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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP16/07/10Page 1
Copyright © NEXCIS – Tous droits réservés
NEXCIS Business Development
Draft V2, 13th September 2010
Habilitation à Diriger de Recherches
Veronica BERMUDEZBENITO
16 June 2011
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
1. Summary
1. Why we are here?
2. State of the Art of Thin Film Solar cells
3. Research Project
1. Why choosing CIGS
2. Closing the gap
3. In(situ characterization
4. Previous Activity
1. Lithium Niobate
2. Periodic Poled Lithium Niobate
3. CdTe for PV
4. Modelling and Characterizing CIGS devices
5. Some indicators
Agenda
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP16/07/10Page 3
Copyright © NEXCIS – Tous droits réservés
Thin Film Solar Cells for future
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Why thin films in the future:
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
2005 2010 2020 2030 2040 2050
Ma
rke
t Sh
are
Novel devices
Other thin films
Thin films
Silicon thin films
Crystalline Si
Thin Films> 15% in 2010 45% in 2020
Source: IEA 2010
Forecast from IEA (BLUE Map) in 2030 : towards a mix of technologies
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Advantages of thin film PV
• Efficient and high performing materials
• Direct bandgap semiconductors
• Better energy output – kWh/KW
• CIGS record at 20%+ conversion efficiency
• Significantly reduced costs
• Less material usage
• Potential for improving costs throughout value chain
• Better aesthetics
• Roadmap of glass3to3glass and flexible substrate
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Solar Today
Google HQ -Solar ProjectSolar farm in Amstein, Germany
Utility Scale Commercial Systems
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Solar Tomorrow: Building Integrated Photovoltaics
Power Buildings will become multi-$T market• BIPV is the fastest growing sector of PV• Building Integration leverages available surface area,
installation costs, and proximity to loads
Revolutionary products through efficient, durable thin-film solar cells embedded into traditional building materials
• Current products unsuitable and not cost effective
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
BIPV Applications
• Roofing
• Most common BIPV application today
• Sunshades
• Energy conservation and reduced building operating costs
• Cooling load mitigation and glare control
• Easiest retrofit for PV
• Overhead glazing (canopies,
skylights, atriums)
• Curtain wall / Facades
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP16/07/10Page 9
Copyright © NEXCIS – Tous droits réservés
Between thin films Why CIGS?
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
State of the art in efficiency. Big gap between R&D and production
Who? Device Aperture Area Efficiency
Würth Solar CIGS (glass) 6500 13.0
AVANCIS CIGSS (glass) 4938 (26 x 26) 13.0 (15.5)
Solar Frontier CIGSS (glass) 3600 (30 x 30) 13.0 (17.2)
Solibro CIGS (glass) 6840 14.2
Global Solar CIGS (flexible) 8390 (3822) 10.5 (13.0)
Miasole CIGS (flexible)* > 1 m2 15.7
Solopower CIGS (flexible) 0.3m x 2.9m 12.0
First Solar cdTe (glass) 6623, high volume 11.3 (12.6)
* Sandwiched between two pieces of glass
Device/ Module Type Efficiency (%) Who?
Cells (0,5 – 1 cm2) > 18 to 20.3* NREL, ZSW, AIST, HZB, AGU, ASC
Submodules (20 – 100 cm2) 15- 17* ZSW, ASC, HZB, Showa Shell
Prototype modules (0,35 – 0’7 m2)
13 – 16* Solar Frontier, Miasolé, Global Solar, Avancis
Commercial Modules (0,7 m2) 12-13 Würth Solar, Solibro, Global Solar, Solar Frontier, Avancis
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Closing the gap between record efficiencies and commercial modules
Target 15%
6%
12%
20.3%
23%
Lab device
Challenging target
Closing the gap
Expanding Tech. Base
Closing the gap
Improvement of fundamental materialknowledge
Derive measurable materialproperties that are predictive of device and module performance
Model the relationshipbetween film growth and material delivery
Industrial processes, beneficial impacts:
( higher throughput and yield( higher degree of reliability and reproductibility( higher module performance
In(Situ ProccesDiagnostics and Control
Better science(basedknowledge of materials properties
Materials and photonicinteralation. Real time diagnosis tools.
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
CIGS based devices. Facing the challenge
SCR
- Charge carriers are generated in absorber layer.
