Rahim Munir

Hybrid organic–inorganic inks flatten the energy landscape in colloidal quantum dot solids

Bandtail states in disordered semiconductor materials result in losses in open-circuit voltage (Voc) and inhibit carrier transport in photovoltaics. For colloidal quantum dot (CQD) films that promise low-cost, large-area, air-stable photovoltaics, bandtails are determined by CQD synthetic polydispersity and inhomogeneous aggregation during the ligand-exchange process. Here we introduce a new method for the synthesis of solution-phase ligand-exchanged CQD inks that enable a flat energy landscape and an advantageously high packing density. In the solid state, these materials exhibit a sharper bandtail and reduced energy funnelling compared with the previous best CQD thin films for photovoltaics. Consequently, we demonstrate solar cells with higher Voc and more efficient charge injection into the electron acceptor, allowing the use of a closer-to-optimum bandgap to absorb more light. These enable the fabrication of CQD solar cells made via a solution-phase ligand exchange, with a certified power conversion efficiency of 11.28%. The devices are stable when stored in air, unencapsulated, for over 1,000 h.

Stable high efficiency two-dimensional perovskite solar cells via cesium doping

Two-dimensional (2D) organic–inorganic perovskites have recently emerged as one of the most important thin-film solar cell materials owing to their excellent environmental stability. The remaining major pitfall is their relatively poor photovoltaic performance in contrast to 3D perovskites. In this work we demonstrate cesium cation (Cs+) doped 2D (BA)2(MA)3Pb4I13 perovskite solar cells giving a power conversion efficiency (PCE) as high as 13.7%, the highest among the reported 2D devices, with excellent humidity resistance. The enhanced efficiency from 12.3% (without Cs+) to 13.7% (with 5% Cs+) is attributed to perfectly controlled crystal orientation, an increased grain size of the 2D planes, superior surface quality, reduced trap-state density, enhanced charge-carrier mobility and charge-transfer kinetics. Surprisingly, it is found that the Cs+ doping yields superior stability for the 2D perovskite solar cells when subjected to a high humidity environment without encapsulation. The device doped using 5% Cs+ degrades only ca. 10% after 1400 hours of exposure in 30% relative humidity (RH), and exhibits significantly improved stability under heating and high moisture environments. Our results provide an important step toward air-stable and fully printable low dimensional perovskites as a next-generation renewable energy source.

Solution-processed inorganic copper(I) thiocyanate (CuSCN) hole transporting layers for efficient p–i–n perovskite solar cells

CuSCN is a highly transparent, highly stable, low cost and easy to solution process HTL that is proposed as a low cost replacement to existing organic and inorganic metal oxide hole transporting materials. Here, we demonstrate hybrid organic–inorganic perovskite-based p–i–n planar heterojunction solar cells using a solution-processed copper(I) thiocyanate (CuSCN) bottom hole transporting layer (HTL). CuSCN, with its high work function, increases the open circuit voltage (Voc) by 0.23 V to 1.06 V as compared with devices based on the well-known poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) (0.83 V), resulting in a superior power conversion efficiency (PCE) of 10.8% without any notable hysteresis. Photoluminescence measurements suggest a similar charge transfer efficiency at the HTL/perovskite interface to PEDOT:PSS. However, we observe more efficient light harvesting in the presence of CuSCN at shorter wavelengths despite PEDOT:PSS being more transparent. Further investigation of the microstructure and morphology reveals differences in the crystallographic texture of the polycrystalline perovskite film, suggesting templated perovskite growth on the surface of CuSCN. The successful demonstration of the solution-processed inorganic HTL using simple and low temperature processing routes bodes well for the development of reliable and efficient flexible p–i–n perovskite modules or for integration as a front cell in hybrid tandem solar cells.

Hybrid Perovskite Thin‐Film Photovoltaics: In Situ Diagnostics and Importance of the Precursor Solvate Phases

Solution-processed hybrid perovskite semiconductors attract a great deal of attention, but little is known about their formation process. The one-step spin-coating process of perovskites is investigated in situ, revealing that thin-film formation is mediated by solid-state precursor solvates and their nature. The stability of these intermediate phases directly impacts the quality and reproducibility of thermally converted perovskite films and their photovoltaic performance.

