RESUMEN
Hybrid metal halide perovskites have demonstrated remarkable performances in modern photovoltaics, although their stabilities remain limited. We assess the capacity to advance their properties by relying on interfacial modulators featuring helical chirality based on P,M-(1-methylene-3-methyl-imidazolium)[6]helicene iodides. We investigate their characteristics, demonstrating comparable charge injection for enantiomers and the racemic mixture. Overall, they maintain the resulting photovoltaic performance while improving operational stability, challenging the role of helical chirality in the interfacial modulation of perovskite solar cells.
RESUMEN
Efficient and robust n-i-p perovskite solar cells necessitate superior organic hole-transport materials with both mechanical and electronic prowess. Deciphering the structure-property relationship of these materials is crucial for practical perovskite solar cell applications. Through direct arylation, two high glass transition temperature molecular semiconductors, DBC-ETPA (202 °C) and TPE-ETPA (180 °C) are synthesized, using dibenzo[g,p]chrysene (DBC) and 1,1,2,2-tetraphenylethene (TPE) tetrabromides with triphenylene-ethylenedioxythiophene-dimethoxytriphenylamine (ETPA). In comparison to spiro-OMeTAD, both semiconductors exhibit shallower HOMO energy levels, resulting in increased hole densities (generated by air oxidation doping) and accelerated hole extraction from photoexcited perovskite. Experimental and theoretical studies highlight the more rigid DBC core, enhancing hole mobility due to reduced reorganization energy and lower energy disorder. Importantly, DBC-ETPA possesses a higher cohesive energy density, leading to lower ion diffusion coefficients and higher Young's moduli. Leveraging these attributes, DBC-ETPA is employed as the primary hole-transport layer component, yielding perovskite solar cells with an average efficiency of 24.5%, surpassing spiro-OMeTAD reference cells (24.0%). Furthermore, DBC-ETPA-based cells exhibit superior operational stability and 85 °C thermal storage stability.
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Self-powered skin optoelectronics fabricated on ultrathin polymer films is emerging as one of the most promising components for the next-generation Internet of Things (IoT) technology. However, a longstanding challenge is the device underperformance owing to the low process temperature of polymer substrates. In addition, broadband electroluminescence (EL) based on organic or polymer semiconductors inevitably suffers from periodic spectral distortion due to Fabry-Pérot (FP) interference upon substrate bending, preventing advanced applications. Here, ultraflexible skin optoelectronics integrating high-performance solar cells and monochromatic light-emitting diodes using solution-processed perovskite semiconductors is presented. n-i-p perovskite solar cells and perovskite nanocrystal light-emitting diodes (PNC-LEDs), with power-conversion and current efficiencies of 18.2% and 15.2 cd A-1 , respectively, are demonstrated on ultrathin polymer substrates with high thermal stability, which is a record-high efficiency for ultraflexible perovskite solar cell. The narrowband EL with a full width at half-maximum of 23 nm successfully eliminates FP interference, yielding bending-insensitive spectra even under 50% of mechanical compression. Photo-plethysmography using the skin optoelectronic device demonstrates a signal selectivity of 98.2% at 87 bpm pulse. The results presented here pave the way to inexpensive and high-performance ultrathin optoelectronics for self-powered applications such as wearable displays and indoor IoT sensors.
RESUMEN
High-performance perovskite solar cells (PSCs) typically require interfacial passivation, yet this is challenging for the buried interface, owing to the dissolution of passivation agents during the deposition of perovskites. Here, this limitation is overcome with in situ buried-interface passivation-achieved via directly adding a cyanoacrylic-acid-based molecular additive, namely BT-T, into the perovskite precursor solution. Classical and ab initio molecular dynamics simulations reveal that BT-T spontaneously may self-assemble at the buried interface during the formation of the perovskite layer on a nickel oxide hole-transporting layer. The preferential buried-interface passivation results in facilitated hole transfer and suppressed charge recombination. In addition, residual BT-T molecules in the perovskite layer enhance its stability and homogeneity. A power-conversion efficiency (PCE) of 23.48% for 1.0 cm2 inverted-structure PSCs is reported. The encapsulated PSC retains 95.4% of its initial PCE following 1960 h maximum-power-point tracking under continuous light illumination at 65 °C (i.e., ISOS-L-2I protocol). The demonstration of operating-stable PSCs under accelerated ageing conditions represents a step closer to the commercialization of this emerging technology.
