Interface Dipole Management of D-A-Type Molecules for Efficient Perovskite Solar Cells.

Interfacial engineering of perovskite films has been the main strategies in improving the efficiency and stability of perovskite solar cells (PSCs). In this study, three new donor-acceptor (D-A)-type interfacial dipole (DAID) molecules with hole-transporting and different anchoring units are designed and employed in PSCs. The formation of interface dipoles by the DAID molecules on the perovskite film can efficiently modulate the energy level alignment, improve charge extraction, and reduce non-radiative recombination. Among the three DAID molecules, TPA-BAM with amide group exhibits the best chemical and optoelectrical properties, achieving a champion PCE of 25.29% with the enhanced open-circuit voltage of 1.174 V and fill factor of 84.34%, due to the reduced defect density and improved interfacial hole extraction. Meanwhile, the operational stability of the unencapsulated device has been significantly improved. Our study provides a prospect for rationalized screening of interfacial dipole materials for efficient and stable PSCs.

Self-Polymerized Spiro-Type Interfacial Molecule toward Efficient and Stable Perovskite Solar Cells.

In the pursuit of highly efficient perovskite solar cells, spiro-OMeTAD has demonstrated recorded power conversion efficiencies (PCEs), however, the stability issue remains one of the bottlenecks constraining its commercial development. In this study, we successfully synthesize a novel self-polymerized spiro-type interfacial molecule, termed v-spiro. The linearly arranged molecule exhibits stronger intermolecular interactions and higher intrinsic hole mobility compared to spiro-OMeTAD. Importantly, the vinyl groups in v-spiro enable in situ polymerization, forming a polymeric protective layer on the perovskite film surface, which proves highly effective in suppressing moisture degradation and ion migration. Utilizing these advantages, poly-v-spiro-based device achieves an outstanding efficiency of 24.54 %, with an enhanced open-circuit voltage of 1.173 V and a fill factor of 81.11 %, owing to the reduced defect density, energy level alignment and efficient interfacial hole extraction. Furthermore, the operational stability of unencapsulated devices is significantly enhanced, maintaining initial efficiencies above 90 % even after 2000 hours under approximately 60 % humidity or 1250 hours under continuous AM 1.5G sunlight exposure. This work presents a comprehensive approach to achieving both high efficiency and long-term stability in PSCs through innovative interfacial design.

4,9- and 4,10-Substituted pyrenes: synthesis, successful isolation, and optoelectronic properties.

We report herein a way to prepare and purify optoelectronic functional 4,9- and 4,10-substituted pyrene isomers. By tuning the size of substituents, the designed 4,9- and 4,10-isomers can be successfully isolated by recycling preparative size-exclusion chromatography (SEC) and/or repeated recrystallization. The structure and purity of the isolated compounds 1-5 have been confirmed by 1H NMR, 13C NMR, and HRMS. The photophysical and electrochemical properties of compounds 1-5 have been studied in detail both experimentally and theoretically. The lowest transitions of these pyrenes, 1-5, are allowed, with moderate to high fluorescence quantum yields and radiative decay rates around 108 s-1. The differences between the electrochemical and photophysical properties of 4,9-, 4,10-, 1,6-, and 2,7-substituted isomers are compared and concluded.

Dendrimer-Encapsulated Halide Perovskite Nanocrystals for Self-Powered White Light-Emitting Glass.

Perovskite nanocrystals (PNCs) have attracted substantial attention due to their inspiring intrinsic merits such as low cost, high performance, and solution processability, but when it comes to the usage of blends of different colored PNCs with the purpose of covering the broadband spectrum field, the high degree of instability remains a major bottleneck. Herein, we report a family of dendritic ammonium ligands that act as stiff shell-encapsulating PNCs for improving their stability and suppressing ion permeability in mixed colloidal PNC solutions. The as-synthesized ligand-encapsulated PNCs notably achieve near-unity photoluminescence quantum yields (PLQYs) and strongly resist the unwanted ion exchange reaction under aggressive anion source attack. To fabricate self-powered white-emitting glass, the stabilized mixed colored PNCs were embedded into the laminated glass, which simultaneously acted as absorbers-emitters for luminescent solar concentrators (LSCs) and emitters for white light-emitting glass.

Monolithically-grained perovskite solar cell with Mortise-Tenon structure for charge extraction balance.

