Conductivity in organic semiconductors hybridized with the vacuum field
E. Orgiu, J. George, J. A. Hutchison, E. Devaux, J. F. Dayen, B. Doudin, F. Stellacci, C. Genet, J. Schachenmayer, C. Genes, G. Pupillo, P. Samori, T. W. Ebbesen
Organic semiconductors have generated considerable interest for their potential for creating inexpensive and flexible devices easily processed on a large scale [1-11]. However technological applications are currently limited by the low mobility of the charge carriers associated with the disorder in these materials [5-8]. Much effort over the past decades has therefore been focused on optimizing the organisation of the material or the devices to improve carrier mobility. Here we take a radically different path to solving this problem, namely by injecting carriers into states that are hybridized to the vacuum electromagnetic field. These are coherent states that can extend over as many as 10^5 molecules and should thereby favour conductivity in such materials. To test this idea, organic semiconductors were strongly coupled to the vacuum electromagnetic field on plasmonic structures to form polaritonic states with large Rabi splittings ca. 0.7 eV. Conductivity experiments show that indeed the current does increase by an order of magnitude at resonance in the coupled state, reflecting mostly a change in field-effect mobility as revealed when the structure is gated in a transistor configuration. A theoretical quantum model is presented that confirms the delocalization of the wave-functions of the hybridized states and the consequences on the conductivity. While this is a proof-of-principle study, in practice conductivity mediated by light-matter hybridized states is easy to implement and we therefore expect that it will be used to improve organic devices. More broadly our findings illustrate the potential of engineering the vacuum electromagnetic environment to modify and to improve properties of materials.
Hybridized molecule/metal interfaces are ubiquitous in molecular and organic devices. The energy level alignment (ELA) of frontier molecular levels relative to the metal Fermi level (EF) is critical to the conductance and functionality of these devices. However, a clear understanding of the ELA that includes many-electron self-energy effects is lacking. Here, we investigate the many-electron effects on the ELA using state-of-the-art, benchmark GW calculations on prototypical chemisorbed molecules on Au(111), in eleven different geometries. The GW ELA is in good agreement with photoemission for…
In the present work we discuss resonant hybridization of the $1S$ quadrupole Wannier-Mott exciton (WE) in a $Cu_2O$ quantum well with the Frenkel (FE) dipole exciton in an adjacent layer of organic DCM2:CA:PA. The coupling between excitons is due to interaction between the gradient of electric field induced by DCM2 Frenkel exciton and the quadrupole moment of the $1S$ transition in the cuprous oxide. The specific choice of the organic allows us to use the mechanism of 'solid state solvation' to dynamically tune the WE and FE into resonance during time $\approx 3.3 \: ns$ (comparable with the b…
It is textbookly regarded that phonons, i.e., an energy quantum of propagating lattice waves, are the main heat carriers in perfect crystals. As a result, in many crystals, e.g., bulk silicon, the temperature-dependent thermal conductivity shows the classical 1/T relationship because of the dominant Umklapp phonon-phonon scattering in the systems. However, the thermal conductivity of many crystalline metal-organic frameworks is very low and shows no, a weakly negative and even a weakly positive temperature dependence (glass-like thermal conductivity). It has been in debate whether the thermal …
The thermal transport properties of biphenylene network (BPN), a novel sp2 -hybridized two-dimensional allotrope of carbon atoms recently realized in experiments [Fan et al., Science, 372 852-856 (2021)], are studied using the density functional theory-driven solution of the Boltzmann transport equation. The thermal transport in BPN is anisotropic and the obtained thermal conductivities are more than an order of magnitude lower than that in graphene, despite similar sp2-hybridized planar-structure of both allotropes. The lower thermal conductivity in BPN is found to originate from enhanced anh…
The intersection volume of two independent 2-level cut Gaussian random fields is proposed to model the open-cell microstructure of organic aerogels. The experimentally measured X-ray scattering intensity, surface area and solid thermal conductivity of both polymeric and colloidal organic aerogels can be accounted for by the model.
