9 talk phthalocyanines old dyes, new molecular...
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Phthalocyanines: Old Dyes New MolecularPhthalocyanines: Old Dyes, New Molecular Materials
Tomás Torres Autonoma University of Madrid andAutonoma University of Madrid and
IMDEA Nanoscience
Facultad de Química, Universidad Nacional Autónoma de Mexico, Mexico, March 26, 2014
1
- Dirk M. Guldi (University of Erlangen)- Tom Aernouts, Paul Heremans (IMEC)
-Michael D. McGehee (Stanford University- Henry Snaith, Richard H. Friend (Universities of Oxford and Cambridge)
Collaborations
Tom Aernouts, Paul Heremans (IMEC)- Rene Janssen (U. Eindhoven)- Michael Graetzel (EPFL) and
Md. Khaja Nazeeruddin (EPFL, Lausanne) )
(Universities of Oxford and Cambridge)- Peter Bauerle (University of Ulm)- James Durrant (Imperial College, London) - Emilio Palomares (ICIQ, Tarragona)
Coworkers
2Spanish Ministry of Science and Education European UnionCommunity of Madrid
Funding
N
N
NMetallo- FreeNNN
N
NM
Metallophthalocyanine
(PcM)
Free Phthalocyanine
(PcH2)
Q-BandB or Soret-Band
- Variety, versatility and architectural flexibility (Tailoring of the electrophysical parameters and modulation of a given property Tunability)
Chem. Commun. 2010, 7090Chem. Commun. 2010, 7090
parameters and modulation of a given property,Tunability)-Capability to form different kinds of condensed phases- Thermal, chemical and optical stability
3
Chem. Commun. 2010, 7090 Chem. Commun. 2010, 7090 , p y- Unusual physical properties (Conducting Properties, Nonlinear Optical Properties,, Optical Properties,, Magnetic Properties,)
Optical Recording Data Near Infrared Dyes
1P
NaphthalocyanineSubphthalocyanine
0.6
0.8
banc
e
Pc
0 2
0.4
Abs
orb
0
0.2
260 360 460 560 660 760260 360 460 560 660 760
Wavelength (nm)
4UV-visible Spectra of Phthalocyanines and Analogues
Applications
MOLECULARELECTRONIC
DEVICES
NLO MATERIALS
Pc-based molecular systemsDEVICES systems
LIGHT- HARVESTINGSYSTEMS
Second Harmonic Generation
Organic and hybrids solar cells
5
Utilization of Pcs in D-A Systems based on Carbon NanostructuresCarbon Nanostructures
Basic understanding of the donor-acceptor properties of phthalocyanines in multicomponent systems
e-eh+
Covalent orsupramolecular
functionalizationfunctionalization
Chem. Soc. Rev. 2013, 42, 8049
Chem. Rev. 2010, 110, 6768-6816
J. Phys. Chem. Lett., 2011, 2, 905-913
Phthalocyanine-fullerene Multicomponent Systems
h .+
spacer acceptor
h
NN
N
N
.-
p pN
N
NNN M
e-- Light-harvesting- Redox Chemistry
S ll l l l ll (OSC)- Photoinduced electron transfer - Small molecule solar cells (OSC)- Polymer solar cells (PSC, BHJSC)- Dye-sensitized solar cells (DSSC)
7Chem. Rev. 2010, 110, 6768-6816
Covalent Phthalocyanines-Fullerene Dyads
AcceptorE 1 = 664 mV
Chem. Commun. 2007, 2000Chem. Commun. 2007, 2000Ered
1 = - 664 mV
Solid State:CT = 0.2 ms
NN
NN
N
M
t-BuNMe
Donor
CT 0.2 ms
NN
NN
NM
t-Bu t-Bu
DonorEox
1 = 853 mVAntenna
abs = 683 nm(o-DCB)
