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Realization of highly reproducible molecular junctions in a nanoparticle-alkanedithiol-nanoelectrode bridge platform
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Experimental Physics. (Electron Microscopy and Nanoenginnering)
Uppsala University, Disciplinary Domain of Science and Technology, Physics, Department of Physics and Astronomy, Theoretical Physics.
Uppsala University, Disciplinary Domain of Science and Technology, Technology, Department of Engineering Sciences, Experimental Physics. (Electron Microscopy and Nanoenginnering)
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Biochemistry and Organic Chemistry.
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(English)Manuscript (preprint) (Other academic)
Keyword [en]
Molecular electronic devices, electrical characterization, alkanedithiols, chemisorbed molecular junctions, nanoparticle-nanoelectrode
National Category
Nano Technology Other Electrical Engineering, Electronic Engineering, Information Engineering Atom and Molecular Physics and Optics
Research subject
Engineering Science with specialization in Materials Analysis; Physics and Astronomy specializing in Theoretical Physics
Identifiers
URN: urn:nbn:se:uu:diva-160622OAI: oai:DiVA.org:uu-160622DiVA: diva2:451954
Projects
KoF U3MEC
Available from: 2011-10-27 Created: 2011-10-27 Last updated: 2013-11-08
In thesis
1. Building Systems for Electronic Probing of Single Low Dimensional Nano-objects: Application to Molecular Electronics and Defect Induced Graphene
Open this publication in new window or tab >>Building Systems for Electronic Probing of Single Low Dimensional Nano-objects: Application to Molecular Electronics and Defect Induced Graphene
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Nano-objects have unique properties due to their sizes, shapes and structure. When electronic properties of such nano-objects are used to build devices, the control of interfaces at atomic level is required.

In this thesis, systems were built that can not only electrically characterize nano-objects, but also allow to analyze a large number of individual nano-objects statistically at the example of graphene and nanoparticle-molecule-nanoelectrode junctions.

An in-situ electrical characterization system was developed for the analysis of free standing graphene sheets containing defects created by an acid treatment. The electrical characterization of several hundred sheets revealed that the resistance in acid treated graphene sheets decreased by 50 times as compared to pristine graphene and is explained by the presence of di-vacancy defects. However, the mechanism of defect insertion into graphene is different when graphene is bombarded with a focused ion beam and in this case, the resistance of graphene increases upon defect insertion. The defect insertion becomes even stronger at liquid N2 temperature.

A molecular electronics platform with excellent junction properties was fabricated where nanoparticle-molecule chains bridge 15-30nm nanoelectrodes. This approach enabled a systematic evaluation of junctions that were assembled by functionalizing electrode surfaces with alkanethiols and biphenyldithiol. The variations in the molecular device resistance were several orders of magnitude and explained by variations in attachment geometries of molecules. 

The spread of resistance values of different devices was drastically reduced by using a new functionalization technique that relies on coating of gold nanoparticles with trityl protected alkanedithiols, where the trityl group was removed after trapping of nanoparticles in the electrode gap. This establishment of a reproducible molecular electronics platform enabled the observation of vibrations of a few molecules by inelastic tunneling spectroscopy. Thus this system can be used extensively to characterize molecules as well as build devices based on molecules and nanoparticles. 

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2011. 109 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 877
Keyword
Graphene, defect induced graphene, molecular electronics, nanoelectrodes, nanoparticles, conductivity, junction, nanomaterial, focused ion beam, surface functionalization, electrical characterization
National Category
Nano Technology Engineering and Technology
Research subject
Engineering Science with specialization in Materials Analysis
Identifiers
urn:nbn:se:uu:diva-160630 (URN)978-91-554-8212-1 (ISBN)
Public defence
2011-12-12, Häggsalen, Ångströmlab, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2011-11-21 Created: 2011-10-27 Last updated: 2011-11-23Bibliographically approved
2. Theoretical studies of a nanoparticle bridge platform for molecular electronics measurements
Open this publication in new window or tab >>Theoretical studies of a nanoparticle bridge platform for molecular electronics measurements
2011 (English)Licentiate thesis, comprehensive summary (Other academic)
Abstract [en]

The main focus of this thesis is the theoretical investigations of a nanogap platform used for molecular electronics measurements under ambient conditions. The nanogap is about 20 nm wide, while the molecules investigated here (octanethiol(OT) and octanedithiol(ODT)) are about 1-1.5 nm long making it impossible to bridge the gap with one molecule. Two different approaches are investigated. In the first approach the electrodes of the nanogap are coated with a layer of OT molecules, and large gold nanoparticles (diameter of about 30 nm) are trapped in the gap creating two molecular junctions with assemblies of molecules. In the second approach the electrodes are kept clean, but instead the gold nanoparticles are coated with doubly functionalized molecules (ODT) and trapped in the gap. Here the nanoparticles are limited in size to about 5 nm, hence it is necessary to consider nanoparticle-molecule chains or small networks to bridge the gap. The first principles modeling of the structure of the metal-molecule junctions combined with elastic and inelastic transport properties is performed using the density functional theory (DFT) combined with the non-equilibrium Green’s functions (DFT-NEGF) method.

