Solvent-less synthesis of organic photonic nanocomposite thin films by remote plasma assisted vacuum deposition.
Institute of Materials Science of Seville
Spanish National Research Council (CSIC)-University of Seville, Spain
Francisco J. Aparicio [email protected] http://www.sincaf.icmse.csic.es/
Plasma deposition of heterogeneous nanostructures with photoactivity
International School on Low Temperature Plasma Physics: Basics and Applications
October 8th 2016
The 1D morphology enables the modulation of the longitudinal or radial composition and structure
Core@shell Hierarchical nanostructures Nanotrees Segmented NWs Homojunctions Heterojunctions Multibranched NWsQDs and MNPs decorated NWs
Enhanced properties / multifunctional systems
Advanced materials for electronics photonics, catalysis, sensing, enegygeneration
WHY 1D NWs, NRs, NBs, NFs??
QDs decorating TiO2 NTs
Single Wire Solar Cells
Briseno et al. JACS 2010, Nano Letters 2011
Examples of Plasma Generated NanoStructures
Silicon QDs; Silicon nanograss.Silicon Solar CellsCheng JMC 2010Xiao J. Phys. D: Appl. Phys. 2011
Low temperature growth of CNTs and CNFsVertical alignment Kato CVD 2006, Science 2003
Graphene
nansheetsand carbon
nanowalls
Ostrikov
Nanoscale
2011
Water repellentCNT-NanocarpetsOstrikov APL 2009
Atmospheric-pressure plasma jetsto improve wound and cancer treatment. Levchenko et al.
Soft organic nanostructures by plasma processingRossi Small 2007
OUTLINE
PECVD of Nanostructured Thin FilmsAd‐species MobilityShadowing
PECVD of 1D HomostructuresMetal Catalyst NanoparticlesPlasma sheath
1D Heterostructures Core@Shell Metal@MetalOxideNanofibersNanorods
1D Heterostructures Core@Shell Oganic@MetalOxide
OUTLINE
PECVD of Nanostructured Thin FilmsAd‐species MobilityShadowing
PECVD of 1D HomostructuresMetal Catalyst NanoparticlesPlasma sheath
1D Heterostructures Core@Shell Metal@MetalOxideNanofibersNanorods
1D Heterostructures Core@Shell Oganic@MetalOxide
PECVD REACTOR (MW-ECR)
TTIP
TiC12H28O4
REMOTE CONFIGURATION
Pressure 10-2-10-3 torr
Journal of The Electrochemical Society (2007), 154, 152
PECVD of Homogenous Nanostructured Thin Films
Expe
rimen
tal S
et-u
p an
d m
ater
ials
Titanium tetraisopropoxide
TiO2 Micro/Nanostructures
Antireflective coatings
Self cleaning surfaces
Separation Membranes
Solar Cells (Grätzel)
Biomaterials
Gas and Humidity Sensors
TiO2: White photoactive compound,Amorphous, or crystalline structure (anatase, rutile)
Controlled Refractive index
High biocompatibility Low cost Good stability and adhesion
High transparency in the visible
PECVD of Homogenous Nanostructured Thin Films
Expe
rimen
tal S
et-u
p an
d m
ater
ials
TiO2 Micro/Nanostructures
Antireflective coatings
Self cleaning surfaces
Separation Membranes
Solar Cells (Grätzel)
Biomaterials
Gas and Humidity Sensors
TiO2: White photoactive compound,Amorphous, or crystalline structure (anatase, rutile)
PECVD of Homogenous Nanostructured Thin Films
Expe
rimen
tal S
et-u
p an
d m
ater
ials
Most important processes taking place during the thin film formation
Plasma
formation of highly reactive species
Fund
amen
tals
PECVD of Homogenous Nanostructured Thin Films
100%O2‐298K 10%O2 25ºC
200nm
500nm
Pure O2 Discharge Ar/O2 DischargeColumnar or dense compact structures can be obtained depending on the plasma gas composition
100%O2 25ºC
500nm
500nm
Plasma Chemistry
Growth Mode
Nanostructure
