Time-resolved Spectroelectrochemical Investigation of Organic Mixed Conductors.

Organic mixed ionic and electronic conductors (OMIECs) are an emerging class of materials that have been applied for a wide range of electrochemical applications. Due to the complexity inherent to the ionic-electroniccoupling, understanding the underlying mechanisms involved in the OMIEC operation is an exciting and very lively research field. In this work, we highlight the use of time-resolved Vis-NIR spectroelectrochemistry tocharacterize these materials. We discuss an example, where we show that by combining this tool with spectraldecomposition, we are able to understand fundamental aspects of the doping in an OMIEC film. The methodswe present here can be generalized and used to characterize any electrochromic material.

Effects of Side-Chain Length and Functionality on Polar Poly(dioxythiophene)s for Saline-Based Organic Electrochemical Transistors.

Understanding the impact of side chains on the aqueous redox properties of conjugated polymers is crucial to unlocking their potential in bioelectrochemical devices, such as organic electrochemical transistors (OECTs). Here, we report a series of polar propylenedioxythiophene-based copolymers functionalized with glyme side chains of varying lengths as well as an analogue with short hydroxyl side chains. We show that long polar side chains are not required for achieving high volumetric capacitance (C*), as short hydroxy substituents can afford facile doping and high C* in saline-based electrolytes. Furthermore, we demonstrate that varying the length of the polar glyme chains leads to subtle changes in material properties. Increasing the length of glyme side chain is generally associated with an enhancement in OECT performance, doping kinetics, and stability, with the polymer bearing the longest side chains exhibiting the highest performance ([µC*]OECT = 200 ± 8 F cm-1 V-1 s-1). The origin of this performance enhancement is investigated in different device configurations using in situ techniques (e.g., time-resolved spectroelectrochemistry and chronoamperometry). These studies suggest that the performance improvement is not due to significant changes in C* but rather due to variations in the inferred mobility. Through a thorough comparison of two different architectures, we demonstrate that device geometry can obfuscate the benchmarking of OECT active channel materials, likely due to contact resistance effects. By complementing all electrochemical and spectroscopic experiments with in situ measurements performed within a planar OECT device configuration, this work seeks to unambiguously assign material design principles to fine-tune the properties of poly(dioxythiophene)s relevant for application in OECTs.

Spectroscopic Tools to Investigate the Electrochemical Doping Kinetics and Efficiency in Organic Semiconductors.

Understanding the electrochemical doping of organic semiconductors plays a crucial role in the current development of organic electronics. In this short review, we present how temperature- and time- dependent visible-near-infrared (Vis-NIR) spectro-electrochemistry and terahertz spectroscopy, combined with multivariate curve resolution analysis, can inform on the fundamental mechanisms governing the doping kinetics and efficiency of two archetypal semiconducting polymers (PEDOT and P3HT). We highlight the experimental procedures and data analysis performed to access (i) the thermodynamic parameters driving the extent and dynamics of electrochemical reactions in doped systems and (ii) how the density and nature of charged species (polarons, bipolarons) impact the charge carrier delocalization, effective THz mobility and hence short-range conductivity.

Photophysics and Charge Generation in Low Energy-offset Blends for Organic Solar Cells.

The power conversion efficiency of organic solar cells has seen a huge improvement in recent years with state-of-the-art solar cells showcasing efficiencies of ∼18.5 %, which is approaching the performance of inorganic and hybrid-perovskite solar cell technologies. This improvement can be mainly attributed to the discovery of highly efficient donor:acceptor blends with a near-zero energetic offset between the molecular orbital levels of the donor and the acceptor component. A distinctive feature of the high efficiency, low energy-offset blends is that they exhibit a concomitant increase in the short-circuit density and the open-circuit voltage of the solar cell. High open-circuit voltage results from the reduced photon energy loss in the exciton dissociation step, while a high short-circuit current density can be attributed to an efficient charge generation process. The reasons for the efficient exciton dissociation and subsequent separation of Coulomb bound electron-hole pair at negligible driving force is not well understood and, in this short review, we highlight recent results which shed light on the mechanism of charge generation in low energy-offset blends.

High-resolution phase-sensitive sum frequency generation spectroscopy by time-domain ptychography.

