Robust Optical Physical Unclonable Function Based on Total Internal Reflection for Portable Authentication.

Physical unclonable functions (PUFs) utilize uncontrollable manufacturing randomness to yield cryptographic primitives. Currently, the fabrication of the most generally employed optical PUFs mainly depends on fluorescent, Raman, or plasmonic materials, which suffer inherent robustness issues. Herein, we construct an optical PUF with high environmental stability via total internal reflection (TIR-PUF) perturbed by randomly distributed polymer microspheres. The response image is transformed into encoded keys via an iterative binning procedure. The concentration of the polymer solution is optimized to debias the bit nonuniformity and maximize encoding capacity. The constructed TIR-PUF shows significantly high encoding capacity (2370) and markedly low total authentication error probability (1.614 × 10-23). The intra-Hamming distance is as low as 0.068, indicating the excellent readout reliability of TIR-PUF. The environmental stability of TIR-PUF has demonstrated promising results under a range of challenging conditions such as ultrasonic washing, high temperature, ultraviolet irradiation, and severe chemical environments. Moreover, the challenge-response pairs of our TIR-PUFs are demonstrated on an authentication system with low-power dissipation, lightweight components, and wireless imaging capture, rendering the possibility of portable authentication for practical applications.

Physical Unclonable Functions Based on Photothermal Effect of Gold Nanoparticles.

Physical unclonable functions (PUFs) based on uncontrollable fabrication randomness are promising candidates for anticounterfeiting applications. Currently, the most popular optical PUFs are generally constructed from the scattering, fluorescent, or Raman phenomenon of nanomaterials. To further improve the security level of optical PUFs, advanced functions transparent to the above optical phenomenon have always been perused by researchers. Herein, we propose a new type of PUF based on the photothermal effect of gold nanoparticles, which shows negligible scattering, fluorescent, or Raman responses. The gold nanoparticles are randomly dispersed onto the surface of fused silica, which can enhance the photothermal effect and facilitate high contrast responses. By tuning the areal density of the gold nanoparticles, the optimized encoding capacity (2319) and the total authentication error probability (3.6428 × 10-24) are achieved from our PUF due to excellent bit uniformity (0.519) and inter Hamming distances (0.503). Moreover, the intra-Hamming distance (0.044) indicates the desired reliability. This advanced PUF with invisible features and high contrast responses provides a promising opportunity to implement authentication and identification with high security.

High-Performance and Stable Perovskite X-ray Detection and Imaging Based on a Ti Cathode.

High-energy radiation detectors with a good imaging resolution, fast response, and high sensitivity are desired to operate at a high electric field. However, strong ion migration triggered by electrochemical reactions at the interface between a high-potential electrode and an organic-inorganic hybrid perovskite limits the stability of radiation detectors under a high electric field. Herein, we demonstrate that such ion migration could be effectively suppressed in devices with a Ti cathode, even at a high electric field of 50 V mm-1, through time-of-flight secondary-ion mass spectrometry. X-ray photoelectron spectroscopy illustrates that Ti-N bonds formed at the interface of MAPbBr3 perovskite single crystals/Ti electrode effectively inhibit the electrochemical reaction in organic-inorganic hybrid perovskite devices and ultimately improve the operating stability under a high electric field. The device with a Ti electrode reaches a high sensitivity of 96 ± 1 mC Gyair-1 cm-2 and a low detection limit of 2.8 ± 0.3 nGy s-1 under hard X-ray energy.

Aging CsPbBr3 Nanocrystal Wafer for Ultralow Ionic Migration and Environmental Stability for Direct X-ray Detection.

The outstanding photoelectric properties of perovskites demonstrate extreme promise for application in X-ray detection. However, the soft lattice of the perovskite results in severe ionic migration for three-dimensional materials, limiting the operation stability of perovskite X-ray detectors. Although ligand-decorated nanocrystals (NCs) exhibit significantly higher stability than three-dimensional perovskites, defects remaining on the interface of NCs could still trigger halide migration under a high bias due to the incomplete ligand decoration. Furthermore, it is still challenging to realize sufficient thickness of absorption layers based on NCs for X-ray detectors through traditional methods. Herein, we develop a centimeter-size and millimeter-thick wafer based on CsPbBr3 NCs through isostatic pressing for X-ray detectors, in which the interfacial defects of NCs are remedied by CsPb2Br5 during aging of wafer in ambient humidity. The wafer shows outstanding sensitivity (200 µC Gyair-1 cm-2) and ultralow dark current drift (1.78 × 10-8 nA cm-1 s-1 V-1 @ 400 V cm-1). Moreover, it shows storage stability with negligible performance degradation for 60 days in ambient humidity. Thus, aging perovskite NC wafers for X-ray detection holds huge potential for next-generation X-ray imaging plates.

