1 1 Architecture, process, and materials for efficient inorganic-organic hybrid solar cells April 13, 2015 Sang Il Seok Center for Solar Energy Materials Research, Korea Research Institute of Chemical Technology, Korea ([email protected]) Future Solar cells Lab., Department of Energy Science, Sungkyunkwan University, Korea. ([email protected]) 2 Global Solar Market Outlook • 2014 Global Demand Forecast : 47GW • 14GW/China, 10GW/ EU (3GW/UK, 2.5GW/Germany..), 8GW/Japan, 7GW/USA, 8GW/ROW (India, MEA, South America, South Africa, ..) • Supply capacity~63GW; effective capacity~45GW • Transition to supply-driven market in 2014 • 2013 Total Installation: 37 GW • 11.3GW/China, 10.3GW/EU, 7.5GW/Japan, 4.8GW/USA, 4.1GW/ROW ~60GW in 2015 Sources: RPIA (European PV industry association)
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Architecture, process, and materials for efficient inorganic-organic hybrid solar cells
April 13, 2015
Sang Il Seok
Center for Solar Energy Materials Research,Korea Research Institute of ChemicalTechnology, Korea([email protected])
Future Solar cells Lab., Department of EnergyScience, Sungkyunkwan University, Korea.([email protected])
2
Global Solar Market Outlook
• 2014 Global Demand Forecast : 47GW• 14GW/China, 10GW/ EU (3GW/UK, 2.5GW/Germany..), 8GW/Japan,
7GW/USA, 8GW/ROW (India, MEA, South America, South Africa, ..)• Supply capacity~63GW; effective capacity~45GW • Transition to supply-driven market in 2014
State-of-art of solar cellsResearch scheme: Why inorganic-organic heterojunction hybrid solar cells? Inorganic-organic hybrid solar cells Sb2S(e)3-based systems APbX3 perovskite-based systems A =CH3NH3, HN=CHNH2; x=I, Br. ClSummary
6
Solar cells
silicon
Polycrystalline (CIGS)
Dye-sensitized solar cell(Solid-state DSSC)
II-VI compounds (CdTe)III-V compounds (GaAs)
free electron –hole pair
bound electron-hole pair
Quantum dots solar cells(Nano-oxide and polymer)
I
II
III Inorganic-organicHybrid solar cells
Organic solar cells(Tandem cells)
State-of-the- Art of Solar cells
Our research area
Main issues in solar cells are Conversion Efficiency Long-term stability Fabrication cost
Nanostructured Sb2S3/P3HT heterojunction solar cells
X
400 500 600 700 8000
20
40
60
80
100
EQ
E (
%)
Wavelength (nm)
P3HT PCPDTBT
20
Panchromatic Photon-Harvesting by Hole-Conducting Materials
300 400 500 600 700 8000
20
40
60
80
EQ
E (
%)
Wavelength (nm)
T/S/P T/S/P-P
PCBM : [6,6]-phenyl-C61-butyric acid methyl ester
Nanostructured Sb2S3/P3HT(PCBM) heterojunction solar cells
11
21
300 400 500 600 700 800 9000
20
40
60
80
100
EQ
E (
%)
Wavelength (nm)
T/S/PCPDTBT-PCBM T/S/PCPDTBT
Nano Lett. 12, 1863 (2012)
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.70
5
10
15
20
Jsc
=16.0 mA/cm2,
Voc
=595 mV,
F.F=65.5%, = 6.3%
Cu
rre
nt
de
ns
ity
(mA
/cm
2)
Voltage (V)
1 sun dark
Panchromatic Photon-Harvesting by Hole-Conducting Materials
Nanostructured Sb2S3/PCPDTBT(PCBM) heterojunction solar cells
TiO2
Sb2S3 PCPDTBT
22
0.0 0.2 0.4 0.60
6
12
18
Cu
rren
t de
nsity
(m
A/c
m2 )
Voltage (V)
Light power
(mW cm-2)
JSC
(mA cm-2)
VOC
(mV)
FF
(%)
PCE
(%)
100
50
10
16.1
9.6
2.0
711.0
672.7
600.1
65.0
67.0
70.0
7.5
8.7
8.4
200 220 240 260 280 300 320 340-0.004
-0.003
-0.002
-0.001
0.000
0.001
TA sample Measure voltage -1.0 V -2.0 V
NoTA sample Measure voltage -1.0 V -2.0 V
DL
TS
Sp
ect
ra (
C/C
0)
Temperature (K)
A
Rate Winodws : 0.9242 Hz
Thioacetamidepost-surface-
treatment
C
S
H3C NH2
Adv. Func. Mater. 24, 3587 (2014)
Sb2S3-based inorganic-organic hybrid solar cells
Passivation after CDD
Champion device
12
23
0.0 0.1 0.2 0.30
4
8
12
16
20
24
Cu
rre
nt
de
nsi
ty (
mA
cm
-2)
Voltage (V)
PCE: 3.12 %
Cu-Sb-TU complex sol
Spin coating Thermal decomposition
Repetition
- 6
- 5
- 4
E r
elat
ive
to v
acuu
m (
eV)
TiO2
4.3 CuSbS2
(Eg: 1.5 eV)
3.85
5.35
PC
PD
TB
T
5.3
HTMLight
sensitizerPhoto-
electrode
Au
5.1
e-
e-
h+h+
mp-TiO2/CuSb2S2/PCPDTBT hybrid solar cells
Angew. Chem. Int. Ed. 54, 4005 (2015)
Process
24
Nature Materials 13, 837 (2014) doi:10.1038/nmat4079 Published online 21 August 2014
13
25
A perovskite structure is any material with the same type ofcrystal structure as calcium titanium oxide (CaTiO3), known asthe perovskite structure ABO3.
