High-efficiency, flexible and large-area red/green/blue all-inorganic metal halide perovskite quantum wires-based light-emitting diodes.

Metal halide perovskites have shown great promise as a potential candidate for next-generation solid state lighting and display technologies. However, a generic organic ligand-free and antisolvent-free solution method to fabricate highly efficient full-color perovskite light-emitting diodes has not been realized. Herein, by utilizing porous alumina membranes with ultra-small pore size as templates, we have successfully fabricated crystalline all-inorganic perovskite quantum wire arrays with ultrahigh density and excellent uniformity, using a generic organic ligand-free and anti-solvent-free solution method. The quantum confinement effect, in conjunction with the high light out-coupling efficiency, results in high photoluminescence quantum yield for blue, sky-blue, green and pure-red perovskite quantum wires arrays. Consequently, blue, sky-blue, green and pure-red LED devices with spectrally stable electroluminescence have been successfully fabricated, demonstrating external quantum efficiencies of 12.41%, 16.49%, 26.09% and 9.97%, respectively, after introducing a dual-functional small molecule, which serves as surface passivation and hole transporting layer, and a halide vacancy healing agent.

Inverted perovskite solar cells using dimethylacridine-based dopants.

Doping of perovskite semiconductors1 and passivation of their grain boundaries2 remain challenging but essential for advancing high-efficiency perovskite solar cells. Particularly, it is crucial to build perovskite/indium tin oxide (ITO) Schottky contact based inverted devices without predepositing a layer of hole-transport material3-5. Here we report a dimethylacridine-based molecular doping process used to construct a well-matched p-perovskite/ITO contact, along with all-round passivation of grain boundaries, achieving a certified power conversion efficiency (PCE) of 25.39%. The molecules are shown to be extruded from the precursor solution to the grain boundaries and the bottom of the film surface in the chlorobenzene-quenched crystallization process, which we call a molecule-extrusion process. The core coordination complex between the deprotonated phosphonic acid group of the molecule and lead polyiodide of perovskite is responsible for both mechanical absorption and electronic charge transfer, and leads to p-type doping of the perovskite film. We created an efficient device with a PCE of 25.86% (reverse scan) and that maintained 96.6% of initial PCE after 1,000 h of light soaking.

Simple and robust phenoxazine phosphonic acid molecules as self-assembled hole selective contacts for high-performance inverted perovskite solar cells.

For inverted perovskite solar cells (PSCs), the interfacial defects and mismatched energy levels between the perovskite absorber and charge-selective layer restrain the further improvement of photovoltaic performance. Interfacial modification is a powerful tool for defect passivation and energy level turning by developing new charge-selective materials. Herein, we report three new molecules, 2BrCzPA, 2BrPTZPA, and 2BrPXZPA as self-assembled hole selective contacts (SA-HSCs) by an economical and efficient synthetic procedure. Benefiting from the stronger electron-donating ability of phenothiazine and phenoxazine compared to that of carbazole, 2BrPTZPA and 2BrPXZPA showed more matched energy levels and decreased energy loss. In addition, the ITO substrate coated with 2BrPTZPA and 2BrPXZPA could induce higher-quality perovskite crystal growth without obvious grain boundaries in the vertical direction. Consequently, the corresponding inverted PSCs with decreased trap state density achieved high power convention efficiencies (PCEs) of 22.06% and 22.93% (certified 22.38%) for 2BrPTZPA and 2BrPXZPA, respectively. Furthermore, the 2BrPXZPA-based device with encapsulation retained 97% of the initial efficiency after 600 h of maximum power point tracking under one sun continuous illumination. Finally, 2BrPXZPA was also used for the surface modification of NiOx, and the inverted PSC based on the NiOx/2BrPXZPA bilayer achieved a higher PCE of 23.66% with an open circuit voltage of 1.21 V. This work extends the design strategy of SA-HSCs for efficient and stable inverted PSCs and promotes the commercialization process.

Vertical Heterogeneous Integration of Metal Halide Perovskite Quantum-Wires/Nanowires for Flexible Narrowband Photodetectors.