298 K 100% O2 10% O2
Deposition rate (nm/min) 5 2.4
Journal of The Electrochemical Society 154 (2007) 152
PECVD of Homogenous Nanostructured Thin Films
100%O2‐298K 10%O2 25ºC
200nm
500nm
Pure O2 Discharge Ar/O2 DischargeColumnar or dense compact structures can be obtained depending on the plasma gas composition
100%O2 25ºC
500nm
500nm
298 K 100% O2 10% O2
Deposition rate(nm/min) 5 2.4
Journal of The Electrochemical Society 154 (2007) 152
PECVD of Homogenous Nanostructured Thin Films
Key Factors:
Shadowing
Ad‐species mobility
Shad
owin
g ef
fect
Progress in Materials Science 76 (2016) 59
Glancing Angle Deposition (GLAD)in a Physical Vapour Deposition (PVD) system
TiO2 by e‐ beam evaporation
Ballistic Models
P < 10‐4 torrmean free path > source‐substrate distance
PECVD of Homogenous Nanostructured Thin Films
Directional deposition flux
Shad
owin
g ef
fect
J. Am. Chem. Soc. 130 (2008), 14755Progress in Materials Science 76 (2016) 59
PECVD of Homogenous Nanostructured Thin Films
Non‐Directional deposition flux
Initi
al g
row
th s
tage
s
A minimum thickness threshold is required to induce the columnar growth
Surface roughness Shadowing effect Microporous and Mesoporous Materials 160 (2012) 1.
PECVD of Homogenous Nanostructured Thin Films
100%O2 25ºC
Diff
usio
n ra
te o
f the
ad-
spec
ies
Monte Carlo Simulation by increasing the diffusion rate (D) of ad‐species
Microporous and Mesoporous Materials 160 (2012) 1.
High diffusion rates preclude the columnar growth by shadowing
PECVD of Homogenous Nanostructured Thin Films
Isotropic flow
Normal Columnar growth
Plas
ma
chem
istr
y (O
ES)
400 500 600 700 800 900
I (u.
a.)
(nm)
100% O2
TiO*Ti*,TiO*
O2+
O
O2+
O
O
O2+, O, Ti, TiO
400 500 600 700 800 900
I (u.
a)
(nm)
10% O2
Ar*, H*
H
More intense fragmentation
Reactive species Ti(high sticking coefficient)
Low surface mobility at the growing surface
Lack of Ti or O2 emission lines
The precursor is just partially decomposed TiOXCYHZ
High surface mobility at the growing surface
PECVD of Homogenous Nanostructured Thin Films
Columnar Growth Dense Thin films
100% O2
Plasma generation of high‐sticking‐coefficient species
(low mobility)
Shadowing
Gro
wth
Mod
e
Columnar Growth
500nm
PECVD of Homogenous Nanostructured Thin Films
Gro
wth
Mod
e10% O2
TiOXCYHZ (high mobility)
200nm
Dense Structure
PECVD of Homogenous Nanostructured Thin Films
Cry
stal
line
Mic
rost
ruct
ures
100%O2 25º C 100%O2 250º C
At high deposition temperature the microstructure is controlled by the development of the crystalline phase
500nm
500nm
500nm
500nm
XRD
PECVD of Homogenous Nanostructured Thin Films
Crystal Growth & Design 9 (2009) 2869
Cry
stal
line
Mic
rost
ruct
ures
10%O2 25 ºC
200nm
500nm
10%O2 250 ºC
200nm
200nm
XRD
PECVD of Homogenous Nanostructured Thin Films
At high deposition temperature the microstructure is controlled by the development of the crystalline phase
Crystal Growth & Design 9 (2009) 2869
Cry
stal
line
Mic
rost
ruct
ures
PECVD of Homogenous Nanostructured Thin Films
Microporous and Mesoporous Materials 118 (2009) 314–324
Crystallization
OUTLINE
PECVD of Nanostructured Thin FilmsAd‐species MobilityShadowing
PECVD of 1D HomostructuresMetal Catalyst NanoparticlesPlasma sheath
1D Heterostructures Core@Shell Metal@MetalOxideNanofibersNanorods
1D Heterostructures Core@Shell Oganic@MetalOxide
How can we promote the development of 1D nanostructures?
