In Situ Reversible Ionic Control for Nonvolatile Magnetic Phases in a Donor/Acceptor Metal‐Organic Framework

Taniguchi, Kouji; Narushima, Keisuke; Sagayama, Hajime; Kosaka, Wataru; Shito, Nanami; Miyasaka, Hitoshi

doi:10.1002/adfm.201604990

Cited by 32 publications

(38 citation statements)

References 63 publications

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“…This compound was selected because its crystal structure (inverse spinel) contains several vacancy sites, whose presence facilitates the migration of Li + . [171] Besides lithium migration, oxygen diffusion has also been used to control the magnetic properties in the near-surface regions and in the bulk of magnetic materials in contact with liquid electrolytes. This novel and effective approach permitted a high cycling stability upon charging/discharging the devices several times.…”

Section: Me Coupling Via Ionic Intercalationmentioning

confidence: 99%

Voltage‐Control of Magnetism in All‐Solid‐State and Solid/Liquid Magnetoelectric Composites

2019

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activities. [1][2][3][4][5][6][7][8][9][10][11][12] From a technological perspective, several low-power ME applications have been envisioned, comprising devices for memory storage and processing, [13,14] tuning and filtering of RF/microwave signals, [15,16] energy conversion and harvesting, [17,18] sensing, [19,20] and actuation. [21,22] By definition, the direct ME effect is manifested when an electric polarization P is induced by usage of a magnetic field H in accordance with Δ Δ to compare the strength of the interaction between electricity and magnetism among different magnetoelectric systems. chemical control of the physical (magnetic) properties in metals and oxide nanostructures; electrostatic doping via field-effect; reversible magnetic phase transitions induced with ionic liquid charging; spintronics; printed electronics; fabrication of solution-processed devices (transistors, etc.)There are some nontrivial reasons explaining why solid/ liquid ME composites developed later than all-solid-state approaches. From an experimental perspective, the usage of conventional aqueous electrolytes poses some restrictions in terms of the operating conditions. Concerning the applied voltage, water electrolysis already occurs at a low voltage of

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Section: Me Coupling Via Ionic Intercalationmentioning

confidence: 99%

Voltage‐Control of Magnetism in All‐Solid‐State and Solid/Liquid Magnetoelectric Composites

2019

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“…The in situ reversible magnetic phase switching between PM and FM phases was demonstrated through the rechargeability of the LIB system, for which a miniaturized LIB cell was inserted into a commercial superconducting quantum interference device (SQUID). This cell is hereafter called the in situ cell . Figure a displays the time dependence of the voltage for the discharge/charge cycles between 2.3 and 3.5 V versus Li/Li + (at 300 K), revealing the rechargeability of the LIB with the 1 ‐cathode.…”

Section: Resultsmentioning

confidence: 99%

“…Am icrocrystalline sample of 1 was ground and mixed in the cathode with conductive acetylene black and polytetrafluoroethylene as ab inder.I nt he dischargep rocess, Li + ions and electrons are simultaneouslyinserted into the cathode material to be Li + x (1) xÀ ,w hereas for the charging process, Li + ions and electrons are eliminated from Li + x (1) xÀ ,a st he following reaction: xLi + + xe À + 1 Ð Li + x (1) xÀ . [29] Figure5ad isplays the open circuit voltages (OCVs) for the discharge process of the LIB incorporating 1 as the cathode. The LIB voltage decreasedw ith discharge capacity,w hich indicates that the electrochemical potential of an electron in the cathode was shifted to ah ighere nergy by electron-doping.…”

Section: Resultsmentioning

confidence: 99%

“…For the in situ magnetization measurements, a miniature LIB with a quartz cell (15×7×5 mm) was prepared . This cell was composed of a Li metal anode, a polypropylene separator, electrolyte (LiTFSA/Py 13 ‐FSA), and the cathode containing 1 .…”

Section: Methodsmentioning

confidence: 99%

“…[3][4][5] Therea re two methods to use the void spaces (i.e.,p ores)i nM OFs/PCPs:b yp re-organizing functional molecules in the pores during the self-assembly syntheticp rocess (for the design of statically controlled functionality), or by insertingf unctional molecules into the pores after framework formationt oa ttempt the guest-induced dynamic control of the functionality.B ased on the formers trategy,b i -or synergistic functions, such as metallic ferromagnets, [6] chiral magnets, [7,8] and switchable ferroelastic transitions, [9] have been demonstrated, in which functionalities in the framework and the molecules or molecular array in the pores mutuallyi nteract to induce as pecific characteristic. [10] Meanwhile, the latter strategy is acurrent growing interest, in which physical properties of frameworks, such as electronic, [11,12] magnetic, [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] and spectroscopic properties [31,32] are modulated by guest molecules/ionsi nsertedi nto the nano-sized pores of the frameworks after framework formation.H owever, the development of MOF/PCP materials, where these technical strategies are assembled in as ingle system, is crucial for the creationo fa finely tuned and accessible functional molecular system.F igure 1a shows an example in which at rigger molecule for the activation/inactivationo faframework function is inserted into the pores during the self-assembly process, which inactivates framework function through host-guest interactions (step-A). The trigger molecule is modulated by an externals timulus,o r ac hemical perturbation, to activate the anticipated framework-function (step-B).…”

