Int
ern
at
i
onal
Journ
al of Ele
ctrical
an
d
Co
mput
er
En
gin
eeri
ng
(IJ
E
C
E)
Vo
l.
10
,
No.
3
,
June
2020
,
pp.
2926
~
2933
IS
S
N:
20
88
-
8708
,
DOI: 10
.11
591/
ijece
.
v
10
i
3
.
pp2926
-
29
33
2926
Journ
al h
om
e
page
:
http:
//
ij
ece.i
aesc
or
e.c
om/i
nd
ex
.ph
p/IJ
ECE
Enh
ancing DSS
C conve
rsio
n
efficien
cy by ozone
-
treated
TiO
2
ph
otoanode and
optimu
m CNT/
PDDA coun
ter electr
ode
Yo
s
hiki
Ku
ro
ka
w
a,
Dang T
rang
Nguy
e
n, Ryot
a Fujim
oto
, Koz
o
Ta
guchi
Depa
rtment
o
f
S
ci
en
ce a
nd
Enginee
ring
,
R
it
sum
ei
kan
Univer
sit
y
,
Japa
n
Art
ic
le
In
f
o
ABSTR
A
CT
Art
ic
le
history:
Re
cei
ved
A
pr
14
, 201
9
Re
vised
N
ov
2
3
,
2019
Accepte
d
Dec
6,
2019
The
conv
ersion
eff
iciency
of
d
ye
-
sensitized
sol
a
r
ce
l
ls
(DS
SC
s)
depe
nds
on
the
p
erf
orm
ance
of
the
photoa
no
de
and
th
e
coun
te
r
elec
trod
e.
In
thi
s
pape
r
,
UV
-
ozone
treat
m
ent
has
bee
n
appl
i
ed
to
the
photoa
node
to
cl
e
an
an
d
inc
re
ase
the
h
y
d
rophil
icit
y
of
the
pho
toa
nod
e.
As
a
result,
the
d
y
e
adsorpti
on
ca
pa
ci
t
y
w
as
improved.
Also,
lo
w
-
cost
m
ult
iwalled
c
arb
on
n
ano
tube
(CNT)
combined
wi
th
p
ol
y
(di
al
l
y
l
d
ime
th
y
la
m
m
onium
chl
orid
e)
(PD
DA
)
was
used
to
f
abr
icat
e
the
count
er
el
e
ct
rod
e.
Th
e
CNT/PDD
A
count
er
ele
ct
rode
was
o
pti
m
iz
ed
to
m
axi
m
iz
e
it
s
per
form
anc
e
.
B
y
using
the
o
zone
-
tr
ea
t
ed
photoa
node
and
opti
m
um
CNT
/PDD
A
count
er
elec
trode,
th
e
conve
rsion
eff
iciency
has
in
cre
ase
d
b
y
about 64%.
Ke
yw
or
d
s
:
CNT/PD
D
A
DS
SC
Ele
ct
ro
ph
or
esi
s d
e
posit
ion
Mult
il
ay
er,
Ozone t
reatm
e
nt
Copyright
©
202
0
Instit
ut
e
o
f Ad
vanc
ed
Engi
n
ee
r
ing
and
S
cienc
e
.
Al
l
rights re
serv
ed
.
Corres
pond
in
g
Aut
h
or
:
Ko
z
o Tag
uc
hi
,
Dep
a
rt
m
ent o
f El
ect
rical
an
d
Com
pu
te
r
E
ng
i
neer
i
ng
,
Ri
tsu
m
ei
kan
Unive
rsity
,
1
-
1
-
1 N
oj
i
-
hi
ga
sh
i,
K
us
at
su,
Sh
iga
, J
a
pa
n.
Em
a
il
:
ta
gu
chi@se.
ritsum
ei
.a
c.jp
1.
INTROD
U
CTION
Nowa
days,
en
vir
on
m
ental
pr
ob
le
m
s
cause
d
by
f
os
sil
f
uels
hav
e
bee
n
e
m
erg
in
g
a
r
ound
t
he
w
or
l
d.
Re
new
a
ble
en
erg
ie
s
rep
la
ci
ng
fossil
fu
el
-
base
d
e
nergi
es
are
ex
pect
ed
to
be
a
vital
so
luti
on
[1
–
3]
.
Fo
r
e
xam
ple,
wind
powe
r,
hy
dr
a
ulic
powe
r,
s
olar
po
wer,
ge
oth
e
rm
al
po
we
r.
Am
ong
them
,
so
la
r
power
is
receive
d
m
or
e
an
d
m
or
e
at
t
ention.
S
olar
cel
ls
are
de
vic
es
that
c
onvert
so
la
r
e
ne
rg
y
int
o
el
ect
ric
powe
r.
The
pr
im
ary
com
m
ercial
so
la
r
cel
l
is
sil
ic
on
ty
pe,
wh
ic
h
produces
hi
gh
co
nversi
on
eff
ic
ie
ncy
bu
t
high
pro
du
ct
io
n
c
ost
.
DS
SC
was
i
nv
e
nted
i
n
19
91
[
4]
,
w
hich
ge
ner
al
ly
co
ns
is
ts
of
a
dye
-
se
nsi
ti
zed
TiO
2
thin
fi
l
m
photo
a
node
,
a
n
el
ect
r
olyt
e,
and
a
c
ounte
r
el
ect
ro
de
.
T
he
phot
oa
node
i
s
usual
ly
m
ade
by
c
oatin
g
TiO
2
on
a
trans
par
e
nt
f
luorine
-
dope
d
SnO
2
coate
d
gl
ass
(F
T
O)
.
D
SSC
has
s
om
e
adv
a
ntage
s
suc
h
as
lo
w
pr
oducti
on
cost, less
to
xic
m
anu
fact
ur
i
ng,
and lig
htwei
ght
[5
–
7]
.
The
c
onversi
on
ef
fici
ency
of
DSSC
s
de
pe
nd
s
on
the
qual
it
y
of
the
dy
ed
TiO
2
photo
a
no
de
an
d
the
cat
al
yt
ic
act
ivit
y
of
the
counter
el
ect
rode.
The
ph
otoa
node
t
hin
-
film
need
s
to
be
in
good
qual
it
y
su
ch
as
un
if
orm
t
hick
ness,
sm
oo
th
s
urface
witho
ut
crac
ks,
a
nd
high
hydro
phil
ic
it
y
.
