All-perovskite tandem solar cells with 3D/3D bilayer perovskite heterojunction.

All-perovskite tandem solar cells promise higher power-conversion efficiency (PCE) than single-junction perovskite solar cells (PSCs) while maintaining a low fabrication cost1-3. However, their performance is still largely constrained by the subpar performance of mixed lead-tin (Pb-Sn) narrow-bandgap (NBG) perovskite subcells, mainly because of a high trap density on the perovskite film surface4-6. Although heterojunctions with intermixed 2D/3D perovskites could reduce surface recombination, this common strategy induces transport losses and thereby limits device fill factors (FFs)7-9. Here we develop an immiscible 3D/3D bilayer perovskite heterojunction (PHJ) with type II band structure at the Pb-Sn perovskite-electron-transport layer (ETL) interface to suppress the interfacial non-radiative recombination and facilitate charge extraction. The bilayer PHJ is formed by depositing a layer of lead-halide wide-bandgap (WBG) perovskite on top of the mixed Pb-Sn NBG perovskite through a hybrid evaporation-solution-processing method. This heterostructure allows us to increase the PCE of Pb-Sn PSCs having a 1.2-µm-thick absorber to 23.8%, together with a high open-circuit voltage (Voc) of 0.873 V and a high FF of 82.6%. We thereby demonstrate a record-high PCE of 28.5% (certified 28.0%) in all-perovskite tandem solar cells. The encapsulated tandem devices retain more than 90% of their initial performance after 600 h of continuous operation under simulated one-sun illumination.

All-perovskite tandem solar cells with improved grain surface passivation.

All-perovskite tandem solar cells hold the promise of surpassing the efficiency limits of single-junction solar cells1-3; however, until now, the best-performing all-perovskite tandem solar cells have exhibited lower certified efficiency than have single-junction perovskite solar cells4,5. A thick mixed Pb-Sn narrow-bandgap subcell is needed to achieve high photocurrent density in tandem solar cells6, yet this is challenging owing to the short carrier diffusion length within Pb-Sn perovskites. Here we develop ammonium-cation-passivated Pb-Sn perovskites with long diffusion lengths, enabling subcells that have an absorber thickness of approximately 1.2 µm. Molecular dynamics simulations indicate that widely used phenethylammonium cations are only partially adsorbed on the surface defective sites at perovskite crystallization temperatures. The passivator adsorption is predicted to be enhanced using 4-trifluoromethyl-phenylammonium (CF3-PA), which exhibits a stronger perovskite surface-passivator interaction than does phenethylammonium. By adding a small amount of CF3-PA into the precursor solution, we increase the carrier diffusion length within Pb-Sn perovskites twofold, to over 5 µm, and increase the efficiency of Pb-Sn perovskite solar cells to over 22%. We report a certified efficiency of 26.4% in all-perovskite tandem solar cells, which exceeds that of the best-performing single-junction perovskite solar cells. Encapsulated tandem devices retain more than 90% of their initial performance after 600 h of operation at the maximum power point under 1 Sun illumination in ambient conditions.

Lattice anchoring stabilizes solution-processed semiconductors.

The stability of solution-processed semiconductors remains an important area for improvement on their path to wider deployment. Inorganic caesium lead halide perovskites have a bandgap well suited to tandem solar cells1 but suffer from an undesired phase transition near room temperature2. Colloidal quantum dots (CQDs) are structurally robust materials prized for their size-tunable bandgap3; however, they also require further advances in stability because they are prone to aggregation and surface oxidization at high temperatures as a consequence of incomplete surface passivation4,5. Here we report 'lattice-anchored' hybrid materials that combine caesium lead halide perovskites with lead chalcogenide CQDs, in which lattice matching between the two materials contributes to a stability exceeding that of the constituents. We find that CQDs keep the perovskite in its desired cubic phase, suppressing the transition to the undesired lattice-mismatched phases. The stability of the CQD-anchored perovskite in air is enhanced by an order of magnitude compared with pristine perovskite, and the material remains stable for more than six months at ambient conditions (25 degrees Celsius and about 30 per cent humidity) and more than five hours at 200 degrees Celsius. The perovskite prevents oxidation of the CQD surfaces and reduces the agglomeration of the nanoparticles at 100 degrees Celsius by a factor of five compared with CQD controls. The matrix-protected CQDs show a photoluminescence quantum efficiency of 30 per cent for a CQD solid emitting at infrared wavelengths. The lattice-anchored CQD:perovskite solid exhibits a doubling in charge carrier mobility as a result of a reduced energy barrier for carrier hopping compared with the pure CQD solid. These benefits have potential uses in solution-processed optoelectronic devices.

