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