Organic semiconductors have attracted increasing interest as thermoelectric converters in recent years due to their intrinsically low thermal conductivity compared to inorganic materials. This boom has led to encouraging practical results, in which the thermal conductivity has predominantly been treated as an empirical number. However, in an optimized thermoelectric material, the electronic component can dominate the thermal conductivity in which case the figure of merit $ZT$ becomes a function of thermopower and Lorentz factor only. Hence design of effective organic thermoelectric materials r…
Molecular wires are essential components for future nanoscale electronics. However, the preparation of individual long conductive molecules is still a challenge. MMX metal-organic polymers are quasi-one-dimensional sequences of single halide atoms (X) bridging subunits with two metal ions (MM) connected by organic ligands. They are excellent electrical conductors as bulk macroscopic crystals and as nanoribbons. However, according to theoretical calculations, the electrical conductance found in the experiments should be even higher. Here we demonstrate a novel and simple drop-casting procedure …
Great success has been achieved in improving the photovoltaic energy conversion efficiency of the organic-inorganic perovskite-based solar cells, but with very limited knowledge on the thermal transport in hybrid perovskites, which would affect the device lifetime and stability. Based on the potential developed from the density functional theory calculations, we studied the lattice thermal conductivity of the hybrid halide perovskite CH3NH3PbI3 using equilibrium molecular dynamics simulations. Temperature-dependent thermal conductivity is reported from 160 K to 400 K, which covers the tetragon…
We report on the temperature dependence of thermal conductivity of single crystalline and polycrystalline organometallic perovskite CH3NH3PbI3. The comparable absolute values and temperature dependence of the two sample's morphologies indicate the minor role of the grain boundaries on the heat transport. Theoretical modelling demonstrates the importance of the resonant scattering in both specimens. The interaction between phonon waves and rotational degrees of freedom of CH3NH3+ sub-lattice emerges as the dominant mechanism for attenuation of heat transport and for ultralow thermal conductivit…
Molecular self-assembly has been extensively used for surface modification of metals and oxides for a variety of applications, including molecular and organic electronics. One of the goals of this research is to learn how the electronic properties of these surfaces can be modified by self-assembled monolayers (SAM). Here, we demonstrate a new type of molecular self-assembly: the growth of organosilane SAMs at the surface of organic semiconductors, which results in a dramatic increase of the surface conductivity of organic materials. For organosilane molecules with a large dipole moment, SAM-in…
We measure the complex impedance between source/drain electrodes and the gate electrode of a pentacene thin-film transistor (TFT) at frequencies 50 Hz < omega/2pi < 20 kHz. Modeling the TFT as a distributed RC network (RC transmission line), we find that the data cannot be explained by a model including only a real, frequency-independent sheet conductivity. Instead, we use the RC transmission line model to extract the frequency-dependent complex sheet conductivity sigma(omega) = sigma'(omega) + jsigma"(omega) of the pentacene film. At high frequencies, sigma(omega) increases with frequency, si…
We present a multiscale modeling of the infrared optical properties of the rubrene crystal. The results are in very good agreement with the experimental data that point to nonmonotonic features in the optical conductivity spectrum and small optical effective masses. We find that, in the static-disorder approximation, the nonlocal electron-phonon interactions stemming from low-frequency lattice vibrations can decrease the optical effective masses and lead to lighter quasiparticles. On the other hand, the charge-transport and infrared optical properties of the rubrene crystal at room temperature…
Light-matter coupling in excitonic materials has been the subject of intense investigation due to emergence of new excitonic materials. Two-dimensional layered hybrid organic/inorganic perovskites (2D HOIPs) support strongly bound excitons at room-temperatures with some of the highest oscillator strengths and electric loss tangents among the known excitonic materials. Here, we report strong light-matter coupling in Ruddlesden-Popper phase 2D-HOIPs crystals without the necessity of an external cavity. We report concurrent occurrence of multiple-orders of hybrid light-matter states via both refl…
The optical conductivity spectra of the rattling phonons in the clathrate Ba$_8$Ga$_{16}$Ge$_{30}$ are investigated in detail by use of the terahertz time-domain spectroscopy. The experiment has revealed that the lowest-lying vibrational mode of a Ba(2)$^{2+}$ ion consists of a sharp Lorentzian peak at 1.2 THz superimposed on a broad tail weighted in the lower frequency regime around 1.0 THz. With decreasing temperature, an unexpected linewidth broadening of the phonon peak is observed, together with monotonic softening of the phonon peak and the enhancement of the tail structure. These observ…
