The quest for electronic ferroelectricity in organic charge-transfer crystals

Organic ferroelectric materials are in demand in the growing field of environmentally friendly, lightweight electronics. Donor-Acceptor charge transfer crystals have been recently proposed as a new class of organic ferroelectrics, which may possess a new kind of ferroelectricity, the so-called electronic ferroelectricity, larger and with faster polarity switching in comparison with conventional, inorganic or organic, ferroelectrics. The current research aimed at achieving ambient conditions electronic ferroelectricity in organic charge transfer crystals is shortly reviewed, in such a way to evidence the emerging criteria that have to be fulfilled to reach this challenging goal.Comment: 6 pages, 7 figures. Proceedings of "2018 SUSTAINABLE INDUSTRIAL PROCESSING SUMMIT AND EXHIBITION

A new type of neutral-ionic interface in mixed-stack organic charge-tranfer crystals: Temperature induced ionicity change in ClMePD-DMeDCNQI

Raman and polarized infrared spectra of the mixed stack charge transfer crystal 2-chloro-5methyl-p-phenylendiamine- -2,5-dimethyl-dicyanoquinonediimine (ClMePD-DMeDCNQI) are reported as a function of temperature. A detailed spectral interpretation allows us to gain new insight into the temperature induced neutral-ionic transition in this compound. In particular, the crossing of the neutral-ionic borderline appears to be quite different from that of the few known temperature induced neutral-ionic phase transitions. First of all, the ionicity change is continuous. Furthermore, the onset of stack dimerization precedes, rather than accompanies, the neutral-ionic crossing. The (second order) phase transition is then driven by the dimerization, but the extent of dimerization is in turn affected by the ionicity change.Comment: LaTex (revTeX), 6 figures. Yields 10 pages postscript (including figures

A new type of neutral-ionic interface in mixed-stack organic charge-tranfer crystals: Temperature induced ionicity change in ClMePD-DMeDCNQI

Raman and polarized infrared spectra of the mixed stack charge transfer crystal 2-chloro-5methyl-p-phenylendiamine- -2,5-dimethyl-dicyanoquinonediimine (ClMePD-DMeDCNQI) are reported as a function of temperature. A detailed spectral interpretation allows us to gain new insight into the temperature induced neutral-ionic transition in this compound. In particular, the crossing of the neutral-ionic borderline appears to be quite different from that of the few known temperature induced neutral-ionic phase transitions. First of all, the ionicity change is continuous. Furthermore, the onset of stack dimerization precedes, rather than accompanies, the neutral-ionic crossing. The (second order) phase transition is then driven by the dimerization, but the extent of dimerization is in turn affected by the ionicity change.Comment: LaTex (revTeX), 6 figures. Yields 10 pages postscript (including figures

Pressure driven neutral-ionic transition in ClMePD-DMeDCNQI

Application of about 0.8 GPa pressure is sufficient to induce the neutral-ionic transition in the mixed stack charge-transfer crystal 2-chloro-5-methyl-$p$-phenylenediamine--2,5-dimethyl-dicyanoquinonediimine ({\CD}). The ionicity increases continuously from $\sim$ 0.35 at ambient conditions to $\sim$ 0.65 when the pressure is raised up to 2 GPa. Moreover, stack dimerization begins well before the crossing of the neutral-ionic interface. The evolution of the transition is similar to what observed in the temperature induced phase change in the same compound. (cond-mat/0101179) A distinguishing feature is represented by the simultaneous presence of domains of molecules with slightly different ionicities across the transition pressure. A comparison of the present example of pressure driven neutral-ionic transition with the well studied cases of tetrathiafulvalene--chloranil and of tetrathiafulvalene--2,5-dichloro-p-benzoquinone puts in evidence the remarkably different evolution of the three transitions.Comment: 6 pages in *.PS format, 5 figure

