Monitoring the state of charge of vanadium redox flow batteries with an EPR-on-a-Chip dipstick sensor.

The vanadium redox flow battery (VRFB) is considered a promising candidate for large-scale energy storage in the transition from fossil fuels to renewable energy sources. VRFBs store energy by electrochemical reactions of different electroactive species dissolved in electrolyte solutions. The redox couples of VRFBs are VO2+/VO2+ and V2+/V3+, the ratio of which to the total vanadium content determines the state of charge (SOC). V(IV) and V(II) are paramagnetic half-integer spin species detectable and quantifiable with electron paramagnetic resonance spectroscopy (EPR). Common commercial EPR spectrometers, however, employ microwave cavity resonators which necessitate the use of large electromagnets, limiting their application to dedicated laboratories. For an SOC monitoring device for VRFBs, a small, cost-effective submersible EPR spectrometer, preferably with a permanent magnet, is desirable. The EPR-on-a-Chip (EPRoC) spectrometer miniaturises the complete EPR spectrometer onto a single microchip by utilising the coil of a voltage-controlled oscillator as both microwave source and detector. It is capable of sweeping the frequency while the magnetic field is held constant enabling the use of small permanent magnets. This drastically reduces the experimental complexity of EPR. Hence, the EPRoC fulfils the requirements for an SOC sensor. We, therefore, evaluate the potential for utilisation of an EPRoC dipstick spectrometer as an operando and continuously online monitor for the SOC of VRFBs. Herein, we present quantitative proof-of-principle submersible EPRoC experiments on variably charged vanadium electrolyte solutions. EPR data obtained with a commercial EPR spectrometer are in good agreement with the EPRoC data.

Long-Term Characterization of Oxidation Processes in Graphitic Carbon Nitride Photocatalyst Materials via Electron Paramagnetic Resonance Spectroscopy.

Graphitic carbon nitride (gCN) materials have been shown to efficiently perform light-induced water splitting, carbon dioxide reduction, and environmental remediation in a cost-effective way. However, gCN suffers from rapid charge-carrier recombination, inefficient light absorption, and poor long-term stability which greatly hinders photocatalytic performance. To determine the underlying catalytic mechanisms and overall contributions that will improve performance, the electronic structure of gCN materials has been investigated using electron paramagnetic resonance (EPR) spectroscopy. Through lineshape analysis and relaxation behavior, evidence of two independent spin species were determined to be present in catalytically active gCN materials. These two contributions to the total lineshape respond independently to light exposure such that the previously established catalytically active spin system remains responsive while the newly observed, superimposed EPR signal is not increased during exposure to light. The time dependence of these two peaks present in gCN EPR spectra recorded sequentially in air over several months demonstrates a steady change in the electronic structure of the gCN framework over time. This light-independent, slowly evolving additional spin center is demonstrated to be the result of oxidative processes occurring as a result of exposure to the environment and is confirmed by forced oxidation experiments. This oxidized gCN exhibits lower H2 production rates and indicates quenching of the overall gCN catalytic activity over longer reaction times. A general model for the newly generated spin centers is given and strategies for the alleviation of oxidative products within the gCN framework are discussed in the context of improving photocatalytic activity over extended durations as required for future functional photocatalytic device development.

Quantification of Nanoscale Density Fluctuations in Hydrogenated Amorphous Silicon.

The nanostructure of hydrogenated amorphous silicon (a-Si∶H) is studied by a combination of small-angle x-ray scattering (SAXS) and small-angle neutron scattering (SANS) with a spatial resolution of 0.8 nm. The a-Si∶H materials were deposited using a range of widely varied conditions and are representative for this class of materials. We identify two different phases that are embedded in the a-Si∶H matrix and quantified both according to their scattering cross sections. First, 1.2 nm sized voids (multivacancies with more than 10 missing atoms) which form a superlattice with 1.6 nm void-to-void distance are detected. The voids are found in concentrations as high as 6×10^{19} cm^{-3} in a-Si∶H material that is deposited at a high rate. Second, dense ordered domains (DOD) that are depleted of hydrogen with 1 nm average diameter are found. The DOD tend to form 10-15 nm sized aggregates and are largely found in all a-Si∶H materials considered here. These quantitative findings make it possible to understand the complex correlation between structure and electronic properties of a-Si∶H and directly link them to the light-induced formation of defects. Finally, a structural model is derived, which verifies theoretical predictions about the nanostructure of a-Si∶H.

