Secondary ion quadrupole mass spectrometer for depth profiling--design and performance evaluation

A quadrupole-based secondary ion mass spectrometer designed for depth profiling is described which combines ultrahigh vacuum construction with high sputtering rate, detection sensitivity, depth resolution, mass spectral purity, and abundance sensitivity. Impurities such as B and Al implanted in Si can be profiled to levels below one part per million atomic (ppma), at a depth resolution equal to that obtained by commercial ion microprobes. The primary beam consists of 5-keV, mass-analyzed (40)Ar(+) ions, focused to about 70 microm in diameter. Its high current density (>25mA/cm(2)) permits adequate beam rastering and electronic signal-gating to optimize depth resolution. A secondary ion extraction lens and spherical energy filter are responsible for achieving abundance sensitivities of five to six orders of magnitude on the low mass side of a matrix peak. The ultrahigh vacuum environment of the sample dramatically reduces molecular peaks containing H, C, and O, allowing even hydrogen to be profiled to concentrations below 10 ppma. Because large amounts of data are generated by multi-element depth profiling, means for automated instrument control and data acquisition have been developed.     

飞行时间二次离子质谱在生物材料和生命科学中的应用(下)

随着仪器性能的不断提高,飞行时间二次离子质谱(TOF-SIMS)在材料表面化学分析中起着越来越重要的作用。TOF-SIMS的主要测试功能包括表面质谱、化学成像及深度剖析,本工作对TOF-SIMS的化学成像及深度剖析2种功能在生物材料和生命科学中的应用做了简单综述,重点介绍了TOF-SIMS成像技术在生物芯片制备工艺中的应用和TOF-SIMS成像和深度剖析技术对生物分子在细胞和生物体组织上空间分布的表征方法;另外,对生物样品的低温制备方法,样品表面添加基质以增强信号强度的实验手段,使用团簇一次离子源提高分子二次离子产额和利用对样品损伤小的C60离子源为轰击源做深度剖析等实验做了简单的介绍;最后,对TOF-SIMS在生物生命材料领域的应用做了展望。     

Influence of ion source configuration and its operation parameters on the target sputtering and implantation process

In the work, investigation of the features and operation regimes of sputter enhanced ion-plasma source are presented. The source is based on the target sputtering with the dense plasma formed in the crossed electric and magnetic fields. It allows operation with noble or reactive gases at low pressure discharge regimes, and, the resulting ion beam is the mixture of ions from the working gas and sputtering target. Any conductive material, such as metals, alloys, or compounds, can be used as the sputtering target. Effectiveness of target sputtering process with the plasma was investigated dependently on the gun geometry, plasma parameters, and the target bias voltage. With the applied accelerating voltage from 0 to 20 kV, the source can be operated in regimes of thin film deposition, ion-beam mixing, and ion implantation. Multi-component ion beam implantation was applied to α-Fe, which leads to the surface hardness increasing from 2 GPa in the initial condition up to 3.5 GPa in case of combined N(2)-C implantation. Projected range of the implanted elements is up to 20 nm with the implantation energy 20 keV that was obtained with XPS depth profiling.     

Developments in molecular SIMS depth profiling and 3D imaging of biological systems using polyatomic primary ions

In principle mass spectral imaging has enormous potential for discovery applications in biology. The chemical specificity of mass spectrometry combined with spatial analysis capabilities of liquid metal cluster beams and the high yields of polyatomic ion beams should present unprecedented ability to spatially locate molecular chemistry in the 100 nm range. However, although metal cluster ion beams have greatly increased yields in the m/z range up to 1000, they still have to be operated under the static limit and even in most favorable cases maximum yields for molecular species from 1 µm pixels are frequently below 20 counts. However, some very impressive molecular imaging analysis has been accomplished under these conditions. Nevertheless although molecular ions of lipids have been detected and correlation with biology is obtained, signal levels are such that lateral resolution must be sacrificed to provide a sufficient signal to image. To obtain useful spatial resolution detection below 1 µm is almost impossible. Too few ions are generated! The review shows that the application of polyatomic primary ions with their low damage cross‐sections offers hope of a new approach to molecular SIMS imaging by accessing voxels rather than pixels to thereby increase the dynamic signal range in 2D imaging and to extend the analysis to depth profiling and 3D imaging. Recent data on cells and tissue analysis suggest that there is, in consequence, the prospect that a wider chemistry might be accessible within a sub‐micron area and as a function of depth. However, these advances are compromised by the pulsed nature of current ToF‐SIMS instruments. The duty cycle is very low and results in excessive analysis times, and maximum mass resolution is incompatible with maximum spatial resolution. New instrumental directions are described that enable a dc primary beam to be used that promises to be able to take full advantage of all the capabilities of the polyatomic ion beam. Some new data are presented that suggest that the aspirations for these new instruments will be realized. However, although prospects are good, the review highlights the continuing challenges presented by the low ionization efficiency and the complications that arise from matrix effects. © 2010 Wiley Periodicals, Inc., Mass Spec Rev 30:142–174, 2011     

