Development of Cu2ZnSn(SXSe1-X)4 thin film solar

cells with 12.06 % cell efficiency using metal

precursors prepared by sputtering method

Jin Hyeok Kim

Department of Materials Science and Engineering,
Chonnam National University, South Korea

Lab.
 Outline

Current Issues on Thin Film Photovoltaics

Part 1 Part 2 Part 3

Photovoltaic Our Research Activity Technical Issues

Overview in CZTSSe TFSCs

-2- Lab.
 Outline

Part 1 Part 2.
Part 2 Part 3
Part 3.

Photovoltaic Our Results on Utilization of

• Results in our Lab •Technical issues
Overview CZTSSe TFSCs Widebandgap TCO

-3- Lab.
 Basic Principles of a Solar Cell
Solar Cell: device using a photovoltaic effect of p-n junction

Light E  Electric E
absorption
ⓔ
AR coationg
generation
front elecrode

n-type layer separation

ⓔ L
p-n junction ⓗⓔ ⓔ O
A Collection
p-type layer ⓗ ⓗⓔ d
Voltage
back electrode

ⓔ electron , ⓗ hole
Dissipation
ⓗ

-4- 4 Lab.
 Classification of Solar Cells
Based on Technology Evolution

Thin Wafer
Crystalline Si Wafer

Thin Film Solar Cell

DSSC

Si thin film
Perovskite
CIGS, CdTe thin film Organic http://www.mpip-
mainz.mpg.de/3492720/Perovs
kite_Solar_Cells

-5- Lab.
 Why Thin Film Solar Cells?

http://cigs-pv.net www.coins-global.com
www.solartodaymag.com

http://trendinsight.biz

 Design-driven projects  Light  Possible to design

 BIPV  Flexible substrates customized modules

-6- Lab.
Annual Photovoltaic Installation
Source: Global Market Outlook for Solar Power / 2017-2021
Supported by: Intersolar Europe, Global Solar Council (GSC)

PV installation in 2017
60 China, 52.83
Intallation Capacity (GW)

50

40

30

20 US, 12 India, 9.2 Japan, 6.1

10 전망치(단위: GW)
0
CHINA US INDIA JAPAN

<자료 : HIS Markit, 2017>

-7- Lab.
 Best Research-Cell Efficiencies

July, 2018

-8- Lab.
 Best Research-Cell Efficiencies

July, 2018

-9- Lab.
 PV Production by Technology
Percentage of Global Annual Production

Fraunhofer Institute for Solar Energy Systems 2017, ISE with support of PSE AG

-10- Lab.
Market Share of Thin-Film Technologies
Percentage of Total Global PV Production

Fraunhofer Institute for Solar Energy Systems 2017, ISE with support of PSE AG

-11- Lab.
 Why Cu2ZnSn(S,Se)4 (CZTSSe)?
Issues in Inorganic Compound Thin Film Solar Cells
Expensive & Toxic
Low-cost and eco-friendly process with high efficiency
CdTe (h = 22.1%)
Cu(In,Ga)(S,Se)2 (h =22.6%) Cu2ZnSn(S,Se)4 (h =12.6%)

High absorption coefficient (~104 cm -1)

Suitable optical band-gap E of (1.0~1.5 eV)
Environmental friendly (non-toxic)
Chemical abundance
-12- Lab.
 Why Cu2ZnSn(S,Se)4 (CZTSSe)?
Minimum cents/W for 23 inorganic PV materials
* Theoretical maximum efficiency
Raw Material Cost (cents/W)

CdTe CIGS CZTS Almost 1/5 of CIGS

9.7E-02 2.3E-02 4.9E-03 material cost

Source : Wadia, Alivisatos, Kammen, Envron. Sci. Technol. 43, 2072 (2009)
-13- Lab.
Cost for CIGS/CZTS PV System

$1.82 per WDC

(c-Si : $1.80 per
WDC)

$0.67
per WDC

(c-Si : $0.65 per WDC)

(Source : On the Path to SunShot – The Role of Advancements in Solar Photovoltaic Efficiency, Reliability, and
Costs )
Materials Cost of CZTS Materials Cost of CIGS
Environ. Sci. Technol.
43, 2072 (2009)

