Graphene research in the Center of Physical Sciences and ... · Cholesterolis Testing of taster H H...
Transcript of Graphene research in the Center of Physical Sciences and ... · Cholesterolis Testing of taster H H...
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Prof. Rimantas Ramanauskas
Institute of Chemistry,
Center for Physical Sciences and Technology,
Vilnius, Lithuania
Brussels | May 15, 2017
Graphene research in the
Center of Physical Sciences
and Technology
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New scientific institution in Lithuania. (www.ftmc.lt)
CENTER FOR PHYSICAL SCIENCES AND TECHNOLOGY
Center for Physical Sciences and Technology
Institute of Chemistry Institute of Physics Institute of Semiconductor
Physics
Founded 1945
Organic chemistry, electrochemistry, metallic coatings
1956 – Institute of Physics -
Mathematics Founded in 1977
Expertise in: lasers technologies, nuclear
physics, environmental research, molecular physics
Science park 1993
Technology Centre - 1981
Founded 1967
Expertise in: optoelectronics, microwave
electronics, electrical engineering, solid state theory, fluctuation
phenomena
2010: State Founded Scientific Research Institute
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Center for Physical Sciences and Technology
Geography of the Sunrise valley
Sunrise Valley Technology and Innovation Centre: west part of Vilnius/ Savanoriai
Sunrise (Saulėtekis) VU+FTMC+VGTU // East part of Vilnius
VU: Laser technologies: Naglis
VGTU: Civil Engineering Research Centre
FTMC FTMC
Chemical technologies: Visoriai/ north part of Vilnius
FTMC: National Institute of Metrology: Goštauto/Lukiškių str. Central part of the city
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Brussels | May 15, 2017 1
Theoretical investgations
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Investigations of electron interaction in
graphene
2
E. Pileckis. Masther thesis,2016
Department of Molecular Compound Physics
Brussels | May 15, 2017
Hipotetic 2D spectrum. ωem is the emission
frequeny, ωexc – the excitation frequency.
The round peaks and diagonale depict
absorbance. Ovale part on the diagonale
shows inhomogeneous spreading. The
area far from the diagonale shows electrn
trasfer beween orbital levels. Dark area
above the diagonale depicts absorption to
higher level.
http://www.chemphys.lu.se/research/techni
ques/2Dspec/
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Investigations of electron interaction in
graphene
3 E. Pileckis. Masther thesis,2016
Department of Molecular Compound Physics Brussels | May 15, 2017
Influence of (as)symetrization. Upper part: Cut of the bloc of the symetric scatter matrix (qc = 0).
Lower part: Cut of the bloc of the assymetric scatter matrix (qc ≈ 0).
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Brussels | May 15, 2017 4
Synthesis
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Brussels | May 15, 2017 5
As grown - Cu
After transfer – SiO2
CVD growth
Department of Physical Technologies
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Brussels | May 15, 2017 6
Graphene transfer
Department of Physical Technologies
METAL FIRST Contact fabrication scheme
RTP anneal: T = 300 ºC t = 4 min Ar atmosphere Follow up: t = 1 h t= 2 h
Wet transfer after CU etch onto metal pattern
Spin coat PMMA
Au or Ni on Si/SiO2
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Brussels | May 15, 2017 7
Characterisation
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Ion-pairing at electrochemical interface:
SERS study of GO adsorption
8 Brussels | May 15, 2017
Graphene oxide
positively charged
negatively
charged
Department of Organic Chemistry
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GO adsorption on Au electrode modified by
positive charge bearing SAM:ion-pairing mechanism
9 Brussels | May 15, 2017
Au / MHP / GO
Au / MHP
Difference
spectrum
Au / GO
Au
Au / MHP / GO
Twofold function of monolayer:
1. Prevention from direct GO interaction with surface;
2. Electrostatic attraction Department of Organic Chemistry
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Mechanism of dependence of GO spectral
parameters on electrode potential
10 Brussels | May 15, 2017 Department of Organic Chemistry
Adsorbed GO might be used for sensing
the potential at interfaces
k=0.5 – 0.7 in the case of SWCNs
[J. Phys. Chem. 2009, p. 1340]
Changes in length of CC take place !
Charge transfer
per C atom
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Electrochemical SERS of GO adsorbed on
Au modified by positively charged SAM
11 Brussels | May 15, 2017 Department of Organic Chemistry
The reduced GO was prepared at Au modified by positive charge bearing SAM.