UV
-
oz
one
t
r
eatm
ent
(o
z
one
treat
m
e
nt)
is
kn
own
a
s
a
m
et
ho
d
f
or
rem
ov
in
g
org
anic
m
at
te
rs
and
im
pr
ov
i
ng
t
he
hydro
phil
ic
it
y
of
su
bst
rates
[
8,
9]
.
O
rganic
m
at
te
rs
rem
ai
nin
g
in
the
TiO
2
ph
oto
a
node
i
m
ped
e
the
dye
ads
orpti
on.
W
it
h
t
he
oz
one
treat
m
ent,
th
e
hy
drophili
ci
ty
of
the
TiO
2
phot
oano
de
is
im
p
rove
d
by
form
ing
f
un
ct
i
on
al
gro
up
s
(
-
CO
O
H,
-
C
O
O,
-
C
O,
-
OH).
More
ov
e
r,
plati
nu
m
(P
t)
is
usual
ly
util
iz
ed
to
fa
br
ic
at
e
th
e
counter
el
ect
rode
of
DS
SC
s
due
to
it
s
high
act
ivit
y
in
re
dox
-
r
eact
io
n
a
nd
supe
rior
el
ect
ro
cat
al
yt
ic
act
ivit
y
[10
–
12]
.
Ne
ve
rthele
ss,
Pt
is
a
ra
re
m
et
a
l
and
high
c
os
t
[
13]
.
T
her
e
f
ore,
lo
w
-
c
os
t
s
ub
sti
tute
m
at
e
rial
s
with
relat
ively
com
par
able
perform
a
nce
a
r
e
need
e
d.
O
ne
prom
isi
ng
al
te
r
native
is
m
ultiw
al
le
d
ca
rbo
n
na
no
t
ub
e
(C
NT),
wh
ic
h
ha
s
ad
va
ntages
of
la
r
ge
su
r
face
ar
ea,
high
el
ect
rical
cond
uctivit
y,
low
c
os
t,
a
nd
chem
ic
al
st
abili
ty
[14
–
16]
.
In
a
dd
it
io
n,
PDD
A
Evaluation Warning : The document was created with Spire.PDF for Python.
In
t J
Elec
&
C
om
p
En
g
IS
S
N:
20
88
-
8708
En
hancin
g D
SSC c
on
ver
sio
n ef
fi
ci
ency b
y
ozone
-
tre
ated Ti
O2 ph
oto
anod
e and
…
(
Yo
s
hi
ki
Kuro
k
aw
a
)
2927
(d
ia
ll
yl
di
m
eth
yl
a
m
m
on
ium
chlo
ride
)
ha
s
a
pro
per
ty
of
el
ect
r
on
-
withdra
wal
from
CNT.
Th
eref
or
e
,
the
c
om
po
sit
e
of
CNT/P
D
DA
c
ou
l
d
be
use
d
to
im
pr
ove
the
pe
rfor
m
ance
of
t
he
c
ounte
r
el
ect
rode
in
D
SSCs
[
16]
.
T
he
pr
es
e
nt
stu
dy
is
f
ocused
on
e
nhanc
i
ng
the
c
onve
rsion
e
ff
i
ci
ency
of
the
DSSC
by
co
nducti
ng
ozone
trea
t
m
ent
of
t
he
TiO
2
photo
a
node
to
im
pr
ove
it
s
dye
a
dsor
ptio
n
ca
pac
it
y,
and
opti
m
izing
the
CNT/
PDDA
c
ounter
el
ect
rode.
In
the
previ
ou
s
stu
dy
,
we
ha
ve
c
onfirm
ed
the
posit
ive
ef
fects
of
C
N
T/PDDA
c
om
bin
at
io
n
on
t
he
perform
ance
of
t
he
c
ounter
el
ect
r
od
e
of
t
he
DS
S
C
[16]
.
In this
pap
e
r
, n
ov
el
res
ults arc
h
ive
d by opti
m
iz
ing
the
CNT/
PDDA
cou
nter
elec
tro
de
a
re
presente
d.
2.
RESEA
R
CH MET
HO
D
2.1.
M
ateri
als
P25
TiO
2
pow
der
(parti
cl
e
siz
e
~20
nm
)
w
as
purc
hase
d
f
ro
m
Aer
osi
l
Co.,
Ltd.
M
ulti
wall
ed
CN
T
coati
ng
li
quid
N
7006L
was
pu
rch
ase
d
f
r
om
KJ
Sp
eci
al
ty
Paper
C
o.,
Ltd.
,
w
hich
co
ntains
6.1
wt%
m
ul
ti
wall
ed
CNT
with
a
n
a
ver
a
ge
diam
eter
of
9.5
nm
an
d
le
ngth
of
1.5
µm
[
17]
.
96
wt%
et
hanol
,
po
ly
et
hyle
ne
glyc
ol
(
PE
G,
aver
a
ge
m
olecular
1500
),
1.2
-
dim
et
hyl
-
3
-
pro
pylim
idazoli
um
iod
ide,
tol
uen
e
,
and
acet
on
it
ril
e
wer
e
purc
ha
sed
f
ro
m
W
ak
o
P
ur
e
C
hem
ical
Indu
st
ries
L
td.
20
wt%
P
DDA
s
olu
ti
on,
Lil
,
I
2
,
4
-
te
rt
-
buty
lpyr
idine,
a
nd
MK
2
dye
(2
-
Cy
an
o
-
3
-
[
5’’’
-
(9
-
et
hyl
-
9H
-
ca
r
baz
ol
-
3
-
yl)
-
3’,
3’’,3’
’’,
4
-
te
tra
-
n
-
hex
yl
-
[2,2’,
5’,2
”
,5
”
,2”’]
-
quarte
rthioph
e
n
-
5
-
yl
]
acryl
ic
aci
d)
we
re
pu
rch
as
ed
from
Sigm
a
Aldri
ch
C
o.
LLC
.
Deio
nized wat
er
was purc
has
ed fr
om
Mon
ot
aR
O
Co
., Lt
d
.
All t
he
c
hem
icals w
ere
use
d a
s r
ecei
ve
d.
