Adam
Berlie
*abcd,
Ian
Terry
e,
Yun
Liu
a and
Marek
Szablewski
e
aResearch School of Chemistry, The Australian National University, Canberra, 2601, Australia
bThe Bragg Institute, Australian Nuclear Science and Technology Organisation, New Illawarra Road, Lucas Heights, NSW 2232, Australia
cISIS Neutron and Muon Source, Science and Technology Facility Council, Harwell Oxford, Oxfordshire, OX11 0QX, UK. E-mail: adam.berlie@stfc.ac.uk
dRIKEN Nishina Center for Accelerator-Based Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
eThe Department of Physics, Durham University, South Road, Durham, DH1 3LE, UK
First published on 2nd June 2016
There is much interest in the search for novel materials that show ferroelectric as well as magneto-electric coupling, such as that observed in multiferroics. Within organic based materials the electronic polarisation can originate from a charge distribution across a molecule or molecules, and so one must search for systems that have an electronic (and magnetic) dipole that is intrinsic. One such material is tetraethylammonium bis-7,7,8,8-tetracyanoquinodimethane (TEA(TCNQ)2) which is a charge transfer system with a single electron that is delocalised across a TCNQ dimer. We show that dielectric measurements yield anomalies at the cation freezing structural distortion and when singlet–triplet excitations freeze. In both cases the electric response is glassy and at low temperature the corresponding magnetic measurements evidence the strong magneto-electric coupling within the material showing scaling behaviour similar to spin glass systems.
Magneto-electric (ME) coupling is a good indication of multiferroic behaviour where recent work on κ-(BEDT-TTF)2 Cu[N(CN)2]Cl (denoted κ-Cl and where BEDT-TTF is bis(ethylenedithio)tetrathiafulvalene), the structure of which comprises of layers of BEDT-TTF cations that undergo antiferromagnetic ordering at 23 K,7 displaying coupling of the magnetism and electronic charge states.8 This is achieved through a freezing of electron density across a molecular dimer within these layers and a coupling through the triangular lattice. MEM(TCNQ)2 (MEM = N-methyl-N-ethylmorpholinium) also shows an anomaly in the dielectric constant (at 9 GHz) at the spin-Peierls transition,9 however no data is available on the frequency dependence. In order to investigate other systems, similar or not, for the potential to show ME coupling, one must consider samples that show strong magnetic interactions between anions; here we consider the charge-transfer salt tetraethylammonium bis-7,7,8,8-tetracyanoquinodimethane (TEA(TCNQ)2), which seems to be an ideal model system.
TEA(TCNQ)2 shows TCNQ stacking along the b-direction (see Fig. 1) where the TCNQ stacks are in sets of 4 (denoted BAA′B′ with an inversion centre between the A and A′ molecules),10 thus creating favourable tetramerisation where a single electron is delocalised across a TCNQ dimer.10,11 As the temperature decreases, there is a gradual increase in the tetramerisation of the TCNQ units along the stack. The TEA cations fluctuate between two different configurations within the crystal structure and at 220 K, they freeze into a disordered state10,12–14 that also effects the TCNQ stack and each dimer behaves as an S = 1/2 entity. The magnetism is dominated by singlet–triplet excitations and this crossover temperature is from ∼120 K. (This transition is from herein denoted as TST), the system shows strong antiferromagnetic coupling (i.e. a singlet state is formed) between the BAA′B′ dimers.13,16,17 One interesting feature of the TCNQ dimer is that the single electronic charge is split across the molecular unit unevenly over the temperature range from 395 to 110 K.10,18 As the temperature increases (T > 345 K) one may expect this charge distribution to become equal. However, at 295 K it is split at qA/e = 0.58 and qB/e = 0.42 (qA and qB denote the charge on the A and B TCNQ molecule respectively and e is the elementary charge) and is most pronounced at 110 K where qA/e = 0.72 and qB/e = 0.28. Consequently this provides much encouragement, as the search for organic ferroelectrics hinges on a polarisation of electron density across a molecule and as such within TEA(TCNQ)2 this may be intrinsic across the TCNQ dimers. Thus this warrants further investigation in order to determine whether there is evidence for ferroelectric behaviour and ME coupling within this material, and whether these strongly interacting TCNQ based systems may be a good model to pursue with regards to novel ferroelectric or even multiferroic samples. Within this work we show dielectric measurements on TEA(TCNQ)2 that display features at both the cation freezing and singlet–triplet transitions. In both cases there is a strong frequency dependence which can be explained by a glassy dipolar state which at low temperatures is coupled with singlet–triplet excitations.