DMTTF-CA revisited: temperature-induced valence and structural instability

We report a detailed spectroscopic investigation of temperature-induced valence and structural instability of the mixed-stack organic charge-transfer (CT) crystal 4,4'-dimethyltetrathiafulvalene-chloranil (DMTTF-CA). DMTTF-CA is a derivative of tetrathiafulvalene-chloranil (TTF-CA), the first CT crystal exhibiting the neutral-ionic transition by lowering temperature. We confirm that DMTTF-CA undergoes a continuous variation of the ionicity on going from room temperature down to $\sim$ 20 K, but remains on the neutral side throughout. The stack dimerization and cell doubling, occurring at 65 K, appear to be the driving forces of the transition and of the valence instability. In a small temperature interval just below the phase transition we detect the coexistence of molecular species with slightly different ionicities. The Peierls mode(s) precursors of the stack dimerization are identified.Comment: 8 pages, 6 figures, Phys. Rev. B forma

Polymorphism, phonon dynamics and carrier-phonon coupling in pentacene

The crystal structure and phonon dynamics of pentacene is computed with the Quasi Harmonic Lattice Dynamics (QHLD) method, based on atom-atom potential. We show that two crystalline phases of pentacene exist, rather similar in thermodynamic stability and in molecular density. The two phases can be easily distinguished by Raman spectroscopy in the 10-100 cm-1 spectral region. We have not found any temperature induced phase transition, whereas a sluggish phase change to the denser phase is induced by pressure. The bandwidths of the two phases are slightly different. The charge carrier coupling to low-frequency phonons is calculated.Comment: 6 pages, 3 figures. Presented at ICFPAM-

Raman Identification of Polymorphs in Pentacene Films

We use Raman spectroscopy to characterize thin films of pentacene grown on Si/SiO x by Supersonic Molecular Beam Deposition (SuMBD). We find that films up to a thickness of about 781 A (∼ 52 monolayers) all belong to the so-called thin-film (TF) phase. The appearance with strong intensity of some lattice phonons suggests that the films are characterized by good intra-layer order. A comparison of the Raman spectra in the lattice and CH bending spectral regions of the TF polymorph with the corresponding ones of the high-temperature (HT) and low-temperature (LT) bulk pentacene polymorphs provides a quick and nondestructive method to identify the different phases

Anomalous dispersion of optical phonons at the neutral-ionic transition: Evidence from diffuse X-ray scattering

Diffuse X-ray data for mixed stack organic charge-transfer crystals approaching the neutral-ionic phase transition can be quantitatively explained as due to the softening of the optical phonon branch. The interpretation is fully consistent with vibrational spectra, and underlines the importance of electron-phonon coupling in low-dimensional systems with delocalized electrons.Comment: 4 pages, 4 figure

Solution equilibrium between two structures of Perylene-F ₂ TCNQ charge transfer co-crystals

We report on the solution growth of the two known structures of Perylene-F(2)TCNQ charge transfer complexes. The transformation accompanied by a marked morphological change from needle 1:1 to platelet 3:2 crystal structure is observed in the mother liquor. Lattice phonon Raman spectroscopy is used for an easy structure identification of the different morphologies before and after the process. X-ray and lattice phonons spectra of reference samples obtained by physical vapor transport is used to identify the two complexes. A fully spectroscopic analysis of the intramolecular Raman modes is presented to estimate the degree of ionicity, which is found to agree with the value previously reported

Phonons and structures of tetracene polymorphs at low temperature and high pressure

Crystals of tetracene have been studied by means of lattice phonon Raman spectroscopy as a function of temperature and pressure. Two different phases (polymorphs I and II) have been obtained, depending on sample preparation and history. Polymorph I is the most frequently grown phase, stable at ambient conditions. A pressure induced phase transition, observed above 1 GPa, leads to polymorph II, which is also obtained at temperatures below 140 K. Polymorph II can also be maintained at ambient conditions. We have calculated the crystallographic structures and phonon frequencies as a function of temperature, starting from the configurations of the energy minima found by exploring the potential energy surface of crystalline tetracene. The spectra calculated for the first and second deepest minima match satisfactorily those measured for polymorphs I and II, respectively. All published x-ray structures, once assigned to the appropriate polymorph, are also reproduced.Comment: 8 pages, 5 figures, RevTeX4, update after referees report