peri-Fused polyaromatic molecular contacts for perovskite solar cells.

Molecule-based selective contacts have become a crucial component to ensure high-efficiency inverted perovskite solar cells1-5. These molecules always consist of a conjugated core with heteroatom substitution to render the desirable carrier-transport capability6-9. So far, the design of successful conjugation cores has been limited to two N-substituted π-conjugated structures, carbazole and triphenylamine, with molecular optimization evolving around their derivatives2,5,10-12. However, further improvement of the device longevity has been hampered by the concomitant limitations of the molecular stability induced by such heteroatom-substituted structures13,14. A more robust molecular contact without sacrificing the electronic properties is in urgent demand, but remains a challenge. Here we report a peri-fused polyaromatic core structure without heteroatom substitution that yields superior carrier transport and selectivity over conventional heteroatom-substituted core structures. This core structure produced a relatively chemically inert and structurally rigid molecular contact, which considerably improved the performance of perovskite solar cells in terms of both efficiency and durability. The champion device showed an efficiency up to 26.1% with greatly improved longevity under different accelerated-ageing tests.

Benchmarking the Match of Porous Carbon Substrate Pore Volume on Silicon Anode Materials for Lithium-Ion Batteries.

Silicon (Si) is one of the most promising anode materials for high-energy-density lithium-ion batteries. However, the huge volume expansion hinders its commercial application. Embedding amorphous Si nanoparticles in a porous carbon framework is an effective way to alleviate Si volume expansion, with the pore volume of the carbon substrates playing a pivotal role. This work demonstrates the impact of pore volume on the electrochemical performance of the silicon/carbon porous composites from two perspectives: 1) pore volume affects the loadings of Si particles; 2) pore volume affects the structural stability and mechanical properties. The smaller pore volume of the carbon substrate cannot support the high Si loadings, which results in forming a thick Si shell on the surface, thereby being detrimental to cycling stability and the diffusion of electrons and ions. On top of that, the carbon substrate with a larger pore volume has poor structural stability due to its fragility, which is also not conducive to realizing long cycle life and high rate performance. Achieving excellent electrochemical performances should match the proper pore volume with Si content. This study will provide important insights into the rational design of the silicon/carbon porous composites based on the pore volume of the carbon substrates.

HCOO- Doping-Induced Multiexciton Emissions in Cs3Cu2I5 Crystals for Efficient X-Ray Scintillation.

Self-trapped exciton (STE) luminescence, typically associated with structural deformation of excited states, has attracted significant attention in metal halide materials recently. However, the mechanism of multiexciton STE emissions in certain metal halide crystals remains largely unexplored. This study investigates dual luminescence emissions in HCOO- doped Cs3Cu2I5 single crystals using transient and steady-state spectroscopy. The dual emissions are attributed to intrinsic STE luminescence originating from the host lattice and extrinsic STE luminescence induced by external dopants, respectively, each of which can be triggered independently at distinct energy levels. Theoretical calculations reveal that multiexciton emission originates from structural distortion of the host and dopant STEs within the 0D lattice in their respective excited states. By meticulously tuning the excitation wavelength and selectively exciting different STEs, the dynamic alteration of color change in Cs3Cu2I5:HCOO- crystals is demonstrated. Ultimately, owing to an extraordinarily high photoluminescence quantum yield (99.01%) and a diminished degree of self-absorption in Cs3Cu2I5:HCOO- crystals, they exhibit remarkable X-ray scintillation characteristics with light yield being improved by 5.4 times as compared to that of pristine Cs3Cu2I5 crystals, opening up exciting avenues for achieving low-dose X-ray detection and imaging.

Sequencing-Dependent Impact of Carbon Coating on Microstructure Evolution and Electrochemical Performance of Pre-lithiated SiO Anodes: Enhanced Efficiency and Stability via Pre-Coating Strategy.