Rev. Mod. Phys. 77 (2005) 489Advances in Physics 62 (2013) 113
PECVD of 1D Nanostructures
Key
Fac
tos
Surface inhomogeneitiesare used to induce the development 1D supported NS
Shadowing effects Diffusion rate of the
ad‐species
Heterogeneous catalytic reactions.
(metal nanoparticles)
Inhomogeneities in the plasma sheath.
Plasma induced surface reaction
Key Factors:
Vapour deposition
CVD and PECVD
PECVD
PECVD of 1D Nanostructures
Rev. Mod. Phys. 77 (2005) 489 and Advances in Physics 62 (2013) 113
Metallic nanoparticles the preferred nucleation seed for the growth of 1D nanostructures
Advances in Physics 62 (2013) 113 J. Vac. Sci. Technol. B 31 (2013) 050801
Silicon Nanowires
Carbon nanotubes
PECVD of 1D Nanostructures
The vapor–liquid–solid process:Thermal growth of metal-catalyzed semiconductorNanowires (CVD and PECVD processes)
1 Thermal activated catalytic dissociation (DIS) of the source gas on the surface of the metal particles(Substrate temperature > 300 ºC)
2 Surface diffusion (SD) of generated ad-species
3 Incorporation (INC) of the ad-species into the growing structure.
LAP: loss of adsorbed particles at interaction with atomic hydrogen
Journal of applied physics 104 (2008) 073301 J. Appl. Phys. 94 (2003) 6005
PECVD of 1D NanostructuresM
etal
lic C
atal
yst f
or th
e gr
owth
of 1
D N
W
The vapor–liquid–solid process:Thermal growth of metal-catalyzed semiconductorNanowires (CVD and PECVD processes)
1 Thermal activated catalytic dissociation (DIS) of the source gas on the surface of the metal particles(Substrate temperature > 300 ºC)
2 Surface diffusion (SD) of generated ad-species
3 Incorporation (INC) of the ad-species into the growing structure. Plasma Effects:
*Ionization/activation of the incoming species*Local surface heating of the Nanoparticles.
Higher dissociation and diffusion LAP: loss of adsorbed particles at interaction with atomic hydrogen
Journal of applied physics 104 (2008) 073301 J. Appl. Phys. 94 (2003) 6005
PECVD of 1D NanostructuresM
etal
lic C
atal
yst f
or th
e gr
owth
of 1
D N
W
Plasma sheath effects
Plas
ma
Shea
th
Phys. D: Appl. Phys. 40 (2007) 2308
Surface inhomogeneities modulates the drop of potential along the plasma sheath
Focalization of the ion current
PECVD of 1D Nanostructures
OUTLINE
PECVD of Nanostructured Thin FilmsAd‐species MobilityShadowing
PECVD of 1D HomostructuresMetal Catalyst NanoparticlesPlasma sheath
1D Heterostructures Core@Shell Metal@MetalOxideNanofibersNanorods
1D Heterostructures Core@Shell Oganic@MetalOxide
Metallic substrates Organic fibers
Thin films
1D Nanostructures
D < 100 nm (2D)
NANOPOROS500nm500nm
Template assisted growth on
PECVD: From Thin Films to Heterogeneous 1D Nanostructures
Core@ShellNanostrucutres
2
Metallic substrates Organic fibers
Thin films
1D Nanostructures
D < 100 nm (2D)
NANOPOROS500nm500nm
Template assisted growth on
PECVD: From Thin Films to Heterogeneous 1D Nanostructures
Core@ShellNanostrucutres
500nm
PECVD on Metallic Substrates
PECVD on Metallic Substrates
500nmCrystalline TiO2 250º C growth on a silver layer
The film microstructure is completely different on the silver covered zone than on the bare silicon substrate.