Charge collection narrowing (CCN) has been reported to be an efficient strategy to achieve optical filter-free narrowband photodetection (NPD) with metal halide perovskite (MHP) single crystals. However, the necessity of utilizing thick crystals in CCN limits their applications in large scale, flexible, self-driven, and high-performance optoelectronics. Here, for the first time, we fabricate vertically integrated MHP quantum wire/nanowire (QW/NW) array based photodetectors in nanoengineered porous alumina membranes (PAMs) showing self-driven broadband photodetection (BPD) and NPD capability simultaneously. Two cutoff detection edges of the NPDs are located at around 770 and 730 nm, with a full-width at half-maxima (fwhm) of around 40 nm. The optical bandgap difference between the NWs and the QWs, in conjunction with the high carrier recombination rate in QWs, contributes to the intriguing NPD performance. Thanks to the excellent mechanical flexibility of the PAMs, a flexible NPD is demonstrated with respectable performance. Our work here opens a new pathway to design and engineer a nanostructured MHP for novel color selective and full color sensing devices.

Heterogeneous 2D/3D Tin-Halides Perovskite Solar Cells with Certified Conversion Efficiency Breaking 14.

As the most promising lead-free one, tin-halides based perovskite solar cells still suffer from the severe bulk-defect due to the easy oxidation of tin from divalent to tetravalent. Here, a general and effective strategy is delivered to modulate the microstructure of 2D/3D heterogeneous tin-perovskite absorber films by substituting FAI with FPEABr in FASnI3 . The introduction of 2D phase can induce highly oriented growth of 3D FASnI3 and it is revealed in the optimal 2D/3D film that 2D phase embraces 3D grains and locates at the surfaces and grain boundaries. The FPEA+ based 2D tin-perovskite capping layer can offer a reducing atmosphere for vulnerable 3D FASnI3 grains. The unique microstructure effectively suppresses the well-known oxidation from Sn2+ to Sn4+ , as well as decreasing defect density, which leads to a remarkable enhanced device performance from 9.38% to 14.81% in conversion efficiency. The certified conversion efficiency of 14.03% announces a new record and moves a remarkable step from the last one (12.4%). Besides of this breakthrough, this work definitely paves a new way to fabricate high-quality tin-perovskite absorber film by constructing effective 2D/3D microstructures.

Dialkylamines Driven Two-Step Recovery of NiOx/ITO Substrates for High-Reproducibility Recycling of Perovskite Solar Cells.

Because of the toxicity of water-soluble lead, the recycling of organic-inorganic lead-halides perovskite solar cells (PSCs) has attracted increasing attention. Here, we report a highly reliable two-step process to recycle cost-dominated indium-tin-oxide (ITO) substrates coated with NiOx and regenerate their based PSCs by function of dialkylamines. The champion recycled PSC can achieve 20% in conversion-efficiency, higher than 17.92% of the fresh one. Strikingly, the regenerated devices can remain superior to the fresh ones in the first 7 of 10 recycles. The comprehensive X-ray photoelectronic spectroscopy analysis reveals that dipropylamine has a suitable interaction with NiOx surfaces by Ni-N coordination, enabling its effective interfacial passivation and template effect of high-quality growth of perovskites. That leads to the suppressed nonradiative recombination of both interfacial and bulk, and finally improves the device performances. The dialkylamines driven two-step recycling process offers a promising and highly reproducible strategy to recycle PSCs, especially the cost-dominated NiOx/ITO substrates.

Interfacial stabilization for inverted perovskite solar cells with long-term stability.

Perovskite solar cells (PSCs) commonly exhibit significant performance degradation due to ion migration through the top charge transport layer and ultimately metal electrode corrosion. Here, we demonstrate an interfacial management strategy using a boron chloride subphthalocyanine (Cl6SubPc)/fullerene electron-transport layer, which not only passivates the interfacial defects in the perovskite, but also suppresses halide diffusion as evidenced by multiple techniques, including visual element mapping by electron energy loss spectroscopy. As a result, we obtain inverted PSCs with an efficiency of 22.0% (21.3% certified), shelf life of 7000 h, T80 of 816 h under damp heat stress (compared to less than 20 h without Cl6SubPc), and initial performance retention of 98% after 2000 h at 80 °C in inert environment, 90% after 2034 h of illumination and maximum power point tracking in ambient for encapsulated devices and 95% after 1272 h outdoor testing ISOS-O-1. Our strategy and results pave a new way to move PSCs forward to their potential commercialization solidly.