In Situ Dual-Interface Passivation Strategy Enables The Efficiency of Formamidinium Perovskite Solar Cells Over 25.

Perovskite solar cells (PSCs) are promising candidates for next-generation photovoltaics owing to their unparalleled power conversion efficiencies (PCEs). Currently, approaches to further improve device efficiencies tend to focus on the passivation of interfacial defects. Although various strategies have been developed to mitigate these defects, many involve complex and time-consuming post-treatment processes, thereby hindering their widespread adoption in commercial applications. In this work, a concise but efficient in situ dual-interface passivation strategy is developed wherein 1-butyl-3-methylimidazolium methanesulfonate (MS) is employed as a precursor additive. During perovskite crystallization, MS can either be enriched downward through precipitation with SnO2 , or can be aggregated upward through lattice extrusion. These self-assembled MS species play a significant role in passivating the defect interfaces, thereby reducing nonradiative recombination losses, and promoting more efficient charge extraction. As a result, a PCE >25% (certified PCE of 24.84%) is achieved with substantially improved long-term storage and photothermal stabilities. This strategy provides valuable insights into interfacial passivation and holds promise for the industrialization of PSCs.

Ultrasensitive and Robust CsPbBr3 Single-Crystal X-ray Detectors Based on Interface Engineering.

Halide lead perovskites have shown great development in recent years for ionizing radiation detection. However, the bias-induced interfacial electrochemical reaction between the perovskite and electrode severely deteriorates detector performance. We report that BCP strongly interacts with Al and constructs a stable Al-BCP chelating interface, resulting in the suppression of a detrimental electrochemical reaction. The fabricated Au/Al/BCP/C60/CsPbBr3/Au detector shows a low dark current of 3 nA with a stable baseline at an extremely high bias of 100 V (∼100 V mm-1). The superior high-bias stability enables a high sensitivity of 7.3 × 104 µC Gyair-1 cm-2 at 100 V. Meanwhile, a low detection limit of 15 nGyair s-1 at 40 V is achieved due to the reduced noise. The outstanding performance of our device exceeds that of most advanced detectors based on CsPbBr3 single crystals. Besides, X-ray imaging with 1 mm spatial resolution is well demonstrated at a low dose rate of 200 nGyair s-1. The interfacial chelating strategy overcomes the technical limitation of bias-induced instability of perovskite radiation detectors and can be anticipated to operate under an extremely high electrical field.

Targeted passivation and optimized interfacial carrier dynamics improving the efficiency and stability of hole transport layer-free narrow-bandgap perovskite solar cells.

Narrow-bandgap mixed Sn-Pb perovskite solar cells (PSCs) have showcased great potential to approach the Shockley-Queisser limit. Nevertheless, the practical application and long-term deployment of mixed Sn-Pb PSCs are still largely impeded by the rapid oxidation of Sn2+ ions and under-optimized carrier transport layer (CTL)/perovskite interfaces that would inevitably incur serious interfacial charge recombination and device performance degradation. Herein, we successfully removed the hole transport layer (HTL) by incorporating a small amount of organic phosphonic acid molecules into perovskites, which could preferably interact with Sn2+ ions (relative to Pb2+ analogues) at the grain boundaries (GBs) throughout the perovskite film thickness via coordination bonding, thus effectively retarding the oxidation of Sn2+, passivating the defects and suppressing the non-radiative recombination. Targeted modification effectively reinforced built-in potential by ∼100 mV, and favorably induced energy level cascade, thus accelerating spatial charge separation and facilitating the hole extraction from perovskite layer to underlying conductive electrodes even in the absence of HTL. Consequently, enhanced power conversion efficiencies up to 20.21% have been achieved, which is the record efficiency for the HTL-free mixed Sn-Pb PSCs, accompanied by a decent photovoltage of 0.87 V and improved long-term stability over 2400 h.