Tetracene Ultrathin Film Growth on Hydrogen-Passivated Silicon.

Inorganic-organic interfaces are important for enhancing the power conversion efficiency of silicon-based solar cells through singlet exciton fission (SF). We elucidated the structure of the first monolayers of tetracene (Tc), an SF molecule, on hydrogen-passivated Si(111) [H-Si(111)] and hydrogenated amorphous Si (a-Si:H) by combining near-edge X-ray absorption fine structure (NEXAFS) and X-ray photoelectron spectroscopy (XPS) experiments with density functional theory (DFT) calculations. For samples grown at or below substrate temperatures of 265 K, the resulting ultrathin Tc films are dominated by almost upright-standing molecules. The molecular arrangement is very similar to the Tc bulk phase, with only a slightly higher average angle between the conjugated molecular plane normal and the surface normal (α) around 77°. Judging from carbon K-edge X-ray absorption spectra, the orientation of the Tc molecules are almost identical when grown on H-Si(111) and a-Si:H substrates as well as for (sub)mono- to several-monolayer coverages. Annealing to room temperature, however, changes the film structure toward a smaller α of about 63°. A detailed DFT-assisted analysis suggests that this structural transition is correlated with a lower packing density and requires a well-chosen amount of thermal energy. Therefore, we attribute the resulting structure to a distinct monolayer configuration that features less inclined, but still well-ordered molecules. The larger overlap with the substrate wave functions makes this arrangement attractive for an optimized interfacial electron transfer in SF-assisted silicon solar cells.

Interdependence of photon upconversion performance and antisolvent processing in thin-film halide perovskite-sensitized triplet-triplet annihilators.

We prepared triplet-triplet annihilation photon upconverters combining thin-film methylammonium lead iodide (MAPI) perovskite with a rubrene annihilator in a bilayer structure. Excitation of the perovskite film leads to delayed, upconverted photoluminescence emitted from the annihilator layer, with triplet excitation of the rubrene being driven by carriers excited in the perovskite layer. To better understand the connections between the semiconductor properties of the perovskite film and the upconversion efficiency, we deliberately varied the perovskite film properties by modifying two spin-coating conditions, namely, the choice of antisolvent and the antisolvent dripping time, and then studied the resulting photon upconversion performance with a standard annihilator layer. A stronger upconversion effect was exhibited when the perovskite films displayed brighter and more uniform photoluminescence. Both properties were sensitive to the antisolvent dripping time and were maximized for a dripping time of 20 s (measured relative to the end of the spin-coating program). Surprisingly, the choice of antisolvent had a significant effect on the upconversion performance, with anisole-treated films yielding on average a tenfold increase in upconversion intensity compared to the chlorobenzene-treated equivalent. This performance difference was correlated with the carrier lifetime in the perovskite film, which was 52 ns and 306 ns in the brightest chlorobenzene and anisole-treated films, respectively. Since the bulk properties of the anisole- and chlorobenzene-treated films were virtually identical, we concluded that differences in the defect density at the MAPI/rubrene interface, linked to the choice of antisolvent, must be responsible for the differing upconversion performance.

Crystallinity and Size Control of Colloidal Germanium Nanoparticles from Organogermanium Halide Reagents.

