One-dimensional anodic TiO2nanotubes coated by atomic layer deposition:Towards advanced applications

Dvořák, Filip; Zazpe Mendioroz, Raúl; Krbal, Miloš; Sopha, Hanna Ingrid; Přikryl, Jan; Ng, Siow Woon; Hromádko, Luděk; Bureš, Filip; Macák, Jan
doi:10.1016/j.apmt.2018.11.005
One-dimensional anodic TiO2nanotubes coated by atomic layer deposition:Towards advanced applications

Author: Dvořák, Filip; Zazpe Mendioroz, Raúl; Krbal, Miloš; Sopha, Hanna Ingrid; Přikryl, Jan; Ng, Siow Woon; Hromádko, Luděk; Bureš, Filip; Macák, Jan
Publisher: Elsevier
Year: 2019
DOI: 10.1016/j.apmt.2018.11.005
Source: https://dspace.vut.cz/bitstreams/1d35e481-2eea-409c-931c-ce1a84f1ba4a/download
Applied
Ma e ials
Today
14
(2019)
1–20
Con en s
lis s
a ailable
a
ScienceDi ec
Applied
Ma e ials
Today
j
ou na
l
h
o
mepage:
www.else ie .com/loca e/apm
One-dimensional
anodic
TiO2nano ubes
coa ed
by
a omic
laye
deposi ion:
Towa ds
ad anced
applica ions
Filip
D o aka,
Raul
Zazpea,b,
Milos
K bala,
Hanna
Sophaa,b,
Jan
P ik yla,
Siowwoon
Ngb,
Ludek
H omadkoa,
Filip
Bu esc,
Jan
M.
Macaka,b,∗
aCen e
o
Ma e ials
and
Nano echnologies,
Facul y
o
Chemical
Technology,
Uni e si y
o
Pa dubice,
Nam.
Cs.
Legii
565,
53002
Pa dubice,
Czech
Republic
bCen al
Eu opean
Ins i u e
o
Technology,
B no
Uni e si y
o
Technology,
Pu kyno a
123,
612
00
B no,
Czech
Republic
cIns i u e
o
O ganic
Chemis y
and
Technology,
Facul y
o
Chemical
Technology,
Uni e si y
o
Pa dubice,
S uden ska
573,
53210
Pa dubice,
Czech
Republic
a
i
c
l
e
i
n
o
A icle
his o y:
Recei ed
21
Sep embe
2018
Recei ed
in
e ised
o m
11
Oc obe
2018
Accep ed
2
No embe
2018
Keywo ds:
A omic
laye
deposi ion
TiO2nano ube
Coa ings
Func ionaliza ion
Aspec
a io
a
b
s
a
c
A omic
laye
deposi ion
(ALD)
ep esen s
a
unique
deposi ion
echnique
ha
allows
o
coa
uni o mly
a -
ious
high
aspec
a io
(HAR)
po ous
nanos uc u es,
in
addi ion
o
i s
adi ional
ole
o
coa
ﬂa
subs a es
(e.g.
Si
wa e s).
Sel -o ganized
anodic
TiO2nano ube
(TNT)
laye s
belong
among
he
mos
in es iga ed
ino ganic
nanos uc u es.
They
possess
highly
unc ional
ma e ials
wi h
p omising
applica ion
po en ial
ac oss
many
echnological
ﬁelds.
He ein,
we
e iew
he
u iliza ion
o
ALD
o
he
unc ionaliza ion
o
anodic
TNT
laye s
by
seconda y
ma e ials
o
ad ance
hei
physicochemical
and
pho oelec ochemical
p ope ies.
Fi s ,
he
applica ion
o
ALD
o
unc ionaliza ion
o
po ous
aluminium
oxide,
which
ep esen
undamen al
HAR
nanos uc u e,
is
b ieﬂy
in oduced.
Then
he
main
expe imen al
pa ame e s
go e n-
ing
he
uni o mi y
and
he
con o mali y
o
ALD
coa ing
wi hin
HAR
nanos uc u es
a e
discussed.
Finally,
he
e iew
ocuses
on
he
use
o
ALD
o
deposi
seconda y
ma e ials
in o
TNT
laye s
o
a ious
pu poses
—
he
in oduc ion
o
pionee ing
s udies
is
ollowed
by
pa icula
examples
o
ALD
based
unc ional-
iza ions
o
coa ed
TNT
laye s
o
op imized
isible-ligh
abso p ion,
cha ge
sepa a ion
and
passi a ion,
(pho o)ca alysis,
s abili y,
gas
sensing,
and
ene gy
s o age.
©
2018
The
Au ho s.
Published
by
Else ie
L d.
This
is
an
open
access
a icle
unde
he
CC
BY-NC-ND
license
(h p://c ea i ecommons.o g/licenses/by-nc-nd/4.0/).
Con en s
1.
In oduc ion
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2
2.
ALD
in o
po ous
aluminium
oxide
—
o e iew
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3
3.
Aspec s
o
ALD
in o
high
aspec
a io
nanos uc u es
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4
4.
ALD
in o
TiO2nano ube
laye s
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4
4.1.
Pionee ing
e o s
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5
4.2.
Ligh
abso p ion
and
pho oelec ochemical
con e sion
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6
4.3.
Cha ge
sepa a ion
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7
4.4.
Pho oca alysis
and
elec oca alysis
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11
4.5.
S abili y
and
imp o ed
physical
p ope ies.
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.13
4.6.
Gas
sensing
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14
4.7.
Ene gy
s o age
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14
5.
Conclusion
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15
Acknowledgemen s.
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.15
Re e ences
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15
Abb e ia ions:
AAO,
anodic
aluminium
oxide;
ALD,
a omic
laye
deposi ion;
CBD,
chemical
ba h
deposi ion;
DSSC,
dye-sensi ized
sola
cell;
EDX,
ene gy-dispe si e
X- ay
spec oscopy;
EOR,
e hanol
oxida ion
eac ion;
FTIR,
Fou ie
ans o m
in a ed
spec oscopy;
HAADF,
high-angle
annula
da k-ﬁeld;
(H)AR,
(high)
aspec
a io;
IPCE,
inciden
pho on
o
elec on
con e sion
e ﬁciency;
MB,
me hylene
blue;
MC,
Mon e
Ca lo;
PEC,
pho oelec ochemical;
QCM,
qua z
c ys al
mic obalance;
QD,
quan um
do s;
SEM,
scanning
elec on
mic oscope;
SILAR,
successi e
ionic
laye
adso p ion
and
eac ion;
(S)TEM,
(scanning)
ansmission
elec on
mic oscope;
TMA,
ime hylaluminium;
TNT,
TiO2nano ube;
UV,
ul a iole
spec al
ange;
is,
isible
spec al
ange;
XRR,
X- ay
eﬂec i i y.
∗Co esponding
au ho .
E-mail
add ess:
[email p o ec ed]
(J.M.
Macak).
h ps://doi.o g/10.1016/j.apm .2018.11.005
2352-9407/©
2018
The
Au ho s.
Published
by
Else ie
L d.
This
is
an
open
access
a icle
unde
he
CC
BY-NC-ND
license
(h p://c ea i ecommons.o g/licenses/by-nc-nd/4.
0/).
2
F.
D o ak
e
al.
/
Applied
Ma e ials
Today
14
(2019)
1–20
1.
In oduc ion
Ti anium
dioxide
(TiO2)
ep esen s
a
ascina ing
and
highly
unc ional
ma e ial.
Un il
now,
TiO2has
ound
i s
main
comme cial
applica ions
in
pigmen s,
ood
indus y
and
cosme ics.
Pionee -
ing
obse a ion
o
pho oca aly ic
decomposi ion
o
wa e
a
TiO2
elec ode
in
1970s
[1]
launched
he
emendous
in e es
in
he
de elopmen
o
applica ions
o
TiO2in
sola
ene gy
con e sion,
ene gy
s o age,
and
pho o-assis ed
bio emedia ion,
which
ep e-
sen
essen ial
componen s
o
he
concep
o
enewable
ene gy
sou ces
and
o
sus ainable
en i onmen
[2].
These
applica ions
also
ake
he
ad an ages
o
TiO2 o
be
a
low
cos
ma e ial
wi h
an
ex emely
low
pho oco osion
a e.
Addi ionally,
hanks
o
inhe -
en
biocompa ibili y,
low
oxici y,
and
high
chemical
s abili y
o
TiO2,
eme gence
o
biomedical
applica ions
o
TiO2,
including
pho-
odynamic
he apy
o
cance
ea men ,
d ug
deli e y
sys ems,
cell
imaging,
biosenso s,
and
gene ic
enginee ing
has
also
aken
place
[3].
TiO2is
a
wide
band
gap
(3.0–3.2
eV)
n- ype
semiconduc o
and
hus
i
abso bs
ligh
only
in
he
UV
spec al
ange.
Gene ally,
he
ma e ial
p ope ies
can
be
uned
by
nanos uc u ing,
ealized
by
a
g adual
dec ease
o
he
cha ac e is ic
size
o
applied
ma e ials
down
o
he
nanome e
scale
[4].
Nanos uc u ing
o
ma e ials
esul s
in
an
ex emely
inc eased
su ace
o
olume
a io
wi h
sig-
niﬁcan
impac
on
ma e ial
physicochemical
p ope ies,
including
ligh
abso p ion.
Since
many
applica ions
o
TiO2a e
o
g ea
ex en
inﬂuenced
by
he
su ace
o
TiO2[5],
nanos uc u ing
o
TiO2 ep-
esen
an
impo an
s ep
o
i s
e ﬁcien
and
ﬂexible
u iliza ion
in
a ious
applica ions.