J. Phys. D: Appl. Phys. 44 (2011) 174016
Amorphous TiO2
SEs
BSE
Crystalline TiO2 (250º C)500nm
500nmAmorphous TiO2 (130º C)on Si Preferential growth on
Metallic nanoparticles
J. Phys. D: Appl. Phys. 44 (2011) 174016
Preferential Growth on Metal NanoParticles (MNP)
Conductive nanoparticles
Local inhomogeneities in the electrical field of the plasma sheath.
Focusing of the positive ion current to the metal nanoparticle
Metal induced catalytic processes
Shadowing (neutral species)
500nm
Preferential Growth on Metal NanoParticles (MNP)
500nm
Growth of Metal@Metal‐Oxide Nanofibers
1) Plasma oxidation a silver Membrane at > 130 ºC
Nanotechnology 17 (2006) 3518Plasma Process. Polym. 4 (2007) 515
Formation of supported core@shell (metal/oxide(Ag@TiO2)) NanoFibers (NF)
2) Plasma deposition of TiO2 > 130 ºC
2‐step process
Insi
ght o
n th
e gr
owth
mod
e
SEM micrographs from a silver foil after different times of oxygen plasma treatment at 130º C. a) 20 min exposure, b) 60 min exposure, c) 120 min exposure, and d) high magnification image from sample (c).
Plasma oxidation induce the formation of heterogeneous structures
Nanotechnology 17 (2006) 3518Plasma Process. Polym. 4 (2007) 515
Formation of supported core@shell (metal/oxide(Ag@TiO2)) NanoFibers (NF)
Internal stress at the Ag/Ag2O/AgO interfaces
Molar volumes of silver oxide and metallic silver, are in an ratio of 1:1.6:1.6 for Ag, Ag2O, and AgO,
Insi
ght o
n th
e gr
owth
mod
e
Prolonged plasma oxidation pre‐treatment
Detection of Ag nanoparticles in the outer shell
Short Plasma TiO2 deposition
Diffusion of Ag to the outer shell at least the first growth
stages
Nanotechnology 17 (2006) 3518Plasma Process. Polym. 4 (2007) 515
Formation of supported core@shell (metal/oxide(Ag@TiO2)) NanoFibers (NF)
Insi
ght o
n th
e gr
owth
mod
e
Diffusion of Ag essential for the NF growth
Non Fiber formation
In‐situ XPS Analysis
Nanotechnology 17 (2006) 3518Plasma Process. Polym. 4 (2007) 515
Formation of supported core@shell (metal/oxide(Ag@TiO2)) NanoFibers (NF)
Ag2O + TiO(CxHy) Ag + TiO2 + CO2 + H2OAg2O + TiO(Ti) Ag + TiO2
Ag2O
TiO2 Ag
Single fibre growth Stages
Proposed chemical reactions
Nanotechnology 17 (2006) 3518Plasma Process. Polym. 4 (2007) 515
Formation of supported core@shell (metal/oxide(Ag@TiO2)) NanoFibers (NF)
Plasma oxidation pre‐treatment
Heterogeneous metallic and a oxidized Ag structures
PECVD TIO2 deposition is enhanced at the Ag2O NPs
plasma sheath inhomogeneities+
The presence of Ag2O
Ag2O + TiO(CxHy) Ag + TiO2 + CO2 + H2OAg2O + TiO(Ti) Ag + TiO2
Stress accumulated in the external layers of the oxygen‐plasma‐treated silver is released by the formation
of a silver wire
NFs only develop at 130º C
TiO2 deposition occurs preferentially on the wire walls and significantly at its tip
plasma sheath effects
+
Migration of Ag and Ag Plasma oxidation
Formation of supported core@shell (metal/oxide(Ag@TiO2)) NanoFibers (NF)
