0000000000235061
AUTHOR
Juha Koivistoinen
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…
Time-Resolved Coherent Anti-Stokes Raman Scattering of Graphene: Dephasing Dynamics of Optical Phonon.
We report dynamics of the G-mode in graphene probed with time-resolved coherent anti-Stokes Raman scattering measurements. By applying BOXCARS excitation geometry with three different excitation wavelengths, various nonlinear processes can be selectively detected due to energy and momentum conservation and temporal sequence of the pulses. The Raman signal due to resonant coherent excitation of the G-mode shows exponential decay with lifetime of ∼325 ± 50 fs. This decay time is shorter than expected based on the line width of the G-mode in the Raman spectrum. We propose that the unexpectedly short dephasing time is a result of dynamic variation of nonadiabatic coupling of the photoexcited el…
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…
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 …
Modification of the supramolecular structure of [(thione)IY] (Y = Cl, Br) systems by cooperation of strong halogen bonds and hydrogen bonds
Four interhalogen complexes of heterocyclic thione ligands N-methylbenzothiazole-2-thione (mbtt) and 2(3)H-benzothiazole-thione (btt) with strong and tunable S⋯I halogen bonds were synthesized and characterized by X-ray single crystal diffraction. The study of the strength and nature of the interactions was supported by computational analysis using the Quantum Theory of Atoms in Molecules (QTAIM). Halogen bond and hydrogen bond directed self-assemblies of thione compounds were efficiently modified by the changes in the halogen bond donor and acceptor structures. In structures [(mbtt)ICl] (1) and [(mbtt)IBr] (2) the interplay of halogen bonds and hydrogen bonds between the thione hydrogens a…
Counterintuitive Mechanisms of the Addition of Hydrogen and Simple Olefins to Heavy Group 13 Alkene Analogues
The mechanism of the reaction of olefins and hydrogen with dimetallenes ArMMAr (Ar = aromatic group; M = Al or Ga) was studied by density functional theory calculations and experimental methods. The digallenes, for which the most experimental data are available, are extensively dissociated to gallanediyl monomers, :GaAr, in hydrocarbon solution, but the calculations and experimental data showed also that they react with simple olefins, such as ethylene, as intact ArGaGaAr dimers via stepwise [2 + 2 + 2] cycloadditions due to their considerably lower activation barriers vis-à-vis the gallanediyl monomers, :GaAr. This pathway was preferred over the [2 + 2] cycloaddition of olefin to monomeric…
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
On-chip purification via liquid immersion of arc-discharge synthesized multiwalled carbon nanotubes
Arc-discharge synthesized multiwalled carbon nanotubes (AD-MWNT) have been proven to be of high quality, but their use is very limited due to difficulties in obtaining them in a clean and undamaged form. Here, we present a simple method that purifies raw AD-MWNT material in laboratory scale without damage, and that in principle can be scaled up. The method consists of depositing raw AD-MWNT material on a flat substrate and immersing the substrate slowly in water, whereby the surface tension force of the liquid–substrate contact line selectively sweeps away the larger amorphous carbon debris and leaves relatively clean MWNTs on the substrate. We demonstrate the utility of the method by prepa…
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…
Time-Gated Raman Spectroscopy for Quantitative Determination of Solid-State Forms of Fluorescent Pharmaceuticals
Raman spectroscopy is widely used for quantitative pharmaceutical analysis, but a common obstacle to its use is sample fluorescence masking the Raman signal. Time-gating provides an instrument-based method for rejecting fluorescence through temporal resolution of the spectral signal and allows Raman spectra of fluorescent materials to be obtained. An additional practical advantage is that analysis is possible in ambient lighting. This study assesses the efficacy of time-gated Raman spectroscopy for the quantitative measurement of fluorescent pharmaceuticals. Time-gated Raman spectroscopy with a 128 X (2) X 4 CMOS SPAD detector was applied for quantitative analysis of ternary mixtures of sol…
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…
Harnessing Fluorescence versus Phosphorescence Ratio via Ancillary Ligand Fine-Tuned MLCT Contribution
A series of gold(I) alkynyl-diphosphine complexes (XC6H4C2Au)PPh2—spacer—PPh2(AuC2C6H4X); spacer = —C2(C6H4)nC2— (A1, n = 2, X = CF3; A2, n = 2, X = OMe; A3, n = 3, X = CF3; A4, n = 3, X = OMe), —(C6H4)n— (B5, n = 3, X = OMe; B6, n = 4, X = OMe) were prepared, and their photophysical properties were investigated. The luminescence behavior of the titled compounds is dominated by the diphosphine spacer, which serves as an emitting ππ* chromophore. The complexes exhibit dual emission, comprising low and high energy bands of triplet (phosphorescence) and singlet (fluorescence) origins, respectively. The electron-donating characteristics of ancillary groups X significantly affect the LLCT/MLCT c…
Non-linear interactions of femtosecond laser pulses with graphene : photo-oxidation, imaging and photodynamics
This thesis presents a study focused on interactions of femtosecond laser pulses with graphene, a one atom thick carbon membrane. Graphene, which exhibits exceptional electronic and optoelectronic properties, could provide considerable advantage over current silicon-based electronics. Graphene alone, being semi-metal, is not sufficient for electronic applications, but requires modification. For this, a set of methods for modifying and measuring the properties of graphene was developed. With the perspective of making graphene a suitable component for electronics, optoelectronics or photonics, ultrashort laser pulses were used for drawing patterns on graphene. The procedure modifies graphene …
Counterintuitive Mechanisms of the Addition of Hydrogen and Simple Olefins to Heavy Group 13 Alkene Analogues
The mechanism of the reaction of olefins and hydrogen with dimetallenes ArMMAr (Ar = aromatic group; M = Al or Ga) was studied by density functional theory calculations and experimental methods. The digallenes, for which the most experimental data are available, are extensively dissociated to gallanediyl monomers, :GaAr, in hydrocarbon solution, but the calculations and experimental data showed also that they react with simple olefins, such as ethylene, as intact ArGaGaAr dimers via stepwise [2 + 2 + 2] cycloadditions due to their considerably lower activation barriers vis-à-vis the gallanediyl monomers, :GaAr. This pathway was preferred over the [2 + 2] cycloaddition of olefin to monomeric…
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
CCDC 1583379: Experimental Crystal Structure Determination
Related Article: Ilya Kondrasenko, Kun-you Chung, Yi-Ting Chen, Juha Koivistoinen, Elena V. Grachova, Antti J. Karttunen, Pi-Tai Chou, Igor O. Koshevoy|2016|J.Phys.Chem.C|120|12196|doi:10.1021/acs.jpcc.6b03064