IBM Research

Current Status and Future

Prospects of Earth-Abundant
Kesterite Photovoltaics
David Mitzi
Duke University

150 Years BASF

March 10, 2015
2012 IBM Corporation

IBM Research

Goal: Low-cost high efficiency thin-film PV devices

using abundant or readily-available elements

Thin-film solar cells and kesterites

Solution processed Cu2ZnSn(S,Se)4 (CZTS) devices
Device/materials understanding and limitations
Concluding remarks and prospects for future

2012 IBM Corporation

Commercial solar technologies

Built-in
electric field

Photon

Conduction band
ep-type
Fermi level
Valence band

n-type
h+

~90% of
the market

Growth in TF PV Led by First Solar and Solar Frontier

Accelerated Technology Roadmap Scenario

Forecast by PV Technology Type

4.5GW of thin-film panels forecast to be shipped during 2015

CIGS and CdTe dominating growth

Two primary chalcogenide-based PV technologies:

Cadmium Telluride

Photons
(sunlight)

glass substrate
TCO
CdS (n-type)
CdTe (p-type)
(3 to 10 m thick)
back metal contact

CIGS= Cu(In,Ga)(S,Se)2
Photons
(sunlight)

encapsulant
TCO
CdS (n-type)
CIS/CIGS (p-type)
(1 to 5 m thick)
Metal (molybdenum)
substrate

Performance
$<0.70/W as of Q2 2013
>7GW cumulative production
14% commercial modules
21.0% laboratory cell

Performance
>1GW cumulative production
14% commercial modules
21.7% laboratory cell

Major Players
First Solar
PrimeStar Solar / GE
Calyxo

Major Players
Solar Frontier
Avancis
Global Solar

Advantages:
1. Direct band gap
Thinner absorber layer
2. Grain boundaries
relatively benign
3. Compatible with
monolithic integration
4. Flexible substrates
possible.
Some issues:
1. Issues with heavy metal
Cd Restricted in
certain markets.
2. Use of scarce elements:
In, Te

Kesterite vs Chalcopyrite Structures:

Cu(In,Ga)(S,Se)2

3+

Cu2ZnSn(S,Se)4

4+
2+
January 31, 2013

CZTS Progress up to 2009

Ni/Al contacts
ITO + i-ZnO
n-type CdS
p-type
Cu2ZnSn(S,Se)4
Mo
Glass

1988: Ito and Nakazawa, PV effect demonstrated in CZTS thin film (In 1977 S.
Wagner demonstrated PV effect in related Cu2CdSnS4#)
1996: First CZTS devices by sequential evaporation/sulfurization0.66% efficiency*
1996-2009: Steady progress in device performance for vacuum-deposited CZTS
2008: CZTS device prepared by sputtering/sulfurization with 6.77% efficiency
#

S. Wagner et. al., J. Cryst. Growth 39, 151 (1977)

* H. Katagiri et. al., Thin Solid Films 517, 2455 (2009)

Basic device structure:

Ni/Al
ITO
i-ZnO
n-CdS

p-CZTSSe

Mo
Glass

0.45 cm2 device area

Some issues for processing

Complex multi-element compound
with narrow stoichiometry range
SnS2

Optimal composition is:

[Cu]/([Zn]+[Sn]) 0.9 and [Zn]/[Sn] 1.2
Sn is volatile Difficult to control
stoichiometry
kesterite
(i.e., CZTSSe)
(I4)
S, Se
Cu2S

ZnS

Cu
Zn

I.D. Olekseyuk et. al., J. Alloys and Compounds 368, 135 (2004)
H. Katagiri et. al., Mater. Res. Symp. Proc. 1165, M04-01 (2009)
A. Weber et. al., J. Appl. Phys. 107, 013516 (2010)

Sn

Why solution processing?

Spray coating

Spin Coating

Doctor blade
Solution/
Suspension

Slit Casting

Anneal

No vacuum required; No high temperature sources; High

throughput (>1000m/min for flexible substrates established)
How to get CZTS into solution?

Hybrid particle/solution hydrazine-based deposition

Zn
M = Cu, Sn
X = S, Se

MnXm

add as powder
N2H5+
N2H4 + X

Selected Properties of N2H4:

ZnX

MXMX-

MXN2H5+

ZnX
N2H5+

ZnX

Basic; Powerful reducing agent

Good solubility of S and Se, as well as many
metal chalcogenides Not Zn(S,Se)!

