Functional Materials by Design for Solar

Energy Conversion
Bill Tumas
Associate Lab Director
Materials and Chemical
Science and Technology


National Renewable
Energy Laboratory
February 19, 2014
bill.tumas@nrel.gov

!""#$%&#" (#) *+) ,"-)./ 0+1+)-
Director W. Tumas (NREL)
Theory A. Zunger, Chief Scientist-Theory (CU)
S. Lany, P. Graf (NREL); V. Stevanovic (CSM)
L. Yu, X. Zhang (CU), A.J. Freeman, G.Trimarchi (Northwestern)
Inorganic D.G. Ginley, Chief Scientist-Experiment (NREL)
Synthesis J.D. Perkins, A Zakutayev, P. Ndione (NREL)
& Characterization D.A. Keszler and J.F. Wager (Oregon State University);
K.R. Poeppelmeier and T.O. Mason (Northwestern University);
M.Toney (SLAC)
Program Integrator L. Kazmerski, John Perkins
Acknowledgement: Center for Inverse Design EFRC
2
Global Energy Challenge:
Sustainable Materials, Processes and Systems












Cost ($/W) Performance
Reliability
Sustainable development is development that
meets the needs of the present without
compromising the ability of future generations to
meet their own needs
UN Bruntland Commission
- Greenhouse Gases
- Land Use
- Water Use
- Resources
- Hazards
- Waste

Integration at Scale
From Horse Power to Horsepower:
The Great Horse-Manure Crisis of the 1890s
Shift Happens
- Eric Morris, UC Davis
Solar Energy Generation
AND
Storage/Use of Solar Energy
Materials ! Processes/Components ! Devices ! Systems


Thermal
(heat)
Electrical
(storage)
Fuels
(chemical)
Solar (light)
Key Solar R&D Needs Addressed at NREL
Applied R&D
Costs and efficiency, performance
Understanding and control defects and interfaces
Processing
Reliability
- Testing
- Prediction, Mechanisms of degradation
Manufacturing
Next Generation
- New absorbers/contacts
- Advanced processing
- New architectures, substrates, balance of system
Fundamental Research
- New materials by design
- Efficiency beyond the Shockley-Queisser limit
- Advanced manufacturing
Cost ($/W) Performance
Reliability
Gap between Cell and Module Efficiencies
Target Functionalities Solar Energy Conversion
Solar Absorber Materials
- Strong solar absorption
Eg, absorptivity, SLME
- Carrier Lifetimes
- Carrier Diffusion
recombination centers/defect
- Doping
- Low cost, non-toxic

Transparent Conductors (n, p)
- Transparency (band-structure)
optical band gap > 3 eV
- Conductivity (defects)
- Minimize hole-killer defects
dopability, avoid formation of O-vacancies
- Maximize hole-producing defects
intrinsic: vacancies, anti-sites, ...
extrinsic: impurity doping
- Enhance hole mobility
Semiconductor high-tech is based on just a handful of
basic species: Si, Ge, GaAs, !
These provide but a limited and sparse scale of
band gaps:



Very ,Very few !.

0 1 2 3
InSb Ge Si InP GaAs AlAs
eV

Some Observations
DOE Basic Research Needs
Workshop report noted Missing Materials:

! the range of materials currently
available for use in photovoltaics is highly
limited compared to the enormous number
of semiconductor materials that can in
principle be synthesized .

EERE invested in incremental refinement of the
usual-suspect materials ( Si, CdTe, CIS !) Most
involved accidental discoveries.


Need broad base of materials with optimized tailored properties
not just few materials
11
Traditional approach: Given a material, what are the properties
Inverse design: Given a desired property, what is the material
Inverse Design: Declare first the functionality you need, then use
theory-guided experiment to iteratively find the material that has this
target functionality
Center for Inverse Design
Center for Inverse Design

* tight coupling of theory and experiment
* iterative attempts at a problem, teaching each other;
* synergism between theory, synthesis and characterization
Center for Inverse Design
Properties of interest
Thermodynamic stability- !H
f

Band structure and optical properties
Defects and doping
Carrier transport mechanism
(band vs. small-polaron)
!
Electronic structure methods
Density functional theory
self-consistent charge density, total-energy
Many body interactions in GW approximation
Quasi-particle energies, optical properties
Credit to VASP group
Theory Tools
Tools for Inverse Design
n|gh-throughput comb|nator|a| exper|menta| approach
PeaLer

