Hiroshi Funakubo

Bio: Hiroshi Funakubo is an academic researcher from Tokyo Institute of Technology. The author has contributed to research in topics: Thin film & Ferroelectricity. The author has an hindex of 47, co-authored 754 publications receiving 10776 citations. Previous affiliations of Hiroshi Funakubo include National Presto Industries & National Institute of Advanced Industrial Science and Technology.

Stabilizing the ferroelectric phase in doped hafnium oxide

Abstract: The ferroelectric properties and crystal structure of doped HfO2 thin films were investigated for different thicknesses, electrode materials, and annealing conditions Metal-ferroelectric-metal capacitors containing Gd:HfO2 showed no reduction of the polarization within the studied thickness range, in contrast to hafnia films with other dopants A qualitative model describing the influence of basic process parameters on the crystal structure of HfO2 was proposed The influence of different structural parameters on the field cycling behavior was examined This revealed the wake-up effect in doped HfO2 to be dominated by interface induced effects, rather than a field induced phase transition TaN electrodes were shown to considerably enhance the stabilization of the ferroelectric phase in HfO2 compared to TiN electrodes, yielding a Pr of up to 35 μC/cm2 This effect was attributed to the interface oxidation of the electrodes during annealing, resulting in a different density of oxygen vacancies in the Gd:Hf

Dimensionality-controlled insulator-metal transition and correlated metallic state in 5d transition metal oxides Sr n+1Ir nO3n+1 (n=1, 2, and infinity)

Abstract: We investigated the electronic structures of the 5d Ruddlesden-Popper series Sr n+1Ir nO3n+1 (n=1, 2, and infinity) using optical spectroscopy and first-principles calculations. As 5d orbitals are spatially more extended than 3d or 4d orbitals, it has been widely accepted that correlation effects are minimal in 5d compounds. However, we observed a Mott insulator-metal transition with a change of bandwidth as we increased n. In addition, the artificially synthesized perovskite SrIrO3 showed a very large mass enhancement of about 6, indicating that it was in a correlated metallic state.

Large remanent polarization of (Bi, Nd)4Ti3O12 epitaxial thin films grown by metalorganic chemical vapor deposition

Abstract: (104)-oriented Bi4Ti3O12, La-substituted Bi4Ti3O12[(Bi3.44La0.56)Ti3O12] and Nd-substituted Bi4Ti3O12[(Bi3.54Nd0.46)Ti3O12] films were epitaxially grown on (111)SrRuO3//(111)SrTiO3 substrates at 700 °C by metalorganic chemical vapor deposition. All deposited films showed strong (104) orientations. The values of the remanent polarization (Pr) and coercive field (Ec) of the (104)-oriented epitaxial (Bi3.54Nd0.46)Ti3O12 thin film were 25 μC/cm2 and 135 kV/cm, respectively. This Pr value was larger than that of the (104)-oriented (Bi3.44La0.56)Ti3O12 film: Pr and Ec values of the (Bi3.44La0.56)Ti3O12 were 17 μC/cm2 and 145 kV/cm, respectively. These good ferroelectric properties of (Bi3.54Nd0.46)Ti3O12 films can be explained by a large tilting of TiO6 octahedra induced by the substitution of Nd3+, the ionic radius of which is smaller than that of La3+. Moreover, this Pr value is almost equal to that of commercially used lead zirconate titanate (PZT) films for nonvolatile ferroelectric random access memory (Fe...

Crystal structure and ferroelectric properties of rare-earth substituted BiFeO3 thin films

Abstract: The influence of ion modification using rare-earth cations on crystal structures, along with the insulating and ferroelectric properties of BiFeO3 (BFO) thin films was investigated. Rare-earth-substituted BFO films with chemical compositions of (Bi1.00−xREx)Fe1.00O3 (x=0–0.15, RE=La and Nd) were fabricated on (111)Pt∕TiO2∕SiO2∕(100)Si substrates using a chemical solution deposition technique. A crystalline phase of rhombohedral BFO was obtained by heat treatment in a N2 atmosphere at 500°C for 5min. The crystal anisotropy and the Curie temperature of BFO were degraded continuously with increasing contents of La3+ or Nd3+ cations. Ion modification using La3+ and Nd3+ cations up to x=0.05 lowered the leakage current density of the BFO film at room temperature from approximately 10−3 down to 10−6A∕cm2. A polarization (P)-electrical field (E) hysteresis loop measured at 10K revealed that the intrinsic remanent polarization of La3+- and Nd3+-substituted BFO films with x=0.05 (44 and 51μC∕cm2, respectively) was...