Freeze Metal Halide Perovskite for Dramatic Laser Tuning: Direct Observation via In Situ Cryo-Electron Microscope.

A frozen-temperature (below -28 °C) laser tuning way is developed to optimize metal halide perovskite (MHP)'s stability and opto-electronic properties, for emitter, photovoltaic and detector applications. Here freezing can adjust the competitive laser irradiation effects between damaging and annealing/repairing. And the ligand shells on MHP surface, which are widely present for many MHP materials, can be frozen and act as transparent solid templates for MHP's re-crystallization/re-growth during the laser tuning. With model samples of different types of CsPbBr3 nanocube arrays,an attempt is made to turn the dominant exposure facet from low-energy [100] facet to high-energy [111], [-211], [113] and [210] ones respectively; selectively removing the surface impurities and defects of CsPbBr3 nanocubes to enhance the irradiation durability by 101 times; and quickly (tens of seconds) modifying a Ruddlesden-Popper (RP) boundary into another type of boundary like twinning, and so on. The laser tuning mechanism is revealed by an innovative in situ cryo-transmission electron microscope (cryo-TEM) exploration at atomic resolution.

Spin Coherence and Spin Relaxation in Hybrid Organic-Inorganic Lead and Mixed Lead-Tin Perovskites.

Metal halide perovskites make up a promising class of materials for semiconductor spintronics. Here we report a systematic investigation of coherent spin precession, spin dephasing and spin relaxation of electrons and holes in two hybrid organic-inorganic perovskites MA0.3FA0.7PbI3 and MA0.3FA0.7Pb0.5Sn0.5I3 using time-resolved Faraday rotation spectroscopy. With applied in-plane magnetic fields, we observe robust Larmor spin precession of electrons and holes that persists for hundreds of picoseconds. The spin dephasing and relaxation processes are likely to be sensitive to the defect levels. Temperature-dependent measurements give further insights into the spin relaxation channels. The extracted electron Landé g-factors (3.75 and 4.36) are the biggest among the reported values in inorganic or hybrid perovskites. Both the electron and hole g-factors shift dramatically with temperature, which we propose to originate from thermal lattice vibration effects on the band structure. These results lay the foundation for further design and use of lead- and tin-based perovskites for spintronic applications.

Dinuclear Gold-Catalyzed para-Selective C-H Arylation of Undirected Arenes by Noncovalent Interactions.

The regioselectivity of C-H functionalization is commonly achieved by directing groups, electronic factors, or steric hindrance, which facilitate the identification of reaction sites. However, such strategies are less effective for reactants such as simple monofluoroarenes due to their relatively low reactivity and the modest steric demands of the fluorine atom. Herein, we present an undirected gold-catalyzed para-C-H arylation of a wide array of monofluoroarenes using air-stable aryl silanes and germanes at room temperature. A high para-regioselectivity (up to 98 : 2) can be realized by utilizing a dinuclear dppm(AuOTs)2 (dppm=bis(diphenylphosphino)methane) as the catalyst and hexafluorobenzene as the solvent. This provides a general and practical protocol for the concise construction of structurally diverse para-arylated monofluoroarenes through C-H activation manner. It features excellent functional group tolerance and a broad substrate scope (>80 examples). Besides, this strategy is also robust for other simple monosubstituted arenes and heteroarenes. Our mechanistic studies and theoretical calculations suggest that para-C-H selectivity arises from highly electrophilic and structurally flexible dinuclear Ar-Au(III)-Au(I) species, coupled with noncovalent interaction induced by hexafluorobenzene.

Efficient All-Perovskite Tandem Solar Cells with Low-Optical-Loss Carbazolyl Interconnecting Layers.

Combining wide-band gap (WBG) and narrow-band gap (NBG) perovskites with interconnecting layers (ICLs) to construct monolithic all-perovskite tandem solar cell is an effective way to achieve high power conversion efficiency (PCE). However, optical losses from ICLs need to be further reduced to leverage the full potential of all-perovskite tandem solar cells. Here, metal oxide nanocrystal layers anchored with carbazolyl hole-selective-molecules (CHs), which exhibit much lower optical loss, is employed to replace poly(3,4-ethylenedioxythiophene) polystyrenesulfonate (PEDOT : PSS) as the hole transporting layers (HTLs) in lead-tin (Pb-Sn) perovskite sub-cells and ICLs in all-perovskite tandem solar cells. Optically transparent indium tin oxide nanocrystals (ITO NCs) layers are employed to enhance anchoring of CHs, while a mixture of two CHs is adopted to tune the surface energy-levels of ITO NCs. The optimized mixed Pb-Sn NBG perovskite solar cells demonstrate a high PCE of 23.2 %, with a high short-circuit current density (Jsc ) of 33.5 mA cm-2 . A high PCE of 28.1 % is further obtained in all-perovskite tandem solar cells, with the highest Jsc of 16.7 mA cm-2 to date. Encapsulated tandem solar cells maintain 90 % of their reference point after 500 h of operation at the maximum power point (MPP) under 1-Sun illumination.

