ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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%.
ABSTRACT
As a result of their attractive optoelectronic properties, metal halide APbI3 perovskites employing formamidinium (FA+ ) as the Aâ cation are the focus of research. The superior chemical and thermal stability of FA+ cations makes α-FAPbI3 more suitable for solar-cell applications than methylammonium lead iodide (MAPbI3 ). However, its spontaneous conversion into the yellow non-perovskite phase (δ-FAPbI3 ) under ambient conditions poses a serious challenge for practical applications. Herein, we report on the stabilization of the desired α-FAPbI3 perovskite phase by protecting it with a two-dimensional (2D) IBA2 FAPb2 I7 (IBA=iso-butylammonium overlayer, formed via stepwise annealing. The α-FAPbI3 /IBA2 FAPb2 I7 based perovskite solar cell (PSC) reached a high power conversion efficiency (PCE) of close to 23 %. In addition, it showed excellent operational stability, retaining around 85 % of its initial efficiency under severe combined heat and light stress, that is, simultaneous exposure with maximum power tracking to full simulated sunlight at 80 °C over 500â h.
ABSTRACT
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.
ABSTRACT
The presence of defects at the interface between the perovskite film and the carrier transport layer poses significant challenges to the performance and stability of perovskite solar cells (PSCs). Addressing this issue, we introduce a dual host-guest (DHG) complexation strategy to modulate both the bulk and interfacial properties of FAPbI3-rich PSCs. Through NMR spectroscopy, a synergistic effect of the dual treatment is observed. Additionally, electro-optical characterizations demonstrate that the DHG strategy not only passivates defects but also enhances carrier extraction and transport. Remarkably, employing the DHG strategy yields PSCs with power conversion efficiencies (PCE) of 25.89% (certified at 25.53%). Furthermore, these DHG-modified PSCs exhibit enhanced operational stability, retaining over 96.6% of their initial PCE of 25.55% after 1050 hours of continuous operation under one-sun illumination, which was the highest initial value in the recently reported articles. This work establishes a promising pathway for stabilizing high-efficiency perovskite photovoltaics through supramolecular engineering, marking a significant advancement in the field.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
Subject(s)
Alkalies , Lead , Crystallization , PolymersABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
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.
ABSTRACT
Passivation of interfacial defects serves as an effective means to realize highly efficient and stable perovskite solar cells (PSCs). However, most molecular modulators currently used to mitigate such defects form poorly conductive aggregates at the perovskite interface with the charge collection layer, impeding the extraction of photogenerated charge carriers. Here, a judiciously engineered passivator, 4-tert-butyl-benzylammonium iodide (tBBAI), is introduced, whose bulky tert-butyl groups prevent the unwanted aggregation by steric repulsion. It is found that simple surface treatment with tBBAI significantly accelerates the charge extraction from the perovskite into the spiro-OMeTAD hole-transporter, while retarding the nonradiative charge carrier recombination. This boosts the power conversion efficiency (PCE) of the PSC from ≈20% to 23.5% reducing the hysteresis to barely detectable levels. Importantly, the tBBAI treatment raises the fill factor from 0.75 to the very high value of 0.82, which concurs with a decrease in the ideality factor from 1.72 to 1.34, confirming the suppression of radiation-less carrier recombination. The tert-butyl group also provides a hydrophobic umbrella protecting the perovskite film from attack by ambient moisture. As a result, the PSCs show excellent operational stability retaining over 95% of their initial PCE after 500 h full-sun illumination under maximum-power-point tracking under continuous simulated solar irradiation.
ABSTRACT
Mixtures of cations or halides with FAPbI3 (where FA is formamidinium) lead to high efficiency in perovskite solar cells (PSCs) but also to blue-shifted absorption and long-term stability issues caused by loss of volatile methylammonium (MA) and phase segregation. We report a deposition method using MA thiocyanate (MASCN) or FASCN vapor treatment to convert yellow δ-FAPbI3 perovskite films to the desired pure α-phase. NMR quantifies MA incorporation into the framework. Molecular dynamics simulations show that SCN- anions promote the formation and stabilization of α-FAPbI3 below the thermodynamic phase-transition temperature. We used these low-defect-density α-FAPbI3 films to make PSCs with >23% power-conversion efficiency and long-term operational and thermal stability, as well as a low (330 millivolts) open-circuit voltage loss and a low (0.75 volt) turn-on voltage of electroluminescence.
ABSTRACT
We present a mechanistic explanation of the BiI3 film formation process and an analysis of the critical factors in preparing high-quality solution-processed BiI3 films. We find that complexation with Lewis bases, relative humidity, and temperature are important factors during solvent vapor annealing (SVA) of films. During SVA, water vapor and higher temperatures limit the formation of the BiI3-dimethylformamide coordination complex. SVA with an optimized water content and temperature produces films with 300-500 nm grains. Films that formed solvent coordination compounds at lower temperatures showed preferential crystal orientation after solvent removal, and we elucidate its implications for carrier transport. Addition of dimethyl sulfoxide to highly concentrated tetrahydrofuran-BiI3 inks prevents film cracking after spin-coating. We have measured a quasi-Fermi level splitting of 1.1 eV and a diffusion length of 70 nm from films processed with optimal temperature and humidity. The best device produced by optimized SVA has a power conversion efficiency of 0.5%, I sc of â¼4 mA/cm2, and V OC of â¼400 mV. The low photocurrent and voltage we attribute to the low diffusion length and the unfavorable band alignment between the absorber and the adjacent transport layers. The deep understanding of the relationship between morphology/crystal structure and optoelectronic properties gained from this work paves the way for future optimization of BiI3-based solar cells.
ABSTRACT
High-bandgap mixed-halide hybrid perovskites have higher open-circuit voltage deficits and lower carrier diffusion lengths than their lower-bandgap counterparts. We have developed a ligand-assisted crystallization (LAC) technique that introduces additives in situ during the solvent wash and developed a new method to dynamically measure the absolute intensity steady-state photoluminescence and the mean carrier diffusion length simultaneously. The measurements reveal four distinct regimes of material changes and show that photoluminescence brightening often coincides with losses in carrier transport, such as in degradation or phase segregation. Further, the measurements enabled optimization of LAC on the 1.75 eV bandgap FA0.83Cs0.17Pb(I0.66Br0.34)3, resulting in an enhancement of the photoluminescence quantum yield (PLQY) of over an order of magnitude, an increase of 80 meV in the quasi-Fermi level splitting (to 1.29 eV), an increase in diffusion length by a factor of 3.5 (to over 1 µm), and enhanced open-circuit voltage and short-circuit current from photovoltaics fabricated from the LAC-treated films.