P obably
he
mos
p ominen
u iliza ion
o
nanos uc u ed
TiO2
is
ep esen ed
by
he
u iliza ion
o
TiO2nanopa icles
in
he
dye-
sensi ized
sola
cell
(DSSC),
in oduced
by
O’Regan
and
G ä zel
[6]
and
by
he
ecen
u iliza ion
in
pe o ski e
sola
cells
[7,8].
Ano he
class
o
nanos uc u ed
TiO2is
p esen ed
by
1-D
nanos uc u ed
ma e ials
such
as
nanowi es,
nano ods,
nanobel s,
and
nano ubes
[9].
1-D
nanoma e ials
sha e
wi h
nanopa icles
(0-D
ma e ials)
he
high
su ace
a ea
and
p omo ional
size
quan um
conﬁnemen
e ec s,
bu
ha e
one
dimensions
ou side
he
nanoscale,
ypically
po e
dep h
o
leng h
(applies
o
ube,
ods,
wi es,
ﬁb es).
1-D
nano-
ma e ials
o e
be e
unidi ec ional
cha ge/ eac an /ion
anspo
p ope ies
and
be e
mechanical
in eg i y.
TiO2nano ube
(TNT)
laye s
p epa ed
by
anodiza ion
o
Ti
ep esen
a
e y
popula
ype
o
1-D
ma e ial
wi h
he
key
ad an ages
o
acile
g ow h,
sel -
o de ing,
well-con olled
geome y,
scalabili y,
high
su ace
a ea,
di ec
con ac
o
me al-suppo ,
and
sui abili y
o
coa ing
by
sec-
onda y
ma e ials
[10–12].
The
impo an
cha ac e is ic
pa ame e
o
TNT
laye s
is
hei
aspec
a io
(AR),
which
is
he
a io
be ween
leng h
and
diame e
o
TNT.
In
gene al,
he
highe
AR
o e s
he
la ge
su ace
a ea
which
enhances
he
beneﬁ s
o
he
nano ube
s uc u es.
Ano he
impo an
aspec
o
TNT
laye s
is
hei
s uc-
u al
a iabili y
–
hey
a e
amo phous
in
he
as-anodized
s a e,
bu
can
be
con e ed,
depending
on
he
empe a u e,
in o
ana ase,
u ile
o
hei
mix u es
[11]
wi h
la ge
ﬂexibili y
owa ds
applica-
ions.
Las ,
bu
no
leas ,
hey
possess
e y
good
adhesion
o
he
unde lying
Ti
subs a es,
howe e ,
upon
speciﬁc
ea men s,
hey
can
be
de ached
in o
ee-s anding
memb anes
[13,14]
o
nano ube
powde s
[15].
To
add ess
complex
unc ionali ies
o
TNT
laye s
in
applica ions,
i
is
beneﬁcial
o
combine
hem
wi h
seconda y
ma e ials.
In
o de
o
keep
ad an ages
o
he
high
su ace
nano ubula
geome y,
i
is
necessa y
o
coa
he
en i e
su ace
o
nano ubes.
The
mos
o en
used
app oaches
o
ﬁll/coa
he
nano ube
laye s,
such
as
elec ode-
posi ion
[16–19],
chemical
ba h
deposi ion
[20–22],
spincoa ing
[23,24],
o
spu e ing
[25–27],
a e
able
o
uni o mly
coa
TNTs
laye s
wi h
speciﬁc
dimensions
(p edominan ly
wi h
a
low
AR).
The
a omic
laye
deposi ion
(ALD)
ep esen s
he
only
deposi ion
Fig.
1.
Illus a ion
o
u iliza ion
o
ALD
o
ad anced
unc ionaliza ion
o
TNT
laye s.
echnique
able
o
coa
uni o mly
highly
po ous
nanos uc u es
o
i ually
any
size
[28].
ALD
is
an
es ablished
deposi ion
echnique
based
on
sequen-
ial
sel -limi ed
adso p ion
o
apou s
o
compa ible
p ecu so s
on
su aces
leading
o
he
o ma ion
o
equi ed
coa ings.
The
sel -
limi ed
adso p ion
is
he
key
aspec
o
ALD
making
i
di e en
om
o he
deposi ion
echniques.
Unde
op imized
condi ions
( em-
pe a u e,
p essu e,
and
exposi ion
ime),
he
p ecu so
molecules
a e
adso bed
all
o e
he
su ace
in
jus
one
monolaye
–
u he
adso p ion
o
p ecu so
molecules
on
he
al eady
occupied
su ace
si es
is
no
allowed.
No
ma e
o
he
geome y
o
he
subs a e,
he
coa ings
p epa ed
by
ALD
ha e
unp eceden ed
con o mi y
all
o e
he
su ace
and
hei
hickness
is
con ollable
on
he
a omic
le el
[29].
As
illus a ed
in
Fig.
1,
ALD
coa ings
can
help
o
une/enhance
many
p ope ies
o
TNT
laye s,
such
as
ligh
abso p ion,
sepa a ion
o
pho ogene a ed
elec on-hole
pai s,
pho oca aly ic
and
elec o-
ca aly ic
p ope ies,
chemical,
he mal,
and
mechanical
s abili y,
gas
sensing,
and
ene gy
s o age.
In
pa icula ,
ALD
is
sui able
o
e y
hin
coa ings
while
i
is
only
o
a
limi ed
ex en
( om
he
poin
o
bo h
high
p ecu so
cos s
and
high
ime
demands)
usable
o
he
g ow h
o
hick
coa ings
(> ens
o
nanome e s).
The
es ic ed
empe a u e
window
o
sel -limi ed
egime
o
ALD
deposi ion
and
high
in es men
cos s
o
he
ools/p ecu so s
ep esen
main
d aw-
back
o
nowadays
ALDs,
bu
hese
a e
o e come
s ep
by
s ep
by
con inuous
ad ancemen s
in
he
ALD
echnology
and
also
ma ke
compe i ion.
Recen ly,
he
usabili y
o
ALD
o
unc ional
coa ings
o
nanos uc u es
owa ds
ene gy/ligh -d i en
applica ions
has
been
ho oughly
e iewed
[29–40].
In
his
e iew,
we
add ess
he
u i-
liza ion
o
ALD
o
ailo
he
unc ionali y
o
anodic
TNT
laye s
o
imp o ed
pe o mance
o
ealize
new
ypes
o
de ices
o
a ious
pu poses.
Fi s ,
we
b ieﬂy
summa ize
he
exis ing
li e a u e
on
ALD
deposi ion
in o
model
1-D
ma e ial
–
po ous
anodic
aluminium
oxide
(AAO)
–
and
in oduce
speciﬁc
heo e ical
ea u es
o
ALD
coa ing
o
HAR
(HAR)
nanos uc u es;
nex
we
ocus
on
he
u iliza-
ion
o
ALD
o
unc ionaliza ion
o
anodic
TNT
laye s.
We
in oduce
pionee ing
s udies
o
ALD
in o
anodic
TNT
laye s
and
ﬁnally
we
ol-
low
by
he
desc ip ion
o
he
u iliza ion
o
ALD
o
imp o ed
ligh
abso p ion,
cha ge
sepa a ion,
(pho o)ca aly ic
p ope ies,
s abil-
i y
(mechanical,
he mal,
and
chemical),
gas
sensing,
and
ene gy
s o age
o
ALD
modiﬁed
TNT
laye s.
F.
D o ak
e
al.
/
Applied
Ma e ials
Today
14
(2019)
1–20
3
2.
ALD
in o
po ous
aluminium
oxide
—
o e iew
Pionee ing
s udies
o
u iliza ion
o
ALD
o
unc ional
coa ing
o
1-D
HAR
nanos uc u es
by
seconda y
ma e ials
we e
pe o med
on
po ous
anodic
aluminium
oxide
(AAO)
–
a
well-es ablished
sel -o de ed
1-D
ma e ial
[41,42].
Po ous
AAO
is
cha ac e ized
by
i s
mechanical,
chemical,
and
he mal
s abili y,
nanoscale
po e
diame e s,
high
su ace-a ea
a io
and
low
cos
ab ica ion.
These
p ope ies
a ac ed
a
conside able
in e es
o
a
wide
numbe
o
applica ions
in
ca alysis,
molecula
sepa a ion,
elec onics
and
pho-
onics,
(bio)senso s,
ene gy
s o age
and
con e sion,
d ug
deli e y,
and
empla ed
syn hesis
among
o he s
e iewed
by
Md
Jani
e
al.
[43].
Po ous
AAO
can
be
ab ica ed
ia
elec ochemical
anodiza ion
o
aluminium.
The
applica ion
o
app op ia ed
p ocessing
pa ame e s
du ing
he
anodiza ion
(e.g.
applied
ol age,
elec oly e
concen-
a ion,
e c.)
allows
a
e y
good
con ol
o
he
po e
size,
he
in e -po e
dis ance,
he
hickness
o
he
po ous
laye
and
he
o e all
AR
o
he
po es.
The
inhe en
high
su ace
a ea
and
AR
makes
po ous
AAO
a
pa icula ly
appealing
nanoscale
empla e
o
in es iga ions
o
he
kine ics
and
mechanisms
o
he
su ace
chemical
eac ions
ha
he
a omic
laye
deposi ion
(ALD)
me hod
is
based
on.
In
pa icula ,
Fou ie
ans o m
in a ed
spec oscopy
(FTIR)
was
employed
o
s udy
he
bina y
chemical
eac ions
o
deposi
SiO2and
Al2O3using
po ous
AAO
as
a
suppo
[44–47].