2.2
. F
ab
ri
ca
ting
th
e
ph
oto
anode
Com
par
ed
to
oth
e
r
thin
-
film
coati
ng
m
et
ho
ds
su
c
h
as
s
pin
c
oatin
g
[
18]
,
sputt
erin
g
[13]
,
doct
or
-
blade
[19]
,
el
ect
rophor
e
sis
deposi
ti
on
m
e
thod
(E
PD)
ha
s
the
ad
va
ntages
of
lo
w
-
c
os
t
eq
uip
m
ent,
shor
t
depositi
on
ti
m
e,
high
repr
oducibili
ty
,
an
d
con
t
ro
ll
able
th
ic
kn
ess
[
20]
.
Ther
e
f
or
e,
in
t
his
researc
h,
E
PD
wa
s
util
iz
ed
to
fa
br
ic
at
e
bo
th
the
photo
a
node
s
a
nd
c
ounte
r
el
ect
rodes.
T
o
pr
e
par
e
TiO
2
colloid
s
olu
ti
on
f
or
EP
D,
0.2 g
P
25 p
ow
der
an
d
0.2 g
P
EG
wer
e
m
ixed
in
40
m
l
et
ha
no
l
at
the
s
pee
d
of
70
0
r
pm
fo
r
24 h
b
y
a
m
agn
et
ic
sti
rr
er.
A
n
al
um
inu
m
plate
(
20
×
20
×
1
m
m
)
and
an
FT
O
gl
ass
(20
×
20
×
1.8
m
m
)
wer
e
us
e
d
as
t
he
EP
D
cat
hode
a
nd
E
PD
a
node
,
r
es
pecti
vely
.
T
he
y
wer
e
place
d
in
par
al
le
l
int
o
the
pre
par
e
d
TiO
2
s
olu
ti
on
wit
h
a
10
m
m
distance
bet
wee
n
the
tw
o
el
ect
rodes
as
s
how
n
in
Fig
ur
e
1.
A
c
onsta
nt
cu
rr
e
nt
of
0.1
2
m
A
from
a
curren
t
s
ourc
e
(R6144,
A
dvantest
)
was
a
ppli
ed
to
the
t
w
o
el
ect
rodes.
T
o
m
ake
f
our
-
la
ye
r
thin
film
,
EPD
was
c
onduct
ed
four
tim
es
with
25
s
e
ach
ti
m
e
fo
ll
ow
e
d
by
60
o
C
dr
yi
ng
for
60
s
.
A
fter
that,
the
as
-
fa
bri
cat
ed
TiO
2
thin
fil
m
s
were
an
nealed
by
an
el
ect
ric
f
urna
ce
(
SMF
-
1,
Asone
)
at
40
0
o
C
(5
o
C/
m
in
ute
heati
ng
rate)
for
60
m
inu
te
s.
Af
te
r
a
nneal
ing,
t
he
ph
oto
a
nodes
wer
e
tre
at
ed
by
a
UV
-
ozone
cl
eane
r
(UV25
3E,
Fil
gen)
with
treat
in
g
wav
el
e
ng
t
h
at
185
nm
and
254
nm
.
The
ozone
treat
m
e
nt
ti
m
e
was
24
h.
Th
e
thic
kness
of
the ph
oto
a
node
s w
as
abo
ut 15
µm
.
Figure
1.
EP
D set
up for fa
br
ic
at
ing
the
ph
otoa
node
In
DSSC
rese
arch,
as
se
ns
it
iz
er
dyes,
ru
t
he
niu
m
-
based
dy
es
are
usual
ly
us
ed
beca
use
ru
t
hen
i
um
dyes
ca
n
a
bsor
b
broa
d
li
ght
band;
as
a
res
ult,
they
reali
ze
hi
gh
co
nvers
ion
ef
fici
ency.
H
ow
e
ve
r,
high
-
c
ost
m
at
erial
and
e
nv
i
ronm
ental
ha
zard
s
a
re
s
ome
pro
blem
s
of
r
uth
e
niu
m
-
base
d
dyes.
T
her
e
f
or
e
,
researc
he
r
s
ha
ve
been
try
in
g
to
fin
d
lo
w
-
c
os
t
a
nd
en
vir
onm
ental
ly
-
fr
ie
nd
ly
dy
es
for
rep
la
ci
ng
r
uth
e
niu
m
-
base
d
dyes
[21
–
23]
.
In
this
resea
rc
h,
orga
nic
MK
2
dye
was
use
d,
wh
ic
h
is
an
env
i
ronm
entally
-
fr
ie
ndly
dye
.
The
se
ns
it
iz
er
dye
so
luti
on
c
onsis
te
d
of
10
m
g
MK2
dye
diss
olv
e
d
i
n
108
m
l
toluene.
T
he
pr
e
pa
red
TiO
2
phot
oano
des
we
re
so
a
ked
in
t
he
dye
so
luti
on
at
25
o
C
f
or
3
h.
Af
te
r
that,
t
he
ir
su
r
faces
were
rinse
d
by
tol
uen
e
a
nd
dei
oniz
ed
wa
te
r
c
onti
nuously
. T
hen, the
d
ye
d p
hotoa
node
s were
dri
ed
at
80
o
C
in a
dr
yi
ng
oven
fo
r 10 m
inu
te
s.
Evaluation Warning : The document was created with Spire.PDF for Python.
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S
N
:
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8708
In
t J
Elec
&
C
om
p
En
g,
V
ol.
10
, No
.
3
,
J
une
2020
:
292
6
-
293
3
2928
2.3.
F
ab
ri
ca
ting
th
e
co
unt
e
r ele
ctrode
To
fa
br
ic
at
e
the
c
ounter
e
le
ct
ro
de
,
a
n
al
umi
nu
m
plate
(
40
×
20
×
1
m
m
)
and
a
n
FT
O
glass
(40×
20
×
1.8
m
m
)
wer
e
use
d
as
the
E
PD
a
node
a
nd
EP
D
cat
hode,
re
sp
e
ct
ively
.
T
he
t
wo
el
ect
r
od
e
s
wer
e
se
t
a
t
9
m
m
distance
as
s
hown
in
Fig
ure
2.
C
on
sta
nt
3
V
from
a
power
s
ource
(AD
-
87
23D)
was
a
pp
l
ie
d
on
the
tw
o
el
ect
rodes
a
nd
EP
D
ti
m
e
was
90
s
.
