Molecular and
Supramolecular Organic
Photovoltaics
UTEP-UCSB PREM Presentation
May 20, 2013
• Nearly 3 millon population
• 84% Hispanic
• ~22,000 students enrolled
at UTEP
The University of Texas at El Paso
PREM People and Concepts
Luis Echegoyen – PI - Chemistry Craig Hawker – co-PI - Materials
Tunna Baruah - Physics
Fred Wudl - Chemistry
Gabby Gandara - Engineering
Kris Delaney – Materials
Juan Noveron - Chemistry
Michael Chabinyc - Materials
Glenn Fredrickson – Chem. Eng.
Jose Nuñez - Chemistry
Chintalapalle Ramana (Mech. Eng.)Ram Seshadri - Chemistry
David Zubia – Elec. Eng.
Dorothy Pak - Materials
Javier Read de Alaniz - Chemistry
Ram Seshadri - Chemistry
 By 2050, additional 30 TW (1012) are needed
Nocera, D.G. et al. Proc. Natl. Acad. Sci. 2006, 103, 15729
 Solar energy has the capability to meet that
demand
Solar Cell
-
+V
Towards Novel Solar Cells
vs
Meso-scale
Organized Molecular Materials
• Novel Molecular
Components
• Supramolecular Order
• Orchestrated electron
dynamics
• Electrochemical cascade
PREM People and Concepts
Luis Echegoyen – PI - Chemistry Craig Hawker – co-PI - Materials
Tunna Baruah - Physics
Fred Wudl - Chemistry
Gabby Gandara - Engineering
Kris Delaney – Materials
Juan Noveron - Chemistry
Michael Chabinyc - Materials
Glenn Fredrickson – Chem. Eng.
Jose Nuñez - Chemistry
Chintalapalle Ramana (Mech. Eng.)Ram Seshadri - Chemistry
David Zubia – Elec. Eng.
Dorothy Pak - Materials
Javier Read de Alaniz - Chemistry
Ram Seshadri - Chemistry
Fred Wudl - Chemistry
Investigation of Indium Free Transparent Conducting Oxides
(C. V. Ramana and K. Delaney & R. Seshadri)
C.V. Ramana et el.,
J. Phys. Chem. B (2004)
• Novel transparent conductive layers that can replace
Indium Tin Oxide (ITO) are warranted
• This PREM team is working together to develop and
understand a new kind of conductive glass made of
WO2 doped wth Titanium
• Theoretical and Experimental Models are under
investigation
W-Ti-Oxide Transparent Films
Optical Constants of Amorphous, Transparent Titanium-Doped Tungsten
Oxide Thin Films
C. V. Ramana, Gaurav Baghmar, Ernesto J. Rubio, and Manuel J. Hernandez
ACS Applied Materials & Interfaces, 2013 Article ASAP
PREM
Investigation of Indium Free Transparent Conducting Oxides
(C. V. Ramana and K. Delaney & R. Seshadri)
Synthesis
Computations
Tungsten (W)
Optical
- Titanium(Ti)
Properties Based Oxides
Electrical
Properties
Crystal
Structure
Morphology &
Composition
10
L. Echegoyen (UTEP) and C. Hawker (UCSB)
F. Wuld (UCSB)
TNT-EMF
C60
Ih-Sc3N@C80
Ih-Y3N@C80
Ih-Lu3N@C80
Ih-Lu3N@C80
Ih-Tm3N@C80
Ih-Tm3N@C80
Ih-Er3N@C80
Ih-Dy3N@C80
Ih-Gd3N@C80
Ih-Nd3N@C80
Ih-Pr3N@C80
D5h-Sc3N@C80
D5h-Sc3N@C80
