Electrochemical process for

thermoelectric nanowire fabrication

Pr Clotilde Boulanger
Groupe « Chimie et Electrochimie des Matériaux »
Institut Jean Lamour– UMR CNRS , Université de Lorraine
 Outlines

 Nanowires
 Synthesis without porous template
 Membrane-based synthesis approach
 Principles of Electroplating
 V2VI3 films: some examples
 Synthesis of V2VI3 nanowires in Alumina membrane
 Experimental parameters
 Characterizations
 Synthesis of V2VI3 nanowires in Polymeric membrane
 Experimental parameters
 Characterizations
 Nanostructured and complex structures: some examples
 Summary
2
 Aims and motivations

Enhancement of conversion efficiency

Z= α 2
nano-objects, nano-structures
(e+p).r • quantum confinement effect
• phonons scattering

Nanowire electrodeposition
Template synthesis or self-assembly growth

Synthesis of Te in RTIL
Szymczak, J. et al.
Electrochemistry Communications, 2012
3
 Nanostructured TE compounds
The dimensionality of the material :
a new variable to tune the thermoelectric properties

Example nanowires of Silicon

ZT @ 200K : 200 fold increase !

A.I.Hochbaum and al., Nature, vol 451 (2008) A.I.Boukai and al.,Nature, vol 451 (2008)
=e+p
decrease of lattice thermal conductivity
boundary scattering of phonons
changes in density of
electronic states

4
 How ?

Synthesis of thermoelectric nanowires

 Synthesis without porous
template
 Electrochemical synthesis on Highly
Oriented Pyrolytic Graphite
Nucleation of Bi2Te3
Menke et al. Langmuir, 2006, 22, 10564
along step edges
and coalescence

 Solution phase growth process (polyol

method)
M Chen Mat Res Bull.2005

 Direct Growth of Semiconductor

Nanowires by stress-induced mass flow
along grain boundaries in the
polycristalline film Shim, Nanoletters 2009
5
 How ?

Synthesis of thermoelectric nanowires

Membrane-based synthesis approach Martin, Charles, Science; 1994
 Pressure injection process :
Technique consists in the pressure injection into an alumina template
with molten Bi2Te3 liquid

P. Jones, T. Huber
ICT 2006

 Electroplating of nanowires through porous template

6
 Electroplating: an attractive route
 Advantages over thermally driven techniques
• More cost-effective
– Non intensive equipment
– Low temperature
– Absence of vacuum
• Thickness control by consumed charge
– From tens of nm to hundreds of µm
– Interesting growth rates
• Wide range of compositions
• Limitation of interdiffusion and chemical reaction
• Scalability (large or small areas)
• Epitaxial deposition (uniform growth)
• Considerably simpler but necessity of electroanalytical study

7
 Electroplating: principle
■ Creation of solid materials directly from
electrochemical reactions onto substrate materials

■ Reduction of ionic precursors in aqueous, non potentiostat

aqueous, ionic liquids, or molten salts A
But also deposit by oxidation i
i
■ Mn+ + ne- M°
V
■ electrons W R C
■ from an external source (electroplating) E E
 in potentiostatic mode Efixed i=f(t) e
 in galvanostatic mode Ifixed E=f(t) Te+I
V e
■ from a chemical reductor (electroless deposition)
No external source, more difficulty to control
the thickness and uniformity of the deposits
Bi3+

8
 Factors of electrocrystallization
Electrical parameters:
• E potential
potentiostat • I current density
• Q consumed charge
A
i i

W R C
Electrode parameters: E E
• Type of substrate e Electrolyte parameters:
• Geometry Te+IV • Nature and Concentration
e • Support electrolyte
• Surface roughness
• Additives
• Temperature
Bi3+
Mass transfer parameters:
• Mode (convection, diffusion)
• Hydrodynamic conditions

9
 Electrode – Electrolyte interface
Electroplating : Interfacial reaction between an electrode and a solution
Electrode = Bulk solution =
Electronic conductor Ionic conducting medium:
- Metal - electrolyte solution
- Semi Conductor - molten salt
- Conducting polymer - solid electrolyte
S

S Solvated
Solvated ion
ion
Adsorption
adion S
Mass transport Migration
Surface diffusion
atom

Incorporation

Nucleation
Growth

Electrode Double layer Bulk solution

Charge transfer + desolvatation

10
 Current – potential relationship

Mn+ + ne- M° aM n

characterized by Nernst Law Eeq EM / M 

0 RT Ln n 0
nF aM 0

If E app < Eeq  electrodeposition  current

 = Eapp(I) - Eeq
potential Eeq
i=io (nF/RT)
linear region

exponential region

Mixed control M°  Mn+ + ne- Buttler-Volmer

Charge and mass transfer
Ilim =f(|Mn+|sol)

current density
Mass transfer control

Limiting current density region Charge transfer control

11
 Current – potential relationship

Stirred solution
potential
Cyclic Voltammetry curves

Current density
ilim

Unstirred solution
potential
Current density

ip

12
 Electrochemical window
Electrodeposited metal
H in aqueous medium He

Li Be Limitation by hydrogen evolution (E~-1.2 V) B C N O F Ne

H2O + 1e-  ½ H2 + OH-
Na Mg Al Si P S Cl Ar

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac Rf Db Sg Bh Hs Mt Uun Uuu Uub Uuq

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

13
 Nucleation
Real surfaces : defects on crystal face  nucleation sites for electrodeposition
Edge dislocation with
the surface
Perfect flat surface
Impurety
adsorbed atom Vacancy in terrace

Adatom
Screw dislocation (same kind as bulk atoms)
Vacancy in the edge Kink, step in the edge

Monoatomic step Adatom on terrace N = N0[1- exp (-At)]

N0 = total number of sites
(maximum possible number of nuclei
per unit surface)
A = nucleation rate constant

A  and At <<1 N  N0At

increase of nuclei number
during the growth process

A  and At>>1 N  N0
immediate activation of all reaction sites
and constant number of nuclei

14
 Growth

3D Pyramidal nucleus
lateral (k2) and vertical (k1)
growths Growth

2D Cylinder nucleus
Growth
Depend on the affinity :
Metal – Metal
Metal - Substrate

