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Ti3C2Tx MXenes have typically a mixed surface termination of oxygen, hydroxyl and fluorine groups (Tx). In this work, we investigate the influence of the surface termination on the vibrational properties of Ti3C2Tx by performing thermal desorption and in situ Raman spectroscopy in ultra-high-vacuum (UHV). Significant changes in the Raman spectra occur after annealing above 600 °C, correlated with the desorption of approximately 80% of the fluorine termination, as confirmed by mass spectrometry and X-ray photoemission spectra. In particular, the intense Raman mode at 203 cm-1, usually attributed to a Ti-C-layer stretching vibration, is strongly damped upon fluorine desorption, while the broad spectral features between 220 and 680 cm-1, usually attributed to surface group vibrations, are not changing significantly. We show that the Raman spectra and the change induced by fluorine desorption are well represented by the phonon density of states instead of zone-center phonon modes. Disorder-induced Raman scattering strongly contributes to the Raman spectra. Moreover, due to the metallic nature of MXenes, charge density fluctuation scattering contributes as well. We show that the two scattering mechanisms, deformation potential and charge density fluctuation, may lead to opposite interpretations concerning the symmetry of the fluorine-related mode at 203 cm-1. This study provides new insights into the interpretation of the Raman spectra of MXenes, especially regarding the relation between surface chemistry and vibrational spectroscopy.
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Conducting polymers are mixed ionic-electronic conductors that are emerging candidates for neuromorphic computing, bioelectronics and thermoelectrics. However, fundamental aspects of their many-body correlated electron-ion transport physics remain poorly understood. Here we show that in p-type organic electrochemical transistors it is possible to remove all of the electrons from the valence band and even access deeper bands without degradation. By adding a second, field-effect gate electrode, additional electrons or holes can be injected at set doping states. Under conditions where the counterions are unable to equilibrate in response to field-induced changes in the electronic carrier density, we observe surprising, non-equilibrium transport signatures that provide unique insights into the interaction-driven formation of a frozen, soft Coulomb gap in the density of states. Our work identifies new strategies for substantially enhancing the transport properties of conducting polymers by exploiting non-equilibrium states in the coupled system of electronic charges and counterions.
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Lithium-ion batteries, essential for electronics and electric vehicles, predominantly use cathodes made from critical materials like cobalt. Sulfur-based cathodes, offering a high theoretical capacity of 1675â mAh g-1 and environmental advantages due to sulfur's abundance and lower toxicity, present a more sustainable alternative. However, state-of-the-art sulfur-based electrodes do not reach the theoretical capacities, mainly because conventional electrode production relies on mixing of components into weakly coordinated slurries. Consequently, sulfur's mobility leads to battery degradation-an effect known as the "sulfur-shuttle". This study introduces a solution by developing a microporous, covalently-bonded, imine-based polymer network grown in situ around sulfur particles on the current collector. The polymer network (i) enables selective transport of electrolyte and Li-ions through pores of defined size, and (ii) acts as a robust host to retain the active component of the electrode (sulfur species). The resulting cathode has superior rate performance from 0.1â C (1360â mAh g-1) to 3â C (807â mAh g-1). Demonstrating a high-performance, sustainable sulfur cathode produced via a simple one-pot process, our research underlines the potential of microporous polymers in addressing sulfur diffusion issues, paving the way for sulfur electrodes as viable alternatives to traditional metal-based cathodes.
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This study shows that the simple approach of keeping anodic TiO2 nanotubes at 70 °C in ethanol for 1â h results in improved photoelectrochemical water splitting activity due to initiation of crystallization in the material amplified by the light-induced formation of a Ti3+ -Vo states under UV 365â nm illumination. For the first time, the light-induced Ti3+ -Vo states are generated when oxygen is present in the reaction solution and are stable when in contact with air (oxygen) for a long time (two months). We confirmed here that the amorphous or nearly amorphous structure of titania supports the survival of Ti3+ species in contact with oxygen. It is also shown that the ethanol treatment substantially improves the morphology of the titania nanotube arrays, specifically, less surface cracking and surface purification from C- and F-based contamination from the electrolyte used for anodizing.
