一般財団法人材料科学技術振興財団　MST List of Products and Services

When measuring the distribution of alkali metals in SiO2 under general analytical conditions, it is known that changes occur in the depth profile concentration distribution due to influences such as the electric field caused by the measurement. In MST, by cooling the sample during SIMS measurements, we suppress changes in the concentration distribution of alkali metals and evaluate the concentration distribution with higher accuracy.

The Ion Polish (IP) method allows for the production of cross-sections with minimal processing damage (such as delamination at interfaces, step differences due to hardness variations, and scratches from polishing) that were problematic in mechanical polishing methods. The positional accuracy of processing is also improved, enabling the creation of wide-area cross-sections that include small features. Due to the minimal damage to the crystals, clean crystal patterns can be obtained. Additionally, since there is no influence from mechanical stress, detailed evaluation of the cross-sectional structure of specific areas can be conducted through AES analysis, SEM observation, and EDX analysis while faithfully preserving the internal structure.

The miniaturization of devices has increased the need for evaluating the depth distribution of impurities in extremely shallow regions. To conduct an accurate assessment, SIMS analysis using a primary ion beam with lower energy (below 1 keV) is required. Figure 1 shows examples of measurements of Si wafers implanted with BF2+ 1 keV, P+ 1 keV, and As+ 1 keV, using a primary ion beam energy of 250 eV to 300 eV.

In semiconductor device manufacturing, it is necessary to investigate what causes thin deposits that lead to defects in order to examine contamination processes. An analysis was conducted using TOF-SIMS on the deposits for which carbon was detected by EDX and quantified by XPS. When compared to the gloves used for standard samples in each process, similar trends were observed with gloves A and B. Furthermore, verification was performed by adhering the standard sample gloves to silicon wafers. As a result, it was found that they were similar to glove A. Adhering standard samples to silicon wafers for verification is an effective method.

The presence of silanol groups (Si-OH) on the surfaces of glass and wafers affects properties such as hydrophobicity and hydrophilicity. Therefore, it is likely to influence subsequent surface treatments, necessitating control. We will introduce a case where the quantification of silanol groups was performed using TOF-SIMS. To conduct the evaluation, calibration curves were created using several types of samples with different concentrations. In the measurement examples, the silanol groups on the surfaces of samples with different materials and conditions were compared. Measurement method: TOF-SIMS Product fields: LSI, memory, electronic components Analysis purpose: Composition evaluation and identification For more details, please download the materials or contact us.

We compared the states of the Si surface after HF treatment and after ozone treatment. In the positive ion spectrum, the peak intensity of Si was different. The weaker Si intensity after HF treatment is due to Si being metallic, while the stronger Si intensity after UV-ozone cleaning and in the As Received state is due to Si being oxide-based. From the negative ion spectrum, fragment ions reflecting the surface state were detected: SiF, SiH, and Six series after HF treatment, and SiO2 series after UV-ozone cleaning and in the As Received state.

For extremely thin films with a thickness of a few nanometers or less, such as natural oxide films on silicon wafers and silicon nitride thin films, we will measure the Si2p spectrum of the sample's surface. By performing waveform analysis on the obtained spectrum, we will determine the proportion of each bonding state and estimate the film thickness from this result and the average free path of photoelectrons (Equation 1).

In the method for preparing thin film samples for TEM observation using FIB, high-energy Ga ions (acceleration voltage of 30 kV) are used, resulting in the formation of a damage layer on the processed surface, which causes a deterioration in the image quality of the TEM. By performing processing at a lower acceleration (2 kV) than conventional methods, the damage layer can be reduced, leading to improved image quality. By reducing the damage on the FIB processed surface through low-acceleration FIB processing, high-quality and reliable data can be obtained in TEM image observation and EELS measurements.

By conducting sample pretreatment, transportation, and measurement under a high-purity inert gas atmosphere, it is possible to evaluate while suppressing surface oxidation and moisture adsorption. ■Examples of Application - Semiconductor electrode materials Evaluation of peeling surfaces can be conducted while minimizing the effects of secondary contamination and oxidation. - Organic EL materials Working in an inert gas atmosphere from the moment of opening prevents material degradation. - Battery materials such as Li If processing in a N2 atmosphere is not possible for materials like Li, treatment can be performed in an Ar atmosphere as an alternative.

