Hydration effect on the electronic transport properties of oligomeric phenylene ethynylene molecular junctions

A first-principles computational method based on the hybrid density functional theory is developed to simulate the electronic transport properties of oligomeric phenylene ethynylene molecular junctions with H2O molecules accumulated in the vicinity as recently reported by Na et al. [Nanotechnology 18 424001 （2007）]. The numerical results show that the hydrogen bonds between the oxygen atoms of the oligomeric phenylene ethynylene molecule and H2O molecules result in the localisation of the molecular orbitals and lead to the lower transition peaks. The H2O molecular chains accumulated in the vicinity of the molecular junction can not only change the electronic structure of the molecular junctions, but also open additional electronic transport pathways. The obvious influence of H2O molecules on the electronic structure of the molecular junction and its electronic transport properties is thus demonstrated.

Charge transfer and variation of potential distributions in the formation of 4, 4＇-bipyridine molecular junction

In this paper the charge transfer and variation of potential distribution upon formation of 4, 4＇-bipyridine molecular junction have been investigated by applying hybrid density-functional theory （B3LYP） at ab initio level. The numerical results show that there exist charge-accumulation and charge-depletion regions located at respective inside and outside of interfaces. The variation of potential distribution is obvious at interfaces. When distance between electrodes is changed, the charge transfer and variation of potential distribution clearly have distance-dependent performance. It is demonstrated that the contact structure between the molecule and electrodes is another key factor for dominating the properties of molecular junction. The qualitative explanation for experimental results is suggested.

Theoretical design of thermal spin molecular logic gates by using a combinational molecular junction

Based on the density functional theory combined with the nonequilibrium Green function methodology,we have studied the thermally-driven spin-dependent transport properties of a combinational molecular junction consisting of a planar four-coordinate Fe molecule and a 15,16-dinitrile dihydropyrene/cyclophanediene molecule,with single-walled carbon nanotube bridge and electrode.Our results show that the magnetic field and light can effectively regulate the thermallydriven spin-dependent currents.Perfect thermal spin-filtering effect and good thermal switching effect are realized.The results are explained by the Fermi-Dirac distribution function,the spin-resolved transmission spectra,the spatial distribution of molecular projected self-consistent Hamiltonian orbitals,and the spin-resolved current spectra.On the basis of these thermally-driven spin-dependent transport properties,we have further designed three basic thermal spin molecular AND,OR,and NOT gates.

Electron Transport Properties of Two-Dimensional Si_1P_1 Molecular Junctions

We focus on two new 21） materials, i.e., monolayer and bilayer silicon phosphides （Sil P1）. Based on the elastic- scattering Green＇s function, the electronic-transport properties of two-dimensional monolayer and bilayer Au- Si1P1-Au molecular junctions are studied. It is found that their bandgaps are narrow （0.16eV for a monolayer molecular junction and 0.26 e V for a bilayer molecular junction）. Moreover, the calculated current-voltage char- acteristics indicate that the monolayer molecular junction provides constant output current （20 hA） over a wide voltage range, and the bilayer molecular junction provides higher current （42 hA）.

Electron Transport Properties of Two-Dimensional Monolayer Films from Au-P-Au to Au-Si-Au Molecular Junctions

We investigate the electronic-transport properties of two-dimensional monolayer films from Au-P-Au molecular junction to Au-Si-Au molecular junction using elastic scattering Green＇s function theory. In the process of replacing the P atoms with Si atoms every other line from the middle of monolayer blue phosphorus molecular structure, the substitution of Si atoms changes the properties of Au-P-Au molecular junction significantly. Interestingly, the current value has a symmetric change as a parabolic curve with the peak appearing in Au-Si_1P_1-Au molecular junction, which provides the most stable current of 15.00 nA in a wide voltage range of 0.70-2.70 V.Moreover, the current-voltage characteristics of the structures indicate that the steps tend to disappear revealing the property similar to metal when the Si atoms dominate the molecular junction.

