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The built-in voltage ( V BI ) is a key parameter for solar cell operation, yet in perovskite solar cells the distribution, magnitude, and origin of the V BI remains poorly understood. In this work, we systematically studied the V BI in pin -type perovskite solar cells based on different hole transport layers (TLs). To this end, we determine the surface photovoltage (SPV) of partial and complete device stacks layer-by-layer by measuring the work function (WF) under dark and light (equivalent AM1.5G) conditions with Kelvin probe (KP) and photoemission spectroscopy (UPS) measurements in 3 different laboratories. We demonstrate that the SPV increases upon the addition of each additional layer until it equals the open-circuit voltage ( V OC ) of the full device. This suggests that both the electron and hole transport layer (HTL/ETL) enlarge the SPV, by improving the separation of photogenerated carriers. Yet, the contribution of both transport layers to the total SPV of the device is small (in the range of ≈100 to 200 meV) and the largest contribution to the SPV originates from the top metal electrode (≈500 meV). The results suggest that the V BI of pin -type perovskite solar cells is largely a result of the work-function difference of the electrodes. With regard to films (or incomplete cell stacks), our simulations can reproduce the measured SPV, and measured quasi-Fermi level splitting (> V OC ) in partial cell stacks without a significant internal field consistent with the experimental data. This work establishes layer-by-layer SPV measurements, which are easily accessible, as a key tool for understanding device performance and internal energetics, similar to layer-by-layer QFLS measurements.

Wide bandgap halide perovskite materials show promising potential to pair with silicon bottom cells. To date, most efficient wide bandgap perovskites layers are fabricated by spin-coating, which is difficult to scale up. Here, we report on slot-die coating for an efficient, 1.68 eV wide bandgap triple-halide (3halide) perovskite absorber, (Cs 0.22 FA 0.78 )Pb(I 0.85 Br 0.15 ) 3 + 5 mol % MAPbCl 3 . A suitable solvent system is designed specifically for the slot-die coating technique. We demonstrate that our fabrication route is suitable for tandem solar cells without phase segregation. The slot-die coated wet halide perovskite is dried by a "nitrogen (N 2 )-knife" with high reproducibility and avoiding antisolvents. We explore varying annealing conditions and identify parameters allowing crystallization of the perovskite film into large grains reducing charge collection losses and enabling higher current density. At 150 °C, an optimized trade-off between crystallization and the PbI 2 aggregates on the film's top surface is found. Thus, we improve the cell stability and performance of both single-junction cells and tandems. Combining the 3halide top cells with a 120 μm thin saw damage etched commercial Czochralski industrial wafer, a 2-terminal monolithic tandem solar cell with a PCE of 25.2% on a 1 cm 2 active area is demonstrated with fully scalable processes., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Numerous phosphorus-rich metal phosphides containing both P-P bonds and metal-P bonds are known from the solid-state chemistry literature. A method to grow these materials in thin-film form would be desirable, as thin films are required in many applications and they are an ideal platform for high-throughput studies. In addition, the high density and smooth surfaces achievable in thin films are a significant advantage for characterization of transport and optical properties. Despite these benefits, there is hardly any published work on even the simplest binary phosphorus-rich phosphide films. Here, we demonstrate growth of single-phase CuP 2 films by a two-step process involving reactive sputtering of amorphous CuP 2+ x and rapid annealing in an inert atmosphere. At the crystallization temperature, CuP 2 is thermodynamically unstable with respect to Cu 3 P and P 4 . However, CuP 2 can be stabilized if the amorphous precursors are mixed on the atomic scale and are sufficiently close to the desired composition (neither too P poor nor too P rich). Fast formation of polycrystalline CuP 2 , combined with a short annealing time, makes it possible to bypass the diffusion processes responsible for decomposition. We find that thin-film CuP 2 is a 1.5 eV band gap semiconductor with interesting properties, such as a high optical absorption coefficient (above 10 5  cm -1 ), low thermal conductivity (1.1 W/(K m)), and composition-insensitive electrical conductivity (around 1 S/cm). We anticipate that our processing route can be extended to other phosphorus-rich phosphides that are still awaiting thin-film synthesis and will lead to a more complete understanding of these materials and of their potential applications.

