Time-resolved Microwave Conductivity Research Articles

Molecular models of PM6 for non-fullerene acceptor organic solar cells: How DAD and ADA structures impact charge separation and charge recombination.

The quadrupole moment of a non-fullerene acceptor (NFA) generated by the constituent electron donor (D) and acceptor (A) units is a significant factor that affects the charge separation (CS) and charge recombination (CR) processes in organic photovoltaics (OPVs). However, its impact on p-type polymer domains remains unclear. In this study, we synthesized p-type molecules, namely acceptor-donor-acceptor (ADA) and donor-acceptor-donor (DAD), which are components of the benchmark PM6 polymer (D: benzodithiophene and A: dioxobenzodithiophene). Planar heterojunction films, a model of bulk heterojunction, were prepared using ADA, DAD, and PM6 as the bottom p-type layers and Y6 NFA as the top n-type layer. Flash-photolysis time-resolved microwave conductivity, femtosecond transient absorption spectroscopy, and quantum mechanical calculations were employed to probe the charge carrier dynamics. Our findings reveal that while the subtle difference in quadrupole moment and energy gradient of the p-type materials has a minimal influence on CS, the molecular type (ADA or DAD) significantly affects the bulk CR. This study expands the understanding of how the p-type component and its conformation at the p/n interface impact the CS and CR in OPVs, highlighting the critical role of molecular donors in optimizing device performance.

A Surface-Reconstructed Bilayer Heterojunction Enables Efficient and Stable Inverted Perovskite Solar Cells.

The efficiency of perovskite photovoltaics remains distant from their theoretical limits, primarily due to high photovoltage losses. Here a strategy is reported to minimize voltage losses by reconstructing the perovskite surface into a bilayer heterojunction (BLH) structure. Unlike conventional low-dimensional capping layers, typically constrained to a few nanometers to prevent low fill factors, this methodology facilitates a more comprehensive reaction with surface defects, allowing a more substantial capping layer (≈50 nanometers) without compromising charge transport integrity. Time-resolved microwave conductivity analysis indicates a significant reduction in trap density at the top region of the perovskite film, showing an order of magnitude lower than that of the pristine sample. Incorporating this BLH in inverted cells results in a remarkably low photovoltage deficit of 325mV, leading to a power conversion efficiency (PCE) of 26.1% (25.72% certified). The encapsulated device maintains 94% of its original efficiency after 1200h of maximum power point tracking under one sun illumination at 65°C.

Unraveling the Positive Effects of Glycine Hydrochloride on the Performance of Pb–Sn‐Based Perovskite Solar Cells

Additives are commonly used to increase the performance of metal‐halide perovskite solar cells, but detailed information on the origin of the beneficial outcome is often lacking. Herein, the effect of glycine hydrochloride is investigated when used as an additive during solution processing of narrow‐bandgap mixed Pb–Sn perovskites. By combining the characterization of the photovoltaic performance and stability under illumination, with determining the quasi‐Fermi level splitting, time‐resolved microwave conductivity (TRMC), and morphological and elemental analysis a comprehensive insight is obtained. Glycine hydrochloride is able to retard the oxidation of Sn2+ in the precursor solution, and at low concentrations (1–2 mol%) it improves the grain size distribution and crystallization of the perovskite, causing a smoother and more compact layer, reducing non‐radiative recombination, and enhancing the lifetime of photogenerated charges. These improve the photovoltaic performance and have a positive effect on stability. By determining the quasi‐Fermi level splitting on perovskite layers without and with charge transport layers it is found that glycine hydrochloride primarily improves the bulk of the perovskite layer and does not contribute significantly to passivation of the interfaces of the perovskite with either the hole or electron transport layer (ETL).

