ProPILE: Probing Privacy Leakage in Large Language Models

The rapid advancement and widespread use of large language models (LLMs) have raised significant concerns regarding the potential leakage of personally identifiable information (PII). These models are often trained on vast quantities of web-collected data, which may inadvertently include sensitive personal data. This paper presents ProPILE, a novel probing tool designed to empower data subjects, or the owners of the PII, with awareness of potential PII leakage in LLM-based services. ProPILE lets data subjects formulate prompts based on their own PII to evaluate the level of privacy intrusion in LLMs. We demonstrate its application on the OPT-1.3B model trained on the publicly available Pile dataset. We show how hypothetical data subjects may assess the likelihood of their PII being included in the Pile dataset being revealed. ProPILE can also be leveraged by LLM service providers to effectively evaluate their own levels of PII leakage with more powerful prompts specifically tuned for their in-house models. This tool represents a pioneering step towards empowering the data subjects for their awareness and control over their own data on the web

Molecular modelling of fused heterocycle-based asymmetric non-fullerene acceptors for efficient organic solar cells

Heterocycle substitution plays a key role in designing an ultra-narrower bandgap (ultra-NBG) small molecule-based (SM) non-fullerene acceptors (NFAs) for organic solar cells (OSCs). The NFAs molecules have great significance because of their ability to improve efficiency, narrow band gap, better charge separation, higher absorption spectra, and overall device performance. However, the impact of heterocycles such as benzoselenadiazole (BSe) on optoelectronics characteristics is still unclear. Herein, seven asymmetric NFAs based on BSe electron-deficient fused-ring core were designed from the reference (R) BTP-Se. All seven NFAs exhibited a strong absorption phenomenon from visible to near-infrared (NIR) region, corresponding to the ultra-NBG and lower excitation energy (Ex). These designed asymmetric materials (BTP1-BTP7) along with R are fully characterized theoretically with various advanced quantum chemical techniques. The optical and optoelectronics features were explored with density functional theory (DFT) and time-dependent (TD-DFT) simulations. The in-depth calculations related to density of state (DOS), transition density of state (TDM), open-circuit voltage, fill factor, and reorganization energy of electrons and holes are performed intensively. BTP3 has an optical band gap narrow of 1.76 eV and an outstanding absorption maximum of 906.85 nm. For charge transfer, a donor:acceptor complex study of BTP3:PBDBT is carried-out. We hope that this may provide a favourable strategy for building highly efficient near infrared (NIR)-based OSCs

Chemo-mechanical failure of solid composite cathodes accelerated by high-strain anodes in all-solid-state batteries

Large volume changes in Li-based anodes during repeated charge-discharge cycling, which can exert additional mechanical stresses on cell components, remain a significant bottleneck for realizing all-solid-state batteries (ASSBs). While a few studies have reported the mechanical deformation of solid electrolyte layers induced by the volume changes in anodes, the possible degradation of composite cathodes has been largely overlooked. Herein, we present a comparative experimental-simulation study of sulfide-based ASSBs assembled with high-strain (Li-In) and zero-strain (Li4Ti5O12 (LTO)) anodes to understand the impact of anode volume changes on the chemo-mechanical degradation of composite cathodes. The Li-In cell suffers from severe capacity loss after ∼120 cycles, whereas the LTO cell shows a capacity retention as high as 76 % over 200 cycles. In-depth chemical and microstructural analyses, coupled with impedance decoupling and mechanical simulations, reveal that the combination of the cathode volume changes and the high-strain Li-In anode perturbs the structural integrity of the LiNi0.88Co0.09Al0.03O2 (NCA) composite cathode and facilitates “dynamic” contacts among the cathode constituents upon repeated cycling. This leads to enhanced parasitic interfacial reactions, as evidenced by the increased amount of resistive phases in the cathode. The resulting chemically/electrochemically heterogeneous interfaces between the NCA and Li6PS5Cl lead to accelerated cracking of the NCA aggregates in the presence of anode-induced stresses. This study highlights the accelerated degradation of composite cathodes driven by high-strain anodes and provides insights into the design of ASSBs with long cycle lifetimes. © 2023 Elsevier B.V.FALS

Deciphering the critical degradation factors of solid composite electrodes with halide electrolytes: Interfacial reaction versus ionic transport

Recently, halide-type Li+ conductors have been revisited for their use in all-solid-state batteries (ASSBs) owing to their stability at high potentials. However, the realization of ASSBs is hindered by the fast performance decay of composite cathodes. From a comparative study using halide and sulfide solid electrolytes (SEs), herein, we reveal the critical degradation factors of halide-SE-based cathodes, which are different from the conventional findings of sulfide-SE-based cathodes. By using impedance decoupling combined with scanning spreading resistance microscopy and force spectroscopy, we elucidate the mechanisms behind the SE-dependent degradation of single-particle LiNi0.8Co0.1Mn0.1O2 (NCM) composite cathodes. Impedance analyses show that NCM-Li6PS5Cl (LPSCl) and NCM-Li3InCl6 (LIC) exhibit considerable increase in interfacial impedance and Li+-transport impedance, respectively, upon cycling. Based on the combined experimental and computational study of microscopic interfacial and mechanical properties, we demontrate that the degradation of NCM-LPSCl originates primarily from the formation of resistive interphases, while the crucial degradation factor of NCM-LIC is the cracking-induced mechanical deformation of the LIC under pressure. Finite element analysis results further reveal how the deformation behavior of the SE materials influences the formation and propagation of cracks in composite cathodes during cycling. This study provides insights into the design of materials and electrodes for ASSBs with high power capabilities and long cycle lifetimes. © 2023FALS

Synergetic Effect of Aluminum Oxide and Organic Halide Salts on Two-Dimensional Perovskite Layer Formation and Stability Enhancement of Perovskite Solar Cells

Funder: Australian Research Council; doi: http://dx.doi.org/10.13039/501100000923Funder: ARC Centre of Excellence in Future Low Energy Electronics TechnologiesAbstractLong‐chain organic halide salts are widely used in perovskite‐based optoelectronic devices for surface passivation owing to their capability to interact with the surface defects of perovskites. Here, aluminum oxide (AlOx) is introduced via atomic layer deposition onto octylammonium iodide (OAI) to exploit the benefits of organic halide salts without generating undesired defects. The devices incorporating AlOx on OAI‐treated perovskite (OAI/AlOx) show enhancement in both device performance and photo‐stability compared to those with only treatment. A diffusion of aluminum from AlOx into the perovskite through surface characterization contributes to a uniform photo‐generated carrier transport in both the surface and the bulk of the perovskite absorber. In addition, it is revealed that light‐induced two‐dimensional perovskite formation on OAI/AlOx. This may be ascribed to preventing the loss of OA cations due to the presence of AlOx, leading to a decrease in the number of iodine anions which suppresses the light‐induced degradation of corresponding devices. Consequently, the devices show over 24% efficiency and retain their efficiency over 1000 hours under continuous light illumination.</jats:p