15
 Nucleation – growth
Electrochemist point of view

Potentiostatic current-time transients

i=f(t) Z3 =overlap of nuclei
Slowing down of nucleation and current 

im
im

Z4 = diffusion of ions in solution

Limiting current

ifree

tm

Z2 = i
Z1 =double layer - growth of independant nuclei
charging current - increase in nb of nuclei
Exemple of 3D nucleation limited by diffusion
16
 Current time transients
Theoretical models of nucleation
3D Nucleation 2D Nucleation
t0 Instantaneous nucleation t0

t1 immediate activation of all reaction sites t1

and constant number of nuclei

t2 t2

Progressive nucleation
t0 t0
increase of nuclei number during the
t1
growth process t1

t2 t2

1 1 Nucléation instantanée 2D

Nucléation progressive 2D

0,8 0,8

0,6
(i/imax)²

0,6

i/imax
0,4 0,4

Nucléation instantanée 3D
Nucléation progressive 3D 0,2
0,2

0
0
0 0,5 1 1,5 2 2,5 3
0 0,5 1 1,5 2 2,5 3
t/tmax t/tmax
17
 Electrocrystallization

Schematic présentation of grain

structures of electrodeposited films

Operating conditions over electrodeposit structure

Arrow: increase of the given parameter

in determining grain sizes

But also
- Chelates
- Other C+ et A-
- Substrate
- pH
- Adsorbed species E

18
 Simplified diagram of electrocrystallization types

Proposed by Winand J. Appl. Electrochem., 21, 377 (1991)

after work of Fischer Electrochimica Acta, 2, 50 (1960)
Dendrites
Bad
FI or

Inhibition intensity
no crystallization
deposit
Hydrogen
evolution

Important parameters:
- Ratio J/Jlim (or J / |Mn+|)
- inhibition intensity

Jdl: limiting current density

FI: Field oriented Isolated crystals
BR: Basis oriented Reproduction
FT: Field Orientated Texture
UD: Unoriented Dispersion

19
 Conditions

 Conducting surface as a seed layer

 Good resist adhesion on the substrate
 Easy access to recesses of plating solution
 Compatibility of plating solution with substrate materials
 Uniform current distribution on the substrate surface
 Dependence of shape and size of the deposits over the
surface characteristics of the substrate

 Further studies on the fundamentals of the nucleation and

growth
to understand the preferential deposition on a particular site
of the electrode substrate
20
 Electrochemistry for TE compounds

Chronological research on TE powder and layers

PbTe Bi2(SeTe)3
Martin Gonzalez
PbSe Michel
Sb2 3
Te
PbSeTe
powder Streltsov Bi2Te3 (BiSb)2Te3
Bi2Te3 Saloniemi Takahashi Bi2Se3 Leimkuhler
Magri Torane Nedelcu
Panson

1964 1990 1995 2000 2005 2010

CoSb Organic medium

CoSb3 BiSb Surfactant adding Molten salt
Sadana Povetkin
Ionic liquid

21
 Chronological research on TE nanowires

2003
BiSb
2004
Bi2(SeTe)3
1999 PbTeSe
1998 (BiSb)2Te3 Sima
Bi2Te3 Martin Gonzalez - Prieto
Bi Sapp
Chien
CoSb3
Prieto

2000 2005 2010

Anodized Aluminium Membrane Polymeric membrane

Growth rate tuning

Control of stoichiometry

22
 Electroplating of V2VI3 compounds

Reduction of tellurite ions (TeIV) in presence of Bismuth

2Bi3+ + 3xTe+IV + 18 e- → Bi2Te3

n-type ternary compound

2Bi3+ + 3xTe4+ + 3(1-x)Se4+ + 18 e- → Bi2(TexSe1-x)3
p-type ternary compound
2(1-x)Sb3+ + 2xBi3+ + 3Te4+ + 18 e- → (Sb1-xBix)2Te3

F. Xiao, C. Hangarter, B. Yoo, Y. Rheem, K.H. Lee, N.V. Myung, Recent progress in electrodeposition
of thermoelectric thin films and nanostructures, Electrochimica Acta 53 (2008) 8103-17.

C. Boulanger, Thermoelectric material electroplating: a historical review, Journal of Electronic Materials

39, 9 (2010) 1818-1827

23
 Electroplating of V2VI3 compounds

Dissolved precursors: Bi3+, Sb3+, Te+IV, Se+IV

Bi2O3, Bi(NO3)3, Bi°, Sb2O3, Te, TeO2, K2TeO3, NaSeO3,

 Weak solubilities of ions → acidic electrolyte

• HNO3 but also HClO4, H2SO4, HCl + NH4F, HNO3 + H3PO4
 For Sb3+, necessity of chelating agent (tartrate / citrate)
 Electrolytes enriched in Bismuth:
Bi/Te or (Te+Se) = 0.75 -1.33 to compare with 0.66
Substrate: conductors not attacked by H+
 Au, Pt, Mo, Ti, stainless steel, Ni, Bi2Te3

Tungsten Titanium Gold Nickel-Chrome Tantalum

Bismuth

24
 Electroplating of V2VI3 compounds

Electrodeposition approach
 Electrochemical study
 investigation of electrolyte behaviour through
voltametric techniques onto microelectrodes
 Electrodeposition onto electrodes
 potentiostatic and galvanostatic deposition
(control of E, I, electrolyte composition)
 Characterization of deposits
• Composition (EPMA, XFS), structure (DRX), morphology
(SEM, AFM)
• Transport properties (Hall effect, Van der Pauw), Seebeck
effect
• Contactless methods (Spectroscopic ellipsometry)

25
 Electrodeposition of Films

Tuning of the composition of electroplated films

in aqueous medium :
Solid solution
between Sb2Te3 and Bi2Te3 BiSbTe3
22
20
18 n-type semiconductor
16
Atomic % of Bi in film