Stable High‐Performance Perovskite Solar Cells via Grain Boundary Passivation

The trap states at grain boundaries (GBs) within polycrystalline perovskite films deteriorate their optoelectronic properties, making GB engineering particularly important for stable high-performance optoelectronic devices. It is demonstrated that trap states within bulk films can be effectively passivated by semiconducting molecules with Lewis acid or base functional groups. The perovskite crystallization kinetics are studied using in situ synchrotron-based grazing-incidence X-ray scattering to explore the film formation mechanism. A model of the passivation mechanism is proposed to understand how the molecules simultaneously passivate the Pb-I antisite defects and vacancies created by under-coordinated Pb atoms. In addition, it also explains how the energy offset between the semiconducting molecules and the perovskite influences trap states and intergrain carrier transport. The superior optoelectronic properties are attained by optimizing the molecular passivation treatments. These benefits are translated into significant enhancements of the power conversion efficiencies to 19.3%, as well as improved environmental and thermal stability of solar cells. The passivated devices without encapsulation degrade only by ≈13% after 40 d of exposure in 50% relative humidity at room temperature, and only ≈10% after 24 h at 80 °C in controlled environment.

Highly efficient polymer solar cells with printed photoactive layer: rational process transfer from spin-coating

Scalable and continuous roll-to-roll manufacturing is at the heart of the promise of low-cost and high throughput manufacturing of solution-processed photovoltaics. Yet, to date the vast majority of champion organic solar cells reported in the literature rely on spin-coating of the photoactive bulk heterojunction (BHJ) layer, with the performance of printed solar cells lagging behind in most instances. Here, we investigate the performance gap between polymer solar cells prepared by spin-coating and blade-coating the BHJ layer for the important class of modern polymers exhibiting no long range crystalline order. We find that thickness parity does not always yield performance parity even when using identical formulations. Significant differences in the drying kinetics between the processes are found to be responsible for BHJ nanomorphology differences. We propose an approach which benchmarks the film drying kinetics and associated BHJ nanomorphology development against those of the champion laboratory devices prepared by spin-coating the BHJ layer by adjusting the process temperature. If the optimization requires the solution concentration to be changed, then it is crucial to maintain the additive-to-solute volume ratio. Emulating the drying kinetics of spin-coating is also shown to help achieve morphological and performance parities. We put this approach to the test and demonstrate printed PTB7:PC71BM polymer solar cells with efficiency of 9% and 6.5% PCEs on glass and flexible PET substrates, respectively. We further demonstrate performance parity for two other popular donor polymer systems exhibiting rigid backbones and absence of a long range crystalline order, achieving a PCE of 9.7%, the highest efficiency reported to date for a blade coated organic solar cell. The rational process transfer illustrated in this study should help the broader and successful adoption of scalable printing methods for these material systems.

Study on the enhanced and stable field emission behavior of a novel electrosprayed Al-doped ZnO bilayer film

A novel electrosprayed bilayer film composed of an over-layer (L2) of aluminium-doped ZnO (AZO) nanoflakes (NF-AZO) and a under-layer (L1) of AZO nanocrystallites structure (NC-AZO) named BL:NF/NC-AZO is studied as an excellent field-emitter. The XRD pattern demonstrated that the doped bilayer film has preferential growth along the c-axis with hexagonal wurtzite structure and the (0 0 2) peak shifted toward the larger angle side after doping. The lowest turn-on field of ∼2.8 V μm−1, highest emission current density of 1.95 mA cm−2 is obtained for BL:NF/NC-AZO under the field of 6.8 V μm−1 and as well as the highest field enhancement factor (β) is estimated to be 4370 ± 3, compared to pure ZnO bilayer film (BL:NF/NC-ZnO) and also better than NC-AZO film and possesses the excellent long term stability of emission current. The PL intensity of doped ZnO bilayer film is very much stronger than pure ZnO bilayer structure. The superior field emission properties are attributed to the better morphologies, Al-doping and better crystallinity of bilayer AZO films.