First,
t
he
c
ount
er
e
le
ct
r
od
e
usi
ng
only
CN
T
(
CNT
coati
ng
li
qu
id
was
us
e
d
direc
tl
y
for
EP
D)
w
as
f
ab
ricat
ed.
Af
te
r
E
PD
t
he
as
-
fa
br
ic
at
e
d
c
ounter
el
ect
r
ode
w
as
dri
ed
at
room
tem
per
at
ur
e
f
or
24
h.
This
c
ounter
el
ect
r
od
e
is
cal
le
d
the
CNT
c
ounter
e
le
ct
ro
de
.
Sec
ond,
the
C
NT/P
DDA
co
unte
r
el
ect
r
ode
wa
s
fa
br
ic
at
ed.
T
he
pr
e
parat
ion
fl
ow
of
the
CNT/P
D
D
A
s
olu
ti
on
use
d
f
or
EP
D
is
s
how
n
in
Figure
3.
20
w
t%
PDD
A
s
olut
ion
was
dilute
d
i
n
deio
nized
water
t
o
obta
in
1
wt%
P
DDA
so
l
ution.
Af
te
r
that,
CNT
c
oatin
g
li
qu
i
d
a
nd
1
wt%
P
DDA
s
olu
t
ion
we
re
m
ixed
with
fi
ve
dif
f
eren
t
rati
os
of
CNT/PD
D
A=
5~
15
/
1
to
obta
in
fi
ve
CNT/PD
D
A
so
luti
ons
for
cond
ucting
E
PD
.
The
EP
D
process
was
the
sam
e
as
above.
T
he
as
-
fa
br
ic
a
te
d
CNT/P
DDA
co
unte
r
el
e
ct
rodes
we
re
dr
ie
d
at
r
oo
m
tem
per
at
ur
e
f
or
24
h.
T
his
counter
el
ect
ro
de
is
cal
le
d
CNT/P
D
D
A
c
ounter
el
ect
rodes.
T
he
thic
kn
e
ss
of
these
counter
el
ect
rodes
was
i
n
the
range
of
10~
13 µm
.
Figure
2.
EP
D set
up for fa
br
ic
at
ing
the
c
ount
er elect
r
od
e
Fig
ure
3.
The
pr
e
par
at
io
n flo
w of
C
NT/P
D
DA
so
luti
ons
us
e
d for
fabrica
ti
ng
CNT/PD
D
A
counter
elec
tro
des
2.4. D
SS
c
on
s
truct
i
on
In
this
resea
rc
h,
we
us
ed
t
he
acet
onit
rile
so
lve
nt
-
base
d
el
ect
ro
ly
te
,
w
hich
co
ns
ist
ed
of
0.6
M
1.2
-
dim
et
hyl
-
3
-
pro
pylim
idazoli
um
iod
ide
,
0.1
M
Lil
,
0.2
M
I
2
,
a
nd
0.5
M
4
-
te
rt
-
buty
lpyridi
ne.
T
he
DS
SC
was
a
ssem
bled
us
i
ng
the
two
fa
br
ic
at
ed
el
e
ct
rodes
a
nd
t
he
el
ect
ro
ly
te
.
As
s
how
n
in
F
igure
4
,
m
asking
ta
pe
m
ade
of
3M
t
ape
(~
45
µm
thick
ness)
wa
s
cut
a
25
mm
2
square
hole
,
the
n
a
dh
e
red
to
t
he
photo
a
node
.
A
su
it
able
am
ou
nt
of
the
el
ect
ro
ly
te
was
dr
oppe
d
on
the
act
ive
a
rea
,
a
nd
t
he
co
unte
r
el
ect
rode
was
pu
t
on
t
op
of
this
a
rea
.
T
wo
binder
cl
ip
s
wer
e
us
ed
t
o
cl
am
p
the
cel
l
f
or
m
easur
e
m
ent.
I
n
this
work,
we
fo
c
use
d
on
fin
ding
the
optim
u
m
con
diti
on
s
of
the
ph
oto
a
node
an
d
counter
el
ect
r
od
e
f
or
im
pr
ovin
g
t
he
c
onve
rsion
eff
ic
ie
ncy
of
t
he
DS
SC.
To
s
ave
ti
m
e
and
lowe
r
the
cost
of
t
his
resea
rc
h
,
t
he
D
SSC
w
as
m
ade
fo
r
short
-
ti
m
e
m
easur
em
ent only
.
Figure
4
.
DSS
C
co
ns
tr
uction
Evaluation Warning : The document was created with Spire.PDF for Python.
In
t J
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-
8708
En
hancin
g D
SSC c
on
ver
sio
n ef
fi
ci
ency b
y
ozone
-
tre
ated Ti
O2 ph
oto
anod
e and
…
(
Yo
s
hi
ki
Kuro
k
aw
a
)
2929
2.5.
C
ha
r
ac
te
ri
z
at
ion me
thod
The
t
hick
ness
of
the
ph
oto
an
ode
a
nd
counter
el
ect
r
od
e
we
re
m
easur
e
d
by
a
ste
p
gauge
(Br
uk
e
r
D
ekta
kXT).
Th
e
ph
ot
oanod
e
surfac
e
was
obser
ved
by
a
sca
nn
i
ng
elec
tron
m
ic
rosco
pe
(SEM
,
Hita
chi
S4300).
T
he
a
bs
or
ban
ce
s
pec
trum
of
the
ph
oto
a
node
was
m
easur
ed
by
a
sp
ect
r
ophoto
m
et
er
(S
him
adzu
U
V
-
3600)
.
T
he
op
en
-
ci
rc
uit
vo
lt
age
(V
oc
),
sho
rt
-
ci
rc
uit
cu
rr
e
nt
den
sit
y
(J
sc
),
fill
facto
r
(
FF)
,
a
nd
c
onve
rsion
eff
ic
ie
ncy
(
η
)
of
the
fabrica
te
d
DS
SC
we
r
e
m
easur
ed
w
it
h
a
s
olar
si
m
ula
t
or
(
O
AI
TriS
OL)
sim
ulati
ng
the
s
un
li
ght
(
AM1.5,
10
0
m
W
/cm
2
).
For
each
e
xperim
ent,
four
sam
ples
wer
e
m
eas
ur
e
d,
an
d
t
he
aver
a
ge
resu
lt
was
presented
i
n
thi
s
pa
per.
