The energy costs associated with separating tightly bound excitons (photoinduced electron-hole pairs) and extracting free charges from highly disordered low-mobility networks represent fundamental losses for many low-cost photovoltaic technologies. We report a low-cost, solution-processable solar cell, based on a highly crystalline perovskite absorber with intense visible to near-infrared absorptivity, that has a power conversion efficiency of 10.9% in a single-junction device under simulated full sunlight. This "meso-superstructured solar cell" exhibits exceptionally few fundamental energy losses; it can generate open-circuit photovoltages of more than 1.1 volts, despite the relatively narrow absorber band gap of 1.55 electron volts. The functionality arises from the use of mesoporous alumina as an inert scaffold that structures the absorber and forces electrons to reside in and be transported through the perovskite.

https://science.sciencemag.org/content/sci/early/2012/10/03/science.1228604.full.pdf

Efficient Hybrid Solar Cells Based on Meso-Superstructured Organometal Halide Perovskites

Organic-inorganic perovskites have shown promise as high-performance absorbers in solar cells, first as a coating on a mesoporous metal oxide scaffold and more recently as a solid layer in planar heterojunction architectures. Here, we report transient absorption and photoluminescence-quenching measurements to determine the electron-hole diffusion lengths, diffusion constants, and lifetimes in mixed halide (CH3NH3PbI(3-x)Cl(x)) and triiodide (CH3NH3PbI3) perovskite absorbers. We found that the diffusion lengths are greater than 1 micrometer in the mixed halide perovskite, which is an order of magnitude greater than the absorption depth. In contrast, the triiodide absorber has electron-hole diffusion lengths of ~100 nanometers. These results justify the high efficiency of planar heterojunction perovskite solar cells and identify a critical parameter to optimize for future perovskite absorber development.

/pdf/electron-hole-diffusion-lengths-exceeding-1-micrometer-in-an-3rhimkkmrj.pdf

Electron-hole diffusion lengths exceeding 1 micrometer in an organometal trihalide perovskite absorber.

https://absimage.aps.org/image/MAR14/MWS_MAR14-2013-000770.pdf

Electron-Hole Diffusion Lengths Exceeding 1 Micrometer in an Organometal Trihalide Perovskite Absorber

Device Characteristics of CZTSSe Thin‐Film Solar Cells with 12.6% Efficiency

Three-dimensional organic-inorganic perovskites have emerged as one of the most promising thin-film solar cell materials owing to their remarkable photophysical properties, which have led to power conversion efficiencies exceeding 20 per cent, with the prospect of further improvements towards the Shockley-Queisser limit for a single‐junction solar cell (33.5 per cent). Besides efficiency, another critical factor for photovoltaics and other optoelectronic applications is environmental stability and photostability under operating conditions. In contrast to their three-dimensional counterparts, Ruddlesden-Popper phases--layered two-dimensional perovskite films--have shown promising stability, but poor efficiency at only 4.73 per cent. This relatively poor efficiency is attributed to the inhibition of out-of-plane charge transport by the organic cations, which act like insulating spacing layers between the conducting inorganic slabs. Here we overcome this issue in layered perovskites by producing thin films of near-single-crystalline quality, in which the crystallographic planes of the inorganic perovskite component have a strongly preferential out-of-plane alignment with respect to the contacts in planar solar cells to facilitate efficient charge transport. We report a photovoltaic efficiency of 12.52 per cent with no hysteresis, and the devices exhibit greatly improved stability in comparison to their three-dimensional counterparts when subjected to light, humidity and heat stress tests. Unencapsulated two-dimensional perovskite devices retain over 60 per cent of their efficiency for over 2,250 hours under constant, standard (AM1.5G) illumination, and exhibit greater tolerance to 65 per cent relative humidity than do three-dimensional equivalents. When the devices are encapsulated, the layered devices do not show any degradation under constant AM1.5G illumination or humidity. We anticipate that these results will lead to the growth of single-crystalline, solution-processed, layered, hybrid, perovskite thin films, which are essential for high-performance opto-electronic devices with technologically relevant long-term stability.