Tunable Key-Size Physical Unclonable Functions Based on Phase Segregation in Mixed Halide Perovskites.

Optical physical unclonable functions (PUFs) have been considered as an effective tool for anti-counterfeiting owing to the uncontrollable manufacturing process and excellent resistance to machine-learning attacks. However, most optical PUFs exhibit fixed challenge-response pairs and static encoding structures after they are manufactured, which significantly impedes the actual development. Herein, we propose a tunable key-size PUF based on reversible phase segregation in mixed halide perovskites with uncontrollable Br/I ratios under variable power densities. The basic performance of encryption keys of low and high power density was evaluated and indicated a high degree of uniformity, uniqueness, and readout repeatability. Merging the binary keys of low and high power density, tunable key-size PUF is realized with higher security. The proposed tunable key-size PUF offers new insights into the development of dynamic-structure PUFs and demonstrates a novel scheme for achieving higher security of anti-counterfeiting and authentication.

Low-intensity-low-temperature stability assessment of perovskite solar cells operating on simulated Martian surface conditions.

Immigration to Mars, which is expected to be powered mainly by photovoltaics, is one of the greatest dreams of humanity. However, the extreme temperature difference and high-energy cosmic radiation on the surface of Mars make it difficult for conventional photovoltaics to operate steadily over time. With their advantages of being lightweight, having a high irradiation tolerance, and an outstanding power conversion efficiency (PCE), perovskite solar cells (PSCs) have shown themselves to be a promising candidate for Martian applications. In this study, we simulated the low-intensity-low-temperature (LILT) environment of the Mars surface, and monitored the in situ device performance of PSCs. Surprisingly, the device PCE was not only maintained at a high level but was even improved slightly. Further investigation revealed that the self-healing effect of perovskites under LILT conditions could be attributed to the light-induced decomposition of the perovskite film and the ß-phase perovskite recrystallization process at the perovskite/hole transport layer interface. Interfacial ß-phase perovskites are stable at low temperatures, which can facilitate charge extraction and protect the perovskite bulk from long-term light damage. This study demonstrated the feasibility of PSCs and provides a reference for Martian applications.

Improving the Performance of Perovskite Solar Cells with Insulating Additive-Modified Hole Transport Layers.

Invert perovskite solar cells (PSCs) present a great potential for next-generation photovoltaics for their flexibility and tandem adaptability. In order to improve the conductivity of the hole transport layer (HTL), such as poly(triarylamine), highly conductive additives (e.g., F4TCNQ, Li-TFSI) were generally applied to achieve a power conversion efficiency (PCE) exceeding 21%. However, these additives significantly affect the long-term stability of the devices due to their humidity sensitivity. In this work, the HTL was counterintuitively optimized with insulating additives, such as polyphenylene sulfide, which enhanced PCE from 19.1 to 21.5% along with a noticeable improvement in device stability with T50 of 574 h under double 85 aging conditions. The performance enhancement is attributed to larger grain sizes in perovskite films on the HTL and better energy-level alignment between the HTL and perovskite after introducing the insulating additives, which compensate negative influence caused by additive-induced reduction in conductivity. Our work demonstrates that low-conductivity additives, rather than the commonly used high-conductivity counterparts, can also contribute to improving the photovoltaic performance in PSCs.

Surface Passivation of MAPbBr3 Perovskite Single Crystals to Suppress Ion Migration and Enhance Photoelectronic Performance.

Recently, organometal halide perovskites (OHPs) have achieved significant advancement in photovoltaics, light-emitting diodes, X-ray detectors, and transistors. However, commercialization and practical applications were hindered by the notorious ion migration issue of OHPs. Here, we report a simple solvent-based surface passivation strategy with organic halide salts (methylammonium bromide (MABr) and phenylethylammonium bromide (PEABr)) to suppress the ion migration of MAPbBr3 single crystals. The surface passivation effect is evidenced by the stronger photoluminescence (PL) intensity and extended PL lifetime. Using the pulse voltage and continuous voltage current-voltage measurements, we found that single crystals with surface passivation showed negligible hysteresis on the surface due to the suppression of ion migration. As a result, the dark current stability of coplanar structure devices was significantly improved. Moreover, the vertical structure X-ray detectors with PEABr treatment exhibited a high sensitivity of 15 280 µC Gyair-1 cm-2 and a low detection limit of 87 nGyair s-1 under 5 V bias. The proposed technology would be a versatile tool to improve the performance of perovskite photoelectronic devices.