The demonstration of significant ferroelectricity in epitaxial Y-doped HfO2 film

Abstract: Ferroelectricity and Curie temperature are demonstrated for epitaxial Y-doped HfO2 film grown on (110) yttrium oxide-stabilized zirconium oxide (YSZ) single crystal using Sn-doped In2O3 (ITO) as bottom electrodes. The XRD measurements for epitaxial film enabled us to investigate its detailed crystal structure including orientations of the film. The ferroelectricity was confirmed by electric displacement filed – electric filed hysteresis measurement, which revealed saturated polarization of 16 μC/cm2. Estimated spontaneous polarization based on the obtained saturation polarization and the crystal structure analysis was 45 μC/cm2. This value is the first experimental estimations of the spontaneous polarization and is in good agreement with the theoretical value from first principle calculation. Curie temperature was also estimated to be about 450 °C. This study strongly suggests that the HfO2-based materials are promising for various ferroelectric applications because of their comparable ferroelectric properties including polarization and Curie temperature to conventional ferroelectric materials together with the reported excellent scalability in thickness and compatibility with practical manufacturing processes.

Progress, Challenges, and Opportunities in Two-Dimensional Materials Beyond Graphene

Abstract: Graphene’s success has shown that it is possible to create stable, single and few-atom-thick layers of van der Waals materials, and also that these materials can exhibit fascinating and technologically useful properties. Here we review the state-of-the-art of 2D materials beyond graphene. Initially, we will outline the different chemical classes of 2D materials and discuss the various strategies to prepare single-layer, few-layer, and multilayer assembly materials in solution, on substrates, and on the wafer scale. Additionally, we present an experimental guide for identifying and characterizing single-layer-thick materials, as well as outlining emerging techniques that yield both local and global information. We describe the differences that occur in the electronic structure between the bulk and the single layer and discuss various methods of tuning their electronic properties by manipulating the surface. Finally, we highlight the properties and advantages of single-, few-, and many-layer 2D materials in...

Physics and Applications of Bismuth Ferrite

Abstract: BiFeO3 is perhaps the only material that is both magnetic and a strong ferroelectric at room temperature. As a result, it has had an impact on the field of multiferroics that is comparable to that of yttrium barium copper oxide (YBCO) on superconductors, with hundreds of publications devoted to it in the past few years. In this Review, we try to summarize both the basic physics and unresolved aspects of BiFeO3 (which are still being discovered with several new phase transitions reported in the past few months) and device applications, which center on spintronics and memory devices that can be addressed both electrically and magnetically.

Fundamentals of zinc oxide as a semiconductor

Abstract: In the past ten years we have witnessed a revival of, and subsequent rapid expansion in, the research on zinc oxide (ZnO) as a semiconductor. Being initially considered as a substrate for GaN and related alloys, the availability of high-quality large bulk single crystals, the strong luminescence demonstrated in optically pumped lasers and the prospects of gaining control over its electrical conductivity have led a large number of groups to turn their research for electronic and photonic devices to ZnO in its own right. The high electron mobility, high thermal conductivity, wide and direct band gap and large exciton binding energy make ZnO suitable for a wide range of devices, including transparent thin-film transistors, photodetectors, light-emitting diodes and laser diodes that operate in the blue and ultraviolet region of the spectrum. In spite of the recent rapid developments, controlling the electrical conductivity of ZnO has remained a major challenge. While a number of research groups have reported achieving p-type ZnO, there are still problems concerning the reproducibility of the results and the stability of the p-type conductivity. Even the cause of the commonly observed unintentional n-type conductivity in as-grown ZnO is still under debate. One approach to address these issues consists of growing high-quality single crystalline bulk and thin films in which the concentrations of impurities and intrinsic defects are controlled. In this review we discuss the status of ZnO as a semiconductor. We first discuss the growth of bulk and epitaxial films, growth conditions and their influence on the incorporation of native defects and impurities. We then present the theory of doping and native defects in ZnO based on density-functional calculations, discussing the stability and electronic structure of native point defects and impurities and their influence on the electrical conductivity and optical properties of ZnO. We pay special attention to the possible causes of the unintentional n-type conductivity, emphasize the role of impurities, critically review the current status of p-type doping and address possible routes to controlling the electrical conductivity in ZnO. Finally, we discuss band-gap engineering using MgZnO and CdZnO alloys.

