Capabilities of femtosecond laser ablation inductively coupled plasma mass spectrometry for depth profiling of thin metal coatings

The capabilities of ultraviolet femtosecond laser ablation inductively coupled plasma mass spectrometry (UV-fs-LA-ICPMS) for depth profile analysis of thin metal coatings were evaluated. A standard sample consisting of a single Cr thin layer of 500 nm +/- 5% on a Ni substrate was used. A fast washout was obtained by a high-efficiency aerosol dispersion ablation cell (V approximately 1 cm3), which allowed single-shot analysis with increased depth resolution. Laser ablation was performed in helium at atmospheric pressure conditions. A laser repetition rate of 1 Hz and low laser fluence (<0.5 J/cm2) were used. Very low ablation rates (<10 nm/pulse) were determined by atomic force microscopy (AFM). Information about the crater geometry and morphology was investigated using scanning electron microscopy and AFM. The depth resolution, calculated via the maximum slope of the tangent in the layer interface region, was smaller than 300 nm. Our data indicate that UV-fs-LA-ICPMS represents a powerful combination of high lateral and depth resolution for the analysis of thin metal coatings. Moreover, an overall ion yield, defined as the ratio of detected ions and ablated atoms, of approximately 5 x 10-5 was estimated for the chromium layer under the operating conditions chosen. The absolute amount of ablated material per laser pulse was approximately 1 pg, which corresponds to a detection limit of 180 microg/g.     

Depth analysis of polymer-coated steel samples using near-infrared femtosecond laser ablation inductively coupled plasma mass spectrometry

The viability of near-infrared femtosecond laser ablation (fs-LA) inductively coupled plasma mass spectrometry (ICPMS) for the in-depth analysis of polymer coatings over galvanized steel substrates has been studied. A good depth resolution was obtained modifying the femtosecond Gaussian beam to a flat-top beam by using a liquid-crystal display. In order to avoid mixing of information coming from successive shots, a low repetition rate was accomplished and signals were monitored shot by shot. Different kinds of coatings were used to demonstrate the capability of femtosecond ablation for depth-profiling analysis. Ablation was conducted under He atmosphere, after sample cell Ar was admixed. The depth profiles obtained by LA-ICPMS are in good agreement with those obtained by GD-OES for the three analyzed samples. In cases where due to averaging over several millimeter sample roughness determines the depth resolution of GD-OES, it was found that LA-ICPMS achieves better depth resolution due to the better lateral resolution. The depth resolution obtained by LA-ICPMS was found to be 240 nm and 2.3 microm, for a hot-dip galvanized steel (HDGS) and a polymer-polymer-coated HDGS, respectively, compared to the 2.2 and 4.5 microm achieved with GD-OES for the same samples.     

Optical and structural characteristics of silicon nanoparticles thin film prepared by laser ablation

In this paper thin film of silicon nanoparticles on glass substrates have been prepared by dip-coating method using colloidal silicon nanoparticles generated by nanosecond laser ablation of silicon wafer in ethanol. The resulting nanoparticles and structural properties and morphology of thin film were characterized by UV-Visible absorption spectrometry, transmission electron microscopy, Fourier transform infrared spectroscopy, X-ray diffraction pattern and atomic force microscopy image. Nanoparticles with diameters ~ 9 nm were observed to be formed in the colloidal solution. The atomic force microscopy image of Si nanoparticles thin film shows that the overall average width is about 80 nm.     

Depth profiling by confocal Raman microspectroscopy: semi-empirical modeling of the Raman response

It has been well documented that the use of dry optics in depth profiling by confocal Raman microspectroscopy significantly distorts the laser focal volume, thus negatively affecting the spatial resolution of the measurements. In that case, the resulting in-depth confocal profile is an outcome of several contributions: the broadening of the laser spot due to instrumental factors and diffraction, the spreading of the illuminated region due to refraction of the laser beam at the sample surface, and the influence of the confocal aperture in the collection path of the laser beam. Everall and Batchelder et al. developed simple models that describe the effect of the last two factors, i.e., laser refraction and the diameter of the pinhole aperture, on the confocal profile. In this work, we compare these theoretical predictions with experimental data obtained on a series of well-defined planar interfaces, generated by contact between thin polyethylene (PE) films (35, 53, 75, and 105 microm thickness) and a much thicker poly(methyl methacrylate) (PMMA) piece. We included two refinements in the above-mentioned models: the broadening of the laser spot due to instrumental factors and diffraction and a correction for the overestimation in the decay rate of collection efficiency predicted by Batchelder et al. These refinements were included through a semiempirical approach, consisting of independently measuring the Raman step-response in the absence of refraction by using a silicon wafer and the actual intensity decay of a thick and transparent polymer film. With these improvements, the model reliably reproduces fine features of the confocal profiles for both PE films and PMMA substrates. The results of this work show that these simple models can not only be used to assist data interpretation, but can also be used to quantitatively predict in-depth confocal profiles in experiments carried out with dry optics.     

