In Situ IR Spectroscopy Studies of Atomic Layer-Deposited SnO₂ on Formamidinium-Based Lead Halide Perovskite

Perovskite photovoltaics has achieved conversion efficiencies of 26.0% by optimizing the optoelectronic properties of the absorber and its interfaces with charge transport layers (CTLs). However, commonly adopted organic CTLs can lead to parasitic absorption and device instability. Therefore, metal oxides like atomic layer-deposited (ALD) SnO2 in combination with fullerene-based electron transport layers have been introduced to enhance mechanical and thermal stability. Instead, when ALD SnO2 is directly processed on the absorber, i.e., without the fullerene layer, chemical modifications of the inorganic fraction of the perovskite occur, compromising the device performance. This study focuses on the organic fraction, particularly the formamidinium cation (FA+), in a CsFAPb(I,Br)3 perovskite. By employing in situ infrared spectroscopy, we investigate the impact of ALD processing on the perovskite, such as vacuum level, temperature, and exposure to half and full ALD cycles using tetrakis(dimethylamido)-Sn(IV) (TDMA-Sn) and H2O. We observe that exposing the absorber to vacuum conditions or water half-cycles has a negligible effect on the chemistry of the perovskite. However, prolonged exposure at 100 °C for 90 min results in a loss of 0.7% of the total formamidinium-related vibrational features compared to the pristine perovskite. Supported by density functional theory calculations, we speculate that FA+ deprotonates and that formamidine desorbs from the perovskite surface. Furthermore, the interaction between TDMA-Sn and FA+ induces more decomposition of the perovskite surface compared to vacuum, temperature, or H2O exposure. During the exposure to 10 ALD half-cycles of TDMA-Sn, 4% of the total FA+-related infrared features are lost compared to the pristine perovskite. Additionally, IR spectroscopy suggests the formation and trapping of sym-triazine, i.e., a decomposition product of FA+. These studies enable to decouple the effects occurring during direct ALD processing on the perovskite and highlight the crucial role of the Sn precursor in affecting the perovskite surface chemistry and compromising the device performance

Atomic insights into the oxygen incorporation in atomic layer deposited conductive nitrides and its mitigation by energetic ions

Oxygen is often detected as impurity in metal and metal nitride films prepared by atomic layer deposition (ALD) and its presence has profound and adverse effects on the material properties. In this work, we present the case study of HfNx films prepared by plasma-assisted ALD by alternating exposures of CpHf(NMe2)3 and H2 plasma. First, we identify the primary source of O contamination in the film. Specifically, we find that the extent of O incorporation in HfNx films is determined by the flux of background H2O/O2 residual gases reaching the HfNx surface during the ALD process and leads to the formation of Hf–O bonds. Then, we report on the decrease in the concentration of Hf–O bonds in the film upon application of an external radiofrequency (rf) substrate bias during the H2 plasma step. The experimental work is accompanied by first principles calculations to gain insights into the O incorporation and its mitigation upon the impingement of energetic ions on the surface. Specifically, we find that the dissociative binding of H2O on a bare HfN surface is highly favored, resulting in surface Hf–OH groups and concomitant increase in the oxidation state of Hf. We also show that energetic cations (H+, H2+ and H3+) lead to the dissociation of surface Hf–OH bonds, H2O formation, and its subsequent desorption from the surface. The latter is followed by reduction of the Hf oxidation state, presumably by H˙ radicals. The atomic-level understanding obtained in this work on O incorporation and its abstraction are expected to be crucial to prevent O impurities in the HfNx films and contribute to the fabrication of other technologically relevant low resistivity ALD-grown transition metal nitride films

Enhanced Self-Assembled Monolayer Surface Coverage by ALD NiO in p-i-n Perovskite Solar Cells