Molecular dynamics simulations combined with periodic electronic structure calculations are performed to decipher structural, thermodynamical and dynamical properties of the interfaced vs. confined water adsorbed in hexagonal 1D channels of the 2D layered electrically conductive Cu3(HHTP)2 and Cu3(HTTP)2 metal-organic frameworks (HHTP=2,3,6,7,10,11-hexahydroxytriphenylene and HTTP = 2,3,6,7,10,11-hexathiotriphenylene). Comparing water adsorption in bulk vs. slab models of the studied 2D MOFs shows that water is preferentially adsorbed on the framework walls via forming hydrogen bonds to the or…
We show that the temperature dependence of conductivity of high mobility organic crystals Pentacene and Rubrene can be quantitatively described in the framework of the model where carriers are scattered by quenched local impurities and interact with phonons by Su-Schrieffer-Hegger (SSH) coupling. Within this model, we present approximation free results for mobility and optical conductivity obtained by world line Monte Carlo, which we generalize to the case of coupling both to phonons and impurities. We find fingerprints of carrier dynamics in these compounds which differ from conventional meta…
The quantum anomalous Hall (QAH) phase is a novel topological state of matter characterized by a nonzero quantized Hall conductivity without an external magnetic field. The realizations of QAH effect, however, are experimentally challengeable. Based on ab initio calculations, here we propose an intrinsic QAH phase in DCA Kagome lattice. The nontrivial topology in Kagome bands are confirmed by the nonzero chern number, quantized Hall conductivity, and gapless chiral edge states of Mn-DCA lattice. A tight-binding (TB) model is further constructed to clarify the origin of QAH effect. Furthermore,…
High thermal conductivity dominated by thermal phonons with mean free paths exceeding hundred nanometer in three-dimensional covalent organic framework derivatives: a molecular dynamics study
Solution-processed, large-area, and flexible electronics largely relies on the excellent electronic properties of sp$^2$-hybridized carbon molecules, either in the form of $π$-conjugated small molecules and polymers or graphene and carbon nanotubes. Carbon with sp-hybridization, the foundation of the elusive allotrope carbyne, offers vast opportunities for functionalized molecules in the form of linear carbon atomic wires (CAWs), with intriguing and even superior predicted electronic properties. While CAWs represent a vibrant field of research, to date, they have only been applied sparingly to…
We report a novel insulator-insulator transition arising from the internal charge degrees of freedom in the two-dimensional quarter-filled organic salt beta-(meso-DMBEDT-TTF)2PF6. The optical conductivity spectra above Tc = 70 K display a prominent feature of the dimer-Mott insulator, characterized by a substantial growth of a dimer peak near 0.6 eV with decreasing temperature. The dimer-peak growth is rapidly quenched as soon as a peak of the charge order shows up below Tc, indicating a competition between the two insulating phases. Our infrared imaging spectroscopy has further revealed a spa…
We performed third-order electrical conductivity measurements on the organic conductor $α$-(BEDT-TTF)$_2$I$_3$ using an ac bridge technique sensitive to nonlinear signals. Third-order conductance $G_3$ is clearly observed even at low electric fields, and interestingly, $G_3$ is critically enhanced above the charge-order transition temperature $T_{\rm CO}=136$~K. The observed frequency dependence of $G_3$ is incompatible with a percolation model, in which a Joule heating in a random resistor network is relevant to the nonlinear conduction. We instead argue the nonlinearity of the relaxation tim…
The outstanding performance of organic-inorganic metal trihalide solar cells benefits from the exceptional photo-physical properties of both electrons and holes in the material. Here, we directly probe the free-carrier dynamics in Cs-doped FAPbI3 thin films by spatiotemporal photoconductivity imaging. Using charge transport layers to selectively quench one type of carriers, we show that the two relaxation times on the order of 1 microsecond and 10 microseconds correspond to the lifetimes of electrons and holes in FACsPbI3, respectively. Strikingly, the diffusion mapping indicates that the diff…
Machine Learning Based Prediction of Proton Conductivity in Metal-Organic Frameworks
Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology（化学与生物分子工程系，韩国科学技术院）；Department of Chemistry and Medical Chemistry, Yonsei University（化学与医学化学系，延世大学）
Effect of spin-orbit coupling (SOC) on Dirac electrons in the organic conductor $α$-(BETS)$_2$I$_3$ [BETS = bis(ethylenedithio)tetraselenafulvalene] has been examined by calculating electric conductivity and spin magnetic susceptibility. A tight-binding (TB) model with real and imaginary transfer energies is derived using first-principles density-functional theory method. The conductivity without the SOC depends on both anisotropies of the velocity of the Dirac cone and the tiling of the cone. Such conductivity is suppressed by the SOC, which gives rise to the imaginary part of the transfer en…