Mixtures of MDMO-PPV, Pc-C60, PCBM
C 2003 13 00
8
J. Mater. Chem. 2003, 13, 700
Non-Covalent Phthalocyanine Multicomponent SystemsSystems
Metal-Ligand Complexes Hydrogen Bonding Complexesg p
APc
Aromatic Donor-Acceptor Interactions
MPc
M = Zn, Ru, Ti
9
Supramolecular Phthalocyanine-Fullerene TriadsThrough Donor-Acceptor Interactionsg p
electron-rich05 1
C4H7O OC4H7
phthalocyanineKa ~ 4.5 x 105 M-1
N
NN
NN
NN
N
Zn
C4H7O OC4H7
Me
NN
NN
N
Pd
C3H7O2SC3H7O2S SO2C3H7
SO2C3H7
N
C4H7OC4H7O
N
Me
NN
NN
NPd
SO2C3H7
SO2C3H7C3H7O2S
C3H7O2S
electron-deficient
10
phthalocyanine
PhthalocyaninePhthalocyanine--based Supramolecular based Supramolecular S t b M t l C di tiS t b M t l C di tiSystems by Metal Coordination Systems by Metal Coordination
R = Complementary Chromophore
RChromophore
N
Ru(II)phthalocyanine-Fullerene Donor-Acceptor E bl
CO
EnsemblesJ. Am. Chem. Soc., 2009, 131, 10484
CON
N
CO
N NN NN
N
NRu
NN
N NN NN
N
N
Ru
N
N
N
NNN
N
N
N
CO2Et
CO2Et
EtO2C
EtO2C CO2EtCO2Et
NN N
NN
NN Ru
N
N
N
N
N
CO
N NN NN
N
N
Ru
N
543
Determination of the influence of the donor and acceptor ratio in the radical ion pair state lifetime.
CO
Phthalocyanine-TNT endohedral metallofullerenes Donor/Acceptor Conjugates for Molecular PhotovoltaicsDonor/Acceptor Conjugates for Molecular Photovoltaics
NNN
N
N
ZnN
e e --
N NNN N
Zn
N
N
ee --e e
Sc3N@C80-Pc
13Angew. Chem. Int. Ed. 2008, 47, 4173-4176
Carbon Nanotubes and Graphenep
Graphene:• 2D carbon sheet of sp2-hybridized carbon• Extraordinary thermal, mechanical and electricalproperties• Ballistic electron transport• Ideal material for optoelectronic applications, among
hi h l llwhich, solar cellsSingle-wall Carbon Nanotubes:• 1D nanowires, rolled-up graphene
M t lli i d ti• Metallic or semiconducting• Extraordinary thermal, mechanical and electricalproperties
Functionalization: Enhance solubility and processing Supramolecular or covalent
14
Supramolecular or covalent
Phthalocyanine-SWNT Covalent Ensembles
J. Am. Chem. Soc. 2007, 129, 5061
15J. Am. Chem. Soc. 2008, 130, 11503
ZnPc-pyrene Conjugates
O
HONN N
OO
O
py j g
N N
NN NO
M
OH
O
OH2Pc
O O
M = H2 H2PcOH2 2 cO
M = Zn ZnPcOH
TEMSWNT
16SWNT/py-H2PcJ. Am. Chem. Soc. 2010, 132, 16202
ZnPc-pyrene Conjugates
Monochromatic J Am Chem Soc 2010 132 1620217
IPCE: 23%J. Am. Chem. Soc. 2010, 132, 16202
Pc-Carbon Nanostructure Materials Assembled through Supramolecular Interactions
Tuning and Optimizing the Intrinsic Interactions between
p
phthalocyanine-based PPV Oligomers and Single-Wall Carbon Nanotubes Toward N-Type / P-Type
18Chem. Sci. 2011, 2, 652
A New Graphene-Pc Covalent Nanohybrid
R
N NHN
NR
R
R
NNH
N
NR
R RR
O
O
O
ONH
N
NHN N N R
R
RR
Angew. Chem. Int. Ed. 2012, 51, 6421–6425
A New Graphene-Pc Nanohybrid
HO NC
B(OH)2+
NC I
K CO Pd(PPh )
CNRNC
K2CO3, Pd(PPh3)4,THF/H2O, reflux, 18 h
Li, 1-pentanol, NH N
NO
O
O
O
CN
CN
R
R+
OHNC
, p ,150 oC, 18 h
1 2
N
NHN
N
HN
N
N
O
R = p-(tBu)(C6H4)O
p-(tBu)(C6H4)OH, K2CO3,
O
OH3
Cl CN
DMF, 90 oC, 3 h
