Organic Photovoltaics at Merck Working with...

Organic Photovoltaics at Merck – Working with SunshineTM

Nicolas Blouin, Miguel Carrasco-Orozco, Toby Cull, Frank Meyer, William

Mitchell, Steve Tierney, Mark James and Mark Verrall

Plastic Electronics 2012, Dresden

Dr Giles Lloyd

Senior Manager, OPV Business Development

Merck Chemicals Limited, UK

Agenda

Giles Lloyd, Plastic Electronics 2012 2

Introduction to Merck Chilworth and OPV Business model 1

2 Development of high performance OPV materials

3

4

Halogen free, stable and efficient OPV data

Current status and roadmap

5 Summary

Merck Chilworth Technical Centre, UK

High spec application labs Creative Chemistry labs

• ~ 90 multinational

staff + students

• Close connection

to UK academia

• State-of-the-art

R&D facilities

• Wide range of

technical skills

“ Innovation and Business Development in

Organic opto-electronic materials ” 3 Giles Lloyd, Plastic Electronics 2012

Performance Materials


Customer Merck sales

Business model

Development expertise

Printable

Formulation

Component /

Device Materials

Merck Organic Electronics Business Model

Printing

Process Application

Co-Development area

• Focus on strengths and expertise in materials and formulations

• Support and customise for practical use of formulations

Giles Lloyd, Plastic Electronics 2012 5 5

Organic Solar Cell: Activities at Merck

OMe

O

S

S*

S

S

* n

Acceptor (electron transporter) – PV-A series

e.g. [C60]PCBM

Donor – Acceptor

Blend

Donor (hole transporter) – PV-D series

e.g. Poly(3-hexylthiophene) (P3HT) Ca/Al

Pedot

ITO

Glass

Current internal R&D focus

Complimentary R&D activity to support

actives development

R&D focus for > 7 % module efficiency

• product development with Nano-C

• In-licensing of PCBM IP

Interfacial layers

e.g. ZnO/Titania-replacement


3rd Gen Solar Cells (OPV) Offer Advantages Application advantages of 3rd generation cells

Flexibility and low weight. Freedom of design

Semitransparent, tunable “attractive” colour

Superior low and diffuse light sensitivity

Positive temperature dependence

High-volume production process

• Scalable processing – Wide area coating

• Low factory investments

• Low cost for system integration

• Fast energy payback

Product examples from customers

Which performance for which application?


Application Mobile

Electronics

Outside

pillars for

urban areas

Outdoor

recreational

remote

BIPV Grid

Connected

Efficiency % < 5% 5-8 % 5-8 % 5-12% > 10%

Lifetime >1 year 3-5 years 3-5 years > 10 years > 10 years

Cost Competitive

compared to

flexible

inorganic PV

Competitive

compared to

flexible

inorganic PV

Competitive

compared to

flexible

inorganic PV

100 €/m² Grid parity

0.15€/kW

Timeframe Present > 2013 > 2013 >2015

Merck Evaluation Models Commercial Devices

8

S

H13C6

n

O

OMe

Polymer

Fullerene

Active Layer

Inverted stack Normal stack

V

Anode(TCO)

HTL and/or EBL

HBL and/or ETL

Cathode (Ag or Cu)

Plastic or Glass Plastic or Glass

Cathode (TCO)

HTL and/or EBL

Anode (Al)

HBL and/or ETL

V

“Lab” device Commercial device

Giles Lloyd, Plastic Electronics 2012

Development of the correct BHJ-morphology with processes (blade coating,

temperature ramps ...) as close as possible to mass production tools

http://www.smartplanet.com/news/tech/10000060/solar-cells-on-your-innocent-smoothie.htm

Step 3. Fine tuning of optimised chemical structure

Maintain all previous good features

Band-gap reduction. Attractive blue colour

Improved performance, PCE 7%

Easy and reproducible coating

9

Development cycle: Identification of leading material


Step 2. Optimisation of chemical structure

Maintain good FF, Voc and thick layers

Improved solubility, non-halogenated solvents

Higher PCE ~ 6% with PCBM[70]

Step 1. Identification of a promising lead

PCE ~ 4.5%, poor solubility

Performance from thick layers ~200 nm.

Good fill factor and VOC

10

Fine-tuning of Optimised Chemical Structure

Research material

Excellent FF and EQE

Solubility in halogen free solvents

Very easy and reproducible coating

Data not corrected for mismatch factor .

