Carbon Science in 2016: Status, Challenges and Perspectives
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Nanosystems, Edge Computing, and the Next Generation Computing Systems
sensors Review Nanosystems, Edge Computing, and the Next Generation Computing Systems Ali Passian * and Neena Imam Computing & Computational Sciences Directorate, Oak Ridge National Laboratory, Oak Ridge, TN 37830, USA; [email protected] * Correspondence: [email protected] Received: 30 July 2019; Accepted: 16 September 2019; Published: 19 September 2019 Abstract: It is widely recognized that nanoscience and nanotechnology and their subfields, such as nanophotonics, nanoelectronics, and nanomechanics, have had a tremendous impact on recent advances in sensing, imaging, and communication, with notable developments, including novel transistors and processor architectures. For example, in addition to being supremely fast, optical and photonic components and devices are capable of operating across multiple orders of magnitude length, power, and spectral scales, encompassing the range from macroscopic device sizes and kW energies to atomic domains and single-photon energies. The extreme versatility of the associated electromagnetic phenomena and applications, both classical and quantum, are therefore highly appealing to the rapidly evolving computing and communication realms, where innovations in both hardware and software are necessary to meet the growing speed and memory requirements. Development of all-optical components, photonic chips, interconnects, and processors will bring the speed of light, photon coherence properties, field confinement and enhancement, information-carrying capacity, and the broad spectrum of light into the high-performance computing, the internet of things, and industries related to cloud, fog, and recently edge computing. Conversely, owing to their extraordinary properties, 0D, 1D, and 2D materials are being explored as a physical basis for the next generation of logic components and processors. Carbon nanotubes, for example, have been recently used to create a new processor beyond proof of principle. -
Three Distinct Torsion Profiles of Electronic Transmission Through
Three Distinct Torsion Profiles of Electronic Transmission through Linear Carbon Wires Marc H. Garner†, William Bro-Jørgensen, Gemma C. Solomon* Nano-Science Center and Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen Ø, Denmark. ABSTRACT. The one-dimensional carbon allotrope carbyne, a linear chain of sp-hybridized carbon atoms, is predicted to exist in a polyynic and a cumulenic structure. While molecular forms of carbyne have been extensively characterized, the structural nature is hard to determine for many linear carbon wires that are made in-situ during pulling experiments. Here, we show that cumulenes and polyynes have distinctively different low-bias conductance profiles under axial torsion. We analyze the change of the electronic structure, Landauer transmission, and ballistic current density of the three types of closed-shell molecular carbynes as a function of the torsion angle. Both polyynic, odd-carbon cumulenic, and even-carbon cumulenic carbon wires exhibit helical frontier molecular orbitals when the end-groups are not in a co-planar configuration. This helical conjugation effect gives rise to strong ring current patterns around the linear wires. Only the transmission of even-carbon polyynic wires follows the well-known cosine-squared law with axial torsion that is also seen in biphenyl-type systems. Notably, the transmission of even-carbon cumulenic carbon wires rises with axial torsion from co-planar towards perpendicular orientation of the end-groups. The three distinct transmission profiles of polyynes, odd-carbon cumulenes, 1 and even-carbon cumulenes may allow for experimental identification of the structural nature of linear carbon wires. Their different electron transport properties under axial torsion furthermore underline that, in the molecular limit of carbyne, three different subclasses of linear carbon wires exist. -
Numerical Investigation of Carbon Nanotube Thin-Film Composites and Devices