Cl CN
A New Graphene-Pc Nanohybrid
1.5
1
Z[nm
]
10.80.60.40.20
0.5
0
X[µm]
A New Graphene-Pc Nanohybrid
N
COOH
N
COOH
4-carboxybenzaldehyde,sarcosine, NMP, 170 oC6 d
EDC,HOBtDMF/THF
6 days
Pc 34 days, rt
HN NN
R
R
RR
NNH
N
NN
HN N
R
R RR
O
O
O
ONH
N
HN
R
N N N R
R
RR
4
dTEM and HRTEM images of graphene-Pc
AFM image and height profile of graphene-Pc
23
A Electron-donating behaviour of graphene in covalent bl ith l t ti hth l iensembles with electron-accepting phthalocyanines
J. Am. Chem. Soc. 2014, in pressS S
R R O
O
O
O
N
NN
N
N
SZnR
SR
O O
NNN
NN NS
SS
O O
O OSS
RRO O
TEM image of 8 on a lacey carbon grid (left) and
24
tapping mode AFM image of 8 on a SiO2 surface
and height profile at position 1 (right).
Pc-Carbon Nanostructure Materials Assembled through Supramolecular Interactions
Approaches towards tunable graphene /phthalocyanine-PPVhybrid systemshybrid systems
This polymer is able to exfoliate pure natural graphite in THFsolutions.
Angew. Chem. Int. Ed. 2011, 50, 3561.
25J. Phys. Chem. Lett. 2011, 2, 905
New Porphyrinoids p y
N NN
N
N N
ZnRN NNR
26
Supramolecular and covalent azulenocyanine-C60 systemsC60 systems
Chem. Commun. 2012, 48, 4058
• To extend the absorption to the NIR
.
27• To compare covalent and non-covalent interactions
Phthalocyanines for Photovoltaic Applications1. Strong absorption (light-harvesting, high extinction coefficients, broad coverage of solar spectrum) 2 HOMO/LUMO l l dj t d t th l t d ( i h d h i t2. HOMO/LUMO levels adjusted to the electrodes (rich redox chemistry, photoinduced electron transfer)3. Procesability (solution-processing or vacuum-technology)3. Procesability (solution processing or vacuum technology)4. Packing in solid state, control of morphology, self-assembling properties 5. Excellent charge transport properties
Soret or B BandQ Band
28
Chem. Commun. 2010, 46, 7090.The Handbook of Porphyrin Science, 2010, World Scientific.Chem. Commun. 2010, 46, 7090.The Handbook of Porphyrin Science, 2010, World Scientific.
Small-Molecule Organic Solar Cells
29
F
FF
ClF F
FF
F
Subphthalocyanines with Extended Conjugation
NN
ClF
F
F
F
FF
N
NN N
N
N
B
F
F
N
NNN
N
N
B
F
Fj g
Adv. Energ. Mater. 2011, 565.
NN
NN
NBF
F
F
F
F
FF
FF
FClFES. Pat. Appl. 2011, P201130667
F FF
Adv. Energ. Mater. 2014, DOI 10.1002aenm.201301413 .
30Recently we have found Power conversion efficiencies of 6.5% using novel vacuum codeposited electron-withdrawing SubPcs dimers as aceptor materials
Perfluorinated Subphthalocyanine dimer: A new Acceptor Material in Small Molecule Bilayer Organic Solar CellsMaterial in Small-Molecule Bilayer Organic Solar Cells
FAdv. Energ. Mater. 2011, 565.F
F
NCl
F
F FF
N
F
F
Adv. Energ. Mater. 2011, 565.
ES. Pat. Appl. 2011,
N
NN N
N
N
B
F
F
N
NNN
N
B
FMixture 1:1 of
P201130667
FF
F
F
F
FClF
Mixture 1:1 oftopoisomers
We have demonstrated FSubPcDimer to be an exceptional novel acceptormaterial with complementary absorption to the donor material SubPc.
