No Arabic abstract
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.
Magnetoelectroluminescence (MEL) of organic semiconductor has been experimentally tuned by adopting blended emitting layer consisting of both hole and electron transporting materials. A theoretical model considering intermolecular quantum correlation is proposed to demonstrate two fundamental issues: (1) two mechanisms, spin scattering and spin mixing, dominate the two different steps respectively in the process of the magnetic field modulated generation of exciton; (2) the hopping rate of carriers determines the intensity of MEL. Calculation successfully predicts the increase of singlet excitons in low field with little change of triplet exciton population.
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 transport can be still described by phonons in metal-organic frameworks. Here, by studying two typical systems, i.e., crystal zeolitic imidazolate framework-4 (cZIF-4) and crystal zeolitic imidazolate framework-62 (c-ZIF62), we prove that the ultralow thermal conductivity in metal-organic frameworks is resulting from the strong phonon intrinsic structure scattering due to the large mass difference and the large cavity between Zn and N atoms. Our mean free path spectrum analysis shows that both propagating and non-propagating anharmonic vibrational modes exist in the systems, and contribute largely to the thermal conductivity. The corresponding weakly negative or positive temperature dependence of the thermal conductivity is stemming from the competition between the propagating and non-propagating anharmonic vibrational modes. Our study here provides a fundamental understanding of thermal transport in metal-organic frameworks and will guide the design of the thermal-related applications using metal-organic frameworks, e.g., inflammable gas storage, chemical catalysis, solar thermal conversion and so on.
Whereas spintronics brings the spin degree of freedom to electronic devices, molecular/organic electronics adds the opportunity to play with the chemical versatility. Here we show how, as a contender to commonly used inorganic materials, organic/molecular based spintronics devices can exhibit very large magnetoresistance and lead to tailored spin polarizations. We report on giant tunnel magnetoresistance of up to 300% in a (La,Sr)MnO3/Alq3/Co nanometer size magnetic tunnel junction. Moreover, we propose a spin dependent transport model giving a new understanding of spin injection into organic materials/molecules. Our findings bring a new insight on how one could tune spin injection by molecular engineering and paves the way to chemical tailoring of the properties of spintronics devices.
Long-range and fast transport of coherent excitons is important for development of high-speed excitonic circuits and quantum computing applications. However, most of these coherent excitons have only been observed in some low-dimensional semiconductors when coupled with cavities, as there are large inhomogeneous broadening and dephasing effects on the exciton transport in their native states of the materials. Here, by confining coherent excitons at the 2D quantum limit, we firstly observed molecular aggregation enabled super-transport of excitons in atomically thin two-dimensional (2D) organic semiconductors between coherent states, with a measured a high effective exciton diffusion coefficient of 346.9 cm2/sec at room temperature. This value is one to several orders of magnitude higher than the reported values from other organic molecular aggregates and low-dimensional inorganic materials. Without coupling to any optical cavities, the monolayer pentacene sample, a very clean 2D quantum system (1.2 nm thick) with high crystallinity (J type aggregation) and minimal interfacial states, showed superradiant emissions from the Frenkel excitons, which was experimentally confirmed by the temperature-dependent photoluminescence (PL) emission, highly enhanced radiative decay rate, significantly narrowed PL peak width and strongly directional in-plane emission. The coherence in monolayer pentacene samples was observed to be delocalized over 135 molecules, which is significantly larger than the values (a few molecules) observed from other organic thin films. In addition, the super-transport of excitons in monolayer pentacene samples showed highly anisotropic behaviour. Our results pave the way for the development of future high-speed excitonic circuits, fast OLEDs, and other opto-electronic devices.
The electronic wavefunctions of an atom or molecule are affected by its interactions with its environment. These interactions dictate electronic and optical processes at interfaces, and is especially relevant in the case of thin film optoelectronic devices such as organic solar cells. In these devices, charge transport and interfaces between multiple layers occur along the thickness or vertical direction, and thus such electronic interactions are crucial in determining the device properties. Here, we introduce a new in-situ spectroscopic ellipsometry data analysis method called DART with the ability to directly probe electronic coupling due to intermolecular interactions along the thickness direction using vacuum-deposited organic semiconductor thin films as a model system. The analysis, which does not require any model fitting, reveals direct observations of electronic coupling between frontier orbitals under optical excitations leading to delocalization of the corresponding electronic wavefunctions with thickness or, equivalently, number of molecules away from the interface in C60 and MeO-TPD deposited on an insulating substrate (SiO2). Applying the same methodology for C60 deposited on phthalocyanine thin films, the analyses shows strong, anomalous features - in comparison to C60 deposited on SiO2 - of the electronic wavefunctions corresponding to specific excitation energies in C60 and phthalocyanines. Translation of such interactions in terms of dielectric constants reveals plasmonic type resonance absorptions resulting from oscillations of the excited state wavefunctions between the two materials across the interface. Finally, reproducibility, angstrom-level sensitivity and simplicity of the method are highlighted showcasing its applicability for studying electronic coupling between any vapor-deposited material systems where real-time measurements during deposition are possible.