-Limited, by the absorber bulk quality, and electronic quality
of the absorber related interfaces.
-After charge separation at p-n junction, recombination
currents will dominate the transport, relaxing the impact of
other interfaces.
- More than 80% of performance losses is related to absorber
quality.
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Crystal structure of Cu(In,Ga)Se2 –chalcopyrite3type3
Elemental
Binary
Ternary,…
DiamondSi, Ge
Zincblende
WurziteCdTe, GaAsChalcopyriteCu(In,Ga)(S,Se)2
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Cu3(In, Ga)3Se Ternary Alloys Molecularity (M) and Stoichiometry (S)
M = [Cu]/([In] + [Ga])
S = 2[Se]/ ([Cu] + 3([In]+[Ga]))
∆∆∆∆M = M (1; ∆∆∆∆S = S – 1
ALL high efficiency
CIGS devices have
∆∆∆∆M < 0 and ∆∆∆∆S > 0
Formation reaction
yCu2Se + (13y) (In,Ga)2 Se3+∆∆∆∆Se Cuy ((In,Ga)13y)2 Se332y+∆∆∆∆Se
Se
Cu In, Ga
Intermetallic Plethora
(In,Ga)2 Se3
(In,Ga) Se
(In,Ga)4 Se3
Cu2 Se
Cu Se
Cu2 Se3
112247
135
112 = CuInSe2
247 = Cu2In4Se7
135 = CuIn3Se5
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
CIGS Complex Non3Stoichiometric Thermochemical Phase Structure
S. Yamazoe, H. Kou and T. Wada, J. Mater. Res., in press.
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Compositional Fluctuations and Carrier Transport in CIGS absorbers
Experimental results HAADF(TEM and Nanoscale EDS
(5(10 nm chracteristic domain size(Chemical composition fluctuations across the domains
p1: Cu:In:Ga:Se = 31:14:7:48p2: Cu:In:Ga:Se = 27:15:9:49p3: Cu:In:Ga:Se = 30:15:6:49
(Dark domains are relatively Cu rich, bright domains are relatively Cu poor.
JB Stanberry et al. APL 87, 2005, 121904
HAADF(TEM: High(Angle Annular Dark(Field Transmission Electron MicroscopyEDS: Energy(Dispersive X(Ray Spectroscopy
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
CIGS Non3Stoichiometry and Atypical Device Behavior
• Peculiar semiconductor behavior:
CIGS PV devices insensitive to % atomic composition variations & extended defects
>19% efficiencies recently reported† over range:
• 0.69 ≤ [Cu]/([In]+[Ga]) ≤ 0.98 (Group I/III ratio)
• 0.21 ≤ [Ga]/([Ga]+[In]) ≤ 0.38 (Group III alloy ratio: Eg
• Empirical Observations
• CIGS PV devices are always copper deficient compared to α(CuInSe2
• Compositions lie in the equilibrium α+β2(phase domain
†Jackson et al., Prog. PV, Wiley & Sons, 2007.
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Characteristics of an Ideal CIGS Manufacturing process and state of the
art of CIGS synthesis
• CIGS Manufacturing method should provide a high device(quality material
• Ability to create intrinsic defect structures limiting recombinations; role of order(disorder transitions?
• Ability to control Group III(VI composition gradients
• Control of extrinsic doping
• Low high processing Rates
• Low thermal budget
• High materials utilization
Process Steps, precursor Characteristics
Multistage coevaporation Binary chalcogenidecompounds
Reduction of Se utilisation and In incorporation
Reactive annealing pure metalfilms (PVD, plating…)
Sputtered metal or alloy films followed by high T annealingin Se/S
Complex intermetallicalloying. Uncontrolledsegregation
Reactive annealing Se/S containing precursors
Incorporate Se followed fromRTP
Multi-step reaction kineticsHelp Se in-diffusion
Reactive annealing particleprecursors
Printed particles followed by high T annealing in Se/S
Difficult recrystallizationkinetics
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Intrinsic defects stronlgy affect optoelectronic properties. Growthconditions
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Influence of Se overpressure and crystal orientation on the Luminescence and thus in electronic chraacteristics
P3
P2
P1
Manuel Romero Courtesy
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
The complexity of mechanisms and unexpected relations. Source materials and kinetics. Selenium case
Nominally same growth conditions, except Sesource:
( E( Se conventional evaporation Se target( R(Se rf(plasma cracked Se(radical beam
( Differences in Voc, FF and Jsc.
