一般財団法人材料科学技術振興財団　MST Product Lineup

It was found that there are water-repellent stains on the surface of the aluminum material. The stained area was adhered to tape (transferred), and analysis was conducted using TOFSIMS. Fragments identical to those from the stained area on the aluminum surface were detected from the "tape surface where the stained area was transferred," suggesting that the substance causing the stain has been transferred to the tape. This method of transferring and collecting the causative substance onto tape is effective for parts that cannot be cut.

XPS allows for the evaluation of bonding states of oxidized components (components bonded with oxygen) and metallic components (components bonded with metals). Additionally, by using argon ion sputtering, it is also possible to evaluate bonding states in the depth direction. * Regarding the passive film on the surface of stainless steel (with a thickness of several tens of nm to several hundred nm), the results of the above measurements showed that (1) there are many Fe oxidized components on the surface side, (2) Cr oxidized components exist below the Fe oxide layer, and (3) Ni oxidized components are almost nonexistent. * Since it includes changes in bonding states due to sputtering, the evaluation is primarily based on relative comparisons.

Stainless steel (SUS) is excellent in corrosion resistance and is used in various industrial products and components. Although it is a material resistant to corrosion, changes in the composition of the surface passive film due to aging or processing can lead to issues. In this instance, we introduce a case study analyzing the state of the metal oxide film on the surface of stainless steel using TOF-SIMS. TOF-SIMS allows for the high-sensitivity acquisition of molecular information in the oxide state, enabling the distribution of oxides ranging from a few nanometers to several tens of nanometers on the surface to be obtained, and spatial distribution can be evaluated through image analysis. Measurement method: TOF-SIMS Product field: Manufacturing equipment and components Analysis purpose: Evaluation of chemical bonding state, composition distribution, and thickness of corrosion layers For more details, please download the materials or contact us.

The decomposition behavior of materials when heated in a vacuum or in inert gases such as nitrogen can differ from that when heated in air. Therefore, when conducting gas emission analysis, it is desirable to heat the materials in an environment that closely resembles the actual conditions to which they are exposed. In this case, a comparison of the gases emitted during the pyrolysis of polystyrene at 550°C in helium and in air was conducted. Only hydrocarbon compounds were detected in helium, whereas reaction products with oxygen, such as benzaldehyde, were also detected in air.

When analyzing and identifying unknown samples such as foreign substances, it is effective to analyze the data comprehensively from multiple measurement methods. We will introduce a case where FT-IR analysis, which is a vibrational spectroscopy method, was combined with XRF analysis, an elemental analysis method in the atmosphere, to identify two types of white powders.

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.

When delamination occurs, it is important to identify the components that have worsened the adhesion at the interface. By using a peeling process to physically delaminate at the interface of interest and measuring the components present on that surface with TOF-SIMS, it is possible to investigate the cause of delamination. TOF-SIMS detects secondary ions that are ionized while maintaining the structure of organic materials, allowing us to obtain information about the origin of the components present at the delamination surface, making it effective for investigating the causes of delamination and the process. Measurement methods: TOF-SIMS, peeling, disassembly Product fields: LSI, memory, manufacturing equipment, components Analysis purposes: Evaluation of chemical bonding states, failure analysis, defect analysis For more details, please download the materials or contact us.

Polymeric materials such as polypropylene (PP) react with oxygen and moisture in the atmosphere when heated, causing changes in their molecular structure. Therefore, when foreign substances or contaminants may be present in polymeric materials, it is necessary to use standard materials processed in the same environment as the measurement sample for comparison data. To investigate how the PP standard material changes due to heat treatment (200°C for 30 minutes), FT-IR and TOF-SIMS measurements were conducted.

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.