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In perovskite solar cells (PSCs) energy level alignment and charge extraction at the interfaces are the essential factors directly affecting the device performance. In this work, we present a modified interface between all-inorganic CsPbI3 perovskite and its hole-selective contact (spiro-OMeTAD), realized by the dipole molecule trioctylphosphine oxide (TOPO), to align the energy levels. On a passivated perovskite film, with n-octylammonium iodide (OAI), we created an upward surface band-bending at the interface by TOPO treatment. This improved interface by the dipole molecule induces a better energy level alignment and enhances the charge extraction of holes from the perovskite layer to the hole transport material. Consequently, a Voc of 1.2 V and a high-power conversion efficiency (PCE) of over 19% were achieved for inorganic CsPbI3 perovskite solar cells. Further, to demonstrate the effect of the TOPO dipole molecule, we present a layer-by-layer charge extraction study by a transient surface photovoltage (trSPV) technique accomplished by a charge transport simulation.
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The surface molecular doping of organic semiconductors can play an important role in the development of organic electronic or optoelectronic devices. Single-crystal rubrene remains a leading molecular candidate for applications in electronics due to its high hole mobility. In parallel, intensive research into the fabrication of flexible organic electronics requires the careful design of functional interfaces to enable optimal device characteristics. To this end, the present work seeks to understand the effect of surface molecular doping on the electronic band structure of rubrene single crystals. Our angle-resolved photoemission measurements reveal that the Fermi level moves in the band gap of rubrene depending on the direction of surface electron-transfer reactions with the molecular dopants, yet the valence band dispersion remains essentially unperturbed. This indicates that surface electron-transfer doping of a molecular single crystal can effectively modify the near-surface charge density, while retaining good charge-carrier mobility.
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Strong molecular dopants for organic semiconductors that are stable against diffusion are in demand, enhancing the performance of organic optoelectronic devices. The conventionally used p-dopants based on 7,7,8,8-tetracyanoquinodimethane (TCNQ) and its derivatives "FxTCN(N)Q", such as 2,3,4,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) and 1,3,4,5,7,8-hexafluorotetracyano-naphthoquinodimethane (F6TCNNQ), feature limited oxidation strength, especially for modern polymer semiconductors with high ionization energy (IE). These small molecular dopants also exhibit pronounced diffusion in the polymer hosts. Here, we demonstrate a facile approach to increase the oxidation strength of FxTCN(N)Q by coordination with four tris(pentafluorophenyl)borane (BCF) molecules using a single-step solution mixing process, resulting in bulky dopant complexes "FxTCN(N)Q-4(BCF)". Using a series of polymer semiconductors with IE up to 5.9 eV, we show by optical absorption spectroscopy of solutions and thin films that the efficiency of doping using FxTCN(N)Q-4(BCF) is significantly higher compared to that using FxTCN(N)Q or BCF alone. Electrical transport measurements with the prototypical poly(3-hexylthiophene-2,5-diyl) (P3HT) confirm the higher doping efficiency of F4TCNQ-4(BCF) compared to F4TCNQ. Additionally, the bulkier structure of F4TCNQ-4(BCF) is shown to result in higher stability against drift in P3HT under an applied electric field as compared to F4TCNQ. The simple approach of solution-mixing of readily accessible molecules thus offers access to enhanced molecular p-dopants for the community.
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Chiral molecules are known to behave as spin filters due to the chiral induced spin selectivity (CISS) effect. Chirality can be implemented in molecular semiconductors in order to study the role of the CISS effect in charge transport and to find new materials for spintronic applications. In this study, the design and synthesis of a new class of enantiopure chiral organic semiconductors based on the well-known dinaphtho[2,3-b:2,3-f]thieno[3,2-b]thiophene (DNTT) core functionalized with chiral alkyl side chains is presented. When introduced in an organic field-effect transistor (OFET) with magnetic contacts, the two enantiomers, (R)-DNTT and (S)-DNTT, show an opposite behavior with respect to the relative direction of the magnetization of the contacts, oriented by an external magnetic field. Each enantiomer displays an unexpectedly high magnetoresistance over one preferred orientation of the spin current injected from the magnetic contacts. The result is the first reported OFET in which the current can be switched on and off upon inversion of the direction of the applied external magnetic field. This work contributes to the general understanding of the CISS effect and opens new avenues for the introduction of organic materials in spintronic devices.