Generalization of the formation of M@MOx (M: Ag, Au @MOx: Si, Ti, Zn) 1D NS
Metal@Metal Oxide NanoStructuresGrowth on Metal
layers
Ag@TiO2/SiO2
Ag@SiO2
Au@TiO2
Ag@ZnO
J. Phys. D: Appl. Phys. 44 (2011) 174016
500nm
Growth of Metal@Metal‐Oxide Nanorods
Supported Ag@TiO2 NanoRods
DC‐ sputtering of Ag NanoParticles
J. Phys. D: Appl. Phys. 44 (2011) 174016
Supported Ag@TiO2 nanoRods
Plasma Oxidation at 130 ºC
Non Plasma O2 oxidation at 130 ºC provides a more regular distribution
J. Phys. D: Appl. Phys. 44 (2011) 174016
DC‐ sputtering of Ag NanoParticles
Plasma Process. Polym. 11 (2014) 164
Supported Ag@TiO2 NanoRods
TEM and ToF‐SIMS characterization of Ag@TiO2 NanoRods
J. Phys. D: Appl. Phys. 44 (2011) 174016Plasma Process. Polym. 11 (2014) 164
Plasma deposition of TiO2 > 130 ºC
Supported Ag@TiO2 and Ag@ZnO NanoRods
SEs BSEAg
@TiO
2Ag
@Zn
O
limited amount of silver available
inhomogeneous inner core formed by the agglomeration of small nuclei silver
Tilte
d N
R
3D reconstruction of the Ag@ZnONanoRods
HAADF-STEM 3D tomographic reconstruction
J. Mater. Chem. 22 (2012) 1341
Supported Ag@ZnO NanoRods
Supported Ag@ZnO NanoRods
SEs BSEAg@ZnO
Ag Nanoparticles in the Nanorod shells
Do they paly a key roll?
Used precursor Diethylzinc (ZnEt2)
Insi
ghts
in th
e gr
owth
mec
hani
sm
Supported Ag@ZnO NanoRods
Nanotechnology 23 (2012) 255303
In situ XPS during exposure of a silver layer to oxygen and ZnEt2
(1) Heating the metallic silver layer under oxygen plasma.
(2a) Exposure of the oxidized silver layer to the ZnEt2 precursor at room temperature chemically reduce the oxidized silver layer, rendering metallic silver andleading to the formation of a ZnO overlayer
(2b) Heating at 132º C in oxygen did not induce any significant change either in the chemical state of the different elements or in the relative intensity of the peaks.(2c) Upon exposure to an oxygen plasma at 132 ºC in (2c), silver becomes reoxidized and a complete reversal of the Zn=Ag intensity ratio occurred. the silver oxide is very mobile and
diffused to cover the ZnO surface were become reoxidazed
Non
‐plasm
a expe
rimen
ts
Insi
ghts
in th
e gr
owth
mec
hani
sm
Supported Ag@ZnO NanoRods
Nanotechnology 23 (2012) 255303
In situ XPS during exposure of a silver layer to oxygen and ZnEt2
(3)‐(6) plasma depositions of ZnO at 132 ºC produced an increase in the amount of deposited ZnO, while surface silver remained oxidized as in (2c).
Insi
ghts
in th
e gr
owth
mec
hani
sm
Supported Ag@ZnO NanoRods
Nanotechnology 23 (2012) 255303
plasma sheath effects / shadowing effects
+
Plasma regenerated AgOx/ZnEt2 surface reactionsPlasma oxidation
i) The oxidized silver layer act as nucleation points for the NRs formation
Insi
ghts
in th
e gr
owth
mec
hani
sm
Supported Ag@ZnO NanoRods
Nanotechnology 23 (2012) 255303
ii) the diffusion of silver or silver oxide to the outer shell contribute to growth of the nanostructure
iii) and IV) most silver has been removed from the substrate layer to decorate the ZnOphase.
