Nanoscale interfacial engineering enables highly stable and efficient perovskite photovoltaics.

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.

Combined Precursor Engineering and Grain Anchoring Leading to MA-Free, Phase-Pure, and Stable α-Formamidinium Lead Iodide Perovskites for Efficient Solar Cells.

α-Formamidinium lead iodide (α-FAPbI3 ) is one of the most promising candidate materials for high-efficiency and thermally stable perovskite solar cells (PSCs) owing to its outstanding optoelectrical properties and high thermal stability. However, achieving a stable form of α-FAPbI3 where both the composition and the phase are pure is very challenging. Herein, we report on a combined strategy of precursor engineering and grain anchoring to successfully prepare methylammonium (MA)-free and phase-pure stable α-FAPbI3 films. The incorporation of volatile FA-based additives in the precursor solutions completely suppresses the formation of non-perovskite δ-FAPbI3 during film crystallization. Grains of the desired α-phase are anchored together and stabilized when 4-tert-butylbenzylammonium iodide is permeated into the α-FAPbI3 film interior via grain boundaries. This cooperative scheme leads to a significantly increased efficiency close to 21 % for FAPbI3 perovskite solar cells. Moreover, the stabilized PSCs exhibit improved thermal stability and maintained ≈90 % of their initial efficiency after storage at 50 °C for over 1600 hours.

Multimodal host-guest complexation for efficient and stable perovskite photovoltaics.

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.

Synergistic Effect of Fluorinated Passivator and Hole Transport Dopant Enables Stable Perovskite Solar Cells with an Efficiency Near 24.

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%.

Crown Ether Modulation Enables over 23% Efficient Formamidinium-Based Perovskite Solar Cells.

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.

Monolithic Organic/Colloidal Quantum Dot Hybrid Tandem Solar Cells via Buffer Engineering.

Monolithically integrated hybrid tandem solar cells (TSCs) that combine solution-processed colloidal quantum dot (CQD) and organic molecules are a promising device architecture, able to complement the absorption across the visible to the infrared. However, the performance of organic/CQD hybrid TSCs has not yet surpassed that of single-junction CQD solar cells. Here, a strategic optical structure is devised to overcome the prior performance limit of hybrid TSCs by employing a multibuffer layer and a dual near-infrared (NIR) absorber. In particular, a multibuffer layer is introduced to solve the problem of the CQD solvent penetrating the underlying organic layer. In addition, the matching current of monolithic TSCs is significantly improved to 15.2 mA cm-2 by using a dual NIR organic absorber that complements the absorption of CQD. The hybrid TSCs reach a power conversion efficiency (PCE) of 13.7%, higher than that of the corresponding individual single-junction cells, representing the highest efficiency reported to date for CQD-based hybrid TSCs.

Micron Thick Colloidal Quantum Dot Solids.

Shortwave infrared colloidal quantum dots (SWIR-CQDs) are semiconductors capable of harvesting across the AM1.5G solar spectrum. Today's SWIR-CQD solar cells rely on spin-coating; however, these films exhibit cracking once thickness exceeds ∼500 nm. We posited that a blade-coating strategy could enable thick QD films. We developed a ligand exchange with an additional resolvation step that enabled the dispersion of SWIR-CQDs. We then engineered a quaternary ink that combined high-viscosity solvents with short QD stabilizing ligands. This ink, blade-coated over a mild heating bed, formed micron-thick SWIR-CQD films. These SWIR-CQD solar cells achieved short-circuit current densities (Jsc) that reach 39 mA cm-2, corresponding to the harvest of 60% of total photons incident under AM1.5G illumination. External quantum efficiency measurements reveal both the first exciton peak and the closest Fabry-Perot resonance peak reaching approximately 80%-this is the highest unbiased EQE reported beyond 1400 nm in a solution-processed semiconductor.

A Chemically Orthogonal Hole Transport Layer for Efficient Colloidal Quantum Dot Solar Cells.

Colloidal quantum dots (CQDs) are of interest in light of their solution-processing and bandgap tuning. Advances in the performance of CQD optoelectronic devices require fine control over the properties of each layer in the device materials stack. This is particularly challenging in the present best CQD solar cells, since these employ a p-type hole-transport layer (HTL) implemented using 1,2-ethanedithiol (EDT) ligand exchange on top of the CQD active layer. It is established that the high reactivity of EDT causes a severe chemical modification to the active layer that deteriorates charge extraction. By combining elemental mapping with the spatial charge collection efficiency in CQD solar cells, the key materials interface dominating the subpar performance of prior CQD PV devices is demonstrated. This motivates to develop a chemically orthogonal HTL that consists of malonic-acid-crosslinked CQDs. The new crosslinking strategy preserves the surface chemistry of the active layer beneath, and at the same time provides the needed efficient charge extraction. The new HTL enables a 1.4× increase in charge carrier diffusion length in the active layer; and as a result leads to an improvement in power conversion efficiency to 13.0% compared to EDT standard cells (12.2%).