Perovskite quantum dots (PQDs) have many properties that make them attractive for optoelectronic applications, including expanded compositional tunability and crystallographic stabilization. While they have not achieved the same photovoltaic (PV) efficiencies of top-performing perovskite thin films, they do reproducibly show high open circuit voltage ( V OC ) in comparison. Further understanding of the V OC attainable in PQDs as a function of surface passivation, contact layers, and PQD composition will further progress the field and may lend useful lessons for non-QD perovskite solar cells. Here, we use photoluminescence-based spectroscopic techniques to understand and identify the governing physics of the V OC in CsPbI 3 PQDs. In particular, we probe the effect of the ligand exchange and contact interfaces on the V OC and free charge carrier concentration. The free charge carrier concentration is orders of magnitude higher than in typical perovskite thin films and could be tunable through ligand chemistry. Tuning the PQD A-site cation composition via replacement of Cs + with FA + maintains the background carrier concentration but reduces the trap density by up to a factor of 40, reducing the V OC deficit. These results dictate how to improve PQD optoelectronic properties and PV device performance and explain the reduced interfacial recombination observed by coupling PQDs with thin-film perovskites for a hybrid absorber layer.

The rear interface of kesterite absorbers with Mo back contact represents one of the possible sources of nonradiative voltage losses (Δ V oc,nrad ) because of the reported decomposition reactions, an uncontrolled growth of MoSe 2 , or a nonoptimal electrical contact with high recombination. Several intermediate layers (IL), such as MoO 3 , TiN, and ZnO, have been tested to mitigate these issues, and efficiency improvements have been reported. However, the introduction of IL also triggers other effects such as changes in alkali diffusion, altered morphology, and modifications in the absorber composition, all factors that can also influence Δ V oc,nrad . In this study, the different effects are decoupled by designing a special sample that directly compares four rear structures (SLG, SLG/Mo, SLG/Al 2 O 3 , and SLG/Mo/Al 2 O 3 ) with a Na-doped kesterite absorber optimized for a device efficiency >10%. The IL of choice is Al 2 O 3 because of its reported beneficial effect to reduce the surface recombination velocity at the rear interface of solar cell absorbers. Identical annealing conditions and alkali distribution in the kesterite absorber are preserved, as measured by time-of-flight secondary ion mass spectrometry and energy-dispersive X-ray spectroscopy. The lowest Δ V oc,nrad of 290 mV is measured for kesterite grown on Mo, whereas the kesterite absorber on Al 2 O 3 exhibits higher nonradiative losses up to 350 mV. The anticipated field-effect passivation from Al 2 O 3 at the rear interface could not be observed for the kesterite absorbers prepared by the two-step process, further confirmed by an additional experiment with air annealing. Our results suggest that Mo with an in situ formed MoSe 2 remains a suitable back contact for high-efficiency kesterite devices.

Copper chalcogenide nanocrystals find applications in photovoltaic inks, bio labels, and thermoelectric materials. We reveal insights in the nucleation and growth during synthesis of anisotropic Cu 2 ZnSnS 4 nanocrystals by simultaneously performing in situ X-ray absorption spectroscopy (XAS) and small-angle X-ray scattering (SAXS). Real-time XAFS reveals that upon thiol injection into the reaction flask, a key copper thiolate intermediate species is formed within fractions of seconds, which decomposes further within a narrow temperature and time window to form copper sulfide nanocrystals. These nanocrystals convert into Cu 2 ZnSnS 4 nanorods by sequentially incorporating Sn and Zn. Real-time SAXS and ex situ TEM of aliquots corroborate these findings. Our work demonstrates how combined in situ X-ray absorption and small-angle X-ray scattering enables the understanding of mechanistic pathways in colloidal nanocrystal formation.