Although the power conversion efficiency values of perovskite solar cells continue to be refreshed, it is still far from the theoretical Shockley-Queisser limit. Two major issues need to be addressed, including disorder crystallization of perovskite and unbalanced interface charge extraction, which limit further improvements in device efficiency. Herein, we develop a thermally polymerized additive as the polymer template in the perovskite film, which can form monolithic perovskite grain and a unique "Mortise-Tenon" structure after spin-coating hole-transport layer. Importantly, the suppressed non-radiative recombination and balanced interface charge extraction benefit from high-quality perovskite crystals and Mortise-Tenon structure, resulting in enhanced open-circuit voltage and fill-factor of the device. The PSCs achieve certified efficiency of 24.55% and maintain >95% initial efficiency over 1100 h in accordance with the ISOS-L-2 protocol, as well as excellent endurance according to the ISOS-D-3 accelerated aging test.

Orientated crystallization of FA-based perovskite via hydrogen-bonded polymer network for efficient and stable solar cells.

Incorporating mixed ion is a frequently used strategy to stabilize black-phase formamidinum lead iodide perovskite for high-efficiency solar cells. However, these devices commonly suffer from photoinduced phase segregation and humidity instability. Herein, we find that the underlying reason is that the mixed halide perovskites generally fail to grow into homogenous and high-crystalline film, due to the multiple pathways of crystal nucleation originating from various intermediate phases in the film-forming process. Therefore, we design a multifunctional fluorinated additive, which restrains the complicated intermediate phases and promotes orientated crystallization of α-phase of perovskite. Furthermore, the additives in-situ polymerize during the perovskite film formation and form a hydrogen-bonded network to stabilize α-phase. Remarkably, the polymerized additives endow a strongly hydrophobic effect to the bare perovskite film against liquid water for 5 min. The unencapsulated devices achieve 24.10% efficiency and maintain >95% of the initial efficiency for 1000 h under continuous sunlight soaking and for 2000 h at air ambient of ~50% humid, respectively.

Heterostructural Nanosheets Consisting of Polycyclic Aromatic Hydrocarbon Shields and Layered Perovskite Cores for Optical Image Encryption.

Optical image encryption technology, in which the emission on/off can be controlled by using specially appointed wavelengths, is useful in information storage and protection. Herein, we report a family of sandwiched heterostructural nanosheets, consisting of three-layered (n = 3) perovskite (PSK) frameworks in center with two different polycyclic aromatic hydrocarbons [triphenylene (Tp) and pyrene (Py)] in periphery. Both heterostructural nanosheets (Tp-PSK and Py-PSK) exhibit blue emissions under UVA-I irradiation; however, different photoluminescent properties are observed under UVA-II. A bright emission of Tp-PSK is attributed to the fluorescence resonance energy transfer (FRET) from Tp-shield to PSK-core, whereas the observed photoquenching phenomenon in Py-PSK is due to the competitive absorption between Py-shield and PSK-core. We exploited the unique photophysical features (on/off emission) of the two nanosheets in a narrow UV window (320-340 nm) for optical image encrypting.

Facile Synthesis of Highly Emissive All-Inorganic Manganese Bromide Compounds with Perovskite-Related Structures for White LEDs.

Lead-free all-inorganic halide materials with different Mn2+-based crystal structures (Cs3MnBr5 and CsMnBr3) were obtained using a convenient synthetic method. Cs3MnBr5 had a bright green emission (522 nm), with a unique single-exponential lifetime (τavg = 236 µs) and a high photoluminescence quantum yield (82 ± 5%). A red emission was observed in the case of the CsMnBr3 structure with a two-exponential fluorescence decay curve, and the lifetime was 1.418 µs (93%) and 18.328 µs (7%), respectively. By a judicious tuning of the synthetic conditions, a mixed phase of Cs3MnBr5/CsMnBr3 was also produced that emitted white light, covering almost the entire visible spectrum. White-light-emitting diodes (WLEDs) with color coordinates (0.4269, 0.4955), a color temperature of (3773 K), and a color rendering index (68) were then fabricated using the as-prepared powder of mixed phases of Cs3MnBr5/CsMnBr3 with a commercial UV LED chip (365 nm).