Silicon monoxide (SiO) has attracted considerable interest as anode material for lithium-ion batteries (LIBs). However, their poor initial Coulombic efficiency (ICE) and conductivity limit large-scale applications. Prelithiation and carbon-coating are common and effective strategies in industry for enhancing the electrochemical performance of SiO. However, the involved heat-treatment processes inevitably lead to coarsening of active silicon phases, posing a significant challenge in industrial applications. Herein, the differences in microstructures and electrochemical performances between prelithiated SiO with a pre-coated carbon layer (SiO@C@PLi) and SiO subjected to carbon-coating after prelithiation (SiO@PLi@C) are investigated. A preliminary carbon layer on the surface of SiO before prelithiation is found that can suppress active Si phase coarsening effectively and regulate the post-prelithiation phase content. The strategic optimization of the sequence where prelithiation and carbon-coating processes of SiO exert a critical influence on its regulation of microstructure and electrochemical performances. As a result, SiO@C@PLi exhibits a higher ICE of 88.0%, better cycling performance and lower electrode expansion than SiO@PLi@C. The pouch-type full-cell tests demonstrate that SiO@C@PLi/Graphite||NCM811 delivers a superior capacity retention of 91% after 500 cycles. This work provides invaluable insights into industrial productions of SiO anodes through optimizing the microstructure of SiO in prelithiation and carbon-coating processes.

Self-power, multiwavelength photodetector based on a Sn-doped Ge quantum dots/hexagonal silicon nanowire heterostructure.

Tin-doped germanium quantum dots (Sn-doped Ge QDs)-decorated hexagonal silicon nanowires (h-Si NWs) were adopted to overcome the low infrared response of silicon and the excess dark current of germanium. High-quality Sn-doped Ge QDs with a narrow bandgap can be achieved through Ge-Sn co-sputtering on silicon nanowires by reducing the contact area between heterojunction materials and Sn-induced germanium crystallization. The absorption limit of the heterostructure is extended to 2.2 µm, and it is sensitive to 375-1550 nm light at 0 V, which has optimality at 1342 nm, with a photo-to-dark current ratio of over 815, a responsivity of 0.154 A/W, and a response time of 0.93 ms. The superior performance of the Sn-doped Ge QDs/h-Si NW photodetector in multiwavelength is attractive for multi-scenario applications.

Nanosecond laser annealing processed surface-structured hyperdoped silicon for efficient near-infrared detection.

Surface-structured engineering of hyperdoped silicon can effectively facilitate the absorption of sub-bandgap photons of pristine single-crystal silicon (sc-Si). Here, we conducted different annealing approaches of ordinary thermal annealing (OTA) and nanosecond laser annealing (NLA) on modification of titanium-hyperdoped silicon (Si:Ti) surface structure, to achieve efficient near-infrared detection. It is presented that both OTA and NLA process can improve the crystallinity of Si:Ti samples. In detail, atomic-resolved STEM characterization illustrates that NLA treatment will further eliminate the amorphous phase on Si:Ti surface to varying degrees. While one-dimensional periodic stacking fault structure of 9R-Si phase is formed at the surface of sc-Si and embedded in the Si matrix during the OTA process, which reveals the seamless interface of 9R-Si/sc-Si along with [1"1" ̅0] direction. Due to the high sub-bandgap light absorption and good crystal structure, the Si:Ti photodetector after NLA treatment with an energy density of 2.6 J/cm² exhibited the highest responsivity, reaching 151 mA/W at 1550 nm even at a low operating voltage of 1 V. We assume the performance enhancement of NLA processed Si:Ti photodetectors can be attributed to two aspects, the one is NLA can reduce the recombination of photo-generated charge carriers in amorphous surface layer by improving crystallization, and the other is that NLA process can weaken the diffusion of titanium impurities due to the extremely rapid treatment rates. This study presents prospects towards surface-structured silicon in infrared light detection.

Monolithic integration of perovskite heterojunction on TFT backplanes through vapor deposition for sensitive and stable x-ray imaging.

