Characterizing Pseudoentropy and Simplifying Pseudorandom Generator Constructions

We provide a characterization of pseudoentropy in terms of hardness of sampling: Let (X,B) be jointly distributed random variables such that B takes values in a polynomial-sized set. We show that B is computationally indistinguishable from a random variable of higher Shannon entropy given X if and only if there is no probabilistic polynomial-time S such that (X,S(X)) has small KL divergence from (X,B). This can be viewed as an analogue of the Impagliazzo Hardcore Theorem (FOCS '95) for Shannon entropy (rather than min-entropy). Using this characterization, we show that if f is a one-way function, then (f(Un),Un) has "next-bit pseudoentropy" at least n+log n, establishing a conjecture of Haitner, Reingold, and Vadhan (STOC '10). Plugging this into the construction of Haitner et al., this yields a simpler construction of pseudorandom generators from one-way functions. In particular, the construction only performs hashing once, and only needs the hash functions that are randomness extractors (e.g. universal hash functions) rather than needing them to support "local list-decoding" (as in the Goldreich--Levin hardcore predicate, STOC '89). With an additional idea, we also show how to improve the seed length of the pseudorandom generator to ~{O}(n3), compared to O(n4) in the construction of Haitner et al.Engineering and Applied Science

A Uniform Min-Max Theorem with Applications in Cryptography

We present a new, more constructive proof of von Neumann\u27s Min-Max Theorem for two-player zero-sum game --- specifically, an algorithm that builds a near-optimal mixed strategy for the second player from several best-responses of the second player to mixed strategies of the first player. The algorithm extends previous work of Freund and Schapire (Games and Economic Behavior \u2799) with the advantage that the algorithm runs in poly(n) time even when a pure strategy for the first player is a distribution chosen from a set of distributions over {0,1}^n. This extension enables a number of additional applications in cryptography and complexity theory, often yielding uniform security versions of results that were previously only proved for nonuniform security (due to use of the non-constructive Min-Max Theorem). We describe several applications, including: a more modular and improved uniform version of Impagliazzo\u27s Hardcore Theorem (FOCS \u2795); regularity theorems that provide efficient simulation of distributions within any sufficiently nice convex set (extending a result of Trevisan, Tulsiani and Vadhan (CCC \u2709)); an improved version of the Weak Regularity Lemma of Frieze and Kannan; a Dense Model Theorem for uniform algorithms; and showing impossibility of constructing Succinct Non-Interactive Arguments (SNARGs) via black-box reductions under uniform hardness assumptions (using techniques from Gentry and Wichs (STOC \u2711) for the nonuniform setting)

Solvent-molecule interaction induced gating of charge transport through single-molecule junctions

To explore solvent gating of single-molecule electrical conductance due to solvent-molecule interactions, charge transport through single-molecule junctions with different anchoring groups in various solvent environments was measured by using the mechanically controllable break junction technique. We found that the conductance of single-molecule junctions can be tuned by nearly an order of magnitude by varying the polarity of solvent. Furthermore, gating efficiency due to solvent–molecule interactions was found to be dependent on the choice of the anchor group. Theoretical calculations revealed that the polar solvent shifted the molecular-orbital energies, based on the coupling strength of the anchor groups. For weakly coupled molecular junctions, the polar solvent–molecule interaction was observed to reduce the energy gap between the molecular orbital and the Fermi level of the electrode and shifted the molecular orbitals. This resulted in a more significant gating effect than that of the strongly coupled molecules. This study suggested that solvent–molecule interaction can significantly affect the charge transport through single-molecule junctions

Cross-plane transport in a single-molecule two-dimensional van der Waals heterojunction

Two-dimensional van der Waals heterostructures (2D-vdWHs) stacked from atomically thick 2D materials are predicted to be a diverse class of electronic materials with unique electronic properties. These properties can be further tuned by sandwiching monolayers of planar organic molecules between 2D materials to form molecular 2D-vdW heterojunctions (M-2D-vdWHs), in which electricity flows in a cross-plane way from one 2D layer to the other via a single molecular layer. Using a newly developed cross-plane break junction (XPBJ) technique, combined with density functional theory calculations, we show that M-2D-vdWHs can be created, and that cross-plane charge transport can be tuned by incorporating guest molecules. More importantly, the M-2D-vdWHs exhibit distinct cross-plane charge transport signatures, which differ from those of molecules undergoing in-plane charge transport