Quantitative analysis of hydrogen in thin films using Time-of-Flight Elastic Recoil Detection Analysis

Determination of atomic concentrations in thin films is one of the key problems in materials science. Time-of-Flight Elastic Recoil Detection Analysis is a powerful method for depth profiling of light and medium mass elements in near surface layers of material. However, due to poor detection efficiency those spectrometers are not commonly used for hydrogen analysis. We have performed some improvements in order to increase detection efficiency and to make spectrometer more suitable for hydrogen analysis. The spectrometer performance was tested on amorphous Si samples implanted with H⁻ and D⁻ and hydrogenised Si standard reference sample. Sensitivity for hydrogen in silicon matrix was found to be several tens of ppm with a surface depth resolution of ~ 15 nm.     

Optimizing depth resolution in confocal Raman microscopy: a comparison of metallurgical, dry corrected, and oil immersion objectives

Spherical aberration is probably the most important factor limiting the practical performance of a confocal Raman microscope. This paper suggests some simple samples that can be readily fabricated in any laboratory to test the performance of a confocal Raman microscope under realistic operating conditions (i.e., a deeply buried interface, rather than the often-selected alternative of a bare silicon wafer or a thin film in air). The samples chosen were silicon wafers buried beneath transparent polymeric or glass overlayers, and a polymer laminate buried beneath a cover glass. These samples were used to compare the performance of three types of objectives (metallurgical, oil immersion, and dry corrected) in terms of depth resolution and signal throughput. The oil immersion objective gave the best depth resolution and intensity, followed by a dry corrected (60x, 0.9 numerical aperture) objective. The 100x metallurgical objective was the worst choice, with degradations of approximately 5x and 8x in the depth resolution and signal from a silicon wafer, comparing a bare wafer with one buried under a 150 microm cover glass. In particular, the high signal level obtained makes the immersion objective an attractive choice. Results from the buried laminate were even more impressive; a 30x improvement in spectral contrast was obtained using the oil immersion objective to analyze a thin (19 microm) coating on a PET substrate, buried beneath a 150 microm cover glass, compared with the metallurgical objective.     

Laser ablation coupled to a flowing atmospheric pressure afterglow for ambient mass spectral imaging

A plasma-based ambient desorption/ionization mass spectrometry (ADI-MS) source was used to perform molecular mass spectral imaging. A small amount of sample material was ablated by focusing 266 nm laser light onto a spot. The resulting aerosol was transferred by a nitrogen stream to the flowing afterglow of a helium atmospheric pressure glow discharge ionization source; the ionized sample material was analyzed by a Leco Unique time-of-flight mass spectrometer. Two-dimensional mass spectral images were generated by scanning the laser beam across a sample surface. The total analysis time for a 6 mm (2) surface, which is limited by the washout of the ablation chamber, was less than 30 min. With this technique, a spatial resolution of approximately 20 microm has been achieved. Additionally, the laser ablation configuration was used to obtain depth information of over 2 mm with a resolution of approximately 40 microm. The combination of laser ablation with the flowing atmospheric pressure afterglow source was used to analyze several sample surfaces for a wide variety of analytes and with high sensitivity (LOD of 5 fmol for caffeine).     

Sample preconcentration using ion-exchange polymer film for laser ablation sampling inductively coupled plasma atomic emission spectrometry

An efficient sample pretreatment/introduction technique for the inductively coupled plasma atomic emission spectrometry (ICP-AES) using ion exchange for analyte preconcentration and matrix separation and laser ablation sampling for sample introduction has been developed. Ammonium pyrrolidine dithiocarbamate (APDC)-polystyrene films are coated on glass plates for analyte preconcentration. Repetitive laser ablation sampling of the polymer film removes the ion-exchanged metal ions from the polymer film as fine particles for sample introduction into the ICP. After immersing the sample probe in a sample solution for 5 min, the ICP emission intensity for laser ablation of the polymer film is a few times larger than that after solution nebulization. The sample probe removes only a small fraction of the sample solution and, therefore, in principle, does not disturb the original solution significantly. Single-pulse laser ablation of the polymer film shows that the ion-exchanged metal ion concentration in the film reduces exponentially with the depth of the polymer film. Ion exchange to the polymer film is probably limited by the rate of metal ion diffusion into the film. Calibration curves for Cu, Hg, Pb, and Zn show linear dynamic range of ～1-2 orders of magnitude. The linear dynamic range for Cu increases to >3 orders of magnitude when using Pb as an internal standard. RSD of the ICP emission intensity is ～8%.     