Cascade surface modification of colloidal quantum dot inks enables efficient bulk homojunction photovoltaics.

Control over carrier type and doping levels in semiconductor materials is key for optoelectronic applications. In colloidal quantum dots (CQDs), these properties can be tuned by surface chemistry modification, but this has so far been accomplished at the expense of reduced surface passivation and compromised colloidal solubility; this has precluded the realization of advanced architectures such as CQD bulk homojunction solids. Here we introduce a cascade surface modification scheme that overcomes these limitations. This strategy provides control over doping and solubility and enables n-type and p-type CQD inks that are fully miscible in the same solvent with complete surface passivation. This enables the realization of homogeneous CQD bulk homojunction films that exhibit a 1.5 times increase in carrier diffusion length compared with the previous best CQD films. As a result, we demonstrate the highest power conversion efficiency (13.3%) reported among CQD solar cells.

Mixed Lead Halide Passivation of Quantum Dots.

Infrared-absorbing colloidal quantum dots (IR CQDs) are materials of interest in tandem solar cells to augment perovskite and cSi photovoltaics (PV). Today's best IR CQD solar cells rely on the use of passivation strategies based on lead iodide; however, these fail to passivate the entire surface of IR CQDs. Lead chloride passivated CQDs show improved passivation, but worse charge transport. Lead bromide passivated CQDs have higher charge mobilities, but worse passivation. Here a mixed lead-halide (MPbX) ligand exchange is introduced that enables thorough surface passivation without compromising transport. MPbX-PbS CQDs exhibit properties that exceed the best features of single lead-halide PbS CQDs: they show improved passivation (43 ± 5 meV vs 44 ± 4 meV in Stokes shift) together with higher charge transport (4 × 10-2 ± 3 × 10-3 cm2 V-1 s-1 vs 3 × 10-2 ± 3 × 10-3 cm2 V-1 s-1 in mobility). This translates into PV devices having a record IR open-circuit voltage (IR Voc ) of 0.46 ± 0.01 V while simultaneously having an external quantum efficiency of 81 ± 1%. They provide a 1.7× improvement in the power conversion efficiency of IR photons (>1.1 µm) relative to the single lead-halide controls reported herein.

Ultrahigh resolution and color gamut with scattering-reducing transmissive pixels.

While plasmonic designs have dominated recent trends in structural color, schemes using localized surface plasmon resonances and surface plasmon polaritons that simultaneously achieve high color vibrancy at ultrahigh resolution have been elusive because of tradeoffs between size and performance. Herein we demonstrate vibrant and size-invariant transmissive type multicolor pixels composed of hybrid TiOx-Ag core-shell nanowires based on reduced scattering at their electric dipolar Mie resonances. This principle permits the hybrid nanoresonator to achieve the widest color gamut (~74% sRGB area coverage), linear color mixing, and the highest reported single color dots-per-inch (58,000~141,000) in transmission mode. Exploiting such features, we further show that an assembly of distinct nanoresonators can constitute a multicolor pixel for use in multispectral imaging, with a size that is ~10-folds below the Nyquist limit using a typical high NA objective lens.

Machine Learning Accelerates Discovery of Optimal Colloidal Quantum Dot Synthesis.

Colloidal quantum dots (CQDs) allow broad tuning of the bandgap across the visible and near-infrared spectral regions. Recent advances in applying CQDs in light sensing, photovoltaics, and light emission have heightened interest in achieving further synthetic improvements. In particular, improving monodispersity remains a key priority in order to improve solar cells' open-circuit voltage, decrease lasing thresholds, and improve photodetectors' noise-equivalent power. Here we utilize machine-learning-in-the-loop to learn from available experimental data, propose experimental parameters to try, and, ultimately, point to regions of synthetic parameter space that will enable record-monodispersity PbS quantum dots. The resultant studies reveal that adding a growth-slowing precursor (oleylamine) allows nucleation to prevail over growth, a strategy that enables record-large-bandgap (611 nm exciton) PbS nanoparticles with a well-defined excitonic absorption peak (half-width at half-maximum (hwhm) of 145 meV). At longer wavelengths, we also achieve improved monodispersity, with an hwhm of 55 meV at 950 nm and 24 meV at 1500 nm, compared to the best published to date values of 75 and 26 meV, respectively.