Turning the Tap: Conformational Control of Quantum Interference to Modulate Single Molecule Conductance

Together with the more intuitive and commonly recognized conductance mechanisms of charge‐hopping and tunneling, quantum interference (QI) phenomena have been identified as important factors affecting charge transport through molecules. Consequently, establishing simple, flexible molecular design strategies to understand, control and exploit QI in molecular junctions poses an exciting challenge. Here we demonstrate that destructive quantum interference (DQI) in meta‐substituted phenylene ethylene‐type oligomers (m‐OPE) can be tuned by changing the position and conformation of pendant methoxy (OMe) substituents around the central phenylene ring. These substituents play the role of molecular‐scale ‘taps’, which can be switched on or off to control the current flow through a molecule. Our experimental results conclusively verify recently postulated magic ratio and orbital product rules, and highlight a novel chemical design strategy for tuning and gating DQI features, to create single‐molecule devices with desirable electronic functions

Room-temperature quantum interference in single perovskite quantum dot junctions.

The studies of quantum interference effects through bulk perovskite materials at the Ångstrom scale still remain as a major challenge. Herein, we provide the observation of room-temperature quantum interference effects in metal halide perovskite quantum dots (QDs) using the mechanically controllable break junction technique. Single-QD conductance measurements reveal that there are multiple conductance peaks for the CH3NH3PbBr3 and CH3NH3PbBr2.15Cl0.85 QDs, whose displacement distributions match the lattice constant of QDs, suggesting that the gold electrodes slide through different lattice sites of the QD via Au-halogen coupling. We also observe a distinct conductance ’jump’ at the end of the sliding process, which is further evidence that quantum interference effects dominate charge transport in these single-QD junctions. This conductance ’jump’ is also confirmed by our theoretical calculations utilizing density functional theory combined with quantum transport theory. Our measurements and theory create a pathway to exploit quantum interference effects in quantum-controlled perovskite materials

Room-temperature quantum interference in single perovskite quantum dot junctions

The studies of quantum interference effects through bulk perovskite materials at the Ångstrom scale still remain as a major challenge. Herein, we provide the observation of room-temperature quantum interference effects in metal halide perovskite quantum dots (QDs) using the mechanically controllable break junction technique. Single-QD conductance measurements reveal that there are multiple conductance peaks for the CH3NH3PbBr3 and CH3NH3PbBr2.15Cl0.85 QDs, whose displacement distributions match the lattice constant of QDs, suggesting that the gold electrodes slide through different lattice sites of the QD via Au-halogen coupling. We also observe a distinct conductance ‘jump’ at the end of the sliding process, which is further evidence that quantum interference effects dominate charge transport in these single-QD junctions. This conductance ‘jump’ is also confirmed by our theoretical calculations utilizing density functional theory combined with quantum transport theory. Our measurements and theory create a pathway to exploit quantum interference effects in quantum-controlled perovskite materials

