Organic Sublattice Research Articles

Organic and inorganic sublattice coupling in two-dimensional lead halide perovskites

Two-dimensional layered organic-inorganic halide perovskites have successfully spread to diverse optoelectronic applications. Nevertheless, there remain gaps in our understanding of the interactions between organic and inorganic sublattices that form the foundation of their remarkable properties. Here, we examine these interactions using pump-probe spectroscopy and ab initio molecular dynamics simulations. Unlike off-resonant pumping, resonant excitation of the organic sublattice alters both the electronic and lattice degrees of freedom within the inorganic sublattice, indicating the existence of electronic coupling. Theoretical simulations verify that the reduced bandgap is likely due to the enhanced distortion index of the inorganic octahedra. Further evidence of the mechanical coupling between these two sublattices is revealed through the slow heat transfer process, where the resultant lattice tensile strain launches coherent longitudinal acoustic phonons. Our findings explicate the intimate electronic and mechanical couplings between the organic and inorganic sublattices, crucial for tailoring the optoelectronic properties of two-dimensional halide perovskites.

Elucidating the Non-Covalent Interactions that Trigger Interdigitation in Lead-Halide Layered Hybrid Perovskites.

Two-dimensional (2D) hybrid organic-inorganic perovskites constitute a versatile class of materials applied to a variety of optoelectronic devices. These materials are composed of alternating layers of inorganic lead halide octahedra and organic ammonium cations. Most perovskite research studies so far have focused on organic sublattices based on phenethylammonium and alkylammonium cations, which are packed by van der Waals cohesive forces. Here, we report a more complex organic sublattice containing benzotriazole-based ammonium cations packed through interdigitated π-π stacking and hydrogen bonding. Single crystals and thin films of four perovskite derivatives are studied in depth with optical spectroscopy and X-ray diffraction, supported by density-functional theory calculations. We quantify the lattice stabilization of interdigitation, dipole-dipole interactions, and inter- as well as intramolecular hydrogen bonding. Furthermore, we investigate the driving force behind interdigitation by defining a steric occupancy factor σ and tuning the composition of the organic and inorganic sublattice. We relate the phenomenon of interdigitation to the available lattice space and to weakened hydrogen bonding to the inorganic octahedra. Finally, we find that the stabilizing interactions in the organic sublattice slightly improve the thermal stability of the perovskite. This work sheds light on the design rules and structure-property relationships of 2D layered hybrid perovskites.

2D Hybrid Perovskites Employing an Organic Cation Paired with a Neutral Molecule.

Two-dimensional (2D) hybrid perovskites harness the chemical and structural versatility of organic compounds. Here, we explore 2D perovskites that incorporate both a first organic component, a primary ammonium cation, and a second neutral organic module. Through the experimental examination of 42 organic pairs with a range of functional groups and organic backbones, we identify five crystallization scenarios that occur upon mixing. Only one leads to the cointercalation of the organic modules with distinct and extended interlayer spacing, which is observed with the aid of X-ray diffraction (XRD) pattern analysis combined with cross-sectional transmission electron microscopy (TEM) and elemental analysis. We present a picture in which complementary pairs, capable of forming intermolecular bonds, cocrystallize with multiple structural arrangements. These arrangements are a function of the ratio of organic content, annealing temperature, and substrate surface characteristics. We highlight how noncovalent bonds, particularly hydrogen and halogen bonding, enable the influence over the organic sublattice in hybrid halide perovskites.

Dynamic Distortions of Quasi-2D Ruddlesden–Popper Perovskites at Elevated Temperatures: Influence on Thermal and Electronic Properties

Ruddlesden–Popper hybrid halide perovskites are quasi-two-dimensional materials with a layered structure and structural dynamics that are determined by the interplay between the organic and inorganic layers. While their optical properties are governed by confinement effects, the atomistic origin of thermal and electronic properties of these materials is yet to be fully established. Here we combine computational and experimental techniques to study A2PbI4 (A = butylammonium (BA), phenethylammonium (PEA)) Ruddlesden–Popper perovskites and compare them with the quintessential perovskite CH3NH3PbI3. We use first-principles density functional theory, molecular dynamics simulations based on machine-learned interatomic potentials, thermal measurements, temperature-dependent Raman spectroscopy, and ultraviolet photoelectron spectroscopy to probe the thermal and electronic properties of these materials at elevated temperatures. Our molecular dynamics simulations demonstrate that dynamic fluctuations in the organic sublattice determine the bulk-average distortions of these materials at room temperature, explaining significant differences in their electronic density of states close to the Fermi level. Furthermore, by analyzing the organic layer dynamics in BA2PbI4 we provide a mechanistic explanation for the phase transition of this material at 274 K and observations from Raman measurements. Our results highlight the role of the organic interlayer for the electronic and thermal transport properties of Ruddlesden–Popper perovskites, paving the way for the design of new hybrid materials for tailored applications.