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The modern picture of negative charge carriers on conjugated polymers invokes the formation of a singly occupied (spin-up/spin-down) level within the polymer gap and a corresponding unoccupied level above the polymer conduction band edge. The energy splitting between these sublevels is related to on-site Coulomb interactions between electrons, commonly termed Hubbard U. However, spectral evidence for both sublevels and experimental access to the U value is still missing. Here, we provide evidence by n-doping the polymer P(NDI2OD-T2) with [RhCp*Cp]2, [N-DMBI]2, and cesium. Changes in the electronic structure after doping are studied with ultraviolet photoelectron and low-energy inverse photoemission spectroscopies (UPS, LEIPES). UPS data show an additional density of states (DOS) in the former empty polymer gap while LEIPES data show an additional DOS above the conduction band edge. These DOS are assigned to the singly occupied and unoccupied sublevels, allowing determination of a U value of â¼1 eV.
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The wide band gap semiconductor κ-Ga2O3 and its aluminum and indium alloys have been proposed as promising materials for many applications. One of them is the use of inter-sub-band transitions in quantum-well (QW) systems for infrared detectors. Our simulations show that the detection wavelength range of nowadays state of the art GaAs/AlxGa1-xAs quantum-well infrared photodetectors (QWIPs) could be substantially excelled with about 1-100 µm using κ-([Al,In]xGa1-x)2O3, while at the same time being transparent to visible light and therefore insensitive to photon noise due to its wide band gap, demonstrating the application potential of this material system. Our simulations further show that the QWIPs efficiency critically depends on the QW thickness, making a precise control over the thickness during growth and a reliable thickness determination essential. We demonstrate that pulsed laser deposition yields the needed accuracy, by analyzing a series of (InxGa1-x)2O3 QWs with (AlyGa1-y)2O3 barriers with high-resolution X-ray diffraction, X-ray photoelectron spectroscopy (XPS) depth profiling, and transmission electron microscopy (TEM). While the superlattice fringes of high-resolution X-ray diffraction only yield an average combined thickness of the QWs and the barrier and X-ray spectroscopy depth profiling requires elaborated modeling of the XPS signal to accurately determine the thickness of such QWs, TEM is the method of choice when it comes to the determination of QW thicknesses.
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In2 O3 , an n-type semiconducting transparent transition metal oxide, possesses a surface electron accumulation layer (SEAL) resulting from downward surface band bending due to the presence of ubiquitous oxygen vacancies. Upon annealing In2 O3 in ultrahigh vacuum or in the presence of oxygen, the SEAL can be enhanced or depleted, as governed by the resulting density of oxygen vacancies at the surface. In this work, an alternative route to tune the SEAL by adsorption of strong molecular electron donors (specifically here ruthenium pentamethylcyclopentadienyl mesitylene dimer, [RuCp*mes]2 ) and acceptors (here 2,2'-(1,3,4,5,7,8-hexafluoro-2,6-naphthalene-diylidene)bis-propanedinitrile, F6 TCNNQ) is demonstrated. Starting from an electron-depleted In2 O3 surface after annealing in oxygen, the deposition of [RuCp*mes]2 restores the accumulation layer as a result of electron transfer from the donor molecules to In2 O3 , as evidenced by the observation of (partially) filled conduction sub-bands near the Fermi level via angle-resolved photoemission spectroscopy, indicating the formation of a 2D electron gas due to the SEAL. In contrast, when F6 TCNNQ is deposited on a surface annealed without oxygen, the electron accumulation layer vanishes and an upward band bending is generated at the In2 O3 surface due to electron depletion by the acceptor molecules. Hence, further opportunities to expand the application of In2 O3 in electronic devices are revealed.