Metal halide perovskites exhibit substantial potential for advancing next-generation x-ray detection. However, fabricating high-performance pixelated imaging arrays remains challenging due to the substantial dark current density and stability issues associated with common organic-inorganic hybrid perovskites. Here, we develop a vapor deposition method to create the first all-inorganic perovskite heterojunction film. The heterojunction introduction effectively reduces the dark current density of detectors to about 0.8 nA·cm-2, satisfying thin-film transistor (TFT) integration standards, while also increases sensitivity to above 2.6 × 104 µC·Gyair-1·cm-2, thus giving rise to a record low detection limit of <1 nGyair·s-1 among all polycrystalline perovskite-based x-ray detectors. The devices also demonstrate remarkable stability across multifarious demanding working conditions. Last, through monolithic integration of the heterojunction film with a 64 × 64 pixelated TFT array, we have achieved high-resolution real-time x-ray imaging, which paves the way for the application of all-inorganic perovskite in low-dose flat-panel x-ray detection.

Sensitive and Low-Noise Perovskite Nanocrystal-Organic Bulk Heterostructure X-ray Detectors Enabled by Sodium Bromide-Assisted In Situ Reparation.

Perovskite nanocrystals (PNCs) offer unique advantages in large-area and thick-film deposition for X-ray detection applications due to the decoupling of the crystallization of perovskite from film formation, as well as their low-temperature and scalable deposition methods. However, the partial detachment of long-chain ligands in PNCs during the purification process would lead to the exposure of surface defects, making it challenging to ensure efficient charge carrier extraction and stable X-ray detection. In this study, we propose a beneficial strategy that involves the in situ reparation of these exposed defects with sodium bromide (NaBr) during the purification process to construct CsPbBr3 PNC-organic bulk heterostructure X-ray detectors. The NaBr-passivated PNCs exhibit stronger photoluminescence intensity and lower trap density in films compared to those of the control samples, confirming the effective passivation of halide vacancy defects. Furthermore, the NiOx hole transport layer with remarkable electron blocking capability is introduced to further suppress the dark current of the devices. Consequently, the optimal devices exhibit a large sensitivity of 4237 µC Gyair-1 cm-2 and a low dark current density of 10 nA cm-2, as well as improved operational stability, which allows for high-contrast and low-dose X-ray imaging applications.

Eliminating Resistance-Capacitance Coupling Shielding for Depicting the Defect Landscape in Perovskite Solar Cells by Capacitance Spectroscopy.

Capacitance spectroscopy techniques have been widely utilized to evaluate the defect properties in perovskites, which contribute to the efficiency and operation stability development for perovskite solar cells (PSCs). Yet the interplay between the charge transporting layer (CTL) and the perovskite on the capacitance spectroscopy results is still unclear. Here, they show that a pseudo-trap-state capacitance signal is generated in thermal admittance spectroscopy (TAS) due to the enhanced resistance capacitance (RC) coupling caused by the carrier freeze-out of the CTL in PSCs, which could be discerned from the actual defect-induced trap state capacitance signal by tuning the series resistance of PSCs. By eliminating the RC coupling shielding effect on the defect-induced capacitance spectroscopy, it is obtain the actual defect density which is 4-folds lower than the pseudo-trap density, and the spatial distribution of defects in PSCs which reveals that the commonly adopted interface passivators can passivate the defects about 60 nm away from the decorated surface. It is further revealed that phenethylammonium ions (PEA+) possess a better passivation capability over octylammonium ions (OA+) due to the deeper passivation depth for PEA+ on the surface defects in perovskite films.

Suppression of Randomness in Electrically Pumped Random Lasing from a ZnO Film-Based Light-Emitting Device on Silicon.