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Inverted perovskite solar cells (PSCs) promise enhanced operating stability compared to their normal-structure counterparts1-3. To improve efficiency further, it is crucial to combine effective light management with low interfacial losses4,5. Here we develop a conformal self-assembled monolayer (SAM) as the hole-selective contact on light-managing textured substrates. Molecular dynamics simulations indicate that cluster formation during phosphonic acid adsorption leads to incomplete SAM coverage. We devise a co-adsorbent strategy that disassembles high-order clusters, thus homogenizing the distribution of phosphonic acid molecules, and thereby minimizing interfacial recombination and improving electronic structures. We report a laboratory-measured power conversion efficiency (PCE) of 25.3% and a certified quasi-steady-state PCE of 24.8% for inverted PSCs, with a photocurrent approaching 95% of the Shockley-Queisser maximum. An encapsulated device having a PCE of 24.6% at room temperature retains 95% of its peak performance when stressed at 65 °C and 50% relative humidity following more than 1,000 h of maximum power point tracking under 1 sun illumination. This represents one of the most stable PSCs subjected to accelerated ageing: achieved with a PCE surpassing 24%. The engineering of phosphonic acid adsorption on textured substrates offers a promising avenue for efficient and stable PSCs. It is also anticipated to benefit other optoelectronic devices that require light management.
RESUMEN
Perovskite solar cells (PSCs) consisting of interfacial two- and three-dimensional heterostructures that incorporate ammonium ligand intercalation have enabled rapid progress toward the goal of uniting performance with stability. However, as the field continues to seek ever-higher durability, additional tools that avoid progressive ligand intercalation are needed to minimize degradation at high temperatures. We used ammonium ligands that are nonreactive with the bulk of perovskites and investigated a library that varies ligand molecular structure systematically. We found that fluorinated aniliniums offer interfacial passivation and simultaneously minimize reactivity with perovskites. Using this approach, we report a certified quasi-steady-state power-conversion efficiency of 24.09% for inverted-structure PSCs. In an encapsulated device operating at 85°C and 50% relative humidity, we document a 1560-hour T85 at maximum power point under 1-sun illumination.
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The industrialization of perovskite solar cells requires adequate materials and processes to make them economically viable and environmentally sustainable. Despite promising results in terms of power conversion efficiency and operational stability, several hole-transport layers currently in use still need to prove their industrial feasibility. This work demonstrates the use of nanocrystalline nickel oxide produced through flash infrared annealing (FIRA), considerably reducing the materials cost, production time, energy, and the amount of solvents required for the hole transport layer. X-ray photoelectron spectroscopy reveals a better conversion to nickel oxide and a higher oxygen-to-nickel ratio for the FIRA films as compared to control annealing methods, resulting in higher device efficiency and operational stability. Planar inverted solar cells produced with triple cation perovskite absorber result in 16.7% power conversion efficiency for 1 cm2 devices, and 15.9% averaged over an area of 17 cm2 .
RESUMEN
The defects located at the interfaces and grain boundaries (GBs) of perovskite films are detrimental to the photovoltaic performance and stability of perovskite solar cells. Manipulating the perovskite crystallization process and tailoring the interfaces with molecular passivators are the main effective strategies to mitigate performance loss and instability. Herein, a new strategy is reported to manipulate the crystallization process of FAPbI3 -rich perovskite by incorporating a small amount of alkali-functionalized polymers into the antisolvent solution. The synergic effects of the alkali cations and poly(acrylic acid) anion effectively passivate the defects on the surface and GBs of perovskite films. As a result, the rubidium (Rb)-functionalized poly(acrylic acid) significantly improves the power conversion efficiency of FAPbI3 perovskite solar cells to approaching 25% and reduces the risk of lead ion (Pb2+ ) leakage continuously via the strong interaction between CO bonds and Pb2+ . In addition, the unencapsulated device shows enhanced operational stability, retaining 80% of its initial efficiency after 500 h operation at maximum power point under one-sun illumination.
