FABRICATION AND INVESTIGATION OF NANOSTRUCTURED MATERIALS USING ACCELERATED HEAVY-ION BEAMS Programme Advisory Committee for Condensed Matter Physics 31st meeting, January 2009 P.Yu.Apel Flerov Laboratory of Nuclear Reactions JINR

Experimental and theoretical investigations with ion beams in the field of material science and nanotechnology:  Investigations of effects of multiple charge ions with energies from  1 keV/u to  10 MeV/u on materials aiming at structure modification, radiation resistance testing, controlled alteration of practically important properties  Implantation-based synthesis of nano-structured materials with unique properties to be applied in electronics, optics, telecommunication, measurement technology, etc.  Investigation of micro- and nanopores produced by the ion track etching method in various materials, for the innovative applications in nanofluidics, sensor technology, modeling biological membranes, etc.  Development of new composite materials based on track membranes, produced by metal coating, plasma treatment, plasmo-chemical grafting, pore filling

Our instruments  Heavy ion accelerators U-400 IC-100 U-400M (a specialized channel to be commissioned in 2010)  Scanning electron microscope JSM-840  Transmission electron microscope EM-125K  Optical spectroscopy methods (in-situ ionoluminescence, etc)  Porometry methods (liquid flow porometry, etc) Due to co-operation with partners also available:  Ion microbeam (at GSI, Darmstadt)  Field emission scanning electron microscopy (Poland, USA, etc.)  High resolution transmission electron microscopy (Russia, USA, etc)  Atomic force microscopy (Russia, Hungary, etc)  Raman scattering, cathodoluminescence, photoluminescence (Russia, Moldova, etc)  X-ray diffractometry (Hungary)  Neutron small-angle scattering (FLNP JINR) (the list is far from being complete)

Ion-induced modification of SiO 2 films with Si nanocrystallites I.V. Antonova, A.G. Cherkov, V.A. Skuratov, M.S. Kagan, J. Jedrzejewski and I. Balberg. Low-dimensional effects in a three-dimensional system of Si quantum dots modified by high-energy ion irradiation. Nanotechnology, 20 (2009) (5pp). surface 30 нм Cross-sectional TEM images of ncSi-SiO 2 layers irradiated by cm −2 90 MeV Kr ions. The arrow shows the direction of the ion tracks. Atomic planes in the nanocrystallites of the irradiated sample are aligned along the ion tracks Ion irradiation makes it possible to modify optical properties of the nanocrystalline structure

Photoluminescence spectrum of ncSi-SiO 2 can be modified using heavy ion irradiation Irradiation: Kr, E = 90 МэВ, сm -2 Layer thickness: 1000 nm Optical properties of nanocrystalline Si in SiO 2 matrix: influence of heavy ion irradiation

Two-component ion-beam technique for production of the “silicon-on-insulator” structure RpRp Implantation of H ions Annealing at 300 o C Annealing at 400 o C BlisteringFlaking The principle can be applied to obtain large-area thin silicon slices that cannot be produced in different ways

Determination of range of slow heavy ions in light targets (Significant improvement of calculations’ precision) Green bars: V. Kuzmin, Nucl. Instr. and Meth. B 249 (2006) 13, ibid 256 (2007) 105, ibid 267 (2009) Experimental data by W. Takeuchi, N. Matsuda, Nucl. Instr. and Meth. B 266 (2008) 877. DFT - Density Functional Theory HF - Hartree-Fock Blue bars: SRIM code

Micro- and nanoporous materials Micrometers Nanometers “Making things small is a great deal today”

The use of track-etched membranes as model porous bodies Single-poreMany-poreOligo-pore Measurements of size and mobility of small particles Phenomena in superfluid helium Hindered diffusion of large and small molecules in capillary pores Fabrication of nanowires and nanotubes Biochemical sensors Magnetic sensors Modeling of biological channels Stimulus-responsive membranes Nanofluidics Molecular sensors Measurements of size and mobility of small particles Hindered diffusion of large and small molecules in capillary pores Fabrication of nanowires and nanotubes Biochemical sensors Magnetic sensors Gas inlet systems Attenuation of high energy particle flux Nanofluidics Phenomena in superconductivity Test theory of reverse osmosis Test model of phonon scattering Filtration of electromagnetic waves Hindered diffusion of large and small molecules in capillary pores Electron and ion field emitters Fabrication of nanowires and nanotubes Electrochemically switchable membranes Biochemical sensors Magnetic sensors Controlled release of particles (liposomes) Gas inlet systems Attenuation of high energy particle flux Modeling of biological channels Stimulus-responsive membranes Atomic beam optics DNA sequencing

Propagation of ultrasonic waves through track- etch membranes as model nanoporous bodies Transmission coefficient for ultrasonic waves propagating through cylindrical micro- and nanopores filled with air. Such measurements (1) make it possible to study the mechanism of ultrasound propagation in the porous space; (2) make it possible to develop non-invasive methods for characterizing and testing porous materials.