Underlying Interface Defect Passivation and Charge Transfer Enhancement via Sulfonated Hole-Transporting Materials for Efficient Inverted Perovskite Solar Cells.

To date, numbers of polymeric hole-transporting materials (HTMs) have been developed to improve interfacial charge transport to achieve high-performance inverted perovskite solar cells (PSCs). However, molecular design for passivating the underlying surface defects between perovskite and HTMs is a neglected issue, which is a major bottleneck to further enhance the performance of the inverted devices. Herein, we design and synthesize a new polymeric HTM PsTA-mPV with the methylthiol group, in which a lone pair of electrons of sulfur atoms can passivate the underlying interface defects of the perovskite more efficiently by coordinating Pb2+ vacancies. Furthermore, PsTA-mPV exhibits a deeper highest occupied molecular orbital (HOMO) level aligned with perovskite due to the π-acceptor capability of sulfur, which improves interfacial charge transfer between perovskite and the HTM layer. Using PsTA-mPV as a dopant-free HTM, the inverted PSCs show 20.2% efficiency and long-term stability, which is ascribed to surface defect passivation, well energy-level matching with perovskite, and efficient charge extraction.

Self-Powered and Low-Noise Perovskite Photodetector Enabled by a Novel Dopant-Free Hole-Transport Material with Bottom Passivation for Underwater Blue Light Communications.

Designing dopant-free hole-transport materials (HTMs) is a facile and effective strategy to realize high-performance organic-inorganic hybrid perovskite (OIHP) photodetectors. Herein, a novel phenothiazine polymer, poly[4-(10H-phenothiazin-10-yl)-N,N-bis(4-methoxyphenyl)aniline] (PPZ-TPA), was synthesized and employed as a promising HTM in OIHP photodetectors. The triphenylamine donor unit was combined with a phenothiazine core, furnishing the polymer with a suitable highest occupied molecular orbital level, favorable thermal stability, and appropriate film morphology. The sulfur atom in the phenothiazine functional group can intentionally passivate the undercoordinated Pb2+ of OIHP films, suppressing nonradiative recombination and yielding an ultralow dark current density of 1.26 × 10-7 A cm-2 under -0.1 V, as well as a low-noise current of 3.75 × 10-13 A Hz-1/2 at 70 Hz. Encouragingly, the self-powered PPZ-TPA-based OIHP photodetectors were successfully integrated into a blue light communication system for the first time, demonstrating their application for receiving and transmitting light signals with a transmission rate of 300 bps. In addition, the PPZ-TPA-based devices exhibit nearly 1 year shelf stability without obvious degradation. We believe that PPZ-TPA demonstrates great potential to achieve high-performance perovskite photodetectors, also providing a strategy for the design of novel HTMs.

Ultrahigh Photogain Short-Wave Infrared Detectors Enabled by Integrating Graphene and Hyperdoped Silicon.

Highly sensitive short-wave infrared (SWIR) detectors, compatible with the silicon-based complementary metal oxide semiconductor (CMOS) process, are regarded as the key enabling components in the miniaturized system for weak signal detection. To date, the high photogain devices are greatly limited by a large bias voltage, low-temperature refrigeration, narrow response band, and complex fabrication processes. Here, we demonstrate high photogain detectors working in the SWIR region at room temperature, which use graphene for charge transport and Te-hyperdoped silicon (Te-Si) for infrared absorption. The prolonged lifetime of carriers, combined with the built-in potential generated at the interface between the graphene and the Te-Si, leads to an ultrahigh photogain of 109 at room temperature (300 K) for 1.55 µm light. The gain can be improved to 1012, accompanied by a noise equivalent power (NEP) of 0.08 pW Hz-1/2 at 80 K. Moreover, the proposed device exhibits a NEP of 4.36 pW Hz-1/2 at 300 K at the wavelength of 2.7 µm, which is exceeding the working region of InGaAs detectors. This research shows that graphene can be used as an efficient platform for silicon-based SWIR detection and provides a strategy for the low-power, uncooled, high-gain infrared detectors compatible with the CMOS process.

Regulating the Intermolecular Hydrogen Bond to Realize Directional Dimension Reduction of Lead Iodide Perovskite toward Low-Dimensional Photovoltaics.

