Towards Long-Term Stable Perovskite Solar Cells: Degradation Mechanisms and Stabilization Techniques.

It is certain that perovskite materials must be a game-changer in the solar industry as long as their stability reaches a level comparable with the lifetime of a commercialized Si photovoltaic. However, the operational stability of perovskite solar cells and modules still remains unresolved, especially when devices operate in practical energy-harvesting modes represented by maximum power point tracking under 1 sun illumination at ambient conditions. This review article covers from fundamental aspects of perovskite instability including chemical decomposition pathways under light soaking and electrical bias, to recent advances and techniques that effectively prevent such degradation of perovskite solar cells and modules. In particular, fundamental causes for permanent degradation due to ion migration and trapped charges are overviewed and explain their interplay between ions and charges. Based on the degradation mechanism, recent advances on the strategies are discussed to slow down the degradation during operation for a practical use of perovskite-based solar devices.

Two-Color Amplified Spontaneous Emission from Auger-Suppressed Quantum Dots in Liquids.

Colloidal quantum-dot (QD) lasing is normally achieved in close-packed solid-state films, as a high QD volume fraction is required for stimulated emission to outcompete fast Auger decay of optical-gain-active multiexciton states. Here a new type of liquid optical-gain medium is demonstrated, in which compact compositionally-graded QDs (ccg-QDs) that feature strong suppression of Auger decay are liquefied using a small amount of solvent. Transient absorption measurements of ccg-QD liquid suspensions reveal broad-band optical gain spanning a wide spectral range from 560 (green) to 675 nm (red). The gain magnitude is sufficient to realize a two-color amplified spontaneous emission (ASE) at 637 and 594 nm due to the band-edge (1S) and the excited-state (1P) transition, respectively. Importantly, the ASE regime is achieved using quasicontinuous excitation with nanosecond pulses. Furthermore, the ASE is highly stable under prolonged excitation, which stands in contrast to traditional dyes that exhibit strong degradation under identical excitation conditions. These observations point toward a considerable potential of high-density ccg-QD suspensions as liquid, dye-like optical gain media that feature readily achievable spectral tunability and stable operation under intense photoexcitation.

Colloidal Semiconductor Nanocrystal Lasers and Laser Diodes.

Lasers and optical amplifiers based on solution-processable materials have been long-desired devices for their compatibility with virtually any substrate, scalability, and ease of integration with on-chip photonics and electronics. These devices have been pursued across a wide range of materials including polymers, small molecules, perovskites, and chemically prepared colloidal semiconductor nanocrystals, also commonly referred to as colloidal quantum dots. The latter materials are especially attractive for implementing optical-gain media as in addition to being compatible with inexpensive and easily scalable chemical techniques, they offer multiple advantages derived from a zero-dimensional character of their electronic states. These include a size-tunable emission wavelength, low optical gain thresholds, and weak sensitivity of lasing characteristics to variations in temperature. Here we review the status of colloidal nanocrystal lasing devices, most recent advances in this field, outstanding challenges, and the ongoing progress toward technological viable devices including colloidal quantum dot laser diodes.

Electrically driven amplified spontaneous emission from colloidal quantum dots.

Colloidal quantum dots (QDs) are attractive materials for realizing solution-processable laser diodes that could benefit from size-controlled emission wavelengths, low optical-gain thresholds and ease of integration with photonic and electronic circuits1-7. However, the implementation of such devices has been hampered by fast Auger recombination of gain-active multicarrier states1,8, poor stability of QD films at high current densities9,10 and the difficulty to obtain net optical gain in a complex device stack wherein a thin electroluminescent QD layer is combined with optically lossy charge-conducting layers11-13. Here we resolve these challenges and achieve amplified spontaneous emission (ASE) from electrically pumped colloidal QDs. The developed devices use compact, continuously graded QDs with suppressed Auger recombination incorporated into a pulsed, high-current-density charge-injection structure supplemented by a low-loss photonic waveguide. These colloidal QD ASE diodes exhibit strong, broadband optical gain and demonstrate bright edge emission with instantaneous power of up to 170 µW.

Optically Excited Lasing in a Cavity-Based, High-Current-Density Quantum Dot Electroluminescent Device.

Laser diodes based on solution-processable materials can benefit numerous technologies including integrated electronics and photonics, telecommunications, and medical diagnostics. An attractive system for implementing these devices is colloidal semiconductor quantum dots (QDs). The progress towards a QD laser diode has been hampered by rapid nonradiative Auger decay of optical-gain-active multicarrier states, fast device degradation at high current densities required for laser action, and unfavorable competition between optical gain and optical losses in a multicomponent device stack. Here we resolve some of these challenges and demonstrate optically excited lasing from fully functional high-current density electroluminescent (EL) devices with an integrated optical resonator. This advance has become possible due to excellent optical gain properties of continuously graded QDs and a refined device architecture, which allows for highly efficient light amplification in a thin, EL-active QD layer.

Two-band optical gain and ultrabright electroluminescence from colloidal quantum dots at 1000 A cm-2.