Cleanly decomposes into N2 + H2 + NH3

Hygroscopic; absorbs CO2 and O2 from
atmosphere inert atm. processing

highly toxic / combustible safety!

T. K. Todorov et. al., Adv. Mater. 22, E156 (2010)

Particle-based slurry

Hybrid particle/solution hydrazine-based deposition

Zn
M = Cu, Sn
X = S, Se

MnXm

add as powder
N2H5+
N2H4 + X

Filtered particle component

ZnX

MXMX-

MXN2H5+

ZnX
N2H5+

ZnX

Particle-based slurry
N2H4ZnX (X=S, Se)

T. K. Todorov et. al., Adv. Mater. 22, E156 (2010)

Hybrid particle/solution hydrazine-based deposition

Zn
M = Cu, Sn
X = S, Se

MnXm

add as powder
N2H5+
N2H4 + X

ZnX

MXMX-

MXN2H5+

ZnX

Cu2ZnSn(S,Se)4
dry

heat
X + N2H4
decomp.
products

heat

T. K. Todorov et. al., Adv. Mater. 22, E156 (2010)

ZnX
N2H5+

Record CZTS device from 2009:

Certified by NRELAug 11, 2009

CZTSSe

Efficiency = 9.7 %
Voc = 0.516 V
Jsc = 28.6 mA/cm2
Fill Factor = 65.4%
Area = 0.44 cm2
Eg = 1.19 eV
Todorov et. al., Adv. Energy Mater. 3, 34 (2013)

Further champion CZTSSe devices (11.1% efficiency):

Certified by Newport Corp.Feb 24, 2012

Efficiency = 11.1 %
Voc = 0.460 V
Jsc = 34.5 mA/cm2
Fill Factor = 69.8 %
Area = 0.45 cm2
Eg = 1.13 eV

Todorov et. al., Adv. Energy Mater. 3, 34 (2013)

Compare 11.1% record device to SQ limit

SQ = ~31%
Define Voc deficit:
def

Voc = Eg/q Voc

rec = 11.1%

def

Voc < 0.5 V for best CIGS

def

Voc > 0.6 V for best CZTS

Jsc 34.5 vs 43.4 mA/cm2: 26%
FF 70% vs 86%

23%

Voc 460 vs 820 mV:

78%

Jsc enhancement through optical stack optimization

11% WR Device (Jsc/JSQ = 0.79)

Can we improve the top stack to reduce the short wavelength losses?

Jsc enhancement through optical stack optimization

Planar Optical Model
(scattering matrix)

Should be optimizing the transmitted light rather than just reflected light
M. Winkler et. al., Energy and Environ. Sci. 7, 1029 (2014)

Jsc enhancement through optical stack optimization

Device Verification
1
2

baseline
improved

New device design leads to ~10% enhancement in Jsc

M. Winkler et. al., Energy and Environ. Sci. 7, 1029 (2014)

Jsc enhancement through optical stack optimization

New WR and first CZTS device over 12% efficiency

M. Winkler et. al., Energy and Environ. Sci. 7, 1029 (2014)

Influences on Fill Factor:

VOC
Voltage
Maximum Power
Current

Rectangle
Fill factor, FF =

VMAX I MAX
VOC I SC

VMAX
IMAX
ISC

RL

M. A. Green, Solid State Electronics 24, 788 (1981)

Influences on Fill Factor:

Neglecting Rsh, FF can be approximated:
FF = (1-rs)

voc ln(voc + 0.72)

voc + 1

Using voc for our CIGS(15%) and

CZTS(11%) devices and rs = 0.04, we get:
FF(CIGS) = 75.0%
Difference is ~5%
FF(CZTS) = 70.2%

Cell

Eff

FF

Jsc

Voc

A/cm2

IBM-CIGSSe

15.2

75.0

32.6

0.623

IBM-CZTSSe

11.1

69.8

34.5

0.460

M. A. Green, Solid State Electronics 24, 788 (1981)

FF deficit in CZTS can to a large

extent be accounted for through
the Voc deficit

Large database of device results available for Voc

Data represents >1000 CZTSSe devices

Voc deficit (V)

Vac. Deposit CZTS

IBM 11.1% CZTSSe

NREL CZTSe

IBM 15.2% CIGSSe

Band Gap (eV)

For all devices, Voc deficit

>0.6 V (for CIGS it is ~0.5 V)
Strong Eg dependence
of Voc deficit (Eg/q Voc)