Controlled Assembly and Anomalous Thermal Expansion of Ultrathin Cesium Lead Bromide Nanoplatelets

Quantum confined lead halide perovskite nanoplatelets are anisotropic materials displaying strongly bound excitons with spectrally pure photoluminescence. We report the controlled assembly of CsPbBr3 nanoplatelets through varying the evaporation rate of the dispersion solvent. We confirm the assembly of superlattices in the face-down and edge-up configurations by electron microscopy, as well as X-ray scattering and diffraction. Polarization-resolved spectroscopy shows that superlattices in the edge-up configuration display significantly polarized emission compared to face-down counterparts. Variable-temperature X-ray diffraction of both face-down and edge-up superlattices uncovers a uniaxial negative thermal expansion in ultrathin nanoplatelets, which reconciles the anomalous temperature dependence of the emission energy. Additional structural aspects are investigated by multilayer diffraction fitting, revealing a significant decrease in superlattice order with decreasing temperature, with a concomitant expansion of the organic sublattice and increase of lead halide octahedral tilt.

Combining π-Conjugation and Cation-π Interaction for Water-Stable and Photoconductive One-Dimensional Hybrid Lead Bromide.

Hybrid lead halide perovskites and their derivatives are important optoelectronic materials but suffer from water instability. Combining both the optoelectronics and the water stability of such systems is a major challenge in material design today. To address this issue, we employ the well-known π-conjugation and cation-π interaction concepts in designing a hybrid lead halide perovskite derivative system. (4,4'-VDP)Pb2Br6 (VDP = vinylenedipyridinium) single crystals are prepared. They have a one-dimensional (1D) arrangement of inorganic Pb-Br sublattices connected via the 4,4'-VDP organic sublattice. The π-conjugation in the 4,4'-VDP sublattice allows electronic communication between the 1D Pb-Br units, reducing the band gap and improving the photoconductivity. Importantly, N+ of one 4,4'-VDP molecular ion interacts with the π-electron cloud of the adjacent one. This intermolecular cation-π interaction extends throughout the organic sublattice, making the hybrid crystal stable when stored under water for more than a year without requiring any encapsulations.

Suppressed Lattice Disorder for Large Emission Enhancement and Structural Robustness in Hybrid Lead Iodide Perovskite Discovered by High‐Pressure Isotope Effect

AbstractThe soft nature of organic–inorganic halide perovskites renders their lattice particularly tunable to external stimuli such as pressure, undoubtedly offering an effective way to modify their structure for extraordinary optoelectronic properties. Here, using the methylammonium lead iodide as a representative exploratory platform, it is observed that the pressure‐driven lattice disorder can be significantly suppressed via hydrogen isotope effect, which is crucial for better optical and mechanical properties previously unattainable. By a comprehensive in situ neutron/synchrotron‐based analysis and optical characterizations, a remarkable photoluminescence (PL) enhancement by threefold is convinced in deuterated CD3ND3PbI3, which also shows much greater structural robustness with retainable PL after high peak‐pressure compression–decompression cycle. With the first‐principles calculations, an atomic level understanding of the strong correlation among the organic sublattice and lead iodide octahedral framework and structural photonics is proposed, where the less dynamic CD3ND3+ cations are vital to maintain the long‐range crystalline order through steric and Coulombic interactions. These results also show that CD3ND3PbI3‐based solar cell has comparable photovoltaic performance as CH3NH3PbI3‐based device but exhibits considerably slower degradation behavior, thus representing a paradigm by suggesting isotope‐functionalized perovskite materials for better materials‐by‐design and more stable photovoltaic application.

Ferroelastic Phase Transition in Formamidinium Tin(IV) Iodide Driven by Organic-Inorganic Coupling.