14 Bi2-xTe3+x % at. Te>62

12
Bi0.5Sb1.5Te3
10
8
y= 0,8281x + 0,52701
2
R =0,9987 Bi2Te2.7Se0.3
6
4
ZnO:Al
2
0
p-type semiconductor
Sb2Te30 2 4 6 8 10 12 14 16 18 20 22 24 26
Atomic % of Bi in electrolyte Bi2+xTe3-x % at. Te<58
Formation of (Bi1-xSbx)2Te3 Bi0.5Sb1.5Te3
0.5 < x < 1

in liquid ionic medium :

Doping with heavy elements such
as Rare Earths (RE) elements
Bi-Te-La
« high cathodic stability, Liquid at room 1-ethyl,1-octylpiperidinium
bis(trifluoromethylsulfonyl)imide
temperature,high thermal stability »

26
 Electroplating of Bi2Te3

[Bi3+] = 10-3 M HNO3 1N HNO3 1N

14 [Bi3+]=[HTeO2+] = 10-3 M
12

10
24
8
j (mA/cm²)

4
Bi° Bi 3+ 16
2
Bi2Te3 Bi3+, Te+IV

Intensité (mA)
0 8
Bi
-2 % (2)

-4
Bi° Bi 3+
-0,4 -0,2 0,0 0,2 0,4 0,6 0
E (V/Ag/AgCl)

14
[HTeO2+] = 10-3 M HNO3 1N -8
12 Bi2Te3
10
Te
8 -16
Te° Te+IV -200 0 200 400 600 800 1 000
j (mA/cm²)

4
Potentiel (mV/ECS)
2
single phase in acidic medium
0
2Bi3++3HTeO2++18 e- +9H+ Bi2Te3+6H2O
-2
Te° Te+IV
-4
-0,4 -0,2 0,0 0,2 0,4 0,6 0,8 1,0 1,2
E (V/Ag/AgCl)
Magri J. Mater. Chem 6, 1996
27
 Electroplating of Bi2Te3

i (µA) [HTeO2+] = 10-3 M

Bi/Te = 1/2
1000
Bi/Te = 2/3
800
Bi/Te = 1 Potential range : -20 to -200 mV/SCE
600
Existence of single phase compounds
400 Bi/Te = 4/3
BixTey
200 Bi/Te = 2
0
-400 -200 0 200 400 600
-200
E E(mV/SCE)
(mV/ECS)
-400

-600

Bi/Te = Bi/Te = Bi/Te

Bi/Te== Bi/Te =
1/2 2/3 11 4/3

E=-90mV/ECS BiTe2 Bi2Te3 BiBi

2Te
2Te
33 BiTe

J Crystal Growth,277, 2005, 274 E=-125mV/ECS BiTe2 BiBi

Bi2Te3 2Te
2Te
33 Bi4Te3

28
 Electroplating of Bi2Te3
0,0
-0,3 -0,2 -0,1 0,0
-0,2

-0,4
E (V/ECS) [Bi3+] = 10-2 M
-0,6 [HTeO2+] = 10-2 M
-0,8

-1,0
HNO3 1N

J (mA/cm )
2
-1,2
Bi 3+,Te+IV
-1,4

-1,6
Bi2Te3
-1,8

-2,0

-2,2

-2,4

Potentiostatic mode Galvanostatic mode

Bi2-xTe3+x

J. Crystal Growth, 277 (2005) 274. 29

 Electroplating of Bi2Te3
Journal of Crystal Growth 296, 2006, 227-233
ch c

 rhomboedral R-3m
Te(1)  layered structure: anisotropy of properties
Bi
Te(2)
 Sab ~ Sc
Bi  rab ~ 1/4 -1/6 . rc
 ab ~ 2 . c
z Te(1)
yx

ZT (basal plane) = 2 x ZT(along c axis)

 orientation knowledge  importance

b a
Preferential orientation
Pole figure analysis fiber texture
Bi2Te3
(11.0)

30
 Electroplating of Bi2Te3

ZT (basal plane) = 2 x ZT(along c axis)

39°

{10.10}
Growth axis

{11.0} {11.0} {10.0}

ch

Bi 2,25 Te 2,75 Bi 2,00 Te 3,00 Bi 1,75 Te 3,25

55 60 65 %Te
growth in the direction of basal planes
Better electrical conductivity, Favorable to thermoelectric properties
J. Crystal Growth 296, 2006, 227 31
Electroplating of Bi2Te3 layers
Journal of Crystal Growth, 277 (2005) 274-283.

32
 Addition of organic species in electrolytes

 Arabic gum : decrease of the surface roughness

 No surface contamination
Without gum With gum
AFM (10x10 µm²)

[Bi]/[Te] = 1 [Te] = 10-2 M

569 nm 51 nm -0.25A/dm2 < J < -0.10A/dm2

0 nm 0 nm

RMS = 92 nm RMS = 9,4 nm

Bi 1,8 Te 3,2 Bi 2,0 Te 3,0 Bi 2,2 Te 2,8
S (µV/K) without gum -75 -65 -50
S (µV/K) with Arabic gum -167 -115 -56
r (µ.m) 15 30 28
ZT 0.59 0.25 0.07

 (cm²/V.s) 8 8 12
n (1020 cm-3) 3.5 5 5
with  = 1 W/m.K (Z=S²/r)
33
 Electroplating of Bi2Te3
Instantaneous nucleation : immediate Progressive nucleation : increase
activation of all reaction sites and constant of nuclei number during the growth
number of nuclei process
i i
ln    a  bt ² 2D ln   c  dt 3
t   t²  2
 i  1.9542    t  
2
 
2
  2
 
1  exp  2.3367  
2
i 1.2254 t
   1  exp   1.2564   3D     
 imax  t/tmax    tmax    imax  t/tmax    tmax   

Potential influence Surfactant influence

1

0.8

(i/imax)² 0.6

0.4

instantaneous nucleation progressive nucleation

0.2
with arabic gum with SDS
0
0 0.5 1 1.5 2 2.5 3
t/tmax

34
 Electroplating of Bi0.5Sb1.5Te3

HClO4 1M + Tartaric Acid 0.1 M

2(1-x)Sb3+ + 2xBi3+ + 3Te4+ + 18 e- (Sb1-xBix)2Te3
E (mV/SCE)
E/mV (vs. ECS)
0,0 Bi-Sb-Te
-300 -250 -200 -150 -100 -50 0 50 100 150 200

c2 c1 ([Bi]+[Sb])/[Te]=1
c3
-0,2

-0,4
[Sb]/[Bi]=3 – [Te]=10-2M
-0,6 IV+ -
Te° Te + 4e 1M HClO4-0,1M C4H6O6
-0,8
-2

