Quantum confinement of electronic particles (negative electrons and positive holes) in nanocrystals produces unique optical and electronic properties that have the potential to enhance the power ...conversion efficiency of solar cells for photovoltaic and solar fuels production at lower cost. These approaches and applications are labeled third generation solar photon conversion. Prominent among these unique properties is the efficient formation of more than one electron−hole pair (called excitons in nanocrystals) from a single absorbed photon. In isolated nanocrystals that have three-dimensional confinement of charge carriers (quantum dots) or two-dimensional confinement (quantum wires and rods) this process is termed multiple exciton generation. This Perspective presents a summary of our present understanding of the science of optoelectronic properties of nanocrystals and a prognosis for and review of the technological status of nanocrystals and nanostructures for third generation photovoltaic cells and solar fuels production.
Certain organic materials can generate more than one electron-hole pair per absorbed photon, a property that could revolutionize the prospects for solar energy. This process, called singlet fission, ...is one possible “exciton multiplication” scheme that could be useful in a variety of photovoltaic device designs from dye-sensitized solar cells to solar cell bilayers to bulk heterojunctions. For such applications to be possible, however, singlet fission must occur with near perfect efficiency in compounds that also have other requisite properties such as strong visible light absorption and photostability. Many recent investigations of singlet fission have focused on crystalline polyacenes, which have been known for some time to undergo singlet fission. While these materials have promise, limitations in stability, cost, and performance may hinder practical application of polyacene solar cells, while their complex photophysics may limit our fundamental understanding of singlet fission in crystalline polyacenes. In this Account, we describe rationally designed singlet fission chromophores whose excited state dynamics should be fairly simple and whose coupling can be well controlled through the formation of covalent dimers, aggregates, or polycrystalline films. In principle, investigations of these chromophores should provide the clearest connection to theoretical concepts explaining how an excited state evolves from a singlet (S1) into two triplets (TT). Realizing the promise of efficient singlet fission rests with two tasks: (i) producing an ideal molecular energy level structure and (ii) inducing the correct type and strength of chromophore coupling. In this Account, we offer theoretical guidance for achieving (i) and consider more extensively recent results aimed at (ii). For (i), theoretical guidance suggests that, in addition to alternant hydrocarbons like tetracene and pentacene, biradicals (i.e., molecules with two independent radical centers) may also be used as the basis for designing chromophores with low-lying triplet states such that the energy relationship 2E(T1) ≤ E(S1) is satisfied. Although molecules that do not fulfill this condition can also exhibit singlet fission from a higher lying or vibrationally excited singlet state, fast relaxation processes will likely reduce the singlet fission yield and complicate determination of the singlet fission mechanism. For (ii), once an appropriate chromophore has been chosen, the task of coupling two or more of them together must be done carefully. We discuss three pathways by which a dimer could undergo singlet fission: (1) A direct route in which slipped cofacial stacking is favorable under certain conditions. Cofacial stacking is common in molecular crystals, and it is likely not a coincidence that recent reports of efficient singlet fission involve slipped-stacked molecules in polycrystalline thin films. (2) A mediated route in which S1 interacts with (TT) through a virtual radical cation/anion state, which may be important in some situations. (3) A two-step route (i.e., through a real charge transfer intermediate) which others have suggested theoretically. We present data on 1,3-diphenylisobenzofuran (DPIBF) dimers that are consistent with this pathway. Finally, we review potential solar photoconversion efficiency gains utilizing singlet fission in several contexts.
