Single molecule electron transport junctions: charging and geometric effects on conductance

A p-benzenedithiolate (BDT) molecule covalently bonded between two gold electrodes has become one of the model systems utilized for investigating molecular transport junctions. The plethora of papers published on the BDT system has led to varying conclusions with respect to both the mechanism and the magnitude of transport. Conductance variations have been attributed to difficulty in calculating charge transfer to the molecule, inability to locate the Fermi energy accurately, geometric dispersion, and stochastic switching. Here we compare results obtained using two transport codes, TRANSIESTA-C and HUCKEL-IV, to show that upon Au-S bond lengthening, the calculated low bias conductance initially increases by up to a factor of 30. This increase in highest occupied molecular orbital (HOMO) mediated conductance is attributed to charging of the terminal sulfur atom and a corresponding decrease in the energy gap between the Fermi level and the HOMO. Addition of a single Au atom to each terminal of the extended BDT molecule is shown to add four molecular states near the Fermi energy, which may explain the varying results reported in the literature.     

Modulation of molecular conductance induced by electrode atomic species and interface geometry

We present a systematic theoretical investigation of the interaction of an organic molecule with gold and palladium electrodes. We show that the chemical nature of the electrode elicits significant geometrical changes in the molecule. These changes, which are characteristic of the electrode atomic species and the interface geometry, are shown to occur at distances as great as 10 Angstrom from the interface, leading to a significant modification of the inherent electronic properties of the molecule. In certain interface geometries, the highest occupied molecular orbital (HOMO) of the palladium-contacted molecule exhibits enhanced charge delocalization at the center of the molecule, compared to gold. Also, the energy gap between the conductance peak of the lowest unoccupied molecular orbital (LUMO) and the Fermi level is smaller for the case of the palladium electrode, thereby giving rise to a higher current level at a given bias than the gold-contacted molecule. These results indicate that an optimal choice of the atomic species and contact geometry could lead to significantly enhanced conductance of molecular devices and could serve as a viable alternative to molecular derivatization.     

二氧化硅栅绝缘层的制备与表面修饰

研究了有机薄膜晶体管的二氧化硅栅绝缘层的性质。二氧化硅绝缘层的制备采用热生长法，氧化气氛是O₂(g)+H₂O(g)，工艺为干氧-湿氧-干氧的氧化过程。制得的绝缘层漏电流在10^-9 A左右。以该二氧化硅作为有机薄膜晶体管的栅绝缘层，并五苯作为有源层制作了有机薄膜晶体管器件。实验表明采用十八烷基三氯硅烷(OTS)进行表面修饰的器件具有OTS/SiO₂双绝缘层结构，可以有效地降低SiO₂栅绝缘层的表面能并改善表面的平整度。修饰后器件的场效应迁移率提高了1.5倍、漏电流从10^-9 A降到10^-10 A、阈值电压降低了5 V、开关电流比从10⁴增加到10⁵。结果显示具有OTS/SiO₂双绝缘层的器件结构能有效改进有机薄膜晶体管的性能。     

Effects of Electronic Correlations for Adiabatic Electrochemical Reactions of Electron Transfer in Electrode Models with Nearly Empty and Nearly Filled Conduction Bands: Adiabatic Free Energy Surfaces

Adiabatic free energy surfaces (AFES) for adiabatic electrochemical reactions of electron transfer (ARET) are computed with exact allowance for electron–electron correlation effects (EECE) in models of electrode with nearly empty and almost filled conduction bands and analyzed on the basis of a diagram of kinetic modes obtained earlier. The EECE role in ARET for an electrode with an arbitrary Fermi level in a conduction band of an arbitrary width is discussed. In the general case, allowing for EECE gives at some model parameters results other than for the Fermi level coinciding with the conduction band center (model of a surface molecule, MSM). As in the case of MSM considered previously, EECE considerably reduce activation free energies and at some model parameters give qualitatively different AFES.     