Perovskite structure=AMX3 Schematic of MX6 octahedra and the organic moiety of the basic AMX3perovskite unit cell and three-dimensional network formed by AMX3 perovskite unit cells.
J. of Nanoparticles, 2013, 531871 (2013)
Schematic of 2D, 1D, and 0D IO-hybrid derived from parent AMX3 type 3D IO-hybrid
Hybrid Perovskites
14
27
Replacing Dye with Perovskite: Current Perovskite Solar Cells are built upon the architectural basis for DSSCs pioneered by Grätzel(EPFL, Switzerland)
3.81 %
3.13 %
mp-CH3NH3PbI(Br)3/electrolyte (LiI(Br)/I(Br)2 in acetonitrile)
(a) IPCE spectra and (b) I-V action scharacteristic for mp-TiO2/CH3NH3PbBr3(solid line) and CH3NH3PbI3/TiO2 (dashed line) 6.5 % (N. G. Park et al., Nanoscale, 3, 4088−4093. 2011)
T. Miyasaka et al., J. Am. Chem. Soc. 131, 6050 (2009)
Perovskite-sensitized solar cells
Architectures
28H. Snaith et al., Science, 338, 643 (2012)Received 31 May 2012
Left: Schematic representation of full device structure, where the mesoporous oxide is either Al2O3 or anatase TiO2. Right: Cross-sectional SEM image of a full device incorporating mesoporous Al2O3. Scale bar, 500 nm. The construction of a planar-junction diode with the structure FTO/compact
Replace Liquid Electrolyte with a Solid Hole Transporting Layer (HTL)
Perovskite-sensitized solar cells
Architectures
15
29
(a) Real solid-state device. (b) Cross-sectional structure of the device. (c) Crosssectional SEM image of the device. (d) Active layer-underlayer-FTO interfacial junction structureN.G. Park eta al., Sci. Report, 2, 591 (2012)Received 5 July 2012
Replace Liquid Electrolyte with a Solid Hole Transporting Layer (HTL)Perovskite-sensitized solar cells
Architectures
30
0.0 0.2 0.4 0.6 0.8 1.0 1.20
4
8
12
16
20
J (m
A/c
m2)
Voltage (V)
P3HT PCPDTBT PCDTBT PTAA Au
0.0 0.2 0.4 0.6 0.8 1.0
0
5
10
15
J (m
A/c
m2 )
Voltage (V)
Voc = 1.0 V Jsc = 16.5 mA/cm2
F.F = 72.7 % η = 12.0 %
6 7 8 9 10 11 12 130
5
10
15
20
25
30
35
Co
un
ts
(%)
Inorganic-organic hybrid perovskite solar cells
Nature Photonics, 7, 486 (2013)
Architectures: new era
16
31
SEM cross-sectional image SEM surface image
Dense nanocomposite and thin upper layers Is different with conventional dye-sensitized structure Perovskite CH3NH3PbI3 as both light harvester and hole conductor
A. Goossens et al., Nano Lett., 5, 1716–1719 (2005)
3D solar cells, with a remarkable energy conversion efficiency of 5%.
