次世代ナノエレクトロニクスを志向した単層及び多層グラフェンナノリボンの電気特性に関する研究

Graphene nanoribbon (GNR) is a narrow strip of carbon atoms which has exceptional properties and are being exploited for various applications, such as in semiconductor electronics, solar cells, and sensors. However, the realization of GNR based devices still needs an extensive research to achieve the commercial specifications. This research is mainly emphasized on the synthesis of high-quality GNR from double-walled carbon nanotubes (DWNTs) and fabrication of field effect transistor (FET) devices. Moreover, the electrical transport properties were also investigated for single-layer GNR (sGNR), multi-layer GNR with and without adsorption of molecular nanoparticles. The electrical transport properties of GNR device was tuned to semiconducting with the adsorption of molecular nanoparticles. This study demonstrates a simple and fast approach to band gap formation in sGNR using Hexaazatriphenylenehexacarbonitrile (HAT-CN6). In this process, sGNRs were synthesized by unzipping of DWNTs followed by casting the solution of HAT-CN6. HAT-CN6 on GNR forms self-assembled nanoparticle and the adsorption of nanoparticles was confirmed by AFM observation. Further, the electric property of pristine sGNR device and the device with HAT-CN6 were measured using point-contact current imaging (PCI-) AFM and also with the FET device. Thus, the adsorbed nanoparticles on sGNR forms the electron trapping sites which result in a necklike structure of sGNR near the adsorbed region of the molecular nanoparticle. The neck region working similar to narrow width GNR (< 10 nm) allows the charge carriers passing through. Such a narrow sGNR has lateral confinement of charge carrier around the neck region hence the device turns to semiconducting. The activation energy of pristine sGNR and the sGNR with HAT-CN6 were calculated by the results of temperature change measurement as about 1.5 meV and 52 meV, respectively. The pristine sGNR has very low activation energy as compared to the device with HAT-CN6. Thus, the device with HAT-CN6 has a large transition from semimetallic to semiconducting property. The device could have various possible application in future electronics industry due to its semiconducting property. Moreover, the study also explains the fabrication of multi-layer GNR (mGNR) field effect transistor (FET) and control of its electrical property with the adsorption of the flat molecular nanoparticle. The stacked mGNR device shows the similar performance to the sGNR device due to lower inter layer coupling. Inter layer interaction was supposed to be lower since the turbostratic stacking of GNR was formed with CVD growth process. Next, HAT-CN6 were casted on the mGNR device to alter the electronic property of GNR. Thus, the adsorbed nanoparticles form the charge carrier trapping sites on mGNR and the channel width was narrowed due to the nanoparticles on GNR. Hence, the charge carriers are confined in a narrow channel and the device is in a transition state from semimetallic to semiconducting, which is similar to narrow width GNR. The on/off ratio and mobility of mGNR-FET device was also improved with the adsorption of the nanoparticle. The fabricated mGNR-FET device has wide area of semiconductor electronics applications in the semiconductor industry. Furthermore, X- and Y-type junctions were also fabricated using GNRs obtained by unzipping of DWNTs. The junction of the synthesized GNR shows semiconducting property whereas the other part shows the semimetallic property. The semiconducting property at the junction was supposed to be due to change in lattice orientation at the junction of two GNRs. Such a junction can have great interest for the device and wiring application in the semiconductor industry. The semiconducting property in the several X-type junctions of wide GNRs (greater than 10 nm) was investigated.九州工業大学博士学位論文 学位記番号：生工博甲第295号 学位授与年月日：平成29年6月30日1 Introduction|2 Methodology|3 Tuning the electrical property of single-layer graphene nanoribbon by adsorption of planar molecular nanoparticles|4 Fabrication of turbostratic multi-layer graphene nanoribbon field effect transistor and investigating the electrical property with the adsorption of HAT-CN666|5 Fabrication of X- and Y-type graphene nanoribbon cross junction and study the electrical transport property|6 Conclusion九州工業大学平成29年

Stability improvement of an efficient graphene nanoribbon field-effect transistor-based sram design