We demonstrate that time-domain ptychography, when applied to a set of broadband vibrational sum frequency spectra, reconstructs amplitude and phase of the vibrational free induction decay from an interfacial sample with a resolution that is independent of up-converting pulse bandwidth and spectrometer resolution. These important improvements require no modifications to most standard homodyne setups, and the method is applicable to other coherent homodyne spectroscopies such as coherent anti-Stokes Raman spectroscopy and transient grating spectroscopy.

Polaron Photoconductivity in the Weak and Strong Light-Matter Coupling Regime.

We investigate the potential for cavity-modified electron transfer in a doped organic semiconductor through the photocurrent that arises from exciting charged molecules (polarons). When the polaron optical transition is strongly coupled to a Fabry-Perot microcavity mode, we observe polaron polaritons in the photoconductivity action spectrum and find that their magnitude depends differently on applied electric field than photocurrent originating from the excitation of uncoupled polarons in the same cavity. Crucially, moving from positive to negative detuning causes the upper and lower polariton photocurrents to swap their field dependence, with the more polaronlike branch resembling that of an uncoupled excitation. These observations are understood on the basis of a phenomenological model in which strong coupling alters the Onsager dissociation of polarons from their dopant counterions by effectively increasing the thermalization length of the photoexcited charge carrier.

Comparing the excited-state properties of a mixed-cation-mixed-halide perovskite to methylammonium lead iodide.

Organic-inorganic perovskites are one of the most promising photovoltaic materials for the design of next generation solar cells. The lead-based perovskite prepared with methylammonium and iodide was the first in demonstrating high power conversion efficiency, and it remains one of the most used materials today. However, perovskites prepared by mixing several halides and several cations systematically yield higher efficiencies than "pure" methylammonium lead iodide (MAPbI3) devices. In this work, we unravel the excited-state properties of a mixed-halide (iodide and bromide) and mixed-cation (methylammonium and formamidinium) perovskite. Combining time-resolved photoluminescence, transient absorption, and optical-pump-terahertz-probe experiments with density functional theory calculations, we show that the population of higher-lying excited states in the mixed material increases the lifetime of photogenerated charge carriers upon well above-bandgap excitation. We suggest that alloying different halides and different cations reduces the structural symmetry of the perovskite, which partly releases the selection rules to populate the higher-energy states upon light absorption. Our investigation thus shows that mixed halide perovskites should be considered as an electronically different material than MAPbI3, paving the way toward further materials optimization and improved power conversion efficiency of perovskite solar cells.

Salt-induced thermochromism of a conjugated polyelectrolyte.

We report here the photophysical properties of a water-soluble conjugated polythiophene with cationic side-chains. When dissolved in aqueous buffer solution (PBS, phosphate buffered saline), there is ordering of the polymer chains due to the presence of the salts, in contrast to pure water, where a random-coil conformation is adopted at room temperature. The ordering leads to a pronounced colour change of the solution (the absorption maximum shifts from 400 nm to 525 nm). Combining resonance Raman spectroscopy with density functional theory computations, we show a significant backbone planarization in the ordered phase. Moreover, the ratio of ordered phase to random-coil phase in PBS solution, as well as the extent of intermolecular interactions in the ordered phase, can be tuned by varying the temperature. Femtosecond transient absorption spectroscopy reveals that the excited-state behaviour of the polyelectrolyte is strongly affected by the degree of ordering. While triplet state formation is favoured in the random-coil chains, the ordered chains show a weak yield of polarons, related to interchain interactions. The investigated polyelectrolyte has been previously used as a biological DNA sensor, based on optical transduction when the conformation of the polyelectrolyte changes during assembly with the biomolecule. Therefore, our results, by correlating the photophysical properties of the polyelectrolyte to backbone and intermolecular conformation in a biologically relevant buffer, provide a significant step forward in understanding the mechanism of the biological sensing.

Structure-Property Relations in Polymer:Fullerene Blends for Organic Solar Cells.