We report on the suppressed randomness in electrically pumped random lasing (RL) from a light-emitting device (LED) based on a metal-insulator-semiconductor (MIS) structure of Au/SiOx (x < 2)/ZnO on a silicon substrate, by means of patterning the light-emitting ZnO polycrystalline film into a number of square blocks separated by streets that are filled with the SiOx insulator. It is found that the RL modes can be remarkably reduced by shrinking the blocks in the absence of interblock optical coupling. Meanwhile, with the imposition of interblock optical coupling by shrinking the streets, the RL modes can be further reduced, and more importantly, the strongest mode wavelength is stabilized around 380 nm, where the ZnO film exhibits the largest optical gain.

All-silicon multidimensionally-encoded optical physical unclonable functions for integrated circuit anti-counterfeiting.

Integrated circuit anti-counterfeiting based on optical physical unclonable functions (PUFs) plays a crucial role in guaranteeing secure identification and authentication for Internet of Things (IoT) devices. While considerable efforts have been devoted to exploring optical PUFs, two critical challenges remain: incompatibility with the complementary metal-oxide-semiconductor (CMOS) technology and limited information entropy. Here, we demonstrate all-silicon multidimensionally-encoded optical PUFs fabricated by integrating silicon (Si) metasurface and erbium-doped Si quantum dots (Er-Si QDs) with a CMOS-compatible procedure. Five in-situ optical responses have been manifested within a single pixel, rendering an ultrahigh information entropy of 2.32 bits/pixel. The position-dependent optical responses originate from the position-dependent radiation field and Purcell effect. Our evaluation highlights their potential in IoT security through advanced metrics like bit uniformity, similarity, intra- and inter-Hamming distance, false-acceptance and rejection rates, and encoding capacity. We finally demonstrate the implementation of efficient lightweight mutual authentication protocols for IoT applications by using the all-Si multidimensionally-encoded optical PUFs.

A universal synthesis strategy of Pd-based trimetallic nanowires for efficient alcohol electrooxidation.

Trimetallic nanowires (NWs) have drawn much attention in efficient alcohol oxidation reaction (AOR) due to their unique features, including high atomic utilization efficiency and fast electron transfer ability. However, a universal strategy to synthesize Pd-based trimetallic NWs with high catalytic performance is still lacking. Herein, we develop a universal method for facile synthesis of PdBiM (M = Pt, Ru, Ir, Co, Cu) NWs with excellent AOR activities. By taking PdBiPt NWs as an example, the formation mechanism was investigated, and it is found that introduction of bismuth (Bi) plays an important role in facilitating the formation of the NW structure. Moreover, the PdBiPt NWs deliver an outstanding performance toward both the ethanol oxidation reaction (EOR) and the methanol oxidation reaction (MOR). Density functional theory (DFT) calculations together with experimental results disclose that the moderate electronic structure of trimetallic PdBiPt NWs can optimize the adsorption of OHads and weaken the adsorption of COads, thereby leading to the substantially enhanced AOR performance. We believe that this work can inspire the design of multimetallic NWs as high-performance catalysts.

Textured anti-reflection and down-conversion composite functional films for high-efficiency solar cells.

Advances in high-efficiency solar cells introduce photon management challenges, including the difficult texturization of flat surfaces and low photon utilization at short wavelengths. While bifacial crystalline silicon solar cells have a front pyramid structure and SiN x layers reduce reflections, managing photons on the flat backside remains a challenge. To enhance light utilization, a soft nanoimprint technique was utilized to create pyramid micro-structured polyurethane films doped with europium (Eu3+) complex. These films, which possess anti-reflection and down-conversion properties, can be applied externally to various high-efficiency solar cells without compromising electrical performance. Research on the backside of bifacial PERC solar cells revealed that the optimal composite functional film increases the integrated current by 5.70%, with a 1.27% gain from down-conversion effects. This specialized film presents a novel approach to interface matching for different types of solar cells.

Amorphous (lysine)2PbI2 layer enhanced perovskite photovoltaics.