D5h-Lu3N@C80
D5h-Dy3N@C80
D5h-Tm3N@C80
E+/+2
E0/+
E0/-
E-/2-
E2-/3-
(E0/+- E0/-)
+1.09
+0.70
-
+1.26104
+0.59
+0.64
+0.64
+0.64
+0.68
+0.65
+0.63
+0.70
+0.58
+0.63
+0.59
+0.35
+0.34
+0.45
+0.41
+0.39
-0.98
-1.26
-1.44
-1.40
-1.42
-1.31
-1.43
-1.42
-1.37
-1.44
-1.42
-1.41
-1.33
-1.41
-1.40
-1.45
-1.37
-1.62
-1.83
-1.76
-1.80
-1.86
-1.86
-1.85
-
-1.87
-2.37
-2.38
-2.18
-
2.24
1.85
2.08
2.04
2.06
1.99
2.08
2.05
2.07
2.02
2.05
2.00
1.67
1.86
1.81
1.84
Large –scale Fullerene Synthesis
Electric discharge
between graphic
eletrodes
HPLC
Isomeric Separation of Ih and D5h Sc3N@C80 by Selective
Chemical Oxidation
Arcing sample
200 mV
5-PBB Column
40
Sc3N@C80 Ih
0,0
-7
-2,0x10
Current /1e-7A
30
-7
-4,0x10
Ih
-7
Ih
-6,0x10
20
D5h
D5h
-7
-8,0x10
1,2
1,0
0,8
10
0,6
0,4
0,2
Potential /V
C60
C70
D5h
+
Fc /Fc
Sc3N@C68
0,0
-0,2
Sc3N@C78
0
0
10
20
30
40
Retention time (min)
50
60
Redox Potentials
Fullerene
Epox (V) vs
Fc/Fc+
Sc3N@Ih-C80
0.59
Sc3N@D5h-C80
0.34
Sc3N@D3-C68
0.33
Sc3N@D3h-C78
0.21
[Fe(η-C5H4COMe)Cp]TFABa
a Connelly,
Oxidizing Agent
Epox (V) vs
Fc/Fc+
[Fe(η-C5H4COMe)Cp]+
0.29
(CH2Cl2)a
“Magic Blue”
0.71
tris-p-bromophenylaminium
or “Magic Blue”
N. G. and Geiger, W. E. Chem. Rev. (1996) 96, 877
Isomeric Separation of Ih and D5h Sc3N@C80 by Selective
Chemical Oxidation
HPLC profile: 5-PBB column - 5mL/min, Toluene
Maira Cerón, Li, Echegoyen, L. et al. An Efficient Method to
Separate Sc3N@C80 Ih and D5h Isomers and Sc3N@C78 by
Selective Oxidation with Acetylferrocenium
[Fe(COCH3C5H4)Cp]+
Chem. Eur. J. 2013 (DOI: 10.1002/chem.201204219) PREM
15
Novel PCBM -Sc3N@D5h-C80 and -Sc3N@D3-C68
PCnBM : phenyl butyric acid methyl ester
solvent
PCBM-Sc3N@C68
Sc3N@D5h-C80
Sc3N@D5h-C80
Silica gel Column
Sc3N@D5h-C80
Sc3N@D3-C68
Sc3N@D5h-C80
PCBM-Sc3N@D5h-C80
J. Noveron (UTEP) M. Chabinyc (UCSB)
L. Jaeger (UCSB)
J. Noveron (UTEP) C. Hawker (UCSB)
Crystal Engineering of Fullerenes
Photo-copolymer Gels
J. Noveron (UTEP) M. Chabinyc (UCSB)
L. Echegoyen (UTEP)
DNA-templated
Nanomaterials
Self-organizing
Molecular
Materials
J.Noveron (UTEP) M. Chabinyc (UCSB)
NanoCapsules
Fullene Clusters
Towards Crystal Engineering of Fullerenes
Supramolecular Scaffolds: Quaternary 4-amino
alkylpyridinium bromide
Identification code
twin4s
Empirical formula
C15 H27 Br N2
Formula weight
315.30
Temperature
100(2) K
Wavelength
0.71073 Å
Crystal system
Triclinic
Space group
P-1
Unit cell dimensions
a = 6.352(2) Å
= 91.135(6)°.
b = 7.319(3) Å
= 96.777(5)°.
c = 18.739(7) Å
 = 112.693(6)°.
Volume
796.1(5) Å3
Z
2
Density (calculated)
1.315 Mg/m3
Absorption coefficient
2.570 mm-1
F(000)
332
Crystal size
0.43 x 0.18 x 0.05 mm3
Theta range for data collection
1.10 to 24.99°.