Tilte
d N
R The Growth direction is driven by the precursor flow
mean free path similar to the dispenser‐substrates distance
Supported Ag@TiO2 NanoRods
Plasma Process. Polym. 11 (2014) 164
Tilte
d N
R
Supported Ag@ZnO NanoRods
Tilted and zig‐zag structures
Nanotechnology 23 (2012) 255303
NanoRods Photoactivity
TiO2 and ZnO: Wide band gap semiconductor with photoactive response under UV illumination
Intr
insi
c pr
oper
ties
Energy Environ. Sci. 5 (2012) 7491
When a semiconductor is irradiated by light of sufficient energy, electrons are excited from the valence band of the semiconductor to the conduction band
Photo‐generation of charge carriers
photocurrents of TiOx thin films during an on–offUV light irradiation cycle
NanoRods Photoactivity
Intr
insi
c pr
oper
ties
Energy Environ. Sci. 5 (2012) 7491
The generated photocarriers migrate to the surface where they are able to reduce and oxidize adsorbed electron acceptors and donors by interfacial charge transfer
Application example: Hydrophilic‐ Super hydrophilic conversion under UV illumination
One of the proposed mechanisms
Applications: Self cleaning sistems. Microfluidics Lab‐on‐a‐chip
Wat
er C
onta
ct A
ngel
Mea
sure
men
ts
θ<90ºHydrophilic
θ>90ºHydrophobic
θ>150ºSuperhydrophobic
LV
SVSL
γ: Interfacial Energy per unit area (surface tension)SV: Solid-VapourLV: Liquid-VapourSL: Solid-Liquid
In flat materials the contact angel depends on the surface composi on → γSL
Nanorods Photoactivity
Energy Environ. Sci. 5 (2012) 7491
Macroscopically, the wettability of solids can be determined bymeasuring the contact angle, which is defined as the angle between the solid surface and the tangent line of the liquid at the contact point between the three phases
Wat
er C
onta
ct A
ngel
Mea
sure
men
tsThe surface structure also has a strong impact on the wettability
Θa: “Apparent” contact angleΘs: Material contact angler: roughness factor (Wenzel)fs: fraction of liquid in contact with the solid
Wenzel Model: Applicable when the liquid penetrates into thegrooves of the rough surface
Nanorods Photoactivity
Energy Environ. Sci. 5 (2012) 7491
Cassie and Baxter Model: the liquid does not penetrates and to vapor pockets underneath the liquid are formed
Contac angle increase due to the microstructure
Hydrophilic material → Smaller CAHydrophobic material → Larger CA
Ag@
TiO
2N
anor
ods
Super hydrophobic Ag@TiO2 NanoRods
Fast Superhydrophobic /Superhydrophilicconversion under UV illumination
Nanorods Photoactivity
Plasma Process. Polym. 11 (2014) 164
Dense films
Ag@
ZnO
Nan
orod
s
Nanorods Photoactivity
Au‐NP NanoRods with photoactivity in the visible range
Fast Superhydrophobic /Superhydrophilic conversion under UV illumination
Super hydrophobic Ag@ZnO NanoRods
J. Mater. Chem. 22 (2012) 1341
OUTLINE
PECVD of Nanostructured Thin FilmsAd‐species MobilityShadowing
PECVD of 1D HomostructuresMetal Catalyst NanoparticlesPlasma sheath
1D Heterostructures Core@Shell Metal@MetalOxideNanofibersNanorods
1D Heterostructures Core@Shell Oganic@MetalOxide
Hybrid ONW@MetalOxide Nanowires
Fabr
icat
ion
appr
oach
Plasma Source
Gas input DEZ input
Quartz balance
Thermal evaporator
Pumping system
Rotating sample holder
Growing process
a) Nucleation
b) ONW
c) Core@shell
ZnO Plasma conditions:T = RT – 200oCp = 10‐3 – 10‐6 mbarP = 400 – 800WGases: Ar, O2, H2
Metallic NP or columnar TiO2
Adv. Funct. Mater. 23 (2013) 5981
OU
TLIN
E
PECVD of Organic NanoWires (ONW)
