Precisely Controlling Polymer Acceptors with Weak Intramolecular Charge Transfer Effect and Superior Coplanarity for Efficient Indoor All-Polymer Solar Cells with over 27% Efficiency.

Indoor photovoltaics (IPVs) are garnering increasing attention from both the academic and industrial communities due to the pressing demand of the ecosystem of Internet-of-Things. All-polymer solar cells (all-PSCs), emerging as a sub-type of organic photovoltaics, with the merits of great film-forming properties, remarkable morphological and light stability, hold great promise to simultaneously achieve high efficiency and long-term operation in IPV's application. However, the dearth of polymer acceptors with medium-bandgap has impeded the rapid development of indoor all-PSCs. Herein, a highly efficient medium-bandgap polymer acceptor (PYFO-V) is reported through the synergistic effects of side chain engineering and linkage modulation and applied for indoor all-PSCs operation. As a result, the PM6:PYFO-V-based indoor all-PSC yields the highest efficiency of 27.1% under LED light condition, marking the highest value for reported binary indoor all-PSCs to date. More importantly, the blade-coated devices using non-halogenated solvent (o-xylene) maintain an efficiency of over 23%, demonstrating the potential for industry-scale fabrication. This work not only highlights the importance of fine-tuning intramolecular charge transfer effect and intrachain coplanarity in developing high-performance medium-bandgap polymer acceptors but also provides a highly efficient strategy for indoor all-PSC application.

Solvent-Induced Bright Emission in Lead-Free Organic-Inorganic Antimony Bromides with Reversible Transformation.

Lead-free low-dimensional organic-inorganic metal halides have gained increasing attention in a wide range of applications due to their low toxicity, outstanding optical performance, and structural tunability. In this work, a general method of incorporating organic molecule into sodium antimony bromides is introduced. The 1D Na3SbBr6(C2H6OS)6 and Na3SbBr6(C4H8OS)6 single crystals exhibit bright yellow and orange emission with PL peaks at 610 and 664 nm, and high photoluminescence quantum yields (PLQYs) of 85% and 60%, respectively. These two compounds can be reversibly converted into each other by the removal and addition of the organic components. Their exceptional luminescent performance enables them to be used as solid-state phosphors for the fabrication of yellow and orange down-conversion LEDs. A white LED with a high color rendering index (CRI) of 95 is also fabricated by using Na3SbBr6(C2H6OS)6 as the yellow phosphor. The universality of this method is demonstrated by synthesizing other members of this family with diverse A-groups, including methylammonium (MA) and formamidinium (FA). This work provides an effective strategy for the development of diverse lead-free and high-performance organic-inorganic hybrid materials and indicates these organic-inorganic hybrid compounds are promising luminescent materials for lighting or displays.

Sterically Controlled Synthesis of Amine-Free CsPbBr3 Nanoplatelets for Stable, Pure-Blue Light Emission.

Metal halide perovskite nanoplatelets (NPLs) have demonstrated excellent optical properties for light-emitting applications and achieved tunable blue luminescence through thickness control. However, their translation into electronic devices has lagged behind due to poor colloidal and film stability. The main reason for this is the deprotonation of their surface-capped ammonium passivating ligands, resulting in NPL aggregation. Here we report the first facile synthesis of amine-free pure-blue CsPbBr3 NPLs with outstanding thermal and light stability. This is achieved by utilizing an amine-free phosphine oxide route with a surface capping molecule exhibiting large steric hindrance to prevent NPL aggregation. Two-dimensional nuclear magnetic resonance (2D NMR) spectroscopy suggests slower ligand exchange in amine-free NPLs compared to the conventional NPLs, which can be attributed to the strong binding strength of the designated ligand. Consequently, the amine-free NPLs exhibited superior stability against radiation, heat and moisture. We further demonstrate the importance of acid-base equilibrium in this amine-free synthesis route. Through solvent neutralization and passivation with various alkali carbonates, the resulting NPLs attained near-unity photoluminescence quantum yield (PLQY) and pure blue emission.