ALD
p ope ies
as
sub-nanome e
hickness
con ol
and
uni o -
mi y
o
he
deposi ed
ma e ial
in o
he
po es
we e
exploi ed
in
u n,
o
sh ink
he
po e
diame e
o
po ous
AAO.
The
educ ion
o
he
po e
diame e
o
molecula
dimensions
by
he
deposi ion
o
Al2O3,
TiO2and
SiO2d ama ically
imp o ed
he
gas
sepa a ion
p ope ies
o
he
po ous
AAO
[48,49].
Elam
e
al.
used
ul ahigh
AR
(AR
≈
5000)
po ous
AAO
o
a
comp ehensi e
s udy
on
uni o mi y
o
ALD
coa ing
o
HAR
s uc u es
[50],
which
will
be
discussed
in
de ail
in
he
nex
sec ion.
ALD
enables
o
deposi
a
whole
ange
o
ma e ials
in o
AAO
as
demons a ed
ex ensi ely
in
li e a u e.
Johansson
e
al.
ﬁ s
pe o med
and
demons a ed
ALD
o
a
me allic
compound
ia
he
deposi ion
o
coppe
nanopa icles
in o
po ous
AAO.
The ein,
homogeneous
pa icle
size
and
pa icle
dis ibu-
ion
along
he
po es
we e
demons a ed
[51].
Following
wo ks
epo ed
on
he
deposi ion
o
di e en
me als
in o
po ous
AAO
using
ALD,
such
as
Pd
[52],
Ni
and
Co
[53,54],
Ru
[55],
P /I
[56],
Ag
[57],
and
P
[58].
Also,
he
deposi ion
o
sulﬁdes
[59],
ni ides
[60],
a
wide
numbe
o
di e en
oxides
as
Al2O3[61–63],
TiO2
[57,62–68],
Ta2O5[66],
Fe2O3[53,54,63,69],
SiO2[63,70–73],
ZnO
[63,74–78],
SnO2[79],
Co3O4[80],
oge he
wi h
he e ojunc ions
TiO2/Sb2S3/CuSCN(no
ALD)
[81]
and
NiO/Sb2S3[82],
mul ilaye ed
s uc u es
as
SiO2/Fe2O3/SiO2[83,84],
Fe3O4/Z O2/Fe3O4[85],
and
Au−CoxFe3−xO4co e–shell
nanowi es
[86]
ha e
been
epo ed.
The
success ul
u iliza ion
o
ALD
o
build-up
o
unc ional
nanos-
uc u es
on
AAO
empla es
o
unable
magne ism
[69]
and
pho o ol aic
de ices
[81]
is
illus a ed
in
Fig.
2.
Po ous
AAO
has
se ed
as
an
excellen
subs a e
o
e alua e
he
abili y
o
no el
p ecu so s
o
coa /inﬁl a e
HAR
subs a es
[59,70,79,80].
The
ALD
sub-nanome e
hickness
con ol
allowed
ﬁne- uning
o
po e
diame e s
[61–63,71,72]
and
e alua e
he
impac
o
educed
po e
diame e
on
he
single-molecule
sens-
ing
p ope ies
[61],
he
memb ane
sepa a ion
p ope ies
[63,71],
and
he
ionic
anspo
h ough
he
nanopo ous
memb anes
[72].
The
deposi ion
o
seconda y
ma e ials
enabled
he
unc ionaliza-
ion
o
po ous
AAO
as
di e en
senso s
[52,56,58,68],
anode
o
Li
ion
ba e ies
[67]
and
pho oanode
o
dye-sensi ized
sola
cells
[74,81,82].
Excep
hese
applica ions,
aking
he
unique
ALD
p op-
e ies
o
con o mal
deposi ion
and
he
wide
ange
o
ma e ials
ha
can
be
deposi ed,
po ous
AAO
has
been
in ensi ely
exploi ed
as
a
empla e
o
he
syn hesis
o
di e en
nanos uc u es.
Nano ubula
s uc u es
o
di e en
na u e
we e
epo ed,
such
as
TiN
nano ubes
Fig.
2.
Illus a ion
o
unc ional
nanos uc u es
based
on
empla es
o
po ous
AAO
u ilizing
ALD.
(a)–(c)
Mic og aphs
(SEM
and
TEM)
o
ALD
deposi ed
i on
oxide
nano-
ubes
o
unable
magne ic
p ope ies,
adop ed
om
[69].
(d)
ALD
deposi ed
TiO2
(g een)
and
Sb2S3( ed)
wi h
(no
ALD)
CuSCN
(yellow)
in
AAO
o
in eg a ion
in o
pho o ol aic
de ice,
ep oduced
om
[81].
(Fo
in e p e a ion
o
he
e e ences
o
colou
in
his
ﬁgu e
legend,
he
eade
is
e e ed
o
he
web
e sion
o
his
a icle.)
(exhibi ing
good
duc ili y
[60]),
ZnO
nano ubes
(wi h
supe io
pho-
oluminescence
cha ac e is ics
[76]),
o
e omagne ic
nano ubes
composed
o
Ni
and
Co
[53,54]
and
Fe2O3[53,54,69]
shown
in
Fig.
2a.
Single
wall
TNTs
[64,66]
and
Ag
loaded
TiO2nano ubes
[57],
whe ein
an
enhanced
pho oca aly ic
ac i i y
compa ed
o
unloaded
TNTs
was
e ealed,
and
hie a chical
mul iwall
TNTs,
ab ica ed
ia
deposi ion
o
al e na ing
TiO2/Al2O3nanolamina es
ollowed
by
we
e ching
o
sac iﬁcial
Al2O3laye
[65],
ha e
been
also
epo ed.
The
ALD
beneﬁ s
we e
also
applied
o
he
ab ica ion
o
mul i-
laye ed
nano ubes,
such
as
TiO2/Sb2S3/CuSCN
o
applica ion
in
solid
s a e
sola
cells
[81]
illus a ed
in
Fig.
2d,
and
SiO2/Fe2O3/SiO2
[83,84]
o
Fe3O4/Z O2/Fe3O4[85],
whose
magne ic
p ope ies
we e
explo ed
and
hei
po en ial
applica ions
o eseen.
Po ous
AAO
also
assis ed
he
ab ica ion
o
Ru
nanowi e
a ays
as
a
pla o m
o
senso
de ices
[55]
and
ZnO
nano ods
[75,76],
and
ALD
coa ed
po ous
AAO
ollowed
by
elec odeposi ion
enabled
he
ab ica-
ion
o
complex
nanos uc u es
as
TiO2-coa ed
Ni
nanowi e
a ays
[64],
Ta2O5-coa ed
Ni
nano ods
[66],
and
Au–Co
e i e
nanowi es
[86].
Likewise,
po ous
AAO
has
been
p oposed
as
sui able
pla o m
o
di e en
heal h
and
en i onmen al
applica ions
–
see
Re .
[87]
and
e e ences
he ein.
In
pa icula ,
ALD
ZnO
coa ed
po ous
AAO
exhibi ed
encou aging
an imic obial
ac i i y
wi h
po en ial
de ma-
ological
applica ions
[77,78].
The
u iliza ion
o
ALD
o
coa ing
po ous
AAO
has
p o ided
a
e y
s ong
mo i a ion
case
o
all
o he
high-aspec
1-D
nanos-
uc u es,
including
nanopo es
[88],
nano ubes
[89,90],
nano ods
[91],
nanowi es
[92],
and
b anching
nanos uc u es
[93,94]
o
a -
ious
ma e ials,
o
be
p ocessed
in
a
simila
ashion.
Among
hose,
TNT
laye s
o med
by
anodiza ion
main ain
o e on
posi ion
and
4
F.
D o ak
e
al.
/
Applied
Ma e ials
Today
14
(2019)
1–20
p omise
o
be
ea ed
by
ALD,
due
o
acile
p epa a ion
and
high
unc ionali y
o
TiO2compa ed
o
o he
ma e ials.
3.
Aspec s
o
ALD
in o
high
aspec
a io
nanos uc u es
In
o de
o
design
an
ALD
p ocess,
leading
o
con o mal
coa ings
o
HAR
nanos uc u es,
i
is
necessa y
o
unde s and
he
kine ics
and
chemis y
o
ha
pa icula
ALD
p ocess
on
he
undamen al
le el.
Nume ous
heo e ical
s udies
we e
de o ed
o
he
desc ip-
ion
o
ALD
su ace
chemis y
and
kine ics.
A
comp ehensi e
e iew
on
heo e ical
aspec s
o
ALD
is
beyond
he
scope
o
his
e iew.
Ins ead,
in
his
sec ion
we
wan
o
ocus
on
impo an
heo e i-
cal
aspec s
go e ning
ALD
in
HAR
nanos uc u es.
The
desc ip ion
o
he
ALD
p ocess
in
he
HAR
nanos uc u es
was
heo e ically
add essed
by
nume ous
models:
a
simple
kine ic
model
[95],
a
kine ic
model
coupled
wi h
Langmui
adso p ion
[96],
Mon e
Ca lo
(MC)
based
simula ions
in
molecula
[50,97–102],
Knudsen
and
di -
usi e
[103]
gas
ﬂow
egimes,
and
nume ic
o
analy ic
solu ions
o
Bol zmann
anspo
equa ion
coupled
wi h
Langmui
adso p ion
models
[104–108].