( Differences in Na and Ga step profile
( Differences in surface roughness, grain size and density of absorber.
Shogo Ishizuka, Akimasa Yamada, Hajime Shibata, Paul Fons, Shigeru Niki. Thin Solid Films, in press
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
The complexity of mechanisms and un expected relations. Source materials and kinetics. Selenium case
Shogo Ishizuka, Akimasa Yamada, Hajime Shibata, Paul Fons, Shigeru Niki. Thin Solid Films, in press
CdS is present at only near surface region of R(Se, while for E(Se depth profiles of Cd and S exhibit a broad distribution, due to presence of surface crevices.
Ga and Se diffuses at Mo/Mo interfaces for R(Se.
EBIC shows a more buried pn(junction in E(Se as pn(junction is formed in a deeper region near the Ga gradient valley according to SIMS.
R( Se E( Se R( Se E( Se
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Difficulties in identifying in(situ/in(line measurable material properties
Closing the gap
Improvement of fundamentalmaterial knowledge
Derive measurable material propertiesthat are predictive of device and module performance
Model the relationship between film growth and material delivery
Industrial processes, beneficial impacts:
( higher throughput and yield( higher degree of reliability and reproductibility( higher module performance
In(Situ Procces Diagnostics and Control
Better science(based knowledgeof materials properties
Materials and photonicinteralation. Real time diagnosistools.
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP16/07/10Page 24
Copyright © NEXCIS – Tous droits réservés
Previous activity
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Education
Degree: Licence in Physics (5 years), obtained in 1996 at Autonoma University of Madrid (UAM)
Speciality in Optics and Materials Structure,
Master degree: Optics and Materials Structure, obtained in 1996 at AutonomaUniversity of Madrid
Subject: “Study and characterization of domain structure of LiNbO3”.
PhD Thesis Materials Science, obtained in 1998 at Autonoma University of MadridSubject: “ Obtention and Characterization of Periodic Structures in LiNbO3 single
crystals doped with Er e Yb”. Realized in the Crystal Growth Laboratory (CGL) of the Materials Physics
Department of the UAMThesis Director: Prof. Ernesto Dieguez
Highest qualification and Extraordinary Prize of the University for Thesis in Science.
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Experience
1995(1998 PhD Thesis in the Crystal Growth Laboratory of Materials PhysicsDepartment at UAM (Spain)
1999(2000 Laboratory of Advanced Technologies (DEIN/SPE/GCO) at CEA(LETI inSaclay (France).European Postdoctoral fellow within Marie Curie Program in the 5th EU Program.
2000(2001 Materials Physics Department, Universidad Autonoma de Madrid (Spain)Post(doctoral fellow
2001(2006 Materials Physics Department, Universidad Autonoma de Madrid (Spain)Researcher in the Tenure Track “Ramon y Cajal” Program. Transformed to AssistantProfessor in 2005.
2005(2009 Institute for the Research and Development of Photovoltaic Energy (IRDEP)
EDF R&D, CNRS, ENSCP mix Institute, Chatou (France)Researcher, Project Manager and Optoelectronic Characterization Laboratory Head
2005(2007 as “Poste Rouge” in CNRS2007(2009 as Engineer(Researcher in EDF R&D
2009(present NEXCIS Photovoltaic Innovation, Rousset (France)Senior Scientist
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Very Promising Basic Material Properties
Possibility of micro-controlling Properties by tailoring Composition and Doping
+
+Tailoring of Different Sample
Structures
A WIDE RANGE OF INTERESTING PHOTONIC APPLICATIONS
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Peculiar trajectory
Ferroelectric domainsin Lithium Niobate
Doping to control domains and laser properties
Semiconductorsfor energy
Thin films for photovoltaicCdTe and CIGS
Closing the gap:
( Deep understanding( In line characterization
Molecularmotors
Based in understanding relationship
between:
3 Material physico3chemical properties
and growth (preparation) process and
history .
(Materials physico3chemical properties
and optoelectronic defect.