Carrier Dynamics of Efficient Triplet Harvesting in AgBiS2 /Pentacene Singlet Fission Solar Cells.

Singlet fission is a process by which an organic semiconductor is able to generate two triplet excitons from a single photon. If charges from the triplets can be successfully harvested without heavy losses in energy, then this process can enable a single-junction solar cell to surpass the Shockley-Queisser limit. While singlet fission processes are commonly observed in several materials, harvesting the resulting triplets is difficult and has been demonstrated with only a few transport materials. Here, transient absorption spectroscopy is used to investigate singlet fission and carrier transfer processes at the AgBiS2 /pentacene (AgBiS2 /Pc) heterojunction. The successful transfer of triplets from pentacene to AgBiS2 and the transfer of holes from AgBiS2 to pentacene is observed. Further singlet fission in pentacene by modifying the crystallinity of the pentacene layer and have fabricated the first singlet fission AgBiS2 /Pc solar cell is enhanced. Singlet fission devices exhibit higher external quantum efficiency compared with the control devices, and thus demonstrating the significant contribution of charges from the singlet fission process.

Splashing-Assisted Femtosecond Laser-Activated Metal Deposition for Mold- and Mask-Free Fabrication of Robust Microstructured Electrodes for Flexible Pressure Sensors.

Flexible pressure sensors play an indispensable role in flexible electronics. Microstructures on flexible electrodes have been proven to be effective in improving the sensitivity of pressure sensors. However, it remains a challenge to develop such microstructured flexible electrodes in a convenient way. Inspired by splashed particles from laser processing, herein, a method for customizing microstructured flexible electrodes by femtosecond laser-activated metal deposition is proposed. It takes advantage of the catalyzing particles scattered during femtosecond laser ablation and is particularly suitable for moldless, maskless, and low-cost fabrication of microstructured metal layers on polydimethylsiloxane (PDMS). Robust bonding at the PDMS/Cu interface is evidenced by the scotch tape test and the duration test over 10 000 bending cycles. Benefiting from the firm interface, the developed flexible capacitive pressure sensor with microstructured electrodes presents several conspicuous features, including a sensitivity (0.22 kPa-1 ) 73 times higher than the one using flat Cu electrodes, ultralow detection limit (<1 Pa), rapid response/recovery time (4.2/5.3 ms), and excellent stability. Moreover, the proposed method, inheriting the merits of laser direct writing, is capable of fabricating a pressure sensor array in a maskless manner for spatial pressure mapping.

Highly Stable Tetrahydrothiophene 1-Oxide Caged Copper Bromide and Chloride Clusters with Deep-Red to Near-IR Emission.

All-inorganic copper(I)-based metal halides have emerged as promising candidates for the replacement of lead perovskites because of their outstanding optical properties. However, the limited structure tunability prohibits their further exploration of properties including red photoluminescence (PL). Here, we report a series of red-emissive lead-free hybrid organic-inorganic copper halides A6(C4H8OS)12[Cu8X13][Cu4X4(OH)(H2O)] (ACX-THTO, A = K, Rb, and Cs; X = Cl, Br; THTO = C4H8OS) with the highest photoluminescence quantum yield (PLQY) of 42%. These compounds possess similar crystal structures, and their emission can be tuned in the spectral range of 676-732 nm by controlling their compositions. Additionally, by removing and adding THTO, the reversible transformation between CsCu2Br3 featuring one-dimensional (1D) chains and Cs6(C4H8OS)12[Cu8Br13][Cu4Br4(OH)(H2O)] (CCB-THTO) with zero-dimensional (0D) clusters can be realized. We also demonstrate that the incorporation of THTO in the crystal structures instead of dimethyl sulfoxide (DMSO) can significantly enhance the stability and PL of compounds with the same inorganic components.

Inkjet printed patterned bank structure with encapsulated perovskite colour filters for modern display.