Lanthanide-Induced Photoluminescence in Lead-Free Cs2AgBiBr6 Bulk Perovskite: Insights from Optical and Theoretical Investigations.

Emphasis was recently placed on the Cs2AgBiBr6 double perovskite as a possible candidate to substitute toxic lead in metal halide perovskites. However, its poor light-emissive features currently make it unsuitable for solid-state lighting. Lanthanide doping is an established strategy to implement luminescence in poorly emissive materials, with the additional advantage of fine-tuning the emission wavelength. We discuss here the impact of Eu and Yb doping on the optical properties of Cs2AgBiBr6 thin films, obtained from the solution processing of hydrothermally synthesized bulk crystalline powders, by combining experiments and density functional theory calculations. Eu(III) incorporation does not lead to the characteristic 5D0 → 7F2 emission feature at 2 eV, while only a weak trap-assisted sub-band gap radiative emission is reported. Oppositely, we demonstrate that incorporated Yb(III) leads to an intense and exclusive photoluminescence emission in the near-infrared as a result of the efficient sensitization of the lanthanide 2F5/2 → 2F7/2 transition.

Piezoelectric Energy Harvester Based on LiNbO3 Thin Films.

This paper reports the results of the influence of the energy of laser pulses during laser ablation on the morphology and electro-physical properties of LiNbO3 nanocrystalline films. It is found that increasing laser pulse energy from 180 to 220 mJ results in the concentration of charge carriers in LiNbO3 films decreasing from 8.6 × 1015 to 1.0 × 1013 cm-3, with the mobility of charge carriers increasing from 0.43 to 17.4 cm2/(V·s). In addition, experimental studies of sublayer material effects on the geometric parameters of carbon nanotubes (CNTs) are performed. It is found that the material of the lower electrode has a significant effect on the formation of CNTs. CNTs obtained at the same growth time on a sample with a Cr sublayer have a smaller diameter and a longer length compared to samples with a V sublayer. Based on the obtained results, the architecture of the energy nanogenerator is proposed. The current generated by the nanogenerator is 18 nA under mechanical stress of 600 nN. The obtained piezoelectric nanogenerator parameters are used to estimate the parameters of the hybrid-carbon-nanostructures-based piezoelectric energy converter. Obtained results are promising for the development of efficient energy converters for alternative energy devices based on lead-free ferroelectric films.

Teaching an Old Anchoring Group New Tricks: Enabling Low-Cost, Eco-Friendly Hole-Transporting Materials for Efficient and Stable Perovskite Solar Cells.

As a key component in perovskite solar cells (PVSCs), hole-transporting materials (HTMs) have been extensively explored and studied. Aiming to meet the requirements for future commercialization of PVSCs, HTMs which can enable excellent device performance with low cost and eco-friendly processability are urgently needed but rarely reported. In this work, a traditional anchoring group (2-cyanoacrylic acid) widely used in molecules for dye-sensitized solar cells is incorporated into donor-acceptor-type HTMs to afford MPA-BT-CA, which enables effective regulation of the frontier molecular orbital energy levels, interfacial modification of an ITO electrode, efficient defect passivation toward the perovskite layer, and more importantly alcohol solubility. Consequently, inverted PVSCs with this low-cost HTM exhibit excellent device performance with a remarkable power conversion efficiency (PCE) of 21.24% and good long-term stability in ambient conditions. More encouragingly, when processing MPA-BT-CA films with the green solvent ethanol, the corresponding PVSCs also deliver a substantial PCE as high as 20.52% with negligible hysteresis. Such molecular design of anchoring group-based materials represents great progress for developing efficient HTMs which combine the advantages of low cost, eco-friendly processability, and high performance. We believe that such design strategy will pave a new path for the exploration of highly efficient HTMs applicable to commercialization of PVSCs.

Oxygen Pressure Influence on Properties of Nanocrystalline LiNbO3 Films Grown by Laser Ablation.

