The Role of Grain Boundaries on Ion Migration and Charge Recombination in Halide Perovskites.

Grain boundaries (GBs) have a significant role in polycrystalline perovskite solar cells (PSCs). However, there is ongoing debate regarding the impact of GBs on the performance and long-term stability of PSCs. Employing the first-principles molecular dynamics for perovskites, the iodine vacancy defect migrations both in bulk and at GBs are investigated. i) The positive iodine vacancy (VI +) is found that have both lower formation energy (1.4 eV) and activation energy (0.18 eV) than those of neutral iodine vacancy (VI), statistically. It indicated the VI + acts as the dominant migrated iodine vacancy rather than VI; ii) the iodine vacancy at GBs has ≈0.48 eV higher activation energy than those in bulk, which leads to the accumulation of iodine vacancy at GBs; iii) the presence of VI + result in a 3-fold increase in charge recombination ratio at GBs, compared to pristine PSCs. Based on quantum molecular dynamics statistical results, which are consistent with experimental measurements, insights into iodine vacancy migration both at GBs and in the bulk are gained. This understanding can be valuable for defects engineering related to ion migration, in order to improve the long-term stability and promote the performance of PSCs.

Multifunctional sulfonium-based treatment for perovskite solar cells with less than 1% efficiency loss over 4,500-h operational stability tests.

The stabilization of grain boundaries and surfaces of the perovskite layer is critical to extend the durability of perovskite solar cells. Here we introduced a sulfonium-based molecule, dimethylphenethylsulfonium iodide (DMPESI), for the post-deposition treatment of formamidinium lead iodide perovskite films. The treated films show improved stability upon light soaking and remains in the black α phase after two years ageing under ambient condition without encapsulation. The DMPESI-treated perovskite solar cells show less than 1% performance loss after more than 4,500 h at maximum power point tracking, yielding a theoretical T80 of over nine years under continuous 1-sun illumination. The solar cells also display less than 5% power conversion efficiency drops under various ageing conditions, including 100 thermal cycles between 25 °C and 85 °C and an 1,050-h damp heat test.

Kinetically Controlled Synthesis of Quasi-Square CsPbI3 Nanoplatelets with Excellent Stability.

Nanoplatelets (NPLs) share excellent luminescent properties with their symmetric quantum dots counterparts and entail special characters benefiting from the shape, like the thickness-dependent bandgap and anisotropic luminescence. However, perovskite NPLs, especially those based on iodide, suffer from poor spectral and phase stability. Here, stable CsPbI3 NPLs obtained by accelerating the crystallization process in ambient-condition synthesis are reported. By this kinetic control, the rectangular NPLs into quasi-square NPLs are tuned, where enlarged width endows the NPLs with a lower surface-area-to-volume ratio (S/V ratio), leading to lower surficial energy and thus improved endurance against NPL fusion (cause for spectral shift or phase transformation). The accelerated crystallization, denoting the fast nucleation and short period of growth in this report, is enabled by preparing a precursor with complete transformation of PbI2 into intermediates (PbI3 -), through an additional iodide supplier (e.g., zinc iodide). The excellent color stability of the materials remains in the light-emitting diodes under various bias stresses.

Operando dynamics of trapped carriers in perovskite solar cells observed via infrared optical activation spectroscopy.

Conventional spectroscopies are not sufficiently selective to comprehensively understand the behaviour of trapped carriers in perovskite solar cells, particularly under their working conditions. Here we use infrared optical activation spectroscopy (i.e., pump-push-photocurrent), to observe the properties and real-time dynamics of trapped carriers within operando perovskite solar cells. We compare behaviour differences of trapped holes in pristine and surface-passivated FA0.99Cs0.01PbI3 devices using a combination of quasi-steady-state and nanosecond time-resolved pump-push-photocurrent, as well as kinetic and drift-diffusion models. We find a two-step trap-filling process: the rapid filling (~10 ns) of low-density traps in the bulk of perovskite, followed by the slower filling (~100 ns) of high-density traps at the perovskite/hole transport material interface. Surface passivation by n-octylammonium iodide dramatically reduces the number of trap states (~50 times), improving the device performance substantially. Moreover, the activation energy (~280 meV) of the dominant hole traps remains similar with and without surface passivation.

