Surface reaction for efficient and stable inverted perovskite solar cells.

Perovskite solar cells (PSCs) with an inverted structure (often referred to as the p-i-n architecture) are attractive for future commercialization owing to their easily scalable fabrication, reliable operation and compatibility with a wide range of perovskite-based tandem device architectures1,2. However, the power conversion efficiency (PCE) of p-i-n PSCs falls behind that of n-i-p (or normal) structure counterparts3-6. This large performance gap could undermine efforts to adopt p-i-n architectures, despite their other advantages. Given the remarkable advances in perovskite bulk materials optimization over the past decade, interface engineering has become the most important strategy to push PSC performance to its limit7,8. Here we report a reactive surface engineering approach based on a simple post-growth treatment of 3-(aminomethyl)pyridine (3-APy) on top of a perovskite thin film. First, the 3-APy molecule selectively reacts with surface formamidinium ions, reducing perovskite surface roughness and surface potential fluctuations associated with surface steps and terraces. Second, the reaction product on the perovskite surface decreases the formation energy of charged iodine vacancies, leading to effective n-type doping with a reduced work function in the surface region. With this reactive surface engineering, the resulting p-i-n PSCs obtained a PCE of over 25 per cent, along with retaining 87 per cent of the initial PCE after over 2,400 hours of 1-sun operation at about 55 degrees Celsius in air.

Green Synthesis of Carboxymethyl Chitosan-Based CuInS2 QDs with Luminescent Response toward Pb2+ Ion and Its Application in Bioimaging.

Polysaccharide-based QDs have attracted great attention in the field of biological imaging and diagnostics. How to get rid of the high heavy metal toxicity resulting from conventional Cd- and Pb-based QDs is now the main challenge. Herein, we offer a simple and environmentally friendly approach for the "direct" interaction of thiol-ending carboxymethyl chitosan (CMC-SH) with metal salt precursors, resulting in CuInS2 QDs based on polysaccharides. A nucleation-growth mechanism based on the LaMer model can explain how CMC-CuInS2 QDs are formed. As-prepared water-soluble CMC-CuInS2 QDs exhibit monodisperse particles with sizes of 5.5-6.5 nm. CMC-CuInS2 QDs emit the bright-green fluorescence at 530 nm when excited at 466 nm with the highest quantum yield of ∼18.0%. Meanwhile, the fluorescence intensity of CMC-CuInS2 QD aqueous solution is quenched with the addition of Pb2+ and the minimal limit of detection is as little as 0.4 nM. Furthermore, due to its noncytotoxicity, great biocompatibility, and strong biorecognition ability, CMC-CuInS2 QDs can be exploited as a possible cell membrane imaging reagent. The imaging studies also demonstrate that CMC-CuInS2 QDs are suitable for Pb2+ detection in live cells and living organisms (zebrafish). Thus, this work offers such an efficient, green, and practical method for creating low-toxicity and water-soluble QD nanosensors for a sensitive and selective detection of toxic metal ion in live cells and organisms.

Green synthesis of glyco-CuInS2 QDs with visible/NIR dual emission for 3D multicellular tumor spheroid and in vivo imaging.

Glyco-quantum dots (glyco-QDs) have attracted significant interest in bioimaging applications, notably in cancer imaging, because they effectively combine the glycocluster effect with the exceptional optical properties of QDs. The key challenge now lies in how to eliminate the high heavy metal toxicity originating from traditional toxic Cd-based QDs for in vivo bioimaging. Herein, we report an eco-friendly pathway to prepare nontoxic Cd-free glyco-QDs in water by the "direct" reaction of thiol-ending monosaccharides with metal salts precursors. The formation of glyco-CuInS2 QDs could be explained by a nucleation-growth mechanism following the LaMer model. As-prepared four glyco-CuInS2 QDs were water-soluble, monodispersed, spherical in shape and exhibited size range of 3.0-4.0 nm. They exhibited well-separated dual emission in the visible region (500-590 nm) and near-infrared range (~ 827 nm), which may be attributable to visible excitonic emission and near-infrared surface defect emission. Meanwhile, the cell imaging displayed the reversibly distinct dual-color (green and red) fluorescence in tumor cells (HeLa, A549, MKN-45) and excellent membrane-targeting properties of glyco-CuInS2 QDs based on their good biorecognition ability. Importantly, these QDs succeed in penetrating uniformly into the interior (the necrotic zone) of 3D multicellular tumor spheroids (MCTS) due to their high negative charge (zeta potential values ranging from - 23.9 to - 30.1 mV), which overcame the problem of poor penetration depth of existing QDs in in vitro spheroid models. So, confocal analysis confirmed their excellent ability to penetrate and label tumors. Thus, the successful application in in vivo bioimaging of these glyco-QDs verified that this design strategy is an effective, low cost and simple procedure for developing green nanoparticles as cheap and promising fluorescent bioprobes.