Al hough
he
s udies
used
di e en
heo e ical
amewo ks,
he
common
idea
desc ibing
he
pa ame e s
leading
o
he
con o mal
coa ing
o
HAR
nanos uc u es
allows
o
d aw
gene al
quali a i e
o e iew,
as
ollows.
One
o
he
key
aspec s
o
achie ing
con o mal
and
uni o m
coa ings
is
o
each
he
sa u a ion
egime
o
on
ALD
deposi ion.
This
si ua ion
occu s
when
he
p ecu so
molecules
ﬁll
(chemiso b
on)
all
a ailable
adso p ion
posi ions
o
he
subs a e
su ace
wi hin
e e y
ALD
cycle
(leading
o
he
sa u a ion
co e age).
The
co e-
sponding
sa u a ing
exposu e
dose
(mul iplica ion
o
sa u a ion
exposu e
ime
and
p essu e
o
p ecu so
molecules)
depends
on
he
su ace
a ea
(numbe
o
a ailable
adso p ion
posi ions
[109]),
he
su ace
eac ion
p obabili y
(su ace
s icking
coe ﬁcien ),
he
di usion
a e,
and
he
ecombina ion
loss
p obabili y
(in
case
o
plasma
ALD
p ocesses)
o
p ecu so
molecules.
Fig.
3
illus a es
he
e olu ion
o
s ep
co e age
p oﬁles
o
HAR
nanos uc u e
unde
cha ac e is ic
deposi ion
egimes
o
ALD
discussed
below.
The
ligh
blue
a ea
oge he
wi h
a ows
indica e
he
e olu ion
o
s ep
co -
e age
p oﬁle
o
HAR
nanos uc u e
(black
a ea).
Black
dashed
lines
ep esen
comple e
co e age
p oﬁle
unde
sa u a ed
egime
o
ALD.
Depending
on
he
su ace
eac ion
p obabili y
o
p ecu so s
and
he
aspec
a io
(AR)
o
nanos uc u e,
he
o ma ion
o
sa u a ed
Fig.
3.
The
illus a ion
o
e olu ion
o
s ep
co e age
p oﬁles
(ligh
blue)
o
HAR
nanos uc u e
(black)
by
ALD
unde
a ious
p ocess
egimes.
Ligh
blue
a ea
and
a ows
indica e
e olu ion
o
s ep
co e age
wi h
inc easing
ALD
exposu e
dose.
Dashed
black
lines
ep esen
co e age
p oﬁles
unde
sa u a ed
egime
condi ions
(sa u a ion
exposu e
dose).
(a)
The
eac ion-limi ed,
(b)
he
di usion-limi ed,
and
(c)
he
ecombina ion-limi ed
egimes
o
ALD
deposi ion.
(Fo
in e p e a ion
o
he
e e ences
o
colou
in
his
ﬁgu e
legend,
he
eade
is
e e ed
o
he
web
e sion
o
his
a icle.)
co e age
du ing
ALD
deposi ion
in o
HAR
s uc u es
can
be
lim-
i ed
ei he
by
he
di usion
o
he
eac ion
abili y
o
p ecu so s
[50].
The
so-called
eac ion-limi ed
egime
akes
place
o
low
su -
ace
eac ion
p obabili y
o
p ecu so
molecules
as
compa ed
o
he
di usion
p obabili y
o
a
gi en
AR.
This
co esponds
o
he
si ua-
ion
when
he
exposu e
ime
and
p essu e
in
combina ion
wi h
he
su ﬁcien
di usion
a e
allow
p ecu so
molecules
o
each
e e y
adso p ion
posi ion
a ailable
wi hin
he
po e/ ench
and
he
only
pa ame e
go e ning
he
co e age
is
he
su ace
eac ion
p oba-
bili y.
The
sa u a ing
exposu e
dose
is
no
a ec ed
by
he
po ous
na u e
o
subs a e
o
be
coa ed
and
nea ly
equals
o
he
sa u a -
ing
dose
o
plana
su aces
wi h
he
equi alen
su ace
a ea
[100].
The
co esponding
s ep
co e age
p oﬁle
o
he
po e/ ench
e ol es
almos
uni o mly
wi h
inc easing
exposu e
as
i
is
schema ically
illus a ed
in
Fig.
3a.
E en
unsa u a ed
co e age
wi hin
one
cycle
o
ALD
can
lead
o
he
g ow h
o
uni o m
coa ings
o
HAR
nanos-
uc u es.
This
is
simila
o
chemical
apo
deposi ion
whe e
he
con o mali y
inc eases
o
low
eac ion
p obabili ies
as
a
esul
o
educed
deple ion
o
p ecu so s
along
he
ia
[110].
On
he
o he
hand,
he
di usion-limi ed
egime
occu s
when
he
eac ion
p obabili y
(s icking
coe ﬁcien )
o
p ecu so
molecules
is
much
la ge
han
hei
di usion
p obabili y
o
each
bo om
o
an
HAR
nanos uc u e.
The
p ecu so
molecules
chemiso b
on
he
a ailable
su ace
si es
successi ely
om
he
en ance-opening
o
he
nanos uc u e
and
he
p ecu so
co e age
p oﬁle
e ol es
in
he
on -like
manne
wi h
he
inc easing
exposu e
as
depic ed
in
Fig.
3b.
The
sa u a ing
exposu e
dose
app oxima ely
scales
wi h
second
powe
o
AR
[50,95].
The
g adien
o
he
co e age
p oﬁle
wi hin
he
on
is
s ep-like
o
eac ion
p obabili y
o
100%
and
i
g adually
smoo hens
wi h
dec easing
eac ion
p obabili y
[97].
In
he
case
o
plasma
ALD
p ocesses,
he
sa u a ion
exposu e
dose
is
s ongly
a ec ed
by
he
ecombina ion
p obabili y
o
he
p ecu so s,
e.g.
he
wall
ecombina ion
o
plasma
adicals
o
ozone
[100,101].
P ecu so
molecules
a he
end
o
unde go
ecombi-
na ion
hen
o
each
bo om
o
HAR.
The
co e age
p oﬁles
in
ecombina ion-limi ed
egimes
a e
complex
and
no
uni o m,
as
i
is
d awn
in
Fig.
3c,
and
he
o ma ion
o
sa u a ion
co e age
is
possible
only
o
he
limi ed
AR
wi h
signiﬁcan
sa u a ion
doses
[100,106,111,112].
Repea ed
ALD
cycles
(wi h
cons an
exposu e
ime)
lead
o
he
g ow h
o
hicke
coa ing
and
consequen ly
o
change
o
cha ac-
e is ic
dimension/ adius
o
opening
o
HAR
nanos uc u e.
As
a
consequence,
when
he
hickness
o
coa ing
is
compa able
o
adius
o
he
opening
o
po e),
he
esul ing
hickness
p oﬁle
is
a ec ed
as
he
di usion
becomes
mo e
limi ed.
Fo
such
cases,
he
expo-
su e
ime
h oughou
epea ed
ALD
cycles
needs
o
be
p ope ly
scaled
in
o de
o
achie e
he
uni o m
hickness
o
he
ﬁnal
coa ing
[107].
Gene ally,
he
wo ks
in oduced
abo e
show
examples
o
se
o
expe imen al
pa ame e s
go e ning
he
uni o mi y
o
ALD
coa -
ing
wi hin
HAR
nanos uc u es.
The
de e mina ion
o
he
su ﬁcien
sa u a ion
dose
o
p ecu so
wi hin
one
ALD
cycle
is
c i ical
o
he
success ul
ALD
o
uni o m
coa ings
o
HAR
nanos uc u es.
In
he
eali y,
he
ALD
p ocess
is
inﬂuenced
by
many
expe imen al
pa ame e s
depending
on
ype
o
p ecu so ,
subs a e
ma e ial,
ALD
p ocess
pa ame e s,
and/o
ALD
eac o
design.
The
esul s
o
simula ion
models
o
ALD
deposi ion
ep esen
quali a i e
suppo
o
expe imen al
de e mina ion
o
pa ame e s
leading
o
sa u a ed
egime
o
ALD
deposi ions,
which
need
o
be
pe o med
and
op i-
mized
o
each
sys em
and
coa ing
ma e ial
indi idually.
4.
ALD
in o
TiO2nano ube
laye s
Anodic
TiO2nano ubes,
p epa ed
by
he
anodiza ion
o
Ti,
go
in o
he
o e on
o
1-D
nanos uc u ed
ino ganic
ma e ials
F.
D o ak
e
al.
/
Applied
Ma e ials
Today
14
(2019)
1–20
5
since
he
de elopmen
o
o ganic
based
elec oly es
(such
as
e hy-
lene
glycol
o
glyce ol),
which
allowed
g ow h
o
HAR
TNT
laye s
[10,113,114].
The
abili y
o
p epa e
HAR
TNT
laye s
ep esen s
a
key
s ep
o
success ul
applica ions
o
TNT
laye s.
The
nex
impo an
s ep
in
he
de elopmen
o
TNT-based
applica ions
is
hei
ailo -
ing
by
seconda y
ma e ials,
which
ep esen s
a
a ge
inhe en ly
sui able
o
ALD
u iliza ion.
4.1.
Pionee ing
e o s
The
ﬁ s
wo ks
de o ed
o
coa ing
o
anodized
TNT
laye s
by
ALD
ha e
been
ocused
on
sensi iza ion
o
TNT
laye s
by
In2S3 o
sola
ene gy
con e sion
[115]
and
on
he
ole
o
Al2O3,
Ta2O5,
and
TiO2ALD
coa ings
on
elec ic
p ope ies
o
coa ed
TNT
laye s
[116].
