0000000000747723
AUTHOR
Andreas Johansson
Effect of humidity on the hysteresis of single walled carbon nanotube field-effect transistors
Single walled carbon nanotube field-effedt transistores (SWCNT FETs) are attributed as possible building blocks for future molecular electronics. But often these transistors seem to randomly display hysteresis in their transfer characteristics. One reason for this is suggested to be water molecules adsorbed to the surface of the gate dielectric in this study we investigate the thysteresis of SWCNT FETs at different relative humidities. We find that SWCNT FETs having atomic layer deposited (ALD) Hf0 2 -Ti0 2 .- Hf0 2 as a gate dielectric retain their. ambient condition hysteresis better in dry N2 environment than the more commonly used SiO 2 gate oxide.
Negative differential resistance in carbon nanotube field-effect transistors with patterned gate oxide.
We demonstrate controllable and gate-tunable negative differential resistance in carbon nanotube field-effect transistors, at room temperature and at 4.2 K. This is achieved by effectively creating quantum dots along the carbon nanotube channel by patterning the underlying, high-kappa gate oxide. The negative differential resistance feature can be modulated by both the gate and the drain-source voltage, which leads to more than 20% change of the current peak-to-valley ratio. Our approach is fully scalable and opens up a possibility for a new class of nanoscale electronic devices using negative differential resistance in their operation.
High-Yield of Memory Elements from Carbon Nanotube Field-Effect Transistors with Atomic Layer Deposited Gate Dielectric
Carbon nanotube field-effect transistors (CNT FETs) have been proposed as possible building blocks for future nano-electronics. But a challenge with CNT FETs is that they appear to randomly display varying amounts of hysteresis in their transfer characteristics. The hysteresis is often attributed to charge trapping in the dielectric layer between the nanotube and the gate. This study includes 94 CNT FET samples, providing an unprecedented basis for statistics on the hysteresis seen in five different CNT-gate configurations. We find that the memory effect can be controlled by carefully designing the gate dielectric in nm-thin layers. By using atomic layer depositions (ALD) of HfO$_{2}$ and T…
Patterning and tuning of electrical and optical properties of graphene by laser induced two-photon oxidation
Graphene, being an ultrathin, durable, flexible, transparent material with superior conductivity and unusual optical properties, promises many novel applications in electronics, photonics and optoelectronics. For applications in electronics, patterning and modification of electrical properties is very desirable since pristine graphene has no band gap. Here we demonstrate a simple all-optical patterning method for graphene, based on laser induced two-photon oxidation. By tuning the intensity of irradiation and the number of pulses the level of oxidation can be controlled to high precision and, therefore, a band gap can be introduced and electrical and optical properties can be continuously t…
Nonlinear photo-oxidation of graphene and carbon nanotubes probed by four wave mixing imaging and spectroscopy (Presentation Recording)
Graphene has high potential for becoming the next generation material for electronics, photonics and optoelectronics. However, spatially controlled modification of graphene is required for applications. Here, we report patterning and controlled tuning of electrical and optical properties of graphene by laser induced non-linear oxidation. We use four wave mixing (FWM) as a key method for imaging graphene and graphene oxide patterns with high sensitivity. FWM produces strong signal in monolayer graphene and the signal is highly sensitive to oxidation providing good contrast between patterned and non-patterned areas. We have also performed photo-oxidation and FWM imaging for air suspended carb…
Making Graphene Luminescent by Direct Laser Writing
Graphene is not intrinsically luminescent, due to a lack of bandgap, and methods for its creation are tricky for device fabrication. In this study, we create luminescent graphene patterns by a simple direct laser writing method. We analyze the graphene using Raman spectroscopy and find that the laser writing leads to generation of line defects after initial formation of point defects. This Raman data enables us to create a model that explains the luminescence by a formation of small domains due to confinement of graphene by line defects, which is conceptually similar to the mechanism of luminescence in graphene quantum dots. peerReviewed
Local photo-oxidation of individual single walled carbon nanotubes probed by femtosecond four wave mixing imaging
