Teruhisa Ootsuka

Reduction of iron diffusion in silicon during the epitaxial growth of β-FeSi2 films by use of thin template buffer layers

We fabricated continuous highly (110)/(101)-oriented β-FeSi2 films on Si (111) substrates by the facing-target sputtering method. An epitaxial thin β-FeSi2 template buffer layer preformed on the silicon substrate was found to be essential in the epitaxial growth of thick β-FeSi2 films. It was proved that the template reduced the iron diffusion into the silicon substrate during thick β-FeSi2 film fabrication. Even though the annealing was performed at high temperature (880 °C) for a long duration (10 h), iron diffusion was effectively hindered by the template. By introducing this template buffer layer, an abrupt interface without appreciable defects between the β-FeSi2 film and the silicon substrate formed. The mechanism for the reduction of iron diffusion by the template buffer layer is discussed.

Enhanced immobilization of acidic proteins in the apatite layer via electrostatic interactions in a supersaturated calcium phosphate solution

Artificial materials coated with a protein-apatite composite layer have great potential in clinical applications as a third generation biomaterial. Such composite materials can be prepared by immersing a surface modified substrate into a supersaturated calcium phosphate solution (CP solution: 142 mM NaCl, 3.75 mM CaCl(2), 1.5mM K(2)HPO(4)·3H(2)O, buffered at pH 7.4 at 25 °C with tris(hydroxymethyl)aminomethane and HCl) supplemented with a protein. In the present study proteins of various molecular weights (MW) and isoelectric points (pI) were used to form a protein-apatite composite layer on a polymeric material to determine how the molecular properties of the protein affect the efficiency of protein immobilization (i.e. the amount of immobilized protein in the apatite layer as a percentage of the total amount of protein in solution). The results indicated that the efficiency of protein immobilization did not correlate with the MW of the protein. In contrast, the efficiency of protein immobilization was strongly related to the pI of the protein. As the pI decreased the efficiency of protein immobilization increased due to the high adsorption affinity of negatively charged acidic proteins for positively charged apatite crystals and/or apatite precursors in the CP solution. Thus, the use of acidic rather than basic proteins improves the immobilization efficiency in the present coating process.

β-FeSi 2 as a Kankyo (environmentally friendly) semiconductor for solar cells in the space application

β-FeSi2 defined as a Kankyo (Environmentally Friendly) semiconductor is regarded as one of the 3-rd generation semiconductors after Si and GaAs. Versatile features about β-FeSi2 are, i) high optical absorption coefficient (>105cm-1), ii) chemical stability at temperatures as high as 937°C, iii) high thermoelectric power (Seebeck coefficient of k ~ 10-4/K), iv) a direct energy band-gap of 0.85 eV, corresponding to 1.5μm of quartz optical fiber communication, v) lattice constant nearly well-matched to Si substrate, vi) high resistance against the humidity, chemical attacks and oxidization. Using β-FeSi2 films, one can fabricate various devices such as Si photosensors, solar cells and thermoelectric generators that can be integrated basically on Si-LSI circuits. β-FeSi2 has high resistance against the exposition of cosmic rays and radioactive rays owing to the large electron-empty space existing in the electron cloud pertinent to β-FeSi2. Further, the specific gravity of β-FeSi2 (4.93) is placed between Si (2.33) and GaAs ((5.33). These features together with the aforementioned high optical absorption coefficient are ideal for the fabrication of solar cells to be used in the space. To demonstrate fascinating capabilities of β-FeSi2, one has to prepare high quality β-FeSi2 films. We in this report summarize the current status of β-FeSi2 film preparation technologies. Modified MBE and facing-target sputtering (FTS) methods are principally discussed. High quality β-FeSi2 films have been formed on Si substrates by these methods. Preliminary structures of n-β-FeSi2 /p-Si and p-β-FeSi2 /n-Si solar cells indicated an energy conversion efficiency of 3.7%, implying that β-FeSi2 is practically a promising semiconductor for a photovoltaic device.

Boron doping for p-type β-FeSi2 films by sputtering method

High quality epitaxial β-FeSi2 thin films prepared by alternate Fe/Si multilayers stacking were doped for p-type by co-sputtering of silicon and boron, in which elemental boron chips were placed on silicon target. The starting β-FeSi2 films before doping were n-type with residual electron concentration of about 2 ×1017 cm-3 and mobility of about 200 cm2/Vs. After doping with boron, β-FeSi2 films showed the same epitaxial crystallinity with continuous structure as that of non-doped one. Doping level of p-type β-FeSi2 films with net hole concentration from 3 ×1017 to 1 ×1019 cm-3 and mobility from 100 to 20 cm2/Vs were successfully achieved. Desired net hole concentration was obtained by varying the area ratio of boron chips on silicon target.

Minority-carrier diffusion length, minority-carrier lifetime, and photoresponsivity of β-FeSi2 layers grown by molecular-beam epitaxy

We have epitaxially grown undoped β-FeSi2 films on Si(111) substrates via atomic-hydrogen-assisted molecular-beam epitaxy. β-FeSi2 films grown without atomic hydrogen exhibited p-type conduction with a hole density of over 1019 cm−3 at room temperature (RT). In contrast, those prepared with atomic hydrogen showed n-type conduction and had a residual electron density that was more than two orders of magnitude lower than the hole density of films grown without atomic hydrogen (of the order of 1016 cm−3 at RT). The minority-carrier diffusion length was estimated to be approximately 16 μm using an electron-beam-induced current technique; this value is twice as large as that for β-FeSi2 prepared without atomic hydrogen. This result could be well explained in terms of the minority-carrier lifetimes measured by a microwave photoconductance decay technique. The 1/e decay time using a 904 nm laser pulse was approximately 17 μs, which is much longer than that for β-FeSi2 prepared without atomic hydrogen (3 μs). The...