Er
r
or
bar
s
in
t
he
pr
ese
nted
fig
ures
we
re
base
d
on
t
he
re
sul
ts
of
the m
easur
ed s
a
m
ples.
3.
RESU
LT
S
A
ND AN
ALYSIS
3.1.
Ph
oto
ano
de ch
ara
c
teriz
at
i
on
The
s
urface
of
the
an
nealed
TiO
2
thin
film
was
ob
s
er
ved
by
S
EM.
Fig
ur
e
5
sh
ows
t
he
s
urf
ace
of
the
f
our
-
la
ye
r
TiO
2
thin
film
.
Alm
os
t
no
crac
k
was
obser
ve
d
on
the
sur
face.
It
ha
s
be
en
pro
ved
th
at
m
ul
ti
la
ye
r
EPD
m
et
ho
d
c
ould
sig
nificant
ly
i
m
pr
ove
t
he
qual
it
y
of
t
hin
film
s
[24
-
26]
.
Fi
gure
6
sho
ws
the
photo
im
ages
of
the
dye
d
photo
a
node
s
w
it
h
an
d
with
out
oz
one
t
reatm
e
nt.
The
photo
a
node
with
the
ozone
treatm
ent
ha
d
a
darker
c
ol
or
t
han
the
ph
oto
a
node
without
t
he
o
zo
ne
treat
m
e
nt.
In
oth
er
words,
the
photo
a
node
with
the
ozone
t
reatm
ent
had
a
dsor
be
d
m
or
e
dye
tha
n
the
phot
oano
de
with
out
the
oz
one
treatm
ent.
The
oz
on
e
treat
m
ent
rem
ov
e
d
r
e
m
ai
nin
g
orga
nic
m
a
t
te
rs
an
d
i
m
pr
ove
s
th
e
hydro
phil
ic
ity
of
the
ph
oto
a
node
surface
and t
he
refor
e
f
aci
li
ta
te
d
the
ad
sorpti
on of
M
K2
dye
.
F
igure
5.
A
n S
EM im
age of
t
he
s
urface
of
the ph
oto
a
node
after
a
nneal
in
g
F
igure
6.
The
photo i
m
ages of
the
d
ye
d
phot
oano
de
s
with
the
o
z
one
treatm
ent
(left)
and
without
th
e o
z
on
e
treatm
ent
(r
ig
ht
)
UV
-
vis
a
bsor
ba
nce
sp
ect
ra
of
the
dyed
phot
oano
des
with
a
nd
with
ou
t
the
ozone
treat
m
e
nt
wer
e
al
s
o
m
easur
ed
.
A
s
sh
ow
n
in
Fi
gure
7,
MK
2
dye
ena
bled
vi
sible
li
gh
t
ab
so
r
ba
nce
f
or
t
he
ph
oto
a
node
s
with
t
he
m
axi
m
u
m
a
bso
rb
a
nce
obta
ined
a
rou
nd
480
nm
.
T
he
ph
oto
a
node
with
oz
on
e
tr
eatm
ent
had
a
bette
r
UV
-
v
is
a
bsor
ba
nce
s
pectr
um
in
the
range
of
40
0
-
800
nm
with
sig
nifica
nt
ly
hig
her
abs
orba
nce
a
nd
a
la
rg
e
r
sp
ect
r
um
.
Fr
om
this
res
ult,
it
can
be
c
onfirm
ed
that
t
he
ozone
t
reatm
ent
can
im
pr
ove
t
he
a
bs
or
ba
nc
e
char
act
e
risti
c of the
ph
oto
a
node.
Figure
7
.
U
V
-
vi
s ab
s
orba
nce s
pectra
of the
dy
ed
ph
oto
a
node
s w
it
h
an
d wit
hout
the
o
z
one
treatm
ent
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N
:
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-
8708
In
t J
Elec
&
C
om
p
En
g,
V
ol.
10
, No
.
3
,
J
une
2020
:
292
6
-
293
3
2930
3.2.
C
ounter
el
ectrod
e
opti
mi
z
at
ion
In
this
s
ubsect
ion
,
the
pe
rform
ance
of
var
i
ou
s
c
ounter
el
ect
rodes
i
n
t
he
DSSC
was
i
nv
e
sti
gated
.
All
ex
per
im
ents
in
this
sec
ti
on
us
ed
t
he
photoa
no
des
without
ozone
treat
m
ent
.
First,
the
C
NT
a
nd
CNT/PD
D
A
c
ounter
el
ect
rod
es
we
re
c
om
par
ed
.
T
he
m
easur
e
d
phot
ovoltai
c
par
am
et
ers
of
the
DSSC
s
us
in
g
the
c
ounter
el
e
ct
rodes
m
ade
of
CN
T
a
nd
C
NT/PDD
A
(C
NT/PDD
A
=
10
:1)
are
li
ste
d
in
Table
1.
T
he
D
SS
C
us
in
g
the
C
NT
c
ounter
el
ect
ro
de
ge
ne
rated
2.78
%
conve
rsion
eff
ic
ie
ncy
whil
e
the
DS
S
C
us
in
g
the
CNT/P
DDA
c
ou
nter
el
ec
tro
de
ge
ne
rated
4.1
2
%
c
onve
rsion
ef
fici
enc
y.
This
was
a
bout
48%
im
pr
ovem
ent.
This
im
pr
ovem
ent w
a
s att
rib
ut
ed
to t
he
pr
e
se
nce
of P
DDA
i
n
the
cou
nter
e
le
ct
ro
de
[
16
]
.
Table
1.
Photo
vo
lt
ai
c pa
ram
e
te
rs
of t
he DSS
Cs m
ade w
it
h
two
di
ff
e
ren
t t
y
pes of co
unte
r e
le
ct
ro
de
s
:
CN
T
and CNT/P
D
D
A
(C
NT
/
P
DDA=
10:1
)
Co
u
n
ter
electrod
e
Js
c (
m
A
/c
m
2
)
Vo
c (
V
)
FF (
%)
η
(
%)
CNT
1
0
.31
0
.67
4
0
.62
2
.78
C
NT/PDD
A
1
2
.82
0
.70
4
5
.64
4
.12
Seco
nd,
the
optim
iz
at
ion
of
the
CNT/P
D
DA
c
ounter
el
ect
rode
was
i
nvest
igate
d.