From optical pumping to electrical pumping: the threshold overestimation in metal halide perovskites.

The threshold carrier density, conventionally evaluated from optical pumping, is a key reference parameter towards electrically pumped lasers with the widely acknowledged assumption that optically excited charge carriers relax to the band edge through an ultrafast process. However, the characteristically slow carrier cooling in perovskites challenges this assumption. Here, we investigate the optical pumping of state-of-the-art bromide- and iodine-based perovskites. We find that the threshold decreases by one order of magnitude with decreasing excitation energy from 3.10 eV to 2.48 eV for methylammonium lead bromide perovskite (MAPbBr3), indicating that the low-energy photon excitation facilitates faster cooling and hence enables efficient carrier accumulation for population inversion. Our results are then interpreted due to the coupling of phonon scattering in connection with the band structure of perovskites. This effect is further verified in the two-photon pumping process, where the carriers relax to the band edge with a smaller difference in phonon momentum that speeds up the carrier cooling process. Furthermore, by extrapolating the optical pumping threshold to the band edge excitation as an analog of the electrical carrier injection to the perovskite, we obtain a critical threshold carrier density of ∼1.9 × 1017 cm-3, which is one order of magnitude lower than that estimated from the conventional approach. Our work thus highlights the feasibility of metal halide perovskites for electrically pumped lasers.

A Multifunctional "Halide-Equivalent" Anion Enabling Efficient CsPb(Br/I)3 Nanocrystals Pure-Red Light-Emitting Diodes with External Quantum Efficiency Exceeding 23.

Pure-red perovskite LEDs (PeLEDs) based on CsPb(Br/I)3 nanocrystals (NCs) usually suffer from a compromise in emission efficiency and spectral stability on account of the surface halide vacancies-induced nonradiative recombination loss, halide phase segregation, and self-doping effect. Herein, a "halide-equivalent" anion of benzenesulfonate (BS- ) is introduced into CsPb(Br/I)3 NCs as multifunctional additive to simultaneously address the above challenging issues. Joint experiment-theory characterizations reveal that the BS- can not only passivate the uncoordinated Pb2+ -related defects at the surface of NCs, but also increase the formation energy of halide vacancies. Moreover, because of the strong electron-withdrawing property of sulfonate group, electrons are expected to transfer from the CsPb(Br/I)3 NC to BS- for reducing the self-doping effect and altering the n-type behavior of CsPb(Br/I)3 NCs to near ambipolarity. Eventually, synergistic boost in device performance is achieved for pure-red PeLEDs with CIE coordinates of (0.70, 0.30) and a champion external quantum efficiency of 23.5%, which is one of the best value among the ever-reported red PeLEDs approaching to the Rec. 2020 red primary color. Moreover, the BS- -modified PeLED exhibits negligible wavelength shift under different operating voltages. This strategy paves an efficient way for improving the efficiency and stability of pure-red PeLEDs.

A Perovskite Photodetector Crossbar Array by Vapor Deposition for Dynamic Imaging.

With the development of perovskite photodetectors, integrating photodetectors into array image sensors is the next target to pursue. The major obstacle to integrating perovskite photodiodes for dynamic imaging is the optoelectrical crosstalk among the pixels. Herein, a perovskite photodiode-blocking diode (PIN-BD) crossbar array with pixel-wise rectifying property by the vapor deposition method is presented. The PIN-BD shows a large rectification ratio of 3.3 × 102 under illumination, suppressing electrical crosstalk to as small as 8.0% in the imaging array. The fast response time of 72.8 ns allows real-time image acquisition by over 25 frames per second. The imaging sensor exhibits excellent imaging capability with a large linear dynamic range of 112 dB with 4096 gray levels and weak light sensitivity under 1.2 lux.