Passivation materials play a crucial role in a wide range of high-efficiency, high-stability photovoltaic applications based on crystalline silicon and state-of-the-art perovskite materials. Currently, for perovskite photovoltaic, the mainstream passivation strategies routinely rely on crystalline materials. Herein, we have invented a new amorphous (lysine)2PbI2 layer-enhanced halide perovskite. By utilizing a solid phase reaction between PbI2 and lysine molecule, an amorphous (lysine)2PbI2 layer is formed at surface/grain boundaries in the perovskite films. The amorphous (lysine)2PbI2 with fewer dangling bonds can effectively neutralize surface/interface defects, achieving an impressive efficiency of 26.27% (certified 25.94%). Moreover, this amorphous layer not only reduces crystal lattice stress but also functions as a barrier against the decomposition of organic components, leading to suppressed de-structuring of perovskite and highly stable perovskite solar cells.

Visualizing the Structure-Property Nexus of Wide-Bandgap Perovskite Solar Cells under Thermal Stress.

Wide-bandgap perovskite solar cells (PSCs) toward tandem photovoltaic applications are confronted with the challenge of device thermal stability, which motivates to figure out a thorough cognition of wide-bandgap PSCs under thermal stress, using in situ atomic-resolved transmission electron microscopy (TEM) tools combing with photovoltaic performance characterizations of these devices. The in situ dynamic process of morphology-dependent defects formation at initial thermal stage and their proliferations in perovskites as the temperature increased are captured. Meanwhile, considerable iodine enables to diffuse into the hole-transport-layer along the damaged perovskite surface, which significantly degrade device performance and stability. With more intense thermal treatment, atomistic phase transition reveals the perovskite transform to PbI2 along the topo-coherent interface of PbI2/perovskite. In conjunction with density functional theory calculations, a mutual inducement mechanism of perovskite surface damage and iodide diffusion is proposed to account for the structure-property nexus of wide-bandgap PSCs under thermal stress. The entire interpretation also guided to develop a thermal-stable monolithic perovskite/silicon tandem solar cell.

Rapid Recovery of Degraded Perovskite Single-Crystal Radiation Detectors via Infrared Healing.

Radiation detectors based on metal halide perovskite (MHP) single crystals (SCs) have exhibited exceptional sensitivity, low detection limit, and remarkable energy resolution. However, the operational stability issue still dramatically impedes their commercialization due to degradation induced by high-energy irradiation and large bias. Here, we propose an innovative infrared healing strategy to restore the devices that have undergone severe damage from both long-term biasing and X-ray irradiation. Compared to the slow and inefficient intrinsic self-healing process of MHPs, the infrared healing method demonstrates the capacity to achieve rapid recovery of the detection performance of the degraded devices within just 1 h. We reveal that the healing mechanism is mainly related to the reduction of the ion-migration activation energy in MHP SCs under infrared illumination, which promotes the back diffusion of the displaced ions to their original lattice positions and remedies defects. Finally, the healing effect is further confirmed through the gamma-ray spectroscopy acquisition with degraded MHP SCs, whose energy resolution at 59.5 keV of 241Am source is improved from 36% to 12% following infrared illumination. These results present infrared healing as a simple and economic method to extend the service life of MHP SC-based detectors.

Strain regulates the photovoltaic performance of thick-film perovskites.

Perovskite photovoltaics, typically based on a solution-processed perovskite layer with a film thickness of a few hundred nanometres, have emerged as a leading thin-film photovoltaic technology. Nevertheless, many critical issues pose challenges to its commercialization progress, including industrial compatibility, stability, scalability and reliability. A thicker perovskite film on a scale of micrometres could mitigate these issues. However, the efficiencies of thick-film perovskite cells lag behind those with nanometre film thickness. With the mechanism remaining elusive, the community has long been under the impression that the limiting factor lies in the short carrier lifetime as a result of defects. Here, by constructing a perovskite system with extraordinarily long carrier lifetime, we rule out the restrictions of carrier lifetime on the device performance. Through this, we unveil the critical role of the ignored lattice strain in thick films. Our results provide insights into the factors limiting the performance of thick-film perovskite devices.