Section: Introductionmentioning

confidence: 99%

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Magnetic Switching by the In Situ Electrochemical Control of Quasi‐Spin‐Peierls Singlet States in a Three‐Dimensional Spin Lattice Incorporating TTF‐TCNQ Salts

Fukunaga

Tonouchi

Taniguchi

et al. 2018

Chemistry A European J

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Magnetic phase switching in a coordination polymer is reported, which is demonstrated by combining two processes: (A) the pre-organization of magnetic/redox-active molecules into a framework, and (B) a post-treatment through electrochemical tuning of the pre-organized molecules. A TTF -TCNQ salt (TTF=tetrathiafulvalene; TCNQ=7,7,8,8-tetracyano-p-quinodimethane) was incorporated into a three-dimensional framework with paddlewheel-type dimetal(II, II) units ([M ]; M=Ru with S=1, 1; and Rh with S=0, 2), where the [M ] and TCNQ units form the coordinating framework, and TTF is located in the pores of framework, forming an irregular π-stacking alternating column with the TCNQ in the framework. In 1, the spins of [Ru ] and TCNQ units make a magnetic correlation through the framework upon decreasing the temperature from 300 K, which is, however, suddenly suppressed below 137 K (=T (1)) by the formation of a spin singlet in the TTF -TCNQ columns, as seen in the spin-Peierls transition (T (2)=200 K). This material was incorporated as a cathode in a Li-ion battery (LIB); a long-range ferrimagnetic correlation was formed through the three-dimensional [{Ru } TCNQ] framework at T =78 K in the discharge process. The reversible magnetic phase switching between the non-volatile ferrimagnetic and paramagnetic states, resulting from the local spin tuning of quasi-spin-Peierls singlet, is demonstrated through the discharge/charge cycling of the LIB.

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Nonvolatile Electric Control of Exchange Bias by a Redox Transformation of the Ferromagnetic Layer

Zehner

Huhnstock

Oswald

et al. 2019

Adv Elect Materials

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actuation devices. [1,2] The electric currentinduced switching of magnetization is one approach, but requires large spin polarized currents. For energy efficient operation, however, the involved dissipative electric currents should be minimal. The electric field control of magnetism is a promising low-power alternative, and increasing research efforts in this direction resulted in the discovery of various mechanisms in single-and two-phase multiferroics, magnetic semiconductors, and at gated metal surfaces allowing for voltage control of magnetic properties. [2,3] The exchange bias (EB), discovered decades ago, became an important property in modern thin-film magnetism, as it offers an elegant way to prepare thermally stable artificial domains and electrodes with a predefined macroscopic magnetization alignment. [4,5] The EB is manifested by a shift of the hysteresis curve of the ferromagnetic layer along the magnetic field axis and is based on a quantum mechanical exchange interaction occurring at the common interface between a thin ferromagnetic (FM) and antiferromagnetic (AFM) layer. EB thin films are extensively used to control the direction of magnetization in magnetic memories, spintronic, and magnetophoretic devices. [6] In the latter, for example, in-plane EB systems are utilized to generate artificial magnetic domain patterns and associated reconfigurable magnetic stray field landscapes, which can be used to locally guide the motion of magnetic micro-and nanoparticles. [7] Consequently, tailoring and control of EB has become a central objective in these research branches. Chemical, mechanical, thermal, and light ion bombardment-based techniques have been developed to tailor the EB, mainly by introducing irreversible material modifications at the AFM/ FM interface, for example, by changing the interface roughness or incorporating impurities. [8] The modification of the EB is not reversible for all of these methods. Moreover, most of them require an additional magnetic field and a sophisticated apparatus, such as vacuum equipment.The electric control of EB would provide an easily integrable alternative, ideally allowing for operando and reversible EB modification. Indeed, reversible control can be achieved by electric current-induced torque in the AFM layer, but Joule heating limits the energy-efficiency. [9] Alternative low power mechanisms for voltage-control of EB are therefore of great Electric manipulation of exchange bias (EB) systems is highly attractive for the development of modern spintronic and magnetophoretic devices. To date, electric control of the EB has mainly been based on multiferroic or resistive switching behavior in specific antiferromagnets, which limits the material choice and accessible EB states. In addition, the effects are mostly volatile, requiring constant voltage application. The continuous and nonvolatile tuning of the EB via electrochemical manipulation of the ferromagnetic layer is presented. In FeO x /Fe/IrMn systems, large changes in the EB field of fully shifted magneti...

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In Situ Reversible Ionic Control for Nonvolatile Magnetic Phases in a Donor/Acceptor Metal‐Organic Framework

Cited by 32 publications

References 63 publications

Voltage‐Control of Magnetism in All‐Solid‐State and Solid/Liquid Magnetoelectric Composites

Voltage‐Control of Magnetism in All‐Solid‐State and Solid/Liquid Magnetoelectric Composites

Magnetic Switching by the In Situ Electrochemical Control of Quasi‐Spin‐Peierls Singlet States in a Three‐Dimensional Spin Lattice Incorporating TTF‐TCNQ Salts

Nonvolatile Electric Control of Exchange Bias by a Redox Transformation of the Ferromagnetic Layer

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