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We investigated the effects of size and energy of large incident Ar cluster ions on the secondary ion emission of Si. The secondary ions were measured using a double deflection method and a time-of-flight (TOF) technique. The size of the incident Ar cluster ions was between a few hundreds and several tens of thousands of atoms, and the energy up to 60 keV. Under the incidence of keV energy atomic Ar ions, mainly atomic Si ions were detected, whereas Si cluster ions were rarely observed. On the other hand, under the incidence of large Ar cluster ions, the dominant secondary ions were Si n + (2 ⩽ n ⩽ 11). It has become clear that the yield ratio of secondary Si cluster ions was determined by the velocity of the incident cluster ions, and this strong dependence of the yield ratio on incident velocity should be related to the mechanisms of secondary ion emission under large Ar cluster ion bombardment.

Secondary ion emission with large gas cluster ion is reviewed from the point of view of secondary ion mass spectroscopy (SIMS). We have proposed to use large cluster ions to realize fragment-free ionization for SIMS analysis for various organic materials, such as amino acids and peptides. When large cluster ions with optimized size and energy were incident on biomolecular samples, the relative yields of the fragment ions decreased drastically with the velocity of incident cluster ions. Molecular depth profiling capability is also demonstrated by using large gas cluster ions as the primary ion for SIMS.

We propose to use cluster ions that are much larger than the molecular ions as primary ions for organic secondary ion mass spectrometry. Incident Ar cluster ion beams with energies from 10 to 20 keV and a mean size of about 1000 atoms/cluster were used. Secondary ions were measured for a thin arginine film target (200 nm) bombarded with large Ar cluster ions using a time-of-flight technique. Molecular ions of arginine and characteristic fragment ions were detected with high sensitivity. When large Ar cluster ions such as Ar1500 were incident on the arginine target, molecular ions of arginine were detected with little fragment ions. This indicates that large cluster ions can ionize arginine molecules without damaging them.

New surface modification processes have been demonstrated using gas cluster ion irradiations. Multiple collision and high energy density collision of cluster ions are responsible for “non-linear phenomena”, which play an important role in the surface modification process. Because of the unique interaction between cluster ions and surface atoms, atomistic mechanisms of cluster ion bombardment must be understood for the further developments of this technology. Cluster size is a unique parameter for cluster ions. One of the fundamental questions in this surface modification technique is the cluster size effect. It is important to use appropriate cluster size in each process. Size dependence of sputtering yields and secondary ion yields with large Ar cluster (N > 300) have been measured.

Surface oxidation of Si assisted by Ar cluster impact with a current density of a few μA/cm 2 under O 2 atmosphere was investigated. Thin-film formation by cluster ion beam presents a number of advantages such as atomic-scale surface smoothing, high density and precise stoichiometry. We used an Ar cluster ion beam with 20 keV and a mean size of 1000 atoms per cluster and measured the emission yields of Si + and SiO + after Ar cluster ion irradiation in O 2 atmosphere using a quadrupole mass spectrometer to investigate the dependence of Si surface oxidation on oxygen partial pressure. It was found that the Si surface was oxidized by Ar cluster ion irradiation in O 2 atmosphere.

We measured the sputtering yield, surface roughness and surface damage of thin leucine films bombarded with Ar cluster ions and examined the usefulness of large gas cluster ions for the depth profiling of organic compounds. Ar cluster ion beams with a mean size of 2000 atoms/cluster and energies from 5 to 30 keV were used. Sputtering yields increased linearly with incident ion energy and were extremely high compared to inorganic materials. Surface damage was investigated by measuring positive secondary ions emitted from the leucine film before and after cluster ion irradiation. After irradiation the leucine surface became smoother. The yield ratio of protonated leucine ions to other fragment ions kept constant before and after Ar cluster ion irradiation. These results indicate that large gas cluster ions are useful for depth profiling of organic compounds.

In this report, we propose to use the incidence of cluster ions that are much larger than molecular ions as a fragment-free ionization technique for organic secondary ion mass spectrometry. Secondary ions were measured for amino acid and peptide targets bombarded with 3, 8 and 13 keV large Ar cluster ions. The relative yields of the fragment ions decreased drastically with increasing incident cluster size. Fragment-free ionization of the molecule was accomplished when large cluster ions with optimized size and energy were incident on a biomolecular sample.

In this work, we characterized the surface damage layer and sputtering yield of polycrystalline L-leucine films before and after irradiation with Ar cluster or monomer ion beams with x ray photoelectron spectroscopy and ellipsometry. Irradiation with Ar monomer ion beams induced heavy damage on the surface of L-leucine films, such as bond breaking and carbonization. In contrast, no significant surface damage was observed in the films irradiated with Ar cluster ion beams. The sputtering yield of L-leucine decreased dramatically with increasing fluence of monomer Ar ions and approached the value of the sputtering yield of graphite; but under irradiation with Ar cluster ion beams, the sputtering yield remained constant with fluence. The differences in sputtering yield behavior were explained in relation with the surface damage layer on organic materials. Thus, cluster ion beams could potentially be used to mill down biological materials without significant damage on the surface and could contribute to various applications in the analysis and processing of life matter.

We report two cases of vasospastic angina associated with anaphylactic reaction caused by nonsteroidal anti-inflammatory drugs (NSAIDs). Both patients exhibited anaphylactic manifestations, such as general rash and urticaria, along with angina pectoris with electrocardiographic ST-segment elevations after suppository administration of diclofenac sodium or indomethacin, the most commonly used NSAIDs. Although these patients had normal coronary arteriograms, intracoronary administration of ergonovine or acetylcholine provoked diffuse coronary artery spasms accompanied by chest pain and ischemic ST-segment changes. It is therefore suggested that an allergic mechanism may be involved as a causative factor of the coronary artery spasm induced by NSAIDs.