Finite Size Effect of Proton
Conductivity of Sol-Gel Derived
Amorphous Aluminosilicate Thin Film
Y. Aokia, H. Harada, H. Habazakia, T. Kunitakeb
a Faculty of Engineering, Hokkaido Univ.
b Institute of Physical and Chemical Research, RIKEN
1. Background
2. Thickness dependency of proton conductivity of a-Al0.1Si0.9Ox thin films with various Al/Si composition
3. Rondom resistor network model of conductivity scaling in a-Al0.1Si0.9Ox thin films
4. Mechanism of finite size effect of the proton conductivity
5. Summary.
ContentsContents
For intermediate temperature fuel cellFor intermediate temperature fuel cell
0.000 0.001 0.002 0.003
0
-1
-2
-3
-4
-5
Log (
σ/
S c
m-1
)
T-1 / K-1
T. Norby, Solid State Ionics 125 (1999) 1.
Target
Amorphous Al0.1Si0.9Ox
Thin filmThin film
(Y. Aoki, et al, Electrochem. Solid State Lett., 2008, 11, P13)
100 200
T/°C400
1. Thermally and chemically stable, and proton conductivity by the presence of Brønsted acid site on the anionic framework
2. Amorphous materials rather suitable for fabricating gas-tight thin electrolyte due to the non-granular form
regime-iii
iiiiv
Size enhancement of proton conductivitySize enhancement of proton conductivity
No percolationPercolationScalingSaturating
ζ
Maximum cluster
d >> ζd ~ ζλ < d < ζd < λ
In aperiodic phase, there is a
random distribution of
protonic pathway because of
structural inhomogeneity
Fast
Slow
Conduction is peroclative!
Y. Aoki et al., JACS, 133, 3471, 2011.; PCCP, 14, 2735, 2012
250°C,
Al0.1Si0.9Ox
Objective
We conducted here a survey of the proton conductivity
and the microstructures for the amorphous
aluminosilicate thin films by changing the Al/Si
composition in order to clear the structure giving
inhomogeneity of conductivity in nm length scale.
Synthesis of AlnSi1-nOx thin film by multiple spin-castSynthesis of AlnSi1-nOx thin film by multiple spin-cast
Hydrolysis
OH
OH
OHOH
OH
OH
OH
OH
Pt
Precursor sol:Al(OsBu)3 + Si(OEt)4 in 1-PrOH with Al/Si = 1/9;30 or 100 mM
Deposition
450°C
10 min
3 times
Al0.1Si0.9Ox
thin film(20-1400 nm)
Cooling
Pt/Sisubstrate
Anodized at 0.5 V (SCE) in 5 M H2SO4
at 40°C
O
MO
OO
OOO
O
O
OOO
O
OM
M
M
O
R
R
R
R
R
ROH
MOH
OHO
OOO
O
O
OHOO
OH
OHM
M
M
OH
Humidified, hot air
3000 rpm20 sec
2 , 5nm /
one spin.
Layer-by-layer spin-cast process is a stepwise film deposition technique from a precursor solution and enables the fabrication of metal oxide film with nm thickness precision.
REPEAT several times
Morphology of a-AlnSi1-nOx thin filmsMorphology of a-AlnSi1-nOx thin filmsIn this study, the a-AlxSi1-xO2-α nanofilms were fabricated on ITO substrate by the surface sol-gel process in a mode of spin-coating.
Substrate(Al plate) 50 nm
2 nm
Void-free, densely-packed layer of amorphous oxide
Al0.1Si0.9Ox film(100 nmd)
Al/Si (by EDX)Notific.
7 / 93
10 / 90
20 / 80
29 / 71
46 / 54
Al7Si93
Al10Si90
Al20Si80
Al30Si70
Al45Si55
Conductivity across filmConductivity across film
0.1 kHz
2 kHz
in dry air: obs.: calc.
Rs
Qox
Rox
Qi
220°C
250°C
ITO layer
Al20Si80
100 nm
Pt
Solartron
Pt
a-Al0.1Si0.9Ox film (120 nmd)a-Al0.1Si0.9Ox film (120 nmd)
50
40
30
20
10
0
cell
volt
age
at
400
/ m
V
- 1.6 - 1.2 - 0.8 - 0.4 0.0
ln([H2]Pt/ [H2]Pd)
theoretical Al45Si55 Al7Si93
[ ][ ] H
Pd
H
Pt
Pd
Pt
F
RT
H
H
F
RTEMF
γ
γ
2ln
22
2 −−=
∆ = 29.0
∆ = 25.0
∆ = 29.4
Pd
Al m
Si n
Ox
Pt 100%
H2
20 ~ 80%
H2
/ Ar
Al7Si93
Al45Si55
Thickness-dependent σ of a-AlnSi1-nOx filmThickness-dependent σ of a-AlnSi1-nOx film
Al7Si93 Al20Si80
Al30Si70 Al45Si55
Al7Si93
Al10Si90
Al20Si80
Al45Si55
Al30Si70
Low Al/Si films reveal the Low Al/Si films reveal the
thickness dependent thickness dependent
conductivityconductivity
250°C,Dry air
0.7 eV
0.8 eV
0.8 eV0.9 eV
Random resistor network calculationRandom resistor network calculation
R1
R2
n
1V
electrode
200 x 200 x n resistor network
R1: poor conductive matrixR2: ion-conductive matrixλ: size of matrixF2: fraction of R2 (<0.249)
G[i][j] = 1/R1 or 1/R2
ii-1 i+1
i-n
i+n
i+nm
i-nm
G[i][i-1]
G[i][i-nm]
G[i][i+1]
G[i][i-n]
G[i][i+n]
G[i][i+nm]
V(i-1)
V(i-nm)
V(i-n)
V(i+1)
V(i+nm)
V(i+n)
V(i)
y z
x
Kirchhoff’s law at each lattice point
( ) 0=−∑j
jiij VVG
G[i][i-1] [V(i-1)-V(i)] + G[i][i+1] [V(i+1)-V(i)]
+ G[i][i-n] [V(i-n)-V(i)] + G[i][i+n] [V(i+n)-V(i)]
+ G[i][i-nm] [V(i-nm)-V(i)] + G[i][i+nm] [V(i+nm)-V(i)] = 0
Kirkpatrick, S. Rev. Mod. Phys. 1973, 45, 574.