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The ability to form multi-heterolayer (opto)electronic devices by solution processing of (molecularly doped) semiconducting polymer layers is of great interest since it can facilitate the fabrication of large-area and low-cost devices. However, the solution processing of multilayer devices poses a particular challenge with regard to dissolution of the first layer during the deposition of a second layer. Several approaches have been introduced to circumvent this problem for neat polymers, but suitable approaches for molecularly doped polymer semiconductors are much less well-developed. Here, we provide insights into two different mechanisms that can enhance the solvent resistance of solution-processed doped polymer layers while also retaining the dopants, one being the doping-induced pre-aggregation in solution and the other including the use of a photo-reactive agent that results in covalent cross-linking of the semiconductor and, perhaps in some cases, the dopant. For molecularly p-doped poly(3-hexylthiophene-2,5-diyl) and poly[2,5-bis(3-tetradecyl-thiophene-2-yl)thieno(3,2-b)thiophene] layers, we find that the formation of polymer chain aggregates prior to the deposition from solution plays a major role in enhancing solvent resistance. However, this pre-aggregation limits inclusion of the cross-linking agent benzene-1,3,5-triyl tris(4-azido-2,3,5,6-tetrafluorobenzoate). We show that if pre-aggregation in solution is suppressed, high resistance of thin doped polymer layers to solvent can be achieved using the tris(azide). Moreover, the electrical conductivity can be largely retained by increasing the tris(azide) content in a doped polymer layer.
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Niobium pentoxides have received considerable attention and are promising anode materials for lithium-ion batteries (LIBs), due to their fast Li storage kinetics and high capacity. However, their cycling stability and rate performance are still limited owing to their intrinsic insulating properties and structural degradation during charging and discharging. Herein, a series of mesoporous Nb2O5@TiO2 core-shell spherical heterostructures have been prepared for the first time by a sol-gel method and investigated as anode materials in LIBs. Mesoporosity can provide numerous open and short pathways for Li+ diffusion; meanwhile, heterostructures can simultaneously enhance the electronic conductivity and thus improve the rate capability. The TiO2 coating layer shows robust crystalline skeletons during repeated lithium insertion and extraction processes, retaining high structural integrity and, thereby, enhancing cycling stability. The electrochemical behavior is strongly dependent on the thickness of the TiO2 layer. After optimization, a mesoporous Nb2O5@TiO2 core-shell structure with a â¼13 nm thick TiO2 layer delivers a high specific capacity of 136 mA h g-1 at 5 A g-1 and exceptional cycling stability (88.3% retention over 1000 cycles at 0.5 A g-1). This work provides a facile strategy to obtain mesoporous Nb2O5@TiO2 core-shell spherical structures and underlines the importance of structural engineering for improving the performance of battery materials.
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Aqueous processing of Ni-rich layered oxide cathode materials is a promising approach to simultaneously decrease electrode manufacturing costs, while bringing environmental benefits by substituting the state-of-the-art (often toxic and costly) organic processing solvents. However, an aqueous environment remains challenging due to the high reactivity of Ni-rich layered oxides towards moisture, leading to lithium leaching and Al current collector corrosion because of the resulting high pH value of the aqueous electrode paste. Herein, a facile method was developed to enable aqueous processing of LiNi0.8 Co0.1 Mn0.1 O2 (NCM811) by the addition of lithium sulfate (Li2 SO4 ) during electrode paste dispersion. The aqueously processed electrodes retained 80 % of their initial capacity after 400 cycles in NCM811||graphite full cells, while electrodes processed without the addition of Li2 SO4 reached 80 % of their capacity after only 200 cycles. Furthermore, with regard to electrochemical performance, aqueously processed electrodes using carbon-coated Al current collector outperformed reference electrodes based on state-of-the-art production processes involving N-methyl-2-pyrrolidone as processing solvent and fluorinated binders. The positive impact on cycle life by the addition of Li2 SO4 stemmed from a formed sulfate coating as well as different surface species, protecting the NCM811 surface against degradation. Results reported herein open a new avenue for the processing of Ni-rich NCM electrodes using more sustainable aqueous routes.