Ce-Substituted Spinel CuCo2O4 Quantum Dots with High Oxygen Vacancies and Greatly Improved Electrocatalytic Activity for Oxygen Evolution Reaction.

Exploring effective electrocatalysts for oxygen evolution reaction (OER) is a crucial requirement of many energy storage and transformation systems, involving fuel cells, water electrolysis, and metal-air batteries. Transition-metal oxides (TMOs) have attracted much attention to OER catalysts because of their earth abundance, tunable electronic properties, and so forth. Defect engineering is a general and the most important strategy to tune the electronic structure and control size, and thus improve their intrinsic activities. Herein, OER performance on spinel CuCo2O4 was greatly enhanced through cation substitution and size reduction. Ce-substituted spinel CuCeδCo2-δOx (δ = 0.45, 0.5 and 0.55) nanoparticles in the quantum dot scale (2-8 nm) were synthesized using a simple and facile phase-transfer coprecipitation strategy. The as-prepared samples were highly dispersed and have displayed a low overpotential of 294 mV at 10 mA·cm-2 and a Tafel slope of 57.5 mV·dec-1, which outperform commercial RuO2 and the most high-performance analogous catalysts reported. The experimental and calculated results all confirm that Ce substitution with an appropriate content can produce rich oxygen vacancies, tune intermediate absorption, consequently lower the energy barrier of the determining step, and greatly enhance the OER activity of the catalysts. This work not only provides advanced OER catalysts but also opens a general avenue to understand the structure-activity relationship of pristine TMO catalysts deeply in the quantum dot scale and the rational design of more efficient OER catalysts.

Free-Standing Conducting Polymer Films for High-Performance Energy Devices.

Thick, uniform, easily processed, highly conductive polymer films are desirable as electrodes for solar cells as well as polymer capacitors. Here, a novel scalable strategy is developed to prepare highly conductive thick poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (HCT-PEDOT:PSS) films with layered structure that display a conductivity of 1400 S cm(-1) and a low sheet resistance of 0.59 ohm sq(-1). Organic solar cells with laminated HCT-PEDOT:PSS exhibit a performance comparable to the reference devices with vacuum-deposited Ag top electrodes. More importantly, the HCT-PEDOT:PSS film delivers a specific capacitance of 120 F g(-1) at a current density of 0.4 A g(-1). All-solid-state flexible symmetric supercapacitors with the HCT-PEDOT:PSS films display a high volumetric energy density of 6.80 mWh cm(-3) at a power density of 100 mW cm(-3) and 3.15 mWh cm(-3) at a very high power density of 16160 mW cm(-3) that outperforms previous reported solid-state supercapacitors based on PEDOT materials.

Metal electrode-free perovskite solar cells with transfer-laminated conducting polymer electrode.

We report perovskite solar cells with a new device structure that employ highly conductive polymer poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) ( PEDOT: PSS) as the top electrode replacing commonly used metal electrodes. The PEDOT: PSS top electrode is prepared from its aqueous solution through a transfer-lamination technique rather than direct spin-coating, which converts the CH(3)NH(3)PbI(3) into PbI(2). Perovskite solar cells with the structure of glass/FTO/c-TiO(2)/m-TiO(2)/CH(3)NH(3)PbI(3)/spiro-OMeTAD/PEDOT:PSS yield a maximum open-circuit voltage (V(OC)) of 1.02 V, and a maximum power conversion efficiency (PCE) of 11.29% under AM1.5 100 mW/cm(2) illumination. The whole device was fabricated in air without high-vacuum deposition which simplifies the processing and lowers the threshold of both scientific research and industrial production of perovskite solar cells.

Enhanced performance of InGaN/GaN based solar cells with an In(0.05)Ga(0.95)N ultra-thin inserting layer between GaN barrier and In(0.2)Ga(0.8)N well.

The effect of ultra-thin inserting layer (UIL) on the photovoltaic performances of InGaN/GaN solar cells is investigated. With UIL implemented, the open-circuit voltage was increased from 1.4 V to 1.7 V, short-circuit current density was increased by 65% and external quantum efficiency was increased by 59%, compared to its counterparts at room temperature under 1-sun AM1.5G illumination. The improvements in electrical and photovoltaic properties are mainly attributed to the UIL which can boost the crystal quality and alleviate strain. Moreover, it can act as a transition layer for higher indium incorporation and an effective light sub-absorption layer in multiple quantum wells.