Cesium acetate-assisted crystallization for high-performance inverted CsPbI3perovskite solar cells.

Efficient inverted (p-i-n) type CsPbI3perovskite solar cells (PSCs) have revealed promising applications due to their excellent thermal and photostability. Regulating the nucleation and crystallization of perovskite film is an important route to improving the performance of CsPbI3PSCs. Herein, we explored cesium acetate (CsAc) as additive to manipulate the crystallization process of CsPbI3perovskite films. By involving in the intermediate phase DMA1-xCsxPbI3-yAcyof perovskite, the pseudo-halide acetate (Ac-) can retard the ion exchange reaction between DMA+and Cs+, leading to a perovskite with dense morphology, low defect density, and a long carrier lifetime. As a result, the optimal CsPbI3PSCs yielded a high power conversion efficiency of 18.3%. Moreover, the encapsulated devices showed excellent operational stability and the devices retained their initial performance following 500 h of operation at the maximum power point under one-sun illumination in ambient conditions.

Efficient and Stable Thin-Film Luminescent Solar Concentrators Enabled by Near-Infrared Emission Perovskite Nanocrystals.

A novel triphenylphosphine (TPP) treatment strategy was developed to prepare the near-infrared emission CsPbI3 nanocrystal (NC)-polymer composite thin-film luminescent solar concentrators (LSCs) featuring high absolute photoluminescence quantum yield (PLQY), low reabsorption, and high stability. The PL emission of the LSCs is centered at about 700 nm with 99.4±0.4 % PLQY and narrow full width at half maximum (FWHM) of 75 meV (30 nm). Compared with LSCs prepared with classic CsPbI3 NCs, the stability of the LSCs after TPP treatments has been greatly improved, even after long-term (30 days) immersion in water and strong mercury-lamp irradiation (50 mW cm-2 ). Owing to the presence of lone-pair electrons on the phosphorus atom, TPP is also used as a photoinitiator, with higher efficiency than other common photoinitiators. Large-area (ca. 75 cm2 ) infrared LSCs were achieved with a high optical conversion efficiency of 3.1 % at a geometric factor of 10.

Anchored Ligands Facilitate Efficient B-Site Doping in Metal Halide Perovskites.

Metal halide perovskites exhibit outstanding optoelectronic properties: superior charge carrier mobilities, low densities of deep trap states, high photoluminescence quantum yield, and wide color tunability. The introduction of dopant ions provides pathways to manipulate the electronic and chemical features of perovskites. In metal halide perovskites ABX3, where A is a monovalent cation (e.g., methylammonium (MA+), Cs+), B is the divalent metal ion(s) (e.g., Pb2+, Sn2+), and X is the halide group (e.g., Cl-, Br-, or I-), the isovalent exchange of A- and X-site ions has been widely accomplished; in contrast, strategies to exchange B-site cations are underexamined. The activation energies for vacancy-mediated diffusion of B-site cations are much higher than those for A- and X-sites, leading to slow doping processes and low doping ratios. Herein we demonstrate a new method that exchanges B-site cations in perovskites. We design a series of metal carboxylate solutions that anchor on the perovskite surface, allowing fast and efficient doping of B-sites with both homovalent and heterovalent cations (e.g., Sn2+, Zn2+, Bi3+) at room temperature. The doping process in the reduced-dimensional perovskites is complete within 1 min, whereas a similar reaction only leads to the surface attachment of dopant ions in three-dimensional structures. We offer a model based on ammonium extraction and surface ion-pair substitution.

Synthetic Control over Quantum Well Width Distribution and Carrier Migration in Low-Dimensional Perovskite Photovoltaics.