3 Defects and growth process and history
Missed in past:
Development of characterization
methods for process monitoring
as the way to control defects
formation. Photonics
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP16/07/10Page 29
Copyright © NEXCIS – Tous droits réservés
Luthium Niobate and the way to fashion their ferroelectric domain structure for optoelectronic applications
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Lithium Niobate a decathlon winner
LN structure has been described as a very distorted perovskite with a tilt rotation of the oxygen triangles around the c axis. Intrinsic defects at the origin of theirproperties
The chemical formula Li0.925(8)Nb1.07(1)O2.64(2) obtained during our work suggest the coexistence of lithium and oxygen vacancies; and their presence is strongly determined by the thermal history of the crystal.
48.4 mol% Li2OCongruent composition
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Ferroelectric domains in lithium niobate
HF:HNO3 (1:2 by vol) at 110°C during 10 min.
19F mapping distribution by SIMS (skils adquiredduring my PhD stages in Padova University)
Ferroelectric Paraelectric
C(axis
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Off centered Czochralski growth of PPLN and APPLN
Λ = 2 vpull/vrot
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Stoichiometric LiNbO3 impacting properties
10 20 30 40 50 60 70 80 90 100 110
316.30
316.32
316.34
316.36
316.38
316.40
316.42
316.44
316.46
316.48
316.50
316.52
316.54
316.56
V(Å
3 )
Temperature (K)
Mínimos locales de Volumen de celda
0 20 40 60 80 100 120 140 160 180 200 220
0.9173
0.9174
0.9175
0.9176
0.9177
0.9178
0.9179
100 K
Spo
ntan
eous
Str
ain
Temperature (K)
58 K
Structural Anomaly in LN at 55K observed with Neutron diffraction, strongly related with stoichiometry
Λ
ΛΛΛΛtheory ΛΛΛΛexperimental Deviation
0wt% 6.63 6.63 0%
2wt% 6.63 3.2 48%
4wt% 6.63 2.55 39%
5.2wt% 6.63 2.05 30.9%
7wt% 6.63 ------
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Controlling the colour and the intensity
Generation of 8 different wavelength from only one pump source
System based on a APPLN:Nd crystal
VR
Mirrors
Pump
R
B
VGVB
2
lC
G
( ) [ ]Ennxnn )()2/(%)21()()2/(2 '3'3
33
''' λλσλλλ −−Λ+−Λ=
Λ= Domain period
σ33 = Electro-optic coefficient
λ= Fundamental wavelength (SHG)
x % = duty cycle
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Thin Films Solar cells based in II3VI compounds”
Cd(g) + Te2(g) Cd(g) + Te2(g) Cd(g) + Te2(g)
Cd(g) + Te2(g) Cd(g) + Te2(g)
Cd(g) Te2(g)
Bi2Te3-x
(s)
CdTe(s)
Subst.
Cd(g) Te2(g)
Bi2Te3-x
(s)
CdTe(s)
Subst.
Cd(g) Te2(g)
Bi2Te3-x
(s)
CdTe(
s)
Subst.Thermal process for the wiskersformation under VLS process.
Using this properties of Bi2Te3(CdTe co(evaporation in a controlled way it should be possible to obtain ordered arrays of hexagonal rod CdTe and thus to enhance performance of final electronic systems
C. M. Ruiz, E. Saucedo, O. Sanz and V. Bermúdez
Journal of Physical Chemistry., in press
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP16/07/10Page 36
Copyright © NEXCIS – Tous droits réservés
Materials for Energy Conversion.Thin film solar cells
CdTeCu(In,Ga)(S,Se)2
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
CdTe: Bi. New intraband material?
Extremely high Jsc (26.31 mA/cm2) for 600 mV of Voc in the case of a CdTe:Bi device withconcentration at 1017 at/cm3.