Low-dispersion mirror with a broad bandwidth and high laser damage resistance.

A low-dispersion mirror (LDM), an important component in ultrafast laser systems, requires both a broad low-dispersion laser-induced damage threshold (LIDT). It is difficult for a traditional quarter-wavelength-based dielectric LDM to achieve these characteristics at the same time. We propose a novel, to the best of our knowledge, low-dispersion mirror (NLDM) that combines periodic chirped layers at the top and alternating quarter-wavelength layers at the bottom. Low dispersion is achieved by introducing a large same group delay (GD) for different wavelengths, so the bandwidth is broadened greatly. In addition, owing to the staggered electric field intensity peak effect in the structure, the NLDM shows the potential for high laser damage resistance. The experiments demonstrated that the NLDM doubles the low-dispersion bandwidth, while the LIDT is also increased compared with the LDM. This novel concept results in improved performance and paves the way toward a new generation of the LDM for ultrafast bandwidth and a high laser applications.

Defect Passivation via Additive Engineering to Improve Photodetection Performance in CsPbI2Br Perovskite Photodetectors.

Solution-processable all-inorganic lead halide perovskites are under intensive attention due to their potential applications in low-cost high-performance optoelectronic devices such as photodetectors. However, solution processing usually generates structural and chemical defects which are detrimental to the photodetection performance of photodetectors. Here, a polymer additive of polyethylene glycol (PEG) was employed to passivate the localized defects in CsPbI2Br films through the Lewis acid-base interaction. The interfacial defects were passivated efficiently by introducing a trace amount of a PEG additive with a concentration of 0.4 mg mL-1 into the CsPbI2Br precursor solution, as suggested by the significantly reduced trap density of state, which was revealed using thermal admittance spectroscopy. Fourier transform infrared spectrum characterization showed that rather than Cs+ or I-, a Lewis acid-base interaction was established between Pb2+ and PEG to passivate the defects in the CsPbI2Br perovskite, which leads to large suppression of noise current. Both specific detectivity and linear dynamic range improved from 4.1 × 109 Jones and 73 dB to 2.2 × 1011 Jones and 116 dB, respectively. Our work demonstrates the feasibility of employing an environmentally stable polymeric additive PEG to passivate defects for high photodetection performance in all-inorganic perovskite photodetectors.

Metallic surface doping of metal halide perovskites.

Intentional doping is the core of semiconductor technologies to tune electrical and optical properties of semiconductors for electronic devices, however, it has shown to be a grand challenge for halide perovskites. Here, we show that some metal ions, such as silver, strontium, cerium ions, which exist in the precursors of halide perovskites as impurities, can n-dope the surface of perovskites from being intrinsic to metallic. The low solubility of these ions in halide perovskite crystals excludes the metal impurities to perovskite surfaces, leaving the interior of perovskite crystals intrinsic. Computation shows these metal ions introduce many electronic states close to the conduction band minimum of perovskites and induce n-doping, which is in striking contrast to passivating ions such as potassium and rubidium ion. The discovery of metallic surface doping of perovskites enables new device and material designs that combine the intrinsic interior and heavily doped surface of perovskites.

Benign ferroelastic twin boundaries in halide perovskites for charge carrier transport and recombination.

Grain boundaries have been established to impact charge transport, recombination and thus the power conversion efficiency of metal halide perovskite thin film solar cells. As a special category of grain boundaries, ferroelastic twin boundaries have been recently discovered to exist in both CH3NH3PbI3 thin films and single crystals. However, their impact on the carrier transport and recombination in perovskites remains unexplored. Here, using the scanning photocurrent microscopy, we find that twin boundaries have negligible influence on the carrier transport across them. Photoluminescence (PL) imaging and the spatial-resolved PL intensity and lifetime scanning confirm the electronically benign nature of the twin boundaries, in striking contrast to regular grain boundaries which block the carrier transport and behave as the non-radiative recombination centers. Finally, the twin-boundary areas are found still easier to degrade than grain interior.

Bilateral alkylamine for suppressing charge recombination and improving stability in blade-coated perovskite solar cells.