σ-dominated charge transport in sub-nanometer molecular junctions

Quantum tunneling conductance of molecular junctions originates from the charge transport through theπ-orbitals(π-transport)and theσ-orbitals(σ-transport)of the molecules,but theσ-transport can not be observed due to the more rapid decay of the tunneling conductance in theσ-system compared to that in theπ-system.Here,we demonstrate that dominantσ-transport can be observed inπ-conjugated molecular junctions at the sub-nanometer scale using the scanning tunneling microscope break junction technique(STM-BJ).We have found that the conductance of meta-connected picolinic acid,which mainly occurs byσ-transport,is∼35 times higher than that of its para-isomer,which is entirely different from what is expected fromπ-transport through these systems.Flicker noise analysis reveals that the transport through the meta-connection exhibits more through-bond transport than the para-counterpart and density functional theory(DFT)shows that theσ-system provides the dominant transport path.These results reveal that theσ-electrons,rather than theπ-electrons,can dominate charge transport through conjugated molecular junctions at the sub-nanometer scale,and this provides a new avenue toward the future miniaturization of molecular devices and materials.

Unexpected current-voltage characteristics of mechanically modulated atomic contacts with the presence of molecular junctions in an electrochemically assisted-MCBJ

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.

Field Effects on the Statistical Behavior of the Molecular Conductance in a Single Molecular Junction in Aqueous Solution

We have combined molecular dynamics simulations with first-principles calculations to study electron transport in a single molecular junction of perylene tetracarboxylic diimide (PTCDI) in aqueous solution under external electric gate fields. It is found that the statistics of the molecular conductance are very sensitive to the strength of the electric field. The statistics of the molecular conductance are strongly associated with the thermal fluctuation of the water molecules around the PTCDI molecule. Our simulations reproduce the experimentally observed three orders of magnitude enhancement of the conductance, as well as the temperature dependent conductance, under the electrochemical gates. The effects of the molecular polarization and the dipole rearrangement of the aqueous solution are also discussed.

Excellent thermoelectric performance in weak-coupling molecular junctions with electrode doping and electrochemical gating

Excellent thermoelectric performance in molecular junctions requires a high power factor, a low thermal conductance, and a maximum figure of merit(ZT) near the Fermi level. In the present work, we used density functional theory in combination with a nonequilibrium Green’s function to investigate the thermoelectric performance of carbon chain-graphene junctions with both strong-coupling and weak-coupling contact between the electrodes and the molecules. The results revealed that a room temperature ZT of 4 could be obtained for the weak-coupling molecular junction, approximately one order of magnitude higher than that reached by the strong-coupling junction. The reason for this is that strong interfacial scattering suppresses most of the phonon modes in weak-coupling systems, resulting in ultralow phonon thermal conductance. The influence of electrode width,electrode doping, and electrochemical gating on the thermoelectric performance of the weak-coupling system was also investigated, and the results revealed that an excellent thermoelectric performance can be obtained near the Fermi level.

Effect of near-field optical angular momentum on molecular junctions

The role of molecular junctions in nanoelectronics is most often associated with electronic transport;however,their precise characterisation hinders their widespread development.The interaction of light with molecular junctions is a supplementary factor for the development of molecular switches,but it has rarely been addressed.The influence of light interaction with molecular junctions on the response of molecules in the near field was demonstrated by properly characterising the optical angular momentum at the junctions.Consequently,the molecular switching dynamics were observed in the Raman signatures of the conducting molecules.The illumination geometry and voltage applied to the junction were changed to demonstrate numerically and experimentally how the Raman intensity can be turned ON and OFF with a difference of nearly five orders of magnitude.These molecular-scale operations result from the combined interaction of a current-induced electronic rearrangement in the molecular junction and a plasmonically enhanced electromagnetic field near the tip of the junction.This study of the effect of optical angular momentum on the near field of the molecular junction shows significant potential for the development of molecular electronics.