mp-TiO2/CIS/C
Architectures
34
Sargent et al., Nature Nanotechnology, 7, 577-582 (2012)
Schematic of the depleted heterojunctionCQD device
Cross-sectional SEM image of the same device
Sargent et al., ACS Nano, 4, 3374–3380 (2010)
Depleted-Heterojunction Colloidal QD Cells
Architectures
18
35
0.0 0.1 0.2 0.3 0.4 0.5 0.60
5
10
15
20
J (m
A/c
m2 )
Voltage (V)
CITSe-pristine CITSe-heat treated
400 600 800 10000
20
40
60
80
EQ
E (
%)
Wavelength (nm)
CITSe-pristine CITSe-heat treated
17.4 mA/cm2 of short circuit current density (Jsc), 0.40 V of open circuit voltage (Voc), 44.1% of fill factor (F.F) and 3.1 %
CITSeThe Cu:In:Te:Se precursor ratio of 1:1:1:2 resulted in Cu0.23In0.36Te0.19Se0.22 alloy QDs
mp-TiO2/CITSe/Au solar cells
ACS Nano, 7, 4756–4763 (2013)
36
3-D mp-TiO2/perovskite nanocomposite and thin film layer] pillared architecture, and new platform for efficient cells
Nature Photonics, 7, 486 (2013)
mp-TiO2/MAPbI3/PTAA hybrid solar cells
Architectures
19
37
Annealing at 100 oCc
Mixture of GBL/DMSO (MAI+PbI2, PbBr2)
With dripping tolueneW/O
a b
Pure GBL (MAI+PbI2, PbBr2)
WithW/O
Process for Bilayer architecture
Toluene dripping
Nature Materials, 13 (2014) 897
38
5 10 15 20 25 30 35 40
Inte
nsi
ty (
a.u
.)
CH3NH
3I-PbI
2-DMSO
PbI2(DMSO)
2
CH3NH
3I
2 theta (degree)
PbI2
a b
c
5 10 15 20 25
* Perovskite **
Inte
nsi
ty (
a.u
.)
*
130 oC
100 oC
RT
2theta (degree)
70 oC
4000 3500 3000 2500 2000 1500 1000 500
Tra
nsm
itta
nce
Wavenumber (cm-1)
C-N stretchC-H bend
S-O stretch
N-H stretchC-H stretch
N-H bend
a, XRD spectra of PbI2, MAI, PbI2(DMSO)2b, FTIR spectrum of PbI2-MAI-DMSO intermediate phasec, XRD spectra of PbI2-MAI-DMSO intermediate phase powder as a function of
PbI2(MAI)(DMSO)-MAI and DMSO intercalation between layers.-Sequence of guest molecules is unconfirmed.
PbI2(MAI)-MAI intercalation into the PbI2 layered structure.-Imaginary structure.
GBL
-GBL
+MAI
+MAI
A plausible mechanism
or DMF
: MAI
Nature Materials, 13 (2014) 897
Process for Bilayer architecture
40
a
50 m
a b
500 nm
H. J. Snaith et al., Nature, 501, 395 (2013)
Solvent-engineeringprocess
Process for Bilayer architecture
21
41
Efficient planar heterojunction perovskite solar cells by vapourdeposition
H.J. Snaith et al., Nature, 2013, 501, 395–398
42
0 100 200 300 4006
8
10
12
14
16
18
20
Average
Reverse
Po
wer
co
nve
rsio
n e
ffic
ien
cy
(%
)
Thickness of mp-TiO2 (nm)
Forward
0
5
10
15
20
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.10
5
10
15
20
25
Forward
Cu
rren
t d
ensi
ty
︵mA
/cm
2
︶
Reverse
Forward
Voltage (V)
Reverse
a c
b
Photovoltaic performance as a function of scan direction and mp-TiO2 thickness layer.
Nature Materials, 13 (2014) 897
Hysteresis issue: Bilayer architecture
22
43
P-I-N
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.90
5
10
15
20
25
reverse scan forward scan
Cu
rren
t d
ensi
ty (
mA
/cm
2 )
Voltage (V)
Scandirection
Jsc
(mAcm-2)Voc
(V)FF(%)
PCE(%)
reverse 19.6 0.846 78.1 12.9
forward 19.6 0.846 75.9 12.6
Glass
ITO
CH3 NH3 PbI3
PCBM
LiF(0.5nm)/A
l
PED
OT:P
SS
Architecture: bilayer structure (balancing between e and h)
N-I-P Depletion
thickness
Energy Environ. Sci., 2014, 7, 2642–2646
44
Band-gap tuning (MA=CH3NH3)
MAPbI3 MAPbBr3
a
b
c
-4.0E (e
V)
-5.44
-3.93MAPbI3
1.5 eV
-5.58
-3.36MAPbBr3
2.2 eV
PTAAAu
-5.2TiO2
Nano Lett. 13, 1764−1769 (2013)
Materials: CH3NH3Pb(I1-xBrx)3
23
45
0.0 0.2 0.4 0.6 0.8 1.0
2
4
6
8
10
12
Effic
ienc
y (%
)
x
500 600 700 800
Ab
sorban
ce
︵a.u.