Germanium (Ge) nanoparticles are gaining increasing interest due to their properties that arise in the quantum confinement regime, such as the development of the band structure with changing size. While promising materials, significant challenges still exist related to the development of synthetic schemes allowing for good control over size and morphology in a single step. Herein, we investigate a synthetic method that combines sulfur and primary amines to promote the reduction of organometallic Ge(IV) precursors to form Ge nanoparticles at relatively low temperatures (300 °C). We propose a reaction mechanism and examine the effects of solvents, sulfur concentration, and organogermanium halide precursors. Hydrosulfuric acid (H2S) produced in situ acts as the primary reducing species, and we were able to increase the particle size more than 2-fold by tuning both the reaction time and quantity of sulfur added during the synthesis. We found that we are able to control the crystalline or amorphous nature of the resulting nanoparticles by choosing different solvents and propose a mechanism for this interaction. The reaction mechanism presented provides insight into how one can control the resulting particle size, crystallinity, and reaction kinetics. While we demonstrated the synthesis of Ge nanoparticles, this method can potentially be extended to other members of the group IV family.

Reaction of porphyrin-based surface-anchored metal-organic frameworks caused by prolonged illumination.

Crystalline surface-anchored metal-organic framework (SURMOF) thin films made from porphyrin-based organic linkers have recently been used in both photon upconversion and photovoltaic applications. While these studies showed promising results, the question of photostability in this organic-inorganic hybrid material has to be investigated before applications can be considered. Here, we combine steady-state photoluminescence, transient absorption, and time-resolved electron paramagnetic resonance spectroscopy to examine the effects of prolonged illumination on a palladium-porphyrin based SURMOF thin film. We find that phototreatment leads to a change in the material's photoresponse caused by the creation of stable products of photodecomposition - likely chlorin - inside the SURMOF structure. When the mobile triplet excitons encounter such a defect site, a short-lived (80 ns) cation-anion radical pair can be formed by electron transfer, wherein the charges are localized at a porphyrin and the photoproduct site, respectively.

On an Easy Way To Prepare Metal-Nitrogen Doped Carbon with Exclusive Presence of MeN4-type Sites Active for the ORR.

Today, most metal and nitrogen doped carbon catalysts for ORR reveal a heterogeneous composition. This can be reasoned by a nonoptimized precursor composition and various steps in the preparation process to get the required active material. The significant presence of inorganic metal species interferes with the assignment of descriptors related to the ORR activity and stability. In this work we present a simple and feasible way to reduce the contribution of inorganic metal species in some cases even down to zero. Such catalysts reveal the desired homogeneous composition of MeN4 (Me = metal) sites in the carbon that is accompanied by a significant enhancement in ORR activity. Among the work of other international groups, our iron-based catalyst comprises the highest density of FeN4 sites ever reported without interference of inorganic metal sites.

Compact Electron Paramagnetic Resonance on a Chip Spectrometer Using a Single Sided Permanent Magnet.

Electron paramagnetic resonance (EPR) spectroscopy provides information about the physical and chemical properties of materials by detecting paramagnetic states. Conventional EPR measurements are performed in high Q resonator using large electromagnets which limits the available space for operando experiments. Here we present a solution toward a portable EPR sensor based on the combination of the EPR-on-a-Chip (EPRoC) and a single-sided permanent magnet. This device can be placed directly into the sample environment (i.e., catalytic reaction vessels, ultrahigh vacuum deposition chambers, aqueous environments, etc.) to conduct in situ and operando measurements. The EPRoC reported herein is comprised of an array of 14 voltage-controlled oscillator (VCO) coils oscillating at 7 GHz. By using a single grain of crystalline BDPA, EPR measurements at different positions of the magnet with respect to the VCO array were performed. It was possible to create a 2D spatial map of a 1.5 mm × 5 mm region of the magnetic field with 50 µm resolution. This allowed for the determination of the magnetic field intensity and homogeneity, which are found to be 254.69 mT and 700 ppm, respectively. The magnetic field was mapped also along the vertical direction using a thin film a-Si layer. The EPRoC and permanent magnet were combined to form a miniaturized EPR spectrometer to perform experiments on tempol (4-hydroxy-2,2,6,6-teramethylpiperidin-1-oxyl) dissolved in an 80% glycerol and 20% water solution. It was possible to determine the molecular tumbling correlation time and to establish a calibration procedure to quantify the number of spins within the sample.