Sequence modulation of tunneling barrier and charge transport across histidine doped oligo-alanine molecular junctions

Series tunneling across peptides composed of various amino acids is one of the main charge transport mechanisms for realizing the function of protein. Histidine, more frequently found in redox active proteins, has been proved to be efficient tunneling mediator. While how it exactly modulates charge transport in a long peptide sequence remains poorly explored. In this work, we studied charge transport of a model peptide junction, where oligo-alanine peptide was doped by histidine at different position,and the series of peptides were self-assembled into a monolayer on gold electrode with soft EGa In as top electrode to form molecular junction. It was found that histidine increased the overall conductance of the peptide, meanwhile, its position modulated the conductance as well. Quantitative analysis by transport model and ultraviolet photoelectron spectroscopy(UPS) indicated a sequence dependent energy landscape of the tunneling barrier of the junction. Density-functional theory(DFT) calculation on the electronic structure of histidine doped oligo-alanine peptides revealed localized highest occupied molecular orbital(HOMO) on imidazole group of the histidine, which decreased charge transport barrier.

Theoretical Design of Molecular Diode Based on Thiol-and Amino-Terminated Molecules

Utilizing density functional theory(DFT)and non-equilibrium Green's function,we systematically studied the electrical transport and rectification properties of thiol-and amino-terminated molecules embedded in graphene nanoribbons.We firstly found the thiol-terminated moleculesshowbetterelectron transport properties compared to the amino-terminated,which can be attributed to the strong electronwithdrawing ability and favorable coupling effects.Secondly,the symmetrical molecules show almost symmetrical current-voltage(-V)curves and exhibit negligible rectification effects.On the other hand,the asymmetrical molecules exhibit asymmetrical I-V curves and better rectification performance.The rectification effect is closely related to molecular asymmetry degrees.For example,the rectification ratio of asymmetric N6((E)-N1-(3-aminopropyl)-but-2-ene-1,4-diamine)molecule is much smaller than the N4(5-phenylthiazole-2,4-diamine)and N5(2,6-diaminohexane-1,1,5-triol)molecules.Furthermore,we found the rectification ratio of the asymmetrical amino-terminated molecules can reach 400,while the biggest rectification ratio of the thiol-terminated molecule can only reach 45.These findings offer crucial insights for future graphene molecular electronic device design.

Phonon-Assisted Spin Current in Single Molecular Magnet Junctions

Owing to the bistable character of the single molecular magnet （SMM）, it can generate 100% spin-polarized currents even connected with normal （N） leads. In this work, we study the phonon-assisted spin current in N- SMM-N systems. We mainly focus on the interplay of SMM＇s bistable character and electron-phonon coupling. It is found that when SMM is trapped in one of the lowest bistable states, it can generate phonon-assisted spin- polarized currents. At the up-spin transport channel, it is accompanied by a phonon-assisted up-spin current, while at the down-spin transport channel, it is accompanied by a phonon-assisted down-spin current.

Effect of Gate Electric Field on Single Organic Molecular Devices

Based on the first-principles computational method and elastic scattering Green＇s function theory, we have investigated the effect of gate electric field on electronic transport properties of a series of single organic molecular junctions theoretically. The numerical results show that the molecular junctions that have redox centers and relatively large dipole moments parallel gate direction can respond to the gate electric field remarkably. The current-voltage properties of 2,5-dimethyl-thiophene-dithiol present N-channel-metal-oxide-semiconductorlike characteristics. Its distinct current-voltage properties can be understood from the evo- lution of eigenvalues, coupling energies, and atomic charges with gate electric field.

The fabrication,characterization and functionalization in molecular electronics

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.

The inelastic electron tunneling spectroscopy of edge-modified graphene nanoribbon-based molecular devices

The inelastic electron tunneling spectroscopy（IETS） of four edge-modified finite-size grapheme nanoribbon（GNR）-based molecular devices has been studied by using the density functional theory and Green＇s function method. The effects of atomic structures and connection types on inelastic transport properties of the junctions have been studied. The IETS is sensitive to the electrode connection types and modification types. Comparing with the pure hydrogen edge passivation systems, we conclude that the IETS for the lower energy region increases obviously when using donor–acceptor functional groups as the edge modification types of the central scattering area. When using donor–acceptor as the electrode connection groups, the intensity of IETS increases several orders of magnitude than that of the pure ones. The effects of temperature on the inelastic electron tunneling spectroscopy also have been discussed. The IETS curves show significant fine structures at lower temperatures. With the increasing of temperature, peak broadening covers many fine structures of the IETS curves.The changes of IETS in the low-frequency region are caused by the introduction of the donor–acceptor groups and the population distribution of thermal particles. The effect of Fermi distribution on the tunneling current is persistent.

