From steam engine to solar cells: can thermodynamics guide the development of future generations of photovoltaics?

Thermodynamics has played a singular role in the development of virtually all energy technologies to-date. This review argues that it also has a role to play in the understanding and design of solar cell operation, particularly looking toward the future, high-efficiency solar cells. After a historical overview of the key developments in the ‘thermodynamics of light,’ the conversion of a monochromatic light beam is used as a starting point to analyze the conversion process, examine the fundamental losses in terms of irreversible entropy generation, and consider in detail one of the key applications: the Shockley–Queisser detailed balance. We review and compare the principal suggestions for the highest theoretical efficiency of solar energy conversion, and analyze one possible embodiment of such a third-generation structure: the hot-carrier solar cell. A somewhat different application of the statistical approach—light trapping—is reviewed at a fundamental level, and the future potential is considered for devices which combine such a ‘thermodynamic squeezing’ of light with latest developments in photonics, leading to a photonic bandgap solar cell. We argue that the widespread use of thermodynamic tools in the current photovoltaics research, especially when combined with the potential benefits to future devices, already indicates that our thinking should not be about if but how thermodynamics can guide us to make better solar cells. © 2016 The Authors. WIREs Energy and Environment published by John Wiley &