Elemental and molecular imaging of human hair using secondary ion mass spectrometry.

Secondary ion mass spectrometry (SIMS) is used to image the spatial distribution of elemental and molecular species on the surface and in cross sections of doped human hair using a magnetic sector SIMS instrument operated as an ion microprobe. Analysis of electrically insulating, non-planar hair samples requires one of two different methods of charge compensation to be used depending on the polarity of the sputtered secondary ions. For detection of positive secondary ions, the hair is imaged using a approximately 0.5 micron diameter, 19.5 keV impact energy, O- microbeam with no auxiliary electron bombardment. For detection of negative secondary ions, a approximately 0.2 micron diameter, 14.5 keV impact energy Cs+ microbeam is used in conjunction with normal incidence, low-energy electron bombardment. Both of these methods allow submicrometer spatial resolution elemental and molecular secondary ion images to be obtained from hair samples without metallic coating of the sample surface prior to analysis. Several examples are presented that reflect potential application areas for these analytical methods.     

3D correlative morphological and elemental characterization of materials at the deep submicrometre scale

This paper shows how X‐ray computed nanotomography (CNT) can be correlated with focused ion beam time‐of‐flight secondary ion mass spectrometry (FIB‐TOF‐SIMS) tomography on the same sample to investigate both the morphological and elemental structure. This methodology is applicable to relatively large specimens with dimensions of several tens of microns whilst maintaining a high spatial resolution of the order of 100 nm. However, combining X‐ray CNT and FIB‐TOF‐SIMS tomography requires innovative sample preparation protocols to allow both experiments to be conducted on exactly the same sample without chemically or structurally modifying the sample between measurements. Moreover, dedicated algorithms have been developed for effective data fusion that is biased with nine degrees of freedom. This methodology has been tested using a porous and heterogeneous solid oxide fuel cell (SOFC) that has features varying in size by three orders of magnitude – from hundreds of nanometre large pores and grains to tens of micron wide functional layers.     

二次离子质谱(SIMS)分析技术及应用进展

二次离子质谱 ( SIMS)比其他表面微区分析方法更灵敏。由于应用了中性原子、液态金属离子、多原子离子和激光一次束 ,后电离技术 ,离子反射型飞行时间质量分析器 ,离子延迟探测技术和计算机图像处理技术等 ,使得新型的 SIMS的一次束能量提高到 Me V,束斑至亚μm,质量分辨率达到 1 5 0 0 0 ,横向和纵向分辨率小于 0 .5μm和 5 nm,探测限为 ng/g,能给出二维和三维图像信息。 SIMS能用于矿物、核物质、陨石和宇宙物质的半定量元素含量和同位素丰度测定 ,能鉴定出高挥发性、热不稳定性的生物大分子 ,能进行横向和纵向剖析 ,能进行单颗粒物、团蔟、聚合物、微电子晶体、生物芯片、生物细胞同位素标记和单核苷酸多肽性分型 ( SNP)测定 ,能观测出含有 2 0 0 0碱基对的脱氧核糖核酸 ( DNA)的准分子离子峰。以SIMS在同位素、颗粒物、大分子、生物等研究领域的应用为重点 ,结合实例 ,对 SIMS仪器和技术进展进行了综述     

深亚微米IC超浅结的SIMS表征

Secondary ion mass spectrometry (SIMS) is a standard technique for characterization of dopant distribution in semiconductor industry. In the ultra-shallow junction (USJ) application, the interested depth scale was extended into the surface transient area of SIMS. There is several improved approach reviewed in this paper that can meet the requirements for the USJ characterization. Sputtering with a low energy primary ion beam incident at a large angle respect to the simple surface normal can effectively minimize the depth of the surface transient area, as well as the length of the profile tail. Oxygen leak can reduce the transient ion yield change, but induces lower depth resolution. Quadrupole SIMS can be used in B profile. As and P profiles, however, need magnetic analyzer with higher mass resolution.     