Bioinspired stability enhancement in deuterium-substituted organic-inorganic hybrid perovskite solar cells.

In hybrid perovskite solar cells (PSCs), the reaction of hydrogens (H) located in the amino group of the organic A-site cations with their neighboring halides plays a central role in degradation. Inspired by the retarded biological activities of cells in heavy water, we replaced the light H atom with its abundant, twice-as-heavy, nonradioactive isotope, deuterium (D) to hamper the motion of H. This D substitution retarded the formation kinetics of the detrimental H halides in Pb-based PSCs, as well as the H bond-mediated oxidation of Sn2+ in Sn-Pb-based narrow-bandgap PSCs, evidenced by accelerated stability studies. A computational study indicated that the zero point energy of D-based formamidinium (FA) is lower than that of pristine FA. In addition, the smaller increase in entropy in D-based FA than in pristine FA accounts for the increased formation free energy of the Sn2+ vacancies, which leads to the retarded oxidation kinetics of Sn2+. In this study, we show that substituting active H with D in organic cations is an effective way to enhance the stability of PSCs without sacrificing photovoltaic (PV) performance. This approach is also adaptable to other stabilizing methods.

Low-Cost Fabrication of Efficient Perovskite Photovoltaics Using Low-Purity Lead Iodide via Powder Engineering.

Low cost is the eternal theme for any commercial production. Numerous efforts have been explored to realize low-cost, high-efficiency perovskite solar cells (PSCs), such as replacing the traditional spin-coating method with an economical printing strategy, simplifying the device structure, reducing the number of functional layers, etc. However, there are few reports on the use of low-cost precursors. Herein, we enable the low-cost fabrication of efficient PSCs based on a very cheaper low-purity PbI2 via powder engineering. The low-purity PbI2 is blended with formamidinium iodide followed by dissolving in a 2-methoxyethanol solvent, and then, the high-quality FAPbI3 powders are formed via an inverse temperature crystallization process and solvent washing after several simple processes to reduce the impurities. As a result, the devices fabricated using the as-synthesized black powders based on the low-purity PbI2 exhibit a champion power conversion efficiency (PCE) of 23.9% and retained ∼95% of the initial PCE after ∼400 h of storage in the conditions of 25 ± 5 °C and 25 ± 5 RH% without encapsulation. In addition, the upscaling fabrication of a 5 cm × 5 cm solar minimodule also demonstrates an impressive efficiency of 19.5%. Our findings demonstrate an economic strategy for the commercialization of PSCs from the perspective of low-cost production.

Nonconjugated fluorescent polymer nanoparticles by self-assembly of PIMA-g-ß-CD for live-cell long-term tracking.

Fluorescent non-conjugated nanoparticles without any π-aromatic building blocks are of great interest in biological applications due to their low cytotoxicity and biocompatibility. Herein, the non-conjugated AIE-active polymer nanoparticles bearing ß-cyclodextrin (ß-CD-PNs) were obtained through self-assembly of amphiphilic poly(isobutylene-alt-maleic anhydride)-g-ß-CD (PIMA-g-ß-CD). Unexpectedly, ß-CD-PNs without conventional AIE fluorophores showed strong fluorescence emission in the aggregated state, excellent photostability and water-solubility. More interestingly, ß-CD-PNs showed excellent biocompatibility and low biotoxicity after being co-incubated with HeLa cells and passaged several times. As a result, the strong blue fluorescence signals could still be detected in HeLa cells after up to 15 generations of passages and showed complete cell morphology. Furthermore, ß-CD-PNs could also be used in zebrafish for bioimaging. The results indicated that ß-CD-PNs was a good choice as a tracer for long-term cell tracking and in vivo imaging agent. Our research provided an effective strategy for developing low-toxicity bioprobes based on ß-CD.

Compositional texture engineering for highly stable wide-bandgap perovskite solar cells.