Programmable and coherent crystallization of semiconductors

Programmable crystallization of thin films produces patterns and bespoke microstructures for semiconductor applications. The functional properties and technological utility of polycrystalline materials are largely determined by the structure, geometry, and spatial distribution of their multitude of crystals. However, crystallization is seeded through stochastic and incoherent nucleation events, limiting the ability to control or pattern the microstructure, texture, and functional properties of polycrystalline materials. We present a universal approach that can program the microstructure of materials through the coherent seeding of otherwise stochastic homogeneous nucleation events. The method relies on creating topographic variations to seed nucleation and growth at designated locations while delaying nucleation elsewhere. Each seed can thus produce a coherent growth front of crystallization with a geometry designated by the shape and arrangement of seeds. Periodic and aperiodic crystalline arrays of functional materials, such as semiconductors, can thus be created on demand and with unprecedented sophistication and ease by patterning the location and shape of the seeds. This approach is used to demonstrate printed arrays of organic thin-film transistors with remarkable performance and reproducibility owing to their demonstrated spatial control over the microstructure of organic and inorganic polycrystalline semiconductors.

Enhanced Electrical Conductivity of Molecularly p-Doped Poly(3-hexylthiophene) through Understanding the Correlation with Solid-State Order

Molecular p-doping of the conjugated polymer poly(3-hexylthiophene) (P3HT) with 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) is a widely studied model system. Underlying structure–property relationships are poorly understood because processing and doping are often carried out simultaneously. Here, we exploit doping from the vapor phase, which allows us to disentangle the influence of processing and doping. Through this approach, we are able to establish how the electrical conductivity varies with regard to a series of predefined structural parameters. We demonstrate that improving the degree of solid-state order, which we control through the choice of processing solvent and regioregularity, strongly increases the electrical conductivity. As a result, we achieve a value of up to 12.7 S cm–1 for P3HT:F4TCNQ. We determine the F4TCNQ anion concentration and find that the number of (bound + mobile) charge carriers of about 10–4 mol cm–3 is not influenced by the degree of solid-state order. Thus, the observed increase in electrical conductivity by almost 2 orders of magnitude can be attributed to an increase in charge-carrier mobility to more than 10–1 cm2 V–1 s–1. Surprisingly, in contrast to charge transport in undoped P3HT, we find that the molecular weight of the polymer does not strongly influence the electrical conductivity, which highlights the need for studies that elucidate structure–property relationships of strongly doped conjugated polymers.

Phase Transition Control for High Performance Ruddlesden-Popper Perovskite Solar Cells

Ruddlesden-Popper reduced-dimensional hybrid perovskite (RDP) semiconductors have attracted significant attention recently due to their promising stability and excellent optoelectronic properties. Here, the RDP crystallization mechanism in real time from liquid precursors to the solid film is investigated, and how the phase transition kinetics influences phase purity, quantum well orientation, and photovoltaic performance is revealed. An important template-induced nucleation and growth of the desired (BA)2 (MA)3 Pb4 I13 phase, which is achieved only via direct crystallization without formation of intermediate phases, is observed. As such, the thermodynamically preferred perpendicular crystal orientation and high phase purity are obtained. At low temperature, the formation of intermediate phases, including PbI2 crystals and solvate complexes, slows down intercalation of ions and increases nucleation barrier, leading to formation of multiple RDP phases and orientation randomness. These insights enable to obtain high quality (BA)2 (MA)3 Pb4 I13 films with preferentially perpendicular quantum well orientation, high phase purity, smooth film surface, and improved optoelectronic properties. The resulting devices exhibit high power conversion efficiency of 12.17%. This work should help guide the perovskite community to better control Ruddlesden-Popper perovskite structure and further improve optoelectronic and solar cell devices.