Room-temperature quantum interference in single perovskite quantum dot junctions

钙钛矿材料由于其高量子产率、载流子迁移率和独特的光致发光特性而在光电材料领域存在诸多潜在的重要应用。研究钙钛矿材料在纳米尺度下电荷输运的独特尺寸效应对钙钛矿光电器件的设计和开发具有重要的指导意义。洪文晶教授课题组基于机械可控裂结技术自主研发了具有皮米级位移调控灵敏度和飞安级电学测量精度的精密科学仪器，对南开大学李跃龙副教授团队合成的钙钛矿量子点进行了深入表征，研究工作成功将量子干涉的研究体系拓展至在光电领域具有重要应用的钙钛矿材料领域，为未来制备基于量子干涉效应的新型钙钛矿器件提供了一种全新的思路。 这一跨学科国际合作研究工作是在化学化工学院洪文晶教授、英国Lancaster 大学物理系Colin J. Lambert教授以及南开大学电子信息与光电工程学院李跃龙副教授的共同指导下完成的。化工系硕士研究生郑海宁、Lancaster University大学Songjun Hou博士、南开大学硕士研究生辛晨光为论文第一作者。博士后林禄春，博士研究生谭志冰、郑珏婷，硕士研究生蒋枫、张珑漪，本科生何文翔、李庆民等参与了论文的研究工作。刘俊扬特任副研究员、师佳副教授和萨本栋微纳米研究院杨扬副教授也参与了部分指导工作。The studies of quantum interference effects through bulk perovskite materials at the Ångstrom scale still remain as a major challenge. Herein, we provide the observation of roomtemperature quantum interference effects in metal halide perovskite quantum dots (QDs) using the mechanically controllable break junction technique. Single-QD conductance measurements reveal that there are multiple conductance peaks for the CH3NH3PbBr3 and CH3NH3PbBr2.15Cl0.85 QDs, whose displacement distributions match the lattice constant of QDs, suggesting that the gold electrodes slide through different lattice sites of the QD via Auhalogen coupling. We also observe a distinct conductance ‘jump’ at the end of the sliding process, which is further evidence that quantum interference effects dominate charge transport in these single-QD junctions. This conductance ‘jump’ is also confirmed by our theoretical calculations utilizing density functional theory combined with quantum transport theory. Our measurements and theory create a pathway to exploit quantum interference effects in quantum-controlled perovskite materials.This work was supported by the National Key R&D Program of China (2017YFA0204902, 2014DFE60170, 2018YFB1500105), the National Natural Science Foundation of China (Nos. 21673195, 21503179, 21490573, 61674084, 61874167), the Open Fund of the Key Laboratory of Optical Information Science & Technology (Nankai University) of China, the Fundamental Research Funds for the Central Universities of China (63181321, 63191414, 96173224), and the 111 Project (B16027), the Tianjin Natural Science Foundation (17JCYBJC41400), FET Open project 767187—QuIET, the EU project BAC-TO-FUEL and the UK EPSRC projects EP/N017188/1, EP/M014452/1. 该工作得到国家重点研发计划课题（2017YFA0204902）、国家自然科学基金（21673195、21503179、21490573）、厦门大学“人工智能分析引擎”双一流重大专项等项目的资助，也得到了固体表面物理化学国家重点实验室、能源材料化学协同创新中心的支持

Structure-Independent Conductance of Thiophene-Based Single-Stacking Junctions.

Intermolecular charge transport is crucial in π-conjugated materials but the experimental investigation remained challenging. Here, we show that charge transport through intermolecular and intramolecular paths in single-molecule and single-stacking thiophene junctions could be investigated using the mechanically controllable break junction (MCBJ) technique. We found that intermolecular charge transport ability through different single-stacking junctions is approximately independent of molecular structures, which contrasts with the strong length dependence of conductance in single-molecule junctions with the same building blocks, and the dominant charge transport path of molecules with two anchors transits from intramolecular to intermolecular paths when the conjugation pattern increased. The increase of conjugation further leads to higher binding probabilities due to the variation in binding energies supported by density functional theory (DFT) calculations. Our results demonstrate that intermolecular charge transport is not only the limiting step but also provides the efficient and dominate charge transport path at the single-molecule scale

Intermolecular coupling enhanced thermopower in single- molecule diketopyrrolopyrrole junctions

Sorting out organic molecules with high thermopower is essential for understanding molecular thermoelectrics. The intermolecular coupling offers a unique chance to enhance the thermopower by tuning the bandgap structure of molecular devices, but the investigation of intermolecular coupling in bulk materials remains challenging. Herein, we investigated the thermopower of diketopyrrolopyrrole (DPP) cored single-molecule junctions with different coupling strengths by varying the packing density of the self-assembled monolayers (SAM) using a customized scanning tunneling microscope break junction (STM-BJ) technique. We found that the thermopower of DPP molecules could be enhanced up to one order of magnitude with increasing packing density, suggesting that the thermopower increases with larger neighboring intermolecular interactions. The combined density functional theory (DFT) calculations revealed that the closely-packed configuration brings stronger intermolecular coupling and then reduces the highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) gap, leading to an enhanced thermopower. Our findings offer a new strategy for developing organic thermoelectric devices with high thermopower