Matrix-enhanced secondary ion mass spectrometry: The Alchemist's solution?

Because of the requirements of large molecule characterization and high-lateral resolution SIMS imaging, the possibility of improving molecular ion yields by the use of specific sample preparation procedures has recently generated a renewed interest in the static SIMS community. In comparison with polyatomic projectiles, however, signal enhancement by a matrix might appear to some as the alchemist's versus the scientist's solution to the current problems of organic SIMS. In this contribution, I would like to discuss critically the pros and cons of matrix-enhanced SIMS procedures, in the new framework that includes polyatomic ion bombardment. This discussion is based on a short review of the experimental and theoretical developments achieved in the last decade with respect to the three following approaches: (i) blending the analyte with a low-molecular weight organic matrix (MALDI-type preparation procedure); (ii) mixing alkali/noble metal salts with the analyte; (iii) evaporating a noble metal layer on the analyte sample surface (organic molecules, polymers).     

A new approach for preventing charging up of soft material samples by coating with conducting polymers in SIMS analysis

Dynamic secondary ion mass spectroscopy (SIMS) analysis of soft materials such as polymer or biomaterial is one of challenging subjects due to the charge up effect brought from the irradiation of a primary ion beam, hampering the collection of secondary ions. Conventional methods against the charging up are the electron beam irradiation for charge compensation and surface coating with metal, normally gold. Those methods require a compromise analytical condition, reducing the primary ion beam current to suppress the range of the charging, which degrading the performances of the SIMS analyses. We have proposed that a thicker conductive layer, capable of delocalizing the charge onto the surface, should be put on a soft insulator sample to avoid charging up. The depth profile of the hair sample coated wholly with a polythiophen-based conducting polymer was successfully measured in longer time without any charging up even in the maximum current of the oxygen primary ion beam (O₂⁺: 7.5 keV, 400 nA) or using an electron beam compensation system. Thus, the proposed method coating with a conductive organic polymer against the charging issue would be expected as a breakthrough on SIMS analysis.     

Surface investigation of solids by the statical method of secondary ion mass spectroscopy (SIMS)

The physical and chemical properties of a solid surface are determined by its uppermost monolayers. Besides other methods like Auger electron spectroscopy (AES) and X-ray electron spectroscopy (ESCA) for example, the chemical composition of these uppermost monolayers can be investigated by the statical method of secondary ion mass spectroscopy (SIMS). In this method a relatively large target area (0.1 cm²) is bombarded with a small primary ion current density (10^?9 A cm^?2). Thus a sputtering time of several hours is achieved for an individual monolayer. A mass analysis of the emitted positive and negative secondary ions gives information about the chemical composition of the uppermost monomolecular layer of the bombarded surface. Important features of SIMS are: detection of chemical compounds; isotope sensitivity; detection of hydrogen and its compounds ; depth resolution in the range of a single monolayer ; low detection limits (< 10^?6 monolayer or < 10^?14 g) for many elements and compounds.The capacity of this method is demonstrated using as examples the initial surface oxidation of metals and semiconductors and adsorption phenomena on clean metal surfaces. In some special cases additional information on the chemical composition of the uppermost monolayer can be obtained by the electron induced ion emission from the surface.     

Sputter depth profiling by secondary ion mass spectrometry coupled with sample current measurements

Ion-induced secondary electron emission determined via sample current measurements (SCM) was employed as a useful adjunct to conventional secondary ion mass spectrometry (SIMS). This paper reports on the results of 3-6 keV O₂⁺ SIMS-SCM sputter depth profiling through CrN/AlN multilayer coatings on nickel alloy, titanium dioxide films deposited on stainless steel, and corrosion layers formed onto surface of magnesium alloy after long-term interaction with an ionic liquid. For Au/AlNO/Ta films on silicon, in addition to SIMS-SCM profiles, the signal of mass-energy separated backscattered Ne⁺ ions was monitored as a function of the depth sputtered as well. The results presented here indicate that secondary electron yields are less affected by “matrix effect” than secondary ion yields, and at the same time, more sensitive to work function variations and surface charging effects. SCM depth profiling, with suppression of “the crater effect” by electronic gating of the registration system is capable of monitoring interfaces in the multilayer structure, particularly, metal-dielectric boundaries. In contrast to SIMS, SCM data are not influenced by the angle and energy windows of an analyser. However, the sample current measurements provide lower dynamic range of the signal registration than SIMS, and SCM is applicable only to the structures with different secondary electron emission properties and/or different conductivity of the layers. To increase the efficiency, SCM should be accompanied by SIMS measurements or predetermined by proper calibration using other elemental-sensitive techniques.     