Trace Element Microanalysis in Iron Meteorites by Laser Ablation ICPMS

A laser ablation microanalysis system has been developed that can analyze trace elements with a sensitivity in the ppb range, using a CETAC LSX-200 laser ablation system with a Finnigan Element. This capability has been applied to a set of iron meteorites to demonstrate the laser microprobe's analytical capability for the determination of platinum group elements (PGEs) with a spatial resolution of ～20 μm, comparable to that of dynamic secondary ion mass spectrometry (SIMS). The laser is shown to provide an accurate means of solid sampling for magnetic sector inductively coupled plasma mass spectrometry (ICPMS), allowing the determination of bulk metal composition, chemical zoning within the sample, and depth profiling. Recovery of the chemical zoning in taenite lamellae was achieved for Ru, Rh, and Pd, which was not previously possible using SIMS. The methods presented here show that magnetic sector ICPMS can be successfully coupled to a laser ablation system, providing the advantages of higher sensitivity of the sector instrument, low background count rates (<0.1 counts/s), and flat-topped spectral peaks, while minimizing tradeoff against the speed of data acquisition required to handle the transient signals from the laser ablation system.     

Auger electron spectroscopy depth profiling studies on stationary and rotated samples of a new model metal/semiconductor multilayer structure

Multilayer structures for application in microelectronics are becoming increasingly complex. A sputter deposited multilayer structure composed of chromium, nickel and silicon layers with a total thickness of 310 nm on a smooth silicon substrate was characterized by transmission electron microscopy (TEM) and by Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) depth profiling. AES depth profiles of the Ni/Cr/Si multilayers were obtained with Ar⁺ ion bombardment at various angles of incidence using stationary and rotated samples. In some cases a strong influence of semiconductor structure on the experimentally obtained metal-metal and metal-semiconductor interface widths was observed. Owing to ion beam induced Si(LVV) Auger electrons in the crater wall of the Ni/Cr/Si sample, a distortional influence on depth resolution during simultaneous AES analysis and ion sputtering was found. Silicide formation during sputtering at the silicon-metal interfaces was confirmed by XPS. The measured compositional depth profiles are explained with respect to the influence of polycrystalline metallic and amorphous semiconductor structures; the effects of ion beam induced topography, atomic mixing and silicide formation are discussed.     

Fabrication of high aspect ratio metal nanotips by nanosecond pulse laser melting

The authors have developed an approach to fabricate sharp and high aspect ratio metal tips using nanosecond pulse laser melting. A quartz wafer covered with a thin chromium (Cr) film was placed on top of a second wafer with a sub-micrometer gap between them and the Cr film facing the second wafer. Then an excimer laser pulse (308?nm wavelength, 20?ns pulse duration) was shone from the back of the quartz wafer and melted the Cr film momentarily (several hundred nanoseconds). It is found that the molten Cr films can self-form discrete metal pillars connecting the two wafers. After separating the two wafers, nanotips were formed at the broken pillar necks. The sharpest tip achieved has an apex diameter 10?nm and height 180?nm. The self-formation of Cr pillars between the two wafers was attributed to the attractive electrostatic force caused by the work function difference of two wafers that were in close proximity. This technique could be extended to other metals, and a periodic uniform tip array could be obtained by pre-patterning the metal into identical isolated mesas and precisely controlling the gap between the two wafers.     

Depth profile analysis of solar cells by Secondary Neutral Mass Spectrometry using conducting mesh

Depth profile analysis of solar cells was performed by Secondary Neutral Mass Spectrometry (SNMS), which is a suitable technique for quantitative analysis of the composition of layered structures. However, in the case of insulating samples or samples prepared on non-conductive substrates (e.g. microslide, oxidized silicon wafer) the charge accumulation on the sample surface due to ion beam bombardment can cause a serious problem by destroying the resolution of depth profile. The high frequency (HF) mode of electron-gas SNMS seems to be a good solution for this problem. Another method to prevent the charge accumulation on a sample surface can be a conducting mesh (e.g. copper, stainless steel) placed on the surface. Using one of the two methods mentioned above can help us to get rid of the charging effect, i.e. to neutralize the surface charge during measurements. But in the case of solar cell analysis these two methods should be applied simultaneously during depth profiling. The experimental results performed on p-i-n:Si (p-type/intrinsic/n-type) diodes have proved that SNMS measurement in HF operation mode combined with a mesh is very efficient in the determination of doping levels of phosphorus and boron with good depth resolution, even in the case of 500-600 nm thick samples.     