Compared to an optimized solar cell with C60 as an acceptor (ca. 3%),this leads to an enhanced photocurrent while preserving the high open-circuit voltage characteristic of SubPc based devices 950mV and a power
31
circuit voltage characteristic of SubPc-based devices, 950mV, and a powerconversion efficiency of 4% was found.
Chlorosubphthalocyanine as Acceptor in Organic PlanarHeterojunction Solar Cell
Ad E M t 2014 DOI 10 1002 201301413
Heterojunction Solar Cell
Adv. Energ. Mater. 2014, DOI 10.1002aenm.201301413 .
Cl Cl
NN N
Cl
Cl Cl
Cl
N
NN
N
N
NB
Cl
ClClN
NN
N
N
NB
ClCl
An optimization of several aspects of planar heterojunction solar cells based onAn optimization of several aspects of planar heterojunction solar cells based ona hexachloro SubPc as an acceptor alternative to C60, and SubNc, absorbing at670 nm, as a donor material is presented. In the resulting device, the threesolar cell parameters J sc (9 mA cm 2) Voc (1030 mv) and FF (71%) are
32
solar cell parameters J sc (9 mA cm-2), Voc (1030 mv) , and FF (71%) areimproved simultaneously leading to a power conversion efficiency of 6.4% (4.4in the case of C60 as an acceptor).
8.4% efficient fullerene-free organic solar cells exploiting long-range exciton energy transfer
Cnops et al. from IMEC have demonstrated a simple three-layerarchitecture comprising two non-fullerene acceptors and a donor in whicharchitecture comprising two non fullerene acceptors and a donor, in whichan energy relay cascade enables efficient two-step exciton dissociation.With an open-circuit voltage close to 1 V, this leads to a remarkablepower conversion efficiency of 8 4%power conversion efficiency of 8.4%.
These results confirm that multilayer cascade structures are an importantlt ti d i hit t t i th f f i
33
alternative device architecture to improve the performance of organicsolar cells beyond that of conventional donor-fullerene systems.
Polymer Bulk Heterojunction Solar Cells
34
+
Phthalocyanine-containing Polythiophenes
SO2C8H17H17C8O2SSO2C8H17H17C8O2S
633 nm Acceptor/Antena
N NNSO2C8H17H17C8O2SN NN
OH C O S S
17 8 2
S
C10H21
N NN
N NNiSO2C8H17
SO2C8H17H17C8O2S
17 8 2
N NN
N NNiO
H17C8O2S
H17C8O2S(CH2)5
S
1:9
FeCl3
O
(CH )
SO2C8H17H17C8O2S UV-Vis (CHCl3): e-
0.3
0.5
ance S
S
(CH2)5
yx
thiophenePc
Ered1 = - 664 mV
0.1
0.2
Abs
orba
C10H21
ny
80%
GPC: in THF36
0300 400 500 600 700 800
Wavelength (nm)
GPC: in THFMW 52200
Solar N-Type
Objectives
Blends Pc-polymer
+
A t Conjugated polymerAcceptorPhthalocyanine
Conjugated polymer
37
N
C(CH3)3(H3C)3C
Phthalocyanine-containing PPV and PT: Grafting approach
OO
N
N
N
N
N
N
NZn
N
N
N
N
N Zn
(H3C)3C C(CH3)3
*O
ON
(H3C)3CN3
OO
N
NN
N
N Zn
C(CH3)3N
NN
*OCH3
OCH319
O
OO
(MW 90000) PPV
*
*O
OCH3
OCH39 1
(MW 90000)N
N
N
N
N
N
N
N Zn
NN
N
N
OO PT
SS
3 0MDMO‐PPV tBu4PcZn PCBM
N-type Phthalocyanines
‐3.0‐3.4
‐3.7
SO
OO
5 3‐5.1
‐4.0
N
NN
N
NS
Zn
O‐5.3
‐6 1‐5.6
NN
N
N
S SO
O
O
O
‐6.1F16PcZn
S SO
OO
OOO
Solar n-Type European NetworkSolar n Type European Network(K. Müllen, R. Janssen, D. Vanderzande, T. Torres, et al.)