Organic solar cells consist of thin films combining an electron donor (often a conjugated polymer) with an electron acceptor (often a fullerene derivative), in a blend commonly referred to as bulk heterojunction material. Charge separation between the donor and the acceptor leads to the generation of carriers, which can be extracted from photovoltaic devices in the form of photocurrent. The generation mechanism of free, extractable charges has caused a lot of controversial discussion in literature. Our research has shown that all the steps involved in charge generation are strongly dependent on the arrangement of the donor and the acceptor (i.e. the structure) of the bulk heterojunction.

Structure-Property Relations in Polymer:Fullerene Blends for Organic Solar Cells.

Organic solar cells consist of thin films combining an electron donor (often a conjugated polymer) with an electron acceptor (often a fullerene derivative), in a blend commonly referred to as bulk heterojunction material. Charge separation between the donor and the acceptor leads to the generation of carriers, which can be extracted from photovoltaic devices in the form of photocurrent. The generation mechanism of free, extractable charges has caused a lot of controversial discussion in literature. Our research has shown that all the steps involved in charge generation are strongly dependent on the arrangement of the donor and the acceptor (i.e. the structure) of the bulk heterojunction.

A close look at charge generation in polymer:fullerene blends with microstructure control.

We reveal some of the key mechanisms during charge generation in polymer:fullerene blends exploiting our well-defined understanding of the microstructures obtained in pBTTT:PCBM systems via processing with fatty acid methyl ester additives. Based on ultrafast transient absorption, electro-absorption, and fluorescence up-conversion spectroscopy, we find that exciton diffusion through relatively phase-pure polymer or fullerene domains limits the rate of electron and hole transfer, while prompt charge separation occurs in regions where the polymer and fullerene are molecularly intermixed (such as the co-crystal phase where fullerenes intercalate between polymer chains in pBTTT:PCBM). We moreover confirm the importance of neat domains, which are essential to prevent geminate recombination of bound electron-hole pairs. Most interestingly, using an electro-absorption (Stark effect) signature, we directly visualize the migration of holes from intermixed to neat regions, which occurs on the subpicosecond time scale. This ultrafast transport is likely sustained by high local mobility (possibly along chains extending from the co-crystal phase to neat regions) and by an energy cascade driving the holes toward the neat domains.

Charge separation pathways in a highly efficient polymer: fullerene solar cell material.

PBDTTPD is one of the best conjugated polymers for solar cell applications (up to 8.5% efficiency). We have investigated the dynamics of charge generation in the blend with fullerene (PCBM) and addressed highly relevant topics such as the role of bulk heterojunction structure, fullerene excitation, and excess energy. We show that there are multiple charge separation pathways. These include electron transfer from photoexcited polymer, hole transfer from photoexcited PCBM, prompt (<100 fs) charge generation in intimately mixed polymer:fullerene regions (which can occur from hot states), as well as slower electron and hole transfer from excitons formed in pure PBDTTPD or PCBM domains (diffusion to an interface is necessary). Very interestingly, all the charge separation pathways are highly efficient. For example, the yield of long-lived carriers is not significantly affected by the excitation wavelength, although this changes the fraction of photons absorbed by PCBM and the amount of excess energy brought to the system. Overall, the favorable properties of the PBDTTPD:PCBM blend in terms of morphology and exciton delocalization allow excellent charge generation in all circumstances and strongly contribute to the high photovoltaic performance of the blend.

Excited-State Dynamics of MAPbBr3: Coexistence of Excitons and Free Charge Carriers at Ultrafast Times.

Methylammonium lead tribromide perovskite (MAPbBr3) is an important material, for example, for light-emitting applications and tandem solar cells. The relevant photophysical properties are governed by a plethora of phenomena resulting from the complex and relatively poorly understood interplay of excitons and free charge carriers in the excited state. In this study, we combine transient spectroscopies in the visible and terahertz range to investigate the presence and evolution of excitons and free charge carriers at ultrafast times upon excitation at various photon energies and densities. For above- and resonant band-gap excitation, we find that free charges and excitons coexist and that both are mainly promptly generated within our 50-100 fs experimental time resolution. However, the exciton-to-free charge ratio increases upon decreasing the phonon energy toward resonant band gap excitation. The free charge signatures dominate the transient absorption response for above-band-gap excitation and low excitation densities, masking the excitonic features. With resonant band gap excitation and low excitation densities, we find that although the exciton density increases, free charges remain. We show evidence that the excitons localize into shallow trap and/or Urbach tail states to form localized excitons (within tens of picoseconds) that subsequently get detrapped. Using high excitation densities, we demonstrate that many-body interactions become pronounced and effects such as the Moss-Burstein shift, band gap renormalization, excitonic repulsion, and the formation of Mahan excitons are evident. The coexistence of excitons and free charges that we demonstrate here for photoexcited MAPbBr3 at ultrafast time scales confirms the high potential of the material for both light-emitting diode and tandem solar cell applications.