Fig
ur
e
8
sho
ws
the
c
onve
rsion
ef
fici
ency
of
t
he
DSSC
as
a
functi
on
of
th
e
CNT/P
D
DA
r
at
io.
As
the
rat
io
was
va
ried
fro
m
5:1
to
15:1
,
t
he
co
nversi
on
e
ff
ic
ie
ncies
we
r
e
3.5
8,
3.75,
4.12,
3.4
8
,
an
d
3.1
7
%,
re
spe
ct
ively
,
as
li
s
te
d
i
n
Table
2
.
T
he
m
axi
m
u
m
conver
si
on
ef
fici
ency
was
ac
hie
ved
at
t
he
rati
o
of
CN
T/PD
DA
=
10:1.
T
he
refor
e
,
we use
d
this
ra
ti
o
as the
opti
m
u
m
r
at
io o
f
t
he
C
NT/PDD
A
c
ounter
elec
tro
de.
Figure
8. The
c
onve
rsion e
ff
ic
ie
ncies of th
e
DS
SCs
u
si
ng
CNT/PD
D
A
c
ounter
elec
tro
de
s w
it
h dif
fer
e
nt
CNT/PD
D
A
ra
ti
os
. E
rror ba
rs
r
e
pr
ese
nt stan
dard
de
viati
on
Table
2.
Photo
vo
lt
ai
c pa
ram
e
te
rs
of t
he DSS
Cs
us
in
g
CNT/
PDDA
co
unte
r
elec
tro
des
with
diff
e
re
nt
CNT
/
PDD
A
ra
ti
o
s
C
NT:PDD
A
Js
c (
m
A
/c
m
2
)
Vo
c (
V
)
FF (
%)
η
(
%)
5
:1
1
1
.81
0
.68
4
4
.41
3
.58
7
.5:1
1
1
,80
0
.70
4
5
.26
3
.75
1
0
:1
1
2
.82
0
.70
4
5
.64
4
.12
1
2
.5:1
1
1
.09
0
.69
4
5
.42
3
.48
1
5
:1
1
0
.45
0
.66
4
5
.83
3
.17
3.3.
Ef
fectiv
e
ness
of
th
e
o
z
one
-
tre
ated
ph
oto
an
ode
on
t
he DSS
C
per
f
orm
an
ce
The
DS
SCs
us
in
g
the
op
tim
u
m
CNT/
PDDA
c
ount
er
el
ect
rodes
(CNT/
P
D
D
A=
10:1
)
a
nd
the
phot
oano
de
s
with
an
d
without
the
oz
on
e
treatm
ent
wer
e
m
easur
ed.
F
ig
ure
9
disp
la
y
s
the
J
-
V
cu
rves
of
these
tw
o
DSS
Cs,
an
d
Table
3
li
sts
thei
r
m
e
asur
e
d
phot
ov
oltai
c
par
am
et
ers.
C
om
par
ed
with
the
DSS
C
us
in
g
the
photo
a
node
with
out
the
ozone
treat
m
e
nt,
t
he
DS
SC
us
in
g
t
he
phot
oano
de
with
the
oz
on
e
treat
m
ent
sh
owe
d
t
he
i
nc
rease
i
n
Jsc
(
from
12
.
82
t
o
14.
12
m
A/c
m
2
)
a
nd
F
F
(fr
om
45
.64
to
49
.39
%)
.
As
a
r
esult,
about
11
%
e
nhancem
ent
in
the
co
nversi
on
ef
fici
ency
was
obta
ine
d
(fro
m
4.12
to
4.5
7
%
).
This
res
ul
t
confirm
ed
the
po
sit
iv
e
e
ff
ect
of
t
he
oz
one
tr
eatm
ent
on
the
perform
ance
of
the
photo
a
no
de.
If
c
om
par
ed
with
the
DS
SC
us
in
g
t
he
C
NT
c
ounter
el
ect
rode
and
the
phot
oa
node
with
out
t
he
oz
on
e
treat
m
ent,
the
DS
S
C
us
i
ng
the
opti
m
u
m
CNT/PD
D
A
c
ounter
el
ect
rode
a
nd
the
ph
oto
a
node
wit
h
th
e
ozone
t
re
atm
ent
sh
owe
d
64
%
i
m
pr
ovem
ent i
n
the
con
ver
si
on e
ff
ic
i
ency
(4.
57% c
om
par
ed
w
it
h 2.7
8
%)
.
Evaluation Warning : The document was created with Spire.PDF for Python.
In
t J
Elec
&
C
om
p
En
g
IS
S
N:
20
88
-
8708
En
hancin
g D
SSC c
on
ver
sio
n ef
fi
ci
ency b
y
ozone
-
tre
ated Ti
O2 ph
oto
anod
e and
…
(
Yo
s
hi
ki
Kuro
k
aw
a
)
2931
F
igure
9. The
J
-
V cu
rv
e
s
of
t
he
D
S
SCs
us
in
g t
he photoa
node
s w
it
h an
d wit
hout the
o
z
one
treatm
ent an
d
the opti
m
u
m
C
NT/PDD
A
c
ounter
el
ect
r
odes
(CNT/
P
DDA=
10
:
1)
Table
3.
Photo
vo
lt
ai
c pa
ram
e
te
rs
of t
he DSS
Cs using
the
phot
oano
des wit
h
a
nd w
it
ho
ut the ozo
ne
t
reatm
ent
and the
opti
m
u
m
CNT/PDD
A
coun
te
r
el
ect
r
od
e
s (
C
NT/P
D
DA =
10
:
1)
Ph
o
to
an
o
d
e
Js
c (
m
A
/c
m
2
)
Vo
c (
V
)
FF (
%)
η
(
%)
W
ith
o
u
t ozo
n
e tr
ea
t
m
en
t
1
2
.82
0
.70
4
5
.64
4
.12
W
ith
o
zo
n
e tr
eat
m
en
t
1
4
.12
0
.67
4
9
.39
4
.57
4.
CONCL
US
I
O
N
In
this
stu
dy,
t
he
DSSC
c
on
ver
si
on
e
ff
ic
ie
ncy
was
im
pr
ov
e
d
by
op
ti
m
iz
ing
the
co
un
te
r
el
ect
r
od
e
and
us
i
ng
t
he
photo
a
node
wi
th
oz
on
e
treat
m
ent.