3+ IV+ -
Bi2Te3 2Bi + 3Te + 18e
J/mA.cm

-1,0

-1,2

-1,4 C1 two phases Bi2Te3 + Te°

3+ 3+ IV+ -
-1,6
xBi + ySb + zTe + (3x+3y+4z)e
-1,8 BixSbyTez
-2,0

-2,2
3+ 3+ IV+ -
C2 two phases BixSbyTez + Te°
-2,4
0,5Bi + 1,5Sb + 3Te + 18e
Bi0,5Sb1,5Te3

C3 single phase Bi0.5Sb1.5Te3

35
 Electroplating of Bi0.5Sb1.5Te3
5,0
4,5
Bi
Sb zone 3 zone 2 zone 1 •E=-0.17 V/SCE
4,0 Te
•([Bi]+[Sb])/[Te] = 1
Composition of films

3,5
3,0
•[Sb]/[Bi]: from 1 to 10
2,5
2,0
Solid solution
1,5 between Sb2Te3 and Bi2Te3
1,0 BiSbTe3
0,5 22
0,0 20
-0,30 -0,25 -0,20 -0,15 -0,10 -0,05 0,00
Potential (V/SCE) 18
16

Atomic % of Bi in film
Bi-Sb-Te
zone 3 14
01.5

E=-0,17 V/ECS
E=-0.17 V/SCE 12 Bi0.5Sb1.5Te3
11.0
10.10

00.15

y= 0,8281x + 0,52701
21.10
02.10

10.19
20.5

01.23
12.5

10 2
R =0,9987
Te° zone 2 8
01.5

E=-0,1 V/SCE
E=-0.1 V/ECS
6
10.10

02.10
00.15
11.0

10.19
20.5

12.5

4
Te° 2
01.5

zone 1
E=-0,02 V/SCE
V/ECS
10.10

E=-0.02 0
02.10
20.5

Sb2Te30 2 4 6 8 10 12 14 16 18 20 22 24 26
Atomic % of Bi in electrolyte
20 30 40 50 60 70 80
2 (Cu=1,54056 Å)
Formation of (Bi1-xSbx)2Te3
0.5 < x < 1
Thin Solid Films 483, 2005, 44
36
 Electroplating of Bi0.5Sb1.5Te3

SEM: morphology
Top view Cross section
Too high J / |Mn+|

Diagram of electrocrystallization types

Rough surface
Winand J. Appl. Electrochem., 21, 377 (1991)
Dendritic layer Fischer Electrochimica Acta, 2, 50 (1960)

Hydrogen
FI or evolution
Inhibition intensity
Important parameters: no J/Jlim
deposit
- Ratio J/Jlim (or J / |Mn+|)
- inhibition intensity Bad
crystallization
Jlim: limiting current density

Dendrites
Powder

37
 Electroplating of Bi0.5Sb1.5Te3
Technique for improving the morphology of electroplated films
Pulse deposition Modification of the nucleation and the grain size

pulsed electroplating in galvanostatic mode I (mA) ou E (mV)

1.9 mM Bi – 5.6 mM Sb - 10 mM Te 0.1 M HT HNO3

0 t (s)

toff
tc
ton
Jm = J c
ton + toff
recovery of species EC or IC

during rest time

Direct mode on Pulsed mode on Pulsed mode on

stainless steel stainless steel gold
[Sb]/[Bi]= 3 [Sb]/[Bi] = 8 [Sb]/[Bi] = 8
(Bi0.25Sb0.75)2Te3 (Bi0.17Sb0.83)2Te2.99 (Bi0.25Sb0.75)2Te3

annealing 1 h at 250°C 1 h at 250°C 2 h at 480°C

Seebeck
coefficient (µV/K) 190 138 108

resistivity (µΩ.m) 545 123 9

power factor
(µW/K2.m)
66 155 1350

J. Applied Electrochem 36, 2006, 440

38
 Towards application

Thick films :

 Li & al, Chem. Mater. 18, 3627 (2006)

Electrolyte :

BiO+ = 13 mM HTeO2+ = 10 mM
HNO3 pH = 0 With Ethylene Glycol 10-40 %

Potentiostatic and Galvanostatic syntheses  thickness up to 350 µm

As After heat Growth speed :

Properties treatment
deposited
(2h at 300°C)
Between 4 to 12.5 µm/h
Seebeck  Good adhesion on the
coefficient -70 -125 substrate
(µV/K)
 Use of ethylene glycol
Electrical resistivity 22 25 not suitable for an
(µΩ.m)
industrial application
Power factor 2.20 6.00
(10-4 W/m.K²)
39
 Towards application

Thick films :

 Glatz & al, Electrochim. Acta 54, 755 (2008)

Electrolyte :

Bi2O3 = 93 mM TeO2 = 80 mM HNO3 pH = 0

Mixed method : potential deposition pulses and zero current resting pulses

Zero current resting pulses allow the

electrolyte homogenization at the
electrode surface

40
 Towards application

Thick films :

 Glatz & al, Electrochim. Acta 54, 755 (2008)

Electrolyte :

Bi2O3 = 93 mM TeO2 = 80 mM HNO3 pH = 0

Mixed method : potential deposition pulses and zero current resting pulses

 Growth rate up to 50 µm.h-1

Seebeck coefficient :
 Great speed of growth
 - 40 µV/K for the Te-rich compound  Use of a pulse method
 + 55 µV/K for the Bi-rich compound

41
 Towards application
i
 Improvement:
A
soluble anode of Bi2Te3 electrolyte auto-regeneration Counter Electrode
 Tests for binary Bi2Te3 depositions V : Soluble anode

 No modification of the electrolyte concentration

even after 100 h 5
Working
 Constant stoichiometry = f(t) = f(thickness) electrode 4