Hybrid perovskites are a technologically relevant family of materials, with potential applications in photovoltaics, solid-state lighting, and radiation detection. Interactions between the inorganic octahedral framework and the organic sublattice have been implicated in the structure and optoelectronic properties, but characterization of these interactions has been challenging, because of competition between organic-inorganic coupling and intraoctahedral interactions. Owing to their decreased octahedral connectivity, vacancy-ordered double perovskites present an ideal case study to examine organic-inorganic coupling in hybrid perovskites and their derivatives. Here, we describe the low-temperature, hysteretic phase transition of formamidinium tin(IV) iodide from the high-symmetry cubic phase to a lower-symmetry monoclinic phase. We propose that the hysteresis stems from organic-inorganic coupling mediated by local and spontaneous strain from the orientations of the formamidinium cations, which result in a ferroelastic phase transition.

Tunable exciton binding energy in 2D hybrid layered perovskites through donor-acceptor interactions within the organic layer.

The strength of electrostatic interactions within semiconductors strongly affects their performance in optoelectronic devices. An important target is the tuning of a material's exciton binding energy-the energy binding an electron-hole pair through the electrostatic Coulomb force-independent of its electronic band gap. Here, we report on the doping of a family of two-dimensional hybrid perovskites, in which inorganic lead halide sheets alternate with naphthalene-based organic layers, with tetrachloro-1,2-benzoquinone (TCBQ). For four out of seven n = 1 perovskites, the incorporation of the electron-accepting TCBQ dopant into the organic sublattice containing the electron-donating naphthalene species enabled the tuning of the materials' 1s exciton binding energy. The naphthalene-TCBQ electron donor-acceptor interactions increased the electrostatic screening of the exciton, in turn lowering its binding energy relative to the undoped perovskite-by almost 50% in one system. Structural and optical characterization showed that the inorganic lattice is not significantly perturbed even though the layer-to-layer spacing increases upon molecular dopant incorporation.

Infrared-pump electronic-probe of methylammonium lead iodide reveals electronically decoupled organic and inorganic sublattices

Organic-inorganic hybrid perovskites such as methylammonium lead iodide (CH3NH3PbI3) are game-changing semiconductors for solar cells and light-emitting devices owing to their defect tolerance and exceptionally long carrier lifetimes and diffusion lengths. Determining whether the dynamically disordered organic cations with large dipole moment benefit the optoelectronic properties of CH3NH3PbI3 has been an outstanding challenge. Herein, via transient absorption measurements employing an infrared pump pulse tuned to a methylammonium vibration, we observe slow, nanosecond-long thermal dissipation from the selectively excited organic mode to the inorganic sublattice. The resulting transient electronic signatures, during the period of thermal-nonequilibrium when the induced thermal motions are mostly concentrated on the organic sublattice, reveal that the induced atomic motions of the organic cations do not alter the absorption or the photoluminescence response of CH3NH3PbI3, beyond thermal effects. Our results suggest that the attractive optoelectronic properties of CH3NH3PbI3 mainly derive from the inorganic lead-halide framework.

Slow thermal equilibration in methylammonium lead iodide revealed by transient mid-infrared spectroscopy

Hybrid organic–inorganic perovskites are emerging semiconductors for cheap and efficient photovoltaics and light-emitting devices. Different from conventional inorganic semiconductors, hybrid perovskites consist of coexisting organic and inorganic sub-lattices, which present disparate atomic masses and bond strengths. The nanoscopic interpenetration of these disparate components, which lack strong electronic and vibrational coupling, presents fundamental challenges to the understanding of charge and heat dissipation. Here we study phonon population and equilibration processes in methylammonium lead iodide (MAPbI3) by transiently probing the vibrational modes of the organic sub-lattice following above-bandgap optical excitation. We observe inter-sub-lattice thermal equilibration on timescales ranging from hundreds of picoseconds to a couple of nanoseconds. As supported by a two-temperature model based on first-principles calculations, the slow thermal equilibration is attributable to the sequential phonon populations of the inorganic and organic sub-lattices, respectively. The observed long-lasting thermal non-equilibrium offers insights into thermal transport and heat management of the emergent hybrid material class.

