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 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.

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 field produced by the VCOs must be known.

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 VO/VO and V/V, the ratio of which to the total vanadium content determines the state of charge (SOC).

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.

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.

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.

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.

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.

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.

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.

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).

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.

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.

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

Unlabelled: 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.

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.

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.

Junction formation and current transport mechanisms in hybrid n-Si/PEDOT:PSS solar cells.

Unlabelled: We investigated hybrid inorganic-organic solar cells combining monocrystalline n-type silicon (n-Si) and a highly conductive polymer poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (

Pedot: PSS). The build-in potential, photo- and dark saturation current at this hybrid interface are monitored for varying n-Si doping concentrations. We corroborate that a high build-in potential forms at the hybrid junction leading to strong inversion of the n-Si surface.

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.

Multi-frequency EDMR applied to microcrystalline thin-film silicon solar cells.

Pulsed multi-frequency electrically detected magnetic resonance (EDMR) at X-, Q- and W-Band (9.7, 34, and 94GHz) was applied to investigate paramagnetic centers in microcrystalline silicon thin-film solar cells under illumination. The EDMR spectra are decomposed into resonances of conduction band tail states (e states) and phosphorus donor states (P states) from the amorphous layer and localized states near the conduction band (CE states) in the microcrystalline layer.

Dye-Sensitized Solar Cell with Integrated Triplet-Triplet Annihilation Upconversion System.

Photon upconversion (UC) by triplet-triplet annihilation (TTA-UC) is employed in order to enhance the response of solar cells to sub-bandgap light. Here, we present the first report of an integrated photovoltaic device, combining a dye-sensitized solar cell (DSC) and TTA-UC system. The integrated device displays enhanced current under sub-bandgap illumination, resulting in a figure of merit (FoM) under low concentration (3 suns), which is competitive with the best values recorded to date for nonintegrated systems.

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.

Lock-in detection for pulsed electrically detected magnetic resonance.

We show that in pulsed electrically detected magnetic resonance (pEDMR) signal modulation in combination with a lock-in detection scheme can reduce the low-frequency noise level by one order of magnitude and in addition removes the microwave-induced non-resonant background. This is exemplarily demonstrated for spin-echo measurements in phosphorus-doped silicon. The modulation of the signal is achieved by cycling the phase of the projection pulse used in pEDMR for the readout of the spin state.

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.

Frequency domain Fourier transform THz-EPR on single molecule magnets using coherent synchrotron radiation.

Frequency domain Fourier transform THz electron paramagnetic resonance (FD-FT THz-EPR) based on coherent synchrotron radiation (CSR) is presented as a novel tool to ascertain very large zero field splittings in transition metal ion complexes. A description of the FD-FT THz-EPR at the BESSY II storage ring providing CSR in a frequency range from 5 cm(-1) up to 40 cm(-1) at external magnetic fields from -10 T to +10 T is given together with first measurements on the single molecule magnet Mn(12)Ac where we studied DeltaM(S) = +/-1 spin transition energies as a function of the external magnetic field and temperature.