Air-assisted high-performance field-effect transistor with thin films of picene

A field-effect transistor (FET) with thin films of picene has been fabricated on SiO2 gate dielectric. The FET showed p-channel enhancement-type FET characteristics with the field-effect mobility, mu, of 1.1 cm2 V-1 s-1 and the on-off ratio of >10(5). This excellent device performance was realized under atmospheric conditions. The mu increased with an increase in temperature, and the FET performance was improved by exposure to air or O2 for a long time. This result implies that this device is an air (O2)-assisted FET. The FET characteristics are discussed on the basis of structural topography and the energy diagram of picene thin films.     

多壁碳纳米管的掺氮改性及场效应管特性研究

以二茂铁为前驱体, 提供催化剂与部分碳源, 三聚氰提供氮源与另外一部分碳源, 在硅基底上制备出了碳纳米管阵列. 碳纳米管为多壁结构, 单根碳纳米管的平均直径为50 nm. 碳纳米管的X射线光电子谱(XPS)在398.4 eV处出现特征峰, 表明为氮掺杂的碳纳米管. 用其制备的场效应管在室温大气环境下稳定地表现为n型场效应特性, 并且具有非常低的关闭状态电流(off-state current)以及良好的负门电压对漏极电流的抑制作用, 单位源漏偏压下漏极电流为100 pA量级. 实验中采用了源/漏电极不对称的绝缘层结构, 使得门电压对源漏两极的电场调制也不对称, 从而实现了对漏电极的门电压调制.     

Scanning tunneling microscopy and scanning tunneling spectroscopy studies of planar and nonplanar naphthalocyanine on graphite (0001). Part 2: tip-sample distance-dependent I-V spectroscopy

Tip-sample distance-dependent current-voltage tunneling spectroscopy on monolayers of base-free naphthalocyanine (Nc), a planar molecule, and tin-naphthalocyanine (SnNc), a nonplanar molecule, has been studied on a freshly cleaved highly oriented pyrolytic graphite (HOPG) surface using a variable-temperature STM at 50 K under ultra-high vacuum conditions. The current-voltage curves show an unsymmetrical diode-like nature especially at large tip-sample distances in both cases. Normalized differential conductivity of all spectra has been considered for further analysis. The ionization and electron affinity levels are compared with the single-molecule local density of states (LDOS) near the Fermi energy using a theoretical calculation for Nc and SnNc. A tip-sample distance-dependent highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) gap shrinking is observed in the case of Nc, in which the filled levels of the molecules are pinned while the unfilled levels near the Fermi energy are shifting toward lower energy. In contrast, there is no such HOMO-LUMO gap shrinking in the case of the SnNc decreasing tip-sample distance. However, a subsequent increase in the tunneling current was observed by almost 1 order of magnitude compared with Nc. A model is proposed to explain this phenomenon where the Nc-graphite interface is considered as a pure capacitive interface.     

The theory of surface-enhanced Raman scattering

By considering the molecule and metal to form a conjoined system, we derive an expression for the observed Raman spectrum in surface-enhanced Raman scattering. The metal levels are considered to consist of a continuum with levels filled up to the Fermi level, and empty above, while the molecule has discrete levels filled up to the highest occupied orbital, and empty above that. It is presumed that the Fermi level of the metal lies between the highest filled and the lowest unfilled level of the molecule. The molecule levels are then coupled to the metal continuum both in the filled and unfilled levels, and using the solutions to this problem provided by Fano, we derive an expression for the transition amplitude between the ground stationary state and some excited stationary state of the molecule-metal system. It is shown that three resonances contribute to the overall enhancement; namely, the surface plasmon resonance, the molecular resonances, as well as charge-transfer resonances between the molecule and metal. Furthermore, these resonances are linked by terms in the numerator, which result in SERS selection rules. These linked resonances cannot be separated, accounting for many of the observed SERS phenomena. The molecule-metal coupling is interpreted in terms of a deformation potential which is compared to the Herzberg-Teller vibronic coupling constant. We show that one term in the sum involves coupling between the surface plasmon transition dipole and the molecular transition dipole. They are coupled through the deformation potential connecting to charge-transfer states. Another term is shown to involve coupling between the charge-transfer transition and the molecular transition dipoles. These are coupled by the deformation potential connecting to plasmon resonance states. By applying the selection rules to the cases of dimer and trimer nanoparticles we show that the SERS spectrum can vary considerably with excitation wavelength, depending on which plasmon and/or charge-transfer resonance is excited.     