Inorganic multicolour perovskite nanocrystals (NCs) of CsPbX3 (X = Cl, Br, I) with high photoluminescence (PL) quantum yield (QY) and saturated colours are considered promising candidates for a high-performance colour conversion layer. However, integration of these materials into industrial applications still faces a significant challenge due to their tendency for aggregation and quenching of the emission during deposition and processing. In this work, we explore a new ink composition with oleylamine (OLA) and hexylphosphonic acid (HPA) ligands in combination with a liquid crystal monomer (LCM) composing a superior solution for an inkjet-printed colour conversion layer. This work provides a simple technique for preparing high-quality perovskite pixels for high-performance displays.

Solution-Processed Red, Green, and Blue Quantum Rod Light-Emitting Diodes.

Solution-processed semiconductor nanocrystals are evolving as potential candidates for future display and lighting applications owing to their size-tunable emission, ultrasaturated colors, and compatibility with large-area flexible substrates. Among them, quantum rods (QRs) are emerging materials for optoelectronic applications, offering polarized emission, high light outcoupling efficiency, color purity, and better stability in solid films. However, synthesizing QRs covering the full visible wavelength region has been a big challenge, particularly in the blue range. Herein, we report for the first time the synthesis of red CdSe/CdS, green CdSe/ZnxCd1-xS/ZnS, and blue CdSe/ZnxCd1-xS/ZnS QRs and their application in red, green, and blue QR-based light-emitting diodes (QR-LEDs). We have improved the charge injection balance into the QRs through embedding a poly(methyl methacrylate) (PMMA) layer between the emissive and electron transport layers. The thin PMMA electron-blocking layer (EBL) suppresses the excessive electron flux and thus promotes charge injection balance and pushes the recombination zone back to the QR layer, resulting in 1.35×, 1.2×, and 1.7× peak external quantum efficiency improvement for red, green, and blue QR-LEDs, respectively. The efficiency roll-off of green and blue QR-LEDs with an EBL is less than 50% at maximum current density. The proposed red, green, and blue QR-LEDs open up an avenue toward further improving the light source efficiency and stability focusing on real device applications.

Solution-Processed, Inverted AgBiS2 Nanocrystal Solar Cells.

AgBiS2 nanocrystals are a promising nontoxic alternative to PbS, CsPbI3, and CdS quantum dots for solution-fabricated nanocrystal photovoltaics. In this work, we fabricated the first inverted (p-i-n) structure AgBiS2 nanocrystal solar cells. We selected spray-coated NiO as the hole-transporting material and used PCBM/BCP as the electron-transporting material. Combining transient photocurrent and photovoltage measurements with femtosecond transient absorption spectroscopy, we investigated the charge collection process on metal oxide/AgBiS2 interfaces and demonstrated that the NiO/AgBiS2 NC junction in the p-i-n configuration is more efficient for charge carrier collection. The fabricated p-i-n solar cells exhibited a 4.3% power conversion efficiency (PCE), which was higher than that of conventional n-i-p solar cells fabricated using the same sample. Additionally, inverted devices showed an ultrahigh short-circuit current (JSC) over 20.7 mA cm-2 and 0.38 V open-circuit voltage (VOC), suggesting their potential for further improvements in efficiency and, eventually, for large-scale production.

Emergent electronic properties in Co-deposited superatomic clusters.

We report an intercluster compound based on co-deposition of the Au cluster [Au9(PPh3)8](NO3)3 and the fulleride KC60(THF). Electronic properties characteristic for a charge interaction between superatoms emerge within the solid state material [Au9(PPh3)8](NO3)3-x(C60)x, as confirmed by UV-VIS and Raman spectroscopy and I-V measurements. These emergent properties are related to the superatomic electronic states of the initial clusters. The material is characterized by Fourier-transform infrared spectroscopy, x-ray diffraction, Raman spectroscopy, and electrical measurements. Structural optimization and ab initio band structure calculations are performed with density functional theory to interpret the nature of the electronic states in the material; Bader charge calculations assign effective oxidation states in support of the superatomic model of cluster interactions.