Objective comparison of scanning ion and scanning electron microscope images

Common and different aspects of scanning electron microscope (SEM) and scanning ion microscope (SIM) images are discussed from a viewpoint of interaction between ion or electron beams and specimens. The SIM images [mostly using 30 keV Ga focused ion beam (FIB)] are sensitive to the sample surface as well as to low-voltage SEM images. Reasons for the SIM images as follows: (1) no backscattered-electron excitation; (2) low yields of backscattered ions; and (3) short ion ranges of 20–40nm, being of the same order of escape depth of secondary electrons (SE) [=(3–5) times the SE mean free path]. Beam charging, channeling, contamination, and surface sputtering are also commented upon.     

NanoSIMS imaging of Bacillus spores sectioned by focused ion beam

Preparation and sectioning of bacterial spores by focused ion beam and subsequent high resolution secondary ion mass spectrometry analytical imaging is demonstrated. Scanning transmission electron microscopy mode imaging in a scanning electron microscope is used to show that the internal structure of the bacterial spore can be preserved during focused ion beam sectioning and can be imaged without contrast staining. Ion images of the sections show that the internal elemental distributions of the sectioned spores are preserved. A rapid focused ion beam top‐sectioning method is demonstrated to yield comparable ion images without the need for sample trenching and section lift‐out. The lift‐out and thinning method enable correlated transmission electron microscopy and high resolution secondary ion mass spectrometry analyses. The top‐cutting method is preferable if only secondary ion mass spectrometry analyses are performed because this method is faster and yields more sample material for analysis; depth of useful sample material is ～300 nm for top‐cut sections versus ～100 nm for electron‐transparent sections.     

The assessment of microscopic charging effects induced by focused electron and ion beam irradiation of dielectrics

Energetic beams of electrons and ions are widely used to probe the microscopic properties of materials. Irradiation with charged beams in scanning electron microscopes (SEM) and focused ion beam (FIB) systems may result in the trapping of charge at irradiation induced or pre-existing defects within the implanted microvolume of the dielectric material. The significant perturbing influence on dielectric materials of both electron and (Ga(+)) ion beam irradiation is assessed using scanning probe microscopy (SPM) techniques. Kelvin Probe Microscopy (KPM) is an advanced SPM technique in which long-range Coulomb forces between a conductive atomic force probe and the silicon dioxide specimen enable the potential at the specimen surface to be characterized with high spatial resolution. KPM reveals characteristic significant localized potentials in both electron and ion implanted dielectrics. The potentials are observed despite charge mitigation strategies including prior coating of the dielectric specimen with a layer of thin grounded conductive material. Both electron- and ion-induced charging effects are influenced by a delicate balance of a number of different dynamic processes including charge-trapping and secondary electron emission. In the case of ion beam induced charging, the additional influence of ion implantation and nonstoichiometric sputtering from compounds is also important. The presence of a localized potential will result in the electromigration of mobile charged defect species within the irradiated volume of the dielectric specimen. This electromigration may result in local modification of the chemical composition of the irradiated dielectric. The implications of charging induced effects must be considered during the microanalysis and processing of dielectric materials using electron and ion beam techniques.     

