Full-Spectral Response Perovskite Solar Cells Through Integration of MXene Modified Near-Infrared Organic Heterojunction and Waveguide-Structure Quantum-Cutting Down-Converter

To date, lead-based perovskite solar cells (PSCs) are optimized to the extreme and achieved an efficiency of as much as 26.1%. Expanding the spectral response is one of the most effective methods for achieving further efficiency breakthroughs. In this study, integrated PSCs are constructed by combining near-infrared (NIR) organic bulk heterojunctions (BHJs) with perovskite layers to broaden the NIR spectral response range. Ultraviolet (UV)-plasma-treated MXene Nb₂CT_x - quantum dots (QDs) are introduced to promote exciton dissociation inside the BHJ and to solve the problems of severe nonradiative exciton recombination and open-circuit voltage (V_oc) loss in IPSCs. In addition, CsPbCl₃:Yb(7%),Li(2%) QDs with quantum-cutting emission and photoluminescence quantum yield of up to 170% act as down-converters to enhance the utilization of UV light. MgF₂ is deposited on the quantum-cutting layer to construct a waveguide-structured anti-reflection layer and further increase UV photon utilization. The champion device achieves superior photoelectric performance with a photoelectric conversion efficiency of 24.3%, V_oc of 1.17 V, a short circuit current of 26.65 mA cm⁻², and a fill factor of 77.95%. Champion devices exhibit excellent UV and long-term stability. This study provides an instructive strategy for fabricating high-performance full-spectral-response PSCs.     

Three‐Dimensional Nanostructured Indium‐Tin‐Oxide Electrodes for Enhanced Performance of Bulk Heterojunction Organic Solar Cells

A three‐dimensional indium tin oxide (ITO) nanohelix (NH) array is presented as a multifunctional electrode for bulk heterojunction organic solar cells for simultaneously improving light absorption and charge transport from the active region to the anode. It is shown that the ITO NH array, which is easily fabricated using an oblique‐angle‐deposition technique, acts as an effective antireflection coating as well as a light‐scattering layer, resulting in much enhanced light harvesting. Furthermore, the larger interfacial area between the electrode and the active layer, together with the enhanced carrier mobility through highly conductive ITO NH facilitate transport and collection of charge carriers. The optical and electrical improvements enabled by the ITO NH electrode result in a 10% increase in short‐circuit current density and power‐conversion efficiency of the solar cells.     

Systematic Investigation of Porphyrin‐Thiophene Conjugates for Ternary Bulk Heterojunction Solar Cells

A family of porphyrins and benzoporphyrins bearing phenyl, thiophenyl, or bithiophenyl groups at their meso‐positions are synthesized and systematically investigated for their potential use in bulk heterojunction solar cells (BHJ‐SCs). Comparative studies of these compounds show that the introduction of the thiophenyl and bithiophenyl groups, and the extension of the porphyrin π‐conjugated system significantly affect both photophysical and electrochemical properties. Binary conventional and ternary converted BHJ‐SCs based on these compounds are fabricated and studied. Results show that remarkable enhancement of the device efficiency is achieved by using the thiophene‐containing benzoporphyrin derivatives as additives for a poly(3‐hexylthiophene) (P3HT):phenyl‐C61‐butyric acid methyl ester blend in the inverted BHJ‐SCs. The optimum BHJ‐SC exhibits a maximum energy conversion efficiency of 4.3%, corresponding to 19% enhancement of the conversion efficiency as compared with the benchmark BHJ‐SCs.     