 Interest of anode to maintain the concentration 3

of cations in the electrolyte 2

Cross section composition

for one film:

1 : 37,96%Bi ; 62,04%Te
2 : 38,00%Bi ; 62.00 %Te
3 : 36,58%Bi ; 63,42%Te
4 : 37,83%Bi ; 62,17%Te
5 : 37,58%Bi ; 62,43%Te

average : 37,38%Bi ; 62,62%Te  0,82

42
 Towards application
Surface
 SEM Roughness < 1 µm

200000
MM130902_01
16 h 16 h
190000

2h 180000

110
170000

160000

150000

Thickness 140000

- Columnar structure
130000

(µm) 120000

Lin (Counts)
110000

- Compact and dense layers 100000

90000

500 80000

70000

6.6379x - 0.1495
450
60000

R² = 0.9984 50000

40000

400 30000

film
20000

350 10000

300 15 20 30 40 50 60 70 80 90

11.0
2-Theta - Scale
MM130902_01 - File: MM130902_01.raw

250 Operations: Background 0.457,1.000 | Strip kAlpha2 0.500 | Import

200
Linear growth rate

01.5
150 substrat
Efficiency ~100 %
100
6,6 µm/h  450 µm

01.20+12.5
00.15+11.6
50

10.10

20.5

21.10
02.10

11.15

30.0
0
0 20 40 60 80 Deposition time (h)
[Bi]/[Te] = 1 [Te] = 2. 10-2 M 20 30 40 50 60 70 80 90 100 110

J = 2 A/cm2 J. Electronic Matetrials in press 2014 43

 Electrodeposition of TE nanowires

potentiostat
A

i
i

e e

W R C
Sputtered layer E E
Te+IV

Bi3+
Membrane

3 HTeO2+ + 18 e- + 2 Bi3+ + 9 H+  Bi2Te3 + 6 H2O

44
 Electrodeposition of TE nanowires

The used templates

 The anodic membranes: porous anodized aluminium oxide films AAO

Anodization of high purity

aluminium in mineral acid
Presence of insulating, dense oxide
layer (called barrier layer) separating the
aluminium substrate and the porous
oxide film
thinning the barrier layer*
Geometric parameters (pores size,
radius, density) linked to anodization
parameters (electrolyte, anodizing
voltage)

* N. Stein et al., Electrochimica Acta,2002

45
 Electrodeposition of TE nanowires

The used templates

 Anodic membranes: porous anodized aluminium oxide films (AAO)

Top view Cross section*

 Porous structure ~ a honeycomb array *Sander, Advanced Mat. 2002
 High pore density > 109 pores/cm²
 Range of thickness = 10 – 100 µm
 Commercial products (filtration) = interconnection between nanopores
The most popular template in the literature but …
The thermal conductivity of AAM overwhelms that of the NW/ template composites

46
 Electrodeposition of TE nanowires

Electrocrystallization
At imposed potential, transient time current curve

FILLING
Current density mA/cm2

GROWTH

UPPER LAYER

NUCLEI

Time (s)
Filling time

47
 Electroplating of V2VI3 nanowires in AAO

Bi2Te3
1999 Sapp Nanoletters, 11, 402
Galvanostatic deposition into commercial Anodized Alumina Membrane  = 200 nm
I = 3.5 mA/cm² |Bi|/|Te| = 25/33 mM

48
 Electroplating of V2VI3 nanowires in AAO
Bi2Te3
1999 Sapp Nanoletters 11, 402
Galvanostatic deposition into Alumina Anodised Membrane  = 200 nm
2001 Prieto J.A.C.S, 123, 7160 2002 Sander Advanced Mat. 14, 665  =45 nm L= 70 µm FR
= 70-80% E = -0.46 V /Hg/HgSO4 |Bi|/|Te| = 75/100 mM

2003 Sander Chem. Mater.,15, 335 Annealing

400°C 3h
E = -0.46 V /Hg/HgSO4 |Bi|/|Te| = 75/100 mM

Bi2(TeSe)3 as- deposited annealed

2003 Martin Gonzalez Nanoletters, 7, 973  =50 /200 nm L= 20 µm FR = 75%
E = 0 V /Ag/AgCl |Bi| / |Te|+|Se| = 7.5 / (9+1) mM
(BiSb)2Te3
2003 Martin Gonzalez Advanced Mat, 15, 1003  =40/200 nm L= 30/16 µm FR = 80/75%
E = -0.17 V /Hg/HgSO4 |Bi|+|Sb| /|Te| = (19+56)/100 mM

49
 Growth rate tuning of V2VI3 nanowires

Problems for electroplating nanowires : AAO

- inhomogeneous growth rates between pores
- eventual composition gradient due to different diffusion coefficients of the ions
constant replenishment of electroactive species
Bi2Te3
2006 Li Nanotechnology, 17, 1706 Pulsed deposition : recovery of species during rest time
E = -1.3 V Au/Cgraph ton = 3 ms, toff = 10 ms |Bi| /|Te| = 10/15 mM
 = 40/60 nmstronger orientation (015)

2008 Lee Nanotechnology, 19 , 365701 Pulsed deposition

Longer rest time  higher preferred orientation
lower Seebeck coefficient, higher Te content

50
 Growth rate tuning of V2VI3 nanowires

Problems for electroplating nanowires : AAO

- inhomogeneous growth rates between pores
- eventual composition gradient due to different diffusion coefficients of the ions.
constant replenishment of electroactive species
Bi2Te3
2006 Li Nanotechnology, 17, 1706 Pulsed deposition : recovery of species during rest time
2008 Lee Nanotechnology, 19 , 365701 Pulsed deposition
2006 Wang J.Phys. Chem. B 110, 12974. rotation of AAM template
E = -0.14 V/SCE |Bi| /|Te| = 2.5/3.3 (a) or 7.5/10 mM (b)