The power conversion efficiencies (PCEs) of perovskite solar cells (PSCs) are already higher than that of other thin film technologies, but laboratory cell-fabrication methods are not scalable. Here, we report an additive strategy to enhance the efficiency and stability of PSCs made by scalable blading. Blade-coated PSCs incorporating bilateral alkylamine (BAA) additives achieve PCEs of 21.5 (aperture, 0.08 cm2) and 20.0% (aperture, 1.1 cm2), with a record-small open-circuit voltage deficit of 0.35 V under AM1.5G illumination. The stabilized PCE reaches 22.6% under 0.3 sun. Anchoring monolayer bilateral amino groups passivates the defects at the perovskite surface and enhances perovskite stability by exposing the linking hydrophobic alkyl chain. Grain boundaries are reinforced by BAA and are more resistant to mechanical bending and electron beam damage. BAA improves the device shelf lifetime to >1000 hours and operation stability to >500 hours under light, with 90% of the initial efficiency retained.

Tailoring Passivation Molecular Structures for Extremely Small Open-Circuit Voltage Loss in Perovskite Solar Cells.

Passivation of electronic defects at the surface and grain boundaries of perovskite materials has become one of the most important strategies to suppress charge recombination in both polycrystalline and single-crystalline perovskite solar cells. Although many passivation molecules have been reported, it remains very unclear regarding the passivation mechanisms of various functional groups. Here, we systematically engineer the structures of passivation molecular functional groups, including carboxyl, amine, isopropyl, phenethyl, and tert-butylphenethyl groups, and study their passivation capability to perovskites. It reveals the carboxyl and amine groups would heal charged defects via electrostatic interactions, and the neutral iodine related defects can be reduced by the aromatic structures. The judicious control of the interaction between perovskite and molecules can further realize grain boundary passivation, including those that are deep toward substrates. Understanding of the underlining mechanisms allows us to design a new passivation molecule, D-4- tert-butylphenylalanine, yielding high-performance p-i-structure solar cells with a stabilized efficiency of 21.4%. The open-circuit voltage ( VOC) of a device with an optical bandgap of 1.57 eV for the perovskite layer reaches 1.23 V, corresponding to a record small VOC deficit of 0.34 V. Our findings provide a guidance for future design of new passivation molecules to realize multiple facets applications in perovskite electronics.

Unveiling the operation mechanism of layered perovskite solar cells.

Layered perovskites have been shown to improve the stability of perovskite solar cells while its operation mechanism remains unclear. Here we investigate the process for the conversion of light to electrical current in high performance layered perovskite solar cells by examining its real morphology. The layered perovskite films in this study are found to be a mixture of layered and three dimensional (3D)-like phases with phase separations at micrometer and nanometer scale in both vertical and lateral directions. This phase separation is explained by the surface initiated crystallization process and the competition of the crystallization between 3D-like and layered perovskites. We further propose that the working mechanisms of the layered perovskite solar cells involve energy transfer from layered to 3D-like perovskite network. The impact of morphology on efficiency and stability of the hot-cast layered perovskite solar cells are also discussed to provide guidelines for the future improvement.

Symmetry-Controlled Electron-Phonon Interactions in van der Waals Heterostructures.

Light-matter interactions in the van der Waals (vdWs) heterostructures exhibit many fascinating properties which can be harnessed to realize optoelectronic applications and probe fundamental physics. Moreover, the electron-phonon interaction in the vdWs heterostructures can have a profound impact on light-matter interaction properties because light excited electrons can strongly couple with phonons in heterostructures. Here, we report symmetry-controlled electron-phonon interactions in engineered two-dimensional (2D) material/silicon dioxide (SiO2) vdWs heterostructures. We observe two Raman modes arising from originally Raman-silent phonon modes in SiO2. The Raman modes have fixed peak positions regardless of the type of 2D materials in the heterostructures. Interestingly, such Raman emissions exhibit various symmetry properties in heterostructures with 2D materials of different crystalline structures, controlled by their intrinsic electronic band properties. In particular, we reveal chiral Raman emissions with reversed helicity in contrast to that of typical valley polarization in honeycomb 2D materials due to the phonon-assisted excitonic intervalley scattering process induced by electron-hole exchange interaction. The observation of the symmetry-controlled Raman scattering process not only provides a deep insight into the microscopic mechanisms of electron-phonon interactions in vdWs heterostructures but also may lead to the realization of valley-phononic devices.