高技术功能薄膜材料电阻率测试新法及微机测试系统

介绍一种适于测量几何形状无规则的薄形样品电阻率的改进直流四探针法(IFPM),同时提出了带背底样品的测试实验修正原理和方法。采用具有标准IEEE—488接口和24路I/0控制接口的PC/XT微机和智能数字仪表组成测试实施系统,在Solartron35 system上用范德堡法(VDPM)和在本系统上用IFPM法对同一块硅单晶片进行了对比测试,二者偏差为4.3％。采用该法还测试研究了直流电弧等离子体喷射技术在陶瓷基底上制备的1μm厚铜-聚丙炔腈(Cu-PPN)金属有机导电薄膜的电阻率与温度的关系,结果表明Cu-PPN薄膜具有非晶半导体的扩展传导机制。研究表明,IFPM法对目前不能沿用传统技术的高技术薄膜材料电阻率测试是一条有效的途径。     

Auger electron spectroscopy and secondary ion mass spectrometry depth profiling with sample rotation

Recently, there has been a rapid increase in the application of multilayered structured materials, as opposed to bulk materials, in many areas of technological development. Accurate characterization of the structure and composition of advanced multilayers such as superlattices, quantum wells, contacts, and coatings is important for materials and device fabrication technology. Surface analysis techniques including Auger electron spectroscopy (AES), X-ray photoelectron spectroscopy, and secondary ion mass spectrometry (SIMS) in conjunction with ion beam sputtering (sputter depth profiling) are at present the most widely used methods for characterization of modern multilayer thin film materials and devices. Ion-beam-induced surface topography, however, can limit depth resolution, and with SIMS, can also cause changes in the secondary ion yield. These changes are due to the high sensitivity of secondary ion yield to the local angle of incidence on sputter-roughened surfaces. Degradation of depth resolution and changes in secondary ion yields during sputter depth profiling have often limited studies of thin film interdiffusion, segregation, oxidation at interfaces, and impurity effects. Much theoretical and experimental work has been carried out to try to improve depth resolution including the use of low ion beam energy, high angle of incidence, and two ion guns. Recent studies of AES and SIMS with sample rotation have shown that depth resolution can be improved substantially and that constant secondary ion yields in SIMS can be achieved. We will first provide an overview of the studies made by various groups to improve depth resolution of metal multilayers using AES with rotation. Next we will review recent investigations of SIMS using sample rotation including studies of the effects of sample rotation on O₂⁺ ion-beam-induced topography, secondary ion yield, and the depth resolution of electronic, metallurgical and dielectric materials. The results presented demonstrate that SIMS with sample rotation provides constant secondary ion yield, and depth-independent depth resolution because sample rotation prevents ion-beam-induced roughness and reduces the effect of the inhomogeneity of low energy ion beams.     

Optical restriction of plasma emission light for nanometric sampling depth and depth profiling of multilayered metal samples

Improvement in depth profiling capabilities of laser-induced breakdown spectrometry (LIBS) for multilayered samples has been attempted. For this purpose, in a typical LIBS experiment, an optical restriction consisting of a pinhole placed between the dichroic mirror and the collecting lenses has been used. This new optical approach allows observing only the light emission coming from the central region of the plume. The microplasma was created on the sample by a pulsed Nd:YAG laser operating at 1064 nm with a homogeneous distribution of energy across the beam. Light emitted by the microplasma was detected with an intensified charge-coupled device (iCCD) multichannel detector. The effect of pinhole diameter and the delay time influence on depth analysis have been assessed. An ablation range of only a few nanometers per pulse has been achieved. Depth profiles of various metals (Cr, Ni, Cu) from multilayered samples have been generated by LIBS and depth resolution at different delay times using various pinhole diameters have been calculated and compared.     