Low‐Temperature Synthesis of Stable CaZn2P2 Zintl Phosphide Thin Films as Candidate Top Absorbers

AbstractThe development of tandem photovoltaics and photoelectrochemical solar cells requires new absorber materials with bandgaps in the range of ≈1.5–2.3 eV, for use in the top cell paired with a narrower‐gap bottom cell. An outstanding challenge is finding materials with suitable optoelectronic and defect properties, good operational stability, and synthesis conditions that preserve underlying device layers. This study demonstrates the Zintl phosphide compound CaZn2P2 as a compelling candidate semiconductor for these applications. Phase‐pure, ≈500 nm‐thick CaZn2P2 thin films are prepared using a scalable reactive sputter deposition process at growth temperatures as low as 100 °C, which is desirable for device integration. Ultraviolet‐visible spectroscopy shows that CaZn2P2 films exhibit an optical absorptivity of ≈104 cm−1 at ≈1.95 eV direct bandgap. Room‐temperature photoluminescence (PL) measurements show near‐band‐edge optical emission, and time‐resolved microwave conductivity (TRMC) measurements indicate a photoexcited carrier lifetime of ≈30 ns. CaZn2P2 is highly stable in both ambient conditions and moisture, as evidenced by PL and TRMC measurements. Experimental data are supported by first‐principles calculations, which indicate the absence of low‐formation‐energy, deep intrinsic defects. Overall, this study shall motivate future work integrating this potential top cell absorber material into tandem solar cells.

Electron Transport over 2D Molecular Materials and Assemblies.

ConspectusTwo-dimensional (2D) molecular materials, in which the major interactions are confined in 2D planes with contrasted force fields acting in between the planes, have been key electronic functional materials since the past decade. Even without referring to the functionals of graphene-based systems, 2D electronic conjugated systems are expected to show extrawide dynamic ranges in electronic density of states (DOS) tuning, effective electron mass, electron mobility, and conductivity. A major advantage of 2D electronic systems is their compatibility with the ubiquitous electronic devices designed using planar structures, such as transistors and memories, which is associated with the utility of 2D active materials. The mobility of electrons in 2D systems is the key to their utility, and various conjugated molecular and 2D materials have been designed to optimize the mobility. This Account begins with an introduction for mobility assessment: using noncontact time-resolved microwave conductivity (TRMC) measurements as a technique to probe differential conductivity upon transient charge carrier injection into the materials. Electronic transport over 2D electronic materials such as graphenes, covalent organic frameworks (COFs), and metal-organic frameworks (MOFs) is discussed with a special emphasis on molecular building blocks, fine-tuning conducting species and linkages, topology of the framework, and controlling molecular doping. The superiority of β-ketoenamine-linked COF over imine-linked COF films in charge transport and dominant in-plane charge carrier mobility over out-of-plane mobility is also illustrated. Systematic molecular engineering of the building blocks of β-ketoenamine-linked COFs with varying degrees of donor-acceptor (D-A) conjugation, torsional angles, and reaction conditions resulted in the modulation of the efficiency of charge carrier generation/transport as well as exciton migration. The advantages of 2D systems are finally discussed in terms of the mobility interplaying with spatial arrangements of molecules as well as the substantial role of intermolecular interactions in stabilizing their condensed phases. The strong correlation between the dispersion of mobility and hierarchical intermolecular interactions sheds light on the way to overcome structural fluctuation on the optimization of charge transport in molecular electronic materials. The point of singularity in the dispersion at an intermolecular distance of d ∼ 0.3 nm is deduced from the overall mobility assessment in condensed phases of conjugated molecules, suggesting key roles of intermolecular electronic coupling: the new concept of electronic conjugation. Exceptional electronic coupling with relatively high charge carrier mobility was also observed, particularly in 2D spatial arrangements of chiral molecules in contrast to 3D analogues, where the reduction of gravitational density of the molecular condensates was impacting DOS: the Wallach's rule. 2D electronic systems are strong candidates for the violation of the long-lasting Wallach's rule in terms of DOS.