NUMERICAL INVESTIGATION OF CARBON NANOTUBE THIN-FILM COMPOSITES AND DEVICES A Dissertation Presented to The Academic Faculty By Man Prakash Gupta In Partial Fulfillment Of the Requirements for the Degree Doctor of Philosophy in Mechanical Engineering Georgia Institute of Technology May 2015 Copyright © Man Prakash Gupta 2015 NUMERICAL INVESTIGATION OF CARBON NANOTUBE THIN-FILM COMPOSITES AND DEVICES Approved by: Dr. Satish Kumar, Adviser Dr. Abhijit Chatterjee School of Mechanical Engineering School of Electrical and Computer Georgia Institute of Technology Engineering Georgia Institute of Technology Dr. Alexander Alexeev Dr. Manos Tentzeris School of Mechanical Engineering School of Electrical and Computer Georgia Institute of Technology Engineering Georgia Institute of Technology Dr. Baratunde Cola School of Mechanical Engineering Georgia Institute of Technology Date Approved: December 5, 2014 ACKNOWLEDGEMENTS The period of last five years during my PhD program has been profoundly transformational for me in many ways. Looking back, I find that it has been truly an enjoyable and intellectually satisfying journey which was made possible by the help and support of a number of people. Among them first and foremost, I would like to thank my mentor and adviser Dr. Satish Kumar for providing the necessary guidance and constant encouragement. He has been incredibly patient and supportive during the entire program. Needless to say, he has been a role model for me and I consider it my privilege to be one of the first graduate students in his research group. I am grateful to my collaborators Dr. Saibal Mukhopadhyay, Dr. Eric Pop, Dr. Minki Cho, Dr. David Estrada and Dr. Ashkan Behnam for allowing me to work with them and having fruitful discussions. -
Carbon Nanotube-Based Three-Dimensional Monolithic Optoelectronic Integrated System
ARTICLE Received 14 Aug 2016 | Accepted 15 Apr 2017 | Published 8 Jun 2017 DOI: 10.1038/ncomms15649 OPEN Carbon nanotube-based three-dimensional monolithic optoelectronic integrated system Yang Liu1, Sheng Wang2, Huaping Liu3,4 & Lian-Mao Peng1,2 Single material-based monolithic optoelectronic integration with complementary metal oxide semiconductor-compatible signal processing circuits is one of the most pursued approaches in the post-Moore era to realize rapid data communication and functional diversification in a limited three-dimensional space. Here, we report an electrically driven carbon nanotube-based on-chip three-dimensional optoelectronic integrated circuit. We demonstrate that photovoltaic receivers, electrically driven transmitters and on-chip electronic circuits can all be fabricated using carbon nanotubes via a complementary metal oxide semiconductor-compatible low-temperature process, providing a seamless integration platform for realizing monolithic three-dimensional optoelectronic integrated circuits with diversified functionality such as the heterogeneous AND gates. These circuits can be vertically scaled down to sub-30 nm and operates in photovoltaic mode at room temperature. Parallel optical communication between functional layers, for example, bottom-layer digital circuits and top-layer memory, has been demonstrated by mapping data using a 2 Â 2 transmitter/receiver array, which could be extended as the next generation energy-efficient signal processing paradigm. 1 Key Laboratory for the Physics and Chemistry of Nanodevices and Academy for Advanced Interdisciplinary Studies, Peking University, Beijing 100871, China. 2 Key Laboratory for the Physics and Chemistry of Nanodevices and Department of Electronics, Peking University, Beijing 100871, China. 3 Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China. -
On the Road to Carbene and Carbyne Complexes
ON THE ROAD TO CARBENE AND CARBYNE COMPLEXES Nobel Lecture, 11 December 1973 by ERNST OTTO FISCHER Inorganic Chemistry Laboratory, Technical University, Munich, Federal Republic of Germany Translation from the German text INTRODUCTION In the year 1960, I had the honour of giving a talk at this university* about sandwich complexes on which we were working at that time. I think I do not have to repeat the results of those investigations today. I would like to talk instead about a field of research in which we have been intensely interested in recent years: namely, the field of carbene complexes and, more recently, carbyne complexes. If we substitute one of the hydrogen atoms in a hydrocarbon of the alkane type - for example, ethane - by a metal atom, which can of course bind many more ligands, we arrive at an organometallic compound in which the organic radical is bound to the metal atom by a σ-bond (Fig. la). The earliest compounds of this kind were prepared more than a hundred years ago; the first was cacodyl, prepared by R. Bunsen (1), and then zinc dialkyls were prepared by E. Frankland (2). Later V. Grignard was able to synthesise alkyl magnesium halides by treating magnesium with alkyl halides (3). Grignard was awarded the Nobel Prize in 1912 for this effort. We may further recall the organo-aluminium compounds (4) of K. Ziegler which form the basis for the low pressure polymerisation, for example of ethylene. Ziegler and G. Natta were together honoured with the Nobel Prize in 1963 for their work on organometallic compounds. -
Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative (Part I) Synthesis of Platinum and Ethynyl-Platinum Corannulenes (Part II)
Zurich Open Repository and Archive University of Zurich Main Library Strickhofstrasse 39 CH-8057 Zurich www.zora.uzh.ch Year: 2012 Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative (Part I) Synthesis of Platinum and Ethynyl-Platinum Corannulenes (Part II) Maag, Roman M Posted at the Zurich Open Repository and Archive, University of Zurich ZORA URL: https://doi.org/10.5167/uzh-164179 Dissertation Published Version Originally published at: Maag, Roman M. Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative (Part I) Synthesis of Platinum and Ethynyl-Platinum Corannulenes (Part II). 2012, University of Zurich, Faculty of Science. Part I: Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative and Part II: Synthesis of Platinum and Ethynyl-Platinum Corannulenes Dissertation zur Erlangung der naturwissenschaftlichen Doktorwurde¨ Dr. sc. nat. vorgelegt der Mathematisch-naturwissenschaftlichen Fakult¨at der Universit¨at Zurich¨ von Roman M. Maag von Winkel ZH Promotionskommitee: Prof. Dr. Jay S. Siegel (Vorsitz) Prof. Dr. Kim K. Baldridge Prof. Dr. Cristina Nevado Prof. Dr. Roger Alberto Zurich,¨ 2012 Abstract of the Dissertation Part I: Synthesis of an Unsymmetrically Pentafunctionalized Corannulene Derivative and Part II: Synthesis of Platinum and Ethynyl-Platinum Corannulenes by Roman M. Maag University of Zurich, 2012 Prof. Dr. Jay S. Siegel, Chair Corannulene (C20H10) is a polyaromatic hydrocarbon that can be considered as the smallest fragment of Buckminsterfullerene exhibiting a curved surface. Among the in- teresting properties of corannulene are rapid bowl inversion and esthetically appealing fivefold symmetry (C5v), which is rare in chemistry. Whereas the first synthesis in 1968 only afforded milligram quantities, several improvements in the synthetic strategy finally culminated in the development of an efficient process which today furnishes corannulene in kilogram quantities. -
Molecular Assembly of Polycyanoarenes with Silver Salts
MOLECULAR ASSEMBLY OF POLYCYANOARENES WITH SILVER SALTS AND SYNTHESIS OF POLYCYCLIC AROMATIC HYDROCARBONS A DISSERTATION IN Chemistry and Pharmaceutical Sciences Presented to the Faculty of the University of Missouri-Kansas City in partial fulfillment of the requirements for the degree DOCTOR OF PHILOSOPHY by GERARDO B. MÁRQUEZ B.Sc. Central University of Venezuela, 1993 Kansas City, Missouri 2012 © 2012 GERARDO B. MÁRQUEZ ALL RIGHTS RESERVEDED MOLECULAR ASSEMBLY OF POLYCYANORENES WITH SILVER SALTS AND SYNTHESIS OF POLYCYCLIC AROMATIC HYDROCARBONS Gerardo Batalla Márquez, Candidate for the Doctor of Philosophy Degree University of Missouri-Kansas City, 2012 ABSTRACT This dissertation encompasses the investigation of two distinct subjects. In the first part, which is in the area of molecular self-assembly, the complexation of organonitrile aryl compounds with three different types of silver (I) salts is examined in the solid state. The assembly of 1-(2,2-dicyanovinyl)naphthalene with silver hexafluoroantimonate resulted in a cationic 3D network. Complexation of 4-(2,2-dicyanovinyl)biphenyl with silver tetrafluoroborate and hexafluoroantimonate from benzene generated two similar structures. While the former displays a cationic 3D network, the latter is defined by cationic 2D sheets. Complexation of 9-(2,2-dicyanovinyl)anthracene with silver hexafluoroantimonate from toluene afforded a cationic 2D ribbon, and from benzene, it yielded cationic 2D sheets. These complexes contained solvent bonded to their structures. However, the hexafluoroantimonate ion is nonbonding. The crystal association of 1,4-bis(cyanovinyl)benzene with silver triflate from benzene yielded neutral 2D sheets whose imperfect-rectangular macrocyclic arrangements are interconnected on both sides by bridges of benzene. On the other hand, the assembly of 1,3- bis(cyanovinyl)benzene with silver triflate from benzene afforded a neutral 3D network formed by two interconnected rings. -
Anti‐Aromatic Versus Induced Paratropicity ... -.:. Michael Pittelkow
