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Research Spending & Results

Award Detail

Awardee:UNIVERSITY OF MISSISSIPPI
Doing Business As Name:University of Mississippi
PD/PI:
  • Jared H Delcamp
  • (662) 915-7482
  • delcamp@olemiss.edu
Award Date:06/06/2015
Estimated Total Award Amount: $ 523,449
Funds Obligated to Date: $ 566,013
  • FY 2015=$523,449
  • FY 2019=$42,564
Start Date:08/01/2015
End Date:07/31/2020
Transaction Type:Grant
Agency:NSF
Awarding Agency Code:4900
Funding Agency Code:4900
CFDA Number:47.049
Primary Program Source:040100 NSF RESEARCH & RELATED ACTIVIT
Award Title or Description:SusChEM: CAREER: Near-IR Absorbing Dyes for Stable Dye-Sensitized Solar Cell Devices
Federal Award ID Number:1455167
DUNS ID:067713560
Parent DUNS ID:067713560
Program:Chem Struct,Dynmcs&Mechansms B
Program Officer:
  • Tingyu Li
  • (703) 292-4949
  • tli@nsf.gov

Awardee Location

Street:100 BARR HALL
City:UNIVERSITY
State:MS
ZIP:38677-1848
County:University
Country:US
Awardee Cong. District:01

Primary Place of Performance

Organization Name:University of Mississippi
Street:405 Coulter Hall
City:Oxford
State:MS
ZIP:38677-1848
County:University
Country:US
Cong. District:01

Abstract at Time of Award

In this CAREER project funded by the Chemical Structure, Dynamic & Mechanism B Program of the Chemistry Division, Professor Jared H. Delcamp of the Department of Chemistry at the University of Mississippi will design and synthesize novel organic materials for the conversion of solar energy to electricity. This program will focus on the rapid synthesis of organic dyes absorbing into the near-infrared solar region and converting this energy to electricity in dye-sensitized solar cell (DSC) devices. This research could lead to the more efficient harvesting of abundant solar energy and helps to reduce our reliance on non-renewable fossil fuels. As part of the funded project, an undergraduate survey course will be developed to promote awareness of active STEM research areas including solar energy research. Both undergraduate students and high school students will be encouraged to participate in original research projects focusing on the development of DSC materials, exposing them to the excitement of STEM-related research. A crucial challenge facing the DSC field is the discovery of efficient sensitizers for the conversion of light in the near-infrared (NIR) range beyond 750 nm. Ideally, these sensitizers should be readily accessible (in fewer than 10 synthetic steps), rely on sustainable organic materials and utilize strongly anchoring functionality to promote long solar cell stabilities. This project will focus on the introduction of pro-aromatic sensitizers to DSC devices. Pro-aromatic materials are known to promote low-energy absorptions from low-molecular weight building blocks by stabilizing excited-state energy levels. Additionally, multiple conjugation pathway scaffolds will be developed for precise tuning of dye energy levels through the use of multiple donors and acceptors. Multiple semiconductor anchoring structures in conjugation with the sensitizer will be employed for both strong binding to the semiconductor and to promote efficient electron injection. Rapid synthetic routes to these materials will be a focus, with C-H activation routes being strategically employed to reduce the number of synthetic steps.

Publications Produced as a Result of this Research

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Huckaba, A. J.; Yella, A.; Brogdon, P.; Murphy, J. S.; Nazeeruddin, Md. K.; Grätzel, M.; Delcamp, J. H. "A Low Recombination Rate Indolizine Sensitizer for Dye Sensitized Solar Cells" Chemical Communications, v.52, 2016, p.8424.

Cheema, H.; Watson, J.; Delcamp, J. H. "Photon Management Strategies in SSM-DSCs: Realization of a >11% PCE Device with a 2.3 V Output" Solar Energy, v.208, 2020, p.747.

Liyanage, N. P.; Cheema, H.; Baumann, A. R.; Zylstra, A. R.; Delcamp, J. H. "Effect of Donor Strength and Bulk on Thieno[3,4-b]-pyrazine-Based Panchromatic Dyes in Dye-Sensitized Solar Cells" ChemSusChem, v.10, 2017, p.2635.

