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, beta ''-(BEDT-TTF) (TCNQ), theta-(BEDT-TTF)(2)X, and alpha-(BEDT-TTF)(2)X. 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 beta ''-(BEDT-TTF)(TCNQ) changes continuously from a uniform metal to a chargeordered metal with increasing temperature. Although charge disproportionation was clearly observed, long-range charge order is not realized. Among six theta-type salts, four compounds with a narrow band show the metal-insulator transition. However, they maintain a large amplitude of charge order (Delta rho similar to 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 (Delta rho < 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 = I-3 salt. In alpha-(BEDT-TTF)(2)I-3 the amplitude of charge order changes discontinuously from small amplitude at high temperature to large amplitude (Delta rho(max similar to)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 alpha-(BEDTTTF)(2)MHg(SCN)(4) (X = NH4, K, Rb, Tl), the fluctuation of charge order is indicated only in the X = NH4 salt. alpha'-(BEDT-TTF)(2)IBr2 shows successive phase transitions to the ferroelectric state keeping a large amplitude of charge order (Delta rho(max similar to)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.