Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands

This paper reviews charge ordering in the organic conductors, β″-(BEDT-TTF) (TCNQ), θ-(BEDT-TTF)2X, and α-(BEDT-TTF)2X. Here, BEDT-TTF and TCNQ represent bis(ethylenedithio)tetrathiafulvalene and 7,7,8,8-tetracyanoquinodimethane, respectively. These compounds, all of which have a quarter-filled band...

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Main Author: Kyuya Yakushi
Format: Article
Language:English
Published: MDPI AG 2012-09-01
Series:Crystals
Subjects:
Online Access:http://www.mdpi.com/2073-4352/2/3/1291
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author Kyuya Yakushi
author_facet Kyuya Yakushi
author_sort Kyuya Yakushi
collection DOAJ
description This paper reviews charge ordering in the organic conductors, β″-(BEDT-TTF) (TCNQ), θ-(BEDT-TTF)2X, and α-(BEDT-TTF)2X. Here, BEDT-TTF and TCNQ represent bis(ethylenedithio)tetrathiafulvalene and 7,7,8,8-tetracyanoquinodimethane, respectively. These compounds, all of which have a quarter-filled band, were evaluated using infrared and Raman spectroscopy in addition to optical conductivity measurements. It was found that β″-(BEDT-TTF)(TCNQ) changes continuously from a uniform metal to a charge-ordered metal with increasing temperature. Although charge disproportionation was clearly observed, long-range charge order is not realized. Among six θ-type salts, four compounds with a narrow band show the metal-insulator transition. However, they maintain a large amplitude of charge order (Δρ~0.6) in both metallic and insulating phases. In the X = CsZn(SCN)4 salt with intermediate bandwidth, the amplitude of charge order is very small (Δρ < 0.07) over the whole temperature range. However, fluctuation of charge order is indicated in the Raman spectrum and optical conductivity. No indication of the fluctuation of charge order is found in the wide band X = I3 salt. In α-(BEDT-TTF)2I3 the amplitude of charge order changes discontinuously from small amplitude at high temperature to large amplitude (Δρmax~0.6) at low temperature. The long-range charge-ordered state shows ferroelectric polarization with fast optical response. The fluctuation of multiple stripes occurs in the high-temperature metallic phase. Among α-(BEDT-TTF)2MHg(SCN)4 (X = NH4, K, Rb, Tl), the fluctuation of charge order is indicated only in the X = NH4 salt. α′-(BEDT-TTF)2IBr2 shows successive phase transitions to the ferroelectric state keeping a large amplitude of charge order (Δρmax~0.8) over the whole temperature range. It was found that the amplitude and fluctuation of charge order in these compounds is enhanced as the kinetic energy (bandwidth) decreases.
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spelling doaj.art-7e25137f80c84ea784a391bbe6ff007b2022-12-22T02:10:30ZengMDPI AGCrystals2073-43522012-09-01231291134610.3390/cryst2031291Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled BandsKyuya YakushiThis paper reviews charge ordering in the organic conductors, β″-(BEDT-TTF) (TCNQ), θ-(BEDT-TTF)2X, and α-(BEDT-TTF)2X. Here, BEDT-TTF and TCNQ represent bis(ethylenedithio)tetrathiafulvalene and 7,7,8,8-tetracyanoquinodimethane, respectively. These compounds, all of which have a quarter-filled band, were evaluated using infrared and Raman spectroscopy in addition to optical conductivity measurements. It was found that β″-(BEDT-TTF)(TCNQ) changes continuously from a uniform metal to a charge-ordered metal with increasing temperature. Although charge disproportionation was clearly observed, long-range charge order is not realized. Among six θ-type salts, four compounds with a narrow band show the metal-insulator transition. However, they maintain a large amplitude of charge order (Δρ~0.6) in both metallic and insulating phases. In the X = CsZn(SCN)4 salt with intermediate bandwidth, the amplitude of charge order is very small (Δρ < 0.07) over the whole temperature range. However, fluctuation of charge order is indicated in the Raman spectrum and optical conductivity. No indication of the fluctuation of charge order is found in the wide band X = I3 salt. In α-(BEDT-TTF)2I3 the amplitude of charge order changes discontinuously from small amplitude at high temperature to large amplitude (Δρmax~0.6) at low temperature. The long-range charge-ordered state shows ferroelectric polarization with fast optical response. The fluctuation of multiple stripes occurs in the high-temperature metallic phase. Among α-(BEDT-TTF)2MHg(SCN)4 (X = NH4, K, Rb, Tl), the fluctuation of charge order is indicated only in the X = NH4 salt. α′-(BEDT-TTF)2IBr2 shows successive phase transitions to the ferroelectric state keeping a large amplitude of charge order (Δρmax~0.8) over the whole temperature range. It was found that the amplitude and fluctuation of charge order in these compounds is enhanced as the kinetic energy (bandwidth) decreases.http://www.mdpi.com/2073-4352/2/3/1291organic conductorBEDT-TTFcharge orderinfrared and Raman spectroscopyvibrational spectroscopyoptical conductivity
spellingShingle Kyuya Yakushi
Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands
Crystals
organic conductor
BEDT-TTF
charge order
infrared and Raman spectroscopy
vibrational spectroscopy
optical conductivity
title Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands
title_full Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands
title_fullStr Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands
title_full_unstemmed Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands
title_short Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands
title_sort infrared and raman studies of charge ordering in organic conductors bedt ttf salts with quarter filled bands
topic organic conductor
BEDT-TTF
charge order
infrared and Raman spectroscopy
vibrational spectroscopy
optical conductivity
url http://www.mdpi.com/2073-4352/2/3/1291
work_keys_str_mv AT kyuyayakushi infraredandramanstudiesofchargeorderinginorganicconductorsbedtttfsaltswithquarterfilledbands