Hybrid particle/solution hydrazine-based deposition

Zn
M = Cu, Sn
X = S, Se

MnXm

add as powder
N2H5+
N2H4 + X

ZnX

MXMX-

MXN2H5+

ZnX

Cu2ZnSn(S,Se)4
dry

heat
X + N2H4
decomp.
products

heat

T. K. Todorov et. al., Adv. Mater. 22, E156 (2010)

ZnX
N2H5+

Hybrid particle/solution hydrazine-based deposition

Zn
M = Cu, Sn
X = S, Se

MnXm

add as powder
N2H5+
N2H4 + X

ZnX
ZnX
MX
N2H5+

MX-

N2H5+
MX-

Cu2ZnSn(S,Se)4
dry

heat
X + N2H4
decomp.
products

heat

ZnX

All-solution hydrazine-based deposition

Zinc salt
M = Cu, Sn
X = S, Se

MnXm

N2H5+

N2H4 + X

MX-

MX-

N2H5+

N2H5+
MX-

Cu2ZnSn(S,Se)4
dry

heat
N2H5+ MX- N2H5+ MXX + N2H4
decomp.
products

MX- N2H5+ MX- N2H5+

T. K. Todorov et. al., IEEE Journal of Photovoltaics 4, 483 (2014)

IBM pure solution approach for CZTSSe

LBIC Study

= 404nm

= 950 nm

Slurry process

= 404nm

= 950 nm

Solution process
Superior smoothness/uniformity of solution-processed layers.
T. K. Todorov et. al., IEEE Journal of Photovoltaics 4, 483 (2014)

Solution process reaching slurry record benchmark

Eff.
(%)

Voc

Jsc

FF

(V)

(mA/cm2)

(%)

Slurry

11.1

460

34.5

70

Solution

11.1 489

33.0

69

Slurry

Pure solution

T. K. Todorov et. al., IEEE Journal of Photovoltaics 4, 483 (2014)

Combining with new optical stack approach 12.6%!

Get both increase in Jsc (2%) and Voc (12%)

relative to previous 11% champion of same Eg
Best Voc deficit for band gap Eg = 1.13eV
(i.e., 0.62 vs 0.67 V for previous 11% device)
While Voc is improved in the current device
Still a long way to go until Voc deficits of
< 0.5V can be achieved (as for highperformance CIGS).
W. Wang et. al., Adv. Energy Mater. 4, 1301465 (2014)

Champion CZTSSe Solar Cells Still large Voc deficit

Voc is better, but nowhere near

good enough!
Where is this Voc deficit coming
from
Voc deficit
= 0.62

-- Interface / grain boundaries?

-- Bulk defects (deep trap and
band tail states)?

Jsc 35.3 vs 43.4 mA/cm2: 23%

FF 70% vs 86%

23%

Voc 513 vs 820 mV:

60%

Grain boundaries in high-performance CZTS

Air annealing used for high-performance devices SnOx and Cu poor at GBs
SnOx can serve to passivate GBs and might even be beneficial if not too thick

K. Sardashti et. al., Adv. Energy Mater. in press (2015)

Band tailing can reduce Voc

Band gap Fluctuations

Electrostatic Potential Fluctuations

e-

EC
EV

h+

Causes : Competition between kesterite and

stannite phase, secondary phases, nonuniform S/(S+Se), non-uniform strain

OPT

e-

EC

h+

EV

Causes : Charged defects

CuZn+, VCu+, ZnCu-, SnZn2-

Voc Deficit :
(Rau et al., APL 2004)
in hom
oc

=V

hom
oc

Band tailing reduces the effective Eg

and therefore reduces achievable Voc

2k BTq
g2

T. Gokmen et. al., Appl. Phys. Lett. 103, 103506 (2013)

Defects in CZTSSe:

Chen et. al., Phys. Rev. B 81, 245204 (2010)

Chen et. al., Appl. Phys. Lett. 101, 223901 (2012).