DESIGN AND PERFORMANCE OF TWO ORTHOGONAL EXTRACTION TIME-OF-FLIGHT SECONDARY ION MASS SPECTROMETERS FOR FOCUSED ION BEAM INSTRUMENTS

The design and performance of two orthogonal extraction time-of-flight mass spectrometers are reported that were adapted to existing focused ion beam microscopes for secondary ion mass spectrometry. The performances of these designs were compared to that of a prototype previously described by our group. The differences include newly designed transfer ion optics and in the use of a larger microscope chamber. The two new prototypes allow a mass resolving power of either 600 Th/Th (compact design) or 3000 Th/Th (high resolution design) while simultaneously achieving a lateral spatial resolution of less than 50 nm. The spectrometers and their performance (effective ion yield, mass resolving power, lateral, and depth resolution) are described and compared. Additionally, example applications are presented with multivariate statistical methods to visualize the data sets. Both time-of-flight mass analyzers use orthogonal extraction which avoids the need to pulse the primary ion beam, and the of use monoisotopic gallium to preserve the mass resolution. The goal of the design was a cost-effective accessory to augment typical focused ion beam-scanning electron microscopy applications as an alternative to the cost of a dedicated secondary ion mass spectrometer. The modified instrument allows excellent non destructive imaging and easy sample access, and benefits from the presence of complementary non destructive analytical and imaging techniques that exploit the presence of an electron microscope.     

Simulation of ion imaging: sputtering, contrast, noise

Scanning ion microscopy has received a boost in the last decade, thanks to the development of novel ion sources employing light ions, like He⁺, or ions from inert gases, like Ne⁺ and Ar⁺. Scanning ion images, however, might not be as easy to interpret as SEM micrographs. The contrast mechanisms are different, and there is always a certain degree of sample sputtering. The latter effect, on the one hand, prevents assessing the resolution on the basis of a single image, and, on the other hand, limits the probing time and thus the signal-to-noise ratio that can be obtained. In order to fully simulate what happens when energetic ions impact on a sample, a Monte Carlo approach is often used. In this paper, a different approach is proposed. The contrast is simulated using curves of secondary electron yields versus the incidence angle of the beam, while the surface modification prediction is based on similar curves for the sputtering yield. Finally, Poisson noise from primary ions and secondary electrons is added to the image. It is shown that the evaluation of an ion imaging tool cannot be condensed in a single number, like the spot size or the edge steepness, but must be based on a more complex analysis taking into account at least three parameters: sputtering, contrast and signal-to-noise ratio. It is also pointed out that noise contributions from the detector cannot be neglected for they can actually be the limiting factor in imaging with focused ion beams. While providing already good agreement with experimental data in some imaging aspects, the proposed approach is highly modular. Further effects, like edge enhancement and detection, can be added separately.     

Electron beam depth profiling in semiconductors

A technique for depth profiling of semiconductors is described based upon the measurement of induced junction currents as a function of beam energy. Using the known energy loss relation and electron hole pair generation rate it is possible to infer quantitative information about the semiconductor structures as a function of depth between ～0·02 and ～5 μm for silicon. Examples of the application of the technique to implanted and electron beam pulse annealed silicon and to a JFET transistor are described. Calculations of diffusion length limits, junction depths, poly-silicon thickness, epitaxial layer thickness and surface recombination velocity are discussed.     

SIMS instrumentation and imaging techniques

Secondary ion mass spectrometry (SIMS) has evolved as a technique for characterizing solids and surfaces which is distinguished by high sensitivity and its applicability to all elements. It can be used for surface research, in-depth concentration profiling, isotopic work, and the identification of compounds. Combined with imaging techniques, these applications can be made with high spatial resolution. In this respect, ion probe microanalysis complements electron probe microanalysis (XRMA and scanning AES).     

一种利用变通的离子散射谱测量进行浓度定标的二次离子质谱深度剖析定量方法

本工作利用一台不作任何较大改动的ＣＡＭＥＣＡ－ＩＭＳ－３ｆ扇形磁铁型二次离子质谱仪对传统的离子散射谱（ＩＳＳ）分析技术进行了适当的变通，并对二次离子质谱分析（ＳＩＭＳ）的深度剖析谱进行了浓度定标。在保留ＳＩＭＳ分析高灵敏度、高深度分辨率的前提下，实现了对块体样品中的掺杂元素的ＳＩＭＳ定量深度剖析。通过与离子注入机标称的注入剂量及卢瑟福背散射的定量分析结果相比较，本方法的定量准确度一般好于１０％。而精确度则好于５％。本文对该方法的背景、基本原理、实验方法，准确度及优缺点等进行了较详细的讨论。     

Silver deposition on freeze-dried cells allows subcellular localization of cholesterol with imaging TOF-SIMS