The development of highly stable and efficient wide-bandgap (WBG) perovskite solar cells (PSCs) based on bromine-iodine (Br-I) mixed-halide perovskite (with Br greater than 20%) is critical to create tandem solar cells. However, issues with Br-I phase segregation under solar cell operational conditions (such as light and heat) limit the device voltage and operational stability. This challenge is often exacerbated by the ready defect formation associated with the rapid crystallization of Br-rich perovskite chemistry with antisolvent processes. We combined the rapid Br crystallization with a gentle gas-quench method to prepare highly textured columnar 1.75-electron volt Br-I mixed WBG perovskite films with reduced defect density. With this approach, we obtained 1.75-electron volt WBG PSCs with greater than 20% power conversion efficiency, approximately 1.33-volt open-circuit voltage (Voc), and excellent operational stability (less than 5% degradation over 1100 hours of operation under 1.2 sun at 65°C). When further integrated with 1.25-electron volt narrow-bandgap PSC, we obtained a 27.1% efficient, all-perovskite, two-terminal tandem device with a high Voc of 2.2 volts.

Wide-Bandgap Metal Halide Perovskites for Tandem Solar Cells.

Metal halide perovskite solar cells (PSCs) have become the most promising new-generation solar cell technology. To date, perovskites also represent the only polycrystalline thin-film absorber technology that has enabled >20% efficiency for wide-bandgap solar cells, making wide-bandgap PSCs uniquely positioned to enable high-efficiency and low-cost tandem solar cell technologies by coupling wide-bandgap perovskites with low-bandgap absorbers. In this Focus Review, we highlight recent research progress on developing wide-bandgap PSCs, including the key mechanisms associated with efficiency loss and instability as well as strategies for overcoming these challenges. We also discuss recent accomplishments and research trends on using wide-bandgap PSCs in perovskite-based tandem configurations, including perovskite/perovskite, perovskite/Si, perovskite/CIGS, and other emerging tandem technologies.

Efficient, stable silicon tandem cells enabled by anion-engineered wide-bandgap perovskites.

Maximizing the power conversion efficiency (PCE) of perovskite/silicon tandem solar cells that can exceed the Shockley-Queisser single-cell limit requires a high-performing, stable perovskite top cell with a wide bandgap. We developed a stable perovskite solar cell with a bandgap of ~1.7 electron volts that retained more than 80% of its initial PCE of 20.7% after 1000 hours of continuous illumination. Anion engineering of phenethylammonium-based two-dimensional (2D) additives was critical for controlling the structural and electrical properties of the 2D passivation layers based on a lead iodide framework. The high PCE of 26.7% of a monolithic two-terminal wide-bandgap perovskite/silicon tandem solar cell was made possible by the ideal combination of spectral responses of the top and bottom cells.

Carrier lifetimes of >1 µs in Sn-Pb perovskites enable efficient all-perovskite tandem solar cells.

All-perovskite-based polycrystalline thin-film tandem solar cells have the potential to deliver efficiencies of >30%. However, the performance of all-perovskite-based tandem devices has been limited by the lack of high-efficiency, low-band gap tin-lead (Sn-Pb) mixed-perovskite solar cells (PSCs). We found that the addition of guanidinium thiocyanate (GuaSCN) resulted in marked improvements in the structural and optoelectronic properties of Sn-Pb mixed, low-band gap (~1.25 electron volt) perovskite films. The films have defect densities that are lower by a factor of 10, leading to carrier lifetimes of greater than 1 microsecond and diffusion lengths of 2.5 micrometers. These improved properties enable our demonstration of >20% efficient low-band gap PSCs. When combined with wider-band gap PSCs, we achieve 25% efficient four-terminal and 23.1% efficient two-terminal all-perovskite-based polycrystalline thin-film tandem solar cells.

Direct thermolysis of CO2 into CO and O2.

Most of the solar-driven thermochemical CO2 dissociation reactions have been focused on two-step processes. In this study, a one step CO2 thermolysis process was considered. It was found that direct thermolysis of CO2 obviously occurred at temperatures as low as 1200 °C within a corundum tube. The reaction rate could be enhanced by several times in the presence of metal oxides, which may be attributed to the catalysis of oxygen vacancies in the metal oxides.

Nonreduction-Active Hole-Transporting Layers Enhancing Open-Circuit Voltage and Efficiency of Planar Perovskite Solar Cells.

Inverted planar perovskite solar cells using poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) as the hole-transporting layer (HTL) are very attractive because of their low-temperature and easy processing. However, the planar cells with the PEDOT:PSS HTL typically display lower open-circuit voltage (VOC) (about 0.90 V) than that of devices with TiO2-based conventional structure (1.0-1.1 V). The underlying reasons are still not clear. In this work, we report the PEDOT:PSS that is intrinsically p-doped can be chemically reduced by methylamine iodide (MAI) and MAPbI3. The reaction reduces the work function (WF) of PEDOT:PSS, which suppresses the efficient hole collection and yields lower VOC. To overcome this issue, we adopt undoped semiconducting polymers that are intrinsically nonreduction-active (NRA) as the HTL for inverted planar perovskite solar cells. The cells display enhanced VOC from 0.88 ± 0.04 V (PEDOT:PSS HTL, reference cells) to 1.02 ± 0.03 V (P3HT HTL) and 1.04 ± 0.03 V (PTB7 and PTB-Th HTL). The power conversion efficiency (PCE) of the devices with these NRA HTL reaches about 17%.