Photo-oxidation of individual, air-suspended single walled carbon nanotubes (SWCNTs) is studied by femtosecond laser spectroscopy and imaging. Individual SWCNTs are imaged by four wave mixing (FWM) microscopy under an inert gas (Ar or N2) atmosphere. When imaging is performed in an ambient air atmosphere, the decay of the FWM signal takes place. Electron microscopy shows that SWCNTs are not destroyed and the process is attributed to photoinduced oxidation reactions which proceed via a non-linear excitation mechanism, when irradiation is performed with ∼30 fs pulses in the visible spectral region (500-600 nm). Photo-oxidation can be localized in specific regions of SWCNTs within optical reso…
High-Speed Memory from Carbon Nanotube Field-Effect Transistors with High-κ Gate Dielectric
We demonstrate 100 ns write/erase speed of single-walled carbon nanotube field-effect transistor (SWCNT-FET) memory elements. With this high operation speed, SWCNT-FET memory elements can compete with state of the art commercial Flash memories in this figure of merit. The endurance of the memory elements is shown to exceed 104 cycles. The SWCNT-FETs have atomic layer deposited hafnium oxide as a gate dielectric, and the devices are passivated by another hafnium oxide layer in order to reduce surface chemistry effects. We discuss a model where the hafnium oxide has defect states situated above, but close in energy to, the band gap of the SWCNT. The fast and efficient charging and discharging…
Femtosecond four-wave-mixing spectroscopy of suspended individual semiconducting single-walled carbon nanotubes.
Femtosecond four-wave-mixing (FWM) experiments of individual suspended semiconducting single-walled carbon nanotubes (SWCNTs) are presented. The chiral indices of the tubes were determined by electron diffraction as (28,14) and (24,14) having diameters of 2.90 and 2.61 nm, respectively. The diameter and semiconducting character of the tubes were additionally confirmed by resonance Raman measurements. The FWM signal showed electronic response from the SWCNTs. The results demonstrate that ultrafast dynamics of individual SWCNTs can be studied by FWM spectroscopies.
Chemical composition of two-photon oxidized graphene
Chemical composition of two-photon oxidized single-layer graphene is studied by micrometer X-ray photoelectron spectroscopy (XPS). Oxidized areas with a size of 2 × 2 μm2 are patterned on graphene by tightly focused femtosecond pulsed irradiation under air atmosphere. The degree of oxidation is controlled by varying the irradiation time. The samples are characterized by four wave mixing (FWM) imaging and Raman spectroscopy/imaging. Micrometer-XPS is used to study local chemical composition of oxidized areas. XPS imaging shows good contrast between oxidized and non-oxidized areas. Gradual oxidation is observed from growth of signals attributed mainly to hydroxyl (Csingle bondOH) and epoxide …
Area‐Selective Atomic Layer Deposition on Functionalized Graphene Prepared by Reversible Laser Oxidation
Publisher Copyright: © 2022 The Authors. Advanced Materials Interfaces published by Wiley-VCH GmbH. Area-selective atomic layer deposition (ALD) is a promising “bottom-up” alternative to current nanopatterning techniques. While it has been successfully implemented in traditional microelectronic processes, selective nucleation of ALD on 2D materials has so far remained an unsolved challenge. In this article, a precise control of the selective deposition of ZnO on graphene at low temperatures (<250 °C) is demonstrated. Maskless femtosecond laser writing is used to locally activate predefined surface areas (down to 300 nm) by functionalizing graphene to achieve excellent ALD selectivity (up to…
Tuning protein adsorption on graphene surfaces via laser-induced oxidation
An approach for controlled protein immobilization on laser-induced two-photon (2P) oxidation patterned graphene oxide (GO) surfaces is described. Selected proteins, horseradish peroxidase (HRP) and biotinylated bovine serum albumin (b-BSA) were successfully immobilized on oxidized graphene surfaces, via non-covalent interactions, by immersion of graphene-coated microchips in the protein solution. The effects of laser pulse energy, irradiation time, protein concentration and duration of incubation on the topography of immobilized proteins and consequent defects upon the lattice of graphene were systemically studied by atomic force microscopy (AFM) and Raman spectroscopy. AFM and fluorescence…
Collective optical resonances in networks of metallic carbon nanotubes
Abstract We demonstrate that thin films of randomly oriented metallic single-walled carbon nanotubes possess optical resonances with significant dispersion. The resonances are observed in the Kretschmann configuration as minima in reflection spectra close to 400 nm and 700 nm wavelengths. The dispersions are visible only when the material is excited with s -polarized light, and most prominent in layers with thickness near 100 nm. We conclude that magnetic plasmon polaritons arising from intertube interactions are a likely explanation. Closeness of the M 11 and M 22 transition energies to the observed resonances points to a possible coupling with excitons.