Metal halide perovskites have achieved photovoltaic efficiencies exceeding 22%, but their widespread use is hindered by their instability in the presence of water and oxygen. To bolster stability, researchers have developed low-dimensional perovskites wherein bulky organic ligands terminate the perovskite lattice, forming quantum wells (QWs) that are protected by the organic layers. In thin films, the width of these QWs exhibits a distribution that results in a spread of bandgaps in the material arising due to varying degrees of quantum confinement across the population. Means to achieve refined control over this QW width distribution, and to examine and understand its influence on photovoltaic performance, are therefore of intense interest. Here we show that moving to the ligand allylammonium enables a narrower distribution of QW widths, creating a flattened energy landscape that leads to ×1.4 and ×1.9 longer diffusion lengths for electrons and holes, respectively. We attribute this to reduced ultrafast shallow hole trapping that originates from the most strongly confined QWs. We observe an increased PCE of 14.4% for allylammonium-based perovskite QW photovoltaics, compared to 11-12% PCEs obtained for analogous devices using phenethylammonium and butylammonium ligands. We then optimize the devices using mixed-cation strategies, achieving 16.5% PCE for allylammonium devices. The devices retain 90% of their initial PCEs after >650 h when stored under ambient atmospheric conditions.

Tailoring the Energy Landscape in Quasi-2D Halide Perovskites Enables Efficient Green-Light Emission.

Organo-metal halide perovskites are a promising platform for optoelectronic applications in view of their excellent charge-transport and bandgap tunability. However, their low photoluminescence quantum efficiencies, especially in low-excitation regimes, limit their efficiency for light emission. Consequently, perovskite light-emitting devices are operated under high injection, a regime under which the materials have so far been unstable. Here we show that, by concentrating photoexcited states into a small subpopulation of radiative domains, one can achieve a high quantum yield, even at low excitation intensities. We tailor the composition of quasi-2D perovskites to direct the energy transfer into the lowest-bandgap minority phase and to do so faster than it is lost to nonradiative centers. The new material exhibits 60% photoluminescence quantum yield at excitation intensities as low as 1.8 mW/cm2, yielding a ratio of quantum yield to excitation intensity of 0.3 cm2/mW; this represents a decrease of 2 orders of magnitude in the excitation power required to reach high efficiency compared with the best prior reports. Using this strategy, we report light-emitting diodes with external quantum efficiencies of 7.4% and a high luminescence of 8400 cd/m2.

Nanoimprint-Transfer-Patterned Solids Enhance Light Absorption in Colloidal Quantum Dot Solar Cells.

Colloidal quantum dot (CQD) materials are of interest in thin-film solar cells due to their size-tunable bandgap and low-cost solution-processing. However, CQD solar cells suffer from inefficient charge extraction over the film thicknesses required for complete absorption of solar light. Here we show a new strategy to enhance light absorption in CQD solar cells by nanostructuring the CQD film itself at the back interface. We use two-dimensional finite-difference time-domain (FDTD) simulations to study quantitatively the light absorption enhancement in nanostructured back interfaces in CQD solar cells. We implement this experimentally by demonstrating a nanoimprint-transfer-patterning (NTP) process for the fabrication of nanostructured CQD solids with highly ordered patterns. We show that this approach enables a boost in the power conversion efficiency in CQD solar cells primarily due to an increase in short-circuit current density as a result of enhanced absorption through light-trapping.

Precise Control of Thermal and Redox Properties of Organic Hole-Transport Materials.

We report design principles of the thermal and redox properties of synthetically accessible spiro-based hole transport materials (HTMs) and show the relevance of these findings to high-performance perovskite solar cells (PSCs). The chemical modification of an asymmetric spiro[fluorene-9,9'-xanthene] core is amenable to selective placement of redox active triphenylamine (TPA) units. We therefore leveraged computational techniques to investigate five HTMs bearing TPA groups judiciously positioned about this asymmetric spiro core. It was determined that TPA groups positioned about the conjugated fluorene moiety increase the free energy change for hole-extraction from the perovskite layer, while TPAs about the xanthene unit govern the Tg values. The synergistic effects of these characteristics resulted in an HTM characterized by both a low reduction potential (≈0.7 V vs. NHE) and a high Tg value (>125 °C) to yield a device power conversion efficiency (PCE) of 20.8 % in a PSC.

Compound Homojunction:Heterojunction Reduces Bulk and Interface Recombination in ZnO Photoanodes for Water Splitting.

Photoelectrochemical water splitting is far more efficient thanks to the novel ZnOSe/ZnO/BZO thin-film photoanodes fabricated in this work. A novel structure is developed for simultaneously suppressing the charge recombination in the ZnO bulk and at the semiconductor-electrolyte interface. This structure achieves a five-fold enhancement in water-splitting performance, compared to that of pristine ZnO photoanodes, when illuminated using visible light.

10.6% Certified Colloidal Quantum Dot Solar Cells via Solvent-Polarity-Engineered Halide Passivation.