New BEDT-TTF/[Fe(C5O5)3]3-Hybrid System: Synthesis, Crystal Structure, and Physical Properties of a Chirality-Induced α Phase and a Novel Magnetic Molecular Metal

The paramagnetic and chiral anion [Fe(C5O5)3]3- (C5O52-=croconate) has been combined with the organic donor BEDT-TTF (=ET=bis(ethylenedithio)tetrathiafulvalene) to synthesize a novel paramagnetic semiconductor with the first chirality-induced alpha phase, alpha-(BEDT-TTF)5[Fe(C5O5)3].5H2O (1), and one of the few known paramagnetic molecular metals, beta-(BEDT-TTF)5[Fe(C5O5)3].C6H5CN (2). Both compounds present layers of BEDT-TTF molecules, with the alpha or beta packing modes, alternating with layers containing the high-spin S=5/2 Fe(III) anions and solvent molecules. In the alpha phase, the alternation of the chiral [Fe(C5O5)3]3- anions along the direction perpendicular to the BEDT-TTF chains induces an alternation of the tilt angle of the BEDT-TTF molecules, giving rise to the observed alpha phase. The alpha phase presents a semiconductor behavior with a high room-temperature conductivity (6 S.cm-1) and an activation energy of 116 meV. The beta phase presents a metallic behavior down to ca. 120 K, where a charge localization takes place with a reentrance to the metallic state below ca. 20 K followed by a metal-semiconductor transition at ca. 10 K. The magnetic properties are dominated by the paramagnetic S=5/2 [Fe(C5O5)3]3- anion with an extra Pauli-type paramagnetism in the metallic beta phase. The ESR spectra confirm the presence of the high-spin Fe(III)-containing anion and show a progressive localization in the organic sublattice along with an antiferromagnetic coupling below ca. 120 K that, in the metallic beta phase, could be at the origin of the transition from the metallic to the activated conductivity regime. The correlation between crystal structure and conductivity behavior has been studied by means of tight-binding band structure calculations which provide a rationalization of the charge distribution and conductivity results.

P-Phenylenediammonium tetrachlorozincate(II)

The structure of the title compound, (C6H10N2)[ZnCl4], contains simple ZnCl4 tetra­hedra in the bc plane creating alternating layers of organic and inorganic sublattices, a feature that is very common for compounds of this type. The two sublattices are held together by coulombic attraction of the cationic organic sublattice and anionic inorganic sublattice and also by hydrogen bonding. The anions are located on general positions. The cations, however, are located on mirror planes. As a result, there are two half-cations in the asymmetric unit.

Thermal, dielectric properties and vibrational spectra of [ n-C 4H 9NH 3] 2[BiBr 5] crystal

[ n-C 4H 9NH 3] 2[BiBr 5] exhibits five solid–solid structural phase transitions; at 309 (1st order), 291 (1st), 240 (1st), 219 (close to 2nd) and at 166 K (1st). The phase transitions at 291 and 240 K are accompanied by distinct dielectric anomalies. The dielectric relaxation process was found to appear over the phases (III) and (I). The infrared spectra for [ n-C 4H 9NH 3] 2[BiBr 5] were measured in the region of the internal vibration of the n-butylammonium cation (4000–400 cm −1) between 12 and 320 K. The temperature changes of wavenumbers and of a width for many of the internal modes of the n-butylammonium clearly indicate the contribution of the organic sublattice to the phase transition mechanism.

New charge transfer salts of two organic π-donors of the tetrathiafulvalene type with the paramagnetic [Cr(NCS) 6] 3– anion

The electrochemical combination of the paramagnetic anion [Cr(NCS) 6] 3– with the organic π-donors bis(ethylenedithio)tetrathiafulvalene (ET) and 4,5-bis(2-hydroxyethylthio)-4′,5′-ethylenedithiotetrathiafulvalene (DHET–EDTTTF) leads to two new radical cation salts, namely (ET) 4[Cr(NCS) 6]·PhCN ( 1) and (DHET– EDTTTF) 2(NEt 4)[Cr(NCS) 6] ( 2). Both have been characterized by X-ray crystallography, magnetic and resistivity measurements. The structure of 1 consists of alternating inorganic layers generated by the anions and organic layers in which the PhCN molecules are inserted; the organic sub-lattice is built up from four different ET units, three of them with a charge distribution of +1, the fourth being neutral. The organic sub-lattice of 2 contains a centrosymmetric [(DHET–EDTTTF •) 2] 2+ dimer, in which the overlap mode is of the eclipsed type. Conductivity measurements indicate that compounds 1 and 2 are semiconductors with room temperature conductivities of 1.4 × 10 –2 and 6.1 × 10 –5 S cm –1 and activation energies of 0.24 and 0.23 eV, in 1 and 2, respectively. For both salts, magnetic measurements indicate ( i) that the organic and inorganic parts are magnetically independent, and ( ii) that the organic units are antiferromagnetically coupled. To cite this article: F. Thétiot et al., C. R. Chimie 6 (2003).