Angewandte Forschungsartikel Chemie Deutsche Ausgabe:DOI:10.1002/ange.201913552 Circulenes Internationale Ausgabe:DOI:10.1002/anie.201913552 Anti-Aromatic versus Induced Paratropicity:Synthesis and InterrogationofaDihydro-diazatrioxa[9]circulene with aProton Placed Directly above the Central Ring Stephan K. Pedersen, Kristina Eriksen, Nataliya N. Karaush-Karmazin, Boris Minaev, Hans gren, Gleb V. Baryshnikov* und Michael Pittelkow* Abstract: We present ahigh-yielding intramolecular oxidative coupling within adiazadioxa[10]helicene to give adihydro- diazatrioxa[9]circulene.This is the first [n]circulene contain- ing more than eight ortho-annulated rings (n > 8). The single- crystal X-raystructure reveals atight columnar packing, with aproton from apendant naphthalene moiety centred directly abovethe central nine-membered ring. This distinct environ- ment induces asignificant magnetic deshielding effect on that particular proton as determined by 1HNMR spectroscopy. The origin of the deshielding effect was investigated computation- ally in terms of the NICS values.Itisestablished that the deshielding effect originates from an induced paratropic ring current from the seven aromatic rings of the [9]circulene structure,and is not due to the nine-membered ring being antiaromatic.UV/Vis spectroscopyreveals more efficient Figure 1. Simplified illustration of the influence of diatropic and para- conjugation in the prepared diazatrioxa[9]circulene compared tropic ring currents on the 1Hchemical shift inside and outside of to the parent helical azaoxa[10]helicenes,and -
Synthesis of Functionalized Benzenoid Macrocycles: an Approach to Accessing Functionalized Cycloparaphenylenes
Synthesis of Functionalized Benzenoid Macrocycles: An Approach to Accessing Functionalized Cycloparaphenylenes by Rolande Meudom A thesis submitted to the Graduate Faculty of Auburn University in partial fulfillment of the requirements for the Degree of Master of Science Auburn, Alabama May 8, 2016 Keywords: Carbon nanotubes, Cycloparaphenylenes, p-terphenylophanes, Bent p-phenylene Macrocycles, Copyright 2016 by Rolande Meudom Approved by Bradley L. Merner, Chair, Assistant Professor of Chemistry and Biochemistry Peter Livant, Associate Professor of Chemistry and Biochemistry Anne E. V. Gorden, Associate Professor of Chemistry and Biochemistry Steven Mansoorabadi, Assistant Professor of Chemistry and Biochemistry Abstract Carbon nanotubes (CNTs) are cylindrically shaped allotropes of carbon with exceptionally good electronic and optical properties. The current state of art for making these CNTs involves heating graphite in a high temperature furnace (above 600 °C). The use of harsh temperatures makes the process unselective and produces CNTs as an inseparable mixture of products. Currently, there is no efficient purification technique for isolating pure CNTs. In order to fully exploit the electronic properties of CNTs, they need to be made as homogeneous and monodispersed structures. Thus, synthetic chemists envisioned using chemical synthesis from the ground-up via a template strategy as a more viable approach to achieve the selective synthesis of uniform CNTs structures with a defined chirality and diameter. This is because the selective synthesis of curved PAHs like [n]ciruclenes and CNT substructures could only be accomplished through chemical synthesis. The work described herein focuses on a new approach to accessing highly distorted p-phenylenes, which does not rely on cross coupling reactions and the use of the Burgess reagent as a mild dehydrative aromatization agent, giving access to highly strained benzenoid macrocycles. -
[7]Helicene to a Planar Hetero[8]Circulene Bodil Lousen,[A] Stephan K
Communication Chemistry—A European Journal doi.org/10.1002/chem.201905339 & Non-Planar Aromatics Compressing aNon-Planar Aromatic Heterocyclic [7]Helicene to a Planar Hetero[8]Circulene Bodil Lousen,[a] Stephan K. Pedersen,[a] Pernille Bols,[a] Kasper H. Hansen,[a] MichelleR.Pedersen,[a] Ole Hammerich,[a] Sergey Bondarchuk,[b] Boris Minaev,[b] Glib V. Baryshnikov,[c] Hans gren,[c, d] and MichaelPittelkow*[a] cally chiral moleculeshave found vast applications in such di- Abstract: This work describes asyntheticapproachwhere verse fields as molecular recognition,catalysis anddetection or anon-planar aromatic heterocyclic [7]helicene is com- emissionofcircularlypolarized light.