippets Experimental setup ‘The LIBS setup used in the experiments is shown schematically in Fig. 1. The Ti:Sapphire amplifier system (Spectra Physies Hurricane i) produced femtosecond laser pulses at wavelength h=800nm, repetition frequency f,=1kHz, and pulse energy E,=200,1. A frequency doubling beta barium borate (BBO) crystal generated pulses with A=400nm. A short pass filter (Thorlabs FGB39) after the BBO crystal blocked the fundamental wavelength. The pulse length t,, was adjusted to maximize the pulse energy of the. Femtosecond laser ablation of Cu thin films Ina first set of experiments we ablated the Cu/glass samples and measured the fs-LIBS spectra as function of the Cu film thickness, The diameter of the beam aperture was da=3mm and the laser pulse energy at the sample was E,~10j1. The spectra were averaged over 14 laser pulses delivered to 14 sites (single shot per site). The fs-LIBS spectra of all samples revealed intense neutral Cu lines around 510-525nm and very low background intensity (Fig. 2a). The signal-to-noise ratio (SNR) of the Cul Fs-laser ablation threshold fluence of thin films In femtosecond laser ablation of bulk metals, different regimes of “gentle ablation” (GA) and “strong ablation” (SA) have been observed at low and high laser fluence F [45], respectively. The threshold fluences and the ablation rates are low and high in the GA and SA regimes. The single pulse ablation depth L depends ona characteristic length € and on the ablation threshold fluence Fa, Le so(F/Fa){ SA 10 = bay Fey = AByla/A SA: £5 thes Fun = ABylbe/Ane In the GA regime at low fluence the characteristic length, Conclusions ‘We applied femtosecond laser pulses to ablate metal and oxide thin films and to perform elemental and molecular imaging by f5-LIBS. For Cu thin films on glass the ablation craters were larger in size (A) than the laser spot size (A,). The crater area varied with the film thickness hcy due to a non-monotonous dependence of the ablation threshold fluence on hcy. The emission efficiency (LIBS signal for Cu/volume of ablation crater) rapidly dropped for films thicker than the optical penetration... Acknowledgements The authors would like to thank H. Pigmayer-Brezina for preparing the Cu film samples and for the SEM measurements, and A. Nimmervoll for help in all matters concerning electronics. We appreciate the supply with YBCO/YSZ samples by R. Semerad (THEVA Diinnschichttechnik GmbH). We acknowledge gratefully the support by the Austrian industrial research initiative PAC and the financial support by the Austrian Research Promotion Agency (project number 843546 imPACts).,References (67) S.P. Banerjee et al. High resolution scanning microanalysis on material surfaces using UV femtosecond laser induced breakdown spectroscopy ‘Opt. Lasers Eng, (2015) . Geertsen etal. Evaluation of laser ablation optical emission spectrometry for microanalysis in aluminium samples Spectrochim. Acta B At. Spectrosc. (1996) K. Kuhn etal. Chemical mapping of mine waste drill cores with laser-induced breakdown spectroscopy (LIBS) and energy dispersive X-ray fluorescence (EDRF) for mineral resource exploration J. Geochem. Explor. (2016) J. Kaiser et al. 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(2007) ~ | View more references Cited by (19) ‘Three-dimensional topographic and multi-elemental mapping by unilateral-shift-subtracting confocal controlled LIBS microscopy 2022, Spectrochimica Acta - Part 8 Atomic Spectroscopy Citation Excerpt Varela et al. analyzed the tungsten carbide of laser cladding coating by traditional LIBS technology, and achieved the lateral resolution of 100 um [20], For the sake of improving the spatial resolution of current LIBS imaging techniques, researchers proposed some advanced methods, including double-pulsed LIBS (DP-LIBS) [21-24], femtosecond LIBS ((5- UBS) [25-27], near-field enhanced atomic emission spectroscopy (NFE-AES) [28-30], microwave-assisted LIBS (MW- Bs) [3132], etc. For example, Schiavo et al. developed a double pulse LIBS instrument for single point analysis of jadeite and berylium, with a transverse resolution of 10 pm [23} Show abstract Methodology and applications of elemental mapping by laser induced breakdown spectroscopy 2021, Analytica Chimica Acta Citation Excerpt: Bulk materials are often covered with thin films to enhance their physical and/or chemical properties. Thin films of ‘copper, as well as YBa2Cu307 (YBCO) - a high-temperature superconducting material - were investigated in the study of ‘Ahamer et al. [173]. A fs-LIBS system was employed to perform high resolution elemental and molecular imaging of the thin film. Show abstract \ LIBS imaging applications 2020, Laser-induced Breakdown Spectroscopy, Second Edition Show abstract V7 Investigation of signal extraction in the frame of LIBS imaging 2019, Spectrochimica Acta - Part & Atomic Spectroscopy Show abstract \ Review of the recent advances and applications of LIBS-based imaging 2019, Spectrochimica Acta - Part B Ator Spectroscopy Citation Excerpt : ‘Moreover, Echelle spectrometers need to read the whole charge-coupled device (CCD) image to obtain the spectrum, ‘which results in an inerease in the readout time and reduces the acquisition rate and operational speed to only several Hz, Inthe literature, Echelle spectrometers have been successfully used either coupled with intensified CCD (ICCD) {60,83,83,94,99,110-115] or electron multiplying CCD (EMCCD) cameras [93]. 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