23 sLage

3

2

ln
C
u
1

1hln lllm ueposluon hyslcal properLy mapplng
1
Ax/8x

1
Ax/8x

Ar, P
2
S gas
S aLom source
uaLa analysls and vlsuallzauon
8l spuuerlng, Lu
8lnary/meLal LargeLs
Ar/P
2
S, Ar, n, C gasses
S, n aLom sources
2x2" sample llbrarles
Composluon (x8l,456)
SLrucLure (x8u, 4%7%")
1ransporL(4pp, Seebeck)
Cpucal (uv-lr,89:
Surface (k, 286;<86)
Mlcroscopy (SLM= >0?:
lgor 8C soware
framework
CusLom-wrluen package of
funcuons
user-asslsLed analysls
@%1% 7A"A".;%"%B/CAC
1h|n h|m comb| approach can do fast screen|ng before bu|k synthes|s
>D6 D#7EF 6GAF= HI= JKL MNOHH: PF >QQBF 8R/CF HHI= NIHHOH MNOHI:S T##U )-$A-VCW
Two Main Approaches for Inverse Design
Design by Design Principles
- Many material systems with
known structure and
composition (e.g. ICSD)
- Functionality unknown
- Complex target properties,
e.g. PV absorptivity,
efficiency, transparent
conductivity
- Search via design principles
for targeted functionalities
Missing Materials
- Many material systems, but
structure unknown
- Many (~ 50100) possible
configurations, requiring
energy minimization and
stability analysis
- Target properties: first
existence, then other
properties

Inverse Design of Solar Absorbers
Design Principle for high absorption
Validate properties for best of class
Theory, synthesis, and characterization
Theory screening
of many candidate
materials for band
gap and absorption
Materials
Screening
Desired: Very high ab-
sorption for cell design
with very thin absorber
Needed: High joint
density of states
Implementing Inverse Design: Solar Absorbers
17
Inorganic Crystal Structure Database: ICSD
> 166,000 crystal structures; updated semi-annually
http://www.fiz-karlsruhe.com/icsd.html
;212,<(/ ='"&2'"0> ;*2,&'(8,(*",011: ?"-"&26
@03"-)- AB,"2/,:%%;?@A
5$&%03$C K%3%1;$ K$&W$$1
;$33 01(0C$ %1C 7B&(0C$
9/7&71 $1$'):
C$6$1C$1& %K(7'6871
,68;%3 K%1C )%6 &:6$
R%;&7' (M): X 171Q'%C0%8D$
'$;74K01%871

Captures physics of absorption, emission and recombination
optical type, gaps and material-dependent non-radiative recombination loss
Yu, Zunger Phys Rev Lett 108, 068701 (2012)
Absorption Screening
High Throughput screening:
First-principles quasi-particle GW
method (G0W0+HSE06)
Provides good band gap estimation
Input:
ICSD structure
No element or stoichiometry
restrictions
Output:
Band gap type
Absorption spectra
Electronic structure
20
High SLME materials include known absorbers
Yu, Zunger Phys Rev Lett 108, 068701 (2012)
Other experimentally confirmed PV
absorbers (less studied)
Yu, Zunger Phys Rev Lett 108, 068701 (2012)
Previously unrecognized high SLME
materials
Yu, Zunger Phys Rev Lett 108, 068701 (2012)
In Cu-III-VI system:
Cu
3
Tl
1+
Se
2
has stronger absorption than CuTl
3+
Se
2

In Cu
3
Tl
1+
Se
2
: more 1| p |n C8, more 1| s |n V8
Yu, Zunger Phys Rev Lett 108, 068701 (2012)
What contro|s the strength of opnca| absorpnon?
26
" Increase p DOS near CBM and s DOS near VBM
1he d|rect trans|non rate (Ierm|'s Go|den ro|e):
GaAs, CdTe
VB
CB
anion p
cation s
DOS
VI s M p
Cu-M-VI
DOS
VI p + Cu d M s
CuInSe
2
(CIS)
Se p + Cu d
In s + Se s
In p
DOS
weak
Liping Yu
Cu-III-VI ! Cu-V-VI
Cu-III(s
2
p
1
)-VI Cu-V(s
2
p
3
)-VI
Al (3+) (3+, 3+)
Ca (3+) As (3+, 3+)
ln (3+) Sb (3+, 3+)
1l (3+,1+) 8l (3+, 3+)
Low valence compound: Cu-V(3+)-VI
High valence compound: Cu-V(5+)-VI
27
Case of Cu-Sb-S:
Cu-Sb
3+
-S vs. Cu-Sb
5+
-S vs. CuInSe
2
(CIS)
8oLh Cu
3
SbS
3
and CuSbS
2
have
sLronger absorpuon Lhan
Cu
3
SbS
4
and ClS for hu > L
g
+A.
A depends on Lhe energy
dlerence beLween lndlrecL gap
and dlrecL gap
CuSbS
2
: 0.03 (L
g
U
- L
g
A
)
Cu
3
SbS
3
: 0.13 (L
g
U
- L
g
A
)
3+= 9F= -1 %BF = !"#$ &'()*+ ,-.()$ /0 1/ 2345/6
vAS: C
0
W
0
[PSL06
Experiment shows same absorption trend
in Cu-Sb-S case
By R. S Kokenyesi and D. A Keszler, Oregon State University
3+= 9F= -1 %BF = !"#$ &'()*+ ,-.()$ /0 1/ 2345/6
More V p in Cu-V
3+
-VI compounds near CBM
VBM
CBM
CBM+2eV
VBM-2eV
V p DOS
E
n
e
r
g
y

(
e
V
)