A low-dimensional organic amine lead halide perovskite is an attractive semiconductor material that has potential application prospects in photovoltaics, light-emitting diodes, detectors, X-ray imaging, and other fields. It has been reported that the photoelectric properties of low-dimensional perovskite can be controlled by adjusting the chain length of organic ammonium, the ratio of precursor components, and van der Waals interaction between amine molecules. Herein, we report the successful synthesis of low-dimensional perovskite (PdEA)PbI4 (PdEA = piperidine ethylammonium) and (MlEA)PbI4 (MlEA = morpholine ethylammonium) single crystals by regulating the intermolecular hydrogen bond of organic ammonium ligands. The two-dimensional (2D) layered structure (PdEA)PbI4 single crystal with a fluorescence reflection peak at 563 nm was produced by the reaction of PdEA with PbO in a concentrated hydroiodic acid aqueous solution. Differently, the (MlEA)PbI4 single crystal prepared by replacing MlEA with PdEA presents a one-dimensional (1D) rod structure, and its fluorescence reflection peak is located at 531 nm. The optical bandgaps of (PdEA)PbI4 and (MlEA)PbI4 perovskite films were about 2.16 and 2.33 eV, respectively. Low-dimensional perovskite solar cells with 2D (PdEA)PbI4 and 1D (MlEA)PbI4 of perovskite films yielded efficiencies of 1.18 and 1.52%, respectively.

Tailored Polymeric Hole-Transporting Materials Inducing High-Quality Crystallization of Perovskite for Efficient Inverted Photovoltaic Devices.

For achieving high-performance p-i-n perovskite solar cells (PSCs), hole transporting materials (HTMs) are critical to device functionality and represent a major bottleneck to further enhancing device stability and efficiency in the inverted devices. Three dopant-free polymeric HTMs are developed based on different linkage sites of triphenylamine and phenylenevinylene repeating units in their main backbone structures. The backbone curvatures of the polymeric HTMs affect the morphology and hole mobility of the polymers and further change the crystallinity of perovskite films. By using PTA-mPV with moderate molecular curvature, p-i-n PSCs with high efficiency of 19.5% and long-term stability can be achieved. The better performance is attributed to the more effective hole extraction ability, higher charge-carrier mobility, and lower interfacial charge recombination. Furthermore, these three polymeric HTMs are synthesized without any noble metal catalyst, and show great advantages in future application owing to the low-cost.

Self-Enhancement of Efficiency and Self-Attenuation of Hysteretic Behavior of Perovskite Solar Cells with Aging.

Spontaneous enhancement of the photovoltaic performance of perovskite solar cells (PSCs) after aging has been reported, but the underlying reasons for such behavior are still under debate. Herein, we demonstrate that this spontaneous improvement effect accompanied by self-attenuation of hysteresis in the current-voltage characteristics is time- and temperature-dependent. Moreover, it is universal to PSCs based on a range of mixed-ion perovskites and coupled to different hole- and electron-transporting materials. Time-resolved confocal fluorescence microscopy and other characterization techniques suggest that the "self-healing" phenomenon is accompanied by the homogenization and enhancement of the charge extraction efficiency as well as suppressed recombination throughout cm2-scale perovskite layers. These dynamic effects need to be accounted for when assessing the initial and stabilized performance of PSCs.

Preparation of Micron-sized Methylamine-PbCl3 perovskite grains by controlling phase transition engineering for selective Ultraviolet-harvesting transparent photovoltaics.

Selective ultraviolet-harvesting transparent perovskite solar cells (T-PSCs) have attracted great interest because of their high transmittance and unique photovoltaic properties, especially in the fields of smart windows for power generation and building glass. However, owing to the unsatisfactory solubility of PbCl2 in most conventional solvents, preparing transparent methylammonium lead chloride (MAPbCl3) films with high quality and sufficient thickness by conventional methods poses a substantial challenge for their application deployment in T-PSCs. In this work, two novel strategies based on an ion-exchange procedure for controlling phase transition engineering (CPTE) are proposed. For CPTE-2, an optimized cubic phase MAPbCl3 film with a large grain size and high full coverage is prepared by transforming the tetragonal phase MAPbI3 precursor into the cubic phase MAPbCl3. Establishing relevant models based on crystal parameters investigates the formation mechanism of this high-quality MAPbCl3 film. Accordingly, the resultant T-PSCs exhibit remarkable film quality and micron-sized grains and reach an optimum efficiency of 0.33% (JSC = 0.66 mA cm-2, VOC = 1.14 V, and FF = 43.72%).

