Laminated Perovskite Photovoltaics: Enabling Novel Layer Combinations and Device Architectures

High‐efficiency perovskite‐based solar cells can be fabricated via either solution‐processing or vacuum‐based thin‐film deposition. However, both approaches limit the choice of materials and the accessible device architectures, due to solvent incompatibilities or possible layer damage by vacuum techniques. To overcome these limitations, the lamination of two independently processed half‐stacks of the perovskite solar cell is presented in this work. By laminating the two half‐stacks at an elevated temperature (≈90 °C) and pressure (≈50 MPa), the polycrystalline perovskite thin‐film recrystallizes and the perovskite/charge transport layer (CTL) interface forms an intimate electrical contact. The laminated perovskite solar cells with tin oxide and nickel oxide as CTLs exhibit power conversion efficiencies of up to 14.6%. Moreover, they demonstrate long‐term and high‐temperature stability at temperatures of up to 80 °C. This freedom of design is expected to access both novel device architectures and pairs of CTLs that remain usually inaccessible

Drying Dynamics of Solution‐Processed Perovskite Thin‐Film Photovoltaics: In Situ Characterization, Modeling, and Process Control

A key challenge for the commercialization of perovskite photovoltaics is the transfer of high‐quality spin coated perovskite thin‐films toward applying industry‐scale thin‐film deposition techniques, such as slot‐die coating, spray coating, screen printing, or inkjet printing. Due to the complexity of the formation of polycrystalline perovskite thin‐films from the precursor solution, efficient strategies for process transfer require advancing the understanding of the involved dynamic processes. This work investigates the fundamental interrelation between the drying dynamics of the precursor solution thin‐film and the quality of the blade coated polycrystalline perovskite thin‐films. Precisely defined drying conditions are established using a temperature‐stabilized drying channel purged with a laminar flow of dry air. The dedicated channel is equipped with laser reflectometry at multiple probing positions, allowing for in situ monitoring of the perovskite solution thin‐film thickness during the drying process. Based on the drying dynamics as measured at varying drying parameters, namely at varying temperature and laminar air flow velocity, a quantitative model on the drying of perovskite thin‐films is derived. This model enables process transfer to industry‐scale deposition systems beyond brute force optimization. Via this approach, homogeneous and pinhole‐free blade coated perovskite thin‐films are fabricated, demonstrating high power conversion efficiencies of up to 19.5% (17.3% stabilized) in perovskite solar cells

Vacuum‐Assisted Growth of Low‐Bandgap Thin Films (FA0.8_{0.8}MA0.2_{0.2}Sn0.5_{0.5}Pb0.5_{0.5}I3_{3}) for All‐Perovskite Tandem Solar Cells

All-perovskite multijunction photovoltaics, combining a wide-bandgap (WBG) perovskite top solar cell (EG ≈1.6–1.8 eV) with a low-bandgap (LBG) perovskite bottom solar cell (EG 33%. While the research on WBG perovskite solar cells has advanced rapidly over the past decade, LBG perovskite solar cells lack PCE as well as stability. In this work, vacuum-assisted growth control (VAGC) of solution-processed LBG perovskite thin films based on mixed Sn–Pb perovskite compositions is reported. The reported perovskite thin films processed by VAGC exhibit large columnar crystals. Compared to the well-established processing of LBG perovskites via antisolvent deposition, the VAGC approach results in a significantly enhanced charge-carrier lifetime. The improved optoelectronic characteristics enable high-performance LBG perovskite solar cells (1.27 eV) with PCEs up to 18.2% as well as very efficient four-terminal all-perovskite tandem solar cells with PCEs up to 23%. Moreover, VAGC leads to promising reproducibility and potential in the fabrication of larger active-area solar cells up to 1 cm²