High-efficiency two-dimensional Ruddlesden–Popper perovskite solar cells

The path towards a high-performance solution-processed kesterite solar cell ☆

2010 WILEY-VCH Verlag Gmb Chalcogenide-based solar cells provide a critical pathway to cost parity between photovoltaic (PV) and conventional energy sources. Currently, only Cu(In,Ga)(S,Se)2 (CIGS) and CdTe technologies have reached commercial module production with stable power conversion efficiencies of over 9 percent. Despite the promise of these technologies, restrictions on heavy metal usage for Cd and limitations in supply for In and Te are projected to restrict the production capacity of the existing chalcogen-based technologies to <100GWp per year, a small fraction of our growing energy needs, which are expected to double to 27 TW by 2050. Earth-abundant copper-zinc-tin-chalcogenide kesterites, Cu2ZnSnS4 and Cu2ZnSnSe4, have been examined as potential alternatives for the two leading technologies, reaching promising but not yet marketable efficiencies of 6.7% and 3.2%, respectively, by multilayer vacuum deposition. Here we show a non-vacuum, slurry-based coating method that combines advantages of both solution processing and particlebased deposition, enabling fabrication of Cu2ZnSn(Se,S)4 devices with over 9.6% efficiency—a factor of five performance improvement relative to previous attempts to use highthroughput ink-based approaches and >40% higher than previous record devices prepared using vacuum-based methods. To address the issue of cost, non-vacuum ‘‘ink’’-based approaches—both from solutions and suspensions—are being developed for chalcogenide-based absorber layer deposition to replace potentially more expensive vacuum-based techniques. True solutions allow intermixing of the constituents at a molecular level and the formation of smooth homogeneous films, as demonstrated with spin-coated CIGS absorber layers from hydrazine (N2H4) solutions. [11–13] The chemically reducing character of hydrazine stabilizes solutions of anions with direct metal-chalcogen bonding for select elements (e.g. Cu, In, Ga, Sn), without the necessity to introduce typical impurities (e.g., C, O, Cl). Suspension approaches employ solid particles designed to be deposited on a substrate and reacted or fused with each other, to form a desired crystalline phase and grain structure. Normally insoluble components can be deposited by this approach using typical liquid-based deposition (e.g., printing, spin coating, slit casting, spraying). Although high-quality large-grained absorber layers can be formed for selected systems using either solutionor particlebased deposition, numerous challenges confront each approach for more general deposition needs. Solution processing is limited by the solubility of many materials of interest (e.g., ZnSe1–xSx in hydrazine solvents—relevant for the deposition of Cu2ZnSnS4 or Cu2ZnSnSe4). In addition, volume contraction upon drying of solution-deposited layers creates stress in the film that may cause crack formation in thicker films. In suspension approaches, a common difficulty is achieving single-phase crystallization among the solid particles. Particle-based approaches (as well as some solution methods) typically require the addition of organic agents to improve wetting and particle dispersion, and to avoid film cracks and delamination. Most of these non-volatile organic additives introduce carbon contamination in the final layer. Because of these challenges, vacuum-based techniques have historically shown superior performance to liquid coating. In the case of the earth-abundant Cu2ZnSn(S,Se)4 materials, ink-based approaches have to date yielded at most <1.6% efficiency devices. Here we demonstrate an hybrid solution-particle approach, using the earth-abundant Cu2ZnSn(S,Se)4 system as an example, which enables fabrication of PV devices with over 9.6% power conversion efficiency. The slurry (or ink) employed for deposition comprises a Cu–Sn chalcogenide (S or S–Se) solution in hydrazine (see Experimental section), with the in situ formation of readily dispersible particle-based Zn-chalcogenide precursors, ZnSe(N2H4) (Figure 1a,d) or ZnS(N2H4) (Figure 1b). Thermogravimetric analysis (TGA) of the isolated selenide particle precursor shows decomposition at approximately 200 8C, with mass loss of about 20%, close to the theoretical value expected upon transition to pure ZnSe (Figure 1c,d). Deposition using this hybrid slurry successfully combines the advantages of solution and suspension deposition routes by use of solutions containing solid particles, wherein both components (i.e., solution and particle) contain metal and chalcogen elements that integrate into the final film. Using the hybrid slurry method (i) solubility limitations are resolved, as virtually any materials system can be constituted by a combination of solid and dissolved components; (ii) the dissolved components can be engineered as an efficient binding media for the particles, eliminating the need of separate organic binders; (iii) solid particles act as stress-relief and crack-deflection centers allowing the deposition of thicker layers than pure solution processes; and (iv) the intimate contact between the two phases allows rapid reaction and homogeneous phase formation. Complete conversion of all constituents of the spin-coated hybrid precursor films into a single-phase, highly crystalline Cu2ZnSn(S,Se)4 is achieved by annealing at 540 8C on a hot plate. Three main types of samples were targeted – high selenium content (A), intermediate sulfoselenide (B) and pure sulfide (C) –

High‐Efficiency Solar Cell with Earth‐Abundant Liquid‐Processed Absorber

Beyond 11% Efficiency: Characteristics of State‐of‐the‐Art Cu2ZnSn(S,Se)4 Solar Cells

A power conversion efficiency record of 10.1% was achieved for kesterite absorbers, using a Cu2ZnSn(Se,S)4 thin-film solar cell made by hydrazine-based solution processing. Key device characteristics were compiled, including light/dark J–V, quantum efficiency, temperature dependence of Voc and series resistance, photoluminescence, and capacitance spectroscopy, providing important insight into how the devices compare with high-performance Cu(In,Ga)Se2. The record kesterite device was shown to be primarily limited by interface recombination, minority carrier lifetime, and series resistance. The new level of device performance points to the significant promise of the kesterites as an emerging and commercially interesting thin-film technology. Copyright © 2011 John Wiley & Sons, Ltd.

Teodor K. Todorov

Papers

Device Characteristics of CZTSSe Thin‐Film Solar Cells with 12.6% Efficiency

The path towards a high-performance solution-processed kesterite solar cell ☆

High‐Efficiency Solar Cell with Earth‐Abundant Liquid‐Processed Absorber

Beyond 11% Efficiency: Characteristics of State‐of‐the‐Art Cu2ZnSn(S,Se)4 Solar Cells

Device characteristics of a 10.1% hydrazine-processed Cu2ZnSn(Se,S)4 solar cell