Developments in advanced manufacturing have promoted the miniaturization of semiconductor electronic devices to a near-atomic scale,which continuously follows the‘top-down’construction method.However,huge challenges...Developments in advanced manufacturing have promoted the miniaturization of semiconductor electronic devices to a near-atomic scale,which continuously follows the‘top-down’construction method.However,huge challenges have been encountered with the exponentially increased cost and inevitably prominent quantum effects.Molecular electronics is a highly interdisciplinary subject that studies the quantum behavior of electrons tunneling in molecules.It aims to assemble electronic devices in a‘bottom-up’manner on this scale through a single molecule,thereby shedding light on the future design of logic circuits with new operating principles.The core technologies in this field are based on the rapid development of precise fabrication at a molecular scale,regulation at a quantum scale,and related applications of the basic electronic component of the‘electrode-molecule-electrode junction’.Therefore,the quantum charge transport properties of the molecule can be controlled to pave the way for the bottom-up construction of single-molecule devices.The review firstly focuses on the collection and classification of the construction methods for molecular junctions.Thereafter,various characterization and regulation methods for molecular junctions are discussed,followed by the properties based on tunneling theory at the quantum scale of the corresponding molecular electronic devices.Finally,a summary and perspective are given to discuss further challenges and opportunities for the future design of electronic devices.展开更多
Due to their unique electronic structure,well-defined metal clusters at the atomic level are promising materials for single-cluster electronics.However,coupling between the electrode and the cluster remains challengin...Due to their unique electronic structure,well-defined metal clusters at the atomic level are promising materials for single-cluster electronics.However,coupling between the electrode and the cluster remains challenging mainly due to the coverage of bulky ligands on the noble clusters.Using the scanning tunneling microscopy break junction(STM-BJ)technique,we have developed a“direct contact”approach to fabrication and investigation of the charge transport through single-cluster junctions of AgCu bimetallic metal clusterswith different halide anchors.Wefound that the electrodes could make contact directly with the surface halides of the single-cluster junctions and experience different contact resistance from different halogen atoms.Experiments and calculations reveal that the halide anchors provided efficient coupling between the cluster and the electrode,and the enhanced coupling with various halide anchors promoted electron transport and improved transmission probability.Our work offers a“direct contact”strategy for interface design between clusters of noble metals and electrodes,an essential step in progress toward single-cluster electronics.展开更多
Spiropyran derivatives are prototype mechanophores with a promising application as molecular sensors because of their changeable structure under external force stimuli.However,the chemical structure evolution under ex...Spiropyran derivatives are prototype mechanophores with a promising application as molecular sensors because of their changeable structure under external force stimuli.However,the chemical structure evolution under external stimuli remains unclear due to the uncertainty and difficulty in distinguishing the structures of different ring-opened merocyanine isomers generated in the force-induced reaction.Here we identify the structure of isomers produced by the force-induced reaction of spiropyran derivatives using a single-molecule conductance measurement and an unsupervised clustering algorithm.We found that the original data from the single-molecule conductance measurement can be divided into four clusters through unsupervised clustering.By introducing a photoinduced reaction and theoretical calculation,we identified and attributed the four clusters of data to the multiple states of the molecular junctions.Our work demonstrates that a single-molecule break junction measurement can distinguish the isomers in the force-induced reaction,suggesting the great potential of single-molecule conductance measurement and unsupervised clustering approaches for structural analysis.展开更多
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 structur...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.展开更多
In this article, we report on the fabrication and transport measurements of Cu quantum point contacts prepared by a novel, electrochemically assisted mechanically controllable break junction (EC-MCBJ) method. By emp...In this article, we report on the fabrication and transport measurements of Cu quantum point contacts prepared by a novel, electrochemically assisted mechanically controllable break junction (EC-MCBJ) method. By employing photolithography and wet-etching processes, suspended electrode pairs were patterned and fabricated successfully on Si microchips. Rather than adopting an acid Cu electroplating solution, a novel alkaline electroplating solution was developed and utilized to establish Cu nanocontacts between electrode pairs. Typically, the widths of the as-fabricated Cu nanocontacts were found to be smaller than 18 nm. A large number