If CIGS is replaced with CZTS

the module cost will be decreased by ~10%
the total PV system cost will be decreased by ~4%
( Source: Materials Availability Expands the Opportunity for Large-Scale Photovoltaics Deployment)

-14- Lab.
 Recent Publications on CZTSSe

480 437
430 Results from Web of Science 409 415411
Keywords: CZTS, CZTSe, Cu2ZnSnS4,..
2018. 2
380
Number of papers

330
Increases rapidly
280 244
230
180 156
130 92
80
37 43 55
30 3 0 3 0 5 4 7 10
-20
2002

2013
2001

2003
2004
2005
2006
2007
2008
2009
2010
2011
2012

2014
2015
2016
2017
2018
Year
-15- Lab.
 Progress in Cell Efficiency of CZTSSe TFSCs
Results from Web of Science
Keywords: CZTS, CZTSe, Cu2ZnSnS4,..
2018. 2.
14
Conversion Efficiency (%)

Adv. Energy Mater

Evaporation
2014; 4: 1301465
PLD
12 Sputtering
Nanocrystal based • W. Wang et al.
Sol-Gel IBM (USA)
10 Electrodeposition • spin-coated precursor
+ annealing (540 °C)
8 • CZT(S,Se) absorber
Prof. Katagiri • Hydrazine (pure solution)
related group • VOC= 513.4 mV
6 • JSC= 35.2 mA/cm2
• FF = 69.8 %
• Eff.=12.6 %
4

0
2001 2004 2007 2010 2013 2016 2019
Year
-16- Lab.
Recent Publications based on Methods
140 2009
Results from Web of Science
(487) 2010
Keywords: CZTS, CZTSe, Cu2ZnSnS4,..
120 2018. 2. 2011
(476) 2012
100 2013
2014 (249)
80 2015
2016
60 (211) 2017
(169) 2018
40
(128)
20
(42)

0
Sputtering Electrodeposition Nanoparticle based Sol-gel
Evaporation Spray method PLD

-17- Lab.
 Major Results from World-Leading Groups
Institute Materials Process Annealing condition ɳ (%) Eg (eV)

Sulfurization followed by selenization

CZTSSe Sputtering 11.53 1.16
Ar atmosphere, 540 ℃, 30 min
Jilin University
Control of selenization time and temperature
CZTSSe Spin-coating 7.48 1.05
Bin Yao N2 atmosphere, 500-600 ℃, 5-30 min
Different Se vapor composition
CZTSe Sputtering 10.41 1.03
Se & Ar atmosphere, 560 ℃, 15 min
Nankai University Depletion region control
CZTSSe Sputtering 10.23 1.13
Y. Zhang Se & Ar atmosphere, 570 ℃, 15 min

CZTSe Electrodeposition N2 atmosphere, 500 ℃, 10 min 8.2

IBM CZTSe Evaporation Se & N2 atmosphere, 590 ℃ 11.6 1.00

David B. Mitzi
Adv. Energy Mater. Hydrazine-based pure solution
CZTSSe Solution based 12.6 1.13
2014 , 4 , 1301465 500 ℃
Two step annealing process
IREC CZTSe Sputtering Se & Sn containing atmosphere 10.1 1.04
Edgardo Saucedo 400 ℃, 30min. / 550 ℃, 15 min
EES, DOI: Two step annealing process
10.1039/c7ee02318a CZGTSe Sputtering Se & Sn containing atmosphere 11.8
400 ℃, 30min. / 550 ℃, 15 min
UNSW Cd doping
CZCTS Sputtering 11.5 13.8
Xiaojing Hao S & SnS atmosphere 560 ℃
ACS Energy Lett. Zn1-xCdxS buffer
CZTS Sputtering 9.2 1.50
2017, 2, 930−936 S atmosphere 560 ℃