Nanostructured front electrodes for perovskite/c-Si tandem photovoltaics

The rise in the power conversion efficiency (PCE) of perovskite solar cells has triggered enormous interest in perovskite-based tandem photovoltaics. One key challenge is to achieve high transmission of low energy photons into the bottom cell. Here, nanostructured front electrodes for 4-terminal perovskite/crystalline-silicon (perovskite/c-Si) tandem solar cells are developed by conformal deposition of indium tin oxide (ITO) on self-assembled polystyrene nanopillars. The nanostructured ITO is optimized for reduced reflection and increased transmission with a tradeoff in increased sheet resistance. In the optimum case, the nanostructured ITO electrodes enhance the transmittance by ∼7% (relative) compared to planar references. Perovskite/c-Si tandem devices with nanostructured ITO exhibit enhanced short-circuit current density (2.9 mA/cm2 absolute) and PCE (1.7% absolute) in the bottom c-Si solar cell compared to the reference. The improved light in-coupling is more pronounced for elevated angle of incidence. Energy yield enhancement up to ∼10% (relative) is achieved for perovskite/c-Si tandem architecture with the nanostructured ITO electrodes. It is also shown that these nanostructured ITO electrodes are also compatible with various other perovskite-based tandem architectures and bear the potential to improve the PCE up to 27.0%

Optimization of SnO2_{2} electron transport layer for efficient planar perovskite solar cells with very low hysteresis†

Nanostructured tin oxide (SnO$_{2}$) is a very promising electron transport layer (ETL) for perovskite solar cells (PSCs) that allows low-temperature processing in the planar n–i–p architecture. However, minimizing current–voltage (J–V) hysteresis and optimizing charge extraction for PSCs in this architecture remains a challenge. In response to this, we study and optimize different types of single- and bilayer SnO$_{2}$ ETLs. Detailed characterization of the optoelectronic properties reveals that a bilayer ETL composed of lithium (Li)-doped compact SnO$_{2}$ (c(Li)-SnO$_{2}$) at the bottom and potassium-capped SnO$_{2}$ nanoparticle layers (NP-SnO$_{2}$) at the top enhances the electron extraction and charge transport properties of PSCs and reduces the degree of ion migration. This results in an improved PCE and a strongly reduced J–V hysteresis for PSCs with a bilayer c(Li)-NP-SnO$_{2}$ ETL as compared to reference PSCs with a single-layer or undoped bilayer ETL. The champion PSC with c(Li)-NP-SnO$_{2}$ ETL shows a high stabilized PCE of up to 18.5% compared to 15.7%, 12.5% and 16.3% for PSCs with c-SnO$_{2}$, c(Li)-SnO$_{2}$ and c-NP-SnO$_{2}$ as ETL, respectively

From Groundwork to Efficient Solar Cells: On the Importance of the Substrate Material in Co‐Evaporated Perovskite Solar Cells

Vacuum‐based deposition of optoelectronic thin films has a long‐standing history. However, in the field of perovskite‐based photovoltaics, these techniques are still not as advanced as their solution‐based counterparts. Although high‐efficiency vacuum‐based perovskite solar cells reaching power conversion efficiencies (PCEs) above 20% are reported, the number of studies on the underlying physical and chemical mechanism of the co‐evaporation of lead iodide and methylammonium iodide is low. In this study, the impact of one of the most crucial process parameters in vacuum processes — the substrate material — is studied. It is shown that not only the morphology of the co‐evaporated perovskite thin films is significantly influenced by the surface polarity of the substrate material, but also the incorporation of the organic compound into the perovskite framework. Based on these studies, a selection guide for suitable substrate materials for efficient co‐evaporated perovskite thin films is derived. This selection guide points out that the organic vacuum‐processable hole transport material 2,2″,7,7″‐tetra(N,N‐di‐p‐tolyl)amino‐9,9‐spirobifluorene is an ideal candidate for the fabrication of efficient all‐evaporated perovskite solar cells, demonstrating PCEs above 19%. Furthermore, building on the insights into the formation of the perovskite thin films on different substrate materials, a basic crystallization model for co‐evaporated perovskite thin films is suggested

