Researchers from the U.S. Department of Energy’s National Renewable Energy Laboratory (NREL) have reported the first solar cell that produces a photocurrent that has an external quantum efficiency greater than 100 percent when photoexcited with photons from the high energy region of the solar spectrum. The fabrication of the high efficiency Quantum Dot Solar Cells is also amenable to inexpensive, high-throughput roll-to-roll manufacturing, which would potentially make them very affordable.
The external quantum efficiency for photocurrent, usually expressed as a percentage, is the number of electrons flowing per second in the external circuit of a solar cell divided by the number of photons per second of a specific energy (or wavelength) that enter the solar cell. None of the solar cells to date exhibit external photocurrent quantum efficiencies above 100 percent at any wavelength in the solar spectrum.
The external quantum efficiency reached a peak value of 114 percent. The newly reported work marks a promising step toward developing Next Generation Solar Cells for both solar electricity and solar fuels that will be competitive with, or perhaps less costly than, energy from fossil or nuclear fuels.
The mechanism for producing a quantum efficiency above 100 percent with solar photons is based on a process called Multiple Exciton Generation (MEG), whereby a single absorbed photon of appropriately high energy can produce more than one electron-hole pair per absorbed photon.
NREL scientist Arthur J. Nozik first predicted in a 2001 publication that MEG would be more efficient in semiconductor quantum dots than in bulk semiconductors. Quantum dots are tiny crystals of semiconductor, with sizes in the nanometer (nm) range of 1-20 nm, where 1 nm equals one-billionth of a meter. At this small size, semiconductors exhibit dramatic effects because of quantum physics, such as:
• rapidly increasing bandgap with decreasing quantum dot size,
• formation of correlated electron-hole pairs (called excitons) at room temperature,
• enhanced coupling of electronic particles (electrons and positive holes) through Coulombic forces,
• and enhancement of the MEG process.
Quantum dots confine the charges and harvest excess energy
Quantum dots, by confining charge carriers within their tiny volumes, can harvest excess energy that otherwise would be lost as heat – and therefore greatly increase the efficiency of converting photons into usable free energy.
The researchers achieved the 114 percent external quantum efficiency with a layered cell consisting of antireflection-coated glass with a thin layer of a transparent conductor, a nanostructured zinc oxide layer, a quantum dot layer of lead selenide treated with ethanedithol and hydrazine, and a thin layer of gold for the top electrode.
In a 2006 publication, NREL scientists Mark Hanna and Arthur J. Nozik showed that ideal MEG in solar cells based on quantum dots could increase the theoretical thermodynamic power conversion efficiency of solar cells by about 35 percent relative to today’s conventional solar cells. Furthermore, the fabrication of Quantum Dot Solar Cells is also amenable to inexpensive, high-throughput roll-to-roll manufacturing.
The new results published in Science by the NREL research team is the first report of MEG manifested as an external photocurrent quantum yield greater than 100 percent measured in operating quantum dot solar cells at low light intensity; these cells showed significant power conversion efficiencies (defined as the total power generated divided by the input power) as high as 4.5 percent with simulated sunlight. While these solar cells are un-optimized and thus exhibit relatively low power conversion efficiency (which is a product of the photocurrent and photovoltage), the demonstration of MEG in the photocurrent of a solar cell has important implications because it opens new and unexplored approaches to improve solar cell efficiencies.
Multiple exciton generation (MEG) is a process that can occur in semiconductor nanocrystals, or quantum dots (QDs), whereby absorption of a photon bearing at least twice the bandgap energy produces two or more electron-hole pairs. Here, we report on photocurrent enhancement arising from MEG in lead selenide (PbSe) QD-based solar cells, as manifested by an external quantum efficiency (the spectrally resolved ratio of collected charge carriers to incident photons) that peaked at 114 ± 1% in the best device measured. The associated internal quantum efficiency (corrected for reflection and absorption losses) was 130%. We compare our results with transient absorption measurements of MEG in isolated PbSe QDs and find reasonable agreement. Our findings demonstrate that MEG charge carriers can be collected in suitably designed QD solar cells, providing ample incentive to better understand MEG within isolated and coupled QDs as a research path to enhancing the efficiency of solar light harvesting technologies.