Limiting factors for charge generation in low-offset fullerene-based organic solar cells.

Free charge generation after photoexcitation of donor or acceptor molecules in organic solar cells generally proceeds via (1) formation of charge transfer states and (2) their dissociation into charge separated states. Research often either focuses on the first component or the combined effect of both processes. Here, we provide evidence that charge transfer state dissociation rather than formation presents a major bottleneck for free charge generation in fullerene-based blends with low energetic offsets between singlet and charge transfer states. We investigate devices based on dilute donor content blends of (fluorinated) ZnPc:C60 and perform density functional theory calculations, device characterization, transient absorption spectroscopy and time-resolved electron paramagnetic resonance measurements. We draw a comprehensive picture of how energies and transitions between singlet, charge transfer, and charge separated states change upon ZnPc fluorination. We find that a significant reduction in photocurrent can be attributed to increasingly inefficient charge transfer state dissociation. With this, our work highlights potential reasons why low offset fullerene systems do not show the high performance of non-fullerene acceptors.

Electrochemical Doping in Ordered and Disordered Domains of Organic Mixed Ionic-Electronic Conductors.

Conjugated polymers are increasingly used as organic mixed ionic-electronic conductors in electrochemical applications for neuromorphic computing, bioelectronics, and energy harvesting. The design of efficient electrochemical devices relies on large modulations of the polymer conductivity, fast doping/dedoping kinetics, and high ionic uptake. In this work, structure-property relations are established and control of these parameters by the co-existence of order and disorder in the phase morphology is demonstrated. Using in situ time-resolved spectroelectrochemistry, resonant Raman, and terahertz (THz) conductivity measurements, the electrochemical doping in the different morphological domains of poly(3-hexylthiophene) (P3HT) is investigated. The main finding is that bipolarons are found preferentially in disordered polymer regions, where they are formed faster and are thermodynamically more favored. On the other hand, polarons show a preference for ordered domains, leading to drastically different bipolaron/polaron ratios and doping/dedoping dynamics in the distinct regions. A significant enhancement of the electronic conductivity is evident when bipolarons start forming in the disordered regions, while the presence of bipolarons in the ordered regions is detrimental for transport. This study provides significant advances in the understanding of the impact of morphology on the electrochemical doping of conjugated polymers and the induced increase in conductivity.

Resolving Nonlinear Recombination Dynamics in Semiconductors via Ultrafast Excitation Correlation Spectroscopy: Photoluminescence versus Photocurrent Detection.

We explore the application of excitation correlation spectroscopy to detect nonlinear photophysical dynamics in two distinct semiconductor classes through time-integrated photoluminescence and photocurrent measurements. In this experiment, two variably delayed femtosecond pulses excite the semiconductor, and the time-integrated photoluminescence or photocurrent component arising from the nonlinear dynamics of the populations induced by each pulse is measured as a function of inter-pulse delay by phase-sensitive detection with a lock-in amplifier. We focus on two limiting materials systems with contrasting optical properties: a prototypical lead-halide perovskite (LHP) solar cell, in which primary photoexcitations are charge photocarriers, and a single-component organic-semiconductor diode, which features Frenkel excitons as primary photoexcitations. The photoexcitation dynamics perceived by the two detection schemes in these contrasting systems are distinct. Nonlinear-dynamic contributions in the photoluminescence detection scheme arise from contributions to radiative recombination in both materials systems, while photocurrent arises directly in the LHP but indirectly following exciton dissociation in the organic system. Consequently, the basic photophysics of the two systems are reflected differently when comparing measurements with the two detection schemes. Our results indicate that photoluminescence detection in the LHP system provides valuable information about trap-assisted and Auger recombination processes, but that these processes are convoluted in a nontrivial way in the photocurrent response and are therefore difficult to differentiate. In contrast, the organic-semiconductor system exhibits more directly correlated responses in the nonlinear photoluminescence and photocurrent measurements, as charge carriers are secondary excitations only generated through exciton dissociation processes. We propose that bimolecular annihilation pathways mainly contribute to the generation of charge carriers in single-component organic semiconductor devices. Overall, our work highlights the utility of excitation correlation spectroscopy in modern semiconductor materials research, particularly in the analysis of nonlinear photophysical processes, which are deterministic for their electronic and optical properties.