(Invited) Dynamic Relaxation of Charge Carrier Mobilities in Organic Photovoltaics

A non-fullerene small molecular acceptor (NFA) is a prominent molecule that shows moderate electron mobility and a narrow bandgap complementary to middle-bandgap p-type conjugated polymers, which leads to great improvement in the performance of organic photovoltaic (OPV) cells. However, little is known about the relaxation of charge carriers, which is key to efficient charge transport. Herein, we report simultaneous time-of-flight (TOF) and time-resolved microwave conductivity (TRMC) measurements[1] employing benzodithiophene-based polymer (PBDB-T):soluble C70-fullerere (PCBM) and PBDB-T:NFA (ITIC or Y6) blends, as benchmark systems[2, 3]. In addition to the conventional TOF mobilities, relaxation of the hole and electron mobility was evaluated by TRMC under an external electric field. Although PBDB-T:ITIC exhibited much faster relaxation than PBDB-T:PCBM, the relaxation in PBDB-T:Y6 was considerably moderate. This is consistent with the energetic disorder estimated from the photoabsorption onset. Interestingly, the slower relaxation of the electrons compared to the holes in PBDB-T:Y6 is in line with the preferred normal device structure. Our work deepens the understanding of the energetics of polymer:NFA blends and offers a basis for achieving efficient NFA properties.Reference[1] Y. Shimata, A. Saeki, J. Phys. Chem. C 121 (2017) 18351.[2] F. Hamada, A. Saeki, ChemSusChem 14 (2021) 3528.[3] S. Li, F. Hamada, R. Nishikubo, A. Saeki, Sustainable Energy Fuels 6 (2022) 756.

Sulfur-Bridged Cationic Diazulenomethenes: Formation of Charge-Segregated Assembly with High Charge-Carrier Mobility.

Sulfur-bridged cationic diazulenomethenes were synthesized and exhibited high stability even under basic conditions due to the delocalization of positive charge over the whole π-conjugated skeleton. As a result of the effective delocalization and the absence of orthogonally oriented bulky substituents, the cationic π-conjugated skeletons formed a π-stacked array with short interfacial distances. A derivative with SbF6- as a counter anion formed a charge-segregated assembly in the crystalline state, rather than the generally favored charge-by-charge arrangement of oppositely charged species based on electrostatic interactions. Theoretical calculations suggested that the destabilization caused by electrostatic repulsion between two positively charged π-conjugated skeletons is compensated by the dispersion forces. In addition, the counter anion SbF6- played a role in regulating the molecular alignment through F⋯H-C and F-S interactions, which resulted in the charge-segregated alignment of the cationic π-skeletons. This characteristic assembled structure gave rise to a high charge-carrier mobility of 1.7 cm2 V-1 s-1 as determined using flash-photolysis time-resolved microwave conductivity.

Colorless Near-Infrared Absorbing Dyes Based on B-N Fused Donor-Acceptor-Donor π-Conjugated Molecules for Organic Phototransistors.

The introduction of a colorless function to organic electronic devices allows responses to light in the near-infrared (NIR) region and is expected to broaden the applications of these devices. However, the development of a colorless NIR dye remains a challenge due to the lack of a rational molecular design for controlling electronic transitions. In this study, to suppress the π-π* transitions in the visible region, polycyclic donor-acceptor-donor π-conjugated molecules with boron bridges (Py-FNTz-B and IP-FNTz-B) are designed and synthesized, which contain pyrrole or indenopyrrole as donor units with fluorinated naphthobisthiadiazole (FNTz) as an acceptor unit. The pyrrole end-capped Py-FNTz-B shows an absorption band in the NIR region without distinct visible-light absorption, which has led to the establishment of colorless characteristics. The indenopyrrole end-capped IP-FNTz-B shows a narrow optical energy gap of 0.87eV in films. Time-resolved microwave conductance and field-effect transistors demonstrate the semiconducting characteristics of these molecules, and Py-FNTz-B-based devices function as NIR phototransistors. Theoretical analyses indicate that the combination of a polyene-like electronic structure with orbital symmetry is important to obtain NIR wavelength-selective absorption. This study suggests that a molecular design based on electronic structures can be effective in the development of colorless NIR-absorbing dyes for organic electronics.