Asunto(s)
Álcalis , Plomo , Cristalización , PolímerosRESUMEN
High-quality perovskite light harvesters and robust organic hole extraction layers are essential for achieving high-performing perovskite solar cells (PSCs). We introduce a phosphonic acid-functionalized fullerene derivative in mixed-cation perovskites as a grain boundary modulator to consolidate the crystal structure, which enhances the tolerance of the film against illumination, heat, and moisture. We also developed a redox-active radical polymer, poly(oxoammonium salt), that can effectively p-dope the hole-transporting material by hole injection and that also mitigates lithium ion diffusion. Power conversion efficiencies of 23.5% for 1-square-centimeter mixed-cation-anion PSCs and 21.4% for 17.1-square-centimeter minimodules were achieved. The PSCs retained 95.5% of their initial efficiencies after 3265 hours at maximum power point tracking under continuous 1-sun illumination at 70° ± 5°C.
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A myriad of studies and strategies have already been devoted to improving the stability of perovskite films; however, the role of the different perovskite crystal facets in stability is still unknown. Here, we reveal the underlying mechanisms of facet-dependent degradation of formamidinium lead iodide (FAPbI3) films. We show that the (100) facet is substantially more vulnerable to moisture-induced degradation than the (111) facet. With combined experimental and theoretical studies, the degradation mechanisms are revealed; a strong water adhesion following an elongated lead-iodine (Pb-I) bond distance is observed, which leads to a δ-phase transition on the (100) facet. Through engineering, a higher surface fraction of the (111) facet can be achieved, and the (111)-dominated crystalline FAPbI3 films show exceptional stability against moisture. Our findings elucidate unknown facet-dependent degradation mechanisms and kinetics.
RESUMEN
Dye-sensitized solar cells (DSCs) convert light into electricity by using photosensitizers adsorbed on the surface of nanocrystalline mesoporous titanium dioxide (TiO2) films along with electrolytes or solid charge-transport materials1-3. They possess many features including transparency, multicolour and low-cost fabrication, and are being deployed in glass facades, skylights and greenhouses4. Recent development of sensitizers5-10, redox mediators11-13 and device structures14 has improved the performance of DSCs, particularly under ambient light conditions14-17. To further enhance their efficiency, it is pivotal to control the assembly of dye molecules on the surface of TiO2 to favour charge generation. Here we report a route of pre-adsorbing a monolayer of a hydroxamic acid derivative on the surface of TiO2 to improve the dye molecular packing and photovoltaic performance of two newly designed co-adsorbed sensitizers that harvest light quantitatively across the entire visible domain. The best performing cosensitized solar cells exhibited a power conversion efficiency of 15.2% (which has been independently confirmed) under a standard air mass of 1.5 global simulated sunlight, and showed long-term operational stability (500 h). Devices with a larger active area of 2.8 cm2 exhibited a power conversion efficiency of 28.4% to 30.2% over a wide range of ambient light intensities, along with high stability. Our findings pave the way for facile access to high-performance DSCs and offer promising prospects for applications as power supplies and battery replacements for low-power electronic devices18-20 that use ambient light as their energy source.
RESUMEN
Photosensitizers yielding superior photocurrents are crucial for copper-electrolyte-based highly efficient dye-sensitized solar cells (DSCs). Herein, two molecularly tailored organic sensitizers are presented, coded ZS4 and ZS5, through judiciously employing dithieno[3,2-b:2â³,3â³-d]pyrrole (DTP) as the π-linker and hexyloxy-substituted diphenylquinoxaline (HPQ) or naphthalene-fused-quinoxaline (NFQ) as the auxiliary electron-accepting unit, respectively. Endowed with the HPQ acceptor, ZS4 shows more efficient electron injection and charge collection based on substantially reduced interfacial charge recombination as compared to ZS5. As a result, ZS4-based DSCs achieve a power conversion efficiency (PCE) of 13.2% under standard AM1.5G sunlight, with a high short-circuit photocurrent density (Jsc ) of 16.3 mA cm-2 , an open-circuit voltage (Voc ) of 1.05 V and a fill factor (FF) of 77.1%. Remarkably, DSCs sensitized with ZS4 exhibit an outstanding stability, retaining 95% of their initial PCE under continuous light soaking for 1000 h. It is believed that this is a new record efficiency reported so far for copper-electrolyte-based DSCs using a single sensitizer. The work highlights the importance of developing molecularly tailored photosensitizers for highly efficient DSCs with copper electrolyte.