Imaging time‐of‐flight secondary ion mass spectrometry (TOF‐SIMS) was used for characterization and subcellular localization of organic ions in leucocytes adhering to glass surfaces. The cells were fixed by freeze drying in 0.15 m ammonium formate buffer at pH 7.2–7.4. The freeze‐dried cells were sputter‐coated with silver, and the silver surface was analysed with imaging TOF‐SIMS. TOF‐SIMS spectra were recorded by scanning the primary ion beam over the analysis area and acquiring positive mass spectra of the ions leaving the surface. The relative brightness of each pixel within the analysis area reflects the signal intensity of a selected ion in that pixel. Data were collected separately at high mass resolution m/Δm > 7000 and at high lateral resolution (= 0.5 µm). The images were analysed by principal component analysis (PCA). The glass‐adhering cells showed a well defined attachment area with a diameter of up to 20 µm, and an equally well defined cell body, containing the nucleus, with a diameter of 8–10 µm. On the raw data images, the obtained cholesterol distributions were consistent with a higher cholesterol content of the cell membrane in the attachment area than in the cell body. Using PCA analysis, silver‐cationized molecular cholesterol was found localized mainly in the attachment area of the cells. Cholesterol was also seen at higher concentration in circular spots of ≤ 1 µm in diameter, probably representing caveolae.     

深度分辨率对多层薄膜样品SIMS分析的影响

组分元素和杂质在多层薄膜样品中深度分布的ＳＩＭＳ剖析结果总是编离其真实的分布情况，这是由一次离子溅射样品时的物理过程以及溅射坑底的不平整所造成的。轰击离子在样吕内所引起的混合效应，以及坑底的不平整导致了某一时刻的二次离子来自样品中的不同深度。因此，为了提高ＳＩＭＳ分析的深度分辨率，必须注意克服这两种影响因素。     

Design and performance of a combined secondary ion mass spectrometry-scanning probe microscopy instrument for high sensitivity and high-resolution elemental three-dimensional analysis

State-of-the-art secondary ion mass spectrometry (SIMS) instruments allow producing 3D chemical mappings with excellent sensitivity and spatial resolution. Several important artifacts however arise from the fact that SIMS 3D mapping does not take into account the surface topography of the sample. In order to correct these artifacts, we have integrated a specially developed scanning probe microscopy (SPM) system into a commercial Cameca NanoSIMS 50 instrument. This new SPM module, which was designed as a DN200CF flange-mounted bolt-on accessory, includes a new high-precision sample stage, a scanner with a range of 100 μm in x and y direction, and a dedicated SPM head which can be operated in the atomic force microscopy (AFM) and Kelvin probe force microscopy modes. Topographical information gained from AFM measurements taken before, during, and after SIMS analysis as well as the SIMS data are automatically compiled into an accurate 3D reconstruction using the software program "SARINA," which was developed for this first combined SIMS-SPM instrument. The achievable lateral resolutions are 6 nm in the SPM mode and 45 nm in the SIMS mode. Elemental 3D images obtained with our integrated SIMS-SPM instrument on Al/Cu and polystyrene/poly(methyl methacrylate) samples demonstrate the advantages of the combined SIMS-SPM approach.     

Specimen coating for high resolution scanning electron microscopy

Thin conducting films, produced by evaporation or soft vacuum sputtering generally show cracks and grain formation, when examined under high resolution scanning electron microscopy (SEM). These artefacts can obscure surface features of coated specimens or cause confusion in the interpretation of micrographs. No such structures have been observed in films produced by ion beam deposition. Ion beam deposition equipment is described in which a cold cathode saddle field ion source, operating at low pressure (15mPa), produces a 2 mm diameter beam of energetic ions (5 keV) and neutrals. With the beam directed onto a target at 30° to glancing incidence, the sputtered material coats the specimens, which are held in a planetary system for good coverage. Conditions favouring fine grain growth are a high nucleation density and low energy transfer to the substrate by thermal conduction or radiation or by particle or photon radiation. These conditions are satisfied by ion beam deposition but evidently not by evaporation or soft vacuum sputtering. With the specimen stationary, sharp shadowing is obtained because the target acts almost as a point source, because of the small diameter of the beam and because there is little scatter at the operating pressure.