We will introduce a case where the thickness of extremely thin films, such as natural oxide films on silicon wafers and silicon nitride thin films, which are less than a few nanometers thick, was calculated using XPS analysis. By measuring the Si2p spectrum of the surface of the Si wafer and performing waveform analysis on the obtained spectrum, we can determine the ratio of the presence of each bonding state, and from this result, it is possible to estimate the film thickness based on the average free path of photoelectrons (Equation 1). XPS allows for non-destructive and simple calculation of thin film thickness on substrates as broad average information.

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.

The functionality of films is known to be determined by factors such as material, thickness, and layer structure. In this study, we evaluated the layer structure of polyethylene-based multilayer films commonly used as food wrap. By confirming that the film is primarily composed of polyethylene using FT-IR, and employing GCIB (Ar cluster) for sputtering, we were able to clearly visualize the structure where polyethylene and nylon 6 are layered within a thickness of 10μm through depth profiling with TOF-SIMS.

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

Ion chromatography is a method for detecting ionic components in liquid samples. Additionally, these components that adhere to the surface of solids (materials) are measured by extracting them by immersing in pure water. MST enables qualitative and quantitative analysis of ions and organic acids contained in liquid samples, evaluation of the amount of ions eluted from material surfaces, and investigation of the causes of material corrosion.

Acrylic resin has superior processability, transmittance, and safety compared to silicate glass, making it widely used as organic glass for windows in aircraft and automobiles, optical instruments such as lenses and prisms, medical materials, daily necessities, and crafts. Mass spectra of representative standard acrylic reagents were obtained using TOF-SIMS. In MST, by comparing the mass spectrum of the analyte with that of the standard reagent, it is possible to estimate the acrylic resin from the detected fragment ions.

Tetramethylammonium hydroxide (TMAH) is used as a developing solution and etching solution in semiconductors. When measuring the concentration of TMAH solution used in Si etching solutions, the large amount of dissolved Si can become an impurity and affect the measurement results. However, evaluation using the IC (ion chromatography) method allows for quantitative analysis of TMAH concentration without being influenced by Si.

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.

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.

XPS is a surface-sensitive technique, so carbon derived from organic contaminants due to the atmosphere is detected at a significant level. Reducing the influence of this carbon from organic contaminants is important for evaluating the original composition of the film. Typically, Ar ion sputtering is used to remove organic contaminants, but damage caused by sputtering may prevent the evaluation of the film's original composition and bonding states. We present an example where the influence of carbon from organic contaminants was reduced by removing the surface oxide layer using wet etching instead of Ar ion sputtering.

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.

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.

Many additives, including plasticizers, are used in polymer materials such as resin products. We present a case study on the qualitative analysis of additives contained in commercially available PVC resin. The components eluted by immersion in an organic solvent were qualitatively analyzed using LC/MS. As a result, components estimated to be DEHP (DOP) as a plasticizer and epoxy fat (plasticizer/stabilizer) were detected. By using standard samples, it is also possible to quantify each detected additive component.

When analyzing additives used in polymer materials such as resin products, it is necessary to separate the polymer materials from the additives. We will introduce a case where a sample pre-treated using the "dissolution-reprecipitation method," which involves dissolving commercially available resin products in a solvent and then precipitating the polymer components to extract the additive components, was analyzed. The results of the LC/MS analysis indicated that a component with a high abundance (m/z=548.50) was estimated to be a type of phenolic antioxidant through LC/MS/MS analysis.

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.

In the process of confirming metal contamination adhered to the wafer surface after the formation of the SiO2 film, a method has traditionally been used where the SiO2 film is dissolved in acid as a pre-treatment for analysis, followed by the analysis of the solution. This method results in analysis that combines metal contamination on the very surface with that within the SiO2 film, making it unsuitable for analyzing only the metal contamination on the very surface. In MST, it is possible to evaluate the metal contamination elements on the wafer's very surface by dissolving only the metal elements adhered to the very surface without dissolving the SiO2 film during the pre-treatment.

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.