Particle‐Arrayed Silver Mesocubes Synthesized via Reducing Silver Oxide Mesocrystals for Surface‐Enhanced Raman Spectroscopy

In this study, we demonstrate an easy particle‐mediated protocol using the specific structure of mesocrystal Ag₂O sacrificial templates to synthesize highly rough‐cubic Ag mesocages. To the best of our knowledge, the mesocrystal particles are reported for the first time as sacrificial templates for synthesizing metal particles. The obtained Ag mesocages show high surface‐enhanced Raman scattering (SERS) sensitivity because of the highly rough topography formed by arrays of uniform individual Ag nanoparticles. Abundant “hot spots” with greatly enhanced local electromagnetic field are promoted densely on the mesocage surface by the plenty of deep and narrow gaps and the hollow structure. The single‐particle SERS signal generated by the Ag mesocage has an enhancement factor of approximately 10⁹, which is approximately four times higher than the Ag mesocage synthesized using single‐crystal Ag₂O particle as a template. Meanwhile, this signal displays a linear dependence on the detected analyte concentration, sensitively down to 1.0 × 10^?12 m .     

Empirical evaluation of metal deposition for the analysis of organic compounds with static secondary ion mass spectrometry (S-SIMS)

Metal-assisted (MetA) SIMS using the deposition of a thin Au or Ag layer on non-conducting samples prior to analysis has been advocated as a means to improve the secondary ion (S.I.) yields of organic analytes. This study focuses on the influence of time and temperature on the yield enhancement in MetA-SIMS using thick layers of poly(vinylbutyral-co-vinylalcohol-co-vinylacetate) (PVB) containing dihydroxybenzophenone (DHBPh) or a cationic carbocyanine dye (CBC) and spin-coated layers of the cationic dye on Si. Pristine samples as well as Au- and Ag-coated ones were kept between −8 °C and 80 °C and analysed with S-SIMS at intervals of a few days over a period of 1 month. The yield enhancement was found to depend strongly on the kind of evaporated metal, the storage temperature and time between coating and analysis.     

Enhancement of oxygen surface kinetics of SrTiO3 by alkaline earth metal oxides

The kinetics of oxygen incorporation into semiconducting metal oxides such as strontium titanate are of particular interest for an application as a fast resistive-type oxygen sensor operating at high temperatures (T > 600 °C), e.g. in automotive exhaust gas monitoring.Based on a frequency-domain analysis of the response signal (resistance R) obtained from an electrically contacted sample exposed to a modulated oxygen partial pressure pO₂ in a fast kinetic measurement setup, the surface transfer controlled response behaviour of undoped and Fe-doped SrTiO₃ single crystals with thicknesses in the order of d = 45–125 μm was investigated with regard to the effect of thin PVD layers with alkaline earth (Ca, Sr, Ba) metal oxide compounds.The results of this electrical characterisation are compared with results obtained from ¹⁸O tracer exchange experiments and subsequent depth profile analysis by secondary ion mass spectrometry (SIMS). Both the electrical measurements and the ¹⁸O self-diffusion experiments revealed an enhancement of oxygen surface exchange kinetics in the case of all three alkaline earth metal oxides investigated.     

Empirical formula for the calculation of secondary ion yields from oxidized metal surfaces and metal oxides

By evaluation of static SIMS data obtained from 15 oxidized metal surfaces in a UHV mass spectrometer, a formula is established which allows the absolute yields of the secondary ions MeO^±n (n = 0, 1, 2, …) to be calculated. The formula contains several empirical parameters, the most important of which is determined by the chemical valency of the metal atoms at the surface. The dependence of the secondary ion yield on the formal valence of the metal in the emitted fragment ion is described by a Gaussian curve. Results from seveal metal oxides obtained by other groups have also been used for testing this dependence.     

UD3 formation on uranium: evidence for grain boundary precipitation

The formation of UD₃ on the surface of annealed uranium was induced at 320°C and 500?mbar pressure. The location of the deuteride (UD₃) precipitates with respect to metal grain boundaries at the sample surface was studied by secondary ion mass spectrometry (SIMS) and focused ion beam (FIB) methods. Ion etching was used to remove the passive oxide layer on the sample surface and reveal the underlying structure of the metal grains. There is strong evidence for the formation of UD₃ phases along the metal grain boundaries at the uranium surface.     

Separation followed by direct SERS detection of explosives on a novel black silicon multifunctional nanostructured surface prepared in a microfluidic channel

The article describes the multifunctionality of a novel black silicon (BS) nanostructured surface covered with a thin layer of noble metal prepared in the a microfluidic channel. It is focused on the separation properties of the BS substrate with direct detection of the separated analytes utilizing surface enhanced Raman spectroscopy. The same BS substrate is providing the stationary phase and a surface enhancement of the Raman signal that has been measured previously to be around 10. As tested molecules, the common components of explosives 1,3 dinitrobenzene and 2,4 dinitrotoluene were used. The separation of selected molecules was achieved with the dried toluene as a mobile phase in a 25 micrometers deep, 5 mm wide, and 4 cm long microfluidic channel during the 2 min. Copyright © 2012 John Wiley & Sons, Ltd.     