In the first approach with the coated electrodes and the large nanoparticles, simulations show that structural irregularities at the electrode interface can lead to a significant variation of the conductance through the molecular film. Due to the size of the nanoparticles, the shape and orientation of the facets will have great influence on how many molecules are connected, affecting the measured resistance of the device.

With the second approach utilizing the functionalized nanoparticles, more stable junctions are obtained since the nanogap is bridged by molecular junctions chemisorbed in both ends. To make chemical bonds to both sides of the junctions, the outer functional group needs to be protected before the trapping of nanoparticles in the gap. Deprotected nanoparticles agglomerate and cannot be trapped. We have inves- tigated the most probable configurations of the molecules in these junctions. During deprotection of the functional group in the gap, a conduction increase have been observed. We have found that the removal of the protection group is not responsible for the increased conduction. Instead, since the deprotected molecule is shorter and the nanoparticles are mobile during deprotection, a reorganization of the nanopar- ticles in the gap occurs. This reorganization leads to decreasing of the tunneling length for the electrons, hence increasing the conduction.

We also demonstrate, that we can obtain the inelastic electron tunneling spectroscopy (IETS) signature of an octanedithiol molecule in this platform. This is done on the network of chemisorbed ODT junctions, where we are able to relate the low-bias Au-S and C-S stretch modes of the molecule to observed peaks in IETS. From this we estimate that the main contribution in the signal comes from chains containing 5, 6 and 7 molecular junctions. To identify the peaks, we have calculated the theoretical spectra for one molecule, from which we are able to extract the important vibrational modes, and their couplings to the electrons. This we then use in a model, including the Coulomb blockade observed in the nanoparticles, to fit the theoretical spectra to the measured one. 

Place, publisher, year, edition, pages
Uppsala: Department of Physics and Astronomy, 2011. 31 p.
National Category
Condensed Matter Physics Nano Technology
Research subject
Physics with spec. in Atomic, Molecular and Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-162061 (URN)
Presentation
2011-11-24, Oseenska rummet, Lägerhyddsvägen 1, Uppsala, 10:59 (English)
Opponent
Supervisors
Available from: 2011-11-23 Created: 2011-11-23 Last updated: 2011-11-24Bibliographically approved
3. Computational Studies of Electron Transport in Nanoscale Devices
Open this publication in new window or tab >>Computational Studies of Electron Transport in Nanoscale Devices
2013 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

In this thesis, a combination of density functional theory (DFT) based calculations and nonequilibrium Green’s functions are employed to investigate electron transport in molecular switches, molecular cords and nanoscale devices.

  Molecular electronic devices have been proposed as an approach to complement today’s silicon based electronic devices. However, engineering of such miniature devices and design of functional molecular components still present significant challenges.

  First, the way to connect a molecule to conductive electrodes has to be controlled. We study, in a nanoelectrode-nanoparticle platform, how structural changes affect the measured conductance and how current fluctuations due to these structural changes can be decreased. We find that, for reproducible measurements, it is important to have the molecules chemically bonded to the surfaces of adjacent nanoparticles. Furthermore, we show by a combination of DFT and theoretical modeling that we can identify signals from single-molecules in inelastic electron spectroscopy measurements on these devices.

  Second, active elements based on molecules, some examples being switches, rectifiers or memory devices, have to be designed. We study molecular conductance switches that can be operated by light and/or temperature. By tuning the substituents on the molecules, we can optimize the shift of the most conducting molecular orbital and increase the effective coupling between the molecule and the electrodes when going from the OFF to the ON-state of the switches, giving high switching ratio (up to three orders of magnitude). We also study so called mechanoswitches that are activated by a mechanical force elongating the molecules, which means that these switches could operate as sensors.

  Furthermore, we have studied two different classes of compounds that may function either as rigid molecular spacers with a well-defined conductance or as molecular cords. In both cases, we find that it is of great importance to match the conjugation of the anchoring groups with the molecular backbone for high conductance.

  The last part of the thesis is devoted to another interesting semiconductor material, diamond. We have accurately calculated the band structure and effective masses for this material. Furthermore, these results have been used to calculate the Hall coefficient, the resistivity and the Seebeck coefficient.

Place, publisher, year, edition, pages
Uppsala: Acta Universitatis Upsaliensis, 2013. i-x, 89 p.
Series
Digital Comprehensive Summaries of Uppsala Dissertations from the Faculty of Science and Technology, ISSN 1651-6214 ; 1090
Keyword
Density functional theory, Molecular electronics, Organosilicon chemistry, Diamond, Molecular switches, Nanoelectrode bridge platform, Molecular cords
National Category
Condensed Matter Physics Physical Chemistry
Research subject
Physics with spec. in Atomic, Molecular and Condensed Matter Physics
Identifiers
urn:nbn:se:uu:diva-209261 (URN)978-91-554-8781-2 (ISBN)
Public defence
2013-11-29, Häggsalen, Ångströmlaboratoriet, Lägerhyddsvägen 1, Uppsala, 10:15 (English)
Opponent
Supervisors
Available from: 2013-11-08 Created: 2013-10-16 Last updated: 2014-01-23

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