Reduced variation of composition

along the wires

51
 Growth rate tuning of V2VI3 nanowires

Problems for electroplating nanowires : AAO

- inhomogeneous growth rates between pores
- eventual composition gradient due to different diffusion coefficients of the ions.
constant replenishment of electroactive species
Bi2Te3
2006 Li Nanotechnology, 17, 1706 Pulsed deposition : recovery of species during rest time
2008 Lee Nanotechnology, 19 , 365701 Pulsed deposition
2006 Wang J.Phys. Chem. B. 110, 12974  = 200 nm rotation of AAM template
2007 Trahey Nanoletters, 7, 2535 Pulsed deposition+ Low T (1-4°C)  FR 93 %,
 = 35 nm E = -0.42 V /MSE ton = 1s + Erest = -0.3V toff = 2s |Bi|/|Te| = 7.5/10 mM

Uniform growth front

Highly oriented wires

52
Electrodeposition of nanowires in organic medium
AAO

2010 Cagnon, Nielsch, Bourgault Phys. Status Solidi B 247, 1384

 = 50 nm DMSO or EG
Higher temperature 110°C , strirring, galvanostatic deposition

PbSe

Sb2S3

53
 Electroplating of other TE nanowires
AAO

CoSb3 :
1999 Behnke 18th ICT
125 mM Citrate 0.196M citric acid - 688 mM Co – 6 mM Sb
First attempts

BiSb :
2003 Prieto J. Am. Chem. Soc. 125, 2388

2006 Keyani Applied Phys. Letters 89, 233106

Potentiostatic deposition in DMSO in AAO
Hybrid device: BiSb NW – Bulk Te
50 mM Bi – 30 mM Sb

54
 TE properties of V2VI3 nanowires
 Characterization of a single NW
2005 Zhou Appl. Phys. Lett .87, 133109 2009 Mavrokefalos J. Appl. Phys. 105, 104318 annealing

 Characterization of NW bundles
2004 Borca Tasciuc 2009 Mannam 2010 Chen
Appl. Phys. Lett. 85 6001 J. Elec. Soc 156, B871 J. Phys. Chem. C, 114, 3385
Photothermoelectric technique r + Seebeck r + Seebeck + LFA

55
 Nanostructures as efficient TE materials

Bismuth Telluride: first results

Zhou, APL, 2005

ZT (@ 300K ) ≈ 0.02

BUT !!!
“High ZT can potentially be obtained in Bi2+XTe3−x nanowires
with an optimized atomic ratio”

56
 Properties of Nanowires
Experimental values of Seebeck coefficient for Bi2Te3 nanowires
Bundle B / Seebeck
Ø L Elaboration
Global composition Individual I Coefficient Orientation Reference
(nm) (µm) mode
Template (µV/K)
Wang J. Appl. Phys.
Bi2Te3 50 100 Potentiostatic B - AAO +270 2004, 96, 615
Jones
Bi2Te3 200 55 Liquid injection B - AAO -100 (110)
Proceeding ICT 2006
Galvanostatic Lee , Nanotechnology
Bi2Te3/Bi2,38Te2,62 40 50 B - AAO + 12/+33 (110)
Potentiostatic 2008, 19, 365701
Mannam J. Elec Soc.
Bi2,25Te2,75/Bi1,50Te3,50 20 / Potentiostatic B - AAO +117/-318 (110)
2009, 156, B871
Lee, Phys Status solidi
Bi2Te3 50 25 Galvanostatic B - AAO + 45 / 55 2010, 4, 43
Pulsed LI , Nanotechnology
Bi2Te3 60 200 B – AAO (015)
Potentiostatic 2006, 17, 1706
Chen, J. Phys. Chem
Bi1.85Te3.15 120 / Potentiostatic B and I – AA0 -65 (110)
2010 , 114, 3385
Zhou , Appl. Phys. Lett.
Bi2,3Te2,7/Bi2,7Te2,3 50 / Galvanostatic I - AAO + 260/-25 (110)
2005, 87, 133109
Mavrokefalos , J. Appl.
Bi2,15Te2,85 55 / Galvanostatic I - AAO -70 Phys. 2009, 105, 104318
Large dispersion of the literature data :
 Difficulties of measurements
 Composition of the nanostructures
 Crystallinity of the samples
57
 Properties of single crystalline nanowires
N Peranio, E Leister, W Töllner, O Eibl, K Nielsch Adv. Funct. Mater. 2012, 22, 151–156

58
 Properties of single crystalline nanowires
AAO

Bassler, S.; Bohnert, T.; Gooth, J.; Schumacher, C.; Pippel, E.; Nielsch, K., Thermoelectric
power factor of ternary single-crystalline Sb2Te3- and Bi2Te3-based nanowires.
Nanotechnology 2013, 24, 495402

Millisecond pulse voltages for electroplating

Diameter 80 nm and 200 nm

Compound Bi15Sb29Te56
p type
S= + 156µV/K
PF 1750µW.K-2m-1
Compound Bi38Te55Se7
p type
S= -115 µV/K
PF 2820 µW.K-2m-1
Increase of PF after annealing under Te atmosphere

59
Properties of single crystalline nanowires
AAO

60
Properties of single crystalline nanowires
AAO

61
 Electrodeposition of nanowires into polymeric membrane
Coll. Dr. E. Toimil Molares
GSI, Darmstadt, Germany

 Polymeric membranes (PC): ( = 30, 60, 90, 120 nm, L = 30 µm)

 Lower  than Anodized Alumina Membrane
 No Heat leakage in micro scale Peltier TE devices

Pores : 30nm<d<120nm
e = 6 - 30 µm

Top view of porous membrane Commercial products :

Disk diameter = 50 after partial chemical etching with PVP hydrophilic
mm (diameter 60nm) treatment

Pores with no tilt and regular shape

 Nanowires growth vertically to the substrate  Ideal configuration for TE devices
Tuning of the pore diameter by calibrated etching rates
 Pores density : 108 to 109 pores/cm²
Maximum aspect ratio : 1/1000 62
 Concept of microdevice

Direct integration of nanowire in legs of Peltier device

n-type p-type

Conditions :
 Output powers 
 filling ratio
 nanowire density 108 - 109cm2
 Thermal gradient
 Contact resistance 

63
 Optimization of the filling ratio

Limiting factors: Improvement:

Pretreatment:
short sonication
Electrolyte impregnation
Wetting agent:
DMSO (50 % v/v)
&
Pulsed deposition
Inhomogeneous growth
rate between pores Lower growth rate:
DMSO (50 % v/v)

Initial value (at Ø 60 nm) Improved value (at Ø 60 nm)

40 % HNO3 0.5M; 80 %
[Bi3+] = 10 mM
[TeIV] = 10 mM J Electr Mat, 39, 2010, 2043
64
 Electrodeposition of V2VI3 nanowires

Electrocrystallization : the filling ratio

E = -100 mV/ AgCl/Ag° With DMSO:
Without DMSO: DMSO 50% vv;
HNO3 0.5M; HNO3 0,5M;
[Bi3+] = 10 mM [Bi3+] = 10 mM
[TeIV] = 10 mM [TeIV] = 10 mM

PC + Platinum layer
E = -100 mV/Ag/AgCl Filling time Filling ratio
without DMSO 831 s 50,6 %
with DMSO 7138 s 79,4 %

DMSO: lower growth rate of NWs leading to a higher filling ratio

C. Frantz Journal of Electronic Materials, 39, 2010
65
 Electrodeposition of Bi2Te3 nanowires
Votammetric behavior on Pt-coated membrane electrodes pore  = 60 nm
HNO3 1M, DMSO 50%v/v [TeIV]=10-2M and [Bi3+]/[TeIV] = 1.5
MA1

A2
A3

MC1
C1

TeIV + 4e- → Te0

C3 C2
Bi3+ + 3e- ↔ Bi0 Scan rate:
5 mV/s

BixTey Te°
2Bi3+ + 3TeIV + 18e- ↔ Bi2Te3
66
 Electrodeposition of Bi2Te3 nanowires

Influence of the applied potential (E)

E=-150mV E=-100mV E=-75mV

Bi : 42,8%at.,Te : 57,2%at. Bi : 40,8%at., Te : 59,2%at. Bi : 34,8%at., Te : 65,2%at.

Enrichement of Bi for more negative applied potential

Stoichiometric compound at -100mV (Bi2,04Te2,96)

pore  = 60 nm 67
 Electrodeposition of Bi2Te3 nanowires
Composition profile
a) b)
Zoom : cap Zoom : bottom
3 40.8 Bi at.% 1
a) b)
32 45.3 Bi at.%
1 40.2 Bi at.%
39.1 Bi at.%
4 40.2 Bi at.% 43.2 Bi at.%
2
35.0 Bi at.%
4 36.3 Bi at.%

1) 45.3 Bi at.% 200nm

5 40.2 Bi at.% 28.9 Bi at.%
Enrichment
2) 43.2 Bi at.%
1) 45.3 of Bi
Bi at.%
200nm
5
Form texture
3) 40.8 Bi at.%
Change 2)of43.2cation
Bi at.% diffusion
6
40.6 Bi at.%
4) 40.6 Bi at.%
Enrichment of Te
3) 40.8 Bi at.%
Polyphased state
5) 40.2 Bi at.%
6 4) 40.6 Bi at.%
Bi2Te3 Te°
Poly-crystalline
6) 40.6 Bi at.%
40.2 Bi at.%
5) 40.2 Bi at.% …
Corrected with an initial
7
7) 40.2 Bi at.%
6) 40.6 Bi at.%
Efixed=-100 mV/Ag/AgCl pulse (E=-300mV; t=2s)
Fig7. EDX mapping and Bright Field images (a) along the nanowire,
7 Electrochimica Acta, 69, 2012, 30 68
(b) of the nanowire head.
 Electrodeposition of Bi2Te3 nanowires
Crystallinity
(01.5) Preferential growth┴ (01.5)

[01.5]*
(01.5)

(01.5)

(01.5)

Single crystal with defaults and strains Nanowire

69
 Bi2Te3 nanowires : Bundle characterization
Coll: Dr L Gravier Switzerland

 Homemade setup for thermoelectric characterizations of ultra-thin devices

 Heat flux generated by two Peltier modules
 Macroscopic thermocouples as surface temperature probes
 Measurements of :
 Seebeck coefficient
 Output power
 Internal resistance

70
 Bi2Te3 nanowires : Bundle characterization
Coll: Dr L Gravier Switzerland

 Sample connected to a load circuit

 Access to conversion efficiency

η = Pout / Pin = … effective ZT

 When the load circuit is open, measure of voltage taking into account T
 Seebeck coefficient

 Output power measured = f(load resistance /internal resistance ratio) at room

temperature
 Specific curve of generator
 Exhibit a maximum output power
 Access to the internal resistance equal to the load resistance
o n-type thermoelectric generator

71
 Bi2Te3 nanowires : Bundle characterization

 Sample connected to a load circuit Example of Bi1,75Te3,25 nanowires

synthesized in Millipore filtration
membranes with 200nm pore diameter,
 Access to conversion efficiency 6µm thickness
η = Pout / Pin = … effective ZT

 When the load circuit is open, measure of voltage taking

into account T
 Seebeck coefficient

 Output power measured = f(load resistance /internal

resistance ratio) at room temperature
 Specific curve of generator
 Exhibit a maximum output power
S = -54.81 ± 0,1 µV/K
 Access to the internal resistance equal to the Rint = 6.85 mΩ
ΔT = 1.52°C
load resistance
o n-type thermoelectric generator

72
 Bi2Te3 nanowires : Bundle characterization

With DMSO

Witness : Ni
Without DMSO

n-type TE generator
Internal resistance reduced with DMSO
Lower Pout in aqueous electrolyte
C. Frantz et al. Journal of Electronic Materials, 39, 2010
73
 Bi2Te3 nanowires : Bundle characterization

Seebeck coefficient evolution = f(E electroplating)

Seebeck coefficient  with more cathodic
conditions
trend linked to the change of composition
nanowires -10
Pores diameter
50 nm
At -50mV highest Seebeck coefficient -20
220 nm

Seebeck Voltage [V/K]

corresponding to the n-type Te-rich compound
-30
At -125mV, Seebeck coefficient negative even Te-rich
if the composition is Bi-rich -40
 due to defaults in the material Bi-rich
-50
Seebeck coefficient  f(pore diameter)
-60