The
wo k
o
Sa ka
e
al.
[111]
p esen s
an
ex ensi e
expe -
imen al
s udy
o
ALD
g ow h
o
In2S3applied
p ac ically
on
he
coa ing
o
TNT
laye s
wi h
AR
o
≈62.
The
ALD
has
been
pe o med
by
u iliza ion
o
indium(III)
ace ylace ona e
(In(acac)3)
and
H2S
p ecu so s.
The
au ho s
pe o med
ho ough
analysis
o
In2S3ALD
p ocess
on
ﬂa
subs a es
ﬁ s .
Qua z
c ys al
mic obalance
(QCM),
X- ay
eﬂec i i y
(XRR),
and
FTIR
we e
used
in
o de
o
moni o
mass
gains
du ing
each
eac an
cycles,
o
measu e
he
g ow h
pe
cycle
and
i s
empe a u e
dependence,
o
e i y
he
sel -limi ed
su ace
chemis y
o
u ilized
p ecu so s,
and
o
iden i y
su ace
species
o med
du ing
sequen ial
su ace
eac ions.
The
e iﬁed
ALD
p ocess
pa ame e s
wi h
inc eased
exposu e
imes
we e
u i-
lized
o
sensi iza ion
o
HAR
TNT
laye s
by
5
nm
hick
In2S3ALD
coa ing
(Fig.
4a).
Un o una ely,
de ailed
SEM
o
TEM
in es iga ions
o
p o e
he
uni o mi y
o
ALD
coa ing
o
TNT
laye
we e
miss-
ing
in
ha
pape .
The
p ominen
e ec
o
he
In2S3coa ing
on
he
pho oelec ochemical
(PEC)
p ope ies
o
he
TNT
laye s
is
illus-
a ed
in
Fig.
4b.
The
In2S3coa ed
TNT
laye s
exhibi ed
a
educed
op ical
band
gap
o
2.07
eV
and
eached
10%
ex e nal
quan um
e ﬁ-
ciency
o
pho on
ene gy
>2.5
eV
while
he
uncoa ed
TNT
laye
was
gene ally
pho o-inac i e
o
pho on
ene gy
<3.0
eV.
The
obse ed
quan um
e ﬁciency
was
signiﬁcan ly
below
he
heo e ically
p e-
dic ed
maximum
quan um
e ﬁciency
(≈70%).
The
limi ed
quan um
e ﬁciency
was
a ibu ed
o
ecombina ion
losses
and
cha ge
col-
lec ion/injec ions
p ocesses.
The
wo k
o
Tupala
e
al.
[116]
p esen s
ALD
coa ings
o
TNT
laye s
wi h
AR
o
≈10
by
selec ed
me al
oxides:
Al2O3,
Ta2O5,
and
TiO2.
TNT
laye s
we e
p epa ed
by
anodiza ion
o
Ti
hin
lay-
e s
e apo a ed
on
ITO
conduc i e
glass.
The
TNT
laye s
p epa ed
on
anspa en
conduc i e
suppo
a e
a
e y
sui able
ma e ial
o
sola
ene gy
applica ions
(e.g.
pe o ski e
sola
cells
[8])
and
hei
unc ionaliza ion
is
an
impo an
echnological
s ep.
The
ALD
was
pe o med
wi h
es ablished
p ecu so s:
ime hylaluminium
(TMA,
Al(CH3)3),
an alum
pen oxide
(Ta(OE )5),
and
i anium
e aisop opoxide
(Ti(OiP )4)
in
combina ion
wi h
wa e .
The
a ge
hickness
o
he
coa ing
was
5
nm.
The
example
o
TiO2coa ed
TNT
laye s
is
shown
in
Fig.
4c.
TNT
laye s
coa ed
by
ALD
we e
shown
o
ha e
highe
elec ic
conduc i i ies
(ac oss
he
laye )
compa ed
o
hei
uncoa ed
coun e pa s,
as
shown
in
Fig.
4d.
Despi e
bo h
hese
pionee ing
wo ks
clea ly
demons a ed
he
unc ionali y
o
ALD
coa ed
TNT
laye s,
hey
did
no
p o ide
any
di ec
e idence
o
uni o mi y
o
ALD
coa ings
wi hin
he
TNT
laye s
(such
as
SEM
and
TEM
images).
The
ollow
up
wo k
o
Macak
e
al.
[117]
p esen ed
in e es ingly
imp o ed
ligh
apping
p ope ies
o
plasma
ALD
In2O3coa ed
TNT
laye s
wi h
AR
up
o
≈80
oge he
wi h
mic oscopic
e idence
o
he
p esence
o
he
In2O3coa ing.
The
ALD
deposi ed
In2O3was
ound
o
success ully
coa
he
en i e
TNT
in e io s
wi h
g adually
dec easing
hickness
o
he
coa ing
om
30
o
5
nm
om
op
o
he
bo om
o
he
TNT
laye
(wi h
AR
≈
80,
and
laye
hickness
o
≈8
␮m),
espec i ely.
The
obse ed
hickness
g adien
o
In2O3 esul ed
om
a
limi a ion
o
plasma
assis ed
ALD
Fig.
4.
Pionee ing
ALD
coa ings
o
TNT
laye s.
(a)
The
In2S3coa ing
o
TNT
laye s
and
(b)
co esponding
quan um
e ﬁciency.
(c)
The
TiO2coa ed
TNT
laye
and
(d)
he
cu en
densi y
h ough
he
TNT
laye
modiﬁed
by
a ious
me al
oxide
coa ings.
(a)
and
(b)
we e
ep oduced
om
[115]
and
(c)
and
(d)
we e
ep oduced
om
[116].

6
F.
D o ak
e
al.
/
Applied
Ma e ials
Today
14
(2019)
1–20
Fig.
5.
ALD
Al2O3coa ing
o
TNT
laye s
wi h
aspec
a io
o
180:
(a)
Inﬂuence
o
exposu e
ime
o
TMA
p ecu so
du ing
one
ALD
cycle
on
uni o mi y
o
hickness
o
Al2O3
coa ing
wi hin
TNT
laye ;
(b–e)
Illus a ion
o
uni o m
hickness
o
Al2O3coa ing
o
5
s
TMA
exposu e
ime
as
e ealed
by
SEM
inspec ion
h ough
ou
di e en
dep h
le els
–
op,
nea - op,
middle,
and
bo om,
espec i ely.
Rep oduced
om
[118].
o
coa
uni o mly
HAR
nanos uc u es
due
o
he
limi ed
li e ime
o
plasma-gene a ed
adicals
and
ecombina ion
e ec s.
Con a y,
u ilizing
he
he mal
ALD
p ocess,
Zazpe
e
al.
[118]
epo ed
uni o m
ALD
deposi ion
o
Al2O3coa ings
wi hin
TNT
lay-
e s
wi h
a
high
AR
o
≈180.
The
con o mali y
o
ALD
Al2O3coa ings
wi h
a ious
exposu e
imes
o
TMA
p ecu so
was
inspec ed
by
SEM
a
di e en
dep h
le els
o
he
TNT
laye s
(and
suppo ed
by
in
si u
QCM
measu emen s
and
STEM
in es iga ions).
Wi h
an
inc easing
exposu e
ime
o
TMA,
he
ALD
coa ing
was
ound
o
be
uni o m
down
o
he
deepes
le els
o
TNT
laye s,
as
shown
in
Fig.
5a.
Op imal
exposu e
ime
led
o
uni o m
coa ings
wi hin
he
en i e
TNT
laye s,
as
demons a ed
by
SEM
images
measu ed
a
ou
di e en
dep h
le els
o
he
coa ed
TNT
laye s,
shown
in
Fig.
5b–e.
The
obse ed
esul s
co espond
o
di usion
limi ed
egime
o
ALD
g ow h,
as
in oduced
in
[50]
and
discussed
in
he
p e ious
sec ion.
These
pionee ing
wo ks
p esen
he
success ul
u iliza ion
o
ALD
o
coa ing
o
TNT
laye s
by
seconda y
ma e ials
wi h
ad anced
unc ionali ies,
ele an
o
sola
ene gy
con e sion
and
o he
op o-
elec onic
applica ions.
Ob ained
esul s
clea ly
demons a e
ha
he
ul a- hin
ALD
coa ing
is
able
o
signiﬁcan ly
al e
he
unc-
ionali y
o
TNT
laye s
and
p o e
ha
ALD
is
he
mos
sui able
and
p ac ical
echnique
o
ailo
p ope ies
o
HAR
nanos uc u es.
Table
1
p esen s
a
comple e
lis
o
epo s
u ilizing
ALD
o
coa -
ing
HAR
anodic
TNT
laye s.
In
he
ollowing
ex ,
hese
epo s
will
be
in oduced
in
hema ically
selec ed
sec ions,
as
illus a ed
in
Fig.
1.
4.2.
Ligh
abso p ion
and
pho oelec ochemical
con e sion
While
he
TiO2e ﬁcien ly
abso bs
ligh
in
he
UV
spec al
ange,
he
main
limi a ion
o
sola -ligh -d i en
applica ions
o
TiO2is
i s
ela i ely
la ge
in insic
band
gap
(3.2
eV
o
ana ase
and
3.0
eV
o
u ile)
which
does
no
allow
ligh
abso p ion
wi hin
he
isible-ligh
spec al
ange.
Besides
a
dye
sensi iza ion
[119]
o
a
me al/non-me al
doping
[120–124],
an
al e na i e
way
o
imp o e
isible-ligh
pho oelec ochemical
(PEC)
pe o mance
o
TiO2is
he
modiﬁca ion
o
TiO2by
a
sui able
na ow
band
gap
semiconduc o .