-18- Lab.
 Major Results from World-Leading Groups

“Top 10” confirmed cell and module results

Progress in Phovoltaics DOI: 10.1002/pip.2978

-19- Lab.
 Research Activities in Korea
Institute Materials Process Annealing condition ɳ (%) Eg (eV)
DGIST
SeS2/Se Graphite box 13.7
J. Mater. Chem. A CZTSSe Sputtering 1.097
300°C 1000sec. / 510°C 1100sec. 12.3
2016, 4, 10151

KAIST CZTS Sputtering S vapor 580°C 30min. 4.59 1.5

KIER CZTSe Co-evaporation - 6.14 1.2

KIST
CZTSSe Electrodeposition Se powder H2S gas 550°C 15min. 9.9 1.14
(SNU*)

Dongguk University CZTSSe Sputtering S vapor 580°C 5min 6.98 1.5

SKKU CZTS Co-sputtering H2S gas 550°C 1 hour 6.75 -

Yeungnam
CZTSe Sputtering Se vapor 500°C 10min. 5.8 1.06
University
Yonsei Hybrid ink-derived
CZTS H2S atmosphere, 550°C, 30min 8.17 1.46
University spin-coating

Chonnam National Controlling Chamber Pressure

CZTSSe Sputtering 11.8 1.0
University 500 Torr, S & Se vapor, 540°C, 7min 30sec
Green Chem., Soft Annealing Process
2016, 18, 700-711 CZTSSe Sputtering 9.24 0.99
300°C 1hour, 580°C 10min
*Present affiliation

-20- Lab.
 Why Cu2ZnSn(S,Se)4 (CZTSSe)?
Still too low cell efficiency compare to CIGS!!

Cu(In,Ga)(S,Se)2 Cu2ZnSn(S,Se)4
(ɳ = 22.6%) (ɳ = 12.6%)

Think about History on Technology Development!

-21- Lab.
 Evolution of Cell Efficiencies in CIGS & CZTS
Key technical issues to improve efficiencies ZSW
Double graded band,
24 Post Deposition Treatment(KF) 22.6% World Best
CIGS Bandgap engineering 22.6% (2016)
CZTS
20
High transmittance TCO
AR coating
ZWS (2015) CZTS AIM
21.7 % Efficiency: 18%
NREL(2008)
Thin CdS thickness 19.9% (2018)
Efficiency (%)

NREL (1999)
16 18.8%
Sputter based
Ga composition control
NREL (1993) Hydrazine based Following CIGS
Slurry method DGIST (2016)  Bandgap engineering
16.9% 13.7%
Band gap control,  PDT treatment (Na, K)
12 IBM (2013)
 High transmittance TCO
Boeing (1988) Morphology improvement 12.6%
12.5% IBM (2012)  Band grading
Sulfo-selenization 11.1%
IBM (2011)  Wide band buffer
condition control
8 Boeing (1981)
IBM (2010) 10%
9.4%
9.7% Progressing CZTS
U. Of Maine (1976) Absorber optimization NNCT (2008)  Enhancing the Voc
6.8%
4 ~6-7 %  Control recombination
 Control absorption loss
 Elimination of defect
NNCT (1996) (Bulk recombination)
0 0.7%  Harvesting extra photon

1970 1980 1990 2000 2010 2020

Year
-22- Lab.
 Outline

Part 1 Part 2 Part 3

Photovoltaic Our Research Activity

Technical Issues
Overview in CZTSSe TFSCs

-23- Lab.
 Preparation of Absorber Layers
Precursor Preparation Annealing process

Precursor Structure
Pre-Treatment
Stacked layer Co-deposition Nano particle
 Elimination of C contained binder
 Homogeneous mixing of metal layers

Annealing Condition
Mo Mo Mo
 Furnace & RTP Process
Sub. Sub. Sub.  S powder & Se pellet : 500 ~ 580 oC

Preparation Methods Polycrystalline CZTSSe

Physical Chemical

 Electrodeposition
 Sputtering  Bath-based
 Evaporation  Sol-Gel
 PLD Mo
 Ink-Based
 CVD Sub.