Ion-modulated radical doping of spiro-OMeTAD for more efficient and stable perovskite solar cells.

Record power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) have been obtained with the organic hole transporter 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenyl-amine)9,9'-spirobifluorene (spiro-OMeTAD). Conventional doping of spiro-OMeTAD with hygroscopic lithium salts and volatile 4-tert-butylpyridine is a time-consuming process and also leads to poor device stability. We developed a new doping strategy for spiro-OMeTAD that avoids post-oxidation by using stable organic radicals as the dopant and ionic salts as the doping modulator (referred to as ion-modulated radical doping). We achieved PCEs of >25% and much-improved device stability under harsh conditions. The radicals provide hole polarons that instantly increase the conductivity and work function (WF), and ionic salts further modulate the WF by affecting the energetics of the hole polarons. This organic semiconductor doping strategy, which decouples conductivity and WF tunability, could inspire further optimization in other optoelectronic devices.

Color-Stable Blue Light-Emitting Diodes Enabled by Effective Passivation of Mixed Halide Perovskites.

Bandgap tuning through mixing halide anions is one of the most attractive features for metal halide perovskites. However, mixed halide perovskites usually suffer from phase segregation under electrical biases. Herein, we obtain high-performance and color-stable blue perovskite LEDs (PeLEDs) based on mixed bromide/chloride three-dimensional (3D) structures. We demonstrate that the color instability of CsPb(Br1-xClx)3 PeLEDs results from surface defects at perovskite grain boundaries. By effective defect passivation, we achieve color-stable blue electroluminescence from CsPb(Br1-xClx)3 PeLEDs, with maximum external quantum efficiencies of up to 4.5% and high luminance of up to 5351 cd m-2 in the sky-blue region (489 nm). Our work provides new insights into the color instability issue of mixed halide perovskites and can spur new development of high-performance and color-stable blue PeLEDs.

Construction of an Iodine Diffusion Barrier Using Network Structure Silicone Resin for Stable Perovskite Solar Cells.

Long-term stability of organic-inorganic hybrid perovskite solar cells (PSCs) is inhibited by ion diffusion. Herein, we introduce a thermally stable and hydrophobic silicone resin layer with a network structure as an interfacial layer between the perovskite and the hole-transporting layer (HTL). Experimental and theoretical investigations confirm that the small Si-O-Si unit in the network forms both Si-I and Pb-O bonds with the perovskite surface, which physically and chemically inhibit the diffusion and self-release of iodine. Besides, the silicone resin layer suppresses the thermal crystallization of spiro-OMeTAD and optimizes the interfacial energy level alignment for hole extraction. The power conversion efficiency (PCE) of a perovskite solar cell with a silicone resin layer is improved to 21.11%. The device maintains more than 90.1% of its original PCE after 1200 h under 85 °C thermal stress, 99.6% after 2000 h under RH ∼55 ± 5%, and 83% of its original PCE after light soaking in air for 1037 h.

Green perovskite light-emitting diodes with simultaneous high luminance and quantum efficiency through charge injection engineering.

Metal halide perovskite light emitting diodes (PeLEDs) have recently experienced rapid development due to the tunable emission wavelengths, narrow emission linewidth and low material cost. To achieve state-of-the-art performance, the high photoluminescence quantum yield (PLQY) of the active emission layer, the balanced charge injection, and the optimized optical extraction should be considered simultaneously. Multiple chemical passivation strategies have been provided as controllable and efficient methods to improve the PLQY of the perovskite layer. However, high luminance under large injection current and high external quantum efficiency (EQE) can hardly be achieved due to Auger recombination at high carrier density. Here, we decreased the electron injection barrier by tuning the Fermi-level of the perovskite, leading to a reduced turn on voltage. Through molecular doping of the hole injection material, a more balanced hole injection was achieved. At last, a device with modified charge injection realizes high luminance and quantum efficiency simultaneously. The best device exhibits luminance of 55,000 cd m-2, EQE of 8.02% at the working voltage of 2.65 V, current density of 115 mA cm-2, and shows EQE T50 stability around 160 min at 100 mA cm-2 injection current density.