Nanostructured Back Reflectors for Efficient Colloidal Quantum-Dot Infrared Optoelectronics.

Colloidal quantum dots (CQDs) can be used to extend the response of solar cells, enabling the utilization of solar power that lies to the red of the bandgap of c-Si and perovskites. To achieve largely complete absorption of infrared (IR) photons in CQD solids requires thicknesses on the micrometer range; however, this exceeds the typical diffusion lengths (≈300 nm) of photoexcited charges in these materials. Nanostructured metal back electrodes that grant the cell efficient IR light trapping in thin active layers with no deterioration of the electrical properties are demonstrated. Specifically, a new hole-transport layer (HTL) is developed and directly nanostructured. Firstly, a material set to replace conventional rigid HTLs in CQD devices is developed with a moldable HTL that combines the mechanical and chemical requisites for nanoimprint lithography with the optoelectronic properties necessary to retain efficient charge extraction through an optically thick layer. The new HTL is nanostructured in a 2D lattice and conformally coated with MoO3 /Ag. The photonic structure in the back electrode provides a record photoelectric conversion efficiency of 86%, beyond the Si bandgap, and a 22% higher IR power conversion efficiency compared to the best previous reports.

Ligand cleavage enables formation of 1,2-ethanedithiol capped colloidal quantum dot solids.

Colloidal quantum dots have garnered significant interest in optoelectronics, particularly in quantum dot solar cells (QDSCs). Here we report QDSCs fabricated using a ligand that is modified, following film formation, such that it becomes an efficient hole transport layer. The ligand, O-((9H-fluoren-9-yl)methyl) S-(2-mercaptoethyl) carbonothioate (FMT), contains the surface ligand 1,2-ethanedithiol (EDT) protected at one end using fluorenylmethyloxycarbonyl (Fmoc). The strategy enables deprotection following colloidal deposition, producing films containing quantum dots whose surfaces are more thoroughly covered with the remaining EDT molecules. To compare fabrication methods, we deposited CQDs onto the active layer: in one case, the traditional EDT-PbS/EDT-PbS is used, while in the other EDT-PbS/FMT-PbS is used. The devices based on the new EDT/FMT match the PCE values of EDT/EDT controls, and maintain a higher PCE over an 18 day storage interval, a finding we attribute to an increased thiol coverage using the FMT protocol.

Multibandgap quantum dot ensembles for solar-matched infrared energy harvesting.

As crystalline silicon solar cells approach in efficiency their theoretical limit, strategies are being developed to achieve efficient infrared energy harvesting to augment silicon using solar photons from beyond its 1100 nm absorption edge. Herein we report a strategy that uses multi-bandgap lead sulfide colloidal quantum dot (CQD) ensembles to maximize short-circuit current and open-circuit voltage simultaneously. We engineer the density of states to achieve simultaneously a large quasi-Fermi level splitting and a tailored optical response that matches the infrared solar spectrum. We shape the density of states by selectively introducing larger-bandgap CQDs within a smaller-bandgap CQD population, achieving a 40 meV increase in open-circuit voltage. The near-unity internal quantum efficiency in the optimized multi-bandgap CQD ensemble yielded a maximized photocurrent of 3.7 ± 0.2 mA cm-2. This provides a record for silicon-filtered power conversion efficiency equal to one power point, a 25% (relative) improvement compared to the best previously-reported results.

Butylamine-Catalyzed Synthesis of Nanocrystal Inks Enables Efficient Infrared CQD Solar Cells.

The best-performing colloidal-quantum-dot (CQD) photovoltaic devices suffer from charge recombination within the quasi-neutral region near the back hole-extracting junction. Graded architectures, which provide a widened depletion region at the back junction of device, could overcome this challenge. However, since today's best materials are processed using solvents that lack orthogonality, these architectures have not yet been implemented using the best-performing CQD solids. Here, a new CQD ink that is stable in nonpolar solvents is developed via a neutral donor ligand that functions as a phase-transfer catalyst. This enables the realization of an efficient graded architecture that, with an engineered band-alignment at the back junction, improves the built-in field and charge extraction. As a result, optimized IR CQD solar cells (Eg ≈ 1.3 eV) exhibiting a power conversion efficiency (PCE) of 12.3% are reported. The strategy is applied to small-bandgap (1 eV) IR CQDs to augment the performance of perovskite and crystalline silicon (cSi) 4-terminal tandem solar cells. The devices show the highest PCE addition achieved using a solution-processed active layer: a value of +5% when illuminated through a 1.58 eV bandgap perovskite front filter, providing a pathway to exceed PCEs of 23% in 4T tandem configurations with IR CQD PVs.