Microwave field mapping for EPR-on-a-chip experiments.

Electron paramagnetic resonance-on-a-chip (EPRoC) devices use small voltage-controlled oscillators (VCOs) for both the excitation and detection of the EPR signal, allowing access to unique sample environments by lifting the restrictions imposed by resonator-based EPR techniques. EPRoC devices have been successfully used at multiple frequencies (7 to 360 gigahertz) and have demonstrated their utility in producing high-resolution spectra in a variety of spin centers. To enable quantitative measurements using EPRoC devices, the spatial distribution of the B1 field produced by the VCOs must be known. As an example, the field distribution of a 12-coil VCO array EPRoC operating at 14 gigahertz is described in this study. The frequency modulation-recorded EPR spectra of a "point"-like and a thin-film sample were investigated while varying the position of both samples in three directions. The results were compared to COMSOL simulations of the B1-field intensity. The EPRoC array sensitive volume was determined to be ~19 nanoliters. Implications for possible EPR applications are discussed.

Internal electric fields control triplet formation in halide perovskite-sensitized photon upconverters.

Halide perovskite-based photon upconverters utilize perovskite thin films to sensitize triplet exciton formation in a small-molecule layer, driving triplet-triplet annihilation upconversion. Despite having excellent carrier mobility, these systems suffer from inefficient triplet formation at the perovskite/annihilator interface. We studied triplet formation in formamidinium-methylammonium lead iodide/rubrene bilayers using photoluminescence and surface photovoltage methods. By studying systems constructed on glass as well as hole-selective substrates, comprising self-assembled layers of the carbazole derivative 2PACz ([2-(9H-carbazol-9-yl)ethyl]phosphonic acid) on indium-doped tin oxide, we saw how changes in the carrier dynamics induced by the hole-selective substrate perturbed triplet formation at the perovskite/rubrene interface. We propose that an internal electric field, caused by hole transfer at the perovskite/rubrene interface, strongly affects triplet exciton formation, accelerating exciton-forming electron-hole encounters at the interface but also limiting the hole density in rubrene at high excitation densities. Controlling this field is a promising path to improving triplet formation in perovskite/annihilator upconverters.

Intermolecular hybridization governs molecular electrical doping.

Current models for molecular electrical doping of organic semiconductors are found to be at odds with other well-established concepts in that field, like polaron formation. Addressing these inconsistencies for prototypical systems, we present experimental and theoretical evidence for intermolecular hybridization of organic semiconductor and dopant frontier molecular orbitals. Common doping-related observations are attributed to this phenomenon, and controlling the degree of hybridization emerges as a strategy for overcoming the present limitations in the yield of doping-induced charge carriers.

Pulsed electrically detected magnetic resonance for thin film silicon and organic solar cells.

In thin film solar cells based on non-crystalline thin film silicon or organic semiconductors structural disorder leads to localized states that induce device limiting charge recombination and trapping. Both processes frequently involve paramagnetic states and become spin-dependent. In the present perspectives article we report on advanced pulsed electrically detected magnetic resonance (pEDMR) experiments for the study of spin dependent transport processes in fully processed thin film solar cells. We reflect on recent advances in pEDMR spectroscopy and demonstrate its capabilities on two different state of the art thin film solar cell concepts based on microcrystalline silicon and organic MEH-PPV:PCBM blends, recently studied at HZB. Benefiting from the increased capabilities of novel pEDMR detection schemes we were able to ascertain spin-dependent transport processes and microscopically identify paramagnetic states and their role in the charge collection mechanism of solar cells.

Relaxation processes in silicon heterojunction solar cells probed via noise spectroscopy.