When evaluating organic foreign substances present in resin, it may be difficult to assess them in their original state depending on the sample and analysis conditions. Therefore, we will introduce a case where evaluation became possible by cross-sectioning the resin to expose the foreign substances at the surface. After exposing foreign substances measuring several tens of micrometers that were mixed into epoxy resin through cross-sectioning, we evaluated them using TOF-SIMS. We were able to identify the components of the foreign substances and confirm their distribution.

In the field of semiconductors and their manufacturing processes, it is considered important to control inorganic and organic substances present in the environment. At MST, it is possible to collect components from the indoor atmosphere using the impinger collection method and analyze the types and quantities of corrosive components in the atmosphere. This time, we will introduce a case analyzed using the impinger collection-ion chromatography method.

One method to obtain the temperature profile of gases generated during sample heating is the EGA-MS method. However, this method introduces the generated gases into the mass spectrometer as a mixture without passing through a GC column, making it difficult to identify the compounds. In such cases, by trapping the gases once and performing GC/MS measurements using the heart-cut EGA method, it becomes possible to separate and identify the compounds. This example presents a case where polyvinyl acetate was measured using the heart-cut EGA method, revealing differences in the decomposition mechanisms depending on the heating temperature.

TOF-SIMS is an effective method for evaluating distribution, as it can simultaneously analyze elemental composition and molecular information of organic and inorganic substances, as well as perform imaging analysis. This document presents a case study analyzing the inner wall of a nozzle. The distribution of the nozzle surface and inner wall was confirmed, and the presence or absence of peaks at various locations was verified. Measurement method: TOF-SIMS Product field: Manufacturing equipment, parts, daily goods Analysis purpose: Composition distribution evaluation For more details, please download the document or contact us.

One method for qualitative analysis of gases generated during sample heating is the pyrolysis GC/MS method, but the EGA*-MS method is effective for investigating the temperature at which each component detected here is generated. This method involves directly introducing the gases generated from the sample during temperature ramping into the mass spectrometer without passing through the GC column. This case presents an example of measuring the temperature profile of gases generated during the heating of polyvinyl acetate. * EGA: Evolved Gas Analysis

SEM-EDX analysis and AES analysis are suitable for simple investigations of discoloration and foreign substances on metal surfaces. However, when the discoloration or foreign substances are thin or small, AES analysis, which provides information from very shallow areas of the surface (about 4-5 nm), is effective. The AES equipment owned by MST can acquire SEM images, allowing AES analysis to be conducted while confirming the areas of interest using SEM images. In this case study, we will present data comparing the evaluation of discoloration on the Cu surface using AES analysis and SEM-EDX analysis. Additionally, we will also present the results of AES depth direction analysis.

When conducting elemental analysis, it is possible to establish an efficient evaluation plan by first using XRF analysis to non-destructively examine the elements contained in the target before moving on to detailed analysis. In this case, we present data from XRF analysis conducted on blades for metal cutting. By performing surface analysis over a wide range on the order of millimeters, we roughly examined the distribution of metallic elements in the material and estimated the metal composition by calculating the elemental composition from the XRF point analysis results of characteristic areas. Measurement method: XRF Product field: Manufacturing equipment, parts, daily necessities Analysis purpose: Composition evaluation, identification, composition distribution evaluation, failure analysis, defect analysis For more details, please download the materials or contact us.

TDS is a method that heats samples in high vacuum (1E-7 Pa) and detects the gases that are released. By heating the sample at a constant rate in high vacuum, it is possible to confirm the temperature dependence of even trace amounts of desorption (at the monolayer level). Additionally, for some components, it is also possible to calculate the number of molecules of the desorbed gas. We will introduce examples of TDS applied to representative materials.

The purpose of evaluating metal contamination on the surface of Si wafers using ICP-MS includes not only the contamination assessment of the Si wafers themselves but also the evaluation of contamination within semiconductor devices and the assessment of the working environment due to Si wafer exposure. Therefore, the analysis of the Si wafer surface is conducted for various purposes. ICP-MS analysis can sensitively obtain the amount of metal contamination on the surface of Si wafers, and it is also possible to specify the evaluation area according to the purpose.