Hybrid Molecular Materials Based upon Organic π-Electron Donors and Inorganic Metal Complexes. Conducting Salts of Bis(ethylenediseleno)tetrathiafulvalene (BEST) with the Octahedral Anions Hexacyanoferrate(III) and Nitroprusside

The synthesis, structure and physical characterization of three new radical salts formed by the organic donor bis(ethylenediseleno)tetrathiafulvalene (BEDS-TTF or BEST) and the paramagnetic hexacyanoferrate(III) anion [Fe(CN) 6] 3− or the photochromic nitroprusside anion [Fe(CN) 5NO] 2− are reported: (BEST) 4[Fe(CN) 6] ( 1), (BEST) 3[Fe(CN) 6] 2·H 2O ( 2) and (BEST) 2[Fe(CN) 5NO] ( 3). Salts 1 and 3 show a layered structure with alternating organic ( β –type packing) and inorganic slabs. Salt 2 shows an original interpenetrated structure probably due to the unprecedented presence of (BEST) 2+ dications. The three salts are semiconductors although salt 1 exhibits a high room temperature conductivity and a semiconducting–semiconducting transition at ca. 150 K which has been attributed to a dimerization in the organic sublattice.

New charge transfer salts based on bis(ethylenedithio)tetrathiafulvalene (ET) and ferro- or antiferromagnetic oxalato-bridged dinuclear anions: syntheses, structures and magnetism of ET5[MM'(C2O4)(NCS)8] with MM' = Cr(III)Fe(III), Cr(III)Cr(III).

Electrochemical combination of the magnetic dinuclear anion [MM'(C2O4)(NCS)8](4-) (MM' = Cr(III)Cr(III), Cr(III)Fe(III)) with the ET organic pi-donor (ET = BEDT-TTF = bis(ethylenedithio)tetrathiafulvalene) gives rise to two new isostructural molecular hybrid salts ET5[MM'(C2O4)(NCS)8], with MM' = CrCr (1), CrFe (2). The molecular structure of compound 1 has been determined by single crystal X-ray diffraction. The particular arrangement of the organic units consists of an unprecedented two-dimensional organic sublattice nearly similar to that observed in kappa-phase structures. For both compounds, the magnetic susceptibility measurements indicate (i) the ET radicals do not contribute to the magnetic moment probably due to the presence of strong antiferromagnetic interaction between them, and (ii) in the anion, the magnetic coupling is antiferromagnetic for 1 (J = -3.65 cm(-1)) and ferromagnetic for 2 (J = 1.14 cm(-1), J being the parameter of the exchange Hamiltonian H = -2JS1S2). The field dependence of the magnetization of compound 2 at 2.0 K gives further evidence of the S = 4 ground-state arising from the interaction between S = 3/2 Cr(III) and S = 5/2 Fe(III). EPR measurements confirm the nature of the magnetic interactions and the absence of any contribution from the organic part, as observed from the static magnetic measurement. Conductivity measurements and electronic band structure calculations show that both salts are semiconductors with low activation energies.

Hybrid molecular materials based upon organic pi-electron donors and metal complexes. Radical salts of bis(ethylenethia)tetrathiafulvalene (BET-TTF) with the octahedral anions hexacyanoferrate(III) and nitroprusside. The first kappa phase in the BET-TTF family.