Improving the primary photoconversion process in a photovoltaiccell by utilizing the excess energy that is otherwise lost as heat can lead to an increase in the overall power conversion efficiency ...(PCE). Semiconductor nanocrystals (NCs) with at least one dimension small enough to produce quantum confinement effects provide new ways of controlling energy flow not achievable in thin film or bulk semiconductors. Researchers have developed various strategies to incorporate these novel structures into suitable solar conversion systems. Some of these methods could increase the PCE past the Shockley–Queisser (SQ) limit of ∼33%, making them viable “third generation photovoltaic” (TGPV) cell architectures. Surpassing the SQ limit for single junction solar cells presents both a scientific and a technological challenge, and the use of semiconductor NCs to enhance the primary photoconversion process offers a promising potential solution. The NCs are synthesized via solution phase chemical reactions prod-ucing stable colloidal solutions, where the reaction conditions can be modified to produce a variety of shapes, compositions, and structures. The confinement of the semiconductor NC in one dimension produces quantum films, wells, or discs. Two-dimensional confinement leads to quantum wires or rods (QRs), and quantum dots (QDs) are three-dimensionally confined NCs. The process of multiple exciton generation (MEG) converts a high-energy photon into multiple electron–hole pairs. Although many studies have demonstrated that MEG is enhanced in QDs compared with bulk semiconductors, these studies have either used ultrafast spectroscopy to measure the photon-to-exciton quantum yields (QYs) or theoretical calculations. Implementing MEG in a working solar cell has been an ongoing challenge. In this Account, we discuss the status of MEG research and strategies towards implementing MEG in working solar cells. Recently we showed an external quantum efficiency for photocurrent of greater than 100% (reaching 114%) at ∼4E g in a PbSe QD solar cell. The internal quantum efficiency reached 130%. These results compare favorably with ultrafast transient spectroscopic measurements. Thus, we have shown that one of the tenets of the SQ limit, that photons only produce one electron–hole pair at the electrodes of a solar cell, can be overcome. Further challenges include increasing the MEG efficiency and improving the QD device structure and operation.
Direct observation of triplet absorption and ground-state depletion upon pulsed excitation of a polycrystalline thin solid film of 1,3-diphenylisobenzofuran at 77 K revealed a 200 ± 30% triplet ...yield, which was attributed to singlet fission.
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.
The efficient and cost-effective direct conversion of solar photons into solar electricity and solar fuels is one of the most important scientific and technological challenges of this century. It is ...estimated that at least 20 terawatts of carbon-free energy (1 and 1/2 times the total amount of all forms of energy consumed today globally), in the form of electricity and liquid and gaseous fuels, will be required by 2050 in order to avoid the most serious consequences of global climate change and to ensure adequate global energy supply that will avoid economic chaos. But in order for solar energy to contribute a major fraction of future carbon-free energy supplies, it must be priced competitively with, or perhaps even be less costly than, energy from fossil fuels and nuclear power as well as other renewable energy resources. The challenge of delivering very low-cost solar fuels and electricity will require groundbreaking advances in both fundamental and applied science. This Thematic Issue on Solar Photon Conversion will provide a review by leading researchers on the present status and prognosis of the science and technology of direct solar photoconversion to electricity and fuels. The topics covered include advanced and novel concepts for low-cost photovoltaic (PV) energy based on chemistry (dye-sensitized photoelectrodes, organic and molecular PV, multiple exciton generation in quantum dots, singlet fission), solar water splitting, redox catalysis for water oxidation and reduction, the role of nanoscience and nanocrystals in solar photoconversion, photoelectrochemical energy conversion, and photoinduced electron transfer. The direct conversion of solar photons to electricity via photovoltaic (PV) cells is a vital present-day commercial industry, with PV module production growing at about 75%/year over the past 3 years. However, the total installed yearly averaged energy capacity at the end of 2009 was about 7 GW-year (0.2% of global electricity usage). Thus, there is potential for the PV industry to grow enormously in the future (by factors of 100-300) in order for it to provide a significant fraction of total global electricity needs (currently about 3.5 TW). Such growth will be greatly facilitated by, and probably even require, major advances in the conversion efficiency and cost reduction for PV cells and modules; such advances will depend upon advances in PV science and technology, and these approaches are discussed in this Thematic