The development of the nanoelectronics semiconductor devices leads to the shrinking of transistors channel into nanometer dimension. However, there are obstacles that appear with downscaling of the transistors primarily various short-channel effects. Graphene nanoribbon field-effect transistor (GNRFET) is an emerging technology that can potentially solve the issues of the conventional planar MOSFET imposed by quantum mechanical (QM) effects. GNRFET can also be used as static random-access memory (SRAM) circuit design due to its remarkable electronic properties. For high-speed operation, SRAM cells are more reliable and faster to be effectively utilized as memory cache. The transistor sizing constraint affects conventional 6T SRAM in a trade-off in access and write stability. This paper investigates on the stability performance in retention, access, and write mode of 15 nm GNRFET-based 6T and 8T SRAM cells with that of 16 nm FinFET and 16 nm MOSFET. The design and simulation of the SRAM model are simulated in synopsys HSPICE. GNRFET, FinFET, and MOSFET 8T SRAM cells give better performance in static noise margin (SNM) and power consumption than 6T SRAM cells. The simulation results reveal that the GNRFET, FinFET, and MOSFET-based 8T SRAM cells improved access static noise margin considerably by 58.1%, 28%, and 20.5%, respectively, as well as average power consumption significantly by 97.27%, 99.05%, and 83.3%, respectively, to the GNRFET, FinFET, and MOSFET-based 6T SRAM design. © 2020 Mathan Natarajamoorthy et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited

Two-Dimensional Electronic Materials and Devices: Opportunities and Challenges

The unprecedented growth of the Internet of Things (IoT) and the 4th Industrial Revolution (Industry 4.0) not only demands dimensional scaling of device technologies but also new types of applications beyond today’s electronics. Two-dimensional (2D) materials, a group of layered crystals (such as graphene and MoS2) with unique properties, have emerged as promising candidates for IoT and Industry 4.0 since they can, not only extend the scaling with unprecedented performance and energy efficiency but also exhibit high potential for novel electronic devices. However, such nanomaterials suffer from significant challenges in process integration, especially in the modules that involves the formation of interfaces between 2D materials and conventional bulk materials. Thus, realizing high-performance energy-efficient 2D electronic devices has been challenging. This dissertation focuses on understanding the fundamental issues in such 2D materials (such as contacts, interfaces and doping) and in identifying applications uniquely enabled by these materials.First, a comprehensive treatment of metal contacts to 2D semiconductors, which has been a huge hurdle for 2D electronic technologies, will be presented. As a pioneering study, new interface physics originating from the unique dimensionality and surface properties have been revealed [1]. Solutions to minimize contact resistance are described though techniques of interface hybridization [2] and seamless contacts [3], [4]. These techniques transform 2D semiconductors from solely scientifically-interesting materials into high-performance field-effect transistor (FET) technologies, such as MoS2 FETs with record-low contact resistances [5], [6] and WSe2 FETs with record-high drive current and mobility [7]. Beyond metal interfaces, dielectric interface is crucial for preserving the carrier mobility in 2D channels, for which a solution enabled by buffer layers has been proposed [8]. On the other hand, the vertical van der Waals interfaces between 2D and 3D semiconductors, which retain the advantages of pristine ultra-thin 2D films as well as maximized tunneling area/field, have been studied and exploited into a novel beyond-silicon transistor technology – the first 2D channel tunnel FET (TFET) [9], which beat the fundamental limitation in the switching behavior of transistors. Recent results from the engineering of such 2D-3D semiconductor interfaces by surface reduction/passivation are described, showing a significant boost of drive current. While conventional diffusion/ion implantation methods are infeasible for 2D materials, two efficient doping techniques that are specific for 2D materials – surface doping [10], [11] and intercalation doping [12] are presented. The theoretical study of surface doping using ab-initio methods helped develop a novel doping scheme that uniquely exploits the Lewis-base like pedigree of 2D semiconductors without disturbing the structural integrity of the 2D atomic layer configuration [13], as well as a novel electrocatalyst based on MoS2 that achieved record high hydrogen evolution reaction (HER) performance [14]. On the other hand, intercalation doping has been employed to demonstrate graphene based transparent electrodes with the best combination of transmittance and sheet resistance [12], and also the first graphene interconnects with excellent performance, reliability and energy-efficiency [15], [16]. Moreover, by uniquely exploiting the high kinetic inductance and conductivity of intercalation doped graphene, a fundamentally different on-chip inductor has been demonstrated [17], [18], with both small form-factors and high inductance values, that were once thought unachievable in tandem. This 2D technique provides an attractive solution to the longstanding scaling problem of analog/radio-frequency electronics and opens up an unconventional pathway for the development of future ultra-compact wireless communication systems. Finally, a novel dissipative quantum transport methodology based on Büttiker probes with band-to-band tunneling capability is developed for 2D FETs [19]. Subsequently, gate-induced-drain-leakage (GIDL), one of the main leakage mechanisms in FETs especially access transistors, is evaluated for the first time for 2D FETs. The results establish the advantages of certain 2D semiconductors in greatly reducing GIDL and thereby support use of such materials in future memory technologies.The dissertation concludes with a vision for how a smart life can be realized in the future by harnessing the capabilities of various 2D technologies in the era of IoT and Industry 4.0.[1] J. Kang, D. Sarkar, W. Liu, D. Jena, and K. Banerjee, “A computational study of metal-contacts to beyond-graphene 2D semiconductor materials,” in IEEE International Electron Devices Meeting, 2012, pp. 407–410.[2] J. Kang, W. Liu, D. Sarkar, D. Jena, and K. Banerjee, “Computational Study of Metal Contacts to Monolayer Transition-Metal Dichalcogenide Semiconductors,” Phys. Rev. X, vol. 4, no. 3, p. 31005, Jul. 2014.[3] J. Kang, D. Sarkar, Y. Khatami, and K. Banerjee, “Proposal for all-graphene monolithic logic circuits,” Appl. Phys. Lett., vol. 103, no. 8, p. 83113, 2013.[4] A. Allain, J. Kang, K. Banerjee, and A. Kis, “Electrical contacts to two-dimensional semiconductors,” Nat. Mater., vol. 14, no. 12, pp. 1195–1205, 2015.[5] W. Liu et al., “High-performance few-layer-MoS2 field-effect-transistor with record low contact-resistance,” in IEEE International Electron Devices Meeting, 2013, pp. 499–502.[6] J. Kang, W. Liu, and K. Banerjee, “High-performance MoS2 transistors with low-resistance molybdenum contacts,” Appl. Phys. Lett., vol. 104, no. 9, p. 93106, Mar. 2014.[7] W. Liu, J. Kang, D. Sarkar, Y. Khatami, D. Jena, and K. Banerjee, “Role of metal contacts in designing high-performance monolayer n-type WSe2 field effect transistors.,” Nano Lett., vol. 13, no. 5, pp. 1983–90, May 2013.[8] J. Kang, W. Liu, and K. Banerjee, “Computational Study of Interfaces between 2D MoS2 and Surroundings,” in 45th IEEE Semiconductor Interface Specialists Conference, 2014.[9] D. Sarkar et al., “A subthermionic tunnel field-effect transistor with an atomically thin channel,” Nature, vol. 526, no. 7571, pp. 91–95, Sep. 2015.[10] Y. Khatami, W. Liu, J. Kang, and K. Banerjee, “Prospects of graphene electrodes in photovoltaics,” in Proceedings of SPIE, 2013, vol. 8824, p. 88240T–88240T–6.[11] D. Sarkar et al., “Functionalization of Transition Metal Dichalcogenides with Metallic Nanoparticles: Implications for Doping and Gas-Sensing,” Nano Lett., vol. 15, no. 5, pp. 2852–2862, May 2015.[12] W. Liu, J. Kang, and K. Banerjee, “Characterization of FeCl3 intercalation doped CVD few-layer graphene,” IEEE Electron Device Lett., vol. 37, no. 9, pp. 1246–1249, Sep. 2016.[13] S. Lei et al., “Surface functionalization of two-dimensional metal chalcogenides by Lewis acid–base chemistry,” Nat. Nanotechnol., vol. 11, no. 5, pp. 465–471, Feb. 2016.[14] J. Li, J. Kang, Q. Cai, W. Hong, C. Jian, and W. Liu, “Boosting Hydrogen Evolution Performance of MoS2 by Band Structure Engineering,” Adv. Mater. Interfaces, vol. 1700303, 2017.[15] J. Jiang et al., “Intercalation doped multilayer-graphene-nanoribbons for next-generation interconnects,” Nano Lett., vol. 17, no. 3, pp. 1482–1488, Mar. 2017.[16] J. Jiang, J. Kang, and K. Banerjee, “Characterization of Self - Heating and Current - Carrying Capacity of Intercalation Doped Graphene - Nanoribbon Interconnects,” in IEEE International Reliability Physics Symposium, 2017, p. 6B.1.1-6B.1.6.[17] X. Li et al., “Graphene inductors for high-frequency applications - design, fabrication, characterization, and study of skin effect,” in IEEE International Electron Devices Meeting, 2014, p. 5.4.1-5.4.4.[18] J. Kang et al., under review.[19] J. Kang et al., under review