Fabrication of carbon nanotube-based field-effect transistors for studies of their memory effects
Carbon nanotube‐based field‐effect transistors (CNTFETs) have been fabricated using nanometer thin dielectric material as the gate insulator film. The demonstrated fabrication technique is highly suitable for preparing devices with low contact resistances between the electrodes and the carbon nanotube, down to 14 kΩ. Electronic transport measurements of the fabricated devices have been conducted on more than 70 FETs. Hysteretic behavior in the transfer characteristics of some CNTFETs was observed.
Surface plasmon effects on carbon nanotube field effect transistors
Herein, we experimentally demonstrate surface plasmon polariton (SPP) induced changes in the conductivity of a carbon nanotube field effect transistor (CNT FET). SPP excitation is done via Kretschmann configuration while the measured CNT FET is situated on the opposite side of the metal layer away from the laser, but within reach of the launched SPPs. We observe a shift of 0.4 V in effective gate voltage. SPP-intermediated desorption of physisorbed oxygen from the device is discussed as a likely explanation of the observed effect. This effect is visible even at low SPP intensities and within a near-infrared range. peerReviewed
Optically Forged Diffraction-Unlimited Ripples in Graphene
In nanofabrication, just as in any other craft, the scale of spatial details is limited by the dimensions of the tool at hand. For example, the smallest details for direct laser writing with far-field light are set by the diffraction limit, which is approximately half of the used wavelength. In this work, we overcome this universal assertion by optically forging graphene ripples that show features with dimensions unlimited by diffraction. Thin sheet elasticity simulations suggest that the scaled-down ripples originate from the interplay between substrate adhesion, in-plane strain, and circular symmetry. The optical forging technique thus offers an accurate way to modify and shape two-dimens…
Laser-induced tuning of graphene field-effect transistors for pH sensing
Here we demonstrate, using pulsed femtosecond laser-induced two-photon oxidation (2PO), a novel method of locally tuning the sensitivity of solution gated graphene field-effect transistors (GFETs) without sacrificing the integrity of the carbon network of chemical vapor deposition (CVD) grown graphene. The achieved sensitivity with 2PO was (25 ± 2) mV pH−1 in BIS-TRIS propane HCl (BTPH) buffer solution, when the oxidation level corresponded to the Raman peak intensity ratio I(D)/I(G) of 3.58. Sensitivity of non-oxidized, residual PMMA contaminated GFETs was 20–22 mV pH−1. The sensitivity decreased initially by 2PO to (19 ± 2) mV pH−1 (I(D)/I(G) = 0.64), presumably due to PMMA residue remova…
Revealing lattice disorder, oxygen incorporation and pore formation in laser induced two-photon oxidized graphene
Abstract Laser induced two-photon oxidation has proven to be a reliable method to pattern and control the level of oxidation of single layer graphene, which in turn allows the development of graphene-based electronic and optoelectronic devices with an all-optical method. Here we provide a full structural and chemical description of modifications of air-suspended graphene during the oxidation process. By using different laser irradiation doses, we were able to show via transmission electron microscopy, electron energy loss spectroscopy, electron diffraction and Raman spectroscopy how graphene develops from its pristine form up to a completely oxidized, porous and amorphous carbon layer. Furt…
Real-time monitoring of graphene patterning with wide-field four-wave mixing microscopy
The single atom thick two-dimensional graphene is a promising material for various applications due to its extraordinary electronic, optical, optoelectronic, and mechanical properties. The demand for developing graphene based applications has entailed a requirement for development of methods for fast imaging techniques for graphene. Here, we demonstrate imaging of graphene with femtosecond wide-field four-wave mixing microscopy. The method provides a sensitive, non-destructive approach for rapid large area characterization of graphene. We show that the method is suitable for online following of a laser patterning process of microscale structures on single-layer graphene. peerReviewed
Second-harmonic Generation Microscopy of Carbon Nanotubes
We image an individual single-walled carbon nanotube (SWNT) by second-harmonic generation (SHG) and transmission electron microscopy and propose that SHG microscopy could be used to probe the handedness of chiral SWNTs.