-140 -120 -100 -80 -60 -40 -20 0

Electrodeposition Voltage [mV/Ag/AgCl]

Bi2.08Te2.92 Bi2Te3 Bi1.57Te3.43

Bi1.75Te3.25
74
 Synthesis of (Bi1-xSbx)2Te3 nanowires

Composition of the electrolyte

 Overall cathodic reaction
xBi+3 + ySb+III + zTe+IV + (3x+3y+4z)e- BixSbyTez

Acidic medium : Nitric acid 1M

Chelating reagent : tartaric acid C4H6O6 (0.6M)…[Sb2(C4H4O6)2]2+

75
 Synthesis of (Bi1-xSbx)2Te3 nanowires

Voltammetric study
 Whatman PC membranes, pores diameter = 50nm, thickness = 8µm

 Voltamperometric response within porous TEM / Calibrated EDX measurements

membrane

 Electroplated at different potentials between 75 and -150mV

 Bismuth depletion
 Antimony enrichment with more cathodic polarization
 Tellurium depletion

76
 Bi0.5Sb1.5Te3 nanowires

HRTEM analyses
 Whatman PC membranes, pores diameter = 50nm, thickness = 8µm
 Cation concentration : |TeIV| = 10mM with (Bi+Sb)/Te = 1 and Sb/Bi = 6
 E = -100mV

10Å
(003)
3.6Å 10Å

(003)
(009)

1 0 n m

 Growth according to (00l) planes

 Growth perpendicularly to the basal
planes
 Observation of twin grain boundaries
77
 Bi0.5Sb1.5Te3 nanowires: Bundle characterization

Seebeck measurements
 Whatman PC membranes, pores diameter = 50nm, thickness = 8µm
 Cation concentration : |TeIV| = 10mM with (Bi+Sb)/Te = 1 and Sb/Bi = 6

 With non homogeneous upper layer : Very high resistance

(>100kΩ)
 Not suitable for application

S= 540 +/-120 µV/K

R=159+/- 3 k

78
 Bi0.5Sb1.5Te3 nanowires: Bundle characterization

Seebeck measurements
 Whatman PC membranes, pores diameter = 50nm, thickness = 8µm
 Cation concentration : |TeIV| = 10mM with (Bi+Sb)/Te = 1 and Sb/Bi = 6

 With non homogeneous upper layer : Very high

resistance (>100kΩ)
 Not suitable for application
 With Electroplated copper upper layer
 High decrease of the internal resistance

Composition S (µV/K) ΔT (°C) R (mΩ) P (nW)

21.5 ±
Bi0.4Sb1.14Te3.46 1.8 6.32 ± 0.004 60
0.07
Bi0.3Sb1.59Te3.11 14.6 ± 0.1 1.55 37.7 ± 0.1 3.4
Bi0.48Sb1.76Te2.76 9.1 ± 0.04 1.89 5.73 ± 0.01 13

 Positive Seebeck coefficient corresponding to p-type nanowires

 Seebeck coefficient depend on the nanowires composition
 Possible contribution of copper explaining the lowered values of Seebeck coefficient

79
 Nanostructured and complex V2VI3 compounds

2005 Lim Advanced Mater., 17, 1488

bundles of BiSbTe/ Bi2Te3 nanowires / patterned within the same AAM
ECD suitable method for fabrication of TE nanodevices

2005 Wang Microelectronic Engineering 77 223

Design of TE micro-generator, composed of n-type and p-type Bi2Te3 nanowire array

80
 Nanostructured and complex V2VI3 compounds

2005 Xu J Solid State Chem., 178, 2163

Heterostructure Polyaniline (low ) / encapsulated Bi2Te3 into AAM
Goal : stronger confinement effect

81
 Nanostructured and complex V2VI3 compounds

2008 Li Crystal growth and design, 8, 771

Bi2(TeSe )3 and (BiSb)2Te3 nanotubes
electroplating onto surface / wall pores of AAM sputtered by gold
with a wall thickness of 40-70 nm modulated by the electroplating time

82
 Electroplating of V2VI3 superlattices
2007 Yoo Advanced Mater., 19, 296 2008 Wang J. Phys. Chem. C., 112, 15190
Pulsed deposition in PC membrane: Pulsed deposition in AAM :
nanowires Bi2Te3/(Bi0.3Sb.0.7)2Te3 nanowire Bi2Te3/Sb
from a unique solution by adjusting min period: 10 nm
potentials

83
 Summary

Electroplating: convenient route for thermoelectric compounds

 Synthesis of films and nanowire arrays
 Thickness from tens to hundreds of µm, growth rates
 Wide range of compositions: binaries and ternaries
 Template synthesis: AAO or Polymeric membranes
 Optimized membrane filling ratio (electrolyte, T, pulse, sonication)
 Comprehensive study
 Voltammetric study  knowledge of operating conditions for
stoichiometric film or NW
 Determination of diffusion coefficients to monitor stoichiometry
 Characterization
 Morphology, stoichiometry, orientation
• Homogeneous composition over the thickness
• Preferential growth: films [110], NW: [110] and [015];
 Importance of electrocrystallization - crystallinity : internal resistance
84
 Acknowledgments

GSI Helmholtzzentrum für Schwerionenforschung GmbH (Darmstadt, Allemagne)

Providing of Polycarbonate foil and irradiation
Dr E. Toimil-Molares

Laboratoire d’Etude des microstructures et de mécanique des matériaux (Metz,

France)
Texture and Transmission Electron Microscope (TEM) Dr Bolle Dr Zhang

Haute Ecole d'Ingénierie et de Gestion du Canton de Vaud,

Yverdon, Suisse

Dr L. Gravier

85
85
 Past and present
Contributors
Electrochimie des Matériaux
Financial
supports
Dr L. Scidone
Dr V. Richoux

Dr D. Del Frari

Dr S. Diliberto
Dr P. Magri Pr J.M. Lecuire

Dr N. Stein

Dr A. Zimmer
Dr S. Michel

Dr S Legeai
Dr C. Frantz
Dr J. Szymszack J. Schoenleber 86