Ultrapure Blue Phosphorescent Organic Light-Emitting Diodes Employing a Twisted Pt(II) Complex.

Described herein is a stable complex, Pt(mpzpyOczpy-mesi), embodying efficient, narrow blue emission. The highly twisted structure of the complex improves the stability and efficiency of photo- and electroluminescence by reducing the intermolecular interactions. The complex in solution shows high photoluminescence efficiency (>95%) and radiative decay rate (Kr = 2.9 × 105 s-1) with a narrow emission spectrum. The bottom-emitting phosphorescent device, BE1, exhibits durable deep blue emission with CIE coordinates of (0.145, 0.166) and 5.2 h of LT50 at an initial luminance of 685 cd/m2. Top-emitting devices, TE1 and TE2, achieve ultrapure blue color with CIEx,y values of (0.141, 0.068) and (0.140, 0.071), respectively. TE4 shows high brightness of 3405 cd m-2 at 50 mA m-2, EQE of 10.2% at 1000 cd/m2, and almost negligible color deviation around (0.135, 0.096) at viewing angles of 0°-60°.

Ferrocene-Induced Perpetual Recovery on All Elemental Defects in Perovskite Solar Cells.

Lead halide perovskites always emerge complex interactions among different elemental ions, which lead to multiple intrinsic imperfections. Elemental defects, such as amine, Pb, and I vacancies at A-, B-, and X-sites, are main issues to deteriorate perovskite solar cells (PSCs). Unfortunately, most previous passivators can only temporarily fix partial inactive vacancies as sacrificial agents. Herein, we propose a recovery agent, ferrocene (Fc), which can form a one-dimensional perovskite with adequate steric cavities and suitable dissociation energy to recover all elemental defects back to active light-harvesting perovskites, and regenerate Fc itself meanwhile. Based on this perpetual chain-reaction cycle, corresponding PSCs maintain >10 000-hour lifetime in inert condition and >1000-hour durabilities under various extreme environments, including continuous 85 °C heating, 50 % relative humidity wetting, and 1-sun light soaking.

Hole-Transporting Low-Dimensional Perovskite for Enhancing Photovoltaic Performance.

Halide perovskites with low-dimensionalities (2D or quasi-2D) have demonstrated outstanding stabilities compared to their 3D counterparts. Nevertheless, poor charge-transporting abilities of organic components in 2D perovskites lead to relatively low power conversion efficiency (PCE) and thus limit their applications in photovoltaics. Here, we report a novel hole-transporting low-dimensional (HT2D) perovskite, which can form a hole-transporting channel on the top surface of 3D perovskite due to self-assembly effects of metal halide frameworks. This HT2D perovskite can significantly reduce interface trap densities and enhance hole-extracting abilities of a heterojunction region between the 3D perovskite and hole-transporting layer. Furthermore, the posttreatment by HT2D can also reduce the crystal defects of perovskite and improve film morphology. As a result, perovskite solar cells (PSCs) can effectively suppress nonradiative recombination, leading to an increasement on photovoltage to >1.20 V and thus achieving >20% power conversion efficiency and >500 h continuous illumination stability. This work provides a pathway to overcome charge-transporting limitations in low-dimensional perovskites and delivers significant enhancements on performance of PSCs.

Full-frame and high-contrast smart windows from halide-exchanged perovskites.

Window glazing plays an essential role to modulate indoor light and heat transmission, which is a prospect to save the energy cost in buildings. The latest photovoltachromic technology has been regarded as one of the most ideal solutions, however, to achieve full-frame size (100% active area) and high-contrast ratio (>30% variable in visible wavelength) for smart window applicability is still a challenge. Here we report a photovoltachromic device combining full-transparent perovskite photovoltaic and ion-gel based electrochromic components in a vertical tandem architecture without any intermediated electrode. Most importantly, by accurately adjusting the halide-exchanging period, this photovoltachromic module can realize a high pristine transmittance up to 76%. Moreover, it possesses excellent colour-rendering index to 96, wide contrast ratio (>30%) on average visible transmittance (400-780 nm), and a self-adaptable transmittance adjustment and control indoor brightness and temperature automatically depending on different solar irradiances.