Optically Clear Films of Formamidinium Lead Bromide Perovskite for Wide-Band-Gap, Solution-Processed, Semitransparent Solar Cells.

Solvent engineering and antisolvent methods have been used extensively to achieve high-quality, homogeneous, and crystalline perovskite thin films. Usually, highly concentrated (>1.1 M) precursor solutions are used to achieve the maximum power conversion efficiency (PCE), and most fabrication studies focus on iodide-based metal halide perovskites (MHPs). However, high concentrations of precursors are not suitable for semitransparent (ST) MHP solar cells (STPSCs), which require thinner films to achieve a high average visible transmittance (AVT). The deposition of high-quality perovskites with variable concentrations in a one-step method is challenging due to the complexity of the antisolvent crystallization process. Here, we have developed an in situ technique based on photoluminescence (PL) measurements to identify the optimum delay time for antisolvent crystallization in formamidinium lead bromide (FAPbBr3). By monitoring the in situ PL, the nucleation, crystal growth, and early perovskite formation phases are easily identified for a range of concentrations. Subsequently, we fabricated opaque and ST solar cells with optically clear, ST perovskite films formed from precursors with varying concentrations. These all-solution-processed STPSCs achieved AVTs of up to 35.6, 42.5, and 49.2%, with the corresponding PCEs of 5.71, 3.25, and 1.86% in p-i-n type, FAPbBr3 perovskite solar cells with transparent Ag nanowire electrodes. These devices show good stability over several weeks and an impressive Voc as high as 1.24 V for STPSCs and 1.38 V for opaque cells produced with a thick Ag electrode. This work demonstrates the potential use of in situ spectroscopy to tailor the film growth of halide perovskites with varying concentrations and the feasibility of using wide-band-gap perovskites for ST solar cells with exceptional clarity and higher Voc.

Photorechargeable Lead-Free Perovskite Lithium-Ion Batteries Using Hexagonal Cs3Bi2I9 Nanosheets.

Materials that enable bifunctional operation in harvesting and storing energy are currently in high demand, due to their potential to efficiently use renewable solar energy. Here, we present a lead-free, all-inorganic, bismuth-based perovskite halide, which acts as a photoelectrode that can harvest energy under illumination without the assistance of an external load in a lithium-ion battery. The battery performance is shown using three different current collectors: copper, fluorine-doped tin oxide (FTO) and carbon felt (CF) to exhibit the electrode's function as a normal coin cell, as a basic photobattery with a transparent collector to elucidate its functional mechanism, and as an optimized photobattery displaying competitive metrics with other photobatteries obtaining a photo conversion efficiency of ∼0.43% for the first discharge. Upon discharging under illumination, we observed an increase in capacity from 410 to 975 mA·h·g-1. Further exploration in anode structure and design provides a path toward more efficient photobatteries.

Single crystals of mixed Br/Cl and Sn-doped formamidinium lead halide perovskites via inverse temperature crystallization.

Hybrid organic-inorganic perovskite mixed halides of FAPbBr3-x Cl x and doped FAPb1-x Sn x Br3 were synthesized using a generalized inverse temperature crystallization (ITC) method. With an appropriate choice of solvents and crystallization temperatures we show that large millimeter sized single crystals of these hybrid perovskites can be grown in a matter of hours to days using ITC. The structural and optical properties of these single crystals were characterized systematically. The mixed metal and mixed halide perovskites displayed a compositional bandgap tuneability in the region of 2.05 eV to 2.57 eV. The electrical properties of the perovskite single crystals were determined using a space-charge limited current (SCLC) method. The trap density determined from SCLC was between 109 and 1011 cm-3 for all perovskites which is exceptionally low. The mobility was found to increase by one order of magnitude on the addition of only 3% Sn for FAPb1-x Sn x Br3 based perovskites which shows promise for enhancing the electrical properties. This demonstrates the generalizability of the ITC method to grow large high-quality perovskite single crystals with enhanced optical and electrical properties. In addition, it was observed for FAPbBr3-x Cl x based perovskites that initially degraded surfaces with suppressed PL emission could be repaired by using an anti-solvent treatment re-enabling the PL emission. Other perovskite compounds did not display any degraded surfaces and exhibited excellent stability in ambient conditions.