Energy conversion devices draw much attention due to their effective usage of energy and resulting decrease in CO2 emissions, which slows down the global warming processes. Fabrication of energy conversion devices based on ferroelectric and piezoelectric lead-free films is complicated due to the difficulties associated with insufficient elaboration of growth methods. Most ferroelectric and piezoelectric materials (LiNbO3, BaTiO3, etc.) are multi-component oxides, which significantly complicates their integration with micro- and nanoelectronic technology. This paper reports the effect of the oxygen pressure on the properties of nanocrystalline lithium niobate (LiNbO3) films grown by pulsed laser deposition on SiO2/Si structures. We theoretically investigated the mechanisms of LiNbO3 dissociation at various oxygen pressures. The results of x-ray photoelectron spectroscopy study have shown that conditions for the formation of LiNbO3 films are created only at an oxygen pressure of 1 × 10-2 Torr. At low residual pressure (1 × 10-5 Torr), a lack of oxygen in the formed films leads to the formation of niobium oxide (Nb2O5) clusters. The presented theoretical and experimental results provide an enhanced understanding of the nanocrystalline LiNbO3 films growth with target parameters using pulsed laser deposition for the implementation of piezoelectric and photoelectric energy converters.

Self-Powered and Broadband Lead-Free Inorganic Perovskite Photodetector with High Stability.

Metal halide perovskite materials have opened up a great opportunity for high-performance optoelectronic devices owing to their extraordinary optoelectronic properties. More than lead halide ones, stable and nontoxic bismuth halide perovskites exhibit more promise in their future commercialization. In this work, we developed for the first time photodetectors based on full-inorganic Cs3Bi2I9-xBrx perovskites and modulate their performance by varying x in the composition systematically. Among those self-powered photodetectors, those based on Cs3Bi2I6Br3 shows the best performance with excellent photosensitivity of 4.1 × 104 at zero bias as well as the responsivity and detectivity reaching 15 mA/W and 4.6 × 1011 Jones, respectively. More strikingly, the full-inorganic perovskite photodetectors exhibit excellent stability in the ambient environment and can maintain over 96% of the initial value after 100 days owing to the high stability of the core perovskite film. The paper definitely paves an alternative and promising strategy for the design of future commercial photodetectors that are self-powered, stable, nontoxic, etc.

Side-Chain Engineering of Donor-Acceptor Conjugated Small Molecules As Dopant-Free Hole-Transport Materials for Efficient Normal Planar Perovskite Solar Cells.

Simultaneously improving efficiency and stability, which are particularly crucial factors for the commercialization of perovskite solar cells (PSCs), remains a major challenge. For high-efficiency normal PSCs, the development of stable dopant-free hole-transport materials (HTMs) seems imperative. Here, we developed potential donor-acceptor small molecules (BTTI) as HTMs for normal planar PSCs. Through tailoring its alkyl side-chain length as BTTI-C6, BTTI-C8, and BTTI-C12, our results show that upon shortening the side chain of BTTI, the hole mobility, film-forming capability, and resultant device performance were remarkably improved, with the device conversion efficiencies of 19.69% for BTTI-C6, 18.89% for BTTI-C8, and 17.49% for BTTI-C12. Meanwhile, compared to those made with the routine doped Spiro-OMeTAD, devices based on our dopant-free HTMs exhibited significantly improved stability. This work paves the way to the development of effective dopant-free HTMs for high-performance PSCs.

Efficient and Stable FASnI3 Perovskite Solar Cells with Effective Interface Modulation by Low-Dimensional Perovskite Layer.