We will introduce a case where the permeability of water (H2O) in a thin film with a thickness of less than 1 µm was evaluated by measuring the distribution of deuterium (D) in the film. When hydrogen (H) is originally present in the thin film, it is difficult to distinguish whether the hydrogen is due to the influence of water. Therefore, treatment with heavy water (D2O) was performed, and the distribution of the naturally occurring isotope deuterium was measured in the depth direction using SIMS. By examining the depth distribution of deuterium, it is possible to estimate how deep the water has penetrated.

Epoxy resin is widely used in electronic component applications such as printed circuit boards and IC encapsulants due to its excellent mechanical properties, chemical resistance, and electrical insulation. Data measured by TOF-SIMS was obtained regarding the reagents of bisphenols, which are commonly used as raw materials for epoxy resin. By comparing the sample measurement data with standard data at MST, it is possible to investigate the origin of the detected fragment ions and estimate the materials used in the epoxy resin.

Measurements can be performed in bulk state without the need for thinning processes like TEM (NBD: Nano Beam Diffraction). It has the high spatial resolution characteristic of SEM and relatively high strain sensitivity. Additionally, there is a possibility of detecting local lattice strain as tensor data.

There are various types of fluorine-based compounds. During the investigation of contamination sources, performing qualitative analysis of the types of fluorine compounds allows us to examine the processes that caused the contamination. Therefore, we conducted an analysis using surface-sensitive TOF-SIMS to determine what is adhering to areas with good water repellency. By utilizing the fact that the fragment patterns of the fluorine-based oils used in each process differ by type, we performed a fingerprint matching and found that a substance corresponding to the oil from process B was adhering.

We will extract small pieces from the wafer chip without breaking it and thin them down for high-resolution TEM observation and analysis. Furthermore, by cutting and preparing samples while leaving the areas to be analyzed, we will conduct TEM observation and analysis of the target areas from any desired direction and provide the data. Through advanced TEM sample preparation techniques, we will meet various observation, analysis, and evaluation needs.

For the two-component mixed epoxy resin, we investigated the curing temperature and the glass transition temperature (Tg), which is an indicator of heat resistance, using Differential Scanning Calorimetry (DSC). When measuring the resin before curing with DSC, it was confirmed that a rapid exothermic reaction began around 103°C (Figure 1). This was due to the polymerization (curing) of the resin occurring as a result of the temperature increase. Furthermore, after air cooling the cured resin to room temperature, a second DSC measurement was conducted, which confirmed a shift of the baseline towards the endothermic side due to the glass transition of the resin, with Tg being approximately 116°C (Figure 2).

Polyimide is a material that is used in various fields, including electronic components, due to its high heat resistance and excellent electrical insulation properties. Since surface modification can enhance adhesion to other materials, it is important to understand the state of the modified layer. In this study, TOF-SIMS measurements were conducted under sputtering conditions that minimize the degradation of organic components, allowing for the evaluation of polyimide components in the depth direction. Using GCIB (Ar cluster) for sputtering enables the measurement of the targeted organic components in the depth direction. *GCIB: Gas Cluster Ion Beam

On the surface of cell culture dishes, treatments are performed to convert hydrophobic plastic surfaces to hydrophilic ones in order to enhance cell adhesion. In this study, the surfaces of dishes that underwent hydrophilic treatment were evaluated using XPS and TOF-SIMS, revealing an increase in OH and CHO groups. By conducting quantitative evaluations with XPS and qualitative evaluations with TOF-SIMS, it is possible to capture how the surface has changed.

We will introduce a case where XRD measurements were conducted by narrowing the X-ray beam to Φ400μm, allowing us to obtain crystal information targeting a specific area rather than the entire surface. In the XRD measurement results of the printed circuit board sample, Cu and BaSO4 were detected at all measurement points (1) to (3), and a peak from Au was detected at the measurement point (1), which is the electrode. This aligns well with the results from XRF measurements. Thus, it is possible to identify crystal structures by targeting regions of several hundred micrometers with different compositions and crystallinities. Measurement methods: XRD, XRF Product fields: LSI, memory, electronic components Analysis purposes: Composition evaluation, identification, structural evaluation For more details, please download the materials or contact us.