-24- Lab.
CZTSSe TFSCs on Various Substrates

On Glass Substrates On Flexible Subtrates

-25- Lab.
 Solar Cell Fabrication Process
Evaporation
RF sputter
CBD
RTA

Sputtering

Grid

Window (n-type) Window (n-type)

Buffer Buffer Buffer

Cu
Sn CZTS absorber Absorber (p-type) Absorber (p-type) Absorber (p-type)
Zn
Back contact Back contact Back contact Back contact Back contact

Substrate (SLG) Substrate (SLG) Substrate (SLG) Substrate (SLG) Substrate (SLG)

Precursor (~1㎛ ) CZTS(~1㎛) CdS (~60 ㎚) n-AZO/i-ZnO Al ( ~1㎛)

( 500㎚/50㎚)
-26- Lab.
 Preparation of Each Single Layers
Single layer deposition using metal targets
Cu 75W Zn 250W 25 mTorr Sn 30W 5mTorr

Difficult to control the uniformity of Zn and Sn unit layers by adjusting process parameters (power, pressure)

-27- Lab.
Preparation of Stacked Precursor Thin Films
Reasonably possible to control the uniformity by adjusting process parameters
(power, pressure, temperature)
Cu (DC) 50 W 5mTorr Sn (DC) 40 W 5 mTorr

CZTS

Mo

SLG

Zn (RF) 40Zn
W 5(RF sputtering)
mTorr Metal stacked precursor

Cu
Sn
Zn

Mo

SLG

-28- Lab.
Preparation of Crystalline Absorber Layers
Sputtering Sulfo-selenization using RTP

Halogen lamps
RTA Chamber Precursors

Ar

S or Se powder Graphite box

Cu

Sn

Zn
Mo

SLG
Mo
Substrate

-29- Lab.
Preparation of Crystalline Absorber Layers

Sulfo-Selenization Process

Metal stacked precursor 580 °C, 20 min. S powder 0.04g

Cu
CZTS
Sn
Zn

Mo Mo

SLG SLG

Layered Metal Precursor Formation of a CZTS Polycrystal

-30- Lab.
 Process Fine Tuning for CdS Buffer Layers
100
Quantum efficiency (%)
80
CNU solar cells show vey low EQE at
60
short wavelength
Jsc
40  Buffer (CdS) optimization
• CIGS(ZSW) 21.7%
20 • CZTSSe(IBM) 12.6%  TCO optimization
• CZTSSe(CNU) 10.4%

0
200 400 600 800 1000 1200
Wavelength (nm)

CdS layer thickness : Deposition time, Temperature, pH, Amount of source

-31- Lab.
 Cross-Sectional BF-TEM Images
(a) 14.5 min. (b) 16.5 min.
TCO
TCO

CdS 26nm

CdS 35nm
CZTSSe
CZTSSe

(c) 18.5 min. (d) 20.5 min.

TCO
TCO
CdS 39nm

CZTSSe CdS 48nm

CZTSSe

-32- Lab.
 Photo Images of Samples
after
Precursor after CdS Final Cells
Sulfo-Selenization

CZTSe

2.5 cm Cell size: 0.45 cm2

CZTSSe
Cell size: 0.31 cm2
Reasonably Uniform Surface Morphology
-33- Lab.
Fabrication of a CZTS TFSC
Cross-sectional TEM image

-34- Lab.
 Cell efficiency of a CZTS TFSC
Current density (mA/cm ) 10
0.012 CZTS with poor performance
2

CIGS with high performance

Voc : 366 mV
8 2
Jsc : 6.22 mA/cm

Current (A)
FF : 34.3% 0.008
h : 0.783%
6 2
Rs : 141 cm
2
Rsh : 400 cm 0.004

4
h = 0.78 % 0.000
2
Shunt current
-0.004
0
0.0 0.1 0.2 0.3 0.4 -1.0 -0.5 0.0 0.5 1.0
Voltage (V) Voltage (V)

Current (A, log scale)