Integrated V p DOS near VBM
I
n
t
e
g
r
a
t
e
d

V

p

D
O
S

n
e
a
r

C
B
M


30
More V s in Cu-V
3+
-VI compounds near VBM
VBM
CBM
CBM+2eV
VBM-2eV
V s DOS
E
n
e
r
g
y

(
e
V
)

Integrated V s DOS near VBM
I
n
t
e
g
r
a
t
e
d

V

s

D
O
S

n
e
a
r

C
B
M


31
Step 3: Experimental Realization
Low temperature synthesis
Polycrystalline absorbers with rapid onset of absorption
(">10
5
cm
-1
at E
G
+0.5 eV)
Keszler et al. Oregon State
substrate
Sb
2
S
3
Cu
Sb
2
S
3
substrate
polycrystalline
Cu-V-VI

+S, 300C
Sclenuc approach of Lhe kap|d Deve|opment" pro[ecL
Lxp|oranon
kesearch Deve|opment
uown-selecuon from many posslblllues
Dev|ces
Mater|a|s
SLaLe of Lhe arL research meLhods
lrom maLerlals Lo devlces (3 sLeps)
redlcuve Lheoreucal calculauons
Plgh-LhroughpuL comblnaLorlal experlmenLs

8road scope of v maLerlals
1esL-cases: Cu-Sn-S and Cu-Sb-S absorbers
nexL-generauon: oxlde-based absorbers
8roadly appllcable Lo wlde range of maLerlals

Exploration of Cu-Sn-S family of materials
Cu
4
SnS
4
- Loo many holes (Ch Cu)
Cu
4
Sn
7
S
16
- lerml level (E
F
) plnnlng
Cu
2
SnS
3
- few holes, no L
l
plnnlng
Cu
2
SnS
3
|s a more prom|s|ng V absorbers than other Cu-Sn-S mater|a|s
Cu-Sn-S theorenca| pred|cnon
7 Cu-Sn-S
mater|a|s
Cu-Sn-S experimental realization
Cu
2
SnS
3
mater|a|
Cu-poor
growth
Zakutayev et al. Appl Phys Lett 103, 253902 (2013)
Designing p-Type Ternary Oxides
Implementing Inverse Design
DEVELOP p-type
TCO design
principles
SEARCH A
2
BO
4

w.r.t. design
principles
IMPROVE
Co
2
ZnO
4
based
on design
principles
Modality 2 = Inverse Design By Design Principles
78*9 9:;( <:'<('.)-=:' 2"(>(<. <-;<$6


78*9 9:;( ?:@8;8.+ 2A:;-):' <-;<$6


B)-'CA-)('<+ 2@-'"DC.)E<.E)( <-;<$6

Anu-bondlng valence band
maxlmum
no bound polarons
Absence of hole-klller defecL
resence of hole-produclng
defecLs
Cpucal band gap > 3 ev
Wlde llgand eld spllmng
(some cases)
-1CC kCLk1ILS DLSIGN kINCILLS
Chose Search Space: A
2
BO
4
Spinels 40 in ICSD
Normal 3-2 Spinels:
A
+3
O
h
site (e.g., Al, Fe, Co)
B
+2
T
d
site (e.g., Mg, Zn, Fe)
Yellow:
Tetrahedral (T
d
)
Blue:
Octahedral (O
h
)
Large famlly of compounds
Wlde range of physlcal and chemlcal properues, low oxygen vacancy
Selection of Ternary A
2
BO
4
Compounds
A broad class for materials discovery
Inverse 3-2 Spinels:
A
+3
O
h
, T
d
sites(e.g., Fe, Co)
B
+2
O
h
site (e.g., Ni)
Dop|ng - types
A
3+
on Td is DONOR
B
2+
on Oh is ACCEPTOR
Paudel et al. Adv. Func. Matl 21, 4493 (2011)
Perkins et al. Phys Rev B, 84, 205207 (2011)
Anti-site defects control properties:
DT-2--No Intrinsic Hole Killer !!

Co
2
(Zn,Ni)O
4
best of class!
Role of Anti-Site Defects in Spinels
AblllLy Lo calculaLe
defecLs and dopanLs ls
crlucal Lo elecLronlc
maLerlals deslgn
(supercell approach)
12 of 40 A
2
BO
4
Spinels Type 2 (Naturally P-Type)
VB
CB
Paudel et al, Advanced Functional Materials, 21, 01469 (2011)
Acceptor
Donor
Low Cost + Non-Toxic ! Take Co
2
ZnO
4
as Prototype
Sputtered Co
2
ZnO
4
Can Be Zn-Rich
Non-Equilibrium Theory
- Excess Zn ! O
h
Site
- AXRD Confirms


Sputtered Films (T
S
= 340C)
- Zn-Rich Spinel Phase
- Conductivity Increases

Annealed Films
- Conductivity Decreases
- Reduced Antisite Defects?
Perkins et al, Phys. Rev. B, 84, 205207 (2011)