GaInP/GaAs tandem solar cells with highly Te- and Mg-doped GaAs tunnel junctions grown by MBE

We report a GaInP/GaAs tandem solar cell with a novel GaAs tunnel junction（TJ） with using tellurium（Te） and magnesium（Mg） as n- and p-type dopants via dual-filament low temperature effusion cells grown by molecular beam epitaxy（MBE） at low temperature. The test Te/Mg-doped GaAs TJ shows a peak current density of 21 A/cm2. The tandem solar cell by the Te/Mg TJ shows a short-circuit current density of 12 m A/cm2, but a low open-circuit voltage range of1.4 V^1.71 V under AM1.5 illumination. The secondary ion mass spectroscopy（SIMS） analysis reveals that the Te doping is unexpectedly high and its doping profile extends to the Mg doping region, thus possibly resulting in a less abrupt junction with no tunneling carriers effectively. Furthermore, the tunneling interface shifts from the intended Ga As n＋＋/p＋＋junction to the AlGaInP/GaAs junction with a higher bandgap AlGaInP tunneling layers, thereby reducing the tunneling peak. The Te concentration of ~ 2.5 × 1020 in GaAs could cause a lattice strain of 10-3 in magnitude and thus a surface roughening,which also negatively influences the subsequent growth of the top subcell and the GaAs contacting layers. The doping features of Te and Mg are discussed to understand the photovoltaic response of the studied tandem cell.

金电极对偶氮苯分子结的结构及其电输运性质的力学调控作用

偶氮苯分子因存在顺反两种异构体而表现出不同的电输运性质.为了揭示电极的机械作用对偶氮苯分子的几何结构以及电输运性质的影响,基于第一性原理计算研究了偶氮苯分子在电极挤压和拉伸作用下的结构变化规律,并利用非平衡格林函数方法计算了偶氮苯分子结在拉伸和压缩过程中以及分子在不同形状电极之间的电输运性质.结果表明,顺式和反式偶氮苯分子在电极作用下都具有较稳定的几何结构.其中顺式偶氮苯分子在电极拉至超过反式偶氮苯分子结平衡电极距离0.1 nm时仍保持为顺式结构.而反式偶氮苯分子在电极挤压下虽然发生了弯曲,但当电极距离压缩至短于顺式偶氮苯分子结0.2 nm时,中间的C—N—N—C二面角仍然保持反式结构.在低偏压下,两电极若为平面电极,则反式偶氮苯分子的电导高于顺式偶氮苯分子;若分子连接于两锥形电极尖端,则顺式偶氮苯分子结的电导更高.特别值得关注的是两种偶氮苯分子的导电能力随电极距离的变化正好相反,顺式偶氮苯分子结的电导随电极距离拉伸而增大,反式偶氮苯分子结的电导则随电极距离的压缩而增大.偶氮苯分子结的电导在电极距离变化时最大变化幅度可达10倍以上.

Claudin18.2分子特征概述及其作为治疗靶点在胃癌中的研究进展

作为紧密连接蛋白(Claudin,CLDN)家族成员之一,Claudin18.2(CLDN18.2)在正常情况下仅在正常胃黏膜上皮细胞中表达,以维持细胞正常功能。但在异常情况下,CLDN18.2在包括胃癌在内的多种恶性肿瘤中呈高表达状态,使其成为治疗前景非常高的新靶点。目前,靶向CLDN18.2的抗肿瘤新药研发如火如荼,药物类型和治疗策略呈现多样化。本文旨在概述CLDN18.2的分子特征,并对胃癌中靶向CLDN18.2的新药/新技术研发现状进行梳理,包括单克隆抗体、双特异性抗体、抗体药物偶联物、嵌合抗原受体T细胞免疫疗法、纳米抗体等。

分子结的非弹性隧道谱和电子-振动的耦合

研究了分子结的非弹性隧道谱,给出了基于微扰理论近似的非平衡格林函数.深入研究了非弹性隧道谱和电子-振动耦合常数的相互关系.同时,还计算了OPV和OPE分子结的IETS,计算结果与有关的实验结果具有很好的可比性.