︶
Wavelength ︵nm ︶
x=0
x=1.0
500 600 700 800
Absorban
ce
︵a.u.
︶
Wavelength ︵nm ︶
. . .
Materials: CH3NH3Pb(I1-xBrx)3
Nano Lett. 13, 1764−1769 (2013)
46
x = 0
x = 0.06
x = 0.29
x = 0.20
35 % 35 %55 % Humidity
0 2 4 6 8 10 12 14 16 18 20 222
3
4
5
6
7
8
9
10
11
12
Efficiency
︵%
︶
DaysNano Lett. 13, 1764−1769 (2013)
Materials: CH3NH3Pb(I1-xBrx)3
24
47
Materials: CH3NH3Pb(I1-xBrx)3
0 5 10 15 202
4
6
8
10
12
14
16
18
20
Scan rate=40ms, Humidity=25%
, y
Eff
icie
ncy
(%)
Days
MAPbI0.85
Br0.15
Reverse scan
MAPbI0.85
Br0.15
Foward scan
MAPbI3 Reverse scan
MAPbI3 Foward scan
48
N
N
N
N O
OO
O
O O
O O
Chemical Formula: C72H62N4O8
Exact Mass: 1110.46
AuHTM(
Compact layer
FTO
CH3NH3PbI3+mp TiO2
0.0 0.2 0.4 0.6 0.8 1.00
5
10
15
20
Cu
rre
nt
de
ns
ity
(mA
/cm
2)
Voltage (V)
spirobifluorene core in the spiro-OMeTAD Pyrene
J. Am. Chem. Soc., 135, 19087 (2013)
Materials: HTMs
25
49
0.0 0.2 0.4 0.6 0.8 1.00
5
10
15
20
Cur
rent
den
sity
︵mA
/cm
2
︶
Voltage (V)
Commercial pp pm po
J. Am. Chem. Soc., 136, 7837 (2014)
Jsc (mA/cm2) Voc (V) FF PCE (%)
merk(pp) Spiro
20.4 1.00 73.7 15.2
pm-Spiro 21.1 1.01 65.2 13.9
po-Spiro 21.2 1.02 77.6 16.7
pp-Spiro 20.7 1.00 71.1 14.9
TiO2
-5.44
-3.93-4.0
E (eV)
MAPbI3
-5.1
Au
-5.22eV -5.31eV -5.22eV
-2.28eV -2.31eV-2.18eV
pp pm po
1 µm
FTO
Materials: HTMs
50
0.0 0.5 1.0 1.5-20
-15
-10
-5
0
5
10
Voltage (V)
Jsc
(mA
/cm
2 )
MAPbBr3
PTAA PF8-TAA PIF8-TAA
-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4-60
-50
-40
-30
-20
-10
0
10
20
MAPbI3/PTAA
MAPbBr3/PTAA
J (m
A/c
m2)
Voltage (V)
PTAA 5.14 eV
5.68 eV5.46 eV
3.93 eV3.38 eV
MAPbI3
5.44 eV5.51 eV
PF8
PIF8
TiO2
4.0 eV
TiO2
4.0 eV
MAPbBr3
1.4V1.29V 1.04V
Energy & Environ Sci. 2014, 7, 2614–2618
Materials: HTMs
26
51
mp-TiO2/FAPbI3/PTAA hybrid solar cells
Materials: Phase stability
Photographs of inorganic-organic hybrid halide powders. Photographs show the color of the as-prepared MAPbI3, annealed FAPbI3 at 170 C, FAPbI3, (FAPbI3)1-x(MAPbI3)x, (FAPbI3)1-x(FAPbBr3)x, and (FAPbI3)1-x(MAPbBr3)x powders with x = 0.15 (from left to right). The (FAPbI3)1-x(MAPbBr3)x powder is the only black powder among the as-prepared FAPbI3-based materials
Nature, 517, 476–480 (2015)
52
10 15 20 25 30 35 40
Inte
nsi
ty (a.
u.)
2theta (degree)
As-prepared powder
170 oC-annealed powder
Powder after 10 days in air
Re-annealed powder
mp-TiO2/FAPbI3/PTAA hybrid solar cells
Materials: Phase stability
XRD spectra of FAPbI3 powders. The as-prepared yellow FAPbI3 powder shows a non-perovskite phase and is converted to perovskite phase by annealing at 170 C. The perovskite FAPbI3 black powder returned to the yellow non-perovskite powder after being stored in air for 10 h; the yellow powder reversibly changed to black perovskite phase by re-annealing at 170 C.