Predicted Extrinsic Dopability
17 Dopants Evaluated
by Theory

Li, Ni, Mg best

Equilibrium Solubility
Limit ~ 5%
Perkins et al, Phys. Rev. B, 84, 205207 (2011)
As shown in Fig. 1(a), the ZnNiCoO spinel thin lms
appear to have no other crystalline phases over a broad portion
at the high-Co region of the ZnONiOCo
3
O
4
composition
range; however, at low-Co regions rocksalt (NiO) and wurtzite
(ZnO) phases are present. The color scale in Fig. 1(a) indicates
the ratio of the sum of XRD intensities of ZnO (002) and NiO
(111) peaks to the intensity of the spinel (311) peak. The com-
positional range of stability for the spinel phase is broader (i.e.,
the minimum amount of Co is lower) for Co
3
O
4
co-doped with
Zn and Ni (ZnNiCoO) compared with Co
3
O
4
doped with
only Zn (ZnCoO) or only Ni (NiCoO). Within the
spinel-only region, the XRD measurements cannot distinguish
between a single-phase spinel solid solution and a multi-phase
mixture of phase-separated spinels, because of the close match
of the lattice parameter of Co
2
ZnO
4
(0.810 nm)
[8]
and Co
2
NiO
4
(0.811 nm).
[9]
The stability range of the ZnNiCoO spinel
remains mostly unaffected by the 500 C air anneal: only
Zn-rich lms (<20 at.% Ni) show a 510 at.% decrease of the
composition range of stability.
As shown in Fig. 1(b), co-doping of Co
3
O
4
with Zn and Ni
decreases the strength of the sub-gap absorption band at 689
nm (1.8 eV), which is a relevant part of the spectrum for PV
applications. We attribute the sub-gap absorption to optical
transition between the Co atoms in tetrahedral (T
d
) and octa-
hedral (O
h
) coordination, because the absorption disappears
above 33 at.% of Zn in ZnCoO (Co
2
ZnO
4
), at which Zn
atoms ll all available T
d
sites (1/3 of total cation sites), and
above 67 at.% of Ni in NiCoO (CoNi
2
O
4
), at which Ni
atoms ll all available O
h
sites (2/3 of total cation sites). The
absence of absorption below the tie-line that connects
Co
2
ZnO
4
and CoNi
2
O
4
[dash-dotted line in Fig. 1(b)] suggests
that the ZnNiCoO thin lms are a mixture of ZnCoO
Figure 1. (Color online) (a) Crystalline phase purity and (b) optical absorption maps of ZnNiCoO thin lms. The dashed and dash-dotted lines indicate
Co
2
ZnO
4
Co
2
NiO
4
and Co
2
ZnO
4
CoNi
2
O
4
tie-lines, respectively. The dotted line indicates a phase boundary with NiO and ZnO. Symbols outlined by black lines in
(a) show 44 points from one combinatorial library.
Figure 2. (Color online) (a) Conductivity of ZnNiCoO thin lms. The dashed and dash-dotted lines indicate Co
2
ZnO
4
Co
2
NiO
4
and Co
2
ZnO
4
CoNi
2
O
4
tie-lines, respectively. The dotted line indicates a phase boundary with NiO and ZnO impurity phases. (b) JV curves and their parameters for PCDTBT:PCBM
bulk heterojunction organic photovoltaic devices with amorphous hole transport layers with Zn
1.65
Co
1.35
O
4
composition. The dashed line indicates a JV curve
measured in the dark.
2