The
pho oexci a ion
connec ed
wi h
he
e ec i e
cha ge
sepa a ion
leading
o
he
elec on
injec ion
o
he
TiO2conduc ion
band
can
signiﬁcan ly
enhance
he
isible-ligh
pho o esponse
o
TiO2based
he e os uc u es,
such
as
nanopa icula e
and
nano ubula
laye s.
In
o de
o
abso b
mos
o
he
inciden
ligh ,
he
ange
o
hick-
nesses
o
he
compac
abso be
laye s
should
be
on
he
mic oscale.
Thus,
he
ALD
does
no
quali y
i sel
as
mos
sui able
deposi ion
echnique
a
ﬁ s
glance
o
his
pu pose,
since
i
is
echnique
sui -
able
o
p oduc ion
o
coa ings
wi h
hickness
on
he
nanome e
scale.
Howe e ,
he
si ua ion
is
diame ically
di e en
in
he
case
when
HAR
nanos uc u es
a e
used
as
subs a es.
Only
a
ew
ens
o
nm
hick
abso be
laye
(o
e en
less)
a e
e ec i e
enough
o
e ﬁ-
cien
sola
ene gy
ha es ing,
as
a
esul
o
emendously
inc eased
speciﬁc
su ace
a ea
o
he
HAR
nanos uc u e,
allowing
o
each
he
e ec i e
abso p ion
mass
o
sensi ize
wi h
compa ably
hinne
coa ings
han
o
plana
subs a es,
and
he
mul iple
ligh
sca e ing
e en s,
p olonging
signiﬁcan ly
op ical
pa h
in
HAR
nanoma e ials
[125–127].
Mo eo e ,
a
low
hickness
o
abso be
laye
is
also
c i -
ical
o
he
educ ion
o
cha ge
ecombina ion
losses
du ing
cha ge
ans e
h ough
he
ma e ial.
The
leng h-scale
o
e ec i e
cha ge
sepa a ion
is
cha ac e ized
by
he
size
o
he
deple ion
laye .
On
he
nanome e
scale,
he
ALD
se es
as
an
excellen
ool
o
deposi-
ion
o
uni o m
coa ings
wi h
minimum
amoun
o
de ec s,
which
ep esen s
undamen al
building
block
o
highly
e ﬁcien
TiO2
nanoma e ials
o
be
used
o
sola
ene gy
con e sion
applica ions.
The
ﬁ s
wo k
u ilizing
ALD
o
coa
TNT
laye s
by
seconda y
isible-ligh
abso bing
ma e ial
was
ca ied
ou
by
Sa ka
e
al.
[115],
as
discussed
in
he
p e ious
sec ion.
The
ollowing
wo k
was
pe o med
by
Huang
e
al.
[128],
who
deposi ed
Co3O4in o
TNT
laye s
wi h
AR
o e
100.
The
ALD
was
pe o med
u ilizing
bis(cyclopen adienyl)cobal (II)
(Co(Cp)2)
and
O3as
ALD
p ecu -
so s.
The
hickness
o
he
coa ing
was
anging
up
o
20
nm
and
i
was
e iﬁed
by
SEM
and
by
he
calib a ion
on
e e ence
Si
wa e .
ALD
Co3O4coa ed
TNT
laye s
we e
explo ed
o
he
isible-ligh
(>420
nm)
induced
pho ocu en
gene a ion.
The
bes
pho ocu en
esponse
was
obse ed
o
TNT
laye s
coa ed
by
Co3O4wi h
a
hick-
ness
o
4
nm.
The
co esponding
PEC
pe o mances
o
he
4
nm
ALD
Co3O4/TNT
laye ,
a
e e ence
Co3O4/TNT
laye
coa ed
by
imp egna-
ion
me hod,
and
a
e e ence
blank
TNT
laye
a e
shown
in
Fig.
6a
and
b.
The
enhanced
PEC
pe o mance
o
ALD
Co3O4/TNT
laye s
was
a ibu ed
o
he
a ou able
band
alignmen
o
Co3O4/TNT
laye s
as
e ealed
by
XPS,
shown
in
Fig.
6c,
and
o
he
ALD
echnique
used,
p o iding
uni o m
Co3O4coa ing
o
con olled
hickness
and
wi h
minimal
amoun
o
de ec s,
which
main ained
he
la ge
open
su -
ace
a ea
o
TNT
laye s
and
minimized
cha ge
ecombina ion
losses.
Howe e ,
i
is
wo h
o
no e
ha
he
epo ed
absolu e
alues
o
he
pho ocon e sion
e ﬁciency
(Fig.
6b)
we e
ex emely
low.
A
signiﬁcan ly
p onounced
posi i e
e ec
on
he
isible-ligh
pho o esponse
can
be
expec ed,
when
CdS
is
u ilized
as
a
ligh
F.
D o ak
e
al.
/
Applied
Ma e ials
Today
14
(2019)
1–20
7
Table
1
Summa y
o
ALD
coa ings
on
TNT
laye s
oge he
wi h
he
in o ma ion
abou
geome y
o
TNT
laye s
(*
di e ence
be ween
inne
and
ou e
ube
diame e
aken
in o
accoun ).
Ma e ial
Yea
L
(␮m)
D
(nm)
AR
Re e ence
ALD
uni o mi y
Al2O32016
20
110
182
[118]
Ligh
abso p ion In2S32010
4
65
62
[115]
Co3O42015
10
85
118
[128]
CdS
2017
0.6
95–56–35
6;
11;
17
[134]
CdS
2018
1–130
80–230
13–897
[125]
MoSeOx2017
5
230
22
[135]
Cha ge
sepa a ion Al2O32014
23
100
230
[139]
Al2O32014
x
97
x
[140]
Al2O3+
QD 2016
1.7
120
14
[141]
TiO2,
Al2O3,
ZnO
+
QD
2017
1.7
110
15
[142]
ZnO
2014
4.5
120
38
(*60)
[143]
ZnO
2014
0.5
60
8
[144,145]
ZnO
+
QD
2016
2.4
97
25
[146]
ZnO
2016
0.5
60
8
[147]
ZnO
+
P3HT
2017
0.5
60
8
[148]
TiO22017
5
230
22
[149]
(Pho o)ca alysis Ti,
Al,
Zn,
Sn,
Cu,
W 2014
7.5
95
79
[175]
Pd
2015
1
70
14
[172]
SnO2+
Pd
2017
1
70
14
[179]
P
2018
7
100
70
[173]
P
2018
1–5–20
80–230–110
13–22–181
[174]
S abili y
and
physical
p ope ies
Al2O3,
TiO2,
Ta2O52012
1
100
10
[116]
In2O32015
0.5–2–8 80–80–100 6–25–80
[117]
Al2O32017
20
110
182
[181]
Gas
sensing
ZnO
2017
5
230
22
[185]
Ene gy
s o age ZnO
Al2O32013
2
100
20
[200]
Al2O32017
5
230
22
[201]
L
=
ube
leng h;
D
=
inne
ube
diame e .
abso be
wi h
TiO2[129].
CdS
is
p edominan ly
deposi ed
in
he
o m
o
quan um
do s
(QD)
by
con en ional
echniques
such
as
chemical
ba h
deposi ion
[20,130],
successi e
ionic
laye
adso p ion
(SILAR)
[21,131],
o
elec odeposi ion
[132],
which
can
gene ally
p o ide
deco a ion
o
HAR
nanos uc u es
wi h
much
mo e
limi ed
uni o mi y
han
ALD.
The
expec ed
e ﬁciency
o
CdS
sensi ized
TNT
laye s
scales
wi h
he
o al
su ace
a ea
o
TNT
laye
as
long
as
he
TNT
laye
can
be
uni o mly
coa ed
by
sensi ize
(and
di usion
leng h
o
cha ge
ca ie s
is
long
enough
o
each
collec ing
elec odes
[133]).
A
di ec
way
o
inc ease
su ace
a ea
(AR)
o
TNT
laye s
is
(i)
o
dec ease
he
diame e
o
nano ubes
(inc ease
hei
a eal
densi y)
o
(ii)
o
inc ease
he
o e all
hickness
o
TNT
laye s.
The
nex
wo
wo ks
well
desc ibe
cases
(i)
and
(ii).
K bal
e
al.
[134]
epo ed
downscaling
he
ube
diame e
o
ALD
CdS
sensi ized
TNT
laye s
o
e ﬁcien
PEC
ene gy
con e sion.
TNT
laye s
wi h
hickness
o
600
nm
and
wi h
di e en
a e age
ube
diame e s
o
35,
56,
and
96
nm
–
ea u ing
a ious
su ace
a eas
(52,
29,
and
23
cm2/cm2,
espec i ely)
–
we e
coa ed
by
6
nm
hick
CdS
laye s
by
ALD
(using
dime hylcadmium
and
H2S
as
p e-
cu so s).
The
co esponding
mo phology
o
CdS
coa ed
TNT
laye s
wi h
a ious
ube
diame e s,
cap u ed
by
SEM,
is
shown
in
Fig.
7a–c.
The
ob ained
inciden
pho on
o
con e sion
e ﬁciencies
(IPCE)
a e
shown
in
Fig.
7d,
espec i ely.
The
CdS
coa ing
o
TNT
laye s
led
o
he
s ong
enhancemen
o
hei
pho o esponse
in
he
isible-ligh
spec al
ange.
The
pho o esponse
ose
wi h
he
dec easing
TNT
laye
ube
diame e
(inc easing
su ace
a ea).