From Groundwork to Efficient Solar Cells: On the Importance of the Substrate Material in Co‐Evaporated Perovskite Solar Cells

Vacuum-based deposition of optoelectronic thin films has a long-standing history. However, in the field of perovskite-based photovoltaics, these techniques are still not as advanced as their solution-based counterparts. Although high-efficiency vacuum-based perovskite solar cells reaching power conversion efficiencies (PCEs) above 20% are reported, the number of studies on the underlying physical and chemical mechanism of the co-evaporation of lead iodide and methylammonium iodide is low. In this study, the impact of one of the most crucial process parameters in vacuum processes—the substrate material—is studied. It is shown that not only the morphology of the co-evaporated perovskite thin films is significantly influenced by the surface polarity of the substrate material, but also the incorporation of the organic compound into the perovskite framework. Based on these studies, a selection guide for suitable substrate materials for efficient co-evaporated perovskite thin films is derived. This selection guide points out that the organic vacuum-processable hole transport material 2,2″,7,7″-tetra(N,N-di-p-tolyl)amino-9,9-spirobifluorene is an ideal candidate for the fabrication of efficient all-evaporated perovskite solar cells, demonstrating PCEs above 19%. Furthermore, building on the insights into the formation of the perovskite thin films on different substrate materials, a basic crystallization model for co-evaporated perovskite thin films is suggested

The Electronic Structure of MAPI‐Based Perovskite Solar Cells: Detailed Band Diagram Determination by Photoemission Spectroscopy Comparing Classical and Inverted Device Stacks

High power conversion efficiency (PCE) perovskite solar cells (PSCs) rely on optimal alignment of the energy bands between the perovskite absorber and the adjacent charge extraction layers. However, since most of the materials and devices of high performance are prepared by solution‐based techniques, a deposition of films with thicknesses of a few nanometers and therefore a detailed analysis of surface and interface properties remains difficult. To identify the respective photoactive interfaces, photoelectron spectroscopy measurements are performed on device stacks of methylammonium‐lead‐iodide (MAPI)‐based PSCs in classical and inverted architectures in the dark and under illumination at open‐circuit conditions. The analysis shows that vacuum‐deposited MAPI perovskite absorber layers are n‐type, independent of the architecture and of the charge transport layer that it is deposited on (n‐type SnO$_{2}$ or p‐type NiO$_{x}$). It is found that the majority of the photovoltage is formed at the n‐MAPI/p‐HEL (hole extraction layer) junction for both architectures, highlighting the importance of this interface for further improvement of the photovoltage and therefore also the PCE. Finally, an experimentally derived band diagram of the completed devices for the dark and the illuminated case is presented

The Electronic Structure of MAPI‐Based Perovskite Solar Cells: Detailed Band Diagram Determination by Photoemission Spectroscopy Comparing Classical and Inverted Device Stacks

High power conversion efficiency (PCE) perovskite solar cells (PSCs) rely on optimal alignment of the energy bands between the perovskite absorber and the adjacent charge extraction layers. However, since most of the materials and devices of high performance are prepared by solution‐based techniques, a deposition of films with thicknesses of a few nanometers and therefore a detailed analysis of surface and interface properties remains difficult. To identify the respective photoactive interfaces, photoelectron spectroscopy measurements are performed on device stacks of methylammonium‐lead‐iodide (MAPI)‐based PSCs in classical and inverted architectures in the dark and under illumination at open‐circuit conditions. The analysis shows that vacuum‐deposited MAPI perovskite absorber layers are n‐type, independent of the architecture and of the charge transport layer that it is deposited on (n‐type SnO₂ or p‐type NiOₓ). It is found that the majority of the photovoltage is formed at the n‐MAPI/p‐HEL (hole extraction layer) junction for both architectures, highlighting the importance of this interface for further improvement of the photovoltage and therefore also the PCE. Finally, an experimentally derived band diagram of the completed devices for the dark and the illuminated case is presented