Device model for poly(o‐methoxyaniline) field‐effect transistor

We present a detailed study of the electric mechanism of a thin poly(o‐methoxyaniline) (POMA) field‐effect transistor. The device was prepared using Al‐Si/SiO₂/(interdigitated gold lines array)/POMA structure as the gate electrode, insulating layer, source‐drain electrodes, and active layer, respectively. A model is presented for the electrical characteristics of such a device that encompasses the disordered properties of the POMA, the source‐drain electrical‐field dependence of hole mobility, and the carrier and mobility gradients in directions perpendicular to the polymer–oxide interface. The fittings of source‐drain current versus source‐drain voltage, having as parameters the gate voltage, is in good agreement with the experimental data, and the dependence of both the carrier saturation velocity and of the carrier mobility with the gate voltage are obtained. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 74–78, 2005     

Conductance switching in diarylethenes bridging carbon nanotubes

The recently reported photoswitching of diarylethene derivative molecules bridging carbon nanotube (CNT) contacts is theoretically analyzed. The short lifetime of the lowest unoccupied molecular orbital (LUMO) indicates that neither the open nor closed form of the molecule can be photoexcited into a charge-neutral excited state for any appreciable length of time preventing photochromic ring opening. Analysis of the highest occupied molecular orbital (HOMO) and LUMO lifetimes also suggests that photoexcitation results in oxidation of the molecules. This either reduces the quantum yield of photochromic ring closing, or it gives rise to the possibility of oxidative ring closing. Analysis of the resistance values and energy levels indicates that the HOMO energy levels of the closed isomers relevant for transport must lie within a few k(B)T of the CNT Fermi level. For armchair contacts, the change in resistance with isomer or substituent group is the result of shifts in the energy level of the molecular HOMO. The coupling of the molecular HOMO to the CNT contacts is insensitive to the isomer type or substituent group. For zigzag CNTs, the conductance is dominated by surface states at the Fermi level on the cut ends of the CNTs so that the conductance is relatively insensitive to the isomer type, and the conductance switching ratio is low. Multiple bridging molecules can interact coherently, resulting in energy splitting, shifting, and interference that cause a nonlinear change in conductance with increasing numbers of molecules. Instead of a factor of 3 increase in conductance expected for three independent channels, a factor of 10(3) increase in conductance is obtained for three bridging molecules.     

电场作用下苏氨酸的电流特性研究

制备了以液态苏氨酸为沟道材料的四端有机场效应晶体管,观测了其随着栅极电压的不同呈现出源漏两极之间不同的电学特异现象;还观测了苏氨酸在外电场作用下,阻抗随着源漏之间电压频率变化的关系,提出一个极性液体模型解释了其导电机理。     

Guidelines for choosing molecular "alligator clip" binding motifs in electron transport devices

We employ a one-electron, tight-binding model of an electrode-molecule-electrode junction to explore the fundamental relationship between adsorption geometry and electron transport, producing exact results (within this model). By varying the chemisorption location (e.g., atop a surface atom or in a hollow site between surface atoms) and the molecule-electrode coupling, we find that the largest currents are realized when the molecule (i) is highly coordinated by the surface and (ii) has favorable overlap with electrode states near the Fermi level. We also show the importance of electrode-induced molecular level shifting for certain adsorption geometries, which can cause molecular levels far from the Fermi level to conduct better than those near the Fermi level. Since all of these factors are greatly influenced by the chemical moiety used to link the molecule to an electrode, these results present a set of guidelines to help choose "alligator clips" for molecular electronic devices.     