High-Quality Chemical Vapor Deposition Graphene-Based Spin Transport Channels

Spintronics reaches beyond typical charge-based information storage technologies by utilizing an addressable degree of freedom for electron manipulation, the electron spin polarization. With mounting experimental data and improved theoretical understanding of spin manipulation, spintronics has become a potential alternative to charge-based technologies. However, for a long time, spintronics was not thought to be feasible without the ability to electrostatically control spin conductance at room temperature. Only recently, graphene, a 2D honeycomb crystalline allotrope of carbon only one atom thick, was identified because of its predicted, long spin coherence length and experimentally realized electrostatic gate tunability. However, there exist several challenges with graphene spintronics implementation including weak spin-orbit coupling that provides excellent spin transfer yet prevents charge to spin current conversion, and a conductivity mismatch due to the large difference in carrier density between graphene and a ferromagnet (FM) that must be mitigated by use of a tunnel barrier contact. Additionally, the usage of graphene produced via CVD methods amenable to semiconductor industry in conjunction with graphene spin valve fabrication must be explored in order to promote implementation of graphene-based spintronics. Despite advances in the area of graphene-based spintronics, there is a lack of understanding regarding the coupling of industry-amenable techniques for both graphene synthesis and lateral spin valve fabrication. In order to make any impact on the application of graphene spintronics in industry, it is critical to demonstrate wafer-scale graphene spin devices enabled by wafer-scale graphene synthesis, which utilizes thin film, wafer-supported CVD growth methods. In this work, high-quality graphene was synthesized using a vertical cold-wall furnace and catalyst confinement on both SiO2/Si and C-plane sapphire wafers and the implementation of the as-grown graphene for fabrication of graphene-based non-local spin valves was examined. Optimized CVD graphene was demonstrated to have ID/G ≈ 0.04 and I2D/G ≈ 2.3 across a 2 diameter graphene film with excellent continuity and uniformity. Since high-quality, large-area, and continuous CVD graphene was grown, it enabled the fabrication of large device arrays with 40 individually addressable non-local spin valves exhibiting 83% yield. Using these arrays, the effects of channel width and length, ferromagnetic-tunnel barrier width, tunnel barrier thickness, and level of oxidation for Ti-based tunnel barrier contacts were elucidated. Non-local, in-plane magnetic sweeps resulted in high signal-to-noise ratios with measured ΔRNL across the as-fabricated arrays as high as 12 Ω with channel lengths up to 2 µm. In addition to in-plane magnetic field spin signal values, vertical magnetic field precession Hanle effect measurements were conducted. From this, spin transport properties were extracted including: spin polarization efficiency, coherence lifetime, and coherence distance. The evaluation of industry-amenable production methods of both high-quality graphene and lateral graphene non-local spin valves are the first steps toward promoting the feasibility of graphene as a lateral spin transport interconnect material in future spintronics applications. By addressing issues using a holistic approach, from graphene synthesis to spin transport implementation, it is possible to begin assessment of the challenges involved for graphene spintronics