The promising tin perovskite solar cells (PSCs) suffer from the oxidation of Sn2+ to Sn4+ , leading to a disappointing conversion efficiency along with poor stability. In this work, phenylethylammonium bromide (PEABr) was employed to form an ultrathin, low-dimensional perovskite layer on the surface of the FASnI3 (FA=formamidinium) absorber film to improve the interface of perovskite/PCBM ([6,6]-phenyl-C61 -butyricacid methyl) in the inverted planar device structure of the ITO (indium-doped tin oxide)/PEDOT:PSS [poly(3,4-ethylenedioxythiophene)/polystyrene sulfonate]/perovskite/[6,6]-phenyl-C61 -butyricacid methyl (PCBM)/BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) electrode. The device efficiency was enhanced from 4.77 to 7.86 % by this PEABr treatment. A series of characterizations proved that this modification could improve the crystallinity of the FASnI3 perovskite by incorporating Br and forming an ultrathin, low-dimensional perovskite layer at the interface, which led to the effective suppression of Sn2+ oxidation, improved band level alignment, and decreased defect density. These effects contributed to the clear enhancement of conversion efficiency. Moreover, this treatment also led to remarkably enhanced device stability, with approximately 80 % of the initial efficiency retained after 350 h light soaking, whereas the control device failed within 140 h. This work deepens our understanding of the suppression effect of PEABr on the oxidation of Sn2+ and paves a new way to fabricate promising tin halide PSCs by facile interface engineering.

Backbone Coplanarity Tuning of 1,4-Di(3-alkoxy-2-thienyl)-2,5-difluorophenylene-Based Wide Bandgap Polymers for Efficient Organic Solar Cells Processed from Nonhalogenated Solvent.

Halogenated solvents are prevailingly used in the fabrication of nonfullerene organic solar cells (NF-OSCs) at the current stage, imposing significant restraints on their practical applications. By copolymerizing phthalimide or thieno[3,4-c]pyrrole-4,6-dione (TPD) with 1,4-di(3-alkoxy-2-thienyl)-2,5-difluorophenylene (DOTFP), which features intramolecular noncovalent interactions, the backbone planarity of the resulting DOTFP-based polymers can be effectively tuned, yielding distinct solubilities, aggregation characters, and chain packing properties. Polymer DOTFP-PhI with a more twisted backbone showed a lower degree of aggregation in solution but an increased film crystallinity than polymer DOTFP-TPD. An organic thin-film transistor and NF-OSC based on DOTFP-PhI, processed with a nonhalogenated solvent, exhibited a high hole mobility up to 1.20 cm2 V-1 s-1 and a promising power conversion efficiency up to 10.65%, respectively. The results demonstrate that DOTFP is a promising building block for constructing wide bandgap polymers and backbone coplanarity tuning is an effective strategy to develop high-performance organic semiconductors processable with a nonhalogenated solvent.

Dopant-Free Small-Molecule Hole-Transporting Material for Inverted Perovskite Solar Cells with Efficiency Exceeding 21.

Hole-transporting materials (HTMs) play a critical role in realizing efficient and stable perovskite solar cells (PVSCs). Considering their capability of enabling PVSCs with good device reproducibility and long-term stability, high-performance dopant-free small-molecule HTMs (SM-HTMs) are greatly desired. However, such dopant-free SM-HTMs are highly elusive, limiting the current record efficiencies of inverted PVSCs to around 19%. Here, two novel donor-acceptor-type SM-HTMs (MPA-BTI and MPA-BTTI) are devised, which synergistically integrate several design principles for high-performance HTMs, and exhibit comparable optoelectronic properties but distinct molecular configuration and film properties. Consequently, the dopant-free MPA-BTTI-based inverted PVSCs achieve a remarkable efficiency of 21.17% with negligible hysteresis and superior thermal stability and long-term stability under illumination, which breaks the long-time standing bottleneck in the development of dopant-free SM-HTMs for highly efficient inverted PVSCs. Such a breakthrough is attributed to the well-aligned energy levels, appropriate hole mobility, and most importantly, the excellent film morphology of the MPA-BTTI. The results underscore the effectiveness of the design tactics, providing a new avenue for developing high-performance dopant-free SM-HTMs in PVSCs.

Understanding the Impact of Cu-In-Ga-S Nanoparticles Compactness on Holes Transfer of Perovskite Solar Cells.