of Cu quantum point contacts were then produced and characterized by a home-built MCBJ setup. In addition to the conventional histogram, where peaks tend to decrease in amplitude with increasing conductance, an anomalous type of conductance histogram, exhibiting different peak amplitudes, was observed. Through statistical analysis of the maximum allowable bending of the Si microchips, and theoretical calculations, we demonstrated that our alkaline Cu electroplating solution affords Cu nanocontacts that are compatible with subsequent MCBJ operations, which is essential for the fabrication of Cu quantum point contacts. As sophisticated e-beam lithography is not required, the EC-MCBJ method is fast, simple, and cost-effective. Moreover, it is likely to be suitable for the fabrication and characterization of quantum point contacts of various metals from their respective electroplating solutions.展开更多
In this article, we report on the characterization of various molecular junctions' current-voltage characteristics (Ⅰ-Ⅴ curves) evolution under mechanical modulations, by employing a novel electrochemically assis...In this article, we report on the characterization of various molecular junctions' current-voltage characteristics (Ⅰ-Ⅴ curves) evolution under mechanical modulations, by employing a novel electrochemically assisted-mechanically controllable break junction (EC-MCBJ) method. For 1,4-benzenedithiol, the Ⅰ-Ⅴ curves measured at constant electrode pair separation show excellent reproducibility, indicating the feasibility of our EC-MCBJ method for fabricating molecular junctions. For ferrocene-bisvinylphenylmethyl dithiol (Fc-VPM), an anomalous type of Ⅰ-Ⅴ curve was observed by the particular control over the stepping motor. This phenomenon is rationalized assuming a model of atomic contact evolution with the presence of molecular junctions. To test this hypothesized model, a molecule with a longer length, 1,3-butadiyne-linked dinuclear ruthenium(H) complex (Ru-1), was implemented, and the Ⅰ-Ⅴ curve evolution was investigated under similar circumstances. Compared with Fc-VPM, the observed Ⅰ-Ⅴ curves show close analogy and minor differences, and both of them fit the hypothesized model well.展开更多
The quantum interference effect in the charge transport through single-phenyl molecules received intensive interests from theory but remained as an experimental challenge. In this paper, we investigated the charge tra...The quantum interference effect in the charge transport through single-phenyl molecules received intensive interests from theory but remained as an experimental challenge. In this paper, we investigated the charge transport through single-molecule benzene dithiol (BDT) junction with different connectivities using mechanically controllable break.junction (MCB]) technique. By further improving the mechanical stability and the electronic measuring component of the MCBJ set-up, we obtained the conductance histograms of BDT molecules (BDTs) from the statistical analysis of conductance-distance traces without data selection. By tuning the connectivity, the conductance of BDTs is determined to be 10-12Go, 10-22Go and 10-10Go for pcra, meta, and ortho connectivity, following the trend that ortfio-BDT 〉 para-BDT 〉 meta-BDT. Furthermore, the displacements of the junctions followed the trend that para 〉 meta 〉 ortho, suggesting the charge transport through the molecules via the gold-thiol bond. The different trends between conductance and displacement for different connectivities suggests the presence of destructive quantum interference effect on meta-BDT, which provides the experimental evidence for the quantum interference effect through single-phenyl molecular junctions.展开更多
基金supported by the National Natural Science Foundation of China(Nos.22173075,21933012,31871877)the National Key Research and Development Program of China(2017YFA0204902)the Fundamental Research Funds for the Central Universities(Nos.20720200068,20720190002).
文摘Developments in advanced manufacturing have promoted the miniaturization of semiconductor electronic devices to a near-atomic scale,which continuously follows the‘top-down’construction method.However,huge challenges have been encountered with the exponentially increased cost and inevitably prominent quantum effects.Molecular electronics is a highly interdisciplinary subject that studies the quantum behavior of electrons tunneling in molecules.It aims to assemble electronic devices in a‘bottom-up’manner on this scale through a single molecule,thereby shedding light on the future design of logic circuits with new operating principles.The core technologies in this field are based on the rapid development of precise fabrication at a molecular scale,regulation at a quantum scale,and related applications of the basic electronic component of the‘electrode-molecule-electrode junction’.Therefore,the quantum charge transport properties of the molecule can be controlled to pave the way for the bottom-up construction of single-molecule devices.The review firstly focuses on the collection and classification of the construction methods for molecular junctions.Thereafter,various characterization and regulation methods for molecular junctions are discussed,followed by the properties based on tunneling theory at the quantum scale of the corresponding molecular electronic devices.Finally,a summary and perspective are given to discuss further challenges and opportunities for the future design of electronic devices.