From Seeds to Islands: Growth of Oxidized Graphene by Two-Photon Oxidation
The mechanism of two-photon induced oxidation of single-layer graphene on Si/SiO2 substrates is studied by atomic force microscopy (AFM) and Raman microspectroscopy and imaging. AFM imaging of areas oxidized by using a tightly focused femtosecond laser beam shows that oxidation is not homogeneous but oxidized and nonoxidized graphene segregate into separate domains over the whole irradiated area. The oxidation process starts from point-like “seeds” which grow into islands finally coalescing together. The size of islands before coalescence is 30–40 nm, and the density of the islands is on the order of 1011 cm–2. Raman spectroscopy reveals growth of the D/G band ratio along the oxidation. Sha…
Liquid-phase alkali-doping of individual carbon nanotube field-effect transistors observed in real-time
The carbon nanotube (CNT) is known to be very sensitive to changes in its surrounding environment. Our study is on the effects of mild, liquid-phase alkali-doping on electronic transport in individual CNTs. We find clear and consistent reversal from p- to n-type behavior, with all seven investigated CNT field-effect transistors (FETs) retaining a similar ON/OFF ratio and subthreshold slope. We have also measured the realtime electronic response during liquid-phase doping, and demonstrate detection of alkali cations with a signal response that ranges over more than three orders of magnitude. The doping is fully reversible upon exposure to oxygen, and the doping cycle is repeatable. We also c…
Ultrastiff graphene
Graphene has exceptionally high in-plane strength, which makes it ideal for various nanomechanical applications. At the same time, its exceptionally low out-of-plane stiffness makes it also flimsy and hard to handle, rendering out-of-plane structures unstable and difficult to fabricate. Therefore, from an application point of view, a method to stiffen graphene would be highly beneficial. Here we demonstrate that graphene can be significantly stiffened by using a laser writing technique called optical forging. We fabricate suspended graphene membranes and use optical forging to create stable corrugations. Nanoindentation experiments show that the corrugations increase graphene bending stiffn…
Reduction-oxidation dynamics of oxidized graphene: Functional group composition dependent path to reduction
Micrometer-sized oxidation patterns containing varying composition of functional groups including epoxy, ether, hydroxyl, carbonyl, carboxyl, were created in chemical vapor deposition grown graphene through scanning probe lithography and pulsed laser two-photon oxidation. The oxidized graphene films were then reduced by a focused x-ray beam. Through in-situ x-ray photoelectron spectroscopy measurement, we found that the path to complete reduction depends critically on the total oxygen coverage and concentration of epoxy and ether groups. Over the threshold concentrations, a complex reduction-oxidation process involving conversion of functional groups of lower binding energy to higher bindin…
Raman Spectroscopy and Low-Temperature Transport Measurements of Individual Single-Walled Carbon Nanotubes with Varying Thickness
We have investigated two metallic and one semiconducting individual single-walled carbon nanotubes (SWNT) and one bundle of two semiconducting nanotubes with a diameter range 1.1−2.9 nm with Raman spectroscopy and low-temperature electric transport measurements. With these two methods, we obtain mutually independent measurements on the basic properties of a specific nanotube. In particular, we obtain data on metallic and semiconducting properties. Evidence of a small band gap for one metallic tube was obtained. For the semiconducting SWNTs with diameters of 2.7−2.9 nm, a special resonance condition was observed which causes an anomalous intensity ratio for the two components of the G-band. …
Measurement of optical second-harmonic generation from an individual single-walled carbon nanotube
We show that optical second-harmonic generation (SHG) can be observed from individual single-walled carbon nanotubes (SWCNTs) and, furthermore, allows imaging of individual tubes. Detailed analysis of our results suggests that the structural noncentrosymmetry, as required for SHG, arises from the non-zero chiral angle of the SWCNT. SHG thus has potential as a fast, non-destructive, and simple method for imaging of individual nanomolecules and for probing their chiral properties. Even more, it opens the possibility to optically determine the handedness of individual SWCNTs.