AIE-Active Tetraphenylethylene Cross-Linked N-Isopropylacrylamide Polymer: A Long-Term Fluorescent Cellular Tracker.

There is a great demand to understand cell transplantation, migration, division, fusion, and lysis. Correspondingly, illuminant object-labeled bioprobes have been employed as long-term cellular tracers, which could provide valuable insights into detecting these biological processes. In this work, we designed and synthesized a fluorescent polymer, which was comprised of hydrophilic N-isopropylacrylamide polymers as matrix and a hydrophobic tetraphenylethene (TPE) unit as AIE-active cross-linkers (DDBV). It was found that when the feed molar ratio of N-isopropylacrylamides to cross-linkers was 22:1, the produced polymers demonstrated the desirable LCST at 37.5 °C. And also, the temperature sensitivity of polymers could induce phase transfer within a narrow window (32-38 °C). Meanwhile, phase transfer was able to lead the florescent response. And thus, we concluded that two responses occur when one stimulus is input. Therefore, the new cross-linker of DDBV rendered a new performance from PNIPAm and a new chance to create new materials. Moreover, the resulted polymers demonstrated very good biocompatibility with living A549 human lung adenocarcinoma cells and L929 mouse fibroblast cells, respectively. Both of these cells retained very active viabilities in the concentration range of 7.8-125 µL/mg of polymers. Notably, P[(NIPAm)22-(DDBV)1] (P6) could be readily internalized by living cells with a noninvasive manner. The cellular staining by the fluorescent polymer is so indelible that it enables cell tracing for at least 10 passages.

Conductivity Enhancement of PEDOT:PSS Films via Phosphoric Acid Treatment for Flexible All-Plastic Solar Cells.

Highly conductive polymer films on plastic substrates are desirable for the application of flexible electronics. Here, we report the conductivity of poly(3,4-ethylenedioxythiophene): poly(styrenesulfonate) ( PEDOT: PSS) can be enhanced to 1460 S/cm via phosphoric acid (H3PO4) treatment. The conductivity enhancement is associated with the partial removal of PSS from the film. The H3PO4 treatment is compatible with plastic substrates, while sulfuric acid (H2SO4) can easily damage the plastic substrate. With the flexible electrode of poly(ether sulfone) (PES)/H3PO4-treated PEDOT: PSS, we have demonstrated flexible all-plastic solar cells (PES/H3PO4-treated PEDOT: PSS/PEI/P3HT:ICBA/EG-PEDOT:PSS). The cells exhibit an open-circuit voltage of 0.84 V, a fill factor of 0.60, and a power conversion efficiency of 3.3% under 100 mW/cm(2) white light illumination.

Polyethylenimine aqueous solution: a low-cost and environmentally friendly formulation to produce low-work-function electrodes for efficient easy-to-fabricate organic solar cells.

Polyethylenimine (PEI) has been widely used to produce low-work-function electrodes. Generally, PEI modification is prepared by spin coating from 2-methoxyethanol solution. In this work, we explore the method for PEI modification on indium tin oxide (ITO) by dipping the ITO sample into PEI aqueous solution for organic solar cells. The PEI prepared in this method could reduce the work function of ITO as effectively as PEI prepared by spin coating from 2-methoxyethanol solution. H2O as the processing solvent is more environmentally friendly and much cheaper compared to the 2-methoxyethanol solvent. The dipping method is also compatible with large-area samples. With low-work-function ITO treated by the dipping method, solar cells with a simple structure of glass/ITO/PEI(dipping)/P3HT:ICBA/PEDOT:PSS(vacuum-free processing) display a high open-circuit voltage of 0.86 ± 0.01, a high fill factor of 66 ± 2%, and power conversion efficiency of 4.4 ± 0.3% under 100 mW/cm(2) illumination.

Highly ordered GaN-based nanowire arrays grown on patterned (100) silicon and their optical properties.

Arrays of GaN-based nanowires have been synthesized on patterned silicon without a catalyst. The spatial density, length and average radius of the nanowires can be well-controlled. The GaN core contains two semipolar facets and a controllable polar facet. The nanowire heterostructures exhibit excellent laser behavior.