| 1. |
- Liedberg, Bo, et al.
(author)
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Self-assembly of alpha-functionalized terthiophenes on gold
- 1997
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In: JOURNAL OF PHYSICAL CHEMISTRY B. - : AMER CHEMICAL SOC. - 1089-5647 .- 1520-6106 .- 1520-5207. ; 101:31, s. 5951-5962
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Journal article (peer-reviewed)abstract
- alpha-Functionalized terthiophenes containing disulfide (-S-T-3-H)(2) and alkanethiol (HS-(CH2)(11)-T-3-H) anchoring groups have been synthesized for direct immobilization onto gold. Monolayer structures of these compounds are prepared by spontaneous assembly from ethanol solutions on evaporated gold substrates and thoroughly characterized by ellipsometry, contact angle goniometry, infrared and X-ray photoelectron spectroscopy, and cyclic voltammetry. The two molecules coordinate to the gold substrate exclusively via the anchoring groups upon formation of gold-thiolate bonds. The kinetics of monolayer formation vary dramatically for the two compounds. The alkanethiol analogue assembles rapidly, within a few minutes, and forms a densely packed and highly organized monolayer, with the alkyl chains in an almost perfect all-trans conformation and the C-alpha-C-alpha axis of the alpha-T-3 units tilted about 14 degrees away from the surface normal. The assembly process is much slower for the disulfide, but an organized monolayer with an average alpha-T-3 chain tilt of about 33 degrees will eventually form when the assembly is allowed to equilibrate with a solution containing the disulfide for at least 1 day. Moreover, the two monolayer assemblies also display a remarkably different electrochemical, behavior. The heterogeneous electron-transfer rate at the disulfide-covered gold substrate is almost indistinguishable from that at bare gold, suggesting that the assembly contains a large number of easily accessible defects. An alternative mechanism for explaining the large electron-transfer rate involving electronic coupling via the conjugated pi-system of the alpha-T-3 units is also proposed. The electrochemical response is significantly reduced for the HS-(CH2)(11)-T-3-H assembly, but another type of defects, the so-called shallow defects originating from sparsely populated areas on the electrode surface, can be identified.
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| 2. |
- Yang, Zhongping, et al.
(author)
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Preparation and characterization of mixed monolayer assemblies composed of thiol analogues of cholesterol and fatty acid
- 1997
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In: Langmuir. - : American Chemical Society. - 0743-7463 .- 1520-5827. ; 13:12, s. 3210-3218
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Journal article (peer-reviewed)abstract
- Mixed self-assembled monolayers provide an attractive model system for investigating the role of different molecules in biological membranes. This paper describes the preparation and characterization of a novel type of mixed monolayer assemblies composed of thiol analogues of cholesterol and fatty acid. The mixed: monolayers are prepared by coadsorbing 11-mercaptoundecanoic acid (MUA) and thiocholesterol(cholest-5-ene-3 beta-thiol, TC) from solution directly onto evaporated gold surfaces. The influence of TC on the molecular composition and conformation in the mixed monolayer is analyzed by using a combination of infrared reflection-absorption spectroscopy (IRAS), X-ray photoelectron spectroscopy (XPS), ellipsometry, contact angle measurement, and cyclic voltammetry. The results indicate that the TC molecules maintain their conformation in the mixed monolayers, whereas the MUA molecules display a significantly more disordered conformation as compared to the MUA molecules in the pure monolayer. Cyclic voltammetry shows that the mixed monolayers are more densely packed and less permeable than the pure TC and MUA monolayers. The kinetics of the coadsorption of TC and MUA from ethanol indicates that adsorption of TC initially is strongly preferred over MUA but that MUA dominates over TC at long coadsorption times. This is because there is a larger energy gain per unit area in forming monolayers with MUA, Further, it is also seen that the number of molecules per unit area changes with the molecular composition, as a consequence of the different sizes of TC and MUA. We present herein a method for calculating the mole fraction of TC on the gold surface, (chi TC), which accounts for this variation. As a consequence of the dissimilar size and shape of the two molecules, the wetting properties of the mixed monolayer are found to be mainly governed by the fractional area of TC, rather than by the molecular composition of TC, (chi TC).