Combined Charge Extraction by Linearly Increasing Voltage and Time-Resolved Microwave Conductivity to Reveal the Dynamic Charge Carrier Mobilities in Thin-Film Organic Solar Cells.

This article reports a purely experiment-based method to evaluate the time-dependent charge carrier mobilities in thin-film organic solar cells (OSCs) using simultaneous charge extraction by linearly increasing the voltage (CELIV) and time-resolved microwave conductivity (TRMC) measurements. This method enables the separate measurement of electron mobility (μe) and hole mobility (μh) in a metal-insulator-semiconductor (MIS) device. A slope-injection-restoration voltage profile for MIS-CELIV is also proposed to accurately determine the charge densities. The dynamic behavior of μe and μh is examined in five bulk heterojunction (BHJ) OSCs of polymer:fullerene (P3HT:PCBM and PffBT4T:PCBM) and polymer:nonfullerene acceptor (PM6:ITIC, PM6:IT4F, and PM6:Y6). While the former exhibits fast decays of μh and μe, the latter, in particular, PM6:IT4F and PM6:Y6, exhibits slow decays. Notably, the high-performing PM6:Y6 demonstrates both a balanced mobility (μe/μh) of 1.0-1.1 within 30 μs and relatively large CELIV-TRMC mobility values among the five BHJs. The results exhibit reasonable consistency with a high fill factor. The proposed new CELIV-TRMC technique offers a path toward a comprehensive understanding of dynamic mobility and its correlation with the OSC performance.

Electronic relaxation in PLD TiO2 films processed with femtosecond UV-laser

Modifications of shallow electron trap states near conduction band was analyzed after surface structuring of TiO2 thin films prepared via pulsed laser deposition method. Laser-induced periodic surface structures (LIPSS) were produced on the large-area films after irradiation with femtosecond KrF laser (λ = 248 nm). While spatial period of LIPSS Λ ≈ 190 ± 10 nm was not affected by laser fluence, coherence was increased with an increase of laser dose. Time-resolved microwave conductivity measurements accompanied by theoretical modelling revealed energetic positions of shallow electron trap states, connected to LIPSS. A possibility to alter the trap states energy via surface structuring of the material was shown.

Identification and Dynamics of Microsecond Long-Lived Charge Carriers for CsPbBr3 Perovskite Quantum Dots, Featuring Ambient Long-Term Stability.

We analyze the stability and photophysical dynamics of CsPbBr3 perovskite quantum dots (PeQDs), fabricated under mild synthetic conditions and embedded in an amorphous silica (SiOx) matrix (CsPbBr3@SiOx), underscoring their sustained performance in ambient conditions for over 300 days with minimal optical degradation. However, this stability comes at the cost of a reduced photoluminescence efficiency. Time-resolved spectroscopic analyses, including flash-photolysis time-resolved microwave conductivity and time-resolved photoluminescence, show that excitons in CsPbBr3@SiOx films decay within 2.5 ns, while charge carriers recombine over approximately 230 ns. This longevity of the charge carriers is due to photoinduced electron transfer to the SiOx matrix, enabling hole retention. The measured hole mobility in these PeQDs is 0.880 cm2 V-1 s-1, underscoring their potential in optoelectronic applications. This study highlights the role of the silica matrix in enhancing the durability of PeQDs in humid environments and modifying exciton dynamics and photoluminescence, providing valuable insights for developing robust optoelectronic materials.

Modification of Visible-Light-Responsive Pb2Ti2O5.4F1.2 with Metal Oxide Cocatalysts to Improve Photocatalytic O2 Evolution toward Z-Scheme Overall Water Splitting.