Activated Electron-Transport Layers for Infrared Quantum Dot Optoelectronics.

Photovoltaic (PV) materials such as perovskites and silicon are generally unabsorptive at wavelengths longer than 1100 nm, leaving a significant portion of the IR solar spectrum unharvested. Small-bandgap colloidal quantum dots (CQDs) are a promising platform to offer tandem complementary IR PV solutions. Today, the best performing CQD PVs use zinc oxide (ZnO) as an electron-transport layer. However, these electrodes require ultraviolet (UV)-light activation to overcome the low carrier density of ZnO, precluding the realization of CQD tandem photovoltaics. Here, a new sol-gel UV-free electrode based on Al/Cl hybrid doping of ZnO (CAZO) is developed. Al heterovalent doping provides a strong n-type character while Cl surface passivation leads to a more favorable band alignment for electron extraction. CAZO CQD IR solar cell devices exhibit, at wavelengths beyond the Si bandgap, an external quantum efficiency of 73%, leading to an additional 0.92% IR power conversion efficiency without UV activation. Conventional ZnO devices, on the other hand, add fewer than 0.01 power points at these operating conditions.

2D matrix engineering for homogeneous quantum dot coupling in photovoltaic solids.

Colloidal quantum dots (CQDs) are promising photovoltaic (PV) materials because of their widely tunable absorption spectrum controlled by nanocrystal size1,2. Their bandgap tunability allows not only the optimization of single-junction cells, but also the fabrication of multijunction cells that complement perovskites and silicon 3 . Advances in surface passivation2,4-7, combined with advances in device structures 8 , have contributed to certified power conversion efficiencies (PCEs) that rose to 11% in 2016 9 . Further gains in performance are available if the thickness of the devices can be increased to maximize the light harvesting at a high fill factor (FF). However, at present the active layer thickness is limited to ~300 nm by the concomitant photocarrier diffusion length. To date, CQD devices thicker than this typically exhibit decreases in short-circuit current (JSC) and open-circuit voltage (VOC), as seen in previous reports3,9-11. Here, we report a matrix engineering strategy for CQD solids that significantly enhances the photocarrier diffusion length. We find that a hybrid inorganic-amine coordinating complex enables us to generate a high-quality two-dimensionally (2D) confined inorganic matrix that programmes internanoparticle spacing at the atomic scale. This strategy enables the reduction of structural and energetic disorder in the solid and concurrent improvements in the CQD packing density and uniformity. Consequently, planar devices with a nearly doubled active layer thicknesses (~600 nm) and record values of JSC (32 mA cm-2) are fabricated. The VOC improved as the current was increased. We demonstrate CQD solar cells with a certified record efficiency of 12%.

Halide Re-Shelled Quantum Dot Inks for Infrared Photovoltaics.

Colloidal quantum dots are promising materials for tandem solar cells that complement silicon and perovskites. These devices are fabricated from solution phase; however, existing methods for making infrared-bandgap CQD inks suffer agglomeration and fusion during solution exchange. Here we develop a ligand exchange that provides robust surface protection and thereby avoids aggregation. First, we exchanged long oleic acid ligands to a mixed system comprising medium-chain ammonium and anionic chloride ligands; we then reshelled the surface using short halides and pseudohalide ligands that enabled transfer to a polar solvent. Absorbance and photoluminescence measurements reveal the retention of exciton sharpness, whereas X-ray photoelectron spectroscopy indicates halide capping. The best power conversion efficiency of these devices is 0.76 power points after filtering through silicon, which is 1.9× higher than previous single-step solution-processed IR-CQD solar cells.

Enhanced Open-Circuit Voltage in Colloidal Quantum Dot Photovoltaics via Reactivity-Controlled Solution-Phase Ligand Exchange.

The energy disorder that arises from colloidal quantum dot (CQD) polydispersity limits the open-circuit voltage (VOC ) and efficiency of CQD photovoltaics. This energy broadening is significantly deteriorated today during CQD ligand exchange and film assembly. Here, a new solution-phase ligand exchange that, via judicious incorporation of reactivity-engineered additives, provides improved monodispersity in final CQD films is reported. It has been found that increasing the concentration of the less reactive species prevents CQD fusion and etching. As a result, CQD solar cells with a VOC of 0.7 V (vs 0.61 V for the control) for CQD films with exciton peak at 1.28 eV and a power conversion efficiency of 10.9% (vs 10.1% for the control) is achieved.