Amino‐Functionalized Conjugated Polymer as an Efficient Electron Transport Layer for High‐Performance Planar‐Heterojunction Perovskite Solar Cells

An amino‐functionalized copolymer with a conjugated backbone composed of fluorene, naphthalene diimide, and thiophene spacers (PFN‐2TNDI) is introduced as an alternative electron transport layer (ETL) to replace the commonly used [6,6]‐Phenyl‐C61‐butyric acid methyl ester (PCBM) in the p–i–n planar‐heterojunction organometal trihalide perovskite solar cells. A combination of characterizations including photoluminescence (PL), time‐resolved PL decay, Kelvin probe measurement, and impedance spectroscopy is used to study the interfacial effects induced by the new ETL. It is found that the amines on the polymer side chains not only can passivate the surface traps of perovskite to improve the electron extraction properties, they also can reduce the work function of the metal cathode by forming desired interfacial dipoles. With these dual functionalities, the resulted solar cells outperform those based on PCBM with power conversion efficiency (PCE) increased from 12.9% to 16.7% based on PFN‐2TNDI. In addition to the performance enhancement, it is also found that a wide range of thicknesses of the new ETL can be applied to produce high PCE devices owing to the good electron transport property of the polymer, which offers a better processing window for potential fabrication of perovskite solar cells using large‐area coating method.     

Nanoscale Elastic Changes in 2D Ti3C2Tx (MXene) Pseudocapacitive Electrodes

Designing sustainable electrodes for next generation energy storage devices relies on the understanding of their fundamental properties at the nanoscale, including the comprehension of ions insertion into the electrode and their interactions with the active material. One consequence of ion storage is the change in the electrode volume resulting in mechanical strain and stress that can strongly affect the cycle life. Therefore, it is important to understand the changes of dimensions and mechanical properties occurring during electrochemical reactions. While the characterization of mechanical properties via macroscopic measurements is well documented, in situ characterization of their evolution has never been achieved at the nanoscale. It is reported here with in situ imaging, combined with density functional theory of the elastic changes of a 2D titanium carbide (Ti₃C₂T_x) based electrode in direction normal to the basal plane (electrode surface) during alkaline cation intercalation/extraction. 2D carbides, known as MXenes, are promising new materials for supercapacitors and various kinds of batteries, and understanding the coupling between their mechanical and electrochemical properties is therefore necessary. The results show a strong correlation between the cations content and the out‐of‐plane elastic modulus. This strategy enables identifying the preferential intercalation pathways within a single particle, which is important for understanding ionic transport in these materials.     

Carbon Nanotube‐Silicon Solar Cells

Due to the high cost of silicon photovoltaics there is currently great interest in finding alternative semiconductor materials for light harvesting devices. Single‐walled carbon nanotubes are an allotrope of carbon with unique electrical and optical properties and are promising as future photovoltaic materials. It is thus important to investigate the methods of exploiting their properties in photovoltaic devices. In addition to already extensive research using carbon nanotubes in organic photovoltaics and photoelectrochemical cells, another way to do this is to combine them with a relatively well understood model semiconductor such as silicon. Nanotube‐silicon heterojunction solar cells are a recent photovoltaic architecture with demonstrated power conversion efficiencies of up to ～14% that may in part exploit the photoactivity of carbon nanotubes.     

Aqueous‐Processed Polymer/Nanocrystal Hybrid Solar Cells with Double‐Side Bulk Heterojunction

Aqueous‐solution‐processed solar cells (ASCs) are promising candidates of the next‐generation large‐area, low‐cost, and flexible photovoltaic conversion equipment because of their unique environmental friendly property. Aqueous‐solution‐processed polymer/nanocrystals (NCs) hybrid solar cells (AHSCs) can effectively integrate the advantages of the polymer (e.g., flexibility and lightweight) and the inorganic NCs (e.g., high mobility and broad absorption), and therefore be considered as an ideal system to further improve the performance of ASCs. In this work, double‐side bulk heterojunction (BHJ), in which one BHJ combines the active material with electron transport material and the other combines the active material with hole transport material, is developed in the AHSCs. Through comparing with the single‐side BHJ device, promoted carrier extraction, enhanced internal quantum efficiency, extended width of the depletion region, and prolonged carrier lifetime are achieved in double‐side BHJ devices. As a result, power conversion efficiency exceeding 6% is obtained, which breaks the bottleneck efficiency around ≈5.5%. This work demonstrates a device architecture which is more remarkable compared with the traditional only donor–acceptor blended BHJ. Under conservative estimation, it provides instructive architecture not only in the ASCs, but also in the organic solar cells (SCs), quantum dot SCs, and perovskite SCs.     