The closely related Green-Kubo and Helfand moment approaches are applied to obtain the thermal conductivity tensor of $β$-1,3,5,7-tetranitro-1,3,5,7-tetrazoctane ($β$-HMX) at $T=300$ K and $P=1$ atm from equilibrium molecular dynamics (MD) simulations. Direct application of the Green-Kubo formula exhibits slow convergence of the integrated thermal conductivity values even for long (120 ns) simulation times. To partially mitigate this slow convergence we developed a numerical procedure that involves filtering of the MD-calculated heat current. The filtering is accomplished by physically justifi…
Metal-organic frameworks (MOFs) symbolize the particular class of hybrid crystalline, nano-porous materials made of either discrete metal ions or clusters with organic linkers. Past studies on MOFs-based materials largely focused on porosity, chemical and structural diversity, gas sorption, sensing, drug delivery, catalysis, and separation applications. However, initial efforts either neglected or have not gained much attention to refine the electrical conductivity of MOFs materials. MOFs reported earlier with poor electrical conductivity impeded to employ in electronics, optoelectronics, and …
Highly oriented polymer films can show considerable anisotropy in the thermoelectric properties leading to power factors beyond those predicted by the widely obeyed power law linking the thermopower $S$ and the electrical conductivity $σ$ as $S\proptoσ^{-1/4}$. This has led to encouraging practical results with respect to the electrical conductivity, notwithstanding that the conditions necessary to enhance $σ$ and $S$ simultaneously are less clear. Here, kinetic Monte Carlo simulations are used to study the impact of structural anisotropy on the thermoelectric properties of disordered organic …
Hybrid conjugated polymer/fullerene filaments based on MEH-PPV/PVP/PCBM are prepared by electrospinning, and their properties assessed by scanning electron, atomic and lateral force, tunnelling, and confocal microscopy, as well as by attenuated total reflection Fourier transform-infrared spectroscopy, photoluminescence quantum yield and spatially-resolved fluorescence. Highlighted features include ribbon-shape of the realized fibers, and the persistence of a network serving as a template for heterogeneous active layers in solar cell devices. A set of favorable characteristics is evidenced in t…
The electronic properties of interfaces between two different solids can differ strikingly from those of the constituent materials. For instance, metallic conductivity, and even superconductivity, have been recently discovered at interfaces formed by insulating transition metal oxides. Here we investigate interfaces between crystals of conjugated organic molecules, which are large gap undoped semiconductors, i.e. essentially insulators. We find that highly conducting interfaces can be realized with resistivity ranging from 1 to 30 kOhm square, and that, for the best samples, the temperature de…
We report measurements of the heat capacity and cross-plane thermal conductivity of 2D (CxH2x+1NH3)2[MAPbBr3]n-1PbBr4 (MA = methylammonium) lead bromide perovskites (2D LHPs) at room temperature as a function of both the octahedral layer thickness (n = 1,2,3) and the organic spacer chain length (x=4,5,6,7,8) using differential scanning calorimetry (DSC) and frequency domain thermoreflectance (FDTR) respectively. We observe ultralow thermal conductivities (0.18-0.51 W/m K) for all 2D LHPs studied, but surprisingly minimal suppression of thermal conductivity with respect to bulk MAPbBr3 (0.5 W/m…
Simultaneously optimizing performances, processability and fabrication cost of organic electronic materials is the continual source of compromise hindering the development of disruptive applications. In this work, we identified a strategy to achieve record conductivity values of one of the most benchmarked semiconducting polymers by doping with an entirely solution-processed, water-free and cost-effective technique. High electrical conductivity for poly(3-hexylthiophene) up to 21 S/cm has been achieved, using a commercially available electron acceptor as both a Lewis acid and an oxidizing agen…
The heat transfer properties of the organic molecular crystal $α$-RDX were studied using three phonon-based thermal conductivity models. It was found that the widely used Peierls-Boltzmann model for thermal transport in crystalline materials breaks down for $α$-RDX. We show this breakdown is due to a large degree of anharmonicity that leads to a dominance of diffusive-like carriers. Despite being developed for disordered systems, the Allen-Feldman theory for thermal conductivity actually gives the best description of thermal transport. This is likely because diffusive carriers contribute to ov…
In recent years, in looking for an important photorefractive application, several studies on electro-optic and photoconductive sol-gel responses have been done. A very important effort has been addressed to establish the appropriate induced-orientation procedure, in order to get the highest electro-optic coefficient. In this way a very high coefficient of 48 pm/V at 831 nm in sol-gel has been already found. Similarly, the importance of the non-linear chromophore concentration into the material electro-optic behavior has been studied. However, the influence of the orientation procedure and the …