The
composi e
ALD
CdS/TNT
laye
wi h
he
smalles
ube
diame e
≈
35
nm
(la ges
su ace
a ea
≈
52
cm2/cm2)
exhibi ed
IPCE
abo e
50%
up
o
470
nm
wi h
he
pho o esponse
onse
a ound
520
nm
(co esponding
wi h
he
band
gap
o
CdS
≈
2.4
eV).
In
a
ollow
up
s udy,
Zazpe
e
al.
[125]
p esen ed
on
he
upscaling
o
he
hickness
o
ALD
CdS
coa ed
TNT
laye s.
Ul a
HAR
TNT
laye s
wi h
hicknesses
be ween
1
␮m
and
130
␮m
(AR
up
o
900)
we e
coa ed
by
ALD
CdS
wi h
hicknesses
be ween
2
nm
and
10
nm.
The
e idence
o
10
nm
CdS
coa ing
o
a
ac ion
o
TNT
laye
ea u ed
by
HAADF
STEM
image
and
STEM/EDX
elemen al
mapping
wi h
co esponding
line
p oﬁles
is
depic ed
in
Fig.
7e–g,
espec i ely.
The
u iliza ion
o
CdS
coa ed
ul a
HAR
TNT
laye s
esul ed
ﬁ s
o
all
in o
a
supe io
PEC
pe o mance,
as
demons a ed
by
high
IPCE
alues
o
a ound
70%.
In
addi ion,
i
esul ed
in
an
appa en
shi
o
he
onse
o
isible-ligh
pho o esponse
o
CdS-TNT
laye s
up
o
675
nm
(≈1.8
eV,
signiﬁcan ly
below
he
band
gap
o
CdS)
while
he
IPCE
a ound
70%
was
kep
in
he
ange
om
300
o
600
nm,
as
i
is
shown
in
Fig.
7h.
The
unexpec edly
signiﬁcan
shi
o
he
onse
o
pho o esponse
was
a ibu ed
o
he
ad an ageous
geome y
o
he
ul a
HAR
TNT
laye s
gi ing
ise
o
mul iple
ligh -sca e ing
e ec s,
which
ex emely
p olong
he
op ical
pa h
o
ligh
wi hin
nanos uc-
u e
as
illus a ed
in
Fig.
7i
and
he e o e
enhances
he
p obabili y
o
cap u ing
ligh
by
sub-band
gap
ansi ions
in
con o mal
and
uni o m
ALD
CdS
coa ings.
The
ob ained
esul s
clea ly
demon-
s a e
he
p oﬁ abili y
o
ALD
o
ligh
ha es ing
applica ions
o
e ec i ely
u ilize
he
deposi ed
ma e ial
in
o m
o
a
uni o m
ul a-
hin
coa ing,
pe ec ly
adop ing
a
la ge
su ace/in e ace
a ea
o
he
suppo
nanos uc u e,
using
TNT
laye
as
a
model
example.
The
imp o ed
pho o esponse
o
ALD
coa ed
TNT
laye s
was
also
p esen ed
by
Ng
e
al.
[135],
who
deposi ed
molybdenum
oxyse-
lenide
(MoSexOy)
coa ing
u ilizing
Mo(CO)6and
(CH3Si)2Se
ALD
p ecu so s.
The
op imal
hickness
o
he
MoSexOycoa ing
o
max-
imal
pho ocu en
gene a ion
and
pho oca aly ic
deg ada ion
o
model
dye
(me hylene
blue
(MB))
was
ound
o
be
wi hin
he
ange
o
2–5
nm.
The
s udy
ep esen s
a
undamen al
s ep
o
u u e
ai-
lo ed
deposi ion
o
ansi ion
me al
dichalcogenides,
such
as
MoSe2
[136],
in o
TNT
laye s
by
ALD.
4.3.
Cha ge
sepa a ion
Gene ally,
one
o
he
key
limi ing
ac o s
o
he
pe o mance
o
sola
cell
de ices
is
he
ecombina ion
o
pho ogene a ed
cha ge
ca ie s.
Main
cha ge
ecombina ion
cen es
a e
ep esen ed
by
de ec s,
ap
s a es
and
cha ge
impu i ies
a
su aces
and
in e aces,
8
F.
D o ak
e
al.
/
Applied
Ma e ials
Today
14
(2019)
1–20
Fig.
6.
PEC
pe o mance
o
4
nm
hick
Co3O4coa ing
o
TNT
laye s
by
ALD.
(a)
The
pho ocu en
densi y
and
(b)
pho ocon e sion
e ﬁciency
o
Co3O4/TNT
laye
he -
e os uc u e
upon
isible-ligh
illumina ion
(>420
nm,
100
mW/cm2).
(c)
Illus a ion
o
band
alignmen
wi hin
he
he e os uc u e
as
de e mined
by
XPS.
Rep oduced
om
[128].
e.g.
Ti3+ in e s i ials
gi ing
ise
o
Ti
3d
s a es
below
conduc ion
band
edge
in
TiO2[137,138].
Fo
HAR
nanos uc u es
(which
a e
also
high
su ace
a ea
ma e ials),
he
p e en ion
o
ecombina ion
a
su aces/in e aces
is
o
u mos
impo ance.
One
way
o
sup-
p ess
he
ecombina ion
on
su ace
de ec s
is
o
p epa e
su aces
wi h
lowes
possible
concen a ion
o
su ace
de ec s.
This
can
be
ealized
ei he
by
op imiza ion
o
he
g ow h
condi ions
o
ha
pa -
icula
ma e ial
i sel
o
by
deposi ion
o
an
o e laye
o
a
sui able
de ec -deple ed
ma e ial
–
passi a ion
laye
–
which
passi a es
he
su ace
de ec s
o
an
unde lying
ma e ial.
Howe e ,
such
an
o e -
laye
should
no
al e
he
p ope ies
o
he
unde lying
ma e ial
and
should
be
e y
hin
no
o
limi
he
cha ge
ans e
h ough
he
laye
i sel .
The
cha ge
ecombina ion
a
he
in e aces
can
be
sup-
p essed
by
a
combina ion
o
compa ible
ma e ials,
o ming
a
high
quali y
in e ace
wi h
low
amoun
o
de ec s
and
wi h
an
inhe en
ene gy
ba ie
o
he
back
ans e
o
elec ons
o
holes.
ALD,
being
inhe en ly
ideal
o
he
deposi ion
o
con o mal
and
uni o m
coa -
ings
wi h
minimal
amoun
o
de ec s
and
hickness
con olled
on
he
nanome e
scale,
ep esen s
e y
p omising
echnique
o
he
g ow h
o
blocking/passi a ing
laye s.
The
c edi
o
ALD
is
eﬂec ed
by
a
high
numbe
o
ecen
s udies
u ilizing
ALD
o
deposi ion
o
blocking
laye s.
Fo
he
case
o
TNT
laye s,
he
ALD
was
u ilized
o
he
deposi ion
o
Al2O3[139–142],
ZnO
[142–148],
and
TiO2[142,149]
hin
coa ings
as
blocking
laye s
in
o de
o
imp o e
he
PEC
pe o mance
o
TNT
laye s.
In
addi-
ion,
he
same
ma e ials
we e
also
u ilized
as
blocking
laye s
in
mesopo ous
TiO2laye s
used
in
DSSC
[150–154].
Wide
band
gap
and
almos
ideal
ALD
g ow h
make
Al2O3a
p o o ypical
ma e ial
o
a
blocking
laye
deposi ed
by
ALD.
ALD
g ow h
o
Al2O3is
usually
ealized
using
TMA
and
wa e
as
p e-
cu so s.
Gui
e
al.
[140]
coa ed
TNT
laye s
by
Al2O3by
10–200
ALD
cycles
a
100–400 ◦C
empe a u e
ange
in
o de
o
enhance
he
PEC
wa e
spli ing
by
he
su ace
passi a ion
o
TNT
laye s.
The
bes
PEC
pe o mance
was
obse ed
o
Al2O3coa ing
by
25
cycles
(2.6
nm)
a
200 ◦C
yielding
1.8
imes
highe
pho ocu en
densi y
han
ba e
TNT
laye s.
Kim
e
al.
[139]
coa ed
TNT
laye s
wi h
AR
o
≈230
by
ul a hin
Al2O3coa ings
wi h
hickness
o
0.1–0.6
nm
(deposi ed
by
1–6
ALD
cycles)
a
200 ◦C
and
subsequen ly
sensi-
ized
hem
wi h
N-719
u henium
based
dye.
The
s udy
showed
ha
al eady
a e
one
ALD
cycle,
he
Al2O3coa ing
led
o
an
inc ease
o
open
ci cui
ol age
and
p olonged
he
elec on
li e
imes.
In
con-
as ,
Al2O3coa ings
deposi ed
by
mo e
han
wo
ALD
cycles
was
ound
o
educe
he
pho ocu en
densi y
as
a
esul
o
an
inc ease
o
he
ene gy
ba ie
o
he
injec ion
o
elec ons
om
he
dye
o
he
TiO2conduc ion
band.
Zeng
e
al.
[141]
examined
he
ole
o
ALD
Al2O3o e laye s
wi h
a ious
hicknesses
on
PEC
pe o mance
o
coa ed
CdS
and
PbS
QD
sensi ized
TNT
laye s.
The
Al2O3o e laye s
we e
deposi ed
by
3–100
ALD
cycles.
The
op imal
hickness
lead-
ing
o
imp o ed
cha ge
collec ion
e ﬁciency
was
ound
o
be
1.5
nm
(achie ed
by
30
ALD
cycles)
yielding
1.6
imes
highe
pho ocu en
densi y
han
o
ba e
QD
sensi ized
TNT
laye s.