SIMS analysis can be applied to various shapes of samples beyond wafers and substrates. In this case study, we will introduce an example of evaluating the distribution of impurities in a wire. The results of evaluating the impurity distribution in the depth direction from the side of the wire (Figure 2) indicate that the impurity profiles of H, O, F, S, and Cl vary in intensity with depth, suggesting that they are localized within the wire. The elemental mapping of the wire cross-section (Figure 3) confirmed the localization of impurities within the wire.

Typically, SIMS measurements are conducted using chips with a flat surface of a few millimeters in size, but analysis can also be performed on small chips or samples with special shapes, typically less than 1 mm in size, by applying a fixed pre-treatment. Some samples that require investigation of trace components may have shapes that are not suitable for analysis under normal conditions, such as tiny chips or wire-like samples (Figure 1). In such cases, analysis is performed after fixation (Figure 2). Additionally, analysis may be possible for cross-sections, side surfaces, or samples with special shapes by applying pre-treatment.

TOF-SIMS has the characteristics of simultaneously evaluating organic and inorganic materials, being capable of analyzing small areas with high sensitivity at the very surface, and allowing evaluation while still in the form of 300mm wafers, making it effective for residue investigations during cleaning processes. We will introduce an analysis case of the removal effect of organic contamination on Si surfaces. TOF-SIMS analysis was conducted on samples where amine-based organic materials were confirmed to be in extremely small quantities by XPS. Even in small areas, it is possible to measure components in such extremely small amounts.

High impact resistance is required for the joints of lead-free solder used in electronic devices such as mobile terminals. To address this issue, solder alloys with trace amounts of elements like Ni have been developed. This document presents a case study comparing the in-plane distribution of a five-component lead-free solder with trace amounts of Ni and Ge added to a Sn-Ag-Cu system, and a three-component solder without additives, using imaging from D-SIMS, which excels in high-sensitivity analysis.

By conducting EBSD analysis on thinned samples, higher spatial resolution can be achieved compared to conventional bulk samples.

In XPS analysis, in addition to the photoelectron peaks used for evaluation, photoelectron peaks from other orbitals and Auger peaks from X-ray excitation are also detected. Depending on the combination of elements, these sub-peaks can overlap with the target peak and interfere with the evaluation. *Typically, a strong photoelectron peak emitted from an inner shell level close to the outer shell is used. In the quantitative calculations of XPS analysis, the removal of such interfering peaks is primarily performed using the following two methods: 1. Removal using sensitivity coefficient ratios 2. Removal using waveform separation

By using a Cs-corrected TEM device that compensates for spherical aberration, it is possible to observe the cross-sectional structure of devices with high resolution. In this case, we present data from high-resolution (HR)-TEM observations of the MTJ: magnetic tunnel junction part, extracted from a commercially available hard disk. Thus, it is possible to clearly observe the structure even in multilayer structures of ultra-thin metal films.

In controlling properties such as adhesion and wettability of polymer films, it is very important to quantitatively evaluate the polar functional groups (alcohol groups) present on the surface. XPS is optimal for quantitative evaluation; however, it is difficult to separate and quantify the adjacent oxidation state (C-O-C) and hydroxyl state (C-OH). In MST, after selectively reacting only the alcohol groups using a chemical modification method on polyvinyl alcohol (PVA), it is possible to quantify them using XPS. We present a case where the alcohol groups in PVA were chemically modified and evaluated using trifluoroacetic anhydride (TFAA). Measurement method: XPS, chemical modification Product fields: Electronic components, daily necessities Analysis purpose: Composition evaluation, identification, chemical bonding state evaluation For more details, please download the materials or contact us.