Colloidal quantum dots (QDs) are attractive materials for the realization of solution-processable laser diodes. Primary challenges towards this objective are fast optical-gain relaxation due to nonradiative Auger recombination and poor stability of colloidal QD solids under high current densities required to obtain optical gain. Here we resolve these challenges and achieve broad-band optical gain spanning the band-edge (1S) and the higher-energy (1P) transitions. This demonstration is enabled by continuously graded QDs with strongly suppressed Auger recombination and a current-focusing device design, combined with short-pulse pumping. Using this approach, we achieve ultra-high current densities (~1000 A cm-2) and brightness (~10 million cd m-2), and demonstrate an unusual two-band electroluminescence regime for which the 1P band is more intense than the 1S feature. This implies the realization of extremely large QD occupancies of up to ~8 excitons per-dot, which corresponds to complete filling of the 1S and 1P electron shells.

An atomistic mechanism for the degradation of perovskite solar cells by trapped charge.

It is unmistakably paradoxical that the most vulnerable aspect of the photoactive organic-inorganic hybrid perovskite is its instability against light. Why and how perovskites break down under light irradiation and what happens at the atomistic level of these materials during the degradation process still remain unanswered. In this paper, we found the culprit and verified the mechanism for the irreversible degradation of hybrid perovskite materials from our experimental investigation and ab initio molecular dynamics (AIMD) simulation. We initially found that the electrostatic charges generated by light irradiation and trapped along the grain boundaries of the perovskite crystal result in oxygen-induced irreversible degradation in dry air. This result, together with our previous experimental finding on the same critical role of trapped charges in the perovskite degradation under moisture, suggests that the trapped charges are the main culprit in both the oxygen- and moisture-induced degradation of perovskite materials. Detailed roles of oxygen and water molecules were investigated using AIMD simulation by tracking the atomic motions in the outermost layers of the oxygen- or water-covered methylammonium lead triiodide (denoted MAPbI3 for CH3NH3PbI3) perovskite crystal with trapped charges. In the first few picoseconds of our simulation, trapped charges start disrupting the crystal structure, leading to a short-range interaction between oxygen or water molecules and the compositional ions of MAPbI3. We found that there exist different degradation pathways depending on both the polarity of the trapped charge and the kind of gas molecule. We also verified that a more structurally stable, multi-component perovskite material (with the composition of MA0.6FA0.4PbI2.9Br0.1) showed much stronger resistance against light-induced degradation than MAPbI3 even in 100%-oxygen ambience or humid air.

Highly Reproducible Large-Area Perovskite Solar Cell Fabrication via Continuous Megasonic Spray Coating of CH3 NH3 PbI3.

A simple, low-cost, large area, and continuous scalable coating method is proposed for the fabrication of hybrid organic-inorganic perovskite solar cells. A megasonic spray-coating method utilizing a 1.7 MHz megasonic nebulizer that could fabricate reproducible large-area planar efficient perovskite films is developed. The coating method fabricates uniform large-area perovskite film with large-sized grain since smaller and narrower sized mist droplets than those generated by existing ultrasonic spray methods could be generated by megasonic spraying. The volume flow rate of the CH3 NH3 PbI3 precursor solution and the reaction temperature are controlled, to obtain a high quality perovskite active layer. The devices reach a maximum efficiency of 16.9%, with an average efficiency of 16.4% from 21 samples. The applicability of megasonic spray coating to the fabrication of large-area solar cells (1 cm2 ), with a power conversion efficiency of 14.2%, is also demonstrated. This is a record high efficiency for large-area perovskite solar cells fabricated by continuous spray coating.

Carbon Nanotubes versus Graphene as Flexible Transparent Electrodes in Inverted Perovskite Solar Cells.

Transparent carbon electrodes, carbon nanotubes, and graphene were used as the bottom electrode in flexible inverted perovskite solar cells. Their photovoltaic performance and mechanical resilience were compared and analyzed using various techniques. Whereas a conventional inverted perovskite solar cells using indium tin oxide showed a power conversion efficiency of 17.8%, the carbon nanotube- and graphene-based cells showed efficiencies of 12.8% and 14.2%, respectively. An established MoO3 doping was used for  carbon electrode-based devices. The difference in the photovoltaic performance between the carbon nanotube- and graphene-based cells was due to the difference in morphology and transmittance. Raman spectroscopy, and cyclic flexural testing revealed that the graphene-based cells were more susceptible to strain than the carbon nanotube-based cells, though the difference was marginal. Overall, despite higher performance, the transfer step for graphene has lower reproducibility. Thus, the development of better graphene transfer methods would help maximize the current capacity of graphene-based cells.

Precise Morphology Control and Continuous Fabrication of Perovskite Solar Cells Using Droplet-Controllable Electrospray Coating System.

Herein, we developed a novel electrospray coating system for continuous fabrication of perovskite solar cells with high performance. Our system can systemically control the size of CH3NH3PbI3 precursor droplets by modulating the applied electrical potential, shown to be a crucial factor for the formation of perovskite films. As a result, we have obtained pinhole-free and large grain-sized perovskite solar cells, yielding the best PCE of 13.27% with little photocurrent hysteresis. Furthermore, the average PCE through the continuous coating process was 11.56 ± 0.52%. Our system demonstrates not only the high reproducibility but also a new way to commercialize high-quality perovskite solar cells.

