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can thermodynamics guide the

development of future generations

of photovoltaics?

Tom Markvart*

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 devel-

opments 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 efﬁ-

ciency 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 funda-

mental level, and the future potential is considered for devices which combine

such a ‘thermodynamic squeezing’ of light with latest developments in photon-

ics, 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 &

Sons, Ltd.

WIREs Energy Environ 2016, 5:543–569. doi: 10.1002/wene.204

called upon to furnish the theoretical tools needed to

their roots in thermodynamics. With origins

dating back to the peak of the industrial revolution,

support even one of the most recent forms of energy

conversion: photovoltaics.

An early mention of thermodynamics with ref-

classical thermodynamics has expanded beyond the erence to the operation of a solar cell was the ‘Shock-

immediate energy sector into a branch of science that ley paradox.’1,a However, we shall show that many

pervades many scientiﬁc disciplines today. It is ideas behind the thermodynamic fundamentals of

solar cell operation date even to a much earlier time.

*Correspondence to: tm3@soton.ac.uk Perhaps it is only a coincidence that Carnot’s classi-

Solar Energy Laboratory, Faculty of Engineering and the Environ- cal paper on the efﬁciency of conversion into

ment, University of Southampton, Southampton, UK mechanical work2 appeared some 15 years before

Conﬂict of interest: The author has declared no conﬂicts of interest what is now considered to be the ﬁrst observation of

for this article. the photovoltaic effect.3 Carnot’s work provided the

© 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd.

This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any

medium, provided the original work is properly cited.

Advanced Review wires.wiley.com/energy

ﬁrst impetus that grew into a quantitative framework thermodynamics. Not surprisingly, what many con-

now called thermodynamics. And it was the applica- sider to be the ﬁrst paper which kick-started the

tion of thermodynamic to electromagnetic radiation quantum theory combined thermodynamics with

that gave rise to quantum mechanics at the turn of electromagnetism, in the concept of black-body radi-

the 20th century laying down, as we shall see, the ation. Here, we review brieﬂy four areas that can be

foundation stones for the understanding of modern considered as the foundation stones for a satisfactory

photovoltaics in thermodynamic terms. understanding of solar energy conversion in thermo-

Our review starts with a brief historical per- dynamic terms.

spective in the section The Foundation Pillars of sev-

eral key concepts that underpin what is now

sometimes called the ‘thermodynamics of light.’ The Size of a Beam of Light

Building on this foundation, we shall chart the prog- Thermodynamics deals with the energy attributes of

ress toward the current understanding by using substance conﬁned in a well-deﬁned volume. Our

examples of ideas, concepts, strategies, and views aim here is to ﬁnd corresponding characteristics for a

that contributed to the ﬁeld. We shall not aim to pro- beam of light. In contrast with geometrical optics

vide a complete list of efﬁciencies4,b but, in which describes light propagation in terms of light

section Light, Heat, and Work, we shall take a look rays, energy conversion requires to deﬁne bundles of

at a range of classical theories aiming to determine rays (light beams) that have ﬁnite dimensions and are

the limits to solar energy conversion and the related able to carry macroscopic amounts of energy. This

process of light emission. The following sections then distinction ﬁrst became apparent in the analysis of

introduce the quantum nature of light into the con- concentration of light5 which requires optimum illu-

version process. In section Quantum Solar Energy mination of the receiver (a solar cell or heated ﬂuid),

Conversion, we examine the kinetics and current without necessitating image formation. The new ﬁeld

considerations of the celebrated detailed balance the- of nonimaging optics therefore deﬁned a new charac-

ory of Shockley and Queisser. Thermodynamics of teristics of the light beam: the étendue.6,c,d A key fea-

Photovoltaic Conversion section then revisits this ture of the étendue which underpins its importance

subject on the basis of thermodynamics, bringing in in optics to its invariance: the étendue of a beam pro-

new perspectives on the conversion process and fun- pagating in a clear and transparent medium is con-

damental energy losses. served (see for e.g., Ref 5 where a proof of this

A key objective of this review is to consider theorem can be found).

