Phthalein dyes in the quinone dianion form (pseudo-D3, colored) are transformed into the lactone dianion form (pseudo-T(d), colorless) through encapsulation in a T(d)-symmetric host even under basic conditions (pH ∼10). The compatibility in size and symmetry between the lactone and the cavity is essential to the transformation. Upon addition of a guest that strongly binds to the cavity, the encapsulated phenolphthalein is expelled, the color of the basic solution is regained, and the host-guest complexation is thus visualized.

Three-dimensional microanalysis of the microstructure of organic materials is important in the development and progress of analytical methods on the micro-to-nanometer scales. We have developed a novel three-dimensional microanalysis method using focused ion beams for section processing (shave-off scanning) and time-of-flight secondary ion mass spectrometry for mapping. Shave-off scanning can effectively create an arbitrary section on a sample set against composites materials with a wide variety of shapes; three-dimensional sample images are then obtained by alternately operating two focused ion beams. In this study, we adapted metal-assisted secondary ion mass spectrometry for three-dimensional microanalysis. We have devised a unique method whereby gold is deposited on a section to be analyzed after every shave-off sectioning by setting a gold plate at the back of the sample. Consequently, gold was observed to be deposited on the created cross-section concurrently with shave-off sectioning, resulting in a substantially enhanced secondary ion intensity.

Three-dimensional microanalysis of the microstructure of organic materials is important in the development and progress of novel materials on the micro-to-nanometer scales. We have developed the three-dimensional microanalysis method using focused ion beams (FIBs) for section processing (shave-off scanning) and mapping for time-of-flight secondary ion mass spectrometry (ToF-SIMS). Shave-off scanning can effectively create an arbitrary section on a sample set against composite materials with a wide variety of shapes; three-dimensional sample images are then obtained by alternately operating two FIBs. From the simulation results, we could set the optimum condition of beam irradiation. In this study, we confirmed the enhancement of secondary ion intensity by Au deposition under ToF-SIMS mapping with the optimized condition, and examine the usefulness of the simulation. The enhanced maps of characteristic polystyrene (PS) fragment ions were obtained. In addition, we observed the distribution of Au deposition by mapping results. These maps showed same tendency. The intensity of PS fragment ions was enhanced according to existence of deposited Au particles. These results indicated that a precise analysis of 3D MetA-SIMS can be realized.

We investigated the thickness distribution of gold particles sputtered by a focused ion beam (FIB) and deposited on a section perpendicular to the irradiated surface. The calculation results were analyzed from the viewpoint of three-dimensional metal-assisted secondary ion mass spectrometry (3D MetA-SIMS), a novel method that uses sputtered metal particles to enhance the signal yield of organic samples. The calculated distributions showed characteristic shapes of deposited gold, which had both a steep area and a flat area. The former area can be used for determination of sputtering feature, and the latter area can be used as the target area in which the sample section is located. The amount of particles on the target area was calculated to be within a reasonable range, implying that 3D MetA-SIMS can be realized with this simple and reasonable process. In summary, we established the foundation for enhancing the scope and effectiveness of 3D MetA-SIMS.

To understand the deposition mechanism during the inductively coupled plasma (ICP) assisted sputter-deposition of transparent conductive Al-doped ZnO (AZO) films, energy flux to a substrate during the deposition was investigated. The total energy flux to a substrate (J) was measured by two types of thermal probes, and the contribution due to charged species was evaluated by the Langmuir probe measurements of plasma parameters. As a result, it was found that i) J was about 3000 Wm-2 for the optimized deposition condition, and ii) J was predominantly contributed by plasma charged species.