The state of the water-repellent surface in water-repellent treatment differs based on whether fluorine-based compounds are distributed in an island-like manner or uniformly. Therefore, we conducted observations of the distribution of fluorine-based compounds using TOF-SIMS. As a result, it was found that they are distributed unevenly. Additionally, by performing qualitative analysis in a 1μm square area, it was determined that the fluorine-based film is Krytox. Measurement method: TOF-SIMS Product field: Electronic components and daily necessities Analysis purpose: Composition evaluation, identification, composition distribution evaluation For more details, please download the materials or contact us.

Polycarbonate (PC) is a type of thermoplastic that has excellent transparency, impact resistance, and heat resistance, and is widely used as a material for solar panels, eyeglass lenses, CDs, automotive parts, and medical devices. In this study, TOF-SIMS analysis was conducted using GCIB (Ar cluster) with a sputter ion beam to evaluate the degradation layer on the surface of PC. *Note: GCIB stands for Gas Cluster Ion Beam.*

Using a two-stage heating method with thermal decomposition GC/MS, we analyzed the material of the sealing agent around the display of commercially available smartphones. By heating the sample at a low temperature (250°C) and measuring the gas components generated using GC/MS, we can detect residual monomers and low molecular weight additives (polymerization initiators, antioxidants). Subsequently, by heating at a high temperature (550°C), we can decompose the polymers and estimate their constituent components. This revealed that the sealing agent is made of a UV-curable material.

Regarding foreign substance analysis, it has traditionally been difficult to analyze using microscopic FT-IR analysis or Raman analysis due to the influence of the substrate. However, with the introduction of micro-sampling tools, it has become possible to reduce that influence. We will introduce examples of analysis for two types of foreign substances.

Copper (Cu), used as wiring material, forms an oxide film in the air. Here, we present a case study evaluating the differences in film thickness due to variations in storage environments. Copper (Cu) wrapped in aluminum foil and copper (Cu) stored in a plastic bag were each kept for 40 days, and the oxide film thickness was measured using TOF-SIMS. Additionally, a continuous investigation over approximately 20 days confirmed reproducibility. TOF-SIMS allows for depth profiling analysis of inorganic materials such as oxides and metals. Measurement method: TOF-SIMS Product fields: Displays, LSI, Memory, Electronic components Analysis purpose: Evaluation of chemical bonding states For more details, please download the materials or contact us.

The surface of copper (Cu) metal exposed to the atmosphere is covered with a natural oxide film, and it is known that such copper surfaces can be broadly classified into the states of "Cu," "Cu2O," "CuO," and "Cu(OH)2." By conducting depth profile analysis of commercially available standard powders of "Cu2O," "CuO," and "Cu(OH)2" using TOF-SIMS, it was found that it is possible to obtain characteristic molecular ions corresponding to each state. Using these molecular ions, it became possible to evaluate the depth profile of the natural oxide film on the surface of metallic Cu. Measurement method: TOF-SIMS. Product fields: Display, LSI, Memory, Electronic components. Analysis purpose: Evaluation of chemical bonding states. For more details, please download the materials or contact us.

TOF-SIMS allows for the acquisition of mass spectra in the depth direction, enabling the analysis of components in very thin layers through qualitative assessment of each layer. In this case, we analyzed a hard disk in the depth direction. As a result, it was found that the diamond-like carbon (DLC) layer formed on the surface has a two-layer structure, with a nitrogen-containing C layer on the surface side and a layer consisting solely of C on the deeper side. This method can also be applied to the depth analysis of graphene films. Measurement method: TOF-SIMS Product fields: Electronic components, manufacturing equipment, parts Analysis objectives: Composition evaluation, identification, composition distribution evaluation For more details, please download the materials or contact us.

DLC (diamond-like carbon) films, which are widely used as coating materials in various fields, are composed of a mixture of carbon elements with sp3 hybrid orbitals corresponding to a diamond structure and carbon elements with sp2 hybrid orbitals corresponding to a graphite structure when viewed from a microscopic perspective. One indicator that determines the properties of DLC films is the sp2/(sp2+sp3) ratio. High-precision quantification of the sp2/(sp2+sp3) ratio in DLC films is possible using XAFS.