new avenues and opportunities for research. Two The element of étendue of a narrow beam of

examples have been chosen in the section Future angular spread δω passing through an area δA is

Directions: Beyond the Shockley-Queisser Limit to deﬁned as

illustrate the potential of thermodynamics to achieve

very high conversion efﬁciencies: the maximum limit δℰ = n2 δAδωcosθ ð1Þ

to the efﬁciency of solar energy conversion and the

hot-carrier solar cells. Light Trapping section exam- where n is the refractive index of the medium and θ

ines a somewhat different application of statistical is the angle between the normal to δA and the direc-

techniques to the capture of solar radiation, without tion of the wave vector k. For an extended beam, the

reference to temperature or heat. total étendue is obtained by an integration of Eq. (1)

giving the étendue of diffuse sunlight propagating in

vacuum or air with directions extending over a com-

plete hemisphere as ℰ = πA.

THE FOUNDATION PILLARS

The étendue has yet another facet of fundamen-

Current photovoltaic technologies—the principal tal signiﬁcance for the thermodynamics of light: it is

focus of this paper—are the product of modern mate- proportional to a volume element in the phase space

rials science, underpinned by the quantum theory. of coordinate variables x, y and wave vector compo-

They have emerged from developments in solid state nents kx, and ky.5,7,e By analogy with the early quan-

electronics and have close relationships with other tum mechanics, the étendue ℰ can thus be considered

solid state devices such as microelectronic circuits. as a measure of the number of quantum states in the

However, we shall see that the roots of their opera- beam available for photon occupation.8 The conser-

tion have deeper and more ancient origins, and the vation of étendue in a clear medium can then be

understanding of the theoretical foundations will interpreted as the invariance of the volume of a beam

bring us to the early days of quantum theory and in the phase space of its transverse coordinates

544 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. Volume 5, September/October 2016

WIREs Energy and Environment From steam engine to solar cells

(an equivalent of the Liouville theorem of classical A further point of note is that the formula for

mechanics), and the conservation of the number of photon density Eq. (2) implies the existence of not

quantum states. This provides a ﬁrm foundation for one but two forms of equilibria: an equilibrium

the analysis of processes that transform the beam, in between levels at different energy, as expressed by

close similarity to the volume variable in statistical the occupation probability (3), and an equilibrium

mechanics and thermodynamics. between different directions of propagation, as

expressed by the multiplicity factor for each energy

level. This latter aspect of Planck’s statistics will be

discussed in more detail in the section Light

Black-Body Radiation Trapping.

Radiation emitted by heated objects—the subject of The statistical nature of Eq. (2), with origins

an intense research activity in the second half of the close to the kinetic theory of gases, required Planck

19th century—gradually evolved into a universal to build bridges between the work of Maxwell,

concept which we now call black-body radiation: Kirchhoff, and particularly Boltzmann10,11,f by bring-

electromagnetic energy in thermal equilibrium with ing into play a relation linking nph with the photon

matter, characterized by the usual thermodynamic ﬂux density ϕν—the number of photons passing

quantities such as temperature, pressure, and volume. through a unit perpendicular area per unit solid angle

The key formula that eventually emerged is the per unit time:

Planck’s distribution law, usually written in terms the

energy density of black-body radiation at a certain nν2

c nph ðT Þ

temperature T. Planck never fully accepted the impli- φν ðT Þ = =2 ρ ν ðT Þ ð4Þ

cation of his theory and the existence of light quanta n 4π c

that we now call photons.9 Having photovoltaics in

The existence of the universal function of tempera-

mind, however, it will be more convenient to work

ture ϕν (T) was already stipulated by Kirchhoff but it

with quantities relating to photons rather than with

was determined, in the form (4), only later by Planck,

the energy of electromagnetic radiation, and we shall

as part of his theory of black-body radiation. The

write Planck’s law in the form

number of photons that propagate in a quasi-

monochromatic beam of frequency width δν with

8πn3 v2

nph = ρv ðT Þ ð2Þ étendue ℰ emitted by a black body at temperature

c3 T and passing through area A per unit time is then,

by (1)