The use of low energy sims to study the chemisorption of CO on Ni(100) and polycrystalline nickel

Adsorption of CO on Ni(100) has been investigated using secondary ion mass spectrometry (SIMS) and Auger electron spectroscopy at 175 and 295 K. Interaction with polycrystalline nickel was examined at 295, 325 and 365 K. All the secondary ions, Ni⁺, Ni₂⁺, NiCO⁺ and Ni₂CO⁺ show large increases in intensity as CO is adsorbed but there is no simple correlation of the secondary ion species with the sequence of linear and bridge-bonded CO species expected from electron energy loss spectroscopy. Adsorption of CO at 175 K on a hydrogen saturated Ni(100) surface, which is thought to permit only bridge-bonded adsorbed CO, does not result in any enhancement of Ni₂CO⁺. The extent of increases in secondary ion yields after CO adsorption on the nickel surfaces are primarily related to the variations in the heat of adsorption as a function of surface coverage. The presence of more weakly-held species is important in enhancing secondary ion yields.     

Combined XPS and SIMS study of amino acid overlayers

Factors influencing the SIMS fragmentation patterns are studied for three simple amino acids-glycine, α-alanine, and serine-deposited onto Ag substrates from aqueous solution. Secondary ion emissions are measured for 1 keV Ar⁺ ions incident at 70° from sample normal as a function of substrate preparation and solution concentration. Studies by XPS and X-ray induced AES prior to SIMS analysis show that the amino acids adsorb in a film on the Ag surface and that the film thickness increases with solution concentration. In addition, considerable amounts of amino acid can be deposited on the surface from a water film retained during extraction from a concentrated solution. On acid etched samples, positive ion fragments of mass AgM, Ag(M ? 45), Ag, M + 1, and M ? 45 are observed, where M is the molecular, weight of the parent amino acid. With the exception of the (M + 1)⁺ fragment, these peak intensities behaved similarly for the different surface concentrations. When the adsorbed film grows too thick, the positive molecular ion emissions drop considerably; this substantiates the need for proximity between the Ag substrate and the amino acid molecule.     

Grafting onto poly(ethylene terephthalate) driven by 172 nm UV light

The reactivity of the surface of poly(ethylene terephthalate) (PET) film under 172 nm UV irradiation (xenon excimer lamp) towards nitrogen-borne 1-octene, n-nonane and heptafluorodecene vapor was investigated. Materials receiving from 0 to 24 J/cm² of UV were examined by X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectroscopy (ToF/SIMS), water and mineral oil contact angle measurement and atomic force microscopy (AFM). A uniform nanoscale layer developed on PET surface attributed to the grafting reaction between photolytically-produced polymer radicals and vapor phase molecules.     

Induced SERS activity in Ag@SiO2/Ag core‐shell nanosphere arrays with tunable interior insulator

In this work, we demonstrated a bottom‐up growth of Ag@SiO₂/Ag core‐shell nanosphere arrays with tunable SiO₂ interior insulator and the optimized surface‐enhanced Raman scattering (SERS) substrate based on a nanostructure performed with both high sensitivity and large‐area uniformity. Their morphological, structural, and optical properties were characterized, and the induced SERS activities were investigated theoretically by the FDTD simulation and experimentally using analyte molecules. An ultrathin SiO₂ shell with tunable thickness can be synthesized pinhole‐free by a chemical vapor deposition, working as an interior insulator between the Ag core and Ag out‐layer coating. A detection limit as low as 10⁻¹² M and an enhancement factor up to 3 × 10⁷ were obtained, and the SERS signal was highly reproducible with small standard deviation. The method opened up a way to create a new class of SERS activity sensor with high‐density ‘hot spots’, and it may play an important role in device design and the corresponding biological and food safety monitoring applications. Copyright © 2016 John Wiley & Sons, Ltd.     

Ag-Cu离子注入玻璃后不同气氛退火的光吸收研究

采用MEVVA源（metal vapor vacuum arc ion source）引出的强束流脉冲Ag,Cu离子先后注入到SiO₂玻璃，x射线光电子能谱仪（XPS）分析显示Ag，Cu大多仍为金属态，有部分氧化态Cu存在.透射电镜观察分析和光学吸收谱都表明在衬底中形成了纳米合金颗粒.结合有效媒质理论，得到模拟的光学吸收谱，与实验结果基本符合，较好地验证了以上结论.样品退火后颗粒发生分解，分解的颗粒在氧化气氛下被氧化，且有部分向样品表面蒸发；在还原气氛下氧化态元素被还原并成核生长.故 关键词： 离子注入 纳米颗粒 退火 光学吸收率     