MRS COMMUNICATIONS www.mrs.org/mrc

As shown in Fig. 1(a), the ZnNiCoO spinel thin lms
appear to have no other crystalline phases over a broad portion
at the high-Co region of the ZnONiOCo
3
O
4
composition
range; however, at low-Co regions rocksalt (NiO) and wurtzite
(ZnO) phases are present. The color scale in Fig. 1(a) indicates
the ratio of the sum of XRD intensities of ZnO (002) and NiO
(111) peaks to the intensity of the spinel (311) peak. The com-
positional range of stability for the spinel phase is broader (i.e.,
the minimum amount of Co is lower) for Co
3
O
4
co-doped with
Zn and Ni (ZnNiCoO) compared with Co
3
O
4
doped with
only Zn (ZnCoO) or only Ni (NiCoO). Within the
spinel-only region, the XRD measurements cannot distinguish
between a single-phase spinel solid solution and a multi-phase
mixture of phase-separated spinels, because of the close match
of the lattice parameter of Co
2
ZnO
4
(0.810 nm)
[8]
and Co
2
NiO
4
(0.811 nm).
[9]
The stability range of the ZnNiCoO spinel
remains mostly unaffected by the 500 C air anneal: only
Zn-rich lms (<20 at.% Ni) show a 510 at.% decrease of the
composition range of stability.
As shown in Fig. 1(b), co-doping of Co
3
O
4
with Zn and Ni
decreases the strength of the sub-gap absorption band at 689
nm (1.8 eV), which is a relevant part of the spectrum for PV
applications. We attribute the sub-gap absorption to optical
transition between the Co atoms in tetrahedral (T
d
) and octa-
hedral (O
h
) coordination, because the absorption disappears
above 33 at.% of Zn in ZnCoO (Co
2
ZnO
4
), at which Zn
atoms ll all available T
d
sites (1/3 of total cation sites), and
above 67 at.% of Ni in NiCoO (CoNi
2
O
4
), at which Ni
atoms ll all available O
h
sites (2/3 of total cation sites). The
absence of absorption below the tie-line that connects
Co
2
ZnO
4
and CoNi
2
O
4
[dash-dotted line in Fig. 1(b)] suggests
that the ZnNiCoO thin lms are a mixture of ZnCoO
Figure 1. (Color online) (a) Crystalline phase purity and (b) optical absorption maps of ZnNiCoO thin lms. The dashed and dash-dotted lines indicate
Co
2
ZnO
4
Co
2
NiO
4
and Co
2
ZnO
4
CoNi
2
O
4
tie-lines, respectively. The dotted line indicates a phase boundary with NiO and ZnO. Symbols outlined by black lines in
(a) show 44 points from one combinatorial library.
Figure 2. (Color online) (a) Conductivity of ZnNiCoO thin lms. The dashed and dash-dotted lines indicate Co
2
ZnO
4
Co
2
NiO
4
and Co
2
ZnO
4
CoNi
2
O
4
tie-lines, respectively. The dotted line indicates a phase boundary with NiO and ZnO impurity phases. (b) JV curves and their parameters for PCDTBT:PCBM
bulk heterojunction organic photovoltaic devices with amorphous hole transport layers with Zn
1.65
Co
1.35
O
4
composition. The dashed line indicates a JV curve
measured in the dark.
2

MRS COMMUNICATIONS www.mrs.org/mrc

Cpucal and LlecLrlcal properues are opumlzed
ln a non-tr|v|a| composluon reglon
Optical and Electrical: Region of Interest
T
S
= 350 C T
S
= 350 C
Three ways to improve conductivity in Co spinels
2+ on C
h
s|te produces ho|es no ho|e k|||ers!
Sx |mprovement
1. Non-equilibrium
growth
20x |mprovement
2. Extrinsic
dopants
10000x |mprovement
3. Induce inverse
spinel phase
Max|m|ze th|s to |ncrease conducnv|ty
New mater|a|s are ||ke|y to have new propernes
ropernes have prev|ous|y been extracted |n ||terature
from an |ncomp|ete set of mater|a|s (e.g. ICSD)
Many have ca|cu|ated propernes for unknown
compounds (e.g. A8k ha|f-neus|er compounds) but
haven't determ|ned the|r stab|||ty (|.e. ex|stence)

Cand|date mater|a|s for a||oy|ng
M|ss|ng Mater|a|s

Cha||enge 1: Structure of an unknown compound
Genera| so|unon:
TB#E%B 6Q%G- T)#+Q
*Q&7AY%&#" MT6T*:
A|ternanve:
39 sLrucLures-Lypes for 800 known A
2
8x
4
CCA+u Lo sorL ouL Lhe ground-sLaLe
sLrucLure
No. Name (examp|e) Space
Group
Cccurrence
1. Splnel (Al
2
MgC
4
) ld3m 233
2. nn (1h
3

4
) l43d 87
3. Cllvlne (Al
2
8eC
4
) nma 48
4. PausmanlLe (Mn
3
C
4
) l4/amd 27
3. henaklLe (Ll
2
WC
4
) 83 14
.
.
.

Sohware deve|opment:
1) Semng up auLomaucally Lhe crysLalllne and magneuc
sLrucLure for each poLenual ground sLaLe
2) AuLomauc deLecuon of errors
3) AuLomauc exLracuon of properues
n|gh - 1hroughput ca|cu|anons
Scope:
406 A
2
8x
4
39 sLrucLure-Lypes for each A
2
8x
4
Several magneuc congurauons
~80 000 GGA+U
calculauons
~10
6
CUh
uslng
ked Mesa nC
Cha||enge 2: Stab|||ty w|th respect to compenng phases
AP
f
(A
m
8
n
x
l
) = L
LoL
(A
m
8
n
x
l
) - (m
0
A
+ n
0
8
+ l
0
x
)
1oLal energy LlemenLal reference
energles
2 A + 8 + 4 x

.
.
.
A
2
8x
4
.
.
.
AP
f
A
2
x
3
+ 8x

A8x
3
+ x A
2
x + x x

Fitted Elemental-phase Reference Energies (FERE) + GGA+U
50
0
-values fit to 252 binary compounds with measured "H
f

Correcnng DI1 for accurate n
f
- ILkL
I|ued L|ementa| keference Lnerg|es - ILkL
Sn
+0.18
Ge
+0.15
Ga
+0.66
Cd
+0.35
Ca
+0.29
Na
+0.17
O
+0.23
S
+0.06
Se
-0.07
Te
-0.11
F
+0.15
Cl
+0.16
N
-0.20
P
-0.68
As
-0.41
Sb
-0.16
Bi
-0.33
Si
+0.43
Al
+0.72
In
+0.41
Zn
+0.43
Hg
+0.17
Cu
+0.05
Ag
-0.12
Ni
+0.08
Co
-0.10
Fe
-0.15
Mn
-0.03
Cr
+0.07
V
-0.45
Ti
+0.05
Sc
+0.49
Be
+0.35