where nph is the number of photons per unit fre-

quency per unit volume, ν is the frequency, c is the

speed of light, h is the Planck constant, kB is the φ ν ðT Þ ℰ

Φ=ℰ δν = Φ o ðT Þ ð5Þ

Boltzmann constant, n is the refractive index of the n2 πA

medium, and ρν (T)—what we now call the occupa-

tion probability of a quantum state—is given by where Φo(T) refers to the photon ﬂux emitted by a

black body into a full hemisphere in vacuum. As the

1 photon ﬂux and the étendue are both conserved, so

ρν ðT Þ = ð3Þ must be the ratio φv /n2, as already evident from the

e hν=kB T − 1

second equation (4). This is the photon ﬂux analogue

When examined in a modern context, several fea- of the brightness theorem.12

tures of Plank’s formulae (2), (3) deserve a special The concept of black body, as a perfect

attention. The occupation probability (3) can be absorber and emitter of radiation, is of a special sig-

viewed as a special case of Bose–Einstein distribution niﬁcance for solar energy conversion as it represents

with the chemical potential equal to zero. In thermo- a good approximation for the radiation emitted by

dynamic terms this means that photons which form the Sun. This similarity provides a powerful basis for

black-body radiation represent pure heat, and have a theoretical understanding: representing the Sun’s

no capacity to perform work in an isothermal proc- radiation as a black body affords a valuable tool that

ess. This point will be taken up again in the sections has been developed over many years, and is available

Quantum Solar Energy Conversion, Thermodynam- in a standard form in most textbooks on thermody-

ics of Photovoltaic Conversion, and Future namics and statistical physics (see e.g., Refs 13

Directions. and 14).

Volume 5, September/October 2016 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. 545

Advanced Review wires.wiley.com/energy

Bringing together the words ‘work’ and ‘thermody- heated body.21 Paraphrased in terms of photons

namics’ immediately evokes the notion of Carnot efﬁ- rather that energies, Kirchhoff surmised that the ratio

ciency. Carnot’s result, although resting ﬁrmly on the of the rate at which photons are emitted by a unit

‘caloric’ concept, marked the birth of a new ﬁeld: area to the absorbing power a is equal to a universal

thermodynamics. With a remarkable insight, Carnot function of only the temperature of the substance

predicted that a quantity Qh of heat, extracted from and the wavelength or frequency of emission21—our

a high-temperature reservoir can be converted to photon ﬂux density (Eq. (4), Figure 1(a)).

work with an efﬁciency at most Planck elaborated on Kirchhoff’s ideas by not-

ing that radiation can only be absorbed or generated

To in a volume element of a body rather than on the sur-

ηC = 1 − ð6Þ face.22 He expressed this balance in terms of the

TS

absorption coefﬁcient αV and the coefﬁcient of emis-

whilst heat Qℓ must be rejected into a low-temperature sion εV (emission rate by a small interior volume into

reservoir (Figure 2(a)).Anticipating the application to a unit solid angle, per unit volume and unit fre-

solar radiation, the temperatures of the high- and low- quency interval, Figure 1(b); see also Ref 23g). A fur-

temperature reservoirs have (6) been set equal at the ther historic contribution was made by Einstein who,

solar temperature TS and the ambient temperature To. in his theory of radiation paper,24 extended Planck’s