[2–5] Structurally related pressedtoyield ahetero[8]circulene containing an inner motifstothe [n]helicenes are the [n]circulenes. These struc- antiaromatic cyclooctatetraene (COT) core. This [8]circu- tures also consist of ortho-annulatedaromatic rings, but in- lene consists of four benzene rings and four heterocyclic stead forms acyclic structure, having acentral ring with n rings, and it is the first heterocyclic[8]circulenecontaining sides.Itisillustrative to view the all-benzene series of [n]circu- three differentheteroatoms. The synthetic pathway pro- lenes,which consistsofthe bowl-shaped carba[5]circulene ceeds via athe flattened dehydro-hetero[7]helicene, (corannulene), the planar carba[6]circulene(coronene) andthe which is partially ahelicene and partially acirculene:itis saddle-shaped[7]- and [8]circulenes. Hetero[8]circulenes incor- non-planar and helically chiral as helicenes, and contains a poratingfour five-membered heterocycles(furans,pyrroles, COT motif like [8]circulenes. The antiaromaticity of the thiophenes)are planar,[6,7] and these structures can be viewed COT core is confirmed by nucleusindependent chemical as containingantiaromaticcyclooctatetraene(COT) cores. -
Calcium-Decorated Carbyne Networks As Hydrogen Storage Media † || † || ‡ † § † Pavel B
LETTER pubs.acs.org/NanoLett Calcium-Decorated Carbyne Networks as Hydrogen Storage Media † || † || ‡ † § † Pavel B. Sorokin, , Hoonkyung Lee, , Lyubov Yu. Antipina, Abhishek K. Singh, , and Boris I. Yakobson*, † Department of Mechanical Engineering and Materials Science, Department of Chemistry, and the Smalley Institute for Nanoscale Science and Technology, Rice University, Houston, Texas 77005, United States ‡ Technological Institute of Superhard and Novel Carbon Materials, Troitsk, Moscow District, 142190, Russian Federation § Materials Research Centre Indian Institute of Science, Bangalore 560012 India ABSTRACT: Among the carbon allotropes, carbyne chains appear outstand- ingly accessible for sorption and very light. Hydrogen adsorption on calcium- decorated carbyne chain was studied using ab initio density functional calculations. The estimation of surface area of carbyne gives the value four times larger than that of graphene, which makes carbyne attractive as a storage scaffold medium. Furthermore, calculations show that a Ca-decorated carbyne can adsorb up to 6 H2 molecules per Ca atom with a binding energy of ∼0.2 eV, desirable for reversible storage, and the hydrogen storage capacity can exceed ∼8 wt %. Unlike recently reported transition metal-decorated carbon nanostructures, which suffer from the metal clustering diminishing the storage capacity, the clustering of Ca atoms on carbyne is energetically unfavorable. Thermodynamics of adsorption of H2 molecules on the Ca atom was also investigated using equilibrium grand partition function. KEYWORDS: Carbyne, carbon chain, calcium, hydrogen storage, density functional theory biquitous carbon allotropes can be ranked by the coordina- atoms in such organometallic complexes play the main role of Ution number of their structures, the number of nearest neigh- adsorbing hydrogen molecules, whereas the graphitic materials serve bors to each C atom, as diamond, graphite, nanotubes and fullerenes, as host for them. -
1. for All Complexes Listed Below, Determine A) Metal Oxidation State B
CH 611 Advanced Inorganic Chemistry – Synthesis and Analysis Practice problems 1. For all complexes listed below, determine a) metal oxidation state b) total number of electrons contributed from metal c) total number of electrons contributed from the ligand set d) total electron count of the complex Please note: use the ionic model unless asked otherwise and comment on any complexes that do not obey the 18VE rule or have CN < 6. 5 i) ( ‐Cp)2Fe 5 ii) [( ‐Cp)2Co] Ionic Model Metal oxidation state: 3+ 3+ Co Metal electron count: 6 Ligand electron count: 6 + 6 Total electron count: 18 iii) Co2(CO)8 CH 611 Advanced Inorganic Chemistry – Synthesis and Analysis Practice problems 2 iv) Ru( ‐en)2H2 v) Mn(4‐salen)Cl Cl Ionic Model N N Metal oxidation state: 3+ Mn3+ Metal electron count: 4 O O Ligand electron count (s only):2+2+2+2+2 Total electron count: 14 A total electron count at the metal of just 14 electrons is predicted using the ionic model but only considering ‐bonds. Both oxide and chloride ligands are capable of ‐donation to the empty metal orbitals making up the 4 extra electrons to comply with the 18VE rule. The nature of this ‐donation can be deciphered using the molecules point group symmetry, the corresponding character table and the method of systematic reduction of non‐shifted/inverted ‐vectors. vi) Ti(iso‐propoxide)4 A total electron count at the metal of just 8 electrons is predicted using the ionic model but only considering ‐bonds. Each isopropoxide ligand is capable of ‐donation to the empty metal orbitals making up the 10 extra electrons to comply with the 18VE rule.