Berkemeister, F. et al., Phys. Rev. B 2007, 76, 024205.
Solving the large sparse matrix of
40000n × 40000n.
Fitting by RRN modelFitting by RRN model
R1: low-resistance pathR2: high-resistance pathλ : unit length of pathF2: fraction of R2
R1
R2
n
1V
electrode
200
200
Al10Si90
Al7Si93
250°C,Dry air
Al7Si93 Al10Si90
R1 / Ω 3.3×1012 6.3×1010
R2 / Ω 2.6×1010 2.2×108
λ / nm 30 40
FR2 0.011 0.092
Length of the conduction path unit is related to some meso-structure.
HRTEM of a-AlnSi1-nOx thin filmsHRTEM of a-AlnSi1-nOx thin films
The condensed domains (dark) with 5-20 nm (~λ)
distributed in the uncondensed matrix (bright).
The condensed domains connected each other to form
consecutive network throughout the film
Al7Si93
Al10Si90
Al20Si80
Al30Si70 Al45Si55
Fcon = 0.18
~ FR2
Fcon = 0.29
Fcon = 0.47 Fcon = 0.53
> Pc (0.254)
Dark Bright
12.1 ± 3.0 11.0 ± 2.0
Difference in density
due to fluctuation of
glass network
Dark Bright
35.5 ± 2.5 30.3 ± 3.9
Al7Si93 uncountable
Al10Si90 0.18
Al20Si80 0.29
Al30Si70 0.47
Al45Si55 0.53
Al/Si < 10
filmF
con
Pc = 0.249 Al/Si > 20
Highly-conducting path
can be identical to the
condensed glassy
matrix
Percolation mechanismPercolation mechanism
Size scaling
Percolation
Condensed glass domain
SummarySummary
The amorphous AlnSi1-nOx thin films prepared by sol-gel
process reveal the percolative proton conductivity because of formation of the conductive high-density glass domain and the poor-conductive low-density domain by the density fluctuation of glass network.
The bulk conductivity of these films is critical to the
concentration and the conductance of the conductive, condensed microdomains. The concentration is proportional to the Al/Si molar ratio and is beyond critical threshold at Al/Si > 20/80, however the conductance is decreased with increasing the Al/Si ratio by the structural modification of an aluminosilicate glass framework.
AcknowledgementsAcknowledgements
This work was financially supported by the Grant-in-Aid of JSPS for Scientific
Research on Young Scientists (B) and by the Global COE Program (Project
No. B01: Catalysis as the Basis for Innovation in Materials Science) from the
Ministry of Education, Culture, Sports, Science and Technology, Japan.
Ionic conduction in amorphous MxSi1-xO2-α nanofilmsIonic conduction in amorphous MxSi1-xO2-α nanofilms
10-2
10-1
100
101
102
103
104
105
106
RA
S / Ω
cm
2
3.02.82.62.42.22.01.81.61.4
103 T
-1 / K
-1
Ge
La
Ti
Zr
Ta
Ce
Hf
Al
W
VSi
400 300 200 100ºC
Ba
FeSn
0.15 Ω cm2
• The strong-acid compounds, M = Al, Hf, Zr and Ti, show the ASR < 0.15 Ω cm2 at T < 400°C in dry air.
• Al0.12Si0.88O1.91 achieve the ASR < 0.15 Ω cm2 at around 300°C.
• Proton conduction in silicate films increases in proportional to the acid strength.Al < Hf < Zr ≈ Ti < Fe ≈ Ta < Sn ≈ Ce < W ≈ La < V ≈Ge < Ba ≈ Si
300°C
in dry air
Aoki, Y. et al. Adv. Mater. 2008, 20, 4387.
Conductivity scaling behaviorConductivity scaling behavior
Hf0.1Si0.9Ox@300°CHf0.1Si0.9Ox@300°C
Al0.1Si0.9Ox@250°C
(power-law scaling)
Al0.1Si0.9Ox@250°C
(power-law scaling)
Hf0.25Si0.75Ox@300°CHf0.25Si0.75Ox@300°C
TDS of HDO in D2O-treated filmTDS of HDO in D2O-treated film
Adsorbed
water
50 nm
500°C
120 nm
300 nm
SiOx
(300 nm)
300°C
cv
Thermally-stable
protonic carriers
of anhydrous
conductivity
Pretreatment: 200°C 6h in D2O/air10-6 Pa, 30 K min-1.
Pretreatment: 200°C 6h in D2O/air10-6 Pa, 30 K min-1.
The protonic
carrier in a-AlSiOx
films is not silanol
group
Conduction pathConduction path
The network made of cross-linking of
Brønsted acid centers may allow the fast
proton transport so as to be the high
conductive pathway.
(i) Local segrgation of silica moiety
and (ii) termination by OH group
disturb the development of pathway
(acid network), lowering the
conductivity.
Chemical diffusion constantChemical diffusion constant
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