Liquid Exfoliation of Layered Materials

Abstract: Background Since at least 400 C.E., when the Mayans first used layered clays to make dyes, people have been harnessing the properties of layered materials. This gradually developed into scientific research, leading to the elucidation of the laminar structure of layered materials, detailed understanding of their properties, and eventually experiments to exfoliate or delaminate them into individual, atomically thin nanosheets. This culminated in the discovery of graphene, resulting in a new explosion of interest in two-dimensional materials. Layered materials consist of two-dimensional platelets weakly stacked to form three-dimensional structures. The archetypal example is graphite, which consists of stacked graphene monolayers. However, there are many others: from MoS 2 and layered clays to more exotic examples such as MoO 3 , GaTe, and Bi 2 Se 3 . These materials display a wide range of electronic, optical, mechanical, and electrochemical properties. Over the past decade, a number of methods have been developed to exfoliate layered materials in order to produce monolayer nanosheets. Such exfoliation creates extremely high-aspect-ratio nanosheets with enormous surface area, which are ideal for applications that require surface activity. More importantly, however, the two-dimensional confinement of electrons upon exfoliation leads to unprecedented optical and electrical properties. Liquid exfoliation of layered crystals allows the production of suspensions of two-dimensional nanosheets, which can be formed into a range of structures. (A) MoS 2 powder. (B) WS 2 dispersed in surfactant solution. (C) An exfoliated MoS 2 nanosheet. (D) A hybrid material consisting of WS 2 nanosheets embedded in a network of carbon nanotubes. Advances An important advance has been the discovery that layered crystals can be exfoliated in liquids. There are a number of methods to do this that involve oxidation, ion intercalation/exchange, or surface passivation by solvents. However, all result in liquid dispersions containing large quantities of nanosheets. This brings considerable advantages: Liquid exfoliation allows the formation of thin films and composites, is potentially scaleable, and may facilitate processing by using standard technologies such as reel-to-reel manufacturing. Although much work has focused on liquid exfoliation of graphene, such processes have also been demonstrated for a host of other materials, including MoS 2 and related structures, layered oxides, and clays. The resultant liquid dispersions have been formed into films, hybrids, and composites for a range of applications. Outlook There is little doubt that the main advances are in the future. Multifunctional composites based on metal and polymer matrices will be developed that will result in enhanced mechanical, electrical, and barrier properties. Applications in energy generation and storage will abound, with layered materials appearing as electrodes or active elements in devices such as displays, solar cells, and batteries. Particularly important will be the use of MoS 2 for water splitting and metal oxides as hydrogen evolution catalysts. In addition, two-dimensional materials will find important roles in printed electronics as dielectrics, optoelectronic devices, and transistors. To achieve this, much needs to be done. Production rates need to be increased dramatically, the degree of exfoliation improved, and methods to control nanosheet properties developed. The range of layered materials that can be exfoliated must be expanded, even as methods for chemical modification must be developed. Success in these areas will lead to a family of materials that will dominate nanomaterials science in the 21st century.

Applications of Modern Ferroelectrics

Abstract: Long viewed as a topic in classical physics, ferroelectricity can be described by a quantum mechanical ab initio theory. Thin-film nanoscale device structures integrated onto Si chips have made inroads into the semiconductor industry. Recent prototype applications include ultrafast switching, cheap room-temperature magnetic-field detectors, piezoelectric nanotubes for microfluidic systems, electrocaloric coolers for computers, phased-array radar, and three-dimensional trenched capacitors for dynamic random access memories. Terabit-per-square-inch ferroelectric arrays of lead zirconate titanate have been reported on Pt nanowire interconnects and nanorings with 5-nanometer diameters. Finally, electron emission from ferroelectrics yields cheap, high-power microwave devices and miniature x-ray and neutron sources.