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We introduce for the first time a core-shell structure composed of nanostructured self-standing titania nanotubes (TNT, light absorber) filled with Au nanowire (AuNW) array (electrons collector) applied to the photoelectrocatalytic water splitting. Its activity is four times higher than that of reference TNT-Ti obtained with the same anodizing conditions. The composite photoanode brings a distinct photocurrent generation (8 mA cm-2 at 1.65 V vs. RHE), and a high incident photon to current efficiency of 35% obtained under UV light illumination. Moreover, the full system concept of selected constitutional materials, based on Au noble metal and the very stable semiconductor TiO2, ensures a stable performance over a long-time range with no photocurrent loss during 100 on-off cycles of light illumination, after 12 h constant illumination and after one-month storage in air. We provide experimental evidence by photoelectron spectroscopy measurements, confirming that the electronic structure of TNT-AuNW is rectifying for electrons and ohmic for holes, while the electrochemical characterization confirms that the specific architecture of the photoanode supports electron separation due to the presence of a Schottky type contact and fast electron transport through the Au nanowires. Although the composite material shows an unchanged electrochemical band gap, typical for plain TiO2, we find this material to be an innovative platform for efficient photoelectrochemical water splitting under UV light illumination, with significant potential for further modifications, for example extension into the visible light regime.
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The ability to insolubilize doped semiconducting polymer layers can help enable the fabrication of efficient multilayer solution-processed electronic and optoelectronic devices. Here, we present a promising approach to simultaneously n-dope and largely insolubilize conjugated polymer films using tetrakis[{4-(1,3-dimethyl-2,3-dihydro-1H-benzo[d]imidazol-2-yl)phenoxy}methyl]methane (tetrakis-O-DMBI-H), which consists of four 2,3-dihydro-1H-benzoimidazole (DMBI-H) n-dopant moieties covalently linked to one another. Doping a thiophene-fused benzodifurandione-based oligo(p-phenylenevinylene)-co-thiophene polymer (TBDOPV-T) with tetrakis-O-DMBI-H results in a highly n-doped film with bulk conductivity of 15 Sâ¯cm-1. Optical absorption spectra provide evidence for film retention of â¼93% after immersion in o-dichlorobenzene for 5 min. The optical absorption signature of the charge carriers in the n-doped polymer decreases only slightly more than that of the neutral polymer under these conditions, indicating that the exposure to solvent also results in negligible dedoping of the film. Moreover, thermal treatment studies on a tetrakis-O-DMBI-H-doped TBDOPV-T film in contact with another undoped polymer film indicate immobilization of the molecular dopant in TBDOPV-T. This is attributed to the multiple electrostatic interactions between each dopant tetracation and up to four nearby anionic doped polymer segments.
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Surface-defect passivation is key to achieving a high photoluminescence quantum yield in lead halide perovskite nanocrystals. However, in perovskite light-emitting diodes, these surface ligands also have to enable balanced charge injection into the nanocrystals to yield high efficiency and operational lifetime. In this respect, alkaline halides have been reported to passivate surface trap states and increase the overall stability of perovskite light emitters. On the one side, the incorporation of alkaline ions into the lead halide perovskite crystal structure is considered to counterbalance cation vacancies, whereas on the other side, the excess halides are believed to stabilize the colloids. Here, we report an organic lithium salt, viz. LiTFSI, as a halide-free surface passivation on perovskite nanocrystals. We show that treatment with LiTFSI has multiple beneficial effects on lead halide perovskite nanocrystals and LEDs derived from them. We obtain a higher photoluminescence quantum yield and a longer exciton lifetime and a radiation pattern that is more favorable for light outcoupling. The ligand-induced dipoles on the nanocrystal surface shift their energy levels toward a lower hole-injection barrier. Overall, these effects add up to a 4- to 7-fold boost of the external quantum efficiency in proof-of-concept LED structures, depending on the color of the used lead halide perovskite nanocrystal emitters.