A comparative study of a polyindole-based microelectrochemical transistor in aqueous and non-aqueous electrolytes

The behaviour of a polyindole-based microelectrochemical transistor in aqueous and non-aqueous electrolytes is described. The polyindole film was grown onto two closely spaced (100 μm) platinum microelectrodes by anodic oxidation of indole (10 mM) from 0.1 M tetrabutylammonium perchlorate in dichloromethane at 1.1 V vs. Ag/AgCl. The polymerization was carried out for a sufficiently long time in order to connect both Pt microelectrodes, which operated as a transistor when immersed in an electrolytic solution. In this transistor, one microelectrode was a “source” and the other a “drain”; the Ag/AgCl wire reference electrode was used as a “gate”. The drain current (current between source and drain) was modulated by varying the gate potential (potential between source and gate) at a fixed drain potential (potential between source and drain). The transconductances of the transistor were estimated as 0.98 mS/cm and 20.6 mS/cm of channel width (separation between two microelectrodes) in aqueous and non-aqueous solutions, respectively. Received: 6 April 1999 / Accepted: 24 August 1999     

Low‐Voltage All‐Polymer Field‐Effect Transistor Fabricated Using an Inkjet Printing Technique

Summary: An all‐polymer field‐effect transistor (FET) fabricated using an inkjet printing technique is presented in this paper. Poly(3,4‐ethylenedioxythiophene) works as the source/drain/gate electrode material because of its good conductivity. Polypyrrole acts as the semiconducting layer. Poly(vinyl pyrrolidone) K60, an insulating polymer with a dielectric constant of 60, operates as the dielectric layer. All the polymers are diluted with deionized water, and can be printed with a piezoelectric inkjet printing system. The device functions at a depletion mode with low operation voltage. It has a field‐effect mobility of 0.1 cm² · V⁻¹ · s⁻¹, an on/off ratio of 2.9 × 10³, and a subthreshold slope of 2.81 V · decade⁻¹.

Schematic of the all‐polymer FET synthesized here.     

Effect of (L:D) Aspect Ratio on Single Polypyrrole Nanowire FET Device

Effect of different aspect ratio (length to diameter ratio, L:D) on single polypyrrole (Ppy) nanowire based field effect transistor (FET) sensor for real time pH monitoring was studied. Ppy nanowires with diameters of ~60, ~80 and ~200 nm were synthesized using electrochemical deposition inside anodized aluminium oxide (AAO) template and were assembled using AC dielectrophoretic alignment followed by maskless anchoring on a pair of gold electrodes separated with different gap lengths. Microfabricated gold electrode patterns with gap size between 1 - 4 μm were developed by means of MEMS technique (photolithography). Using field effect transistor geometry with pair of microfabricated gold contact electrodes serving as a source and a drain, and a platinum (Pt) mesh (anchored in a microfluidic channel) was used as a gate electrode. When effect of different aspect ratio of the nanowire were compared, higher sensitivity was recorded for higher aspect ratio. The sensitivity was further improved by modulating the gate potential. These FET sensors based on single polypyrrole nanowire exhibited excellent and tunable sensitivity towards pH variations.     

Prediction of the terminations and Miller planes of the tetragonal zirconia thin films as a gate dielectric layer in integrated-circuit industry

In this paper, we investigate the structures and insulating characters of the tetragonal zirconia (t-ZrO₂) thin films with various possible terminations within the lower-index Miller planes (001) and (100). It is found that, firstly, a shift towards higher energy region makes the valence band of the OO-terminated thin films of the (001) Miller plane of t-ZrO₂ cross the Fermi level E_F and thus are unusable as a gate dielectric oxide in integrated-circuit (IC) industry because of large-leakage current. Secondly, a new splitting state presented just below the bottom of conduction band, and the Fermi level E_F drops between them, which imply that the Zr-terminated thin films of the (001) Miller plane of t-ZrO₂ are also unusable as a gate dielectric oxide in IC industry because of large leakage current. Thirdly, the insulating character disappears completely for Zr + OO-terminated thin films of the (001) Miller plane of t-ZrO₂ and thus is also unusable as a gate dielectric oxide in IC industry because of metal character. Fourthly, the insulating character is maintained for the ZrO₂-terminated thin films of the (100) Miller plane and thus is usable as a gate dielectric oxide in IC industry.     