Track membranes: a unique possibility of control over the pore tortuosity All pores are perpendicular to surface All pores are tilted at 45 o Two pore arrays crossing each other at an angle of 60 о Two pore arrays crossing each other at an angle of 90 о Track membranes with pores oriented differently, offer a unique chance to study the influence of - tilt angle - presence of pore crossings - angle of pore crossing - number of pore crossings on the transmission of ultrasound through the pore space. tortuosity

Asymmetrical (shaped) nanopores Nanofluidic diode Modelling biological channels Molecular sensors in resistive-pulse technique Atomic beam optics

Exposure to UV light Polymer Latent tracks Photo-oxidized layer Fabrication of highly-asymmetrical nanopores NaOH + surfactant Micrometer scale Nanometer scale Apel P.Yu., Blonskaya I.V., Dmitriev S.N. et al. Nanotechnology, 2007, 18,

Properties of highly asymmetrical nanopores In electrolyte solutions, asymmetric ion-track nanopores resemble properties of biological ion channels: selectivity for cations over anions rectification of electrical current voltage-gating d  30 nm Maximum rectification at electrolyte concentrations typical of biological tissue

Ionic conductance properties of narrow channels can be studied depending on the shape and size of the nanopore. Track etching technique provides unique possibilities of control over geometrical characteristics of artificial nanopores having electrically charged pore walls Ionic selectivity is found to critically depend on the configuration of the narrow pore tip “Bad” rectifier “Good” rectifier Properties of highly asymmetrical nanopores

Atom beam nanolithography using highly asymmetrical track-etched nanopores FLNR JINR (Dubna) + Institute of Spectrosopy RAN (Troitsk) The method allows creation of a «nano- image» of a template with a reduction by a factor of 10 4 and a resolution of nm. At a pore density of 10 8 см -2, 100 million of identical images can be obtained in one exposure (“nano-cloning”) Track-etched membrane with the 30 nm profiled pores AFM-image of an object created using Cr atoms Balykin et al. JETP Letters, 2006

Further prospects: Asymmetrical track membranes with regular structure Irradiation in Darmstadt using microbeam Asymmetrical etching in Dubna

Polymer-polymer composites: development of organic light-emitting diodes Pores of a track membrane can be filled with a light- emitting polymer Flexible light- emitting panels can be created

Nanopore track membranes of Si 3 N 4 films for nanofluidics Irradiation with 710 MeV Bi ions

Nanopore track membranes of thin Si 3 N 4 films for nanofluidics A DC B Irradiation with Bi (Е = 710 МэВ, dE/dx = 35 кэВ/нм), etching with H 3 PO 4 at 150 о С. Unique radiation resistance of silicon nitride made it possible to produce pores as small a few nanometers in diameter I.Vlassiuk, P.Yu.Apel, S.N.Dmitriev et al. Proc. Nat Acad Sci., 2009, 106:

Nanopore track membranes of thin Si 3 N 4 films for nanofluidics Alexa Fluor 568 dye (МW  800) is retained by the nanoporous Si 3 N 4 membrane Rhodamine 123 (МW  400) is passing through the nanoporous Si 3 N 4 membrane Si 3 N 4 membrane

Separation of proteins (bovine serum albumine and immunoglobulin) using nanoporous Si 3 N 4 Diffusion of low-molecular weight fluorofore Diffusion of labeled BSA (МW=67кDa) Diffusion of labeled IgG (МW=150 кDa)

Collaborators Institute of Spectroscopy (Troitsk, Russia) A.V.Shubnikov Institute of Crystallography (Moscow, Russia) Das GSI Helmholtzzentrum (Darmstadt, Germany) Institute of Acoustics (Madrid, Spain) Institute of Nuclear Chemistry and Technology (Warsaw, Poland) California University (Irvine, CA, USA) Laboratory of Low-Dimensional Semiconductor Structures, Institute of Applied Physics (Moldova) Institute of Semiconductor Physics (Novosibirsk, Russia) Ioffe Physicotechnical Institute (St. Petersburg, Russia) Eötvös University (Budapest, Hungary) P.N.Lebedev Physical Institute of RAS (Moscow, Russia) Chemical Faculty, M.V.Lomonosov Moscow State University (Moscow, Russia) Institute of Nuclear Physics (Rez, Prague)

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