Organic semiconductors based on small conjugated molecules generally behave as insulators when undoped, but the hetero-interfaces of two such materials can show electrical conductivity as large as in a metal. Although charge transfer is commonly invoked to explain the phenomenon, the details of the process and the nature of the interfacial charge carriers remain largely unexplored. Here we use Schottky-gated heterostructures to probe the conducting layer at the interface between rubrene and PDIF-CN2 single crystals. Gate-modulated conductivity measurements demonstrate that interfacial transpor…
Conductive polymers or "organic metals" are highly engineered nanostructured materials made from organic building blocks. They are candidates as molecular wires for nanotechnology applications in molecular electronics. The conduction in these polymers is due to the presence of delocalized molecular orbitals. In this work, we present the synthesis of chloride doped polyaniline by bulk oxidative chemical polymerization using a solid aniline salt as a monomer instead of liquid aniline to diminish toxic hazards. The FTIR and UV-visible spectra confirmed the expected structure of the polymer. The e…
Doped films of organic small molecules are investigated with respect to their thermoelectric properties. A variety of hosts and dopants, for both n and p-doping, are compared. C$_{60}$ n-doped by Cr$_2$(hpp)$_4$ or o-MeO-DMBI-I are found to be the most promising material systems with a maximum of ZT$_\text{M}$ = 0.069 at T$_\text{M}$ = 40°C, assuming a doping-independent thermal conductivity due to phonon-based heat transport. This value is 16% of the current record reported for optimized devices employing the doped polymer PEDOT:PSS.
We present a simple but powerful method to determine the thicknesses of the accumulation and depletion layers and the distribution curve of injected carriers in organic field effect transistors. The conductivity of organic semiconductors in thin film transistors was measured in-situ and continuously with a bottom contact configuration, as a function of film thickness at various gate voltages. Using this method, the thicknesses of the accumulation and depletion layers of pentacene were determined to be 0.9 nm (VG=-15 V) and 5 nm (VG=15 V).
In this work, we introduce models for deriving lower limits for the key parameters doping efficiency, charge carrier concentration, and charge carrier mobility from conductivity data of doped organic semiconductors. The models are applied to data of thin layers of Fullerene C60 n-doped by four different n-dopants. Combining these findings with thermoelectric Seebeck data, the energetic position of the transport level can be narrowed down and trends for the absolute values are derived.
The conductivity of organic semiconductors is measured {\it in-situ} and continuously with a bottom contact configuration, as a function of film thickness at various gate voltages. The depletion layer thickness can be directly determined as a shift of the threshold thickness at which electric current began to flow. The {\it in-situ} and continuous measurement can also determine qualitatively the accumulation layer thickness together with the distribution function of injected carriers. The accumulation layer thickness is a few mono layers, and it does not depend on gate voltages, rather depends…
The surface conductivity is measured by a four-probe technique for pentacene and rubrene single-crystals laminated on polarized and nearly unpolarized molecular monolayers with application of perpendicular electric fields. The polarization of the self-assembled monolayers (SAMs) shifts the threshold gate voltage, while maintaining a very low subthreshold swing of the single-crystal devices (0.11 V/decade). The results, excluding influences of parasitic contacts and grain boundaries, demonstrate SAM-induced nanoscale charge injection up to ~10^12 cm^-2 at the surface of the organic single cryst…
Despite the highly porous nature with significantly large surface area, metal organic frameworks (MOFs) can be hardly used in electronic, and optoelectronic devices due to their extremely poor electrical conductivity. Therefore, the study of MOF thin films that require electron transport or conductivity in combination with the everlasting porosity is highly desirable. In the present work, thin films of Co3(NDC)3DMF4 MOFs with improved electronic conductivity are synthesized using layer-by-layer and doctor blade coating techniques followed by iodine doping. The as-prepared and doped films are c…
Programming electronic states in conductive metal-organic frame-works through crystallization-enabled proton management
School of Physics and Astronomy, Shanghai Jiao Tong University（上海交通大学物理与天文学院）；School of Materials Science and Engineering, Peking University（北京大学材料科学与工程学院）；College of Chemistry and Molecular Engineering, Peking University（北京大学化学与分子工程学院）
We identify a universality in the Fermi level change of Van der Waals interacting semiconductor interfaces-based Schottky junctions. We show that the disappearing of quasi-Fermi level pinning at a certain thickness of semiconductor films for both intrinsic (undoped) and extrinsic (doped) semiconductors, over a wide range of bulk systems including inorganic, organic, and even organic-inorganic hybridized semiconductors. The Fermi level (EF) position located in the energy bandgap was dominated by not only the substrate work function, but also the thickness of semiconductor films, in which the fi…