Tuning protein adsorption on graphene surfaces via laser-induced oxidation
An approach for controlled protein immobilization on laser-induced two-photon (2P) oxidation patterned graphene oxide (GO) surfaces is described. Selected proteins, horseradish peroxidase (HRP) and biotinylated bovine serum albumin (b-BSA) were successfully immobilized on oxidized graphene surfaces, via non-covalent interactions, by immersion of graphene-coated microchips in the protein solution. The effects of laser pulse energy, irradiation time, protein concentration and duration of incubation on the topography of immobilized proteins and consequent defects upon the lattice of graphene were systemically studied by atomic force microscopy (AFM) and Raman spectroscopy. AFM and fluorescence…
From Seeds to Islands: Growth of Oxidized Graphene by Two-Photon Oxidation
The mechanism of two-photon induced oxidation of single-layer graphene on Si/SiO2 substrates is studied by atomic force microscopy (AFM) and Raman microspectroscopy and imaging. AFM imaging of areas oxidized by using a tightly focused femtosecond laser beam shows that oxidation is not homogeneous but oxidized and nonoxidized graphene segregate into separate domains over the whole irradiated area. The oxidation process starts from point-like “seeds” which grow into islands finally coalescing together. The size of islands before coalescence is 30–40 nm, and the density of the islands is on the order of 1011 cm–2. Raman spectroscopy reveals growth of the D/G band ratio along the oxidation. Sha…
Shaping graphene with optical forging: from a single blister to complex 3D structures
Properties of graphene, such as electrical conduction and rigidity can be tuned by introducing local strain or defects into its lattice. We used optical forging, a direct laser writing method, under an inert gas atmosphere, to produce complex 3D patterns of single layer graphene. We observed bulging of graphene out of the plane due to defect induced lattice expansion. By applying low peak fluences, we obtained a 3D-shaped graphene surface without either ablating it or deforming the underlying Si/SiO2 substrate. We used micromachining theory to estimate the single-pulse modification threshold fluence of graphene, which was 8.3 mJ cm−2, being an order of magnitude lower than the threshold for…
Multimodal nonlinear imaging of suspended carbon nanotubes using circular polarizations
In this work, multimodal nonlinear microscopy of suspended CNTs using circular polarizations (CP) was reported. Significant variations in the SHG and THG signals of the CNTs between left hand circular polarization (LHCP) and right hand circular polarization (RHCP) were observed. The variations in the nonlinear signals can be associated to the unique properties of the CNTs such as chirality.
Diversity at the nanoscale : laser-oxidation of single-layer graphene affects Fmoc-phenylalanine surface-mediated self-assembly
We report the effects of a laser-oxidized single layer graphene (SLG) surface on the self-assembly of amphiphilic gelator N-fluorenylmethoxycarbonyl-L-phenylalanine (Fmoc-Phe) towards an gel–SLG interface. Laser oxidation modulates the levels of hydrophobicity/hydrophilicity on the SLG surface. Atomic force, scanning electron, helium ion and scattering scanning nearfield optical microscopies (AFM, SEM, HIM, s-SNOM) were employed to assess the effects of surface properties on the secondary and tertiary organization of the formed Fmoc-Phe fibres at the SLG–gel interface. S-SNOM shows sheet-like secondary structures on both hydrophobic/hydrophilic areas of SLG and helical or disordered structu…
Preparation of graphene nanocomposites from aqueous silver nitrate using graphene oxide’s peroxidase-like and carbocatalytic properties
AbstractThe present study evaluates the role of graphene oxide’s (GO’s) peroxidase-like and inherent/carbocatalytic properties in oxidising silver nitrate (AgNO3) to create graphene nanocomposites with silver nanoparticles (GO/Ag nanocomposite). Activation of peroxidase-like catalytic function of GO required hydrogen peroxide (H2O2) and ammonia (NH3) in pH 4.0 disodium hydrogen phosphate (Na2HPO4). Carbocatalytic abilities of GO were triggered in pH 4.0 deionised distilled water (ddH2O). Transmission electron microscope (TEM), scanning electron microscope (SEM), cyclic voltammetry (CV) and UV-Vis spectroscopy aided in qualitatively and quantitatively assessing GO/Ag nanocomposites. TEM and …
Background-Free Second-Harmonic Generation Microscopy of Individual Carbon Nanotubes
We use polarized second-harmonic generation (SHG) microscopy to investigate pristine air-suspended carbon nanotubes (CNT). We show that SHG originates from CNT chirality, allowing also different response for the two circular polarizations of fundamental light.