RESUMEN
There exists a considerable density of interaggregate grain boundaries (GBs) and intra-aggregate GBs in polycrystalline perovskites. Mitigation of intra-aggregate GBs is equally notable to that of interaggregate GBs as intra-aggregate GBs can also cause detrimental effects on the photovoltaic performances of perovskite solar cells (PSCs). Here, we demonstrate full-scale GB mitigation ranging from nanoscale intra-aggregate to submicron-scale interaggregate GBs, by modulating the crystallization kinetics using a judiciously designed brominated arylamine trimer. The optimized GB-mitigated perovskite films exhibit reduced nonradiative recombination, and their corresponding mesostructured PSCs show substantially enhanced device efficiency and long-term stability under illumination, humidity, or heat stress. The versatility of our strategy is also verified upon applying it to different categories of PSCs. Our discovery not only specifies a rarely addressed perspective concerning fundamental studies of perovskites at nanoscale but also opens a route to obtain high-quality solution-processed polycrystalline perovskites for high-performance optoelectronic devices.
RESUMEN
Improvements to perovskite solar cells (PSCs) have focused on increasing their power conversion efficiency (PCE) and operational stability and maintaining high performance upon scale-up to module sizes. We report that replacing the commonly used mesoporous-titanium dioxide electron transport layer (ETL) with a thin layer of polyacrylic acid-stabilized tin(IV) oxide quantum dots (paa-QD-SnO2) on the compact-titanium dioxide enhanced light capture and largely suppressed nonradiative recombination at the ETL-perovskite interface. The use of paa-QD-SnO2 as electron-selective contact enabled PSCs (0.08 square centimeters) with a PCE of 25.7% (certified 25.4%) and high operational stability and facilitated the scale-up of the PSCs to larger areas. PCEs of 23.3, 21.7, and 20.6% were achieved for PSCs with active areas of 1, 20, and 64 square centimeters, respectively.
RESUMEN
We present a facile molecular-level interface engineering strategy to augment the long-term operational and thermal stability of perovskite solar cells (PSCs) by tailoring the interface between the perovskite and hole transporting layer (HTL) with a multifunctional ligand 2,5-thiophenedicarboxylic acid. The solar cells exhibited high operational stability (maximum powering point tracking at one sun illumination) with a stabilized T S80 (the time over which the device efficiency reduces to 80% after initial burn-in) of ≈5950 h at 40 °C and a stabilized power conversion efficiency (PCE) over 23%. The origin of high device stability and performance is correlated to the nano/sub-nanoscale molecular level interactions between ligand and perovskite layer, which is further corroborated by comprehensive multiscale characterization. These results provide insights into the modulation of the grain boundaries, local density of states, surface bandgap, and interfacial recombination. Chemical analysis of aged devices showed that molecular passivation suppresses interfacial ion diffusion and inhibits the photoinduced I2 release that irreversibly degrades the perovskite. The interfacial engineering strategies enabled by multifunctional ligands can expedite the path towards stable PSCs.
RESUMEN
Formamidinium lead iodide perovskites are promising light-harvesting materials, yet stabilizing them under operating conditions without compromising optimal optoelectronic properties remains challenging. We report a multimodal host-guest complexation strategy to overcome this challenge using a crown ether, dibenzo-21-crown-7, which acts as a vehicle that assembles at the interface and delivers Cs+ ions into the interior while modulating the material. This provides a local gradient of doping at the nanoscale that assists in photoinduced charge separation while passivating surface and bulk defects, stabilizing the perovskite phase through a synergistic effect of the host, guest, and host-guest complex. The resulting solar cells show power conversion efficiencies exceeding 24% and enhanced operational stability, maintaining over 95% of their performance without encapsulation for 500 h under continuous operation. Moreover, the host contributes to binding lead ions, reducing their environmental impact. This supramolecular strategy illustrates the broad implications of host-guest chemistry in photovoltaics.