The development of a highly active photocatalyst for visible-light water splitting requires a high-quality semiconductor material and a cocatalyst, which promote both the migration of photogenerated charge carriers and surface redox reactions. In this work, a cocatalyst was loaded onto an oxyfluoride photocatalyst, Pb2Ti2O5.4F1.2, to improve the water oxidation activity. Among the metal oxides examined as cocatalysts, RuO2 was found to be the most suitable, and the O2 evolution activity depended on the preparation conditions for Ru/Pb2Ti2O5.4F1.2. The highest activity was obtained with RuCl3-impregnated Pb2Ti2O5.4F1.2 heated under a flow of H2 at 523 K. The H2-treated Ru/Pb2Ti2O5.4F1.2 showed an O2 evolution rate an order of magnitude higher than those for the analogues without the H2 treatment (e. g., RuO2/Pb2Ti2O5.4F1.2). Physicochemical analyses by X-ray absorption fine-structure spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and time-resolved microwave conductivity measurements indicated that the optimized photocatalyst contained partially reduced RuO2 species with a particle size of ~5 nm. These partially reduced species effectively trapped the photogenerated charge carriers and promoted the oxidation of water into O2. The optimized Ru/Pb2Ti2O5.4F1.2 could function as an O2-evolving photocatalyst in Z-scheme overall water splitting, in combination with an Ru-loaded, Rh-doped SrTiO3 photocatalyst.

Vacuum-Processed Propylene Urea Additive: A Novel Approach for Controlling the Growth of CH3NH3PbI3 Crystals in All Vacuum-Processed Perovskite Solar Cells.

In this study, we present a novel method for controlling the growth of perovskite crystals in the vacuum thermal evaporation process by utilizing a vacuum-processable additive, propylene urea (PU). By coevaporation of perovskite precursors with PU to form the perovskite layer, PU, acting as a Lewis base additive, retards the direct reaction between the perovskite precursors. This facilitates a larger domain size and reduced defect density. Following the removal of the residual additive, the perovskite layer, exhibiting improved crystallinity, demonstrates reduced charge recombination, as confirmed by a time-resolved microwave conductivity analysis. Consequently, there is a notable enhancement in open-circuit voltage and power conversion efficiency, increasing from 1.05 to 1.15 V and from 17.17 to 18.31%, respectively. The incorporation of a vacuum-processable and removable Lewis base additive into the fabrication of vacuum-processed perovskite solar cells offers new avenues for optimizing these devices.

Tail states suppression via surface-modification of wide-bandgap perovskites for high-efficiency all-perovskite photovoltaic tandems

As an essential light-absorbing material in perovskite-based tandem solar cells, wide-bandgap (WBG) perovskite has garnered extensive attention. Nevertheless, due to severe non-radiative recombination from tail states, as well as photoinduced phase segregation and unoptimized charge transfer, WBG perovskite solar cells (PSCs) typically display significant open-circuit voltage (VOC) loss and low fill factor (FF). In this work, we report to modify the 1.68 eV WBG perovskite film upon optimized surface passivation with 1,3-propane-diammonium iodide (PDAI2). Time-resolved microwave conductivity measurement is employed to analyze the tail states, mobilities of charge carriers and the rate constants of recombination in perovskite films. The results indicate that the optimized surface modification strategy not only enhances film quality, boosts carrier transport, but also suppresses tail states and therefore diminishes non-radiative recombination, consequently elevating the VOC and FF of the device. Hence, the PDAI2-assisted WBG PSCs deliver an optimal efficiency of 21.48 %, accompanied by a VOC of 1.243 V. Furthermore, the integration of a narrow-bandgap tin–lead PSC with a semi-transparent WBG PSC results in a four-terminal perovskite/perovskite tandem solar cell, showcasing an efficiency surpassing 28 %. Our research offers a practical approach for producing efficient WBG PSCs and tandem solar cells.

Missing Excitons: How Energy Transfer Competes with Free Charge Generation in Dilute-Donor/Acceptor Systems.