Issue. Industrial and domestic electricity utilization accounts for only about 30% of the total energy consumed globally. Most ({approx}70%) of our energy consumption is in the form of liquid and gaseous fuels. Presently, solar-derived fuels are produced from biomass (labeled as biofuels) and are generated through biological photosynthesis. The global production of liquid biofuels in 2009 was about 1.6 million barrels/day, equivalent to a yearly output of about 2.5 EJ (about 1.3% of global liquid fuel utilization). The direct conversion of solar photons to fuels produces high-energy chemical products that are labeled as solar fuels; these can be produced through nonbiological approaches, generally called artificial photosynthesis. The feedstocks for artificial photosynthesis are H{sub 2}O and CO{sub 2}, either reacting as coupled oxidation-reduction reactions, as in biological photosynthesis, or by first splitting H{sub 2}O into H{sub 2} and O{sub 2} and then reacting the solar H{sub 2} with CO{sub 2} (or CO produced from CO2) in a second step to produce fuels through various well-known chemical routes involving syngas, water gas shift, and alcohol synthesis; in some applications, the generated solar H{sub 2} itself can be used as an excellent gaseous fuel, for example, in fuel cells. But at the present time, there is no solar fuels industry. Much research and development are required to create a solar fuels industry, and this Thematic Issue presents several reviews on the relevant solar fuels science and technology. The first three manuscripts relate to the daunting problem of producing solar fuels. Lewis and colleagues present a comprehensive review of solar water splitting based on semiconductor electrodes. The semiconductor electrodes are either in direct contact with an aqueous electrolyte, creating a semiconductor-liquid junction, in which case this defines a true photoelectrochemical (PEC) configuration, or the semiconductors can form buried p-n junctions connected to metal anodes and/or cathodes, in which case various combination of PV and PEC cell configurations are possible. The issues of cell energetics, cell efficiency, photocorrosion, and electrocatalysis are discussed in detail. Nocera et al. first discuss the global energy problem and review the issues and technologies for solar energy storage. Then they focus on solar fuels as the best option for solar energy storage at sufficient scale to solve the looming energy crisis.
Band edge positions of semiconductors determine their functionality in many optoelectronic applications such as photovoltaics, photoelectrochemical cells and light emitting diodes. Here we show that ...band edge positions of lead sulfide (PbS) colloidal semiconductor nanocrystals, specifically quantum dots (QDs), can be tuned over 2.0 eV through surface chemistry modification. We achieved this remarkable control through the development of simple, robust and scalable solution-phase ligand exchange methods, which completely replace native ligands with functionalized cinnamate ligands, allowing for well-defined, highly tunable chemical systems. By combining experiments and ab initio simulations, we establish clear relationships between QD surface chemistry and the band edge positions of ligand/QD hybrid systems. We find that in addition to ligand dipole, inter-QD ligand shell inter-digitization contributes to the band edge shifts. We expect that our established relationships and principles can help guide future optimization of functional organic/inorganic hybrid nanostructures for diverse optoelectronic applications.
Photoexcitation of a semiconductor with photons above the semiconductor band gap creates electrons and holes that are out of equilibrium. The rates at which the photogenerated charge carriers return ...to equilibrium via thermalization through carrier scattering, cooling by phonon emission, and radiative and nonradiative recombination are important issues. The relaxation processes can be greatly affected by quantization effects that arise when the carriers are confined to regions of space that are small compared with their deBroglie wavelength or the Bohr radius of bulk excitons. The effects of size quantization in semiconductor quantum wells (carrier confinement in one dimension) and quantum dots (carrier confinement in three dimensions) on the respective carrier relaxation processes are reviewed, with emphasis on electron cooling dynamics. The implications of these effects for applications involving radiant energy conversion are also discussed.
In this book, expert authors describe advanced solar photon conversion approaches that promise highly efficient photovoltaic and photoelectrochemical cells with sophisticated architectures on the one ...hand, and plastic photovoltaic coatings that are inexpensive enough to be disposable on the other. Their leitmotifs include light-induced exciton generation, junction architectures that lead to efficient exciton dissociation, and charge collection by percolation through mesoscale phases. Photocatalysis is closely related to photoelectrochemistry, and the fundamentals of both disciplines are covered in this volume.
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