Carnot’s efﬁciency proved to be an inspired foundation photon balance to describe transitions between the

for what was to become the second law of thermody- quantum states of matter and showed that a consist-

namics. Since an ideal heat engine operates in a cyclical ency with the Planck radiation law required the exist-

manner, the working medium returns to the same ence of stimulated emission (Figure 1(c)). Einstein’s

point at the beginning of the cycle. Neither the proper- detailed balance, initially developed for atomic lines,

ties of the working medium nor the properties of the was later generalized to molecules by Kennard25,26

surroundings thus enter the argument. and Stepanov.27,28

We shall see that—perhaps surprisingly— Although discussed for more than 100 years,

Carnot efﬁciency appears profusely in the numerous the thermodynamic issues highlighted in this

formulae that have been suggested for solar energy section and the underpinning assumptions continue

conversion and that will be discussed in the sections to come under scrutiny to this day. Questions relat-

that follow. Equally important, however, is to exam- ing to entropy associated with absorption and emis-

ine the subtle but important differences between the sion of radiation29,30 and the associated assumption

operation of a solar energy converter and the Carnot of reciprocity31 retain the attention of the research

engine which—as we shall see—cause the efﬁciencies community, and will only be resolved with further

achievable in solar energy conversion to be lower research. Other relations between absorption and

than the value (6). The analysis of different models emission of light, including a geometrical interpreta-

and reasons to explain this difference are among the tion, will be examined when we investigate the foun-

key objectives of this paper. dations of light trapping.

Emission of Radiation LIGHT, HEAT, AND WORK

The relationship between the absorption and emis- The Foundation Pillars section has set the scene by

sion of radiation is a key characteristic of the energy an outline of several scientiﬁc disciplines which con-

exchange between matter and the radiation ﬁeld. The nect light with thermodynamics. However, little has

intense research effort in this ﬁeld has brought about been said how these tools can be applied to the

several different expressions of what we may now actual conversion processes, and what constraints

call detailed balance between absorption and emis- apply when light is transformed into other useful

sion of radiation. Indeed, some of this work paved energy forms such as mechanical work, electricity, or

the way to the discovery of Planck’s radiation chemical energy. This section takes the ﬁrst step in

formula.20 this direction with a snapshot of several early the-

The three different relations between absorp- ories which use thermodynamics to describe solar

tion and emission of radiation by matter are sum- energy conversion. The conversion process is usually

marized in Figure 1. The ﬁrst general relationship considered without making any signiﬁcant assump-

between absorption and emission was formulated by tions about the conversion device. The ideas in this

546 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. Volume 5, September/October 2016

WIREs Energy and Environment From steam engine to solar cells

Absorbed

4pav fv dV

Absorbed Emitted

Spontaneous Stimulated

Absorbed: aΦin

dV

B No nph ANexc ANexc rv

Emitted: Φout

Emitted

4pevdV

A = ÚÚÚÚ B

c3

(a) Kirchhoff (b) Planck (c) Einstein

FI GU RE 1 | Different facets of the balance and reversibility between absorption and emission of radiation. (a) Kirchhoff’s law relating the

photon emission rate Φout to the absorptivity a and the photon emission rate Φo(T) of a black body. Kirchhoff’s law holds for the total emission as

well as for its spectral components. (b) Planck’s relation between the emission (εv) and absorption (αv) coefﬁcients at frequency v for a small

volume element in the interior of a body. (c) Einstein’s relation, linking the photon absorption and emission rates to transitions between quantum

levels of the medium. No and Nexc denote the numbers of atoms in the ground and excited states, respectively.

section can also be described as emerging from classi- grouped under a heading of ‘ﬁnite time thermodyna-

cal (rather than quantum) physics, to be contrasted mics’.32,h This section takes a brief look at two exam-

with the discussion in later sections where emphasis ples in application to solar energy conversion.