Quantum-Dot Tandem Solar Cells Based on a Solution-Processed Nanoparticle Intermediate Layer.

Tandem cells are one of the most effective ways of breaking the single junction Shockley-Queisser limit. Solution-processable phosphate-buffered saline (PbS) quantum dots are good candidates for producing multiple junction solar cells because of their size-tunable band gap. The intermediate recombination layer (RL) connecting the subcells in a tandem solar cell is crucial for device performance because it determines the charge recombination efficiency and electrical resistance. In this work, a solution-processed ultrathin NiO and Ag nanoparticle film serves as an intermediate layer to enhance the charge recombination efficiency in PbS QD dual-junction tandem solar cells. The champion devices with device architecture of indium tin oxide/S-ZnO/1.45 eV PbS-PbI2/PbS-EDT/NiO/Ag NP/ZnO NP/1.22 eV PbS-PbI2/PbS-EDT/Au deliver a 7.1% power conversion efficiency, which outperforms the optimized reference subcells. This result underscores the critical role of an appropriate nanocrystalline RL in producing high-performance solution-processed PbS QD tandem cells.

Luminescent Down-Conversion Semiconductor Quantum Dots and Aligned Quantum Rods for Liquid Crystal Displays.

Herein, emerging applications of luminescent semiconductor nanocrystals are addressed, such as quantum dots and quantum rods as down-conversion materials used in liquid crystal displays (LCD). Their precisely tunable emission wavelengths and narrow emission bandwidths offer high color purity resulting in a wide color gamut with vivid colors for LCDs. Anisotropic materials, such as quantum rods, have the additional advantage of polarized emission, which can bring a significant improvement to the efficiency of LCD displays. The basic optical properties of these nanomaterials are considered, with a focus on quantum rods, and the challenges and progress in their assembly are discussed. Different techniques for quantum rod alignment are introduced such as shear-oriented, electric field and magnetic field assisted assembly, mechanical rubbing, stretching, and electrospinning. The photoalignment approach allows for an easy arrangement of quantum rods in-plane, and the implications of this method to patterning are considered. Different configurations of LCDs utilizing semiconductor quantum dots and quantum rods as down-conversion layers are also presented, and the potential applications that are enabled by the wide range of emerging materials are highlighted.

Room Temperature Mid-IR Detection through Localized Surface Vibrational States of SnTe Nanocrystals.

Quantum dots (QDs) are now well established as promising materials for room temperature mid-infrared (MIR) detection beyond 3 µm. Here, we have replaced commonly reported mercury based quantum dots with less toxic SnTe and PbSnTe. Inverse MIR detection at room temperature is demonstrated with planar, solution, and air-processed PbSnTe and SnTe QD devices. The detection mechanism is shown to be mediated by an interaction between MIR radiation and the vibrational stretches of adsorbed hydroxyl species. Devices are shown to possess mA/W responsivity via a reduction in conductance due to MIR irradiation and, unlike classic MIR photoconductors, are unaffected by visible wavelengths. As such, these devices offer the possibility of MIR thermal imaging that has an intrinsic solution to the blinding caused by higher energy light sources.

Photo-Electrosensitive Memristor Using Oxygen Doping in HgTe Nanocrystal Films.