On the non-bonding valence band and the electronic properties of poly(triazine imide), a graphitic carbon nitride.

Graphitic carbon nitrides are covalently-bonded, layered, and crystalline semiconductors with high thermal and oxidative stability. These properties make graphitic carbon nitrides potentially useful in overcoming the limitations of 0D molecular and 1D polymer semiconductors. In this contribution, we study structural, vibrational, electronic and transport properties of nano-crystals of poly(triazine-imide) (PTI) derivatives with intercalated Li- and Br-ions and without intercalates. Intercalation-free poly(triazine-imide) (PTI-IF) is corrugated or AB stacked and partially exfoliated. We find that the lowest energy electronic transition in PTI is forbidden due to a non-bonding uppermost valence band and that its electroluminescence from the π-π* transition is quenched which severely limits their use as emission layer in electroluminescent devices. THz conductivity in nano-crystalline PTI is up to eight orders of magnitude higher than the macroscopic conductivity of PTI films. We find that the charge carrier density of PTI nano-crystals is among the highest of all known intrinsic semiconductors, however, macroscopic charge transport in films of PTI is limited by disorder at crystal-crystal interfaces. Future device applications of PTI will benefit most from single crystal devices that make use of electron transport in the lowest, π-like conduction band.

Interplay between Side Chain Density and Polymer Alignment: Two Competing Strategies for Enhancing the Thermoelectric Performance of P3HT Analogues.

A series of polythiophenes with varying side chain density was synthesized, and their electrical and thermoelectric properties were investigated. Aligned and non-aligned thin films of the polymers were characterized in the neutral and chemically doped states. Optical and diffraction measurements revealed an overall lower order in the thin films with lower side chain density, also confirmed using polarized optical experiments on aligned thin films. However, upon doping the non-aligned films, a sixfold increase in electrical conductivity was observed for the polythiophene with the lowest side chain density compared to poly(3-hexylthiophene) (P3HT). We found that the improvement in conductivity was not due to a larger charge carrier density but an increase in charge carrier mobility after doping with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ). On the other hand, doped aligned films did not show the same trend; lower side chain density instead led to a lower conductivity and Seebeck coefficient compared to those for P3HT. This was attributed to the poorer alignment of the polymer thin films with lower side chain density. The study demonstrates that optimizing side chain density is a synthetically simple and effective way to improve electrical conductivity in polythiophene films relevant to thermoelectric applications.

A Quasi-2D Polypyrrole Film with Band-Like Transport Behavior and High Charge-Carrier Mobility.

Quasi-2D (q2D) conjugated polymers (CPs) are polymers that consist of linear CP chains assembled through non-covalent interactions to form a layered structure. In this work, the synthesis of a novel crystalline q2D polypyrrole (q2DPPy) film at the air/H2 SO4 (95%) interface is reported. The unique interfacial environment facilitates chain extension, prevents disorder, and results in a crystalline, layered assembly of protonated quinoidal chains with a fully extended conformation in its crystalline domains. This unique structure features highly delocalized π-electron systems within the extended chains, which is responsible for the low effective mass and narrow electronic bandgap. Thus, the temperature-dependent charge-transport properties of q2DPPy are investigated using the van der Pauw (vdP) method and terahertz time-domain spectroscopy (THz-TDS). The vdP method reveals that the q2DPPy film exhibits a semiconducting behavior with a thermally activated hopping mechanism in long-range transport between the electrodes. Conversely, THz-TDS reveals a band-like transport, indicating intrinsic charge transport up to a record short-range high THz mobility of ≈107.1 cm2 V-1 s-1 .