TOF-SIMS detects secondary ions originating from molecules and visualizes their distribution. By estimating the components derived from the ion species detected from abnormal areas, it is possible to investigate which process the anomaly occurred in. When abnormal areas (such as discoloration or adhesion) are found on wafers or products, conducting TOF-SIMS measurements can help distinguish whether the issue is due to watermarks from cleaning and drying, alterations in the base material, or contaminants from a different process, making it effective for identifying the causes of defects.

AES analysis is a method for obtaining compositional information from the surface down to a depth of several nanometers, and it is an effective analysis for investigating the composition of contaminants and foreign substances that occur on the surface during the manufacturing process. Since it rarely detects information about the substrate or base material, it allows for a simple examination of only the abnormal areas, such as foreign substances, without preprocessing. Additionally, by conducting surface analysis, it is possible to obtain elemental distribution images. In this case study, we will present data evaluated using AES analysis regarding foreign substances present on a Si wafer.

AES analysis is a method for obtaining compositional information from the surface to a depth of several nanometers. By performing AES measurements on the cross-section of a sample to obtain elemental distribution images, it is possible to clearly evaluate the layered structure. In addition to evaluating layered structures and conducting elemental analysis of the inner walls of trenches and holes, combining mechanical processing and ion beam processing allows for the assessment of thin alloy layers and phenomena such as diffusion and segregation of elements. In this case, we will present data evaluated using AES analysis for a thin film deposited on a silicon substrate.

The WA (Wafer Analyzer) is a device that heats wafers with a diameter of φ76 to 300mm to elevate their temperature, gasifying organic contaminants adhered to the wafer surface and trapping them in a collection tube. As a result, it can concentrate compounds such as phthalate esters and cyclic siloxanes, which are considered causes of device characteristic impacts and manufacturing troubles, allowing for high-sensitivity measurement using GC/MS. Quantification using hexadecane is also possible. - Evaluation of organic contaminants on one side of the wafer is possible. - Detection of easily volatile components is possible since vacuum pumping is not required. - Organic components can be detected with high sensitivity (for 300mm wafers, on the order of 0.01ng/cm²). - Quantification using hexadecane conversion is possible.

Sn is used as the main raw material for solder, which is also used in semiconductor manufacturing. The gases in the solder can cause void formation, so it is important to control the amount of encapsulated gas in the solder and its main raw material, Sn. The results of investigating the gases released by heating Sn to a temperature above its melting point using TDS analysis are shown below. By heating the sample above its melting point, it is possible to evaluate the surface-adsorbed components and the components of the encapsulated gas in the sample.

In the solution that dissolves the SiN film (Si3N4) on the Si wafer, there is a Si matrix derived from the film in addition to the target impurity metal elements. Therefore, accurate and highly sensitive analysis cannot be performed directly on the dissolved solution itself. Thus, after dissolving the SiN film on the Si wafer, we enabled the analysis of impurity metal elements in the SiN film without the influence of the Si matrix by applying additional treatment. An example of conducting high-sensitivity analysis using ICP-MS with commercially available Si wafers with SiN films is provided.

GPC (Gel Permeation Chromatography) is one of the separation modes of HPLC and is a method for evaluating the molecular weight of polymer compounds. It can determine several average molecular weights (Mn), weight average molecular weight (Mw), and polydispersity (Mw/Mn) in a single analysis, and it is also possible to compare the distribution profiles. It is also referred to as SEC (Size Exclusion Chromatography).

Carbon materials, widely used in industrial components and medical devices, have different properties depending on their structure and crystallinity, making it important to evaluate their state. This document presents evaluation examples using high-sensitivity and high-spatial-resolution Raman spectroscopy. The distribution of the crystalline state of graphite, a carbon material, was visualized through mapping. It allows for a visual capture of the quantity of defects, whether high or low.