Dye-sensitized nanocrystalline solar cells (DSSC)( )
40
Photovoltaic device based on DSSC2
loade
D*/D
inanocrystalline I/I basedorganic dye
yTiO2 film
I /I3 basedelectrolyte
electrolyte0
-0.5
e-
hνII3
D/D++0.5
hTCOcoated
I3 +0.25 hν
41e- flow
Platinized TCO coated
external circuit
TiO2 PtV
Some of the Most Successful Dyes
COOTBA
NN
Ru
NCSN
HOOC
11% 9,5%C6H13 C8H17O OC8H17
12.3 and 13 %
S
S
NN
NCS
HOOC
11% 9,5%
N NZn CO2HN
6 13 8 17 8 17
N N
RNC CO2H
JK-2COOTBA
N719 N N
C6H13 OC8H17C8H17O
N
N N
NZn CO2HN
6 13
Science, 2011, 629Nature Chem. 2014, 6, 242
R 11%
R = C6H13 YD2
Chem. Commun., 2010, 46, 7090-7108
Dye-sensitized nanocrystalline solar cells based on RuPcs
N
CH3
N
N
N
NCOOH
N
NN
N
N
N
NRu
N
NN
N
NNRu
N
HOOCN
N
Catalysis of Recombination and Limitation on Open Circuit Voltage for Dye Sensitized Photovoltaic Cells using Organic Dyes
HOOC
H3C
Photovoltaic Cells using Organic Dyes.overall efficiencies around 3.5%
Slow electron injection and efficient electron injection are compatible due to the long lifetime of the injecting state, the Ru-phthalocyanine triplet state.
Pc-based device with the highest efficiency found using a near-IR dye
TT1 Fig. 2. Device made using a mesoporous semiconducting N N
N
O(H3C)3C
OH
Angew. Chem. Int. Ed., 2007, 46, 8358-8362Angew. Chem. Int. Ed., 2007, 46, 8358-8362
8
film of titanium oxide nanoparticles, sensitised with TT1, and a red/ox electrolyte (iodine/iodide).N
NN
N
NZn
4
6
mA
/cm
2 )
TT1W900
Fig. 1. The light-to-electron conversion efficiency is higher than 80% at 690 nm
(H3C)3C C(CH3)3
0
2
Cur
rent
( W900g
0.0 0.1 0.2 0.3 0.4 0.5 0.6-2
Voltage (V)
Effi i i f th i f li ht tEfficiencies for the conversion of light-to-electricity of 3.5 %, when irradiated with simulated sun light 1.5 AM G at 100mW/cm2
Open-circuit voltage (Voc) of 663 30 mVp g ( )
TT1/TiO2 DSSC with an active area of 0.158 cm2
Carboxy-Phthalocyanines Ener. Environm. Sci. 2011, 4, 189.Ener. Environm. Sci. 2011, 4, 189.
CO2HO
, ,, ,
TT2
TT3N
(H3C)3C CO2H
TT4
N
NN
N
NNM
CO2H
O
TT5N
(H3C)3C C(CH3)3
CO2H
TT6
M = Zn, Mg, Mn, Ti, H2
CO2H
TT7 TT8Efficiencies for the conversion of light-to-electricity of 4.7 %, when irradiated
CO2H
CN
CO2H
CN
TT15 TT16
y ,with simulated sun light 1.5 AM G at 100mW/cm2
CO2H
CO2H
CO2H
CO2H
Novel Phthalocyanines
N
(H3C)3CCOOH
COOH
N
NN
N
N
N
NZn
N
(H3C)3C C(CH3)3
Chem. Sci. 2011, 1145Chem. Sci. 2011, 1145C e Sc 0 , 5C e Sc 0 , 5
Angew. Chem. Int. Ed., 2012, 51, 4375 –4378Angew. Chem. Int. Ed., 2012, 51, 4375 –4378
ChemPhysChem 2014, in press.ChemPhysChem 2014, in press.