Mg
+0.55
Sr
+0.51
Ba
+0.54
Li
+0.21
K
+0.28
Rb
+0.29
Au
-1.26
Pd
-0.27
Pt
-0.43
Rh
-0.53
Ir
-0.19
La
+0.20
Zr
+0.72
Hf
+0.72
Y
+0.66
Nb
+0.36
Ta
+0.40

0
(FERE) =
0
(GGA+U) + #
0
(FERE)
cations anions
U=3 eV U=5 eV
30
0
values ued uslng measured AP
f
values of 232 blnary pnlcudes, chalcogenldes and halldes
V. Stevanovic, S. Lany, X. Zhang, and A. Zunger, Phys. Rev. B 85, 115104 (2012)
ILkL Va||danon - 1ernar|es
55 ternary compounds with measured "H
f

V. Stevanovic, S. Lany, X. Zhang, and A. Zunger, Phys. Rev. B 85, 115104 (2012)
Lxamp|e: Mn
2
S|C
4

Theory:
Structure: Olivine
"H
f
= -2.53 eV/atom
Experiment:
Structure: Olivine
"H
f
= -2.56 eV/atom
How it Works: Mn
2
SiO
4

Theory:
Structure: Olivine
"H
f
= -2.53 eV/atom
Experiment:
Structure: Olivine
"H
f
= -2.56 eV/atom
Example: Mn
2
SiO
4

Theory:
Structure: Olivine
"H
f
= -2.53 eV/atom
Experiment:
Structure: Olivine
"H
f
= -2.56 eV/atom
Example: Mn
2
SiO
4

-4.18 eV < "$
O
< -3.16 eV

Finch et al.
J. Cryst. Growth,
29, 269 (1975)
T = 1600 K, p
O2
= 10
-10
atm
% "$
O
=

-3.45 eV
Theory:
Structure: Olivine
"H
f
= -2.53 eV/atom
Experiment:
Structure: Olivine
"H
f
= -2.56 eV/atom
Example: Mn
2
SiO
4
, growth conditions


Theory:
Structure: Olivine
"H
f
= -2.53 eV/atom
Experiment:
Structure: Olivine
"H
f
= -2.56 eV/atom
Growth:
T = 1600 K
p
O2
= 10
-10
atm
experiment
Mn : Si = 2 : 1
High-throughput Discovery of New A
2
BX
4
Compounds
(A,B)
X
Rules:(1) only one transition metal at a time
(2) respect possible oxidation
states
Total 656 possible combinations
250 are reported
406 are not reported (missing compounds)
Predicted New A
2
BO
4
Out of 63 missing oxides
46 not stable
17 stable
Newly predicted:
Hg
2
SiO
4
In
2
HgO
4

Ti
2
BeO
4
Ti
2
SrO
4

Ti
2
BaO
4
Ti
2
ZnO
4

V
2
BeO
4
V
2
SiO
4

7 already predicted by
Hautier et al., Chem. Mater., 2010
OXIDES
A
2
BX
4
search:
~80000 individual total-energy
calculations
(incl. structures and magnetic
configurations)
Results Sulfides

We predict:
Hg
2
GeS
4
,
Al
2
TiS
4
,
Al
2
VS
4
,
Al
2
CoS
4
,
Al
2
NiS
4
,
In
2
VS
4
,
Sc
2
BaS
4
,
Ti
2
MgS
4
,!
Out of 92 not reported
34 stable,
1 undermined
57 not stable
Be
Mg
Ca
Sr
Ba
Zn
Cd
Hg
Al
Ga
In
Sn
Sc
Ti
V
Cr
Mn
Fe
Co
Ni
Cu
Be Mg Ca Sr Ba Zn Cd Hg Si Ge Sn Ti V Cr Mn Fe Co Ni Cu
CID Predicted Ternary Materials
!
3
FG
1
?-.()8-;C ?-8' *):EA -'" /" (;(?('.CH
IE. :> JK1 #-)8-=:'C0 13L -)( E')(A:).("
544 A)("8<.(" C.-@;(0 55 E'"(.()?8'("0 -'" /5K A)("8<.("
':. C.-@;(
!FG ?-.()8-;C M8.9 K (;(<.):'CH
IE. :> N51 #-)8-=:'C0 1KK -)( E')(A:).("
3/O A)("8<.(" C.-@;(0 5K E'"(.()?8'("0 -'" 3/O A)("8<.("
':. C.-@;(
X. Zhang, V. Stevanovic, M. d'Avezac, S. Lany, and A. Zunger, Phys. Rev. B, 86, 014109 (2012)
X. Zhang et al., Adv. Funct. Mater. 22, 14251435 (2013).
30 compounds
F-43m
15 compounds
Pnma
6 compounds
P2
1
/c
2 compounds
P6
3
/mmc
2 compounds
R-3m
1 compound
P-3m1
1 compound
P4
2
/mmc
1 compound
Imm2
Identification of ABX ternary materials
k-ray d|racnon |s usua||y the pre||m|nary too| to
|dennfy a new mater|a|.