Trapped charge-driven degradation of perovskite solar cells.

Perovskite solar cells have shown unprecedent performance increase up to 22% efficiency. However, their photovoltaic performance has shown fast deterioration under light illumination in the presence of humid air even with encapulation. The stability of perovskite materials has been unsolved and its mechanism has been elusive. Here we uncover a mechanism for irreversible degradation of perovskite materials in which trapped charges, regardless of the polarity, play a decisive role. An experimental setup using different polarity ions revealed that the moisture-induced irreversible dissociation of perovskite materials is triggered by charges trapped along grain boundaries. We also identified the synergetic effect of oxygen on the process of moisture-induced degradation. The deprotonation of organic cations by trapped charge-induced local electric field would be attributed to the initiation of irreversible decomposition.

Control of I-V hysteresis in CH3NH3PbI3 perovskite solar cell.

Mismatch of current (I)-voltage (V) curves with respect to the scan direction, so-called I-V hysteresis, raises critical issue in MAPbI3 (MA = CH3NH3) perovskite solar cell. Although ferroelectric and ion migration have been proposed as a basis for the hysteresis, origin of hysteresis has not been apparently unraveled. We report here on the origin of I-V hysteresis of perovskite solar cell that was systematically evaluated by the interface-dependent electrode polarizations. Frequency (f)-dependent capacitance (C) revealed that the normal planar structure with the TiO2/MAPbI3/spiro-MeOTAD configuration showed most significant I-V hysteresis along with highest capacitance (10(-2) F/cm(2)) among the studied cell configurations. Substantial reduction in capacitance to 10(-3) F/cm(2) was observed upon replacing TiO2 with PCBM, indicative of the TiO2 layer being mainly responsible for the hysteresis. The capacitance was intensively reduced to 10(-5) F/cm(2) and C-f feature shifted to higher frequency for the hysteresis-free planar structures with combination of PEDOT: PSS, NiO, and PCBM, which underlines the spiro-MeOTAD in part contributes to the hysteresis. This work is expected to provide a key to the solution of the problem on I-V hysteresis in perovskite solar cell.

Highly Reproducible Perovskite Solar Cells with Average Efficiency of 18.3% and Best Efficiency of 19.7% Fabricated via Lewis Base Adduct of Lead(II) Iodide.

High efficiency perovskite solar cells were fabricated reproducibly via Lewis base adduct of lead(II) iodide. PbI2 was dissolved in N,N-dimethyformamide with equimolar N,N-dimethyl sulfoxide (DMSO) and CH3NH3I. Stretching vibration of S═O appeared at 1045 cm(-1) for bare DMSO, which was shifted to 1020 and 1015 cm(-1) upon reacting DMSO with PbI2 and PbI2 + CH3NH3I, respectively, indicative of forming the adduct of PbI2·DMSO and CH3NH3I·PbI2·DMSO due to interaction between Lewis base DMSO and/or iodide (I(-)) and Lewis acid PbI2. Spin-coating of a DMF solution containing PbI2, CH3NH3I, and DMSO (1:1:1 mol %) formed a transparent adduct film, which was converted to a dark brown film upon heating at low temperature of 65 °C for 1 min due to removal of the volatile DMSO from the adduct. The adduct-induced CH3NH3PbI3 exhibited high charge extraction characteristics with hole mobility as high as 3.9 × 10(-3) cm(2)/(V s) and slow recombination rate. Average power conversion efficiency (PCE) of 18.3% was achieved from 41 cells and the best PCE of 19.7% was attained via adduct approach.

Janus-compartmental alginate microbeads having polydiacetylene liposomes and magnetic nanoparticles for visual lead(II) detection.

Janus-compartmental alginate microbeads having two divided phases of sensory polydiacetylene (PDA) liposomes and magnetic nanoparticles were fabricated for facile sensory applications. The sensory liposomes are composed of PDA for label-free signal generation and 1,2-dipalmitoyl-sn-glycero-3-galloyl (DPGG) lipids whose galloyl headgroup has specific interactions with lead(II). The second phase having magnetic nanoparticles is designed for convenient handling of the microbeads, such as washing, solvent exchange, stirring, and detection, by applying magnetic field. Selective and convenient colorimetric detection of lead(II) and efficient removal of lead(II) by alginate matrix at the same time are demonstrated.

Biomimetic detection of aminoglycosidic antibiotics using polydiacetylene-phospholipids supramolecules.

We rationally designed highly sensitive and selective polydiacetylene (PDA)-phospholipids liposomes for the facile detection of aminoglycosidic antibiotics. The detecting mechanism mimics the cellular membrane interactions between neomycin and phosphatidylinositol-4,5-bisphosphate (PIP(2)) phospholipids. The developed PDA-PIP(2) sensory system showed a detection limit of 61 ppb for neomycin and was very specific to aminoglycosidic antibodies only.