CZTS with poor performance
-2 CIGS with high performance

• Low shunt resistance -3 Low diffusion current

• Low diffusion current
-4
• High recombination rate
• High series resistance -5

-6
-1.0 -0.5 0.0 0.5 1.0
Voltage (V)
-35- Lab.
Processing Parameters to Be Controlled
Precursor Preparation
 Buffer thickness
 Cd-free buffer
 i-ZnO thickness
 Target material Cu  AZO thickness
 Thickness Sn  Electrical properties of TCO layers
 Stacking order Zn  Band gaps of n-type layers
 Barrier layer Mo (Back contact)  Deposition Temp. of n-type layers
Glass
Al
 Temperature Sulfo-Selenization
 Ramp Rate Cell
Fabrication AZO
 Duration Time
 Soft annealing i-ZnO
 Post annealing ZdS, Zn(O,S)
treatment
 Partial Pressure Cu2ZnSn(S,Se)4 Cu2ZnSn(S,Se)4
(S, Se)
 MoSSe2 Mo (Back contact) Mo (Back contact)
interfacial layer Glass Glass
 Alkali control

-36- Lab.
Improving Cell Efficiency: Optimization of Annealing Process

Microstructure and Composition Control

Se/(S+Se): 1 Se/(S+Se): 0.5 Se/(S+Se): 0

Se/(S+Se)
Ratio

510 ºC 530 ºC 540 ºC

Annealing
Temp.

7 min. 10 min. 15 min.

Annealing
Time

-37- Lab.
 Optimization of Composition of Absorber Layers

Controlling absorber layer composition ratio

Precursor composition ratio Examples on composition ratio changes
10 -2
6.0x10

Cu/(Zn+Sn) Cu secondary phase

8
Efficiency (%)

-2
4.0x10
=0.57

Current (A)
6 -2
2.0x10
Cu poor
Cu rich
4
0.0

2
-1.0 -0.5 0.0 0.5 1.0
Voltage (V)
0

0.4 0.5 0.6 0.7 0.8 0.9

Cu/(Zn+Sn) ratio
10
CZTSSe
Zn/Sn
8
Efficiency (%)

=1.59 ZnS
6

4
Zn secondary phase
2 Zn rich

0 ZnS, SnO2 secondary phase

• Easy formation of secondary phases
1.0 1.2 1.4 1.6 1.8 2.0
Zn/Sn ratio • Small composition window for CZTSSe formation

-38- Lab.
 Fine Tuning on CdS Buffer Layers

Control of CdS deposition temperature Control of CdS deposition time

-2
5.0x10 -1
CdS60
-2 -2
4.0x10 CdS80

Log(Current(A))
-3
-2
3.0x10
Current

-4
-2
2.0x10 -5

-2 -6
1.0x10 CdS60
-7 CdS80
0.0
-8
-1.0 -0.5 0.0 0.5 1.0 -1.0 -0.5 0.0 0.5 1.0
Voltage Voltage(V)
0.1 3.0
100

Quantum efficiency (%)

1
14.5 min.
2 16.5 min.
2.5
80
J0(mA/cm )

18.5 min.
Gsh (S/cm )

0.01
2

Rs ( cm)
0.1
20.5 min.
2.0
A

1
60
1E-3 0.01
1.5
40
1E-3
1E-4 1.0 0
CdS60 CdS80 CdS60 CdS80 20
Samples Samples

High quality diode obtained in a cell with a CdS 0

400 600 800 1000 1200
buffer prepared at low temperature Wavelength (nm)

-39- Lab.
Improving Cell Efficiency: Window-Control
Reduction of series resistance by controlling i-ZnO layer
12

Current density (mA/Cm )

2
Voc : 451 mV
10 Jsc : 6.137 mA/cm
2

FF : 29.2 %
AZO 8 n : 0.81 %
2
Rs : 268 cm
2
6 Rsh : 1000 cm
i-ZnO (100 nm)
CdS (40 nm) 4

2
CZTS
0
50 nm 0.0 0.1 0.2 0.3 0.4 0.5
Voltage (V)
20

Current density (mA/Cm )

2
Voc : 429 mV
2
Jsc : 14.71 mA/cm
15 FF : 39.78 %
AZO n : 2.514 %
2
Rs : 62 cm
i-ZnO (60 nm) Rsh : 500 cm
2
10
CdS (50 nm)

5
CZTS
50 nm 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Voltage (V)
-40- Lab.
Improving Cell Efficiency: Interface Control