Index ranges
-7<=h<=7, -8<=k<=8, 0<=l<=22
Reflections collected
2742
Independent reflections
2742 [R(int) = 0.0000]
Completeness to theta = 24.99°
97.5 %
Absorption correction
Semi-empirical from equivalents
Max. and min. transmission
0.8931 and 0.4046
Refinement method
Full-matrix least-squares on F2
Data / restraints / parameters
2742 / 0 / 172
Goodness-of-fit on F2
0.782
Final R indices [I>2sigma(I)]
R1 = 0.0287, wR2 = 0.0942
R indices (all data)
R1 = 0.0317, wR2 = 0.0962
Largest diff. peak and hole
0.616 and -0.417 e.Å-3
c
b
a
c
a
b
c
Future Directions
 Develop ultra-thin layers with
anionic fullerenes
 Increase complexity of the
hydrophilic space to control
fullerene interactions
DNA-templated
Nanomaterials
 DNA is used to
store genetic
information in
biological
organism
 In 1990’s it was
discovered that
DNA can generate
any structure
conceivable by
just changing its
sequence
Nanostructured materials via
DNA-template Photopolymerization
Nanostructured materials via
DNA-template Photopolymerization
SAXS DATA SHOW ORDERING OF DNA Strands in Parallel
-SAXS data show well defined ordered peak at d=14.54nm
2D SAXS DATA
25%
-Peak position (d spacing) same at two concentrations, suggesting
that is is defined by molecular interactions. Intensity increases with
concentration due to more scattering material
-SAXS pattern show strong alignment of the structure along a
preferred orientation – this is also very interesting because it could
lead to anisotropic properties
50%
800
25%
50%
Intensity
600
400
d=14.54 nm
200
Azimuthally averaged SAXS
profile (range marked by lines in
2D diffraction pattern)
0
0.0
0.5
1.0
-1
Q (nm )
1.5
Data collected at UCSB MRL X-ray Facility
Nanostructured materials via
DNA-template Photopolymerization
DNA-template formation of intricate
supramolecular fullerene nanostructures
Photo-copolymer Gels
Fullerene-binding Columns
Novel Fullerene HPLC Columns
Gemini Surfactants
3 mm
v
intens.[a.u.]
MALDI Gemini c60
mass spec
70
{[(ZnL)2(BipyC60)]((OTf)2}+2
60
Molecular Weight 2956.36
1020.46
50
40
30
20
10
0
990
1000
1010
1020
1030
1040
1050
1060
1070
m/z
Coarse-grained Model (Materials Studio – Mesodyn)
4+
Optimization  Equilibration 
Dynamics
32 ns
64 ns
Instruments available from UCSB – UTEP PREM
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
11.
12.
Electroparamagnetic Resonance Spetroscopy (EPR)
Cryo-EM (2 nm resolution)
AFM (nano-photovoltaic probe)
Rheometer
FEI Inspect S Electron Scanning Microscope
FEI Tecnai G2 Sphera Microscope for Life Science Studies
Small Angle X-ray Scattering (SAXS)
Varian Cary Eclipse Fluorimeter
MicroMeritics TriStar Porosimeter
High Temperature Powder XRD
Inductively Coupled Plasma
Physical Properties Measurement System
 (many more)
Research Experiences for Undergraduates
• Exchange UCSB and UTEP
undergraduates for summer REU
programs (4 in each direction)
• Mentored research experiences in
PREM research groups (Summer
2012: 15 interns in UCSB PREM labs)
• UTEP students included in
RISE/CAMP internship cohort
• Participation in skills development and
career development workshops and
seminars
Network of Excellence: Steering PREM graduates
into other PREMs for graduate school
• Faculty seminar exchange
and integrate studentmeetings
• Summer REUs
UCSB-UTEP Undergraduate Colloquium
Connect UTEP and UCSB undergraduates to increase
awareness of opportunities at partner institution
• Annual end-of-summer
poster session
• Alternate between
UCSB and UTEP site
• At UTEP – in
connection with COURI
Symposium
Materials Science Ambassadors
• PREM graduate students assist
with K-12 outreach activities at
local schools – based on UTEP
program, to be launched at
UCSB
• It’s a Material World - UCSB
• Build-a-Buckyball and Solar Car
Workshops - UCSB
Outreach Programs
Materials Science
Ambassadors
• Develop Relationship with Math/Science Teachers
• Service Learning
• Nexus - Research Shadowing Program
ExciTES Summer
Institute
• Summer Camp for 6th – 10th graders
• Modular Inquiry-based, Team-based Activities
Materials Research
Outreach Program
• Grad and postdoc poster session
• Meeting and engaging industrial partners
ExciTES = Excellence in Technology, Engineering and Science
Evaluating the Impact of our Programs
Metrics of success
• REU evaluation using URSSA
instrument
• Participants continue on to graduate
school in science and engineering
• Participants enroll in graduate school at
partner site
• Undergraduates participate in
conferences and publications
• Graduate students participate in K-12
outreach
Fundamental
Molecular and
Interfacial Design for
Next Generation
Photovoltaic Systems