Fo
he
illus a ion
o
p ope ies
o
Al2O3ALD
coa ing
o
TNT
laye s,
he
s uc u e
o
30
ALD
cycles
Al2O3coa ed
QD-TNT
laye s
and
PEC
e ﬁciency
wi h
model
o
beneﬁcial
in e ace
band
alignmen
o
ALD
Al2O3coa ed
QD-TNT
laye s
a e
shown
in
Fig.
8a–c.
Fundamen al
mechanisms
behind
he
passi a ion
e ec
o
Al2O3o e laye s
can
be
lea ned
om
he
ﬁeld
o
silicon
sola
cells
[155].
Al2O3coa ings
help
o
educe
he
su ace/in e ace
ecombi-
na ion
a e
by
(i)
passi a ion
o
su ace/in e ace
de ec s,
so-called
chemical
passi a ion
which
is
ealized
by
hyd ogen
inco po a ed
na u ally
in
bulk
Al2O3[156]
and
(ii)
by
signiﬁcan
educ ion
o
he
concen a ion
o
one
ype
o
cha ge
ca ie
a
he
su ace/in e ace
by
an
elec ic
ﬁeld
deno ed
as
ﬁeld
e ec
passi a ion,
ha
s ems
om
he
inhe en
accumula ion
o
nega i e
cha ge
in
Al2O3nea
he
in e ace,
connec ed
o
de ec s
in
o m
o
Al
acancies
and
O
in e s i ials
[157].
The
highe
is
he
empe a u e
o
ALD
p ocess,
he
lowe
amoun
o
hyd ogen
is
ound
in
Al2O3,
esul ing
in
less
e ec-
i e
chemical
passi a ion
[158].
The
op imal
empe a u e
ange
o
Al2O3ALD
deposi ion
is
ound
o
be
be ween
150
and
250 ◦C.
The
pos -deposi ion
annealing
o
Al2O3imp o es
he
passi a ion
e ec
wi h
onse
abo e
300 ◦C
as
i
p omo es
di usion
o
H
owa ds
he
in e ace
and
also
inc eases
he
nega i e
cha ge
accumula ed
in
Al2O3.
The
hickness
also
a ec s
he
passi a ion
capabili y
o
Al2O3.
The
chemical
passi a ion
s a s
o
be
limi ed
o
coa ings
hinne
han
5
nm,
while
he
ﬁeld
e ec
passi a ion
emains
down
o
2
nm.
On
he
o he
hand,
inc eased
hickness
o
he
passi a ion
laye
limi s
i s
cha ge
ans e
p ope ies.
The
ade-o
be ween
F.
D o ak
e
al.
/
Applied
Ma e ials
Today
14
(2019)
1–20
9
Fig.
7.
ALD
coa ing
o
TNT
laye s
by
CdS
ligh -abso be
laye
o
imp o ed
isible-ligh
pho o esponse.
(a–c)
SEM
images
o
6
nm
CdS
coa ed
TNT
laye s
wi h
a e age
ube
diame e s
35
nm,
56
nm,
and
95
nm,
espec i ely,
scale
ba
100
nm.
(d)
IPCE
o
TNT
laye s
wi h
a ious
nano ube
diame e
sensi ized
by
6
nm
hick
ALD
CdS
coa ing
upon
illumina ion
wi h
a
monoch oma ized
ligh
sou ce
(e)
High
angle
annula
da k
ﬁeld
(HAADF)
STEM
image
and
( )
STEM/EDX
elemen al
map
o
ac ion
o
nano ube
coa ed
by
10
nm
hick
CdS
o e laye ,
he
g een
a ows
ma k
he
co esponding
elemen al
line
p oﬁles
shown
in
(g).
(h)
IPCE
o
TNT
laye s
wi h
a ious
hicknesses
sensi ized
by
5
nm
hick
ALD
CdS
coa ing.
(i)
Illus a ion
o
mul iple
ligh
sca e ing
e ec s
p olonging
he
op ical
pa h
o
ligh
in
TNT
laye
and
acili a ing
e ﬁcien
ligh
ha es ing.
(a–d)
Rep oduced
om
[134]
and
(e–i)
ep oduced
om
[125].
he
passi a ion
and
cha ge
ans e
p ope ies
yields
op imal
Al2O3
hicknesses
o
a ound
2
nm
employed
as
capping
passi a ion
laye
[155].
The
abo e
discussed
esul s
clea ly
demons a e
he
unique-
ness
o
ALD
o
ailo
he
coa ings
o
HAR
nanos uc u es
on
a omic
le el
and
ul ahigh
p ecision,
non- easible
o
al e na i e
deposi-
ion
echniques.
In
an
analogous
way
o
Al2O3,
se e al
wo ks
add essed
o
which
ex en
he
PEC
pe o mance
o
TNT
laye s
based
pho oan-
odes
can
beneﬁ
om
he
seconda y
coa ing
by
hin
ZnO
o e laye ,
deposi ed
by
ALD.
ZnO
ep esen s
a
di ec
band
gap
semiconduc-
o
wi h
he
band
gap
alue
(3.4
eV)
close
o
TiO2,
which
is
known
o
p omo e
e ﬁciency
o
DSSC
[159].
Jeong
e
al.
[143]
coa ed
TNT
laye s
by
10
nm
hick
ZnO
(using
50
ALD
cycles)
and
sensi ized
i
by
N719
dye.
The
ZnO
coa ing
was
ound
o
o m
a
pa icula e-like
deco a ion
o
TNT
laye s
inc easing
he
su ace
a ea
o
he
pho oan-
ode.
The
sho
ci cui
pho ocu en
densi y
imp o ed
om
3.98
o
4.31
mA/cm2.
Co espondingly,
he
e ﬁciency
imp o ed
om
1.23
o
1.42%
by
ZnO
coa ing.
The
posi i e
e ec
o
he
ZnO
coa ing
was
a ibu ed
o
he
inc eased
su ace
a ea
o
ZnO
coa ed
TNT
laye s
and
o
he
high
isoelec ic
poin
o
ZnO
o ming
an
inhe en ly
posi-
i e
cha ge
a
he
ZnO/elec oly e
in e ace,
acili a ing
an
e ﬁcien
dye
adso p ion.
Mo eo e ,
he
di e ence
o
TiO2and
ZnO
isoelec ic
poin s
caused
a
nega i e
shi
o
he
TiO2conduc ion
band,
esul ing
in
an
inc eased
ene gy
le el
di e ence
wi h
he
liquid
elec oly e
leading
o
an
inc eased
open
ci cui
ol age.
In
se e al
s udies,
Cai
e
al.
[144,145,147,148]
inspec ed
he
e ec
o
2,
5,
and
10
nm
hick
ZnO
coa ing
(deposi ed
by
10,
25,
and
50
ALD
cycles)
on
he
PEC
pe o mance
o
ZnO/TNT
lay-
e s
and
o
unc ionalized
poly(3-hexyl hiophene)/ZnO/TNT
laye s.
The
bes
PEC
pe o mance
was
e ealed
o
2
nm
hick
ZnO
ﬁlm
(10
ALD
cycles).
The
pho ocu en
densi y
ose
by
a
ac o
o
1.6
and
he
esul s
o
impedance
spec oscopy
poin ed
o
he
imp o ed
cha ge
sepa a ion
ea u ed
by
lowe ed
cha ge- ans e
esis ance,
nega i e
shi
o
ﬂa
band
po en ial,
and
longe
elec on
li e imes.
The
addi ionally
poly(3-hexyl hiophene)
unc ionalized
ZnO/TNT
laye s
showed
inc eased
ligh
abso p ion
and
p omo ed
pho oluminescence
quenching
as
a
ma k
o
sup essed
adia i e
ecombina ion
o
pho ogene a ed
cha ge
ca ie s
[148].
Zeng
e
al.
[146]
deposi ed
a
hin
ZnO
laye
by
ALD
as
an
in e -
laye
o
PbS
and
CdS
QD
sensi ized
TNT
laye s.
The
au ho s
u ilized
TNT
laye s
wi h
a ious
hicknesses
(1.5–2.8
␮m)
and
coa ed
hem
by
ALD
ZnO
wi h
hickness
be ween
0.7
and
10.5
nm
(5,
10,
30,
and
70
ZnO
ALD
cycles).
The
ALD
ZnO/TNT
laye s
we e
a e wa ds
loaded
by
CdS/PbS
QD
using
SILAR
echnique.
Illus a i e
SEM
and
TEM
images
o
TNT
laye
coa ed
by
ALD
ZnO
(30
ALD
cycles
equi a-
len
o
hickness
o
4.5
nm)
and
deco a ed
by
PbS/CdS
QD
a e
shown
in
Fig.
8d
and
e.
The
obse ed
inc ease
o
he
ligh
abso p ion
and
he
PEC
pe o mance
a e
ZnO
coa ing
was
mos
p onounced
o
he
2.4
␮m
hick
TNT
laye s
wi h
CdS/PbS
QD
loaded
o e
coa ing
o
10
ALD
cycles
o
ZnO
(1.5
nm
hick)
esul ing
in
he
maximum
16
F.
D o ak
e
al.
/
Applied
Ma e ials
Today
14
(2019)
1–20
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One-dimensional anodic TiO2nanotubes coated by atomic layer deposition:Towards advanced applications

Abstract

One-dimensional anodic TiO2nanotubes coated by atomic layer deposition:Towards advanced applications