A centrifugal microfluidic pressure regulator scheme for continuous concentration control in droplet-based microreactors.

Droplet microfluidics is an emerging tool in many biological and chemical application areas such as digital polymerase chain reaction (PCR) and in vitro diagnosis because of its extremely small sample volume and wide range of possibilities for on-demand adjustment of droplet properties. Although centrifugal microfluidics has been reported as a viable scheme for droplet generation, there is not much progress as far as droplet manipulation and droplet-based reactions are concerned. In this paper, we report a microfluidic pressure regulator scheme along with the use of microcapillaries for periodic droplet generation and the subsequent fusion. This scheme enables fine control over droplet generation and the fusion process by varying the rotational frequency. To control the solution concentration in droplets, we have implemented several fusion devices, including one-to-one mode using a symmetric structure and ratio-adjustable mode with an asymmetric structure. As an application example, we performed cell transfection using the reported droplet-based technique, which resulted in considerable improvement in terms of transfection efficiency compared to the traditional bulk approach. In another example, we synthesized quasi-2D perovskites with controllable compositions and tunable photoluminescence peaks, thus confirming the volumetric accuracy of this approach down to the nano-liter scale. Compared to the common pressure pulsation approach, our centrifugal force actuation scheme offers the advantages of compactness and highly parallel batch processing. We anticipate that the new scheme will find many applications in cell biology and chemical synthesis.

van der Waals Transition-Metal Oxide for Vis-MIR Broadband Photodetection via Intercalation Strategy.

Defects engineering can broaden the absorption band of wide band gap van der Waals (vdW) materials to the visible or near-IR regime at the expense of material stability and photoresponse speed. Herein, we introduce an atomic intercalation method that brings the wide band gap vdW α-MoO3 for vis-MIR broadband optoelectronic conversion. We confirm experimentally that intercalation significantly enhances photoabsorption and electrical conductivity buts effects negligible change to the lattice structure as compared with ion intercalation. Charge transfer from the Sn atom to the lattices induces an optoelectrical change. As a result, the Sn-intercalated α-MoO3 shows room temperature, air stable, broadband photodetection ability from 405 nm to 10 µm, with photoresponsivity better than 9.0 A W-1 in 405-1500 nm, ∼0.4 A W-1 at 3700 nm, and 0.16 A W-1 at 10 µm, response time of ∼0.1 s, and peak D* of 7.3 × 107 cm Hz0.5 W-1 at 520 nm. We further reveal that photothermal effect dominates in our detection range by real-time photothermal-electrical measurement, and the materials show a high temperature coefficient of resistance value of -1.658% K-1 at 300 K. These results provide feasible route for designing broadband absorption materials for photoelectrical, photothermal, or thermal-electrical application.

Tertiary Amines Differentiated from Primary and Secondary Amines by Active Ester-Functionalized Hexabenzoperylene in Field Effect Transistors.

Herein, we report two novel derivatives of hexabenzoperylene (HBP) that are functionalized with ester groups. Methyl acetate functionalized HBP (1) in single crystals self-assembles into a supramolecular nanosheet, which has a two-dimensional π-stack of HBP sandwiched between two layers of ester groups. With the same self-assembly motif, active ester-functionalized HBP (2) in field effect transistors has enabled differentiation of tertiary amines from primary and secondary amines, in agreement with the fact that active ester reacts with primary and secondary amines but not with tertiary amines to form amides.

Abnormal Synergetic Effect of Organic and Halide Ions on the Stability and Optoelectronic Properties of a Mixed Perovskite via In Situ Characterizations.