Toward High‐Temperature Stability of PTB7‐Based Bulk Heterojunction Solar Cells: Impact of Fullerene Size and Solvent Additive

The use of fullerene as acceptor limits the thermal stability of organic solar cells at high temperatures as their diffusion inside the donor leads to phase separation via Ostwald ripening. Here it is reported that fullerene diffusion is fully suppressed at temperatures up to 140 °C in bulk heterojunctions based on the benzodithiophene‐based polymer (the poly[[4,8‐bis[(2‐ethylhexyl)oxy]‐benzo[1,2‐b:4,5‐b′]dithiophene‐2,6‐diyl][3‐fluoro‐2‐[(2‐ethylhexyl)carbonyl]‐thieno[3,4‐b]thiophenediyl]], (PTB7) in combination with the fullerene derivative [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₀BM). The blend stability is found independently of the presence of diiodooctane (DIO) used to optimize nanostructuration and in contrast to PTB7 blends using the smaller fullerene derivative PC₇₀BM. The unprecedented thermal stability of PTB7:PC₇₀BM layers is addressed to local minima in the mixing enthalpy of the blend forming stable phases that inhibit fullerene diffusion. Importantly, although the nanoscale morphology of DIO processed blends is thermally stable, corresponding devices show strong performance losses under thermal stress. Only by the use of a high temperature annealing step removing residual DIO from the device, remarkably stable high efficiency solar cells with performance losses less than 10% after a continuous annealing at 140 °C over 3 days are obtained. These results pave the way toward high temperature stable polymer solar cells using fullerene acceptors.     

Capacitance Spectroscopy for Quantifying Recombination Losses in Nonfullerene Small‐Molecule Bulk Heterojunction Solar Cells

The light intensity dependence of the main photoelectrical parameters of the nonfullerene small‐molecule bulk heterojunction (BHJ) solar cells p‐DTS(FBTTh₂)₂:perylene diimide (T1:PDI) shows that the nongeminate recombination losses play an important role in this system. A simple approach for the quantitative analysis of capacitance spectroscopy data of the organic BHJ solar cells, which allows to determine the density of free charge carriers as a function of applied bias under standard working conditions, is demonstrated. Using the proposed capacitance spectroscopic technique, the nongeminate recombination losses in the T1:PDI solar cells are quantitatively characterized in the scope of the bimolecular‐ and trap‐assisted recombination mechanisms. Their contributions are separately analyzed within a wide range of the applied bias.     

Heterojunction‐Depleted Lead‐Free Perovskite Solar Cells with Coarse‐Grained B‐γ‐CsSnI3 Thin Films

Perovskite solar cells (PSCs) have been emerging as a breakthrough photovoltaic technology, holding unprecedented promise for low‐cost, high‐efficiency renewable electricity generation. However, potential toxicity associated with the state‐of‐the‐art lead‐containing PSCs has become a major concern. The past research in the development of lead‐free PSCs has met with mixed success. Herein, the promise of coarse‐grained B‐γ‐CsSnI₃ perovskite thin films as light absorber for efficient lead‐free PSCs is demonstrated. Thermally‐driven solid‐state coarsening of B‐γ‐CsSnI₃ perovskite grains employed here is accompanied by an increase of tin‐vacancy concentration in their crystal structure, as supported by first‐principles calculations. The optimal device architecture for the efficient photovoltaic operation of these B‐γ‐CsSnI₃ thin films is identified through exploration of several device architectures. Via modulation of the B‐γ‐CsSnI₃ grain coarsening, together with the use of the optimal PSC architecture, planar heterojunction‐depleted B‐γ‐CsSnI₃ PSCs with power conversion efficiency up to 3.31% are achieved without the use of any additives. The demonstrated strategies provide guidelines and prospects for developing future high‐performance lead‐free PVs.