Ag NPs on Si(100)
PtOEP NWs
Self-assembly by π-stacking
Physical Vapour deposition of ONW
Langmuir 26 (2010) 5763
Organic Nanowires (ONW)
Zinc phthalocyanine
Columnar ZnOthin film growth on a flat substrate
Hybrid Nanowires
ONW@ZnO
Hybrid ONW@MetalOxide Nanowires
Adv. Funct. Mater. 23 (2013) 5981
Hybrid ONW@MetalOxide Nanowires
Conformal growth of the semiconductor shell over the organic core
Adv. Funct. Mater. 23 (2013) 5981
Hybrid ONW@MetalOxide Nanowires
Hybrid nanowires with different inorganic shells
Adv. Funct. Mater. 23 (2013) 5981 Scientific Reports 6 (2016) 20637
Hybrid ONW@MetalOxide Nanowires
Hybrid nanowires with different inorganic shells
10%O2‐298K
100%O2‐298KThin film on a flat substrate
Adv. Funct. Mater. 23 (2013) 5981 Scientific Reports 6 (2016) 20637
Hybrid ONW@MetalOxide Nanowires
Vertical alignment due to plasma sheath
Charge accumulation at the ONW tips Coulomb Repulsion
Alignment of the flexible ONW
Growth of a rigid inorganic shell
Adv. Funct. Mater. 23 (2013) 5981
Hybrid ONW@MetalOxide Nanowires Photoactivity
Initial WCA
Dense TiO2 films < 90º
Ag@TiO2 Nanorods 150 º
ONW@TiO2Nanowires
180 º
Fast Superhydrophobic/Superhydrophilicconversion under UV illumination
Hybrid ONW@MetalOxide NanowiresNan
oMem
bran
esfor liquid‐liq
uid sepa
ratio
n
NANOMEMBRANE
Fluidic separation based in nanometric structures.
Applications:
Microbiology (pharmaceutical industry)
Food industry
Water filtration
Nanoelectronics (sensing, microfluidics cells ).
PLoS ONE 9 (2014) e89712 Thermal Science 19 (2015) 1267
Hybrid ONW@MetalOxide Nanowires
ONW@TiO2 Oxide over metallic filters
3 um
Nan
oMem
bran
esfor liquid‐liq
uid sepa
ratio
nMaster Thesis, José Mª Román Cabrerizo, University of Seville
Hybrid ONW@MetalOxide Nanowires
ONW@TiO2 Oxide over metallic filters Nan
oMem
bran
esfor liquid‐liq
uid sepa
ratio
nMaster Thesis, José Mª Román Cabrerizo, University of Seville
Water and Diiodomethane
mixture
Filtered Diiodomethane
Hybrid ONW@MetalOxide Nanowires
Phot
olum
ines
cenc
e
Principles of Fluorescence Spectroscopy 3rd Ed (Lakowicz)
Hybrid ONW@MetalOxide Nanowires
Fluorescence microscopy of the organic core
Photoluminesce spectra of different hybrid systems
The organic core preserve the
photofunctionalproperties
Photonics effects
Stronger emission at the NW tips
Phot
olum
ines
cenc
e
Hybrid ONW@MetalOxide Nanowires
Nan
o-op
tical
-Fib
erOptical Fiber Working principle
The contrast between the refractive index of the core and shell enables the efficient confinement of the light propagation to the high refractive index material
Critical angle for total reflection θ = arcsin(n1/n2)
Hybrid ONW@MetalOxide Nanowires
Photoluminescence of the inner organic core
Luminescent nano‐optical‐fibers
Luminescent organic core @ high refractive index shell
High refractive index shell Low refractive index coreAdv. Funct. Mater. 23 (2013) 5981
Hybrid systems with different shell
Inorganic Nanotubes
Fabrication of Inorganic nanotubes by annealing
Scientific Reports 6 (2016) 20637
Inorganic NanotubesPh
otol
umin
esce
nce
and
sens
ing
appl
icat
ion
Photoluminescence of ZnO nanotubes
Photo‐response to environmental O2
Scientific Reports 6 (2016) 20637
The Nanotechnology on Surfaces group
OU
TLIN
E
http://www.sincaf.icmse.csic.es/
Tenured ScientistsAna Borras Angel Barranco
20072013
F.J. Aparicio2010
Manuel Macias Montero
2015Maria Alcaire
Alejandro Nicolas Filippin
Agustin R. Gonzalez‐Elipe
Group Leader