The
C
N
T/PDDA
c
ount
er
el
ect
rode
ha
s
bee
n
opti
m
i
zed
to
m
axi
m
iz
e
the
DS
SC
c
onve
rs
ion
e
ff
ic
ie
ncy.
In
a
dd
it
io
n,
t
he
oz
o
ne
treat
m
ent
im
pr
ov
e
d
t
he
dye
ad
sorpt
ion
of
TiO
2
thin
film
ph
oto
a
node
a
nd
increase
d
th
e
co
nv
e
rsion
eff
ic
ie
ncy
of
the
D
S
SC
by
ab
out
11
%.
Fr
om
the
ex
pe
rim
ental
resu
lt
s,
t
he
c
onve
rsi
on
e
ff
ic
ie
ncy
of
the
DS
SC
was
su
cce
ssf
ul
ly
i
m
pr
oved
by
ab
ou
t
64%
by u
si
ng the
ozone
-
treat
e
d photoa
node
a
nd the
opti
m
u
m
CNT/PDD
A
coun
te
r
el
ect
r
od
e
.
ACKN
OWLE
DGE
MENTS
The
a
uthors
wi
sh
to
tha
nk
the
Mi
nem
oto
la
bo
rat
or
y
of
Ri
ts
um
ei
kan
unive
rsity
for
pr
ov
i
di
ng
us
with
the
us
e
of
s
ol
ar
si
m
ulator
(OAI,
TriS
OL
),
ste
p
ga
ug
e
(BRUK
ER
Dek
ta
kXT),
a
nd
s
pectr
opho
tom
e
te
r
(S
H
IMA
DZ
U,
UV
-
36
00)
.
REFERE
NCE
S
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Shali
n
i,
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asunda
r
a
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bhu,
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c
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asu,
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ura
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z
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la
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nte
r
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e
le
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trode
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r
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orm
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y
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e
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e
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t
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at
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ult
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ensit
i
ze
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SC
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“
El
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ct
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ophore
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on
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o
r
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ration
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ote
in
inc
lusion
bodie
s
from
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ri
a
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ong
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rm
Stab
ilit
y
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c
-
D
y
e
-
Sensi
tized
Solar
Cel
ls B
ase
d
on
An Alk
y
l
-
Functionalized
C
arb
a
z
ole
D
y
e
,
”
En
ergy
En
vi
ron.
Sci.
,
vol.
2
,
no
.
9
,
pp
.
1109
–
1114,
200
9.
[22]
C.
Ko
eni
gsm
ann
e
t
al.
,
“
Subs
ti
tut
ion
of
a
h
y
dro
xamic
acid
anc
h
or
in
to
the
MK
-
2
d
y
e
for
enha
n
ce
d
photovolta
i
c
per
form
anc
e
and
wate
r
stab
il
i
t
y
i
n
a
DS
SC
,
”
Phys
.
Chem.
Chem.
Phy
s.
,
vol
.
16
,
n
o.
31
,
pp
.
16629
–
16641,
2014
.
[23]
A.
K.
Arof
et
al
.
,
“
Eff
ic
i
ency
E
nhanc
ement
b
y
Mixed
Cation
E
ffe
ct
in
D
y
e
-
Sen
siti
ze
d
Solar
Cells
with
A
PV
D
F
Based
Gel
Pol
ym
er
El
e
ct
ro
l
y
te,
”
Int
.
J. Hy
droge
n
Ene
rgy
,
vo
l. 3
9,
no
.
6
,
pp
.
292
9
–
2935,
2014
.
[24]
Y.
Kurokawa,
D.
T
.
Ngu
y
en
,
an
d
K.
T
aguc
hi
,
“
Optimum
condi
ti
ons
for
titani
um
oxide
thi
n
f
il
m
on
d
y
e
-
sensitize
d
solar
c
el
ls
using
orga
nic d
y
e
sensiti
z
er
-
MK
2,
”
Int
.
J. Che
m.
Eng
.
A
ppl.
,
vol
.
9
,
no
.
6
,
pp
.
200
–
205
,
2
018.
[25]
D.
T
.
Ngu
y
en,
Y
.
Kurok
awa
,
R.
Fuji
m
oto,
and
K.
Ta
gu
chi
,
“
Enh
anc
ing
th
e
eff
i
cienc
y
of
PM
MA
-
base
d
qu
asi
-
soli
d
el
e
ct
rol
y
t
e
d
y
e
-
s
ensit
ized
solar
c
el
ls
b
y
ozon
e
tr
ea
tment
of
Ti
O
2
thi
n
fi
lms
,
”
J.
Japan
So
c.
Ap
pl.
El
e
ct
rom
agn
.
Me
ch.
,
vo
l. 27, n
o.
1
,
pp
.
97
–
101
,
2019.
[26]
A.
S.
Shikoh,
Z.
Ahm
ad,
F.
Touati,
R
.
A.
Shakoor
,
and
S.
A.
Al
-
M
uhta
seb,
“
Optimization
of
ITO
gl
ass/Ti
O2
base
d
DS
SC
photo
-
anode
s
through
elec
trophor
et
i
c
d
e
positi
on
and
sin
te
ring
techniques
,
”
Ceram.
In
t.
,
vol.
43,
no
.
13
,
pp.
10540
–
1054
5,
2017
.
BIOGR
AP
H
I
ES
OF
A
UTH
ORS
Yos
hik
i
Kurok
a
w
a
was
born
in
Shiga,
Jap
an
on
April
26,
1994.
He
recei
ved
a
b
ac
he
lor’s
degr
e
e
in
th
e
Depa
r
tment
of
Sc
ie
n
ce
and
Engi
ne
eri
ng
from
Ri
tsum
ei
kan
Univ
ersity
,
Shiga
,
Jap
an
i
n
Marc
h
2017
an
d
was
admit
te
d
to
a
postgradu
ate
cou
rse
at
the
sam
e
Univer
si
t
y
in
April
2017
.
He
al
so
bel
ongs
to
an
elec
tron
ics
s
y
stem
cour
se
in
the
Depa
r
tm
ent
of
Sci
ence
a
nd
Engi
n
ee
r
ing.