A fast |dennhcanon of the new A8k compounds |n
mu|nphas|c samp|es |s poss|b|e by s|mu|anng the
pauern of the pred|cted structure.
58 Stable and
NOT reported ABX
18 electron
compounds
The symmetry of a
predicted stable
compound makes
possible:
1) Simulation of
diffraction pattern
2) Fast identification
in the experimental
pattern
Fast identification in multiphasic sample
(110) zone
Simulation
Experiment
F-43m
Predicted crystal
structure
&P-?A;(H
nfIrSb
QD1/?
nfIrSb, 2rkh8|, Sckh1e,
1aCoSn, 1aIrGe, VIrS|,
VkhS| and nfkh have
been shown to
crysta|||ze |n the|r
pred|cted
crysta| structure.
With
Confirmation
By
Electron diffraction
Identification of ABX ternary materials
The symmetry of a
predicted stable
compound makes
possible:
1) Simulation of
diffraction pattern
2) Fast identification
in the experimental
pattern
Single crystallite
X. Zhang et al. submitted to Nature Materials
Example: TaCoSn A Semiconductor from 3 metals
Experiment:
Thin film growth

Potential absorber
applications
Functionality of ABX ternary materials

1heorenca| ca|cu|anons on pred|cted (and then synthes|zed)
A8k mater|a|s prov|de |nformanon about the|r propernes.
Indirect band gap of 1.3 eV
Absorption onset at 1.6 eV
High absorption above 1.8 eV
CalculaLed uCS
CalculaLed uCS
>F Z%[+1%/-$= -1 %BF= PF >7F DR-7F 6#GF HIJ= HOO\] MNOHI:
Missing TaCoSn Compound
Not known in ICSD or ICDD

Large stability range

Predicted to have semi-
conducting gap ~ 1.3 eV
(GGA + U)
Validation: Growth of New TaCoSn
Predicted Structure
XRD: Predicted & Measured
TaCoSn Grown
>F Z%[+1%/-$= -1 %BF= PF >7F DR-7F 6#GF HIJ= HOO\] MNOHI:
Idennhcanon |n
mu|nphas|c
samp|es
Iuncnona||ty
Structure
determ|nanon
Stab|||ty
Inverse
Des|gn ?
E
x
p
e
r
i
m
e
n
t

Experiment
E
x
p
e
r
i
m
e
n
t

Experiment
Inverse Design provides a scientific framework to
accelerate the discovery of new materials
Summary
- lnverse ueslgn
1heory LxperlmenL Coupllng ls Crlucal
1heory and LxperlmenLal 1ools
- ueslgn vla ueslgn rlnclples
Selecuon crlLerla for v absorbers
Co
2
ZnC
4
from A
2
8x
4
! p-Lype 1CC
Search for mlsslng maLerlals and Lhelr funcuonallLy
- MaLerlals ueslgn Approach 8roadly Appllcable
CLher luncuonallues
- MeLasLablllLy, SynLheslzablllLy



cooperation and innovation
without borders to
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emerging and revolutionary
solar electricity
technologies toward the
extended-time success of
Indias Jawaharlal Nehru
National Solar Mission and
the U.S. DOE SunShot
Program




Solar Energy
Research Institute
for India and US

SERIIUS
seriius.org
Research Thrusts
T
h
r
u
s
t
s

Sustainable
Photovoltaics
(PV)
Multiscale
Concentrated
Solar Power (CSP)
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Energy
Integration (SEI)
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c
t
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v
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t
i
e
s

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r
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j
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t
s

Core Projects
E
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r
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h

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b
u
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P
V

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d
v
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e
d

P
r
o
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e
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/
T
e
c
h
n
o
l
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g
y

M
u
l
t
i
s
c
a
l
e

M
o
d
e
l
i
n
g

a
n
d

R
e
l
i
a
b
i
l
i
t
y

H
i
g
h
-
T
,

C
l
o
s
e
d
-
C
y
c
l
e
,

B
r
a
v
t
o
n

C
y
c
l
e

L
o
w
-
T

O
r
g
a
n
i
c

R
a
n
k
i
n
e

C
y
c
l
e

T
h
e
r
m
a
l

S
t
o
r
a
g
e

&

H
y
b
r
i
d
i
z
a
t
i
o
n

R
o
a
d
m
a
p
p
i
n
g
,

A
n
a
l
y
s
i
s

a
n
d

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s
s
e
s
s
m
e
n
t

G
r
i
d

I
n
t
e
g
r
a
t
i
o
n

a
n
d

E
n
e
r
g
y

S
t
o
r
a
g
e

Consortium Projects

CONSORTIUM PROJECTS: disruptive, transformative R&D
CORE PROJECTS: core industry partner-led and focused
SERIIUS R&D Thrusts
Core Projects
Consortium Projects
Core Projects
Consortium Projects
Developing Low Cost Atmospheric
Processing