Due to its characteristics such as high hardness and high wear resistance, DLC (diamond-like carbon) films are utilized in a wide range of fields. These films are materials that lie between graphite and diamond, and the separation of sp2 (graphite structure) and sp3 (diamond structure) within the film to obtain the sp2/(sp2+sp3) ratio is one of the important factors that determine the properties of the film. Here, we will introduce an example of evaluating this sp2/(sp2+sp3) ratio by analyzing the C1s spectrum using XPS.

In semiconductor devices, their performance is greatly influenced by the combination of work functions of various materials that make up the device. Therefore, attempts have been made to control the work function through surface treatments and modifications, and it is important to verify their effects. This document presents an example of evaluating the change in work function of ITO (Sn-doped In2O3), used as an electrode material in organic ELs and solar cells, before and after surface plasma treatment using UPS analysis.

In XPS analysis, the binding state evaluation of the material surface is conducted by observing the energy of photoelectrons obtained through X-ray irradiation. It allows for the assessment of whether metal elements are in an oxidized state, and for elements with significant energy shifts (chemical shifts) due to oxidation, it also enables the evaluation of the presence and proportion of multiple valences. Below are the main metal elements and oxides for which multiple valence evaluations are possible.

Self-assembled monolayers (SAMs), which are oriented organic films, have their functions and properties, such as surface wettability and adsorption, altered by orientation and orientation angle. Using XAFS with synchrotron radiation, it is possible to evaluate the orientation and orientation angle of organic film materials by analyzing the X-ray incidence angle dependence of peak intensity.

The electron diffraction method using an electron microscope is classified into three types based on the way the electron beam is incident on the sample. The characteristics of each type and examples of data are presented. It is necessary to choose the appropriate method according to the size of the evaluation object and the analysis purpose.

Volatile organic compounds (VOCs) are used during the cleaning of semiconductors and industrial products and may be present in trace amounts in cleaning water, etc. VOCs in water are a concern because even in trace amounts, they can cause odors and health issues. Therefore, environmental standards and discharge standards have been established, and methods capable of measuring low concentrations are required. This case presents an example of detecting trace VOC components (sub-ppb level) in water by introducing components concentrated by P&T (Purge & Trap) into GC/MS.

Knowledge about the effects of contamination and oxidation during sample transport is important in surface analysis where the detection depth is on the nanometer order. Therefore, we examined the impact of contamination and oxidation due to differences in storage methods on Si wafers. In storage with wrapping paper and aluminum foil, there is a tendency for the peaks of organic materials caused by secondary contamination to be weaker. When samples are wrapped and stored in the matte side of aluminum foil during storage and transport, it can suppress contamination and oxidation compared to other storage methods.

In the analysis of foreign substances, it is important to appropriately select the analytical methods based on the size of the foreign substance, the expected materials, and the condition of the substrate. By combining techniques such as optical microscopy, elemental analysis (XRF), and bonding state analysis (XRD, FT-IR), it is possible to gain insights into the multiple components contained in the powder. This document presents examples of qualitative analysis of powder foreign substances using the aforementioned methods.

If you want to qualitatively evaluate metallic foreign substances, analyzing only the very surface may result in information about the oxide film present on the surface of the foreign substance, and you may not obtain information about the foreign substance itself. By performing depth analysis using TOF-SIMS, it is possible to evaluate the composition and state of the foreign substance located deeper than the oxide film. This document presents case studies evaluating the state of three locations that are believed to contain aluminum-based foreign substances.

Polyimide resin is excellent in heat resistance, chemical resistance, and toughness, and also has high insulation properties, making it used in various applications, including insulation materials for electronic devices. However, due to its almost non-existent solvent solubility, the analytical methods for structural determination are limited. This case introduces an example of thermal decomposition GC/MS measurement of commercially available polyimide resin. Multiple thermal decomposition products reflecting the polymer structure were observed in high-boiling components with long retention times, demonstrating that this method is a powerful means for structural determination.

In the fabrication of Si-based semiconductor devices, various processes such as ion implantation and annealing are performed. It is considered important to confirm the degree of irradiation defects and the extent of crystallinity recovery before and after these processes in order to control the manufacturing process. Photoluminescence (PL) measurements at low temperatures are one effective means of investigating these aspects. An example of PL measurements of samples that underwent ion implantation on a Si substrate followed by annealing treatment is presented.