Cheema, H.; Baumann, A.; Loya, E. K.; Brogdon, P.; McNamara, L. E.; Carpenter, C. A.; Hammer, N. I.; Mathew, S.; Risko, C.; Delcamp, J. H. "A NIR Absorbing Indolizine-Porphyrin Push-Pull Dye for Dye-Sensitized Solar Cells" ACS Appl. Mater. Interfaces, v.11, 2019, p.16474.

Liyanage, N.; Yella, A.; Nazerruddin, Md. K.; Grätzel, M.; Delcamp, J. H. "Desymmetrization of Thieno[3,4-b]pyrazine via C-H Activation and Applicaiton as an Electron Deficient ?-Bridge in D-A-?-A DSCs" ACS Appl. Mater. Interfaces, v.8, 2016, p.5376.

Huckaba, A. J.; Yella, A.; McNamara, L. E.; Steen, A. E.; Murphy, J. S.; Carpenter, C. A.; Puneky, G. D.; Hammer, N. I.; Nazeeruddin, M. K.; Grätzel, M.; Delcamp, J. H. "Molecular Design Principles of Near-Infrared Absorbing and Emitting Indolizine Dyes" Chemistry - A European Journal, v.22, 2016, p.15536.

Liyanage, N.; Yella, A.; Nazerruddin, Md. K.; Grätzel, M.; Delcamp, J. H. "Desymmetrization of Thieno[3,4-b]pyrazine via C-H Activation and Applicaiton as an Electron Deficient ?-Bridge in D-A-?-A DSCs" ACS Applied Materials and Interfaces, v.8, 2016, p.5376.

Brogdon, P.; Cheema, H.; Delcamp, J. H. "NIR Absorbing Metal-Free Organic, Porphyrin, and Phthalocyanine Dyes for Panchromatic DSCs" ChemSusChem, v.11, 2018, p.86.

Liyanage, N.; Yella, A.; Nazerruddin, Md. K.; Grätzel, M.; Delcamp, J. H. "Desymmetrization of Thieno[3,4-b]pyrazine via C-H Activation and Applicaiton as an Electron Deficient ?-Bridge in D-A-?-A DSCs" ACS Applied Materials and Interfaces, v.8, 2016, p.5376.

Baumann, A.; Curiac, C.; Delcamp, J. H. "Approaches to The Hagfeldt Donor and Use of Next Generation Bulky Donor Designs in Dye-Sensitized Solar Cell Dyes" ChemSusChem, v.13, 2020, p.2503.

Huckaba, A. J.; Yella, A.; Brogdon, P.; Murphy, J. S.; Nazeeruddin, Md. K.; Grätzel, M.; Delcamp, J. H. "A Low Recombination Rate Indolizine Sensitizer for Dye Sensitized Solar Cells" Chemical Communications, v.52, 2016, p.8424.

Peddapuram, A.; Cheema, H.; McNamara, L. E.; Zhang, Y.; Hammer, N. I.; Delcamp, J. H. "Quinoxaline-based Dual Donor, Dual Anchor Organic Dyes for Dye-Sensitized Solar Cells" Appl. Sci., v.8, 2018, p.1421. doi:10.3390/app8091421 

Huckaba, A. J.; Yella, A.; Brogdon, P.; Murphy, J. S.; Nazeeruddin, Md. K.; Grätzel, M.; Delcamp, J. H. "A Low Recombination Rate Indolizine Sensitizer for Dye Sensitized Solar Cells" Chem. Commun., v.52, 2016, p.8424.

Zhang, Y.; Cheema, H.; McNamara, L.; Hunt, L. A.; Hammer, N. I.; Delcamp, J. H. "Ullazine Donor-? bridge-Acceptor Organic Dyes for DSCs" Chem. Eur. J., v.24, 2018, p.5939.

Cheema, H.; Watson, J.; Peddapuram, A.; Delcamp, J. H. "A 25 mA/cm^2 Dye-Sensitized Solar Cell Based on a Near-Infrared-Absorbing Organic Dye and Application of the Device in SSM-DSCs" Chem. Commun., v.56, 2020, p.1741.

Baumann, A.; Watson, J.; Delcamp, J. H. "Robust, Scalable Synthesis of the Bulky Hagfeldt Donor for Dye‐Sensitized Solar Cells" ChemSusChem, v.13, 2020, p.283.