Colloidal quantum dot (CQD) solar cells are solution-processed photovoltaics with broad spectral absorption tunability. Major advances in their efficiency have been made via improved CQD surface passivation and device architectures with enhanced charge carrier collection. Herein, we demonstrate a new strategy to improve further the passivation of CQDs starting from the solution phase. A cosolvent system is employed to tune the solvent polarity in order to achieve the solvation of methylammonium iodide (MAI) and the dispersion of hydrophobic PbS CQDs simultaneously in a homogeneous phase, otherwise not achieved in a single solvent. This process enables MAI to access the CQDs to confer improved passivation. This, in turn, allows for efficient charge extraction from a thicker photoactive layer device, leading to a certified solar cell power conversion efficiency of 10.6%, a new certified record in CQD photovoltaics.

Enhancing the driving field for plasmonic nanoparticles in thin-film solar cells.

The scattering cross-section of a plasmonic nanoparticle is proportional to the intensity of the electric field that drives the plasmon resonance. In this work we determine the driving field pattern throughout a complete thin-film silicon solar cell. Our simulations reveal that by tuning of the thicknesses of silicon and transparent conductive oxide layers the driving field intensity experienced by an embedded plasmonic nanoparticle can be enhanced up to a factor of 14. This new insight opens the route towards more efficient plasmonic light trapping in thin-film solar cells.

Reducing Perovskite/C60 Interface Losses via Sequential Interface Engineering for Efficient Perovskite/Silicon Tandem Solar Cell.

Wide-bandgap (WBG) perovskite solar cells hold tremendous potential for realizing efficient tandem solar cells. However, nonradiative recombination and carrier transport losses occurring at the perovskite/electron-selective contact (e.g. C60 ) interface present significant obstacles in approaching their theoretical efficiency limit. To address this, a sequential interface engineering (SIE) strategy that involves the deposition of ethylenediamine diiodide (EDAI2 ) followed by sequential deposition of 4-Fluoro-Phenethylammonium chloride (4F-PEACl) is implemented. The SIE technique synergistically narrows the conduction band offset and reduces recombination velocity at the perovskite/C60 interface. The best-performing WBG perovskite solar cell (1.67 eV) delivers a power conversion efficiency (PCE) of 21.8% and an impressive open-circuit voltage of 1.262 V. Moreover, through integration with double-textured silicon featuring submicrometer pyramid structures, a stabilized PCE of 29.6% is attained for a 1 cm2 monolithic perovskite/silicon tandem cell (certified PCE of 29.0%).

Scalable Solution-Processed Hybrid Electron Transport Layers for Efficient All-Perovskite Tandem Solar Modules.

All-perovskite tandem solar cells offer the potential to surpass the Shockley-Queisser (SQ) limit efficiency of single-junction solar cells while maintaining the advantages of low-cost and high-productivity solution processing. However, scalable solution processing of electron transport layer (ETL) in p-i-n structured perovskite solar subcells remains challenging due to the rough perovskite film surface and energy level mismatch between ETL and perovskites. Here, scalable solution processing of hybrid fullerenes (HF) with blade-coating on both wide-bandgap (≈1.80 eV) and narrow-bandgap (≈1.25 eV) perovskite films in all-perovskite tandem solar modules is developed. The HF, comprising a mixture of fullerene (C60 ), phenyl C61 butyric acid methyl ester, and indene-C60 bisadduct, exhibits improved conductivity, superior energy level alignment with both wide- and narrow-bandgap perovskites, and reduced interfacial nonradiative recombination when compared to the conventional thermal-evaporated C60 . With scalable solution-processed HF as the ETLs, the all-perovskite tandem solar modules achieve a champion power conversion efficiency of 23.3% (aperture area = 20.25 cm2 ). This study paves the way to all-solution processing of low-cost and high-efficiency all-perovskite tandem solar modules in the future.

Homogeneous crystallization and buried interface passivation for perovskite tandem solar modules.

Scalable fabrication of all-perovskite tandem solar cells is challenging because the narrow-bandgap subcells made of mixed lead-tin (Pb-Sn) perovskite films suffer from nonuniform crystallization and inferior buried perovskite interfaces. We used a dopant from Good's list of biochemical buffers, aminoacetamide hydrochloride, to homogenize perovskite crystallization and used it to extend the processing window for blade-coating Pb-Sn perovskite films and to selectively passivate defects at the buried perovskite interface. The resulting all-perovskite tandem solar module exhibited a certified power conversion efficiency of 24.5% with an aperture area of 20.25 square centimeters.