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Surface smoothing of a barium borosilicate glass substrate by irradiation of ionic liquid ion beams were investigated. 1-ethyl-3-methylimidaolium tetrafluoroborate (EMIM-BF4) and 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6) were used for the source liquid. Surface roughness represented as the arithmetic mean value decreased from 0.17 nm to 0.13 nm by the BMIM-PF6 negative ion beam. Secondary electron microscope (SEM) observation for the glass surface irradiated with the BMIM-PF6 negative ion beam showed a clear image without an electrical charge-up, though the EMIM-BF4 negative ion beam irradiated glass yielded a charged up image. X-ray photoelectron spectroscopy (XPS) analysis implied that the surface layer including cation-anion pair of BMIM-PF6 was deposited by the BMIM-PF6 negative ion beam irradiation, while an insulated surface with barium fluoride was formed by the EMIM-BF4 negative ion beam irradiation.
Ionic liquid (IL) ion sources with different emitter tip materials and tip numbers were developed and examined on ion beam characteristics with respect to its ILs wettability. As a result of ion current measurements, the most stable emission current was obtained for the graphite emitter tip and the ion current increased with increase of the tip number. The results indicate that the emitter wettability corresponding to the supplying flow rate and the number of emission site play an important role to stabilize and increase the beam current.
We developed a polyatomic cluster ion beam system for materials processing, and polyatomic clusters of materials such as alcohol and water were produced by an adiabatic expansion phenomenon. In this article, cluster formation is discussed using thermodynamics and fluid dynamics. To investigate the interactions of polyatomic cluster ions with solid surfaces, various kinds of substrates such as Si(100), SiO2, mica, polymethyl methacrylate, and metals were irradiated by ethanol, methanol, and water cluster ion beams. To be specific, chemical reactions between radicals of polyatomic molecules and surface Si atoms were investigated, and low-irradiation damage as well as high-rate sputtering was carried out on the Si(100) surfaces. Furthermore, materials processing methods including high-rate sputtering, surface modification, and micropatterning were demonstrated with ethanol and water cluster ion beams.
Apatite films were deposited onto titanium (Ti) metal substrates by an electrodeposition method under a pulse current. Metastable calcium phosphate solution was used as the electrolyte. The ion concentration of the solution was 1.5 times that of human body fluid, but the solution did not contain magnesium ions at 36.5 °C. We used an average current density of 0.01 A/cm2 and current-on time (TON) equal to current-off time (TOFF) of 10 ms, 100 ms, 1 s, and 15 s. The adhesive strength between apatite and Ti substrates were relatively high at TON = TOFF = 10 ms. It is considered that small calcium phosphate (C–P) crystals with low crystallinity were deposited on the Ti surface without reacting with other C–P crystals, H2O, and HCO3− in the surrounding environment. This resulted in relaxation of the lattice mismatch and enhancement of the adhesive strength between the apatite crystals and Ti substrates.
Polyethylene (PE) and silicone rubber substrates were irradiated at an acceleration voltage of 7kV and a dose of 1×1015 ions/cm2 by the simultaneous use of oxygen cluster and monomer ion beams, and then soaked in CaCl2 solution. Apatite-forming ability of the substrates was examined using a metastable calcium phosphate solution that had 1.5 times the ion concentrations of a normal simulated body fluid (1.5SBF). After the irradiation, the hydrophilic functional groups such as COOH and silicon oxide cluster (SiOx) were formed at the PE and silicone rubber surfaces, respectively. The hydrophilicity of the substrates was remarkably improved by the irradiation. The irradiated PE and silicone rubber substrates formed apatite in 1.5SBF, whereas unirradiated ones did not form it. These results suggest that the functional groups such as COOH groups and Si-OH groups induced apatite nucleation in 1.5SBF.
In order to understand the damage formation by cluster ion irradiation, Si substrates were irradiated with Ar cluster ions at the acceleration energy of 1–20keV. The mean size of cluster was about 3000 atoms. The amount of damage after Ar cluster ion irradiation was measured with Rutherford backscattering spectrometry (RBS). The amount of damage was decreased with decrease of the energy and no damage formed at less than 2keV. This energy of 2keV represents the threshold energy to generate damage with the cluster size of 3000. According to Molecular dynamics (MD) simulation, the damage formation with cluster ion irradiation also depends on cluster size. The size dependence of amount of damage has been investigated experimentally. The cluster size distribution could be changed with the ionization condition and could be measured using Time-of-Flight (TOF) method. The threshold energy was increased with cluster size. These results indicate that undamaged films can be created by using large size of cluster ion with low acceleration energy.
New surface modification processes have been demonstrated using gas cluster
ion irradiations because of their unique interaction between cluster ions
and surface atoms. For example, high quality ITO films could be obtained by
O2 cluster ion assisted deposition at room temperature. It is
necessary to understand the role of cluster ion bombardment during film
formation for the further developments of this technology. Variable
Temperature Scanning Tunneling Microscope (VT-STM) in Ultra High Vacuum
(UHV) allows us to study ion bombardment effects on surfaces and nucleation
growth at various temperatures.
The irradiation effects between Ar cluster ion and Xe monomer ion were
compared. When a Si(111) surface with Ge deposited to a few Å was annealed
to 400°C, it was observed that many islands of Ge were formed. The surface
with the Ge islands was irradiated by these ions. In the STM image of
cluster-irradiated surface, large craters with diameter of about 100 Å were
observed, while only small traces with diameter of about 20 Å were observed
in monomer-irradiated surface. The number of Ge atoms displaced by one Ar
cluster ion impact was much larger than that by one Xe ion impact. This
result indicates that Ar cluster ion impacts can enhance the physical
modification of Ge islands. When the sample irradiated with Ar cluster was
annealed at 600°C, the hole remained, but the outer rim of the crater
disappeared and the surface structure was reconstructed at the site of the
rim. The depth of damage region in the target became shallower with decrease
of the impact energy. These results indicate that low damage and useful
surface modification can be realized using the cluster ion beam.
SiO2 films were prepared at a substrate temperature of 100°C by the simultaneous use of a microwave ion source and an ICB system. Transparent and good insulating SiO2 films could be obtained by using 02 gas ions, and they were thermally and chemically stable. Furthermore, both the ionization energy and the incident energy of the 02 gas ions were found to enhance the chemical reaction between SiO and 02 molecules, resulting in the Si02 film formation at a low substrate temperature.
Aluminum oxide (A12O3), nitride(A1N) and silicon nitride(SiN) films were prepared at a low substrate temperature of 100°C. Film resistivity was higher than 5x1013 Ω-cm and the breakdown voltage was greater than 3x10° V/cm. The films deposited on sapphire and silicon substrates were very flat, and were chemically and thermally stable. The A1-O, A1-N and Si-N bonds could be formed effectively by using both ionized clusters and reactive gas ions, and transparent and good quality films were obtained. Through these results, the simultaneous use of an ionized cluster beam (ICB) system and a microwave ion source was found to have a high potential for preparing oxide and nitride films at a low substrate temperature.
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