Nanocrystal-based electronic devices with multiple functionalities offer one avenue toward novel passive and active electronic components. Here, we exhibit a planar and fully air-processed thin film device that demonstrates a photoinduced memristive behavior and can be used as a transistor, photodetector, or memory device. Following long-term (60 h) air exposure, unpackaged nanocrystal films develop reliable memristive characteristics in tandem with temperature, gate, and photoresponse. The on/off values of more than 50 are achieved, and the devices show long-term stability, producing repeatable metrics over days of measurement. The on/off behavior is shown to be dependent on the previous charge flow and carrier density, implying a memristive rather than switching behavior. These observations are described within a long-term trap-filling model. This work represents an advance in the integration of nanocrystal films into electronic devices, which may lead to the development of multifunctional electronic components.

Controlled Growth of CH3 NH3 PbI3 Using a Dynamically Dispensed Spin-Coating Method: Improving Efficiency with a Reproducible PbI2 Blocking Layer.

It is commonly believed that excess PbI2 has beneficial effects for perovskite solar cells owing to the modification of charge-transport behavior at interfaces, by surface passivation and by blocking electron-hole recombination. Here, we introduce a dynamically dispensed spin-coating technique in a two-step deposition to form a perovskite layer with controllable quantities of crystalline PbI2 . Using this technique, the concentration of CH3 NH3 I solution is kept constant at the reaction interface, ensuring smooth growth of films. By changing the spinning rate during the reaction, the PbI2 conversion ratio and perovskite cuboid size can be optimized, resulting in a power conversion efficiency improvement over control devices. This dynamically dispensed technique represents a repeatable method for compositional control in perovskite solar cells and improves our understanding of how a PbI2 blocking layer improves the performance of perovskite solar cells.

Identification of dipole disorder in low temperature solution processed oxides: its utility and suppression for transparent high performance solution-processed hybrid electronics.

The ability to deposit high-quality inorganic semiconductors and dielectrics from solution at low process temperatures (∼200 °C) has become a very important research focus. During the course of our investigation, we identify the presence of an induced dipole present in solid state solution processed inorganic oxide insulator layers processed at reduced temperature (200-350 °C) from either molecular precursors, or well-dispersed metal oxide nanoparticles. Chemical composition analysis coupled with electrical measurements shows that the dielectric instability occurs due to proton migration via the Grotthuss mechanism inducing a long lived dipole disorder. Thus we established conditions for suppressing this effect to afford "ideal" high-k dielectric layer. Using this methodology, solution processed all inorganic thin film transistors (TFTs) with charge carrier mobilities exceeding 6 cm2 V-1 s-1 operating at low voltage (5 V) have been achieved. In addition, we show the broad utility of the perovskite high-k dielectric when processed with state of the art polymer and single crystal organic semiconductors yielding mobilities of approx. 7 cm2 V-1 s-1 at only 4 V. These transparent devices demonstrate excellent electrical device stability and a threshold voltage shift of only 0.41 V over 14 h, which is comparable, or better than sputtered oxide films.

Hot-carrier cooling and photoinduced refractive index changes in organic-inorganic lead halide perovskites.

Metal-halide perovskites are at the frontier of optoelectronic research due to solution processability and excellent semiconductor properties. Here we use transient absorption spectroscopy to study hot-carrier distributions in CH3NH3PbI3 and quantify key semiconductor parameters. Above bandgap, non-resonant excitation creates quasi-thermalized carrier distributions within 100 fs. During carrier cooling, a sub-bandgap transient absorption signal arises at ∼ 1.6 eV, which is explained by the interplay of bandgap renormalization and hot-carrier distributions. At higher excitation densities, a 'phonon bottleneck' substantially slows carrier cooling. This effect indicates a low contribution from inelastic carrier-impurity or phonon-impurity scattering in these polycrystalline materials, which supports high charge-carrier mobilities. Photoinduced reflectivity changes distort the shape of transient absorption spectra and must be included to extract physical constants. Using a simple band-filling model that accounts for these changes, we determine a small effective mass of mr=0.14 mo, which agrees with band structure calculations and high photovoltaic performance.