1016
1017
1018
1019
104
105
106
107
108
109
1010
1011
undoped CdTe
Re
sis
tiv
ity
(ΩΩ ΩΩ
.cm
)
Bi conc (at./cm3)
First Principles study of Bi doped CdTethin film solar cells: electronic and optical properties Y. Seminovski et al. ETSI UPM, Madrid
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP 38
Equivalent circuit ⇒⇒⇒⇒ separate each layer to identify different problems in process
Optoelectronic diagnostic of a serial resistance based problem. (Back diode)
CIS
CdS
ZnO
Mo
RC1
R//ZnO
Rjonction
R//Mo
MoS2
R?ZnO
RC2
RMoS2
Iph ID1 ID2
Rsh
RC4
RC3
Rsh2
IRCIS
CdS
ZnO
Mo
RC1
R//ZnO
Rjunction
R//Mo
Mo(Se,S)2
RZnO
RC2
RMoS2
Iph ID1 ID2
Rsh
RC4
Rc3
RDR
IR2 3 4 5 6 7 8
420
480
540
600
660
720 Voc Rs
eff(%)
Voc
(mV
)
0
2
4
6
8
10
12
Rs (O
hm/cm
2)
-20
-15
-10
-5
0
5
-200 -100 0 100 200 300 400 500 600
Experimental data sample D Fitted curve with reverse diode Curve without reverse diode
J(mA/cm2)
V(mV)
s
R
ph
R
J
ph
J IRI
IIn
I
IIn
kT
qV +
−−
−=
00
lnln
-1 .0 -0 .5 0 .0 0 .5 1.0 1 .5
0 .0
2 .0n
4 .0n
6 .0n
8 .0n
10 .0n
Cap
acita
nce(
F)
Vbias
(V )
16 11C -2 -3d 14 39-1 9-2 -4a 14 56-2 -3d 14 29-1 9-1 -1a
13.31.936.3376
12.53.448.6594
5.355.361.8603
4.39.069.8671
RSEffFFVoc
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
S at the origin of CuxSe and thus origin of the back diode through CuIn5S8
Cu(S,Se)
Before chemical etching
150 200 250 300 350 400 450 500
(3)
(2)
No
rm.
Int.
(a.u
.)
Raman shift (cm-1)
(1)
Cu(S,Se)
CuIn5S8
Cu(S,Se) grain
CIS grain
1,15 1,20 1,25 1,30 1,35 1,40 1,45 1,50 1,55 1,60 1,65 1,701
10
100
Rs
(max
)
2Se/(Cu+3In)
Rs increases significantly for m >1.3
Agrees with compositional range leading to formation of CuSe secondary phase
CuSe at back layer region likely leading to formation of secondary phases (CuS + CuIn5S8) degrading Rs
Experimental data for very high Rs values suggest relationship with presence of CuIn5S8
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
In situ monitoring techniques. Precursor composition monitoring
m
50 100 150 200 250 300 350
Cu-Se
Ram
an in
tens
ity (a
.u.)
Raman shift (cm-1)
Cu-Se
Se
OVC
CISe Problem: strong signal from H2O (aqueous electrolyte solution) in 100 – 250 cm(1 spectral range
Possibility to define optimal values of I(CISe) & I (Se +CuSe) corresponding to m ≥ 1.3 (in spite of high noise level)
in(situ detection of deviations of m below 1.3
1.1 1.2 1.3 1.4 1.5 1.6 1.7
60000
80000
100000
120000
140000
160000
180000
200000
220000
240000
260000
Inte
nsita
t Ray
leig
h (a
.u.)
2Se/(Cu+3In)
Decrease of IR at higher values of m: Possibility to detect deviations of m also
above optimal range of values
1,1 1,2 1,3 1,4 1,5 1,6 1,7
Inte
ns
ity
(S
e +
Cu
Se
mo
des)
2Se/(Cu+3In)
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Excitation with laser probe from BWtek system (785 nm): quasi resonant
excitation conditions in S-rich CuIn(S,Se)2 alloy:
Reduction of tint in more than
one order of magnitude (down to
seconds)
Efficient excitation of several
modes (in addition to A1 peak)
200 300 400 500 600 700 800 900
E(L)/B2(L)
E(L)
A1
Inte
nsity
(a.
u.)
Raman shift (cm-1)
E(L)/B2(L)
2nd order
Alternative: Raman in quasiresonant conditions (matched to a given composition):
Case example: Analysis of composition of S rich CuIn(Sx,Se13x)2
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Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Fitting of Intensity of E(L)/B2(L) mode at about 340
cm(1: exponential dependence of intensity of
bands on alloy composition
High sensitivity for detection of deviations of values of x in Srich alloys
65 70 75 80 85 90 95 100
0
20000
40000
60000
80000
100000
120000 y = A1*exp(x/t1) + y0 Chi^2/DoF = 1584241.43866R^2 = 0.99927 y0 4622.04913 ±941.66472A1 0.12088 ±0.05329t1 7.29108 ±0.23256
E(L
)/B
2(L
) in
ten
sit
y (
a.u
.)