Probing the Gelation Synergies and Anti-Escherichia coli Activity of Fmoc-Phenylalanine/Graphene Oxide Hybrid Hydrogel
The N-fluorenyl-9-methyloxycarbonyl (Fmoc)-protected amino acids have shown high antimicrobial application potential, among which the phenylalanine derivative (Fmoc-F) is the most well-known representative. However, the activity spectrum of Fmoc-F is restricted to Gram-positive bacteria only. The demand for efficient antimicrobial materials expanded research into graphene and its derivatives, although the reported results are somewhat controversial. Herein, we combined graphene oxide (GO) flakes with Fmoc-F amino acid to form Fmoc-F/GO hybrid hydrogel for the first time. We studied the synergistic effect of each component on gelation and assessed the material’s bactericidal activity on Gram…
Electronic transport in intermediate sized carbon nanotubes
We have studied systematically basic transport properties of multiwalled carbon nanotubes in a relatively unexplored diameter range, corresponding to tubes just slightly larger than single- or double-walled tubes to tubes up to 17 nm in diameter. We find in all the smaller tubes a gap in the transport data which increases with decreasing tube diameter. Within the gap region of several tubes, negative differential resistance was observed at small or moderate biases and at bias values that scaled inversely with the tube diameter. For this latter type of behavior of the conductance, we tentatively propose interlayer resonant tunneling as the cause.
Revealing lattice disorder, oxygen incorporation and pore formation in laser induced two-photon oxidized graphene
Laser induced two-photon oxidation has proven to be a reliable method to pattern and control the level of oxidation of single layer graphene, which in turn allows the development of graphene-based electronic and optoelectronic devices with an all-optical method. Here we provide a full structural and chemical description of modifications of air-suspended graphene during the oxidation process. By using different laser irradiation doses, we were able to show via transmission electron microscopy, electron energy loss spectroscopy, electron diffraction and Raman spectroscopy how graphene develops from its pristine form up to a completely oxidized, porous and amorphous carbon layer. Furthermore, …
Electronic transport measurements and Raman spectroscopy on carbon nanotube devices
An individual single wall carbon nanotube (SWCNT) device has been fabricated and measured using both low temperature transport and Raman measurements. With these mutually independent methods we can study the correlation between the techniques on semiconducting or metallic behavior of the tube. Furthermore, we study the structure of the nanotube by probing Raman measurements at different spots along the tube axis.
Optical Forging of Graphene into Three-Dimensional Shapes
Atomically thin materials, such as graphene, are the ultimate building blocks for nanoscale devices. But although their synthesis and handling today are routine, all efforts thus far have been restricted to flat natural geometries, since the means to control their three-dimensional (3D) morphology has remained elusive. Here we show that, just as a blacksmith uses a hammer to forge a metal sheet into 3D shapes, a pulsed laser beam can forge a graphene sheet into controlled 3D shapes in the nanoscale. The forging mechanism is based on laser-induced local expansion of graphene, as confirmed by computer simulations using thin sheet elasticity theory. peerReviewed
Triggering a transient organo-gelation system in a chemically active solvent
A transient organo-gelation system with spatiotemporal dynamic properties is described. Here, the solvent actively controls a complex set of equilibria that underpin the dynamic assembly event. The observed metastability is due to the in situ formation of a secondary solvent, acting as an antagonist against the primary solvent of the organogel. peerReviewed