Although a compact holes-transport-layer (HTL) film has always been deemed mandatory for perovskite solar cells (PSCs), the impact their compactness on the device performance has rarely been studied in detail. In this work, based on a device structure of FTO/CIGS/perovskite/PCBM/ZrAcac/Ag, that effect was systematically investigated with respect to device performance along with photo-physics characterization tools. Depending on spin-coating speed, the grain size and coverage ratio of those CIGS films on FTO substrates can be tuned, and this can result in different hole transfer efficiencies at the anode interface. At a speed of 4000 r.p.m., the band level offset between the perovskite and CIGS modified FTO was reduced to a minimum of 0.02 eV, leading to the best device performance, with conversion efficiency of 15.16% and open-circuit voltage of 1.04 V, along with the suppression of hysteresis. We believe that the balance of grain size and coverage ratio of CIGS interlayers can be tuned to an optimal point in the competition between carrier transport and recombination at the interface based on the proposed mechanism. This paper definitely deepens our understanding of the hole transfer mechanism at the interface of PSC devices, and facilitates future design of high-performance devices.

Novel Molecular Doping Mechanism for n-Doping of SnO2 via Triphenylphosphine Oxide and Its Effect on Perovskite Solar Cells.

Molecular doping of inorganic semiconductors is a rising topic in the field of organic/inorganic hybrid electronics. However, it is difficult to find dopant molecules which simultaneously exhibit strong reducibility and stability in ambient atmosphere, which are needed for n-type doping of oxide semiconductors. Herein, successful n-type doping of SnO2 is demonstrated by a simple, air-robust, and cost-effective triphenylphosphine oxide molecule. Strikingly, it is discovered that electrons are transferred from the R3P+ O- σ-bond to the peripheral tin atoms other than the directly interacted ones at the surface. That means those electrons are delocalized. The course is verified by multi-photophysical characterizations. This doping effect accounts for the enhancement of conductivity and the decline of work function of SnO2 , which enlarges the built-in field from 0.01 to 0.07 eV and decreases the energy barrier from 0.55 to 0.39 eV at the SnO2 /perovskite interface enabling an increase in the conversion efficiency of perovskite solar cells from 19.01% to 20.69%.

Influence of mixed organic cations on the structural and optical properties of lead tri-iodide perovskites.

Perovskites with mixed organic cations possess better properties in some aspects as compared to their pure counterparts. However, the structural and optical properties of these mixed-type perovskites have been rarely investigated. In this study, probable structures of mixed organic cation perovskites, MAxFA1-xPbI3 (x = 1, 0.8, 0.6, 0.4 and 0.2), were comparatively discussed. Saturation of excitonic emission at 1.66 eV indicates limited orthorhombic phase at 30 K in MAPbI3, which confirms the co-existence of orthorhombic and tetragonal phases at low temperatures. Based on the comprehensive temperature- and power-dependent measurements, it is found that defects are activated in mixed organic cation perovskites under low excitation power at room temperature, whereas this process is not observed in pure MAPbI3. At high excitation power, free exciton recombination is suppressed due to exciton-exciton interaction for all samples. Analysis of stability against temperature based on these photoemission processes shows that the structure with comparable organic cation proportion is more stable; this can be explained by uniformly distributed strains existing at the boundaries between MAPbI3 and FAPbI3 molecules. These analyses of structural and optical properties of mixed organic cation perovskites are meaningful in dictating the future optoelectronic devices.

Printable Fabrication of a Fully Integrated and Self-Powered Sensor System on Plastic Substrates.

Wearable and portable devices with desirable flexibility, operational safety, and long cruising time, are in urgent demand for applications in wireless communications, multifunctional entertainments, personal healthcare monitoring, etc. Herein, a monolithically integrated self-powered smart sensor system with printed interconnects, printed gas sensor for ethanol and acetone detection, and printable supercapacitors and embedded solar cells as energy sources, is successfully demonstrated in a wearable wristband fashion by utilizing inkjet printing as a proof-of-concept. In such a "wearable wristband", the harvested solar energy can either directly drive the sensor and power up a light-emitting diode as a warning signal, or can be stored in the supercapacitors in a standby mode, and the energy released from supercapacitors can compensate the intermittency of light illumination. To the best of our knowledge, the demonstration of such a self-powered sensor system integrated onto a single piece of flexible substrate in a printable and additive manner has not previously been reported. Particularly, the printable supercapacitors deliver an areal capacitance of 12.9 mF cm-2 and the printed SnO2 gas sensor shows remarkable detection sensitivity under room temperature. The printable strategies for device fabrication and system integration developed here show great potency for scalable and facile fabrication of a variety of wearable devices.