The mixed cation lead mixed halide perovskite (MLMP) Csx FA1-x PbIy Br3-y is one of the most promising candidates for both single-junction and tandem solar cells due to its high efficiency and remarkable stability. However, the composition effect on thermal stability and photovoltaic performances has not yet been comprehensively investigated. Therefore, the interplay between composition, crystal structure, morphology, and optoelectronic properties under heat stress, is systematically elucidated here through a series of in situ characterizations. It is revealed for the first time that the FA+ and Br- release synchronously at first even under mild annealing. This leads to a serious FA- and Br-deficiency issue, with only 88.3% of Br and 90.2% of FA retained after annealing at 100 °C, which significantly magnifies the hysteresis, phase segregation, and instability issues. Finally, a trace amount of FA+ and Br- is introduced onto the post-annealed MLMP surface to compensate for the deficiency through vacancy filling. The degradation lifetime to 80% of the initial efficiency (t80 ) is improved from 504 to 1056 h and the hysteresis issue is also well resolved. This work highlights the importance of the synergetic composition effect of the organic cation and halide anion on stability and efficiency optimization for long-term applications.

Broadside Nanoantennas Made of Single Silver Nanorods.

Directional optical nanoantennas are often realized by nanostructured systems with ingenious or complex designs. Herein we report on the realization of directional scattering of visible light from a simple configuration made of single Ag nanorods supported on Si substrates, where the incident light can be routed toward the two flanks of each nanorod. Such an intriguing far-field scattering behavior, which has not been investigated so far, is proved to result from the near-field coupling between high-aspect-ratio Ag nanorods and high-refractive-index Si substrates. A simple and intuitive model is proposed, where the complicated plasmon resonance is found to be equivalent to several vertically aligned electric dipoles oscillating in phase, to understand the far-field properties of the system. The interference among the electric dipoles results in wavefront reshaping and sidewise light routing in a similar manner to the broadside antenna described in the traditional antenna theory, allowing for the naming of these Si-supported Ag nanorods as "broadside nanoantennas". We have carried out comprehensive experiments to understand the physical origins behind and the affecting factors on the directional scattering behavior of such broadside nanoantennas.

Facet-Dependent Property of Sequentially Deposited Perovskite Thin Films: Chemical Origin and Self-Annihilation.

Quantification of intergrain length scale properties of CH3NH3PbI3 (MAPbI3) can provide further understanding of material physics, leading to improved device performance. In this work, we noticed that two typical types of facets appear in sequential deposited perovskite (SDP) films: smooth and steplike morphologies. By mapping the surface potential as well as the photoluminescence (PL) peak position, we revealed the heterogeneity of SDP thin films that smooth facets are almost intrinsic with a PL peak at 775 nm, while the steplike facets are p-type-doped with 5-nm blue-shifted PL peak. Considering the reaction process, we propose that the smooth facets have well-defined crystal lattices that resulted from the interfacial reaction between MAI and PbI2 domains containing low trap states density. The steplike facets are MAI-rich originated from the grain boundaries of PbI2 film and own more trap states. Conversion of steplike facets to smooth facets can be controlled by increasing the reaction time through Ostwald ripening. The improved stability, photoresponsivity up to 0.3 A/W, on/off ratio up to 3900, and decreased photo response time to ∼160 µs show that the trap states can be annihilated effectively to improve the photoelectrical conversion with prolonged reaction time and elimination of steplike facets. Our findings demonstrate the relationship between the facet heterogeneity of SDP films and crystal growth process for the first time, and imply that the systematic control of crystal grain modification will enable amelioration of crystallinity for more-efficient perovskite photoelectrical applications.

Nonstoichiometric acid-base reaction as reliable synthetic route to highly stable CH3NH3PbI3 perovskite film.