We have employed state-of-the-art cross-correlation noise spectroscopy (CCNS) to study carrier dynamics in silicon heterojunction solar cells (SHJ SCs). These cells were composed of a light absorbing n-doped monocrystalline silicon wafer contacted by passivating layers of i-a-Si:H and doped a-Si:H selective contact layers. Using CCNS, we are able to resolve and characterize four separate noise contributions: (1) shot noise with Fano factor close to unity due to holes tunneling through the np-junction, (2) a 1/f term connected to local potential fluctuations of charges trapped in a-Si:H defects, (3) generation-recombination noise with a time constant between 30 and 50 µs and attributed to recombination of holes at the interface between the ITO and n-a-Si:H window layer, and (4) a low-frequency generation-recombination term observed below 100 K which we assign to thermal emission over the ITO/ni-a-Si:H interface barrier. These results not only indicate that CCNS is capable of reveling otherwise undetectable relaxation process in SHJ SCs and other multi-layer devices, but also that the technique has a spatial selectivity allowing for the identification of the layer or interface where these processes are taking place.

On the modeling of amplitude-sensitive electron spin resonance (ESR) detection using voltage-controlled oscillator (VCO)-based ESR-on-a-chip detectors.

In this paper, we present an in-depth analysis of a voltage-controlled oscillator (VCO)-based sensing method for electron spin resonance (ESR) spectroscopy, which greatly simplifies the experimental setup compared to conventional detection schemes. In contrast to our previous oscillator-based ESR detectors, where the ESR signal was encoded in the oscillation frequency, in the amplitude-sensitive method, the ESR signal is sensed as a change of the oscillation amplitude of the VCO. Therefore, using VCO architecture with a built-in amplitude demodulation scheme, the experimental setup reduces to a single permanent magnet in combination with a few inexpensive electronic components. We present a theoretical analysis of the achievable limit of detection, which uses perturbation-theory-based VCO modeling for the signal and applies a stochastic averaging approach to obtain a closed-form expression for the noise floor. Additionally, the paper also introduces a numerical model suitable for simulating oscillator-based ESR experiments in a conventional circuit simulator environment. This model can be used to optimize sensor performance early on in the design phase. Finally, all presented models are verified against measured results from a prototype VCO operating at 14 GHz inside a 0.5 T magnetic field.

Rapid-scan electron paramagnetic resonance using an EPR-on-a-Chip sensor.

Electron paramagnetic resonance (EPR) spectroscopy is the method of choice to investigate and quantify paramagnetic species in many scientific fields, including materials science and the life sciences. Common EPR spectrometers use electromagnets and microwave (MW) resonators, limiting their application to dedicated lab environments. Here, novel aspects of voltage-controlled oscillator (VCO)-based EPR-on-a-Chip (EPRoC) detectors are discussed, which have recently gained interest in the EPR community. More specifically, it is demonstrated that with a VCO-based EPRoC detector, the amplitude-sensitive mode of detection can be used to perform very fast rapid-scan EPR experiments with a comparatively simple experimental setup to improve sensitivity compared to the continuous-wave regime. In place of a MW resonator, VCO-based EPRoC detectors use an array of injection-locked VCOs, each incorporating a miniaturized planar coil as a combined microwave source and detector. A striking advantage of the VCO-based approach is the possibility of replacing the conventionally used magnetic field sweeps with frequency sweeps with very high agility and near-constant sensitivity. Here, proof-of-concept rapid-scan EPR (RS-EPRoC) experiments are performed by sweeping the frequency of the EPRoC VCO array with up to 400 THz s-1, corresponding to a field sweep rate of 14 kT s-1. The resulting time-domain RS-EPRoC signals of a micrometer-scale BDPA sample can be transformed into the corresponding absorption EPR signals with high precision. Considering currently available technology, the frequency sweep range may be extended to 320 MHz, indicating that RS-EPRoC shows great promise for future sensitivity enhancements in the rapid-scan regime.

Potential of PEDOT:PSS as a hole selective front contact for silicon heterojunction solar cells.