Reduction of series resistance by controlling MoS2 layer

7

Current density (mA/Cm )

2
Voc : 360 mV
6 Jsc : 3.77 mA/cm
2

FF : 39.5 %
5 h : 0.5 %
2
Rs : 182 cm
4 2
Rsh : 3787 cm
3
2
1
100 nm
0
0.0 0.1 0.2 0.3 0.4
Voltage (V)
20

Current density (mA/Cm )

2
Voc : 429 mV
2
Jsc : 14.71 mA/cm
15 FF : 39.78 %
n : 2.514 %
2
Rs : 62 cm
2
10 Rsh : 500 cm

CZTS
5
MoS2 100 nm
Mo 0
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Voltage (V)
-41- Lab.
Improving Cell Efficiency: Sulfo-Selenization
Possible to control bandgaps of CZTSSe absorbers
Property change by S/Se ratio Result of optimized device
2.0 40

Current density (mA/cm )

CZTSe
CZTSe
CZTSe

Cu/(Zn+Sn) Cu/Sn Zn/Sn

2
S/(S+Se)
(S+Se)/M S/(S+Se) 35
CZTSSe Voc : 481 mV
Intensity (arb.unit)

Composition ratio
338
287

2
373

0 Jsc : 26.02 mA/cm

0.39 1.5 30 7.71 % FF : 61.58 %
0.47 25 Eff : 7.71 %
0.53
1.0 20
0.68
0.72 15 CdS/TCO
0.76
0.5 10
CZTSSe
CZTS

5 Mo
CZTS

CZTS

1
242
174
196

0.0 0
200 300 400 500 1 0.76 0.72 0.68 0.53 0.47 0.39 0 0.0 0.1 0.2 0.3 0.4 0.5 0.6
-1
S/(S+Se) Voltage (V)
Raman Shift (cm )
40 100
Current density(mA/cm )

100
Quantum efficiency (%)

S/(S+Se)
2

S/(S+Se) Band gap

1 1.45
35 1
0.76 1.23
0.76 80 80
0.72 1.22
30 0.72 0.68 1.18
0.68 0.53 1.15

QE (%)
25 0.53 60 0.47 1.14 60
0.47 0.39 1.10
20 0.39 0 0.92
0 40 40
15
10
20 20
5
Eg : 1.15 eV
0 0 0
0.0 0.2 0.4 0.6 400 600 800 1000 1200 1400 400 600 800 1000 1200
Voltage(V) Wavelength (nm) Wavelength (nm)

-42- Lab.
 Improving Cell Efficiency: Soft Annealing Process

Bulk and Interfacial Defect Control

Ar+S+Se
520℃ Soft annealed
With Soft annealing
Ar
300℃

10 min. 10 min.

Ar+S+Se
Metal alloy
520℃
Mo
Without
Soft annealing

10 min.

100 35

Current density (mA/cm )

2
3
Quantum efficiency (%)

10
W/O Soft annealing 30
80
τ = 302 ps
25
PL intensity

2
With Soft annealing
60 10 Jsc improvement
τ = 413 ps 20

Diffusion length 15
40
control
10
1 10
20
5

0 0
400 600 800 1000 1200 0 3 6 9 12 15 18 0 100 200 300 400 500
Wavelength (nm) Time(ns) Voltage (mV)
-43- Lab.
 Improving Cell Efficiency: High Pressure Process

Uniformity and Composition Control

Schematic diagram of vapor Conversion efficiency & STEM
transport in a graphite box
9 1300

Chamber pressure (Torr)

1200

Efficiency (%)
8
1100

7
1000

6 900

800
5
350 400 450 500 550 600 650 700 750 800 450 500 550 600 650 700 750
Initial pressure (torr) Initial chaber pressure (Torr)

400 Torr 700 Torr

• Efflux of source vapor due to low

external pressure for annealing
process using graphite box

-44- Lab.
 Anti-Reflection Coating Layer
Thickness of MgF2 Applying MgF2 Layer

MgF2

i-ZnO/AZO
CdS • Formation of MgF2 using
CZTSSe E-beam evaporation
(MgF2 100 nm)
Mo Back contact