RESUMEN
Metal halide perovskites of the general formula ABX3-where A is a monovalent cation such as caesium, methylammonium or formamidinium; B is divalent lead, tin or germanium; and X is a halide anion-have shown great potential as light harvesters for thin-film photovoltaics1-5. Among a large number of compositions investigated, the cubic α-phase of formamidinium lead triiodide (FAPbI3) has emerged as the most promising semiconductor for highly efficient and stable perovskite solar cells6-9, and maximizing the performance of this material in such devices is of vital importance for the perovskite research community. Here we introduce an anion engineering concept that uses the pseudo-halide anion formate (HCOO-) to suppress anion-vacancy defects that are present at grain boundaries and at the surface of the perovskite films and to augment the crystallinity of the films. The resulting solar cell devices attain a power conversion efficiency of 25.6 per cent (certified 25.2 per cent), have long-term operational stability (450 hours) and show intense electroluminescence with external quantum efficiencies of more than 10 per cent. Our findings provide a direct route to eliminate the most abundant and deleterious lattice defects present in metal halide perovskites, providing a facile access to solution-processable films with improved optoelectronic performance.
RESUMEN
To develop photosensitizers with high open-circuit photovoltage (Voc) is a crucial strategy to enhance the power conversion efficiency (PCE) of co-sensitized solar cells. Here, we show a judiciously tailored organic photosensitizer, coded MS5, featuring the bulky donor N-(2',4'-bis(dodecyloxy)-[1,1'-biphenyl]-4-yl)-2',4'-bis(dodecyloxy)-N-phenyl-[1,1'-biphenyl]-4-amine and the electron acceptor 4-(benzo[c][1,2,5]thiadiazol-4-yl)benzoic acid. Employing MS5 with a copper (II/I) electrolyte enables a dye-sensitized solar cell (DSC) to achieve a strikingly high Voc of 1.24 V, with the Voc deficit as low as 130 mV and an ideality factor of merely 1.08. The co-sensitization of MS5 with the wider spectral-response dye XY1b produces a highly efficient and stable DSC with the PCE of 13.5% under standard AM1.5 G, 100 mW cm-2 solar radiation. Remarkably, the co-sensitized solar cell (active area of 2.8 cm2) presents a record PCE of 34.5% under ambient light, rendering it very attractive as an ambient light harvesting energy source for low power electronics.
RESUMEN
Long-term durability is critically important for the commercialization of perovskite solar cells (PSCs). The ionic character of the perovskite and the hydrophilicity of commonly used additives for the hole-transporting layer (HTL), such as lithium bis(trifluoromethanesulfonyl)imide (Li-TFSI) and tert-butylpyridine (tBP), render PSCs prone to moisture attack, compromising their long-term stability. Here we introduce a trifluoromethylation strategy to overcome this drawback and to boost the PSC's solar to electric power conversion efficiency (PCE). We employ 4-(trifluoromethyl)benzylammonium iodide (TFMBAI) as an amphiphilic modifier for interfacial defect mitigation and 4-(trifluoromethyl)pyridine (TFP) as an additive to enhance the HTL's hydrophobicity. Surface treatment of the triple-cation perovskite with TFMBAI largely suppressed the nonradiative charge carrier recombination, boosting the PCE from 20.9% to 23.9% and suppressing hysteresis, while adding TFP to the HTL enhanced the PCS's resistance to moisture while maintaining its high PCE. Taking advantage of the synergistic effects resulting from the combination of both fluoromethylated modifiers, we realize TFMBAI/TFP-based highly efficient PSCs with excellent operational stability and resistance to moisture, retaining over 96% of their initial efficiency after 500 h maximum power point tracking (MPPT) under simulated 1 sun irradiation and 97% of their initial efficiency after 1100 h of exposure under ambient conditions to a relative humidity of 60-70%.
RESUMEN
The use of molecular modulators to reduce the defect density at the surface and grain boundaries of perovskite materials has been demonstrated to be an effective approach to enhance the photovoltaic performance and device stability of perovskite solar cells. Herein, we employ crown ethers to modulate perovskite films, affording passivation of undercoordinated surface defects. This interaction has been elucidated by solid-state nuclear magnetic resonance and density functional theory calculations. The crown ether hosts induce the formation of host-guest complexes on the surface of the perovskite films, which reduces the concentration of surface electronic defects and suppresses nonradiative recombination by 40%, while minimizing moisture permeation. As a result, we achieved substantially improved photovoltaic performance with power conversion efficiencies exceeding 23%, accompanied by enhanced stability under ambient and operational conditions. This work opens a new avenue to improve the performance and stability of perovskite-based optoelectronic devices through supramolecular chemistry.