When I entered the solar technology space in 2008 I did the usual background learning. Pretty quickly I discovered a problem with the standard model for how solar cells work.
The standard textbook explanation of a solar cell describes sunlight exciting electrons across a semiconductor band gap. These excited carriers are then separated by a built-in electric field at the p–n junction, which supposedly drives a continuous direct current through an external circuit.
This model is thermodynamically flawed. It implies that a static electric field can perform continuous work in a closed circuit without any heat rejection. This amounts to a violation of the second law of thermodynamics. In effect, the standard model describes a perpetual motion machine of the second kind. It lacks a proper accounting of energy flow, entropy production, and thermodynamic cycling.
Basically the standard model has been good enough, up to now. And since it’s a field of hybrid scientists and engineers (neither fowl nor chook) that stop thinking and starting fiddling as soon as they can, almost no one seems to have spotted their problem.
What the Classical Thermodynamic Model Adds
There is an alternative classical thermodynamic model proposed by Alicki, Jenkins, and colleagues that addresses this issue. It reinterprets the solar cell as a thermodynamic heat engine. In this view:
The solar photons constitute a hot thermal reservoir
The semiconductor lattice provides a cold bath
The electron gas acts as the working substance
The interface between the p-type and n-type regions serves as a self-oscillating piston
This model, really just a hypothesis, restores consistency with the laws of thermodynamics. It introduces a cyclic process that modulates photon absorption and drives net electrical work. The timing of heat input relative to the piston motion follows the Rayleigh–Eddington criterion. The model also recovers realistic efficiency limits, such as the Shockley–Queisser bound, using classical Carnot-style reasoning.
What this Classical Thermodynamic Model Cannot Resolve
While this reinterpretation corrects the logical structure of the standard model, it remains incomplete in several ways:
It is not derived from microscopic quantum principles.
It does not include carrier statistics, band structure, or quantized energy levels.
It cannot predict device characteristics such as current–voltage curves or quantum efficiency.
The proposed oscillating piston mechanism remains a theoretical concept without direct experimental confirmation.
It does not address quantum effects that are important in nanoscale and high-efficiency solar cell designs.
Why I think a Quantum Thermodynamic Model Is Necessary
A full understanding of solar cell operation requires a framework that combines thermodynamics with quantum mechanics. A quantum thermodynamic model does this by:
Representing the solar cell as an open quantum system in contact with thermal reservoirs.
Using time-dependent Hamiltonians and master equations to track work, heat, and entropy at the microscopic level.
Supporting accurate modeling of recombination, coherence, hot-carrier behavior, and energy transfer dynamics.
A complete and predictive theory of solar energy conversion must be built on a quantum thermodynamic foundation.
Or we could just reframe the standard solar cell model in a thermodynamically consistent way.
How to Restate the Standard Solar Cell Model Without Violating Thermodynamics
The standard textbook model of solar cells often describes light creating electron-hole pairs, which are then separated by a built-in electric field. This field is said to drive a direct current through an external circuit.
Taken literally, this violates the second law of thermodynamics because it suggests that a static electrostatic field can perform continuous work in a closed loop without any heat rejection or entropy production.
However, the model can be restated in a thermodynamically consistent way with the following adjustments:
1. Energy source
The energy comes from a continuous flux of solar photons. These photons act as a high-temperature heat source, exciting electrons from the valence to the conduction band.
2. Carrier separation
The built-in electric field does not supply energy. It helps guide photo-excited carriers to opposite contacts, reducing recombination but not performing net work. The true driving force for sustained current is the non-equilibrium carrier distribution maintained by ongoing photon absorption.
3. Work extraction
Electrical work is extracted when carriers move through the external circuit from a region of high chemical potential to low. This potential difference corresponds to the separation of quasi-Fermi levels under illumination.
4. Thermodynamic cycle
Although not explicit in the standard model, a thermodynamic cycle exists. Each absorbed photon initiates a cycle that includes excitation, thermalization, carrier separation, recombination, and heat rejection.
5. Entropy and heat rejection
Excess photon energy is released as heat to the lattice, and recombination (especially radiative) returns some energy to the environment. These processes ensure compliance with the second law by exporting entropy.
The standard model becomes thermodynamically valid when reframed as a non-equilibrium steady-state system. Energy input comes from photons, work is extracted through quasi-Fermi level gradients, and entropy is rejected via phonons and emitted photons. The built-in field is not a power source, but a structural feature that aids charge separation. This restatement aligns the model with fundamental thermodynamic principles.
The practical implications of restating the solar cell model in a thermodynamically consistent way include the following:
1. Improved conceptual clarity for design
Engineers and physicists can more accurately identify where useful energy is extracted and where losses occur. This supports better targeting of efficiency improvements, especially in managing recombination and thermalization losses.
2. Correct energy accounting in simulations
Device models that include non-equilibrium carrier populations, quasi-Fermi level separation, and entropy export can more accurately reflect real-world performance. This enables predictive modeling for next-generation solar cells.
3. Foundation for novel architectures
Understanding that solar cells function as heat engines allows exploration of new designs that explicitly include internal dynamic elements or structured baths. For example, hot-carrier solar cells or thermophotovoltaic systems can be optimized with this framework.
4. Thermodynamic benchmarking
Using a consistent model allows real devices to be compared to fundamental limits like Carnot efficiency or entropy generation per photon, helping to evaluate practical trade-offs between efficiency and complexity.
5. Educational value
Teaching photovoltaic physics from a thermodynamically correct standpoint avoids misleading concepts, such as the notion that a static electric field powers current. This supports clearer understanding among students and professionals.
6. Relevance to quantum and nanoscale devices
As devices shrink and quantum effects become non-negligible, the consistent treatment of work, heat, and entropy becomes essential. This thermodynamic framing integrates more easily with quantum thermodynamic models used for nanoscale energy systems.
Summary
And that’s my last thought on solar, ever. I’ll leave it to others to sort out the details, either the restated standard model or the quantum thermodynamic model (the former is a limit of the latter), because they’ll have to if they want to drive cell efficiencies up beyond 30% for low-cost dual junction devices. Mark my words.