He
is
now
in
th
e
se
cond
y
e
ar.
He
is
m
aki
ng
a
stud
y
of
photo
ca
t
aly
st
b
y
usin
g
el
e
ct
rophore
si
s
deposit
ion
in the
gra
dua
te c
ourse
.
D.
Trang
N
guyen
was
born
in
Hung
Yen,
Vi
etnam
in
1986.
H
e
r
ecei
ved
the
B
S
degr
e
e
in
200
9
from
the
Depa
rtment
of
Te
l
e
comm
unic
at
ion
S
y
stems
Han
oi
Univer
sit
y
of
Scie
n
ce
an
d
Te
chno
log
y
,
Ha
noi,
Vi
et
n
am.
A
fte
r
tha
t
,
he
recei
ved
the
ME
i
n
2011
from
th
e
Dep
art
m
ent
o
f
El
e
ct
r
oni
cs
and
El
e
ct
ri
ca
l
Eng
in
ee
ring
,
Donggu
k
Univer
sit
y
,
Se
oul,
South
Kore
a.
From
2011
to
2014,
he
compl
et
ed
his
Ph.D.
progra
m
in
in
tegrat
ed
scie
n
ce
and
eng
ine
er
ing
at
R
it
sum
ei
kan
Univer
sit
y
,
K
y
ot
o,
Jap
an.
After
e
arn
ing
h
is
Ph.D.
,
h
e
was
a
qualit
y
assuranc
e
e
ngi
nee
r
at
T
aka
ko
Industrie
s,
Inc
.
f
rom
2015
to
201
7.
Curr
ent
l
y
,
h
e
is
a
senior
rese
a
rch
er
at
th
e
Ri
tsum
ei
kan
Glob
a
l
Innova
ti
on
Rese
arc
h
Organi
za
t
io
n,
Ri
tsum
ei
kan
Univer
sit
y
.
His
fie
lds
o
f
int
er
est
include
Biofu
el
Cel
ls,
Solar
Cell
s,
Biosensors, an
d
H
y
drog
en Energ
y
.
Ry
ota
Fujimoto
was
born
in
Os
aka
,
Japa
n
on
Feb
rua
r
y
2
9
,
199
6
.
He
recei
ved
a
ba
che
lor’s
degr
ee
in
th
e
Depa
r
tment
of
Sc
ie
n
ce
and
Engi
ne
eri
ng
from
Ri
tsum
ei
kan
Univ
ersity
,
Shiga
,
Jap
an
i
n
Marc
h
201
8
an
d
was
admit
te
d
to
a
postgradu
ate
cou
rse
at
the
sam
e
Univer
sit
y
in
April
201
8
.
He
al
so
bel
ongs
to
an
elec
tron
ics
s
y
stem
cour
se
in
the
Depa
r
tment
of
Sci
ence
a
nd
Engi
n
ee
r
ing.
He
is
now
in
th
e
se
cond
y
e
ar.
He
is
m
aki
ng
a
stud
y
of
photo
ca
t
aly
st
b
y
usin
g
el
e
c
trophore
si
s
deposit
ion
in the
gra
dua
te c
ourse
.
Evaluation Warning : The document was created with Spire.PDF for Python.
In
t J
Elec
&
C
om
p
En
g
IS
S
N:
20
88
-
8708
En
hancin
g D
SSC c
on
ver
sio
n ef
fi
ci
ency b
y
ozone
-
tre
ated Ti
O2 ph
oto
anod
e and
…
(
Yo
s
hi
ki
Kuro
k
aw
a
)
2933
Koz
o
Tagu
chi
was
born
in
K
y
o
to,
Jap
an,
on
De
ce
m
ber
18,
1968
.
He
r
ecei
ved
th
e
B.
E.,
M.E
.
,
an
d
Dr.
Eng
.
Degr
ees
in
e
le
c
trica
l
e
ngine
er
ing
from
Rit
sum
ei
kan
Univer
sit
y
,
K
y
oto
,
Japa
n
,
in
1991
,
1993,
and
19
96,
respe
c
ti
ve
l
y
.
In
1996,
he
joi
n
ed
Fuku
y
ama
Uni
ver
sit
y
,
Hiroshi
m
a,
Japa
n
,
wher
e
he
had
be
en
e
ngage
d
in
r
ese
arc
h
and
d
evel
opm
ent
on
the
opti
c
al
fib
er
t
rap
ping
s
y
st
em,
sem
ic
onduct
or
r
ing
la
sers
and
t
hei
r
appl
icati
on
for
opto
el
e
ct
ron
i
c
d
evi
c
es,
and
p
ol
y
m
eric
optica
l
wave
guide
s
for
opti
c
al
interc
on
nec
t
ion.
In
1996
–
2003,
h
e
work
ed
as
an
assista
nt
and
le
c
ture
r
i
n
Fuku
y
ama
Univ
ersity
.
In
2003
,
he
m
oved
to
Ri
t
sum
ei
ka
n
Unive
rsit
y
,
Shig
a,
Jap
an,
and
cur
ren
tly
,
he
is
a
pro
fessor
of
th
e
D
epa
rtm
ent
of
e
le
c
tric
al
and
e
lectr
oni
c
e
ngine
er
ing.
From
2006
to
2007
,
he
was
a
visi
ti
n
g
profe
ss
or
a
t
U
nive
rsit
y
of
St
Andrews
(Scotl
a
nd,
Unit
ed
King
dom
).
From
2014
to
2015,
he
was
a
v
isit
ing
profe
ss
or
at
Nan
y
a
ng
Technol
ogi
cal
Univer
sit
y
(Sing
apor
e).
In
2019
,
he
was
a
v
isit
in
g
profe
ss
or
at
U
nive
rsit
y
of
Ba
th
(Unit
ed
Kingdo
m
).
His
cur
ren
t
r
ese
arc
h
int
er
ests
inc
lud
e
c
el
l
trap,
m
ic
roflu
idi
c
ce
l
l
-
base
d
de
vic
es,
d
y
e
-
sensi
ti
z
ed
solar
cell
s
,
biofuel
c
el
ls
,
biosensors,
and
h
y
droge
n
en
erg
y.
Dr.
T
a
guchi i
s
a
m
ember
of
the
JJ
AP
.
Evaluation Warning : The document was created with Spire.PDF for Python.