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Heterostructures made from metal oxide semiconductors (MOS) are fundamental for the development of high-performance gas sensors. Since their importance in real applications, a thorough understanding of the transduction mechanism is vital, whether it is related to a heterojunction or simply to the shell and core materials. A better understanding of the sensing response of heterostructured nanomaterials requires the engineering of heterojunctions with well-defined core and shell layers. Here, we introduce a series of prototypes CNT-nMOS, CNT-pMOS, CNT-pMOS-nMOS, and CNT-nMOS-pMOS hierarchical core-shell heterostructures (CSHS) permitting us to directly relate the sensing response to the MOS shell or to the p-n heterojunction. The carbon nanotubes are here used as highly conductive substrates permitting operation of the devices at relatively low temperature and are not involved in the sensing response. NiO and SnO2 are selected as representative p- and n-type MOS, respectively, and the response of a set of samples is studied toward hydrogen considered as model analyte. The CNT-n,pMOS CSHS exhibit response related to the n,pMOS-shell layer. On the other hand, the CNT-pMOS-nMOS and CNT-nMOS-pMOS CSHS show sensing responses, which in certain cases are governed by the heterojunctions between nMOS and pMOS and strongly depends on the thickness of the MOS layers. Due to the fundamental nature of this study, these findings are important for the development of next generation gas sensing devices.
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The charge transport of crystalline organic semiconductors is limited by dynamic disorder that tends to localize charges. It is the main hurdle to overcome in order to significantly increase charge carrier mobility. An innovative design that combines a chemical structure based on sulfur-rich thienoacene with a solid-state herringbone (HB) packing is proposed and the synthesis, physicochemical characterization, and charge transport properties of two new thienoacenes bearing a central tetrathienyl core fused with two external naphthyl rings: naphtho[2,3-b]thieno-[2''',3''':4'',5'']thieno[2â³,3â³:4',5']thieno[3',2'-b]naphtho[2,3-b]thiophene (DN4T) and naphtho[1,2-b]thieno-[2''',3''':4'',5'']thieno[2'',3'':4',5']thieno[3',2'-b]naphtho[1,2-b]thiophene are presented. Both compounds crystallize with a HB pattern structure and present transfer integrals ranging from 33 to 99 meV (for the former) within the HB plane of charge transport. Molecular dynamics simulations point toward an efficient resilience of the transfer integrals to the intermolecular sliding motion commonly responsible for strong variations of the electronic coupling in the crystal. Best device performances are reached with DN4T with hole mobility up to µ = 2.1 cm2 V-1 s-1 in polycrystalline organic field effect transistors, showing the effectiveness of the electronic coupling enabled by the new aromatic core. These promising results pave the way to the design of high-performing materials based on this new thienoacene, notably through the introduction of alkyl side-chains.
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Molecular doping is a key process to increase the density of charge carriers in organic semiconductors. Doping-induced charges in polymer semiconductors result in the formation of polarons and/or bipolarons due to the strong electron-vibron coupling in conjugated organic materials. Identifying the nature of charge carriers in doped polymers is essential to optimize the doping process for applications. In this work, we use Raman spectroscopy to investigate the formation of charge carriers in molecularly doped poly(3-hexylthiophene-2,5-diyl) (P3HT) for increasing dopant concentration, with the organic salt dimesityl borinium tetrakis(penta-fluorophenyl)borate (Mes2B+ [B(C6F5)4]-) and the Lewis acid tris(pentafluorophenyl)borane [B(C6F5)3]. While the Raman signatures of neutral P3HT and singly charged P3HT segments (polarons) are known, the Raman spectra of doubly charged P3HT segments (bipolarons) are not yet sufficiently understood. Combining Raman spectroscopy measurements on doped P3HT thin films with first-principles calculations on oligomer models, we explain the evolution of the Raman spectra from neutral P3HT to increasingly doped P3HT featuring polarons and eventually bipolarons at high doping levels. We identify and explain the origin of the spectral features related to bipolarons by tracing the Raman signature of the symmetric collective vibrations along the polymer backbone, which - compared to neutral P3HT - redshifts for polarons and blueshifts for bipolarons. This is explained by a planarization of the singly charged P3HT segments with polarons and rather high order in thin films, while the doubly charged segments with bipolarons are located in comparably disordered regions of the P3HT film due to the high dopant concentration. Furthermore, we identify additional Raman peaks associated with vibrations in the quinoid doubly charged segments of the polymer. Our results offer the opportunity for readily identifying the nature of charge carriers in molecularly doped P3HT while taking advantage of the simplicity, versatility, and non-destructive nature of Raman spectroscopy.