Metal halide perovskites have attracted tremendous attention due to their excellent electronic properties. Recent advancements in device performance and stability of perovskite solar cells (PSCs) have been achieved with the application of self-assembled monolayers (SAMs), serving as stand-alone hole transport layers in the p-i-n architecture. Specifically, phosphonic acid SAMs, directly functionalizing indium-tin oxide (ITO), are presently adopted for highly efficient devices. Despite their successes, so far, little is known about the surface coverage of SAMs on ITO used in PSCs application, which can affect the device performance, as non-covered areas can result in shunting or low open-circuit voltage. In this study, we investigate the surface coverage of SAMs on ITO and observe that the SAM of MeO-2PACz ([2-(3,6-dimethoxy-9H-carbazol-9-yl)ethyl]phosphonic acid) inhomogeneously covers the ITO substrate. Instead, when adopting an intermediate layer of NiO between ITO and the SAM, the homogeneity, and hence the surface coverage of the SAM, improve. In this work, NiO is processed by plasma-assisted atomic layer deposition (ALD) with Ni(MeCp)2 as the precursor and O2 plasma as the co-reactant. Specifically, the presence of ALD NiO leads to a homogeneous distribution of SAM molecules on the metal oxide area, accompanied by a high shunt resistance in the devices with respect to those with SAM directly processed on ITO. At the same time, the SAM is key to the improvement of the open-circuit voltage of NiO + MeO-2PACz devices compared to those with NiO alone. Thus, the combination of NiO and SAM results in a narrower distribution of device performance reaching a more than 20% efficient champion device. The enhancement of SAM coverage in the presence of NiO is corroborated by several characterization techniques including advanced imaging by transmission electron microscopy (TEM), elemental composition quantification by Rutherford backscattering spectrometry (RBS), and conductive atomic force microscopy (c-AFM) mapping. We believe this finding will further promote the usage of phosphonic acid based SAM molecules in perovskite PV. </p

Electrochemical Sensing with Spatially Patterned Pt Octahedra Electrodes

Locally controlling the position of electrodes in 3D can open new avenues to collect electrochemical signals in complex sensing environments. Implementing such electrodes via an electrical network requires advanced fabrication approaches. This work uses corner lithography and Pt ALD to produce electrochemical 3D electrodes. The approach allows the fabrication of (sub)micrometer size Pt octahedra electrodes spatially supported over 3D fractal-like structures. As a proof of concept, electrochemical sensing of ferrocyanide in biofouling environments, e.g., bovine serum albumin (BSA) and Pseudomonas aeruginosa (P. aeruginosa), is assessed. Differences between before and after BSA addition show a reduction in the active electrode surface area (ΔAeff) ≈49% ± 7% for the flat electrode. In comparison, a ΔAeff reduction of 25% ± 2% for the 3D electrode has been found. The results are accompanied by a 24% ± 16% decrease in peak current for the flat Pt substrate and a 14% ± 5% decrease in peak current for the 3D electrode 24 h after adding BSA. In the case of P. aeruginosa, the 3D electrode retains electrochemical signals, while the flat electrode does not. The results demonstrate that the 3D Pt electrodes are more stable than their flat counterparts under biofouling conditions.</p

Area-selective atomic layer deposition of In2O3 : H using a μ-plasma printer for local area activation

Researchers present a novel method for area-selective atomic layer deposition (AS-ALD) large-area electronics. It is a direct-write ALD process of In 2O 3:H, a highly promising and relevant transparent conductive oxide (TCO) material which makes use of printing technology for surface activation. first the surface of H-terminated silicon materials is locally activated by a μ-plasma printer in air or O 2, and In 2O 3:H is deposited selectively on the activated areas. The selectivity stems from the fact that ALD In 2O 3:H leads to very long nucleation delays on H-terminated silicon materials

Crystalline silicon solar cells with thin poly-SiO_x carrier-selective passivating contacts for perovskite/c-Si tandem applications