Evidence for band tailing

15% CIGSSe
1.0

11% CZTSSe
1.0

Eg PL

Eg

0.4
0.2
0.0

600

800

0.6
0.4
dEQE/d

0.2

dEQE/d

400

arb. unit

0.6

EQE (%)

0.8

arb. unit

EQE (%)

0.8

PL

1000

1200 1400

(nm)

0.0

400

600

800

1000 1200 1400

(nm)

DOS ( ) ( ) ln(1 EQE ( )) EQE ( )

Tailing in EQE below band gap suggest tailing in density of states (DOS)
CZTSSe has roughly twice more tailing compared to CIGSSe
PL spectrum has a wider peak at much lower energy than Eg for CZTSSe
T. Gokmen et. al., Appl. Phys. Lett. 103, 103506 (2013)

Interesting TR-PL data for CZTSSe

11% CZTSSe

15% CIGSSe

TRPL (normalized)
(normalized)

TRPL (normalized)
(normalized)

0.1

4K

0.01
1E-3
1E-4

300 K
0

10

20

30

40

50

2000 4000 6000 8000 10000

0.1

4K

0.01
300 K

1E-3
1E-4

t (ns)

10

20

30

40

50

t (ns)

Room temperature : Comparable lifetimes (~5 ns)

Low temperature : Lifetime increases 3 orders of magnitude for CZTSSe ( ~10s)
T. Gokmen et. al., Appl. Phys. Lett. 103, 103506 (2013)

Evidence for Electrostatic Potential Fluctuations

TRPL (normalized)

2000 4000 6000 8000 10000

CZTSSe

0.1

Electrostatic Potential
Fluctuations

OPT

e-

4K

EC

0.01
300 K

1E-3
1E-4

10

20

h+

30

40

50

EV

e- and h+ localized at low T

t (ns)
Low temperature lifetime increases 3 orders of magnitude for CZTSSe
Can be understood in terms of electrostatic potential fluctuations
We propose that these electrostatic potential fluctuations (amplitude ~
60 meV) and associated band tailing are responsible for the bulk of the
Voc deficit issue.
T. Gokmen et. al., Appl. Phys. Lett. 103, 103506 (2013)

Impact of double In2S3/CdS emitter on Voc:

quick anneal

Indium diffusion into CZTSSe increases carrier

density and improves Voc for given Eg
New record low Voc deficit achieved (593 mV)
New Voc deficit record

J. Kim, H. Hiroi, et. al., DOI: 10.1002/adma.201402373 (2014)

High-performance kesterite films made by evaporation

substrate

Thermal co-evaporation of CZTS in a high

vacuum chamber with base pressure 10-9 Torr
Cu, Zn, and Sn: Knudsen-type cells
S, Se: valved thermal crackers
Target composition: Cu/Sn ~1.8, Zn/Sn ~1.2
(Cu poor and Zn rich conditions)

Cu

Zn

Sn

Se

Substrate heated to ~ 150oC and rotate at 10-20

rpm during growth
For a complete solar device: hot plate annealing
at 540C for 5 min

K. Wang et. al., Appl. Phys. Lett. 97, 143508 (2010).

High-performance kesterite films made by evaporation

Very uniform films & very low [S]

Voc deficit = 578 mV
Y. S. Lee et. al., Adv. Energy Mater. 1401372 (2014).

Conclusions
Continued promising progress
on efficiency of both small cells
and submodules for CZTSSe

Progress has come mostly

from Jsc and FF, but some
recent progress on Voc as well
(new Voc deficit record of 578 mV)

Voc deficit remains the

dominant issue for CZTSSe

The data supports the idea that

this Voc deficit is predominantly
arising from band tailing associated
with electrostatic potential
fluctuations Need to find a way to
resolve this.

Many Thanks / Co-Workers

IBM Watson

IBM:
Santanu Bag
Aaron R. Barkhouse
S. Jay Chey
Richard Ferlita
Thomas Goislard de Monsabert
Tayfun Gokmen
Supratik Guha
Oki Gunawan
Richard Haight

Marinus Hopstaken
Sunit Mahajan
Xiaofeng Qiu
Sean Seefeld
Jiang Tang
Sathish Thiruvengadam
Teodor Todorov
Wei Wang
Mark Winkler
Yu Zhu

TOK Corp.:
Akimasa Nakamura
Masaru Kuwahara
Kouichi Misumi
Hidenori Miyamoto
Yubun Kikuchi

Solar Frontier:
Hiroki Sugimoto
Homare Hiroi

IBM - Tokyo Ohka Kogyo Co. - Solar

Frontier Joint Development Project

Thank you for your attention!

Contact information for speaker:

Dept. of Mech. Eng. and Materials Science
Edmund T. Pratt Jr. School of Engineering
Duke University
Box 90300 Hudson Hall
Durham, NC 27708-0300
david.mitzi@duke.edu