基金This work was supported by the National Key Research and Development Program of China(grant no.2017YFA0204902)the Fundamental Research Funds for Central Universities(grant no.20720180064)the Beijing National Laboratory for Molecular Sciences(grant no.BNLMS202005).
文摘Due to their unique electronic structure,well-defined metal clusters at the atomic level are promising materials for single-cluster electronics.However,coupling between the electrode and the cluster remains challenging mainly due to the coverage of bulky ligands on the noble clusters.Using the scanning tunneling microscopy break junction(STM-BJ)technique,we have developed a“direct contact”approach to fabrication and investigation of the charge transport through single-cluster junctions of AgCu bimetallic metal clusterswith different halide anchors.Wefound that the electrodes could make contact directly with the surface halides of the single-cluster junctions and experience different contact resistance from different halogen atoms.Experiments and calculations reveal that the halide anchors provided efficient coupling between the cluster and the electrode,and the enhanced coupling with various halide anchors promoted electron transport and improved transmission probability.Our work offers a“direct contact”strategy for interface design between clusters of noble metals and electrodes,an essential step in progress toward single-cluster electronics.
基金supported by the National Natural Science Foundation of China(grant nos.22173075,21933012,61901402,31871877,and 21774106)the National Key R&D Program of China(grant no.2017YFA0204902)+1 种基金the Fundamental Research Funds for the Central Universities(grant nos.20720200068 and 20720190002)the Natural Science Foundation of Fujian Province(grant no.2018J06004).
文摘Spiropyran derivatives are prototype mechanophores with a promising application as molecular sensors because of their changeable structure under external force stimuli.However,the chemical structure evolution under external stimuli remains unclear due to the uncertainty and difficulty in distinguishing the structures of different ring-opened merocyanine isomers generated in the force-induced reaction.Here we identify the structure of isomers produced by the force-induced reaction of spiropyran derivatives using a single-molecule conductance measurement and an unsupervised clustering algorithm.We found that the original data from the single-molecule conductance measurement can be divided into four clusters through unsupervised clustering.By introducing a photoinduced reaction and theoretical calculation,we identified and attributed the four clusters of data to the multiple states of the molecular junctions.Our work demonstrates that a single-molecule break junction measurement can distinguish the isomers in the force-induced reaction,suggesting the great potential of single-molecule conductance measurement and unsupervised clustering approaches for structural analysis.
基金supported by the National Natural Science Foundation of China(21722305,21933012,31871877)the National Key R&D Program of China(2017YFA0204902)+4 种基金Natural Science Foundation of Fujian Province(2018J06004)Beijing National Laboratory for Molecular Sciences(BNLMS202010 and BNLMS202005)the Fundamental Research Funds for the Central Universities(20720220020,20720220072,20720200068,20720190002)supported by the Engineering and Physical Sciences Research Council(EPSRC,EP/M014452/1,EP/P027156/1,and EP/N03337X/1)the European Commission,the Future and Emerging Technologies(FET)Open project 767187-QuIET and the European(EU)project Bac-to-Fuel.
文摘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.
基金Acknowledgements This work was supported by the National Natural Science Foundation of China (Nos. 21503179, 21403181, 61573295, 21522508, 21673195, 21533006, and 61071010), the National Basic Research Program of China (No. 2015CB932300), the Natural Science Foundation of Fujian Province (No. 2016J05162), the Fundamental Research Funds for the Central Universities in China (Xiamen University, Nos. 20720170035 and 20720160092), and the Young Thousand Talent Project of China.