Energy transfer across the donor-acceptor interface in organic photovoltaics is usually beneficial to device performance, as it assists energy transport to the site of free charge generation. Here, we present a case where the opposite is true: dilute donor molecules in an acceptor host matrix exhibit ultrafast excitation energy transfer (EET) to the host, which suppresses the free charge yield. We observe an optimal photochemical driving force for free charge generation, as detected via time-resolved microwave conductivity (TRMC), but with a low yield when the sensitizer is excited. Meanwhile, transient absorption shows that transferred excitons efficiently produce charge-transfer states. This behavior is well described by a competition for the excited state between long-range electron transfer that produces free charge and EET that ultimately produces only localized charge-transfer states. It cannot be explained if the most localized CT states are the intermediate between excitons and the free charge in this system.

Non-resonant phase sensitive approach for time resolved microwave conductivity in photoactive thin films

Time-resolved microwave conductivity (TRMC) is a contactless technique utilized for the investigation of carrier density, transport properties, trapping phenomena, and recombination parameters in charge transport materials. Traditional TRMC methods rely on resonant cavities or resonators, which impose limitations on the frequency range and accuracy of measurements. In this study, we introduce an innovative approach that employs a non-resonant coplanar transmission line and a microwave interferometric detection scheme to investigate the phase-dependent complex microwave conductivity. Additionally, we demonstrate unique calibration techniques for determining the absolute complex microwave conductivity by combining transient photoconductivity (TPC) and electron spin resonance (ESR) as complementary methods. By utilizing a phase-sensitive microwave interferometer, our detection scheme significantly enhances measurement sensitivity and eliminates the need for a resonant cavity. This broadband detection system enables direct measurement of phase-dependent changes in film conductivity (Δσ). Moreover, it allows us to measure subtle variations in sample photoconductivity upon optical excitation and accommodates greatly restricted volumes (∼nL) consistent with typical device sizes. Here we demonstrate the utility of this technique on a series of poly(3-hexylthiophene) (P3HT) and the electron acceptor [6,6]-phenylC61-butyric acid methyl ester (PCBM) thin films with varying concentrations of PCBM and film thickness.

An n-type semiconducting diazaporphyrin-based hydrogen-bonded organic framework.

Significant effort has been devoted to the development of materials that combine high electrical conductivity and permanent porosity. This paper discloses a diazaporphyrin-based hydrogen-bonded organic framework (HOF) with porosity and n-type semiconductivity. A 5,15-diazaporphyrin Ni(ii) complex with carboxyphenyl groups at the meso positions afforded a HOF due to hydrogen-bonding interactions between the carboxy groups and meso-nitrogen atoms. The thermal and chemical stabilities of the HOF were examined using powder X-ray diffraction analysis, and the charge-carrier mobility was determined to be 2.0 × 10-7 m2 V-1 s-1 using the flash-photolysis time-resolved microwave conductivity (FP-TRMC) method. An analogous diazaporphyrin, which does not form a HOF, exhibited mobility that was 20 times lower. The results presented herein highlight the crucial role of hydrogen-bonding networks in achieving conductive pathways that can tolerate thermal perturbation.

Exploration of Solution-Processed Bi/Sb Solar Cells by Automated Robotic Experiments Equipped with Microwave Conductivity.

Solution-processed inorganic solar cells with less toxic and earth-abundant elements are emerging as viable alternatives to high-performance lead-halide perovskite solar cells. However, the wide range of elements and process parameters impede the rapid exploration of vast chemical spaces. Here, we developed an automated robot-embedded measurement system that performs photoabsorption spectroscopy, optical microscopy, and white-light flash time-resolved microwave conductivity (TRMC). We tested 576 films of quaternary element-blended wide-bandgap Cs-Bi-Sb-I semiconductors with various compositions, organic salt additives (MACl, FACl, MAI, and FAI, where MA and FA represent methylammonium and formamidinium, respectively), and thermal annealing temperatures. Among them, we found that the maximum power conversion efficiency (PCE) was 2.36%, which is significantly higher than the PCE of 0.68% for a reference film without an additive. Machine learning (ML) and statistical analyses revealed significant features and their relationships with TRMC transients, thereby demonstrating the advantages of combining ML and automated experiments for the high-throughput exploration of photovoltaic materials.