Through the optimization of the perovskite precursor composition and interfaces to selective contacts, we achieved a p-i-n-type perovskite solar cell (PSC) with a 22.3% power conversion efficiency (PCE). This is a new performance record for a PSC with an absorber bandgap of 1.63 eV. We demonstrate that the high device performance originates from a synergy between (1) an improved perovskite absorber quality when introducing formamidinium chloride (FACl) as an additive in the "triple cation" Cs 0.05 FA 0.79 MA 0.16 PbBr 0.51 I 2.49 (Cs-MAFA) perovskite precursor ink, (2) an increased open-circuit voltage, V OC , due to reduced recombination losses when using a lithium fluoride (LiF) interfacial buffer layer, and (3) high-quality hole-selective contacts with a self-assembled monolayer (SAM) of [2-(9 H -carbazol-9-yl)ethyl]phosphonic acid (2PACz) on ITO electrodes. While all devices exhibit a high performance after fabrication, as determined from current-density voltage, J - V , measurements, substantial differences in device performance become apparent when considering longer-term stability data. A reduced long-term stability of devices with the introduction of a LiF interlayer is compensated for by using FACl as an additive in the metal-halide perovskite thin-film deposition. Optimized devices maintained about 80% of the initial average PCE during maximum power point (MPP) tracking for >700 h. We scaled the optimized device architecture to larger areas and achieved fully laser patterned series-interconnected mini-modules with a PCE of 19.4% for a 2.2 cm 2 active area. A robust device architecture and reproducible deposition methods are fundamental for high performance and stable large-area single junction and tandem modules based on PSCs.

The earth-abundant ternary compound BaZrS 3 , which crystallizes in the perovskite-type structure, has come into view as a promising candidate for photovoltaic applications. We present the synthesis and characterization of polycrystalline perovskite-type BaZrS 3 thin films. BaZrO 3 precursor layers were deposited by pulsed laser deposition and sulfurized at various temperatures in an argon-diluted H 2 S atmosphere. We observe increasing incorporation of sulfur for higher annealing temperatures, accompanied by a red shift of the absorption edge, with a bandgap of E g = 1.99 eV and a large absorption strength >10 5 cm -1 obtained for sulfurization temperatures of 1000 °C. X-ray diffraction analysis and SEM indicate enhanced crystallization at the higher annealing temperatures, but no evidence for a crystalline solid solution between the BaZrO 3 and BaZrS 3 phases is found. The charge carrier sum mobility estimated from optical-pump-terahertz-probe spectroscopy indicates increasing mobilities with increasing sulfurization temperature, reaching maximum values of up to ∼2 cm 2 V -1 s -1 .

Ambient-pressure Kelvin probe and photoelectron yield spectroscopy methods were employed to investigate the impact of the KF and RbF postdeposition treatments (KF-PDT, RbF-PDT) on the electronic features of Cu(In,Ga)Se 2 (CIGSe) thin films and the CdS/CIGSe interface in a CdS thickness series that has been sequentially prepared during the chemical bath deposition (CBD) process depending on the deposition time. We observe distinct features correlated to the CBD-CdS growth stages. In particular, we find that after an initial CBD etching stage, the valence band maximum (VBM) of the CIGSe surface is significantly shifted (by 180-620 mV) toward the Fermi level. However, VBM positions at the surface of the CIGSe are still much below the VBM of the CIGSe bulk. The CIGSe surface band gap is found to depend on the type of postdeposition treatment, showing values between 1.46 and 1.58 eV, characteristic for a copper-poor CIGSe surface composition. At the CdS/CIGSe interface, the lowest VBM discontinuity is observed for the RbF-PDT sample. At this interface, a thin layer with a graded band gap is found. We also find that K and Rb act as compensating acceptors in the CdS layer. Detailed energy band diagrams of the CdS/CIGSe heterostructures are proposed.

CuI has been recently rediscovered as a p-type transparent conductor with a high figure of merit. Even though many metal iodides are hygroscopic, the effect of moisture on the electrical properties of CuI has not been clarified. In this work, we observe a 2-fold increase in the conductivity of CuI after exposure to ambient humidity for 5 h, followed by slight long-term degradation. Simultaneously, the work function of CuI decreases by almost 1 eV, which can explain the large spread in the previously reported work function values. The conductivity increase is partially reversible and is maximized at intermediate humidity levels. On the basis of the large intragrain mobility measured by THz spectroscopy, we suggest that hydration of grain boundaries may be beneficial for the overall hole mobility.

