NREL & Colorado School of Mines Researchers Capture Excess Photon Energy to Produce Solar Fuels



Photo shows a lead sulfide quantum dot solar cell. A lead sulfide quantum dot solar cell developed by researchers at NREL. Photo by Dennis Schroeder.




Scientists at the U.S. Department of Energy’s National Renewable Energy Laboratory (NREL) have developed a proof-of-principle photoelectrochemical cell capable of capturing excess photon energy normally lost to generating heat.


Using quantum dots (QD) and a process called Multiple Exciton Generation (MEG), the NREL researchers
were able to push the peak external quantum efficiency for hydrogen generation to 114 percent.


The advancement could significantly boost the production of hydrogen from sunlight by using the cell to split water at a higher efficiency and lower cost than current photoelectrochemical approaches.

Details of the research are outlined in the Nature Energy paper Multiple exciton generation for photoelectrochemical hydrogen evolution reactions with quantum yields exceeding 100%, co-authored by Matthew Beard, Yong Yan, Ryan Crisp, Jing Gu, Boris Chernomordik, Gregory Pach, Ashley Marshall, and John Turner.

All are from NREL; Crisp also is affiliated with the Colorado School of Mines, and Pach and Marshall are affiliated with the University of Colorado, Boulder.




Beard and other NREL scientists in 2011 published a paper in Science that showed for the first time how MEG allowed a solar cell to exceed 100 percent quantum efficiency by producing more electrons in the electrical current than the amount of photons entering the solar cell.




“The major difference here is that we captured that MEG enhancement in a chemical bond rather than just in the electrical current,” Beard said.

“We demonstrated that the same process that produces extra current in a solar cell can also be applied to produce extra chemical reactions or stored energy in chemical bonds.”

The maximum theoretical efficiency of a solar cell is limited by how much photon energy can be converted into usable electrical energy, with photon energy in excess of the semiconductor absorption bandedge lost to heat.

The MEG process takes advantages of the additional photon energy to generate more electrons and thus additional chemical or electrical potential, rather than generating heat. QDs, which are spherical semiconductor nanocrystals (2-10 nm in diameter), enhance the MEG process.




In current report, the multiple electrons, or charge carriers, that are generated through the MEG process within the QDs are captured and stored within the chemical bonds of a H2 molecule.

NREL researchers devised a cell based upon a lead sulfide (PbS) QD photoanode. The photoanode involves a layer of PbS quantum dots deposited on top of a titanium dioxide/fluorine-doped tin oxide dielectric stack.

The chemical reaction driven by the extra electrons demonstrated a new direction in exploring high-efficiency approaches for solar fuels.

Funds for the research came from the Department of Energy’s Office of Science.

NREL is the U.S. Department of Energy’s primary national laboratory for renewable energy and energy efficiency research and development. NREL is operated for the Energy Department by The Alliance for Sustainable Energy, LLC.

NREL: Nanoscale confinement leads to new all-inorganic perovskite with exceptional solar cell properties – Using Quantum Dots to Create Increased Solar Cell Efficiency: Colorado School of Mines


confinement-for-qdots-100816-nanoscaleconAshley Marshall, Erin Sanehira and Joey Luther with solutions of all-inorganic perovskite quantum dots, showing intense photoluminescence when illuminated with UV light. Credit: National Renewable Energy Laboratory

Scientists with the Energy Department’s National Renewable Energy Laboratory (NREL) for the first time discovered how to make perovskite solar cells out of quantum dots and used the new material to convert sunlight to electricity with 10.77 percent efficiency.

The research, Quantum dot-induced phase stabilization of a-CsPbI3 perovskite for high-efficiency photovoltaics, appears in the journal Science. The authors are Abhishek Swarnkar, Ashley Marshall, Erin Sanehira, Boris Chernomordik, David Moore, Jeffrey Christians, and Joseph Luther from NREL. Tamoghna Chakrabarti from the Colorado School of Mines also is a co-author.co-school-of-mines-222925_original

In addition to developing quantum dot , the researchers discovered a method to stabilize a crystal structure in an all-inorganic perovskite material at room temperature that was previously only favorable at high temperatures. The crystal phase of the inorganic material is more stable in .

Most research into perovskites has centered on a hybrid organic-inorganic structure. Since research into perovskites for photovoltaics began in 2009, their efficiency of converting sunlight into electricity has climbed steadily and now shows greater than 22 percent power conversion efficiency. However, the organic component hasn’t been durable enough for the long-term use of perovskites as a solar cell.

NREL scientists turned to quantum dots-which are essentially nanocrystals-of cesium lead iodide (CsPbI3) to remove the unstable and open the door to high-efficiency quantum dot optoelectronics that can be used in LED lights and photovoltaics. NREL 20140609_buildings_26954_hp

The nanocrystals of CsPbI3 were synthesized through the addition of a Cs-oleate solution to a flask containing PbI2 precursor. The NREL researchers purified the nanocrystals using methyl acetate as an anti-solvent that removed excess unreacted precursors. This step turned out to be critical to increasing their stability.

Contrary to the bulk version of CsPbI3, the nanocrystals were found to be stable not only at temperatures exceeding 600 degrees Fahrenheit but also at room temperatures and at hundreds of degrees below zero. The bulk version of this material is unstable at , where photovoltaics normally operate and convert very quickly to an undesired crystal structure.

NREL scientists were able to transform the nanocrystals into a thin film by repeatedly dipping them into a methyl acetate solution, yielding a thickness between 100 and 400 nanometers. Used in a solar cell, the CsPbI3 nanocrystal film proved efficient at converting 10.77 percent of sunlight into electricity at an extraordinary high open circuit voltage. The efficiency is similar to record quantum dot solar cells of other materials and surpasses other reported all-inorganic perovskite solar cells.

Explore further: Rubidium pushes perovskite solar cells to 21.6 percent efficiency

More information: A. Swarnkar et al. Quantum dot-induced phase stabilization of -CsPbI3 perovskite for high-efficiency photovoltaics, Science (2016). DOI: 10.1126/science.aag2700