(D) and (G) linearly depend on E with slopes 4.7 ± 0.3 and 5.9 ± 0.3 cm-1/V,
respectively. The effect was explained in terms of changes in the CC bond length
induced by the electrochemical doping. This phenomenon might be explored in
analysis of the E in diverse environments.
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Enhanced microwave-to-terahertz
absorption in graphene
12 Brussels | May 15, 2017
K. Batrakov,et al. Appl. Phys. Lett. 108, 123101 (2016)
Department of Optoelectronics
Measured data. Dependence of (a) s-wave
and (b) p-wave transmittance through
graphene on substrate on frequency and
angle of incidence for one graphene layer film.
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Enhanced microwave-to-terahertz
absorption in graphene
13 Brussels | May 15, 2017
P.P. Kuzhir,et al. J. Nanophotonics. 11, 032511 (2017)
Department of Optoelectronics
SEM images of graphene hexagonal domains
corresponding to (a) 20 μm-GRA and
(c) 400 μm-GRA samples, when the synthesis
was stopped before graphene covered the
whole copper substrate. (b), (d) optical images
of graphene samples after chemical treatment
obtained according to technique proposed in
Ref. 28. The disks drawn with a thin dotted
line in (b) and (d) indicate the graphene
domains in case of small and large grain size
samples, respectively.
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Brussels | May 15, 2017 14
Modification
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Graphene oxide modification with
chitosan
15
Graphene oxide modification with chitosan
R. Celiešiūtė, et al., Chemija, 24 (2013) 296
Deapartment of Nanoengineering
O
HOHO
OH
NH2
OO O
O OO
OH
HOHNOH
HO+H2N
OH
HO OH
OH
n
HOOC
O-
OH
O
O
O
OH
OO
O
HO
Brussels | May 15, 2017
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Graphene oxide reduction
16
Deapartment of Laser Technology
Temperature distribution in the double zigzag structure of graphite oxide coating formed by localized laser reduction method measured by thermo-visual camera.
0.1 1 101
10
100
1000
GOUV
GO
Re
sis
tan
ce, k
Irradiation dose, J/cm2
• No need in complex heating systems (thermal GO reduction) or hazardous chemicals (chemical GO reduction);
• Controllable level of reduction; • Precise focusing and beam guiding
allows forming of complex patterns; • Scalability.
Graphite oxide (GO)
Graphite Oxidation using strong
oxidizing agents
Multilayer
Brussels | May 15, 2017
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Laser induced modification of
graphene/chitosan composites
17
Deapartment of Laser Technology
Laser treatment improves electrochemical characteristics of graphene/chitosan composite films which are used as electrodes for bio-sensing applications.
Graphene/chitosan
ITO
Glass
Focused laser beam
Laser induced changes in material properties
Brussels | May 15, 2017
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a
Cap
g
b c d
e f
Graphene-Alumina heterostructured films
with nanotube morphology
A. Jagminas, et. al.. J. Phys. Chem. C 120 (2016) 9490-9497.
Department of Electrochemical Materials Science
Porous alumina/graphene oxide film with non-typical
nanotubed morphology and cell caps at the surface side
were formed via anodizing of aluminium in the aqueous
solutions of organic acid at the critical current densities.
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Brussels | May 15, 2017 18
Applications
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Graphene contacts
19
Deapartment of Physical Technologies
Brussels | May 15, 2017
Graphene/gold and
Graphene/nickel
contacts
0 30 60 90 120
10
100
Rc,
k
m
t, min
Au/Gr
Ni/Gr
NiC/Gr
0 30 60 90 120
1
2
3
4
5
6
Au/Gr
Ni/Gr
NiC/Gr
Rsh,
k
/sq
t, min
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Deapartment of Physical Technologies
Graphene: Contact Annealing
Improvement of electrical contacts by annealing
Testing & Analysis explain the changes
due to annealing
Graphene Work Function, eV
Metallic Contact
Au (i)
Au (T)
Ni (i)
Ni (T)
p-type
n-type
Scanning Probe Microscopy
Tests by Kelvin Probe Force Micrsocopy
(KPFM)
Measured characteristics:
1) maps of the contact potential differencs
(CPD);
2) the work function of graphene on the
contact.