Substrate (SLG)

12 0.50

Open circuit voltage (V)

MgF2 MgF2
0.49

Efficiency (%) 0.48

10
0.47

0.46
I𝐧𝐜𝐢𝐝𝐞𝐧𝐭 𝐥𝐢𝐠𝐡𝐭 𝐰𝐚𝐯𝐞 𝐥𝐞𝐧𝐠𝐭𝐡 = 4n(MgF2:1.37)×d
8 0.45
A(W/O) A(MgF2) B(W/O) B(MgF2) A(W/O) A(MgF2) B(W/O) B(MgF2)
at 550 nm, d = 100 nm Samples Samples
at 500 nm, d = 91 nm
• about 1% increasement of cell efficiency

-45- Lab.
 Evolution of Cell Efficiency in our Lab.
14 Certified by KITECH
Sputtering (Sulfide targets)
Sputtering (Metal targets) CZTSSe (12.06%)
12 Electrodeposition
Certified by KIER
Efficiency (%)

Flexible Substrate
10 CZTSSe (11.8%)

Certified by KIER
8 CZTSSe (10.4%)

6 Certified by KIER
CZTSSe (8.00%)
GET-Future
4 Start Certified by KITECH
CZTSSe (5.5%)
2 CZTS
(0.6%) KIER
CZTS Korea Institute of
0 (1.2%) Energy Research

KITECH
Q4Q1Q2Q3Q4Q1Q2Q3Q4Q1Q2Q3Q4Q1Q2Q3Q4Q1Q2Q3Q4Q1Q2Q3Q4Q1 Korea Institute of
2012 2013 2014 2015 2016 2017 2018 Industrial Technology

-46- Lab.
 Key issues in improving Cell Efficiency
Our recent CZTS-based results
CZTSSe
12 CdS
Uniformity
(12.8=06%)
Temperature
Certified Value
Efficiency (%)

Annealing By KITECH
10 pressure Ni/Al grid
Heating
temperature AR coating
8 TCO
optimization
S+Se
6 Metal
target
Se Soft annealing
pellet
H2S gas
4 Se
MoSe2
control
amount Se pellet
Sulfide Composition
target Soft annealing
2 ratio
Heating
Annealing pressure
temperature

0
M6 M9 M12 M3 M6 M9 M12 M3 M6 M9 M12 M3 M6
2014 2015 2016 2017
-47- Lab.
 Fabrication of a CZTSSe Submodule
Cross-sectional schematic of a submodule
Ag

AZO P3
i-ZnO
CdS
CZTS P2
Ag
MO P1
SLG

P1 : Mo, P2 : CZTS absorber, CdS and i-ZnO layers, P3 : AZO

P1 scribing P2 scribing P3 scribing

P3 P2 P1

Laser Hand Hand

-48- Lab.
Fabrication of a CZTSSe Submodule
Sample size: 5 X 5 cm2

-49- Lab.
 Fabrication of a CZTSSe Submodule
Voc & Isc could be controlled by changing module structure
135 45
2
Area : 33.30 [cm ] Area : 16.3 [cm2]
120
Cell : 3ea 3 cells 40
Cell : 6ea
6 cells
105 35
Current [mA]

Current [mA]
90 30

75 25

60 20 Voc : 3.37[V]
Voc : 1.21[V]
Isc : 113.09[mA] Isc : 32.97[mA]
45 15
Jsc : 3.43[mA] Jsc : 2.02[mA]
30 FF : 30 [%] FF : 37 [%]
10
Eff : 1.23 [%] Eff : 2.55 [%]
15 Rs : 7 [ohm] 5 Rs : 57[ohm]
Rsh : 15 [ohm] Rsh : 183 [ohm]
0 0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Voltage [V] Voltage [V]
45
Area : 22.65 [cm2]
40 8 cells
Cell : 8ea
35 Voc Isc Jsc FF η
# of cell
(V) (mA) (mA/cm2 ) (%) (%)
Current [mA]