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| 3. |
- Lestelius, Magnus, et al.
(author)
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Order/disorder gradients of n-alkanethiols on gold
- 1999
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In: Colloids and Surfaces B. - : Elsevier. - 0927-7765 .- 1873-4367. ; 15:1, s. 57-70
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Journal article (peer-reviewed)abstract
- This paper explores the interfacial properties of one-dimensional molecular gradients of alkanethiols (HS-(CH2)(n)- X) on gold. The kinetics and thermodynamics of monolayer formation are important issues for these types of mixed molecular assemblies. The influence of chain length difference on the contact angles with hexadecane (HD), theta(a) and theta(r), and the hysteresis, has been studied by employing alkanethiols HS-(CH2)(n)-CH3, with n = 9, 11, 13, 15 and 17, in the preparation of the self-assembled monolayers (SAM) gradients. The contact angles with hexadecane, at the very extreme ends of the gradients, show characteristic values of a highly ordered CH3-like assembly: theta(a) = 45-50 degrees. In the middle of the gradients theta(a) drops noticeably and exhibits values representative for CH2-like polymethylenes, theta(a) = 20-30 degrees, indicating a substantial disordering of the protruding chains of the longer component in the gradient assembly. As expected, the exposure of CH2-groups to the probing liquid increases with increasing differential chain length of the two n-alkanethiol used, in this case eight methylene units. However, the contact angles always display a non-zero value which means that even at a chain length difference of eight methylene units there is a substantial exposure of methyl (CH3) groups to the probing liquid. With infrared reflection-absorption spectroscopy (IRAS) we have monitored the structural behavior of the polymethylene chains along the gradient. We find complementary evidence for disordered chains in the gradient region, and the IRAS results correlate well with the contact angle measurements. (C) 1999 Elsevier Science B.V. All rights reserved.
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| 4. |
- Sani, Negar
(author)
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Addressability and GHz Operation in Flexible Electronics
- 2016
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Doctoral thesis (other academic/artistic)abstract
- The discovery of conductive polymers in 1977 opened up a whole new path for flexible electronics. Conducting polymers and organic semiconductors are carbon rich compounds that are able to conduct charges while flexed and are compatible with low-cost and large-scale processes including printing and coating techniques. The conducting polymer has aided the rapidly expanding field of flexible electronics, leading to many new applications such as electronic skin, RFID tags, smart labels, flexible displays, implantable medical devices, and flexible sensors.However, there are several remaining challenges in the production and implementation of flexible electronic materials and devices. The conductivity of organic conductors and semiconductors is still orders of magnitude lower compared to their inorganic counterparts. In addition, non-flexible inorganic semiconductors still remain the materials of choice for high frequency applications; since the charge carrier mobility and thus operational speed of the organic materials are limited. Therefore, there remains a high demand to combine the high frequency operation of inorganic semiconductors with the flexible fabrication methods of organic systems for future electronics.In addition to the challenges in the choice of materials in flexible electronics, the upscaling of the flexible devices and implementing them in circuits can also be complicated. Lack of non-linearity is an issue that arises when flexible devices with linear behavior need to be incorporated in an array or matrix form. Non-linearity is important for applications such as displays and memory arrays, where the devices are arranged as matrix cells addressed by their row and column number. If the behavior of cells in the matrix is linear, addressing each cell affects the adjacent cells. Therefore, inducing non-linearity and, consequently, addressability in such linear devices is the first step before scaling up into matrix schemes.In this work, non-linear organic/inorganic hybrid devices are produced to overcome the limitations mentioned above and leverage the advantages of both organic and inorganic materials. Two novel methods are developed to incorporate non-flexible inorganic semiconductors into ultra-high frequency (UHF) flexible devices. In the first method, Si is ground into a powder with micrometer-sized particles and printed through standard screen printing. For the first time, allprinted flexible diodes operating in the GHz range are produced. The energy harvesting application of the printed diodes is demonstrated in a flexible circuit coupling