Feasibility of depth profiling of animal tissue by ultrashort pulse laser ablation

Experiments were performed to examine the feasibility of mass spectrometry (MS) depth profiling of animal tissue by ~75 fs, 800 nm laser pulses to expose underlying layers of tissue for subsequent MS analysis. Matrix assisted laser desorption ionization mass spectrometry (MALDI-MS) was used to analyze phospholipids and proteins from both intact bovine eye lens tissue and tissue ablated by ultrashort laser pulses. Laser desorption postionization mass spectrometry (LDPI-MS) with 10.5 eV single photon ionization was also used to analyze cholesterol and other small molecules in the tissue before and after laser ablation. Scanning electron microscopy was applied to examine the ablation patterns in the tissue and estimate the depth of the ablation craters. Ultrashort pulse laser ablation was found to be able to remove a layer of several tens of micrometers from the surface of eye lens tissue while leaving the underlying tissue relatively undamaged for subsequent MS analysis. MS analysis of cholesterol, phospholipids, peptides, and various unidentified species did not reveal any chemical damage caused by ultrashort pulse laser ablation for analytes smaller than ~6 kDa. However, a drop in intensity of larger protein ions was detected by MALDI-MS following laser ablation. An additional advantage was that ablated tissue displayed up to an order of magnitude higher signal intensities than intact tissue when subsequently analyzed by MS. These results support the use of ultrashort pulse laser ablation in combination with MS analysis to permit depth profiling of animal tissue.     

Determination of Thermophysical Properties for Polymer Films using Conduction Analysis of Laser Heating

Determination of the thermophysical properties of thin film materials is important for modeling and optimizing laser microvia drilling of organic substrates in microelectronics applications. Techniques to measure the density, thermal conductivity, thermal diffusivity, thermal decomposition point, and specific ablation heat of thin polymer films are described. An experimental apparatus was set up for laser heating of the sample. To measure the thermal diffusivity, an analytic heat transfer model is developed. One-dimensional heat conduction is assumed due to the small thickness of the film compared to the radius of the laser beam. The value of thermal diffusivity is obtained by fitting the experimental data to the theory. The specific ablation heat is obtained by measuring the mass loss during laser ablation. The experimental apparatus and the property determination methodology can also be applied to thin samples of other materials.     

Application of novel azo metal thin film in optical recording

The absorption spectrum of spin-coated azo metal thin film showed a comparatively large absorption band in the wavelength region (500–600 nm), which matched with the wavelength of the GaAlInP semiconductor diode laser (630–650 nm). The optical recording performance of the film was investigated.     

Substrate-assisted laser desorption of neutral peptide molecules.

The ultraviolet (248-nm) laser desorption of neutral peptide molecules is found to be greatly enhanced by applying a thin layer of the sample (500 monolayers) on top of an ultraviolet-absorbing organic substrate, sinapinic acid. With this sample preparation, peptides as large as gramicidin S are desorbed as intact neutral molecules. The samples are examined with laser desorption/chemical ionization (LD/CI) Fourier transform mass spectrometry. The neutrals desorbed by this method have approximately 1 eV less internal energy than those desorbed directly from a metal film surface. The organic substrate aids the desorption of neutrals when the laser wavelength is not strongly absorbed by the peptide sample (248 nm), but is not effective in aiding the desorption of neutrals when the laser wavelength is strongly absorbed by the sample (193 nm).     

Three dimensional analysis of self-structuring organic thin films using time-of-flight secondary ion mass spectrometry

Selective sub-micrometer structuring of phase-separating organic semiconductor materials has recently got into focus for providing the opportunity of further improvements in optoelectronic device applications. Here we present a 3D-time-of-flight secondary ion mass spectrometry (3D-TOF-SIMS) depth profiling investigation on spin-coated blends consisting of [6,6]-phenyl-C₆₁-butyric acid methyl ester (PCBM) and a cationic cyanine dye (1,1′-diethyl-3,3,3′,3′-tetramethylcarbocyanine iodide). TOF-SIMS provides the required lateral and depth resolution to resolve material and molecular inhomogeneities and phase separation in the blend. The data are illustrating the three-dimensional arrangement of the substances involved and confirm results of earlier studies using atomic force microscopy, UV-vis spectroscopy and x-ray photoelectron spectroscopy, and which have shown well distinguishable morphological features. The formation of this domain structure has been found to be dependent on the absolute as well as the individual film thickness, in accordance with models based on thin liquid two-layer films. Honey-comb like primary structures with micrometer dimension were found in samples containing small amounts of dye molecules in the deposition solution. In this case a thin dye deposit on PCBM was detected, which is well separated from the dye layer at the substrate. For this type of sample, we discuss an extended model of film formation based on partial depletion of dye molecules during film solidification, resulting in two individual dye layers.