We assess a tandem photoelectrochemical cell consisting of a W:BiVO 4 photoanode top absorber and a CuBi 2 O 4 photocathode bottom absorber for overall solar water splitting. We show that the W:BiVO 4 photoanode oxidizes water and produces oxygen at potentials ≥0.7 V vs RHE when CoPi is added as a cocatalyst. However, the CuBi 2 O 4 photocathode does not produce a detectable amount of hydrogen from water reduction even when Pt or RuO x is added as a cocatalyst because the photocurrent primarily goes toward photocorrosion of CuBi 2 O 4 rather than proton reduction. Protecting the CuBi 2 O 4 photocathode with a CdS/TiO 2 heterojunction and adding RuO x as a cocatalyst prevents photocorrosion and allows for photoelectrochemical production of hydrogen at potentials ≤0.3 V vs RHE. A tandem photoelectrochemical cell composed of a W:BiVO 4 /CoPi photoanode and a CuBi 2 O 4 /CdS/TiO 2 /RuO x photocathode produces hydrogen which can be detected under illumination at an applied bias of ≥0.4 V. Since the valence band of BiVO 4 and conduction band of CuBi 2 O 4 are adequately positioned to oxidize water and reduce protons, we hypothesize that the applied bias is required to overcome the relatively low photovoltages of the photoelectrodes, that is, the relatively low quasi-Fermi level splitting within BiVO 4 and CuBi 2 O 4 . This work is the first experimental demonstration of hydrogen production from a BiVO 4 -CuBi 2 O 4 -based tandem cell and it provides important insights into the significance of photovoltage in tandem devices for overall water splitting, especially for cells containing CuBi 2 O 4 photocathodes.

Halide perovskites are a strong candidate for the next generation of photovoltaics. Chemical doping of halide perovskites is an established strategy to prepare the highest efficiency and most stable perovskite-based solar cells. In this study, we unveil the doping mechanism of halide perovskites using a series of alkaline earth metals. We find that low doping levels enable the incorporation of the dopant within the perovskite lattice, whereas high doping concentrations induce surface segregation. The threshold from low to high doping regime correlates to the size of the doping element. We show that the low doping regime results in a more n-type material, while the high doping regime induces a less n-type doping character. Our work provides a comprehensive picture of the unique doping mechanism of halide perovskites, which differs from classical semiconductors. We proved the effectiveness of the low doping regime for the first time, demonstrating highly efficient methylammonium lead iodide based solar cells in both n-i-p and p-i-n architectures.

We have developed a new noninvasive optical method for monitoring charge carrier diffusion and mobility in semiconductor thin films in the direction perpendicular to the surface which is most relevant for devices. The method is based on standard transient absorption measurements carried out in reflectance and transmittance modes at wavelengths below the band gap where the transient response is mainly determined by the change in refractive index, which in turn depends on the distribution of photogenerated carriers across the film. This distribution is initially inhomogeneous because of absorption at the excitation wavelength and becomes uniform over time via diffusion. By modeling these phenomena we can determine the diffusion constant and respective mobility. Applying the method to a 500 nm thick triple cation FAMACs perovskite film revealed that homogeneous carrier distribution is established in few hundred picoseconds, which is consistent with mobility of 66 cm 2  (V s) -1 .

Doped spiro-OMeTAD at present is the most commonly used hole transport material (HTM) in n-i-p-type perovskite solar cells, enabling high efficiencies around 22%. However, the required dopants were shown to induce nonradiative recombination of charge carriers and foster degradation of the solar cell. Here, in a novel approach, highly conductive and inexpensive water-free poly(3,4-ethylenedioxythiophene) (PEDOT) is used to replace these dopants. The resulting spiro-OMeTAD/PEDOT (SpiDOT) mixed films achieve higher lateral conductivities than layers of doped spiro-OMeTAD. Furthermore, combined transient and steady-state photoluminescence studies reveal a passivating effect of PEDOT, suppressing nonradiative recombination losses at the perovskite/HTM interface. This enables excellent quasi-Fermi level splitting values of up to 1.24 eV in perovskite/SpiDOT layer stacks and high open-circuit voltages ( V OC ) up to 1.19 V in complete solar cells. Increasing the amount of dopant-free spiro-OMeTAD in SpiDOT layers is shown to enhance hole extraction and thereby improves the fill factor in solar cells. As a consequence, stabilized efficiencies up to 18.7% are realized, exceeding cells with doped spiro-OMeTAD as a HTM in this study. Moreover, to the best of our knowledge, these results mark the lowest nonradiative recombination loss in the V OC (140 mV with respect to the Shockley-Queisser limit) and highest efficiency reported so far for perovskite solar cells using PEDOT as a HTM.