Effect of Pt and Ti on Ni/Ag/(Pt or Ti)/Au p-ohmic contacts of GaN based flip-chip LEDs

In this paper, we report the dependence of Ni/Ag/diffusion barrier (D.B)/Au p-ohmic contact on Pt^D.B and Ti^D.B for GaN based flip-chip light emitting diodes (FC LEDs). It is shown that D.B metals have strongly influenced on the reflectance and contact resistivity of contacts. We present these results are caused by the variation of the morphology and atomic distribution due to D.Bs. The roles of Pt^D.B and Ti^D.B on Ni/Ag/D.B/Au p-GaN ohmic contacts are analyzed using the confocal laser scanning microscopy (CLSM) measurement and the secondary ion mass spectroscopy (SIMS) profiles in details.     

High reflective p-GaN/Ni/Ag/Ti/Au Ohmic contacts for flip-chip light-emitting diode (FCLED) applications

The fabrication of high reflective Ni/Ag/(Ti, Mo)/Au Ohmic contacts for flip-chip light-emitting diode (FCLED) are proposed and considered, Ni/Ag/Au Ohmic contacts are also fabricated to compare their resulting reflectivities. From secondary ion mass spectrometry (SIMS) depth profiles, it indicates that the Au in-diffusion occurs in Ni/Ag/Au contacts after annealing. It is considered that Au in-diffusion, which is intermixed with Ag, Ni and GaN in Ni/Ag/Au contacts after annealing, is responsible for the resulting low reflectance (63% at the wavelength of 465 nm). To avoid Au in-diffusion and enhance the reflectivity, a diffusion barrier metal (Ti or Mo) between Ni/Ag and Au is fabricated and examined. It is demonstrated and found that an insertion of diffusion barrier metal of Ti enables to block Au diffusion effectively and also improve the reflectivity significantly, up to 93%.     

Controlling SERS intensity by tuning the size and height of a silver nanoparticle array

It is demonstrated that the surface-enhanced Raman scattering (SERS) intensity of R6G molecules adsorbed on a Ag nanoparticle array can be controlled by tuning the size and height of the nanoparticles. A firm Ag nanoparticle array was fabricated on glass substrate by using nanosphere lithography (NSL) combined with reactive ion etching (RIE). Different sizes of Ag nanoparticles were fabricated with seed polystyrene nanospheres ranging from 430 nm to 820 nm in diameter. By depositing different thicknesses of Ag film and lifting off nanospheres from the surface of the substrate, the height of the Ag nanoparticles can be tuned. It is observed that the SERS enhancement factor will increase when the size of the Ag nanoparticles decreases and the deposition thickness of the Ag film increases. An enhancement factor as high as 2×10⁶ can be achieved when the size of the polystyrene nanospheres is 430 nm in diameter and the height of the Ag nanoparticles is 96 nm. By using a confocal Raman mapping technique, we also demonstrate that the intensity of Raman scattering is enhanced due to the local surface plasmon resonance (LSPR) occurring in the Ag nanoparticle array.     

Photoexcitation of electron-hole pairs during SIMS

During analysis with SIMS (secondary ion mass spectroscopy) a HeNe laser beam was focussed on the sample surface. While sputtering Si with oxygen ions, the laser irradiation produced a strong increase of the target current and the SIMS intensities as well. This was found for lightly p-doped Si only, whereas no effect was observed for highly p-doped or n-doped Si. To explain this we assume that a depletion layer exists under the surface oxide layer and free charged carriers are created therein by laser excitation. The laser induced effects observed in the SIMS intensity or the target current can be used for measuring the profile of an ion beam or for measuring the alignment of an ion beam at a laser marked target. In addition, laser irradiation combined with SIMS allows one to measure qualitatively both the profile of the doping impurity and its electrically active part.     

Quantitative fundamental SIMS studies using O implant standards

The use of dilute ‘minor-isotope’ ¹⁸O implant reference standards for quantification of surface oxygen levels during steady-state SIMS depth profiling is demonstrated. Some results of two types of quantitative fundamental SIMS studies with oxygen (¹⁶O) primary ion bombardment and/or oxygen flooding (O₂ gas with natural isotopic abundance) are presented: (1) Determination of elemental useful ion yields, UY(X^±), and sample sputter yields, Y, as a function of the oxygen fraction c_O measured in the total flux emitted from the sputtered surface. Examples include new results for positive secondary ion emission of several elements (X = B, C, O, Al, Si, Cu, Ga, Ge, Cs) from variably oxidized SiC or Ge surfaces. (2) The dependence of exponential decay lengths λ(Au^±) in sputter depth profiles of gold overlayers on silicon on the amount of oxygen present at the sputtered silicon surface. The latter study elucidates the (element-specific) effects of oxygen-induced surface segregation artifacts for sputter depth profiling through metal overlayers into silicon substrates.