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Deapartment of Physical Technologies
Graphene: Contact Annealing
Improvement of electrical contacts by annealing
Raman spectra analysis: surface mapping for the 2G line:
the maps of the peak shift of the 2G line display the differences of
the interaction between metals and substrate.
Graphene on Ni annealed Graphene on Au annealed
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Development of graphene supported
catalysts
21 Deapartment of Catalysis Brussels | May 15, 2017
FOR FUEL CELLS
Direct Borohydride
Fuel Cells (DBFCs)
Direct Methanol Fuel
Cells (DMFCs)
Direct Ethanol Fuel
Cells (DEFCs)
Fabrication of graphene
powder supported
catalysts by means of
microwave synthesis:
non-noble M/graphene
catalysts (M = Co, Ni,
Cu, Fe, etc.)
Pt-M/graphene
catalysts (M = Co, Ni,
Cu, Fe, Mo, W, etc.)
Au-M/graphene
catalysts (M = Co, Ni,
Cu)
FOR HYDROGEN
GENERATION
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Development of graphene powder
supported catalysts
22
L. Tamašauskaitė-Tamašiūnaitė, et. al. “Metal/graphene
catalyst preparation method”. Lithuanian patent LT 6311
B (2016-09-12).
Deapartment of Catalysis Brussels | May 15, 2017
Microwave reactor Monowave 300
(Anton Paar).
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Development of graphene powder
supported catalysts
23 Deapartment of Catalysis Brussels | May 15, 2017
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Development of biosensors
Chip biosensors: Hardware and chip
24 R. Celiešiūtė, et al., Chemija, 24 (2013) 296
Deapartment of Nanoengineering
Brussels | May 15, 2017
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Sensor to ascorbate (vitamin C)
Sensor to ascorbate (vitamin C)
Graphene-chitosan
composite film
25
Ascorbic acid (vit. C)
OO
OHHO
HO
OH
Brussels | May 15, 2017
R. Celiešiūtė, et al., Chemija, 24 (2013) 296
Deapartment of Nanoengineering
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Biosensor for glucose
AFM image of
biosensor morphology
26
OHO
HO
OH
NH2
OO O
O OO
OH
HO NH2OH
HONH2
+
OH
HO OHOH
nO-
OH
O
OOO
OOO
HO
NH
NN
N
HN
HN
HOOC
-OOCO
O
NH
Testing of tasters
Venckus et al., Electroanalysis,26 (2014) 2273
Deapartment of Nanoengineering Brussels | May 15, 2017
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Biosensor for cholesterol
OHO
HO
OH
NH2
OO O
O OO
OH
HO NH2OH
HONH2
+
OH
HO OHOH
nO-
OH
O
OOO
OOO
HO
NH
NN
N
HN
HN
HOOC
-OOCO
O
NH
Calibration of biosensor in 0,1 M PB pH 7.0,
at -0.40 V vs Ag/AgCl
CH3
CH3CH3
CH3
CH3
HO
Cholesterolis
Testing of taster
HH
H
H
HO Cholesterol
27
Deapartment of Nanoengineering Brussels | May 15, 2017
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Biosensor for glutamate
OHO
HO
OH
NH2
OO O
O OO
OH
HO NH2OH
HONH2
+
OH
HO OHOH
nO-
OH
O
OOO
OOO
HO
NH
NN
N
HN
HN
HOOC
-OOCO
O
NH
Calibration of biosensor in 0,1 M PB pH 7.0,
at -0.40 V vs Ag/AgCl
CH3
CH3CH3
CH3
CH3
HO
Cholesterolis
Testing of taster
HH
H
H
HO Cholesterol
28
Celiešiūtė et al., Electroanalysis, in revision
Deapartment of Nanoengineering Brussels | May 15, 2017
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Projects related to graphene research
European Social Fund project via Global Grant Measure, No. VP1-3.1-ŠMM-07-K-01-124,Nano- and lasertechnology application to the investigation and modification of graphene and to the development and miniaturisation of (bio)sensors for food quality control. 2011-2015, 359 k€
Lithuanian Research Council project „Towards Future Technologies“, No. LAT 11/2016, Graphene supercapacitor powered FET all carbon circuit for sensing applications. 2016-2018, 299 k€
29
Brussels | May 15, 2017
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Thank you for your attention!