30

25
3 1.21 113.09 3.43 30 1.23
20 Voc : 3.74[V]
Isc : 40.31[mA]
15 Jsc : 1.78[mA] 6 3.37 32.97 2.02 37 2.55
FF : 42 [%]
10
Eff : 2.76 [%]
Rs : 41[ohm]
8 3.74 40.31 1.78 42 2.76
5
Rsh : 253 [ohm]
0 Size of a submodule is ~25 cm2
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0
Voltage [V]
-50- Lab.
Operation of a CZTSSe Submodule

Size of a sub-module is 25 cm2 (5X5 cm2)

-51- Lab.
 Outline

Part 1 Part 2 Part 3

Photovoltaic Our Results on

Technical Issues
Overview CZTSSe TFSCs

-52- Lab.
 Characteristics of Our Best Cell
J-V Curve & QE TEM & EDS Line scanning
Ni/Al Top, MgF2 AR
40
Current density (mA/cm )
2

35
30
25
20 Efficiency : 12.06 %
FF : 59.78 %
15 2
Jsc : 38.67 mA/cm
10 Voc : 521.77 mV
5
0
0 100 200 300 400 500
Voltage (mV) STEM-HAADF Image and EDS mapping
100
Quantum efficiency (%)

80

60 1.0 Secondary
MG756
0.8 phase
2
[hln(1-EQE)]

40 0.6

0.4
ZnSe
20 0.2
1.12 eV SnO
0.0
0.9 1.0 1.1 1.2
Energy (eV)
1.3 1.4 1.5 MoSe2
0
400 600 800 1000 1200
Wavelength (nm)

-53- Lab.
Technical Issues to Improve Cell Efficiency
Comparison of IV Characteristics
Minimizing bulk recombination
J-V Curve Cation disorders
40
Current density (mA/cm )
2

Grain boundaries
30
Minimizing interfacial recombination
Absorber/Buffer
20
Absorber/Mo interface
10 • CZTSSe (IBM)
• CZTSSe (CNU)

0
0 200 400 Minimizing photon loss
Voltage (mV) Wide band-gap TCO
Optimization of grid structure
CZTSSe CZTSSe JNU/ Cd-free Zn(O,S) buffer layer
(전남대) (IBM) IBM (%)
Thin buffer
Voc (mV) 521.7 513.4 101.6
Anti-reflection coating
Jsc (mA/cm2) 38.6 35.2 109.7
Fill Factor 59.7 69.8 85.5 Optimization of Rs & Rsh
ɳ (%) 12.0 12.6 95.2 Improving junction quality
Voc deficit (mV) 598 617 96.9 Carbon layer (Mo/CZTS)
※ Vocdef = Eg/q – Voc
Diffusion barrier (Mo/CZTS)
※ IBM Adv. Energy Mater. 4 (2014) 1301465 Defect control

-54- Lab.
 Various approaches to improve Voc
Origins of Voc: GBs, Interfaces, Defects
Results in Low MCCLT, electrostatic potential fluctuations, and tail states
Can be Minimized by Passivation, Doping, Post Annealing Treatment
 Absorber/Buffer Interface
 Alkaline (Na, K): surface passivation
 Double emitter: increasing carrier density
 Passivation with a dielectric layer

 Absorber Layer
Buffer (CdS)
 Alkaline (Na, K): increasing grain size
 Post air annealing: GB passivation
Cu2ZnSn(S,Se)4
 Doping: minimizing cation disorder (CuZn-, ZnCu+)
Mo (Back contact)
Glass  Absorber/Back-Contact Interface
 Passivation with a dielectric layer
 Optimizing sulfo-selenization process:
(reducing secondary phases)

-55- Lab.
 Summary

12.06% CZTSSe thin film solar cells without

additional treatment to minimize Voc deficit could
be fabricated successfully
NEXT STEP
• Doping: minimizing bulk cation disorder
• Passivation: top and bottom interface of the absorber
• Band gap grading: minimizing recombination loss
• Harvesting: controlling the photon loss, carrier collection

Fabrication of CZTSSe thin film solar cells with

WORLD BEST efficiency !!

-56- Lab.
Thank you

-57- Lab.