Electrocrystallised metal–tetracyanoquinodimethane salts with high electrical conductivity

Kathirgamanathan, Poopathy; Rosseinsky, David R.

doi:10.1039/c39800000839

Cited by 39 publications

(35 citation statements)

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“…The nanoscale electrocrystallization can potentially be applied to various organic conductors because it is based on the bulk electrocrystallization. 10 In particular, Kathirgamanathan et al [20][21][22] have reported that the bulk electrocrystallization of this material with tetra--n--butylammonium nitrate in acetonitrile yields bulk single crystals that consist of partially oxidized TTF molecules. Tetrathiafulvalene (TTF, Figure 1) is well known as a component of organic conducting crystals.…”

Section: -15mentioning

confidence: 99%

Tetrathiafulvalene-based nanocrystals: site-selective formation, device fabrication, and electrical properties

Hasegawa

2015

J. Mater. Chem. C

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A tetrathiafulvalene(TTF)--based nanocrystal was site--selectively synthesized only in the gap between two electrochemical electrodes by using a nanoscale electrocrystallization method. Furthermore, the nanocrystal was directed to form a bridge between two electrodes using alternating current (AC) electrolysis. The nanocrystal was found to have a one--dimensional π--π stacking structure of TTF molecules, which is the source of its high electrical conductivity. Further, when we reused the two electrochemical electrodes as the source and drain electrodes, a two--terminal device could be readily obtained. The electrical conductivity of the nanocrystal was comparable to that of a partially oxidized bulk crystal. A bottom--gate--type FET was also obtained when the device was fabricated on a silicon substrate. A weak field effect was observed even though the nanocrystal has a metallic nature. The nanoscale electrocrystallization is considered to be applicable to nanocrystal fabrication using various organic molecules. We expect that further enhancement of this method will lead to the development of eco--friendly nanofabrication processes. 11-12We have reported site--selective fabrication of nanocrystals in the gap between two electrodes by alternating current (AC) electrolysis. Unlike the electrochemical fabrication of conductive organic bulk A tetrathafulvalene(TTF)-based nanocrystal was selectively synthesized only in the gap between two electrodes using a nanoscale electrocrystallization. A two-terminal TTF-based device and an FET could be readily obtained via an eco-friendly nanofabrication process.

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Section: -15mentioning

confidence: 99%

Tetrathiafulvalene-based nanocrystals: site-selective formation, device fabrication, and electrical properties

Hasegawa

2015

J. Mater. Chem. C

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“…Both ions, continuously produced during the electrolysis reaction, migrate in the electric field to the opposite electrodes and precipitate as CuTCNQ in the presence of their counterions. Whereas the cathode reaction has already been used to form CuTCNQ films on vitreous carbon, gold, and platinum from ACN solution containing TCNQ and Cu + or Cu 2+ , 18,19 and TCNQ crystals in H 2 O containing Cu 2+ , 20,21 no paper has reported on electrodeposition of CuTCNQ on Cu substrates by the anode reaction. The most likely reason for this might be the impossibility to control the process electrochemically since Cu metal in a TCNQ containing ACN solution reacts already spontaneously without applied voltage ͓Eq.…”

Section: ͑1͒mentioning

confidence: 99%

Nonvolatile Cu∕CuTCNQ∕Al memory prepared by current controlled oxidation of a Cu anode in LiTCNQ saturated acetonitrile

Müller

Genoe

Heremans

2006

Applied Physics Letters

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In this letter we propose a preparation method of the metal organic charge transfer complex Cu-tetracyanoquinodimethane ͑CuTCNQ͒ for use in nonvolatile organic memories. The method, consisting in current controlled oxidation of a Cu electrode in LiTCNQ saturated acetonitrile, is attractive because CuTCNQ growth is limited strictly to anodically polarized Cu metal, and because of material and solvent compatibilities with the requirements of the complementary metal-oxide-semiconductor ͑CMOS͒ copper back end-of-line process. Crossbar memories of this CuTCNQ exhibit superior performance compared to corresponding devices prepared by the standard method, which we attribute to a higher compactness of the CuTCNQ layer.

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“…Comparison of the different metal ions reveals that the M-N distances in the alkali-metal salts and in the thallium Slow diffusion of solutions of DCNQIs and metal iodides [66] or electrocrystallization [67] were utilized in growing crystals of the salts under discussion. Moreover, single crystals of DCNQI copper or silver salts can easily be grown by immersion of a copper or silver wire, respectively, in a solution of DCNQIs in acetonitrile.r68.…”

Section: Structural Propertiesmentioning

confidence: 99%

DCNQIs—new electron acceptors for charge‐transfer complexes and highly conducting radical anion salts

1991

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Review: Organic conducting materials show potential for applications in, for example, electrostatic shielding or in pressure sensing. In the past, research aimed at the optimization of the properties of these materials e.g. the charge‐transfer (CT) complex tetrathiafulvalene/tetracyanoquinodümine (TTF/TCNQ, see figure) have concentrated mainly on varying the structure of the donor (TTF). Here, in contrast, the recent progress made in the identification, synthesis, and characterization of new acceptors suitable for use in CT complexes, the N,N'‐dicyanoquinonediimines (DCNQIs) is reviewed.

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Electrocrystallised metal–tetracyanoquinodimethane salts with high electrical conductivity

Abstract: Conductivities/Q-l cm-l from ca.to 800 [for Cu(TCNQ)] are obtained for salts, often novel, of the formulation M(TCNQ), or M(TCNQ), (solvent),, prepared by cathodic electrocrystallisation from tetracyanoquinodimethane (TCNQ) in the presence of metal (M) salts, where the M are

Cited by 39 publications

References 0 publications

Tetrathiafulvalene-based nanocrystals: site-selective formation, device fabrication, and electrical properties

Tetrathiafulvalene-based nanocrystals: site-selective formation, device fabrication, and electrical properties

Nonvolatile Cu∕CuTCNQ∕Al memory prepared by current controlled oxidation of a Cu anode in LiTCNQ saturated acetonitrile

DCNQIs—new electron acceptors for charge‐transfer complexes and highly conducting radical anion salts

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