Liyanage, N. P.; Cheema, H.; Baumann, A. R.; Zylstra, A. R.; Delcamp, J. H. "Effect of Donor Strength and Bulk on Thieno[3,4-b]-pyrazine-Based Panchromatic Dyes in Dye-Sensitized Solar Cells" ChemSusChem, v.10, 2017, p.2635.

Peddapuram, A.; Cheema, H.; Adams, R. E.; Schmehl, R. H.; Delcamp, J. H. "A Stable Panchromatic Green Dual Acceptor, Dual Donor Organic Dye for Dye-Sensitized Solar Cells" J. Phys. Chem. C, v.121, 2017, p.8770.

Ranathunge, T. A.; Ngo, D.; Karunarathna, D.; Attanayake, N. H.; Chandrasiri, I.; Brogdon, P.; Delcamp, J. H.; Rajapakse, R. M. G.; Watkins, D. L. "Designing Hierarchical Structures of Complex Electronically Conducting Organic Polymers via One-Step Electro-Polymerization" J. Mater. Chem. C, v.8, 2020, p.5934.

Cheema, H.; Peddapuram, A.; Adams, R. E.; McNamara, L.; Hunt, L. A.; Le, N.; Watkins, D. L.; Hammer, N. I.; Schmehl, R. H.; Delcamp, J. H. "Molecular Engineering of NIR Absorbing Thienopyrazine Double Donor, Double Acceptor Organic Dyes for DSCs" The Journal of Organic Chemistry, v.82, 2017, p.12038.

Brogdon, P.; Giordano, F.; Puneky, G. A.; Dass, A.; Zakeeruddin, S. M.; Zazeeruddin, Md. K.; Grätzel, M.; Tschumper, G.; Delcamp, J. H. "A Computational and Experimental Study of Thieno[3,4-b]thiophene as a Proaromatic ?-Bridge in DSCs" Chemistry - A European Journal, v.22, 2016, p.694.

Cheema, H.; Baumann, A.; Loya, E. K.; Brogdon, P.; McNamara, L. E.; Carpenter, C. A.; Hammer, N. I.; Mathew, S.; Risko, C.; Delcamp, J. H. "Near-Infrared-Absorbing Indolizine-Porphyrin Push?Pull Dye for Dye-Sensitized Solar Cells" ACS Appl. Mater. Interfaces, v.11, 2019, p.16474. doi:10.1021/acsami.8b21414 

Brogdon, P.; Giordano, F.; Puneky, G. A.; Dass, A.; Zakeeruddin, S. M.; Zazeeruddin, Md. K.; Grätzel, M.; Tschumper, G.; Delcamp, J. H. "A Computational and Experimental Study of Thieno[3,4-b]thiophene as a Proaromatic ?-Bridge in DSCs" Chem. Eur. J., v.22, 2016, p.694.

Peddapuram, A.; Cheema, H.; Adams, R. E.; Schmehl, R. H.; Delcamp, J. H. "A Stable Panchromatic Green Dual Acceptor, Dual Donor Organic Dye for Dye-Sensitized Solar Cells" The Journal of Physical Chemistry C, v.121, 2017, p.8770.

Zhang, Y.; Cheema, H.; London, A. E.; Morales, A.; Azoulay, J. D.; Delcamp, J. H. "Panchromatic Cross-Conjugated ?-Bridge NIR Dyes for DSCs" Phys. Chem. Chem. Phys., v.20, 2018, p.2438.

Brogdon, P.; Giordano, F.; Puneky, G. A.; Dass, A.; Zakeeruddin, S. M.; Zazeeruddin, Md. K.; Grätzel, M.; Tschumper, G.; Delcamp, J. H. "A Computational and Experimental Study of Thieno[3,4-b]thiophene as a Proaromatic ?-Bridge in DSCs" Chemistry - A European Journal, v.22, 2016, p.694.

Brogdon, P.; Cheema, H.; Delcamp, J. H. "Low-Recombination Thieno[3,4-b]thiophene-based Photosensitzers for DSCs" ChemSusChem, v.10, 2017, p.3624.