Single junction crystalline silicon (c-Si) solar cells are reaching their practical efficiency limit whereas perovskite/c-Si tandem solar cells have achieved efficiencies above the theoretical limit of single junction c-Si solar cells. Next to low-thermal budget silicon heterojunction architecture, high-thermal budget carrier-selective passivating contacts (CSPCs) based on polycrystalline-SiOx (poly-SiOx) also constitute a promising architecture for high efficiency perovskite/c-Si tandem solar cells. In this work, we present the development of c-Si bottom cells based on high temperature poly-SiOx CSPCs and demonstrate novel high efficiency four-terminal (4T) and two-terminal (2T) perovskite/c-Si tandem solar cells. First, we tuned the ultra-thin, thermally grown SiOx. Then we optimized the passivation properties of p-type and n-type doped poly-SiOx CSPCs. Here, we have optimized the p-type doped poly-SiOx CSPC on textured interfaces via a two-step annealing process. Finally, we integrated such bottom solar cells in both 4T and 2T tandems, achieving 28.1% and 23.2% conversion efficiency, respectively.</p

Proton Radiation Hardness of Perovskite Tandem Photovoltaics.

Monolithic [Cs0.05(MA0. 17FA0. 83)0.95]Pb(I0.83Br0.17)3/Cu(In,Ga)Se2 (perovskite/CIGS) tandem solar cells promise high performance and can be processed on flexible substrates, enabling cost-efficient and ultra-lightweight space photovoltaics with power-to-weight and power-to-cost ratios surpassing those of state-of-the-art III-V semiconductor-based multijunctions. However, to become a viable space technology, the full tandem stack must withstand the harsh radiation environments in space. Here, we design tailored operando and ex situ measurements to show that perovskite/CIGS cells retain over 85% of their initial efficiency even after 68 MeV proton irradiation at a dose of 2 × 1012 p+/cm2. We use photoluminescence microscopy to show that the local quasi-Fermi-level splitting of the perovskite top cell is unaffected. We identify that the efficiency losses arise primarily from increased recombination in the CIGS bottom cell and the nickel-oxide-based recombination contact. These results are corroborated by measurements of monolithic perovskite/silicon-heterojunction cells, which severely degrade to 1% of their initial efficiency due to radiation-induced recombination centers in silicon.F.L. acknowledges financial support from the Alexander von Humboldt Foundation via the Feodor Lynen program and thanks Prof. Sir R. Friend for supporting his Fellowship at the Cavendish Laboratory. This work was supported by the European Research Council (ERC) under the European Union’s Horizon 2020 research and innovation programme (HYPERION, grant agreement number 756962). M.J, A.A.A., E.K., and S.A. acknowledge financial support from the German Federal Ministry of Education and Research (BMBF) via program “Materialforschung für die Energiewende” (grant no. 03SF0540), by the German Federal Ministry for Economic Affairs and Energy (BMWi) through the ‘PersiST’ project (Grant No. 0324037C). T.B. C.A.K. and R.S. acknowledge funding by BMWi through the speedCIGS (grant no. 0324095E) and EFFCIS project (grant no. 0324076D). D.K. and M.C. acknowledge financial support from the Dutch Ministry of Economic Affairs, via The Top-consortia Knowledge and Innovation (TKI) Program ‘‘Photovoltaic modules based on a p-i-n stack, manufactured on a roll-to-roll line featuring high efficiency, stability and strong market perspective’’ (PVPRESS) (TEUE118010) and “Bridging the voltage gap” (BRIGHT) (1721101). K. F. acknowledges the George and Lilian Schiff Fund, the Engineering and Physical Sciences Research Council (EPSRC), the Winton Sustainability Fellowship, and the Cambridge Trust for funding. S.D.S. acknowledges the Royal Society and Tata Group (UF150033). The authors acknowledge the EPSRC for funding (EP/R023980/1). This project has received funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie grant agreement No. 841265. A.R.B. acknowledges funding from a Winton Studentship, Oppenheimer Studentship, and funding from the Engineering and Physical Sciences Research Council (EPSRC) Doctoral Training Centre in Photovoltaics (CDT-PV). K.G. acknowledges the Polish Ministry of Science and Higher Education within the Mobilnosc Plus program (Grant No. 1603/MOB/V/2017/0)