Perovskite solar cells have received worldwide interests due to swiftly improved efficiency but the poor stability of the perovskite component hampers the device fabrication under normal condition. Herein, we develop a reliable nonstoichiometric acid-base reaction route to stable perovskite films by intermediate chemistry and technology. Perovskite thin-film prepared by nonstoichiometric acid-base reaction route is stable for two months with negligible PbI2-impurity under ∼65% humidity, whereas other perovskites prepared by traditional methods degrade distinctly after 2 weeks. Route optimization involves the reaction of PbI2 with excess HI to generate HPbI3, which subsequently undergoes reaction with excess CH3NH2 to deliver CH3NH3PbI3 thin films. High quality of intermediate HPbI3 and CH3NH2 abundance are two important factors to stable CH3NH3PbI3 perovskite. Excess volatile acid/base not only affords full conversion in nonstoichiometric acid-base reaction route but also permits its facile removal for stoichiometric purification, resulting in average efficiency of 16.1% in forward/reverse scans.

Ultrathin efficient perovskite solar cells employing a periodic structure of a composite hole conductor for elevated plasmonic light harvesting and hole collection.

We developed a molecule/polymer composite hole transporting material (HTM) with a periodic microstructure for morphology replication of a corrugated Au electrode, which in combination plays a dual role in the optical and electronic enhancement of high performance perovskite solar cells (PSCs). The electro-optics revealed that perovskite couldn't readily extinct the red light even though the thickness increased to 370 nm, but we found that the quasi periodic microstructure composite (PMC) HTM in combination with the conformal Au electrode could promote the absorption through the enhanced cavity effects, leading to comparable absorption even using much thinner perovskite (240 nm). We identified that the cavity was the combination of Fabry-Pérot interferometer and surface plasmonic resonance, with light harvesting enhancement through surface plasmon polariton or waveguide modes that propagate in the plane of the perovskite layer. On the other hand, the PMC HTM increased hole conductivity by one order of magnitude with respect to standard spiro-OMeTAD HTM due to molecular packing and self-assembly, embodying traceable hole mobility and density elevation up to 3 times, and thus the hysteresis was greatly avoided. Owing to dual optical and electronic enhancement, the PMC PSC afforded high efficiency PSC using as thin as 240 nm perovskite layer, delivering a V(oc) of 1.05 V, J(sc) of 22.9 mA cm(-2), FF of 0.736, and efficiency amounting to 17.7% PCE, the highest efficiency with ultrathin perovskite layer.

Hybrid halide perovskite solar cell precursors: colloidal chemistry and coordination engineering behind device processing for high efficiency.

The precursor of solution-processed perovskite thin films is one of the most central components for high-efficiency perovskite solar cells. We first present the crucial colloidal chemistry visualization of the perovskite precursor solution based on analytical spectra and reveal that perovskite precursor solutions for solar cells are generally colloidal dispersions in a mother solution, with a colloidal size up to the mesoscale, rather than real solutions. The colloid is made of a soft coordination complex in the form of a lead polyhalide framework between organic and inorganic components and can be structurally tuned by the coordination degree, thereby primarily determining the basic film coverage and morphology of deposited thin films. By utilizing coordination engineering, particularly through employing additional methylammonium halide over the stoichiometric ratio for tuning the coordination degree and mode in the initial colloidal solution, along with a thermal leaching for the selective release of excess methylammonium halides, we achieved full and even coverage, the preferential orientation, and high purity of planar perovskite thin films. We have also identified that excess organic component can reduce the colloidal size of and tune the morphology of the coordination framework in relation to final perovskite grains and partial chlorine substitution can accelerate the crystalline nucleation process of perovskite. This work demonstrates the important fundamental chemistry of perovskite precursors and provides genuine guidelines for accurately controlling the high quality of hybrid perovskite thin films without any impurity, thereby delivering efficient planar perovskite solar cells with a power conversion efficiency as high as 17% without distinct hysteresis owing to the high quality of perovskite thin films.