Aperiodic Multilayer Graphene Based Tunable and Switchable Thermal Emitter at Mid-infrared Frequencies

Over the past few decades, there have been tremendous innovations in electronics and photonics. The development of these ultra-fast growing technologies mostly relies on fundamental understanding of novel materials with unique properties as well as new designs of device architectures with more diverse and better functionalities. In this regard, the promising approach for next-generation nanoscale electronics and photonics is to exploit the extraordinary characteristics of novel nanomaterials. There has been an explosion of interest in graphene for photonic applications as it provides a degree of freedom to manipulate electromagnetic waves. In this thesis, to tailor the broadband blackbody radiation, new aperiodic multilayer structures composed of multiple layers of graphene and hexagonal boron nitride (hBN) are proposed as selective, tunable and switchable thermal emitters. To obtain the layer thicknesses of these aperiodic multilayer structures for maximum emittance/absorptance, a hybrid optimization algorithm coupled to a transfer matrix code is employed. The device simulation indicates that perfect absorption efficiency of unity can be achieved at very narrow frequency bands in the infrared under normal incidence. It has been shown that the chemical potential in graphene enables a promising way to design electrically controllable absorption/emission, resulting in selective, tunable and switchable thermal emitters at infrared frequencies. By simulating different aperiodic thermal emitters with different numbers of graphene layers, the effect of the number of graphene layers on selectivity, tunability, and switchability of thermal emittance is investigated. This study may contribute towards the realization of wavelength selective detectors with switchable intensity for sensing applications

2D materials based nanopore structures as single molecule sensors

Nanopores are impedance based bio-sensors. The principle of nanopore sensors is analogous to that of a Coulter counter. A nanoscale aperture (the nanopore) is formed in an insulating membrane separating two chambers filled with conductive electrolyte. Charged molecules are driven through the pore under an applied electric voltage (a process known as electrophoresis), thereby modulating the ionic current through the nanopore. The temporary modulation of ionic current due to translocation of the molecule provides useful information about the structure, length, orientation and sequence. This versatile approach permits the label-free, amplification-free analysis of charged biopolymers. The major challenges facing nanopore based techniques for practical sequencing applications are the limitations on temporal and spatial resolution. The finite thickness of membranes limit the spatial resolution of the measurement as multiple nucleotides occupy the pore at a given instant, reducing the sensitivity of the signal making single nucleotide resolution difficult to achieve. Graphene and MoS¬2 as a single layer material of the same order of thickness as the nucleotide separation in a DNA strand presents an exciting alternative to commercial Silicon nitride membranes. These materials also provide potential for exploration of field effect mechanisms which can be an alternative mechanism detect the individual nucleotides in the DNA strand. The possibility and feasibility of using the unique electrical properties of embedded active layers of graphene and MoS2 in stacked membranes has been explored here. The embedded graphene layers presented unique insights into the electrochemical properties of graphene edges in an embedded nanopore structure. The lack of a bad gap in graphene (unless extremely narrow constrictions are fabricated, which is very challenging) makes MoS2 (monolayers have a direct band gap of 1.85 eV) the more favorable material for charge based detection. The electrical properties of both graphene and MoS2 channels are reported here. Additionally we also studied the DNA transport through nanopores in freely suspended MoS2 membranes as well as integration of MoS2 in our stacked architecture. The other major challenge is to control/slow down DNA transport to within bandwidth limitation of commercial instruments to ensure reliable nucleotide separation in the blockade signal. The application of graphene-DNA hydrophobic attractions as a method to reduce DNA translocation speed is reported. A final device with integrated graphene, MoS2 and dielectric layers could provide the required structure to achieve DNA sequencing. In addition atomic layer thin membranes could also improve the diagnostic capabilities of nanopore detection. The atomic layer thickness of these membranes could enable spatial mapping of size differences of an individual molecule. We report the ability of MoS2 membrane to distinguish free DNA from DNA-protein complex molecules. The ability to detect the presence of methyl binding domain proteins on methylated sites of DNA is valuable to the field of cancer diagnostics and such thin membranes could provide a pathway for spatial mapping of individual methylated sites