The synthesis, structure, and physical characterization of two new radical salts formed with the organic donor bis(ethylenethia)tetrathiafulvalene (BET-TTF) and the octahedral anions hexacyanoferrate(III), [Fe(CN)(6)](3-), and nitroprusside, [Fe(CN)(5)NO](2-), are reported. These salts are (BET-TTF)(4)(NEt(4))(2)[Fe(CN)(6)] (1) (monoclinic space group C2/c with a = 38.867(7) A, b = 8.438(8) A, c = 11.239(6) A, beta = 90.994(9) degrees, V = 3685(4) A(3), Z = 4) and (BET-TTF)(2)[Fe(CN)(5)NO].CH(2)Cl(2) (2) (monoclinic space group C2/c with a = 16.237(6) A, b = 18.097(8) A, c = 12.663(7) A, beta = 106.016(9) degrees, V = 3576(3) A(3), Z = 4). In salt 1 the organic BET-TTF molecules are packed in orthogonal dimers, forming the first kappa phase observed for this donor. The analysis of the bond distances and the electronic and IR spectra suggests a degree of ionicity of 1/4 per BET-TTF molecule, in agreement with the stoichiometry of the salt. The electrical properties show that 1 is a semiconductor with a high room-temperature conductivity (11.6 S cm(-1)) and a low activation energy (45 meV), in agreement with the band structure calculations. The magnetic susceptibility of 1 shows, besides the paramagnetic contribution from the anion, a temperature-independent paramagnetism (TIP) of the Pauli type due to the electronic delocalization observed at high temperatures in the organic sublattice. This Pauli type paramagnetism is confirmed by the ESR spectra that also show a Dysonian line when the magnetic field is parallel to the conducting plane, typical of metallic and highly conducting systems. Salt 2 presents an unprecedented packing of the organic molecules that form zigzag tunnels where the anions and the solvent molecules are located. The stoichiometry indicates that all the BET-TTF molecules bear a charge of +1, and accordingly, 2 behaves as a semiconductor with a very low room-temperature conductivity. The magnetic properties of this salt indicate that the unpaired electrons on the organic molecules are strongly antiferromagnetically coupled, giving rise to a diamagnetic behavior of 2, as the nitroprusside anion is also diamagnetic.

Organic/inorganic molecular conductors based upon perylene and Lindquist-type polyoxometalates

The preparation, structures and physical properties of the organic/inorganic radical salts based upon perylene (per) and Lindquist type polyoxometalates (POMs) are reported. Three new hybrid salts have been prepared: (per)5[Mo6O19] (1), (per)5[W6O19] (2), and (per)5[VW5O19] (3). Only structures 1 (P, Z = 2) and 3 (P, Z = 2) were fully determined as compound 2 was found to have unit cell parameters practically identical to 1 and, therefore, is considered isostructural with the latter. The structures consist of interpenetrated organic and mixed organic/inorganic layers in the ac plane alternating along the a direction. The organic layers present a novel packing mode of the perylene molecules that consists of criss-cross chains formed by two alternating dimers running along the c axis. Besides the ability to induce novel packings in the organic sublattice, the possibility offered by the POMs of varying the charge while maintaining the size and shape of the anion has enabled the control of the electronic band filling and, therefore, of the electrical and magnetic properties. Thus, salts 1 and 2, where the anionic charge is −2, are diamagnetic and present lower room temperature conductivities, while salt 3, where the anionic charge is −3, has an unpaired electron and presents a higher room temperature conductivity and a lower activation energy. Thermopower measurements show that salts 1 and 2 present hole-type conduction whereas salt 3 exhibits electron-dominating electrical transport.

Structural features of the Bechgaard salts and related compounds

We present an overview of the structural instabilities and of the structural transitions exhibited by the Bechgaard salts (TMTSF)2X, the Fabre salts (TMTTF)2X, and related compounds. In the (TMTTF)2X and (BCPTTF)zX series with centrosymmetric anions X, such as PF6, a 2k~ bond instability leads to the formation of a spin-Peierls (SP) ground state. A quantitative analysis of its one dimensional (ID) pretransitional fluctuations, previously performed in the BCPTTF series, is extended to the inorganic SP compound CuGeOs. In the (TMTSF)2X series, the 1D 2k~ charge density wave (CDW) structural fluctuations vanish at low temperature when the spin density wave correlations develop. However the detection of very weak 2k~ and 4k~ satellite reflections shows that the density wave ground state of (TMTSF)2PF6 unexpectedly presents a mixed spin-charge character. In salts with X non-centrosymmetric, the anions, disordered at room temperature, order in a superlattice upon cooling. However, because of their coupling with the organic sublattice, these ordering lead to important modifications of the electronic properties. Finally, we report a quantitative analysis of the 1D 2k~ and 4k~ CDW lattice fluctuations observed in the TTF-TCNQ family, allowing to extract the exponent K, governing the collective instabilities of the Luttinger liquid.