Electronic states of thiophene/phenylene co-oligomers: Extreme-ultra violet excited photoelectron spectroscopy observations and density functional theory calculations

We have investigated electronic states in the valence electron bands for the thin films of three thiophene/phenylene co-oligomer (TPCO) compounds, 2,5-bis(4-biphenylyl)thiophene (BP1T), 1,4-bis(5-phenylthiophen-2-yl)benzene (AC5), and 1,4-bis{5-[4-(trifluoromethyl)phenyl]thiophen-2-yl}benzene (AC5-CF3), by using extreme-UV excited photoelectron spectroscopy (EUPS). By comparing both EUPS spectra and secondary electron spectra between AC5 and AC5-CF3, we confirm that CF3 substitution to AC5 deepens valence states by 2 eV, and increases the ionization energy by 3 eV. From the cut-off positions of secondary electron spectra, the work functions of AC5, AC5-CF3, and BP1T are evaluated to be 3.8 eV, 4.8 eV, and 4.0 eV, respectively. We calculate molecular orbital (MO) energy levels by the density functional theory and compare results of calculations with those of experiments. Densities of states obtained by broadening MO levels well explain the overall features of experimental EUPS spectra of three TPCOs.

Arsenic doping of n-type β-FeSi2 films by sputtering method

High quality epitaxial n-type β-FeSi2 thin films prepared by alternate Fe/Si multilayer deposition were doped with arsenic as impurity by sputtering method. Doping sources were heavily arsenic-doped silicon chips placed on the surface of silicon target. The starting β-FeSi2 films before doping were typically n-type with a residual electron concentration of about 1.0 ×1017 cm-3 and a mobility of about 260 cm2/Vs. When arsenic concentration changed from 7.0 ×1017 to 1.9 ×1018 cm-3, net electron concentration increased from about 2.0 ×1017 to 4.0 ×1017 cm-3, and electron mobility decreased from 250 to 160 cm2/Vs. Secondary ion mass spectroscopy (SIMS) measurements showed a homogeneous arsenic distribution in β-FeSi2 films and a small diffused region (about 50 nm) at the interface between β-FeSi2 and a Si substrate. Arsenic-doped β-FeSi2 films exhibited epitaxial growth in the (110)/(101) orientation and a continuous structure without cracks. However, other crystalline orientations together with pinholes appeared when the arsenic doping concentration increased.

Enhancement of critical current density in YBa2Cu3O7 films using a semiconductor ion implanter

An up-to-11-fold enhancement was observed in the in-magnetic-field critical current density (Jc) in epitaxial YBa2Cu3O7 films on CeO2-buffered SrTiO3 substrates by irradiation with 200- to 750-keV Si and 200-keV B ions. This enhancement indicates that ion beams in the range of 100 to 1000 keV, which are widely used for modifying the conductive properties of semiconducting materials, can significantly improve the vortex-pinning properties in second-generation superconducting wires. Also observed was a scaling relation between Jc and the density of the vacancies (i.e., of Frenkel pairs) produced by the nuclear collisions between incident ions and target atoms, suggesting that this density is a key parameter in determining the magnitude of the Jc enhancement. Also observed was an additional Jc enhancement by a modification of the depth distribution of the vacancies, thus demonstrating the flexibility in controlling artificial pinning center (APC) properties in physical APC introduction.

Observation of Work Functions, Metallicity, Band Bending, Interfacial Dipoles by EUPS for Characterizing High- k/Metal Interfaces

EUPS (EUV excited photoelectron spectroscopy) is a novel photoelectron spectroscopy technique, in which a sample is excited with 4.86 nm (255 eV), 3‐ns pulse EUV light emitted from a laser‐produced plasma and the resulting electron spectrum is analyzed with a time‐of‐flight (TOF) analyzer. EUPS gives information of the topmost atoms because the escape depth of photo‐electrons excited by 4.86 nm light is only 0.5 nm. EUPS can evaluate band‐bending because the peak density of the excitation light on the sample is extremely high, so that bent electronic bands in semiconductors can be flattened. Secondary electron spectra, from which the vacuum level of the material surface can be determined, are obtained very quickly owing to the use of a TOF analyzer, The metal gate related issues are one of the most challenging topics facing CMOS technology. This paper demonstrates EUPS as a powerful method for characterizing high‐k/metal interfaces by showing data from direct observations of interfacial dipoles.

Effects of pn Doping in Thiophene/Phenylene Co-oligomers Thin Films

Doping effects in thiophene/phenylene co-oligomers (TPCOs) have been studied by means of extreme-UV (EUV) excited photoelectron spectroscopy (EUPS) and electro-luminescence experiments. Doped poly-crystalline films were fabricated by p-type doping with MoO3 to inherent p-type TPCO, BP1T (2,5-bis(4-biphenylyl)thiophene), and by n-type doping with Cs2CO3 to n-type AC5-CF3 (1,4-bis{5-[4-(trifluoromethyl)phenyl]thiophen-2-yl}benzene), respectively. Doping concentrations were 2% in both cases. The work function of BP1T was shifted from 4.0 to 4.3 eV and that of AC5-CF3 was shifted from 4.8 to 3.9 eV. The energy shifts are reasonable directions for p- and n-type doping. We also confirmed higher current injection with the doping films.