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Thermodynamics, Entropy, Information and the Efficiency of Solar Cells


For well over 50 years, the limits to photovoltaic energy conversion have been known and codified, and have played a vital role in the push for technological breakthroughs to reach - and even attempt to surpass - those limits. This limit, known as the Shockley-Queisser detailed-balance limit, was found by using only the most basic of thermodynamic assumptions, and therefore provides an upper bound that is difficult to contest without violating the laws of thermodynamics. Many different schemes have been devised to improve a solar cell's efficiency beyond this limit, with various benefits and drawbacks for each method.

Since the field of solar cell research has been analyzed and dissected for so long by a large variety of researchers, it is quite hard to say or discover anything new without repeating the work of the past. The approach taken in this work is to analyze solar cells from the joint perspective of thermodynamics and information theory. These two subjects have recently been appreciated to be highly interrelated, and using the formalism of Missing Information, we can differentiate between different novel technologies, as well as devise new limits for new and existing methodologies.

In this dissertation, the fundamentals of photovoltaic conversion are analyzed from the most basic of principles, emphasizing the thermodynamic parameters of the photovoltaic process. In particular, an emphasis is made on the voltage of the device, as opposed to the current. This emphasis is made since there is a direct relation between the open-circuit voltage of a solar cell and the fundamental equations of thermodynamics and the Free Energy of the system. Moreover, this relation extends to the entropy of the system, which subsequently relates to the field of Information Theory. By focusing on the voltage instead of the current, realizations are made that are not obvious to the majority or researchers in the field, and in particular to efforts of surpassing the Shockley-Queisser limit, known as "3rd generation" concepts.

After analyzing the standard single-junction cell, other forms of surpassing the detailed-balance limit are presented and discussed, from the viewpoint of entropy and its relation to the amount of information lost or produced in the photovoltaic conversion process. In addition to the well-known 3rd generation methods: up- and down-conversion, carrier multiplication and intermediate band solar cells, other ideas are discussed such as using Feedback to shift the optimal bandgap of the cell, and the use of spectral splitting to completely utilize the solar spectrum. The focus on entropy (and the open-circuit voltage) as the primary variable of interest uncovers new limitations to these processes, and denotes preferences of certain technologies over others.

Using this parallel approach provides insights into the field that were either neglected or not realized. This work thus provides a new set of guidelines for searching for and analyzing innovative techniques to maximize the power conversion efficiency from solar cells.

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