(Keynote) Recent Insights on Carrier Generation, Transport, and Extraction in Metal Oxide Photoelectrodes

After the absorption of light, the next steps in any artificial photosynthetic system are the generation, transport, and extraction of photoexcited charge carriers. These steps are well understood in solid state systems based on traditional semiconductors, such as Si and III-V absorbers, resulting in quantum efficiencies close to one for optimized devices. For metal oxide-based absorbers, which have attracted much interest in the past decades because of their relatively good (photo)chemical stability and low cost, the reported efficiencies tend to be much lower. This is often attributed to recombination at defects. While these may indeed adversely affect the efficiency, there are several other fundamental loss mechanisms in metal oxides that are not always fully appreciated. For example, certain metal ions exhibit localized d-d transitions that do not result in mobile charge carriers, resulting in a photogeneration yield < 1. Recent work showed that it is possible to quantify the fraction of mobile photoexcited carriers, from which an upper limit of the achievable photocurrent can be derived [1]. Losses can also occur in the form of recombination or carrier localization during transport. The chance of reaching the interface is often expressed as the carrier diffusion length, which in turn depends on the carrier lifetime and its mobility. Convenient contact-free methods to determine these parameters are time-resolved microwave conductivity (TRMC) and time-resolved THz spectroscopy (TRTS) [2]. Here, one of the challenges is to determine whether the decay in photoconductivity is due to a decay in carrier concentration (i.e., recombination), carrier mobility (trapping, polaron formation), or both. We recently developed a general analysis method for determining the diffusion length which is valid for time-dependent mobilities as well as time-dependent lifetimes [3]. Intringuingly, this method revealed a carrier diffusion length of only 15 nm for BiVO4, which is significantly shorter than previously reported values by us and others. The only way this short diffusion length can be reconciled with the high photocurrent densities reported for this material is by assuming field-assisted charge separation. The role of the electric field is, however, poorly understood in the photoelectrochemistry and photocatalysis communities [4]. In a system without externally applied bias, the electric field does not separate the charges; instead, charge separation is driven by the presence of selective contacts. During my presentation I will review these concepts and discuss how a better understanding of loss mechanisms, the role of the electric field, and selective contacts may help us design more efficient metal oxide-based photoelectrodes.

Perovskite Solar Cell Using Isonicotinic Acid as a Gap-Filling Self-Assembled Monolayer with High Photovoltaic Performance and Light Stability.

High photovoltaic performance and light stability are required for the practical outdoor use of lead-halide perovskite solar cells. To improve the light stability of perovskite solar cells, it is effective to introduce a self-assembled monolayer (SAM) between the carrier transport layer and the perovskite layer. Several alternative approaches in their molecular design and combination with multiple SAMs support high photovoltaic conversion efficiency (PCE). Herein, we report a new structure for improving both PCE and light stability, in which the surface of an electron transport layer (ETL) was modified by combining a fullerene-functionalized self-assembled monolayer (C60SAM) and a suitable gap-filling self-assembled monolayer (GFSAM). Small-sized GFSAMs can enter the gap space of the C60SAM and terminate the unterminated sites on the ETL surface. The best GFSAM in this study was formed using an isonicotinic acid solution. After a light stability test for 68 h at 50 °C under 1 sun illumination, the best cell with C60SAM and GFSAM showed a PCE of 18.68% with a retention rate of over 99%. Moreover, following outdoor exposure for six months, the cells with C60SAM and GFSAM exhibited almost unchanged PCE. From the valence band spectra of the ETLs obtained using hard X-ray photoelectron spectroscopy, we confirmed a decrease in the offset at the ETL/perovskite interface owing to the additional GFSAM treatment on the C60SAM-modified ETL surface. Time-resolved microwave conductivity measurements demonstrated that the additional GFSAM improved electron extraction at the C60SAM-modified ETL/perovskite interface.