We show that the highly conductive polymer poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) can successfully be applied as a hole selective front contact in silicon heterojunction (SHJ) solar cells. In combination with a superior electron selective heterojunction back contact based on amorphous silicon (a-Si), mono-crystalline n-type silicon (c-Si) solar cells reach power conversion efficiencies up to 14.8% and high open-circuit voltages exceeding 660 mV. Since in the PEDOT:PSS/c-Si/a-Si solar cell the inferior hybrid junction is determining the electrical device performance we are capable of assessing the recombination velocity (v I ) at the PEDOT:PSS/c-Si interface. An estimated v I of ~400 cm/s demonstrates, that while PEDOT:PSS shows an excellent selectivity on n-type c-Si, the passivation quality provided by the formation of a native oxide at the c-Si surface restricts the performance of the hybrid junction. Furthermore, by comparing the measured external quantum efficiency with optical simulations, we quantify the losses due to parasitic absorption of PEDOT:PSS and reflection of the device layer stack. By pointing out ways to better passivate the hybrid interface and to increase the photocurrent we discuss the full potential of PEDOT:PSS as a front contact in SHJ solar cells.

Increased upconversion performance for thin film solar cells: a trimolecular composition.

Photochemical upconversion based on triplet-triplet annihilation (TTA-UC) is employed to enhance the short-circuit currents generated by two varieties of thin-film solar cells, a hydrogenated amorphous silicon (a-Si:H) solar cell and a dye-sensitized solar cell (DSC). TTA-UC is exploited to harvest transmitted sub-bandgap photons, combine their energies and re-radiate upconverted photons back towards the solar cells. In the present study we employ a dual-emitter TTA-UC system which allows for significantly improved UC quantum yields as compared to the previously used single-emitter TTA systems. In doing so we achieve record photo-current enhancement values for both the a-Si:H device and the DSC, surpassing 10-3 mA cm-2 sun-2 for the first time for a TTA-UC system and marking a record for upconversion-enhanced solar cells in general. We discuss pertinent challenges of the TTA-UC technology which need to be addressed in order to achieve its viable device application.

Unveiling the Hybrid n-Si/PEDOT:PSS Interface.

We investigated the buried interface between monocrystalline n-type silicon (n-Si) and the highly conductive polymer poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) ( PEDOT: PSS), which is successfully applied as a hole selective contact in hybrid solar cells. We show that a post-treatment of the polymer films by immersion in a suitable solvent reduces the layer thickness by removal of excess material. We prove that this post-treatment does not affect the functionality of the hybrid solar cells. Through the thin layer we are probing the chemical structure at the n-Si/ PEDOT: PSS interface with synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). From the HAXPES data we conclude that the Si substrate of a freshly prepared hybrid solar cell is already oxidized immediately after preparation. Moreover, we show that even when storing the sample in inert gas such as, e.g., nitrogen the n-Si/SiOx/ PEDOT: PSS interface continues to further oxidize. Thus, without further surface treatment, an unstable Si suboxide will always be present at the hybrid interface.

High resolution in-operando microimaging of solar cells with pulsed electrically-detected magnetic resonance.

The in-operando detection and high resolution spatial imaging of paramagnetic defects, impurities, and states becomes increasingly important for understanding loss mechanisms in solid-state electronic devices. Electron spin resonance (ESR), commonly employed for observing these species, cannot meet this challenge since it suffers from limited sensitivity and spatial resolution. An alternative and much more sensitive method, called electrically-detected magnetic resonance (EDMR), detects the species through their magnetic fingerprint, which can be traced in the device's electrical current. However, until now it could not obtain high resolution images in operating electronic devices. In this work, the first spatially-resolved electrically-detected magnetic resonance images (EDMRI) of paramagnetic states in an operating real-world electronic device are provided. The presented method is based on a novel microwave pulse sequence allowing for the coherent electrical detection of spin echoes in combination with powerful pulsed magnetic-field gradients. The applicability of the method is demonstrated on a device-grade 1-µm-thick amorphous silicon (a-Si:H) solar cell and an identical device that was degraded locally by an electron beam. The degraded areas with increased concentrations of paramagnetic defects lead to a local increase in recombination that is mapped by EDMRI with ∼20-µm-scale pixel resolution. The novel approach presented here can be widely used in the nondestructive in-operando three-dimensional characterization of solid-state electronic devices with a resolution potential of less than 100 nm.