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Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands
Toyota Physical and Chemical Research Institute, 41-1, Yokomichi, Nagakute, Aichi 480-1192, Japan
Received: 22 May 2012; in revised form: 4 July 2012 / Accepted: 20 July 2012 / Published: 18 September 2012
Abstract: 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.
Keywords: organic conductor; BEDT-TTF; charge order; infrared and Raman spectroscopy; vibrational spectroscopy; optical conductivity
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MDPI and ACS Style
Yakushi, K. Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands. Crystals 2012, 2, 1291-1346.
Yakushi K. Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands. Crystals. 2012; 2(3):1291-1346.
Yakushi, Kyuya. 2012. "Infrared and Raman Studies of Charge Ordering in Organic Conductors, BEDT-TTF Salts with Quarter-Filled Bands." Crystals 2, no. 3: 1291-1346.