PV-D

4600

0

-0.5 0.0 0.5 1.0-15

-10

-5

0

5

10

Jsc = -10.97 mA cm-2

Voc = 785 mV

FF = 69.7 %

= 6 %

Curr

ent

Density

(mA

cm

-2)

Appied Voltage (V)

Polymer OPV-33

Latest Polymers

Absorption onset ~750 nm

EQE reaches 55-60%

VOC improved to 800 mV

Improved solubility

Royal blue colour

7% average

-0.5 0.0 0.5 1.0-15

-10

-5

0

5

10

Voc

= 800.00 mV

Jsc

= 10.78 mA cm-2

FF = 73.22

PCE = 6.31%

Cu

rre

nt

De

nsity (

mA

cm

-2)

Applied Voltage (V)

Polymer OPV-46

Chemistry

Development


Research material


New Donor Polymer Hero Cells > 8% - Chlorinated solvents

11

Hero cells have > 8% efficiency - no blocking layers

- no special optical „tricks‟

- standard device structure

- thick layers > 200 nm !!!

Merck quotes > 7% as average, easy to achieve efficiency for best polymer

Donor : PV-A600 Donor : PV-A700

Architecture Env. Voc

(mV)

Jsc (mA) FF PCE (%) Thickness

Standard (Ca)/ non-halog N2 820 -11.8 72.2 7.0 267

Inverted (ZnO) / non-halog N2 770 -13.4 52.3 5.4 433

Halogen free formulation deliver performance


Table shows average values

12

Standard architecture Inverted architecture

-0.6 -0.4 -0.2 0.0 0.2 0.4 0.6 0.8 1.0-15

-10

-5

0

5

10

Jsc (

mA

cm

-2)

voltage (V)

Development Increases Thermal Stability – 120oC for 0.5h


0min5min

10min20min

30min

0.5

1.0

1.5

2.0

2.5

3.0

PC

E (

%)

P3HT improves

performance, then

stable (VOC, JSC,

FF and PCE) PCE

is stable.

0min5min

10min10min

20min30min

1

2

3

4

5

6

PC

E (

%)

For Research

material about 15%

decrease in PCE is

observed, mainly due

to loss in fill factor.

0min5min

10min20min

30min

3.5

4.0

4.5

5.0

5.5

6.0

PC

E (

%)

For latest donor

materials there is a

decrease in JSC upon

heating, but is

compensate by the

increased VOC; PCE

is stable. Inverted stack: ITO/ZnO/Blend/Pedot/Ag

Annealing 120oC in N2

Pipeline Developments

Compared to previous donor materials:

Higher solubility in organic solvents (> 50

mg/ml in xylenes at r.t.)

Increased Voc

But lower Fill Factor (to be optimised!)


-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2-20

-15

-10

-5

0

5

10

15

20

Cu

rre

nt

De

nsity (

mA

/cm

2)

Voltage (V)

-0.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2-20

-15

-10

-5

0

5

10

15

20

Cu

rre

nt

de

nsity (

mA

/cm

2)

Voltage (V)

Cell

Architecture

Voc

(mV)

Jsc

(mA/cm2)

FF

(%)

PCE

(%)

Standard

(Ca) 888 -11.7 68.4 7.1

Inverted

(ZnO) 868 -14.8 46.7 6.0

15

Merck’s Progress for Organic Photovoltaics (Merck’s average data)

1

2

3

4

5

6

7

Q1 ‘9 Q2 ‘9 Q3 ‘9 Q4 ‘9 Q1 ‘10 Q2 ‘10

[C70] PCBM based

[C60] PCBM based

% efficiency in

standard single cell

Q3 ‘10 Q4 ‘10 Q1 ‘11 Q2 ‘11 Q3 ‘11 Q4 ‘11

Internal reference P3HT

PV-D

Q1 ‘12

8

[C70] PCBM non-chlorinated solvent

Roadmap milestones chlorinated/

non-chlorinated formulations [C60] PCBM non-chlorinated solvent


Q2 ‘12


Merck OPV Roadmap

2011

> 7 % (average)

> 9 % (average)

> 5 % module efficiency on

plastic in manufacturing line

Halogen-free formulation

Roll out to (R&D) market in

scale for large area coating

trials

GEN 2

GEN 3

Improved donor polymer scaled

Novel acceptor material

introduced

First supply of GEN 3

environmentally friendly ink

formulation for mass production

Halogen-free INK released

(superior efficiency and stability)

> 8 % (average)

> 6 % module efficiency on


Improved donor polymer

(R&D)

New donor polymer

Halogen-free formulation

( new polymer : PCBM )

Improved stability

Supply of Gen 2 material for

widespread R&D coating

trials (Halogen free)

Replacement of current buffer

layers with alternative material

>7 % module efficiency on


2012 2013

LAB

PILOT PRODUCTION

Colour portfolio

16

Summary

Strong progress in polymer (donor) development

PCE moving towards 8%

Voc > 800 mV & FF > 70%

Ease of processing from non-halogenated solvents

Attractive blue colour for applications

New polymers in pipeline show higher potential for increased PCE

Strategic partnership in-place with Nano-C for PCBM supply and active R&D

agreement on novel fullerene molecules (acceptor)


Merck Portfolio for OPV Applications

PV-D Donor Polymer Materials

PV-A Acceptor Materials

Portfolio Extension...


Contact: [email protected]

Organic Photovoltaics at Merck Working with...

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