Huckaba, A. J.; Yella, A.; McNamara, L. E.; Steen, A. E.; Murphy, J. S.; Carpenter, C. A.; Puneky, G. D.; Hammer, N. I.; Nazeeruddin, M. K.; Grätzel, M.; Delcamp, J. H. "Molecular Design Principles of Near-Infrared Absorbing and Emitting Indolizine Dyes" Chem. Eur. J., v.22, 2016, p.15536.


Project Outcomes Report

Disclaimer

This Project Outcomes Report for the General Public is displayed verbatim as submitted by the Principal Investigator (PI) for this award. Any opinions, findings, and conclusions or recommendations expressed in this Report are those of the PI and do not necessarily reflect the views of the National Science Foundation; NSF has not approved or endorsed its content.

 

            Through this project a better understanding of low energy light absorbing organic dye designs has been found as a key intellectual merit. Multiple new concepts and structures were probed during this project. Dyes designed with specific architectural elements were found to have uniquely stabilized features after light absorption that enable the use of low energy light for processes such as charge separation across two different materials. The use of these dyes in solar cell devices has led to efficiencies of >10% solar-to-electric conversion using readily available, abundant materials. Theses dyes have shown world record dye-sensitized solar cell device photocurrent outputs with organic dyes at 25 mA/cm2 which is dramatically higher than the prior reports of <20 mA/cm2. This addresses a critical need within dye-sensitized light absorption fields since these technologies have been limited in only utilizing higher energy light in the visible region. With the invention of these dyes, substantially lower energy light than previously known is capable of being turned into electricity rather than being wasted. These dyes were also used in a record setting solar-to-fuel device that does not use any precious metals and is capable of directly making hydrogen from water and sunlight.

            Within the solar cell devices tested for this project, traditional designs have used a single dye anchoring point to the surface of the solar cell devices which are in a liquid environment. This single point anchoring systems has been widely suggested to be a weak point in terms of solar cell stability with this technology. If the dye detaches from the surface it would be ineffective in the liquid layer. Within this project a new dual anchor dye design approach has been but forward that shows exceptionally long-lasting dye-sensitized solar cell devices that pass a stress-test which is typically equated to 10 years of ambient environmental exposure with a less than 10% loss in performance over this time frame. This is an important finding for the furthering of the dye-sensitized solar cell field toward practical applications.

            Additionally, dyes in these systems work by moving electrons from one region of the molecule to another. A classic limitation to this approach is the region where the electrons begin at limits how easily the charge can be moved and often requires higher energy light to move charge than is desirable for many applications. Within in this project, a novel strategy was put forward that allows electrons to originate from multiple areas but transfer to the same region as if they had originated at a single area. This type of molecular funneling of electrons is preliminarily shown to be very encouraging and allowed surpassing of the limitations of systems with single regions of electron origin. This strategy was shown to work well in initial DSC devices and has led to dramatic performance enhancements over the classic benchmark systems.

            Concerning broader impacts, dye sensitized interfacial systems are at the interface of computational, physical spectroscopic, molecular synthetic, synthetic methods, surface, and materials chemistries. Additionally, optical physics and engineering widely explore dye-sensitized interfaces as well and will benefit from the knowledge gained under this project. Increased fundamental understanding of dye-sensitized solar cell device components in any one area impacts all remaining areas. One of the largest cross-discipline impacts from this project is in synthetic methods chemistry which is being directly expanded through studies on synthetic paths to previously inaccessible dye structures. Physical spectroscopic chemistry has also been directly affected by collaborative efforts to determine how long the dyes using the designs mentioned above exist in photoexcited states. Spectroscopic areas were also impacted in showing how these designs can allow for efficient, long-lived charge transfer across interfaces.

            Society in general benefits from a further developing of specialized skilled workers with good perspectives on future research directions in science and technology areas. Additionally, numerous students were employed and funded to continue their training and work during this project, which aids the US job market in maintaining lower unemployment rates. Boosting the education level of participants on this project also leads to general societal improvement by the introduction of members with enhanced problem-solving skill sets. Additionally, the fundamental research pursued on this award is influential toward a number of fields outside the primary (solar cell) field including: telecommunications, photoelectrochemical cells, secure displays, photosensors, night vision, and chemical methodology.

 

 


Last Modified: 09/09/2020
Modified by: Jared H Delcamp

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