an antenna and the display to the diode.A second and simpler room-temperature method based on lamination was later developed, which further improves device performance and operational frequency. For the first time, a flexible semiconducting composite film consisting of Si micro-particles, glycerol, and nano-fibrillated cellulose is produced and used as the semiconducting layer of the UHF diode.The diodes fabricated through both mentioned processes are demonstrated in energy harvesting applications in the GHz range; however, they can also serve as rectifiers or non-linear elements in any other flexible and UHF circuit.Furthermore, a new approach is developed to induce non-linearity and hence addressability in linear devices in order to make their implementation in flexible matrix form feasible. This is accomplished by depositing a ferroelectric layer on a device electrode and thus controlling charge transfer through the electrode. The electrode current becomes limited to the charge displacement current established in the ferroelectric layer during polarization. Thus, the current does not follow the voltage linearly and non-linearity is induced in the device. The polarization voltage is dictated by the thickness of the ferroelectric layer. Therefore, the switching voltage of the device can be tuned by adjusting the ferroelectric layer thickness. In this work, the organic ferroelectric poly(vinylidene fluoride-co-trifluoroethylene) (P(VDF-TrFE)) is used due to its distinctive properties such as stability, high polarizability and simple processability. The polarization of P(VDF-TrFE) through an electrolyte and an electrophoretic liquid is investigated. In addition, a simple model is presented in order to understand the field and potential distribution, and the ferroelectric polarization, in the P(VDF-TrFE)-electrolyte contact. The induction of non-linearity through P(VDF-TrFE) is successfully demonstrated in novel addressable and bistable devices and memory elements such as non-linear electrophoretic display cells, organic ferroelectrochromic displays (FeOECDs), and ferroelectrochemical organic transistors (FeOECTs).
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| 5. |
- Ullah Khan, Zia, et al.
(author)
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Thermoelectric Polymers and their Elastic Aerogels
- 2016
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In: Advanced Materials. - : John Wiley & Sons. - 0935-9648 .- 1521-4095.
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Journal article (peer-reviewed)abstract
- Electronically conducting polymers constitute an emerging class of materials for novel electronics, such as printed electronics and flexible electronics. Their properties have been further diversified to introduce elasticity, which has opened new possibility for "stretchable" electronics. Recent discoveries demonstrate that conducting polymers have thermoelectric properties with a low thermal conductivity, as well as tunable Seebeck coefficients - which is achieved by modulating their electrical conductivity via simple redox reactions. Using these thermoelectric properties, all-organic flexible thermoelectric devices, such as temperature sensors, heat flux sensors, and thermoelectric generators, are being developed. In this article we discuss the combination of the two emerging fields: stretchable electronics and polymer thermoelectrics. The combination of elastic and thermoelectric properties seems to be unique for conducting polymers, and difficult to achieve with inorganic thermoelectric materials. We introduce the basic concepts, and state of the art knowledge, about the thermoelectric properties of conducting polymers, and illustrate the use of elastic thermoelectric conducting polymer aerogels that could be employed as temperature and pressure sensors in an electronic-skin.
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| 6. |
- Yang, Z. P., et al.
(author)
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Thiocholesterol on gold : A nanoporous molecular assembly
- 1996
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In: Langmuir. - : American Chemical Society. - 0743-7463 .- 1520-5827. ; 12:7, s. 1704-1707
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Journal article (peer-reviewed)abstract
- The formation of thiocholesterol (TC) monolayers on gold has been studied by ellipsometry, contact angle measurements, infrared spectroscopy, and cyclic voltammetry. Subsequent treatment of the TC assembly with 11-mercaptodeuterioundecanoic acid (MDUA) shows that the average surface coverage is about 65% of that of a self-assembled alkanethiolate monolayer and that it has a large number of molecular defects. These defects exist because of a mismatch between the size and shape of the TC molecule and the pinning distance at the Au(111) crystal lattice. Potential uses of these defect-rich structures are microelectrode arrays for electroanalytical and biosensor applications.
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