Fig. 1 Crystal structure of TEA(TCNQ)2 showing the inherent tetramerisation and stacking of the TCNQ molecules along the b-axis at room temperature. Note that this shows the average structure as below 220 K, there is a freezing of the TEA cations into one of two positions refined in ref. 15. |
(1) |
Although both anomalies be will considered, we will firstly discuss the frequency dependent behaviour at ∼220 K. As mentioned previously, there is some form of hysteretic behaviour associated with the transition and so when taking the temperature of the maximum of the peak (TP) within the loss, two values will be obtained corresponding to heating and cooling of the sample. Using the Arrhenius equation, it is possible to analyse the data to obtain a value for the energy gap associated with the statistical population of the excited and ground states. A plot of ln(f) vs. 1/Tmax was made (see inset to Fig. 3) and within the plot there are two clearly different regimes with a difference in slopes that occur between 20 kHz and 30 kHz. Fitting to the data provides unreasonable values for the activation energy (Ea) and nominal time scale of the fluctuations/attempt frequency (f0), as shown in the inset of Fig. 3. Instead a better model is the Vogel–Fulcher law (VF);
(2) |
At ln(f) ≈ 10 or f ≈ 22 kHz, there is a definite change in slope shown clearly in Fig. 3. This change in slope may be due to the fact that the measurements are sensitive to different relaxations or processes, although the two processes are likely to be related. Measures of energy gap associated with the transition are of the order of ∼2000 K,21,27 therefore one may allocate the high frequency (f > 20 kHz) behaviour to the increasing interactions within the TCNQ stacks. The difference may be due to the different time scales of measurements. The process with an Ea = 749 K from our measurements may therefore be due to the ordering of the TEA cations at ∼210 K. The lower energy associated with the cation freezing again supports the idea that the structural distortion may be due to the freezing of the cations which in turn causes the interactions between TCNQ dimers and tetramers to increase leading to a strongly coupled Mott state.13
The magnetism of TEA(TCNQ)2 has been previously studied where there is a gradual tetramerisation of the TCNQ units below 250 K,17 which is also seen in our data (see inset to Fig. 4). When differentiating the magnetic susceptibility data one finds the steepest part of the slope is approximately 100 K which can be considered to be where the singlet–triplet excitations freeze out and the system is locked into a singlet ground state. This transition matches well with the low temperature features seen in the C and loss data for the sample. This is demonstrated in Fig. 4, where the loss and differentiated susceptibility of the sample are compared and there is a definite correlation between the two datasets. Ultimately this means that the magnetic transition is coupled to the electronic polarisation and the magnetic ordering may trigger an electric dipole ordering.
The frequency dependence of the peak within the loss can be analysed in a similar manner to the cation freezing distortion above. Note that TST, the temperature associated with the condensing of the system into the singlet phase, was from the loss data and defined as the intersection of two straight lines as shown in the upper inset of Fig. 5. The strong frequency dependence and the unreasonable fitting parameters from the Arrhenius behaviour (see ESI†) points to a more glassy or relaxor state. One must therefore use the VF law to describe the data (see ESI†). In order to calculate a reasonable value for T0 the frequency dependence of the peak was plotted as it tends to f = 0 (see the lower inset of Fig. 5) where T0 = 43(2) K. Using the Mydosh criterion one can look at the frequency dependence of the transition where ϕ = 0.1, which is, for the spin glass analogue, similar to cluster glasses or super spin glasses.28 Within TEA(TCNQ)2 the sample may undergo a transition where the electric dipoles order in local clustered regions. For the VF analysis it was found that the best fits to the data produced values for Ea/kB and f0 of 423 K and 4.8 × 108 Hz respectively. Therefore these represent the energy scale required for an excitation from the ground state, but since both the magnetic and electrical behaviour is coupled, a perturbation in one causes a perturbation in the other.
Since there are strong analogies between dipolar and spin glasses, it is worth attempting further analysis of the anomaly in the dielectric loss associated with singlet–triplet transition. One model used within spin glasses is critical scaling behaviour,28 described by
(3) |
Both the cation freezing and singlet–triplet (ST) crossovers are observed in the dielectric data and as mentioned above this implies that in the case of the ST transition, the magnetic and electronic polarisation are strongly coupled. This is evidence that the sample behaves similarly to κ-Cl,8 which is a multiferroic at low temperatures. The multiferroic behaviour in κ-Cl is dominated by a freezing of electric dipoles across a cationic BEDT-TTF dimer (each BEDT-TTF is an electron donor). The TCNQ dimers within our sample, behave in an opposite manner and are the electron acceptors. Although charge-ordering is common within low dimensional charge transfer salts31 this can manifest as differences in critical and ferroelectric transition temperatures. Therefore within TEA(TCNQ)2, since a charge difference exists across the TCNQ dimers that results in an electric dipole, which may be able to fluctuate and be polarisable even below the temperature at which the TEA cation configuration freezes. Since the P space group contains an inversion centre, this may simply represent a spatially averaged structure and one interpretation of the dipolar ordering could come from the local regions where the freezing of the TEA cations produces a static disorder, where the inversion symmetry of the average structure could be broken. At TST the magnetic exchange between TCNQ dimers may cause a freezing of the magnetic moments and the system enters a quasi-static state. This in turn causes a freezing or locking of the fluctuations of the electronic dipole moments across the TCNQ dimers. This leads to static electric dipole due to the inequivalent electron density distribution across a TCNQ dimer and could lead to ferroelectric or multiferroic ordering.
There is a lot of interest in the search for organic systems for technological applications and we have presented data for a material that highlights the applicability and potential of TCNQ based organic charge transfer salts in which there is a strong magneto-electric coupling. Hopefully the usefulness of these type of π-stacked systems has been highlighted when designing materials where a coupling between the magnetism and electrical properties is desirable, such as within multiferroics.
Footnote |
† Electronic supplementary information (ESI) available. See DOI: 10.1039/c6tc01538g |
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