Integration
Materials/
devices
integrated onto
flexible
substrates
Inks and synthesis
Understanding
metalorganic
decomposition
Molecular
precursor design
Synthesis to
desired
materials
Inks:
Absorbers
Transparent
conductors
Contacts/
Packaging
Deposition
Desired
precursor with
no residual
organics
Designed to
densify with and
allow grain
growth
Compatible with
other layers
Processing
Device quality:
Rapid
thermal
processing
Optical
Processing
Acknowledgements: CID EFRC
T0'&/2' ;2/"(' M/S28<#0&('8D 61%^ %"U 61+U-"1CD ['%CB%&$(><3B410
+FUH R0S2 K"/12:D m($/ T2'9"/8D ;&2*$0/ ?0/:D `/6'": l09)&0:2SD
T2&2' K'07D m)/ F2" ?)(D 8%+B _UA#"-= `%#V-A 8-".= aA"G-
5#BBA".-)= P#CR ?%)&"@ T%:$B3 Cx<D$E%;@
<3K$'&7 2'%1;$(;/$m@ <'P%C0: T0P/%:3B(/P01
+7'&/W$(&$'1
-10D$'(0&:
n2/ T(2**21-2"2'D `'& I'22-0/D 4(- @08(/D K"0/,0'1(
4'"-0',$"@ 0-". 3%"= >)Q+" _%.%)%b%= PA7# !7= c%"E-) 9%7=
4#7%A" T%+&-)= c-B$A" DR%".= P-)-7/ `%))AC= c%)B 4AG[-)C=
UD%1 A&%463$'@ +0;73% 9$'':@ e$$'3$ L37$&@ <C%4 F%W
,'$)71 A&%&$
-10D$'(0&:
R()# n28^12'D m($/ F0#2'D 4#E-)1 c#[-"/-CA= P%-d6-#[ `-#=
T)-. >".-B#C= 5)A%" 8-B%e= 4%7 4%$AGR%"U)%"= y$'$4:
<1C$'(71@ e7''%1B&;/ y0$'%&B4@ ?$1 f%&$'(@ U44$301$
<3&(;/B3
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y7%11% ?$m1)$'
L737'%C7 A;/773 7R
T01$(
E1060/ ;&2S0/(S",D a")V2/ l$0/#
Summary
- lnverse ueslgn
1heory LxperlmenL Coupllng ls Crlucal
1heory and LxperlmenLal 1ools
- ueslgn vla ueslgn rlnclples
Selecuon crlLerla for v absorbers
Co
2
ZnC
4
from A
2
8x
4
! p-Lype 1CC
Search for mlsslng maLerlals and Lhelr funcuonallLy
- MaLerlals ueslgn Approach 8roadly Appllcable
CLher luncuonallues
- MeLasLablllLy, SynLheslzablllLy

Acknowledgements: CID EFRC
T0'&/2' ;2/"(' M/S28<#0&('8D 61%^ %"U 61+U-"1CD ['%CB%&$(><3B410
+FUH R0S2 K"/12:D m($/ T2'9"/8D ;&2*$0/ ?0/:D `/6'": l09)&0:2SD
T2&2' K'07D m)/ F2" ?)(D 8%+B _UA#"-= `%#V-A 8-".= aA"G-
5#BBA".-)= P#CR ?%)&"@ T%:$B3 Cx<D$E%;@
<3K$'&7 2'%1;$(;/$m@ <'P%C0: T0P/%:3B(/P01
+7'&/W$(&$'1
-10D$'(0&:
n2/ T(2**21-2"2'D `'& I'22-0/D 4(- @08(/D K"0/,0'1(
4'"-0',$"@ 0-". 3%"= >)Q+" _%.%)%b%= PA7# !7= c%"E-) 9%7=
4#7%A" T%+&-)= c-B$A" DR%".= P-)-7/ `%))AC= c%)B 4AG[-)C=
UD%1 A&%463$'@ +0;73% 9$'':@ e$$'3$ L37$&@ <C%4 F%W
,'$)71 A&%&$
-10D$'(0&:
R()# n28^12'D m($/ F0#2'D 4#E-)1 c#[-"/-CA= P%-d6-#[ `-#=
T)-. >".-B#C= 5)A%" 8-B%e= 4%7 4%$AGR%"U)%"= y$'$4:
<1C$'(71@ e7''%1B&;/ y0$'%&B4@ ?$1 f%&$'(@ U44$301$
<3&(;/B3
-10D$'(0&: 7R L737'%C7
Q ?7B3C$'
`123 l)/#2'D ?"*"/# o)D H0kB1 w/%1)D P#CR 0#)U
AH<L @"92 4(/2:D 9A"U% 9A7= c-$A" 61#"-= 3-YR#+ 6RA=
y7%11% ?$m1)$'
L737'%C7 A;/773 7R
T01$(
E1060/ ;&2S0/(S",D a")V2/ l$0/#