Recently we have found Power Conversion efficiencies higher
Angew. Chem. Int. Ed., 2012, 51, 1895-1898Angew. Chem. Int. Ed., 2012, 51, 1895-1898
46
Recently we have found Power Conversion efficiencies higher than of 6% using a new Pc as dye in classical DSSC
SynthesisPh Ph
OHCl
Cl
CN
CN+
K2CO3, DMF, 90 oC,36 h, 30%
OOPhPh
PhPh
Ph Ph
NC
NC
NC
NC
O
OI
Ph Ph
Ph
+ratio, 1:5
15%
DMAE, ZnCl2, 140 oC OH
CuI, PdCl2(PPh3)2Et3N, THF, 55 oC, 60%
N
NN
N
N
NN
O
O
O
O
Zn
Ph
Ph
Ph
Ph
PhPh
Et3N, THF, 55 C, 60%N
O
O I
Ph
Ph
Ph Ph
NaClO2, H3NSO3,THF/H O
IBX, DMSO/THFN N
N
O
O
O
O
PhPh
Ph
Ph
Ph
Ph
Ph Ph
N N
N
O
O
O
O
PhPh
Ph
Ph
Ph
Ph
Ph Ph
N N
N
O
O
O
O
PhPh
Ph
Ph
Ph
Ph
Ph Ph
THF/H2Ort
80% 60%N
NN
N
N
N
N
O
O
Zn
Ph
Ph
N
NN
N
N
N
N
O
O
Zn
Ph
Ph
Ph Ph
N
NN
N
N
N
N
O
O
Zn
Ph
PhPh Ph
OH
Ph PhO COOH
Ph Ph
TT40
Panchromatic absorption materials for solar cells Panchromatic absorption materials for solar cells TT1 can be combined with other dyes to widen theTT1 can be combined with other dyes to widen the absorption of light into the visible region. IPCE spectra of the co-sensitised DSSC
Co-sensitised DSSC
NN
O(H3C)3C
OH 8090
100
S
S
N
NN
N
N
N
NZn
3040506070
IPC
E (%
)
TT1 JK2 JK2(1h)+TT1(1h)
S
NC CO2H
(H3C)3C C(CH3)3
TT‐1 400 500 600 700 8000
102030I
( ) ca. 8 %JK‐2
Wavelength (nm)
The photoresponse of the “molecular cocktail” extends up to 700 nm with photon-to-electron conversion efficiencies of 60% for the whole spectrum.photon to electron conversion efficiencies of 60% for the whole spectrum. The overall device efficiency was 7.77%
Energy Relay Dyey
New designHigh energy photons are absorbed by highly photoluminescent chromophores (PTCDI)
Nature Photonics 2009, 3, 406 - 411Nature Photonics 2009, 3, 406 - 411- High energy photons are absorbed by highly photoluminescent chromophores (PTCDI)unattached to the titania and undergo Förster resonant energy transfer (FRET) to organic sensitizing dye (TT1).-This novel architecture allows for broader spectral absorption, an increase in dye loading,
49
p p , y g,and relaxes the design requirements for the sensitizing dye. We demonstrate a 26% increase in power conversion efficiency.
Energy Relay Dyes
The energy relay dye 4-(Dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl) -4H-pyran (DCM), was used with a near-infrared sensitizing dye,TT1 i h ll i ffi i f h d i i dTT1, to increase the overall power conversion efficiency of the dye-sensitizedsolar cell (DSC) from 3.5% to 4.5%. The unattached DCM dyes exhibit anaverage excitation transfer efficiency (ETE) of 96% inside of the TT1 covered,
t t d TiO filmesostructured TiO2 films.
NN :NN :,
O
NDCM
Chem.Phys.Chem. 2011, 12, 657Chem.Phys.Chem. 2011, 12, 657
A spirobifluorene (spiro-TBT) can act as a secondary absorber in solid-stateSolid-state excitonic solar cells
A spirobifluorene (spiro TBT) can act as a secondary absorber in solid state excitonic solar cells (ss-XSCs). Blending with a hole-transporting material (spiro-OMeTAD) and used in conjunction with a near-infrared dye (TT1) results in an extended spectral response which yields a notable increase in short-circuit current and power conversion efficiencyand power conversion efficiency.
Coworkers
52Spanish Ministry of Science and Education European UnionCommunity of Madrid
Funding