文摘In this article, we report on the fabrication and transport measurements of Cu quantum point contacts prepared by a novel, electrochemically assisted mechanically controllable break junction (EC-MCBJ) method. By employing photolithography and wet-etching processes, suspended electrode pairs were patterned and fabricated successfully on Si microchips. Rather than adopting an acid Cu electroplating solution, a novel alkaline electroplating solution was developed and utilized to establish Cu nanocontacts between electrode pairs. Typically, the widths of the as-fabricated Cu nanocontacts were found to be smaller than 18 nm. A large number of Cu quantum point contacts were then produced and characterized by a home-built MCBJ setup. In addition to the conventional histogram, where peaks tend to decrease in amplitude with increasing conductance, an anomalous type of conductance histogram, exhibiting different peak amplitudes, was observed. Through statistical analysis of the maximum allowable bending of the Si microchips, and theoretical calculations, we demonstrated that our alkaline Cu electroplating solution affords Cu nanocontacts that are compatible with subsequent MCBJ operations, which is essential for the fabrication of Cu quantum point contacts. As sophisticated e-beam lithography is not required, the EC-MCBJ method is fast, simple, and cost-effective. Moreover, it is likely to be suitable for the fabrication and characterization of quantum point contacts of various metals from their respective electroplating solutions.
基金This work was supported by the National Basic Research Program of China (Nos. 2011YQ030124, 2014CB845603, and 2015CB932301), National Natural Science Foundation of China (Nos. 91427304, 21321062, 21303114, 21403181, and 21503179), Natural Science Foundation of Fujian Province (No. 2012J05034), and by CNRS UMR 8640 PASTEUR and LIA CNRS NanoBioCatEchem.
文摘In this article, we report on the characterization of various molecular junctions' current-voltage characteristics (Ⅰ-Ⅴ curves) evolution under mechanical modulations, by employing a novel electrochemically assisted-mechanically controllable break junction (EC-MCBJ) method. For 1,4-benzenedithiol, the Ⅰ-Ⅴ curves measured at constant electrode pair separation show excellent reproducibility, indicating the feasibility of our EC-MCBJ method for fabricating molecular junctions. For ferrocene-bisvinylphenylmethyl dithiol (Fc-VPM), an anomalous type of Ⅰ-Ⅴ curve was observed by the particular control over the stepping motor. This phenomenon is rationalized assuming a model of atomic contact evolution with the presence of molecular junctions. To test this hypothesized model, a molecule with a longer length, 1,3-butadiyne-linked dinuclear ruthenium(H) complex (Ru-1), was implemented, and the Ⅰ-Ⅴ curve evolution was investigated under similar circumstances. Compared with Fc-VPM, the observed Ⅰ-Ⅴ curves show close analogy and minor differences, and both of them fit the hypothesized model well.
基金supported by the Ministry of Science and Technology of China(No. SQ2017YFJC020081)the National Natural Science Foundation of China(Nos. 21673195,21503179)+2 种基金Fundamental Research Funds for the Central Universities in China (Xiamen University: No. 20720170035)Natural Science Foundation of Fujian Province(No. 2016J05162)the Young Thousand Talent Project of China
文摘The quantum interference effect in the charge transport through single-phenyl molecules received intensive interests from theory but remained as an experimental challenge. In this paper, we investigated the charge transport through single-molecule benzene dithiol (BDT) junction with different connectivities using mechanically controllable break.junction (MCB]) technique. By further improving the mechanical stability and the electronic measuring component of the MCBJ set-up, we obtained the conductance histograms of BDT molecules (BDTs) from the statistical analysis of conductance-distance traces without data selection. By tuning the connectivity, the conductance of BDTs is determined to be 10-12Go, 10-22Go and 10-10Go for pcra, meta, and ortho connectivity, following the trend that ortfio-BDT 〉 para-BDT 〉 meta-BDT. Furthermore, the displacements of the junctions followed the trend that para 〉 meta 〉 ortho, suggesting the charge transport through the molecules via the gold-thiol bond. The different trends between conductance and displacement for different connectivities suggests the presence of destructive quantum interference effect on meta-BDT, which provides the experimental evidence for the quantum interference effect through single-phenyl molecular junctions.
基金This work was supported by National Key R&D Project of China(2017YFA0204902)National Natural Science Foundation of China(21722305,21673195,21973079)+2 种基金FET Open project 767187–Qu IETthe EU project BAC-TO-FUELthe UK EPSRC grants EP/N017188/1,EP/P027156/1 and EP/N03337X/1