Silicon nanowire ion sensitive field effect transistor with integrated Ag/AgCl electrode: pH sensing and noise characteristics

We have fabricated Si nanowire (SiNW) based ion-sensitive field effect transistors (ISFETs) for biosensing applications. The ability to prepare a large number of sensors on a wafer, the use of standard silicon microfabrication techniques resulting in cost savings, and potential high sensitivity are significant advantages in favor of nanoscale SiNW ISFETs. The SiNW ISFETs with embedded Ag/AgCl reference electrode were fabricated on a standard silicon-on-insulator wafer using electron-beam lithography and conventional semiconductor processing technology. The current-voltage characteristics show an n-type FET behavior with a relatively high on/off current ratio, reasonable sub-threshold swing value, and low gate-leakage current. The pH responses of the ISFETs with different pH solutions were characterized at room temperature which showed a clear lateral shift of the drain current vs. gate voltage curve with a change in the pH value of the solution and a sensitivity of 40 mV pH(-1). The low frequency noise characteristics were investigated to evaluate the signal to noise ratio and sensing limit of the devices.     

Low-Bias Conductance Mechanism of Diarylethene Isomers:a First-Principle Study

The structure-property relationship of diarylethene (DAE)-derivative molecular isomers, which involve ring-closed and ring-open forms, is investigated by employing the non-equilibrium Green's function formalism combined with density functional theory. Molecular junctions are formed by the isomers connecting to Au(111) electrodes through flanked pyridine groups. The difference in electronic structures caused by different geometry structures for the two isomers, particularly the interatomic alternative single bond and double bond of the ring-closed molecule, contributes to the vastly different low-bias conductance values. The lowest unoccupied molecular orbital (LUMO) of the isomers is the main channel for electron transport. In addition, more electrons transferred to the ring-closed molecular junction in the equilibrium condition, thereby decreasing the LUMO energy to near the Fermi energy, which may contribute to a larger conductance value at the Fermi level. Our findings are helpful for understanding the mechanism of low-bias conductance and are conducive to the design of high-performance molecular switching based on diarylethene or diarylethene-derivative molecules.     

Study on the interaction between tetracene and Cu(110) surface

The electronic structure of tetracene on Cu (110) surface has been studied by using ultraviolet photoemission spectroscopy (UPS). The emission features from the organic molecule are located from 1 to 10 eV below the Fermi level, and they shift in binding energy with increasing the coverage of the organic material. For the surface with multilayer of tetracene, six well-resolved features were found at 1.90, 3.40, 4.70, 5.95, 6.95, and 9.15 eV below the Fermi level, respectively. On the surface with a lower coverage of tetracene, angle-resolved UPS measurements suggest that the molecular plane is parallel to the substrate. Density functional theory calculation confirms the flat-lying adsorption mode and shows that the tetracene molecule prefers to be adsorbed on the long bridge site with its long axis in the [110] azimuth.     

Molecular conductance switch-on of single ruthenium complex molecules

Thiol-tethered Ru(II) terpyridine complexes were synthesized for a voltage-driven molecular switch and used to understand the switch-on mechanism of the molecular switches of single metal complexes in the solid-state molecular junction in a vacuum. Molecularly resolved scanning tunneling microscopy (STM) images revealed well-defined single Ru(II) complexes isolated in the highly ordered dielectric monolayer. When a negative sample-bias was applied, the threshold voltage to the high conductance state in the molecular junctions of the Ru(II) complex was consistent with the electronic energy gap between the Fermi level of the gold substrate and the lowest ligand-centered redox state of the metal complex molecule. As an active redox center leading to conductance switching in the molecule, the lowest ligand-centered redox state of Ru(II) complexes was suggested to trap an electron injected from the gold substrate. Our suggestions for a single-molecule switch-on mechanism in the solid state can provide guidance in a design that improves the charge-trapping efficiency of the ligands with different metal substrates.