[S] %
Case example: Analysis of composition of S rich CuIn(Sx,Se13x)2
200 300 400 500 600 700 800 900
[S] = 70%[S] = 77%[S] = 86%
[S] = 89%
[S] = 91%
Inte
nsity
(a.
u.)
Raman shift (cm-1)
[S] = 100%1/2
0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000
inte
nsity
(a.
u.)
Raman shift (cm-1)
[S] = 100%
[S] = 78%
[S] = 89%
[S] = 77%
[S] = 70%
Moreover:
0,35 0,40 0,45 0,50 0,55 0,60 0,65
1,450
1,455
1,460
1,465
1,470
1,475
1,480
1,485
1,490
1,495
Exi
ton
posi
tion
(eV
)
Voc (V)
Voc tends to increase with EPL.
43
Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Coloured regions: possibility to obtain resonant excitation with different lasers
Extension to alternative quaternary CIGS based alloys
Matching excitation wavelength to Eg: possibility to assess composition of
Cu(In,Ga)(S,Se)2 alloys with different Ga/(In+Ga) and/or S/(S+Se) contents:
0,0 0,2 0,4 0,6 0,8 1,0
1,0
1,2
1,4
1,6
1,8
2,0
2,2
2,4
2,6
Gap
(eV
)
Ga/(In+Ga)
Laser
CuInSe2
1064nm976nm
785nm
512nm
671nm
488nm
633nmCuGaSe2
CuGaS2
CuInS2
44
Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
NaCN etching
Removal Cu(S,Se) secondary phases
RTP recrystallisationunder selenising and/or sulphurising conditions
Cu(In,Ga)(S,Se)2
Electrodeposition
Metallic or CuInSe2precursors
CBD of CdS buffer layer
RF-sputtering of ZnO window layer
Electrodeposition based process
In3line/ in3situ: Raman scattering monitoring of ED3CIGS films and
processes
Identification of phases and alloys (chemical composition)
Monitoring of crystalline quality & Ga, S and Se incorporation
Assessment of NaCN etching (disappearance of Cu(S,Se) modes)
& CdS deposition
45
Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Photoluminescence set3up13 Spectroscopy: study of radiative defects and quality of material
Metzger and Repins, et al. Thin Solid Films 517 (2009) p.2360, and EMRS, May 2008
46
Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Photoluminescence set3up
23 Mappping: process control
CdS
ZnO
CISSe
47
Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP16/07/10Page 47
Copyright © NEXCIS – Tous droits réservés
Some indicators
48
Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Some numbers
1996 1998 2000 2002 2004 2006 2008 2010 20120
2
4
6
8
10
12
14N
um
be
r o
f P
ub
lic
ati
on
s, IS
I
Year of Publication
Total ISI papers: 99
Sum of Times Cited: 741
Average Citations per Item: 7.5 (6.1)
h(index: 13
Conference Proceedings: 30
Oral Presentations: 14
Invited presentations: 7
Keynotes: 1
3 Patents (submitted)
49
Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Awards
1) PhD Thesis Prize Universidad Autónoma de Madrid, 1998/1999
2) Finalist in “The EU Descartes Prize 2003” within the frame of the EuropeanProject “Molecules in Motion: hydrogen bond(assembled molecular machines (MOLS(IN(MOTION).
3) Young Prize 2004 in Science and Technology by Universidad Complutense de Madrid Foundation
4) 2007 Schieber Prize from International Organization on Crystal Growth. With invited Plenary Conference. http://www.iocg.org/“Engineered Periodic Poled Lithium Niobate Structures doped with RareEarth for multi self(frequency conversion “
50
Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
Others
2 thesis co(supervised (1 France, 1 Spain)
7 Stages supervised in France and Spain.
14 Seminars in France, Italy, Belgium, Spain, Germany
Associate Editor of Journal of Renewable and Sustainable Energy
Expert for AERES and EU in FP7
Pormoting Women in Science and Engineering
51
Habilitation à Diriger de Recherches. Veronica BERMUDEZBENITO16 June 2011. université AixMarseille. IM2NP
We are just speaking of produced watts?