is placed on quantum converters. An early model based on the conversion of

Based on the Sun as a source of black-body solar power was proposed by Castañs and collea-

radiation at a temperature TS of 6000 K and taking gues33,34 and by Jeter35 for what is now referred to

the low-temperature reservoir as the surroundings at as photothermal efﬁciency. The heat input to the

an ambient temperature of To = 300 K (these num- engine is taken as the difference between the black-

bers will be used throughout this review), a ready body energy ﬂux received from the Sun at tempera-

estimate for the maximum efﬁciency of a solar energy ture TS and the black-body ﬂux emitted by the con-

converter using the Carnot efﬁciency (6) gives a limit verter at a temperature Tc. This heat is then

of 95%. It soon becomes apparent, however, that converted with the Carnot efﬁciency for a converter

this limit is too generous and cannot be reached even operating between the temperatures Tc and the ambi-

by an ideal theoretical device. Clearly, a number of ent temperature To. The resulting power efﬁciency

features and facets of the conversion processes should can then be written as

be taken into account if the efﬁciency limit is to have

( 4 )

at least a semblance of reality.

Tc To

ηPT = 1− 1− ð7Þ

TS Tc

Energy and Power. The Photothermal and

Endoreversible Engines The value of ηPT usually quoted represents the maxi-

The ﬁrst concern that comes to mind is of the Carnot mum with respect to the converter temperature Tc;

efﬁciency as an energy efﬁciency: a ratio of two num- for TS = 6000 K and To = 300 K, the optimum Tc is

bers, each with the dimension of energy. The efﬁ- equal to 2544 K.

ciency of a useful solar energy converter is invariably A different approach to model the dynamic

understood to mean the power output divided by (rather than static) operation of the engine is to

power incident on the device: it is therefore a power ascribe the resulting losses to the heat ﬂow which

efﬁciency. As the argument behind Carnot efﬁciency supplies and takes away energy to and from the

rests on equilibrium thermodynamics, it is clear that engine (Figure 2(b)). As these losses (which are pro-

the power efﬁciency of the Carnot engine is zero. portional to the difference of temperatures of the

A similar problem in a more general setting has been reservoirs and the inlet and output to the heat engine)

the subject of research for many years and is often occur outside the ideal heat engine/converter, this

Volume 5, September/October 2016 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. 547

Advanced Review wires.wiley.com/energy

Th

Th

Th

Thi

Qh

Photons

engine engine

Rejected

Ql heat

Tli

To

To

Tl

Th Th Th

heat heat heat

To To To

F I G U R E 2 | Different heat engines that have, at various times, been considered in the context of solar energy conversion. (a) A schematic

diagram of Carnot cycle which will form the starting point for our discussions. The engine absorbs heat Qh from a high-temperature reservoir at

temperature Th and rejects heat Qℓ into a low-temperature reservoir, assumed throughout this paper to be at the temperature of the surroundings

To. (b) A schematic representation of the endoreversible engine (after Ref 15). The jagged lines show the heat supply by conduction to and from

the Carnot engine, operating between two reservoirs at temperatures Thi and Tli. (c) The general scheme of a solar energy converter16 where

photons are absorbed as high-temperature heat at temperature Th, rejecting heat at temperature To while emitting photons in a separate channel

and performing work. (d) An optical heat pump proposed by Weinstein17 as a model for electroluminescence. Electrical input (viewed as work)

supplemented by the low-grade heat at temperature To is converted into photon emission, equivalent to high-temperature heat at temperature Th.

(e) An optical heat pump considered by Chukova as a thermodynamic model for a photoluminescence device.18 (f ) Scheme of a light emitting

device, serving as a thermodynamic model for a solar cell.19

type of engine is usually called endoreversible. The The power and energy efﬁciencies of the photo-

resulting energy efﬁciency at the maximum power thermal and Curzon–Ahlborn engines are compared

output then comes out as 15,36–38 in Figure 3, highlighting the losses due to a ﬁnite rate

of turnover of the engine. A notable feature of these

1=2

To graphs is the existence of a maximum turnover rate

ηCA = 1 − ð8Þ Qmax for each engine where the dynamic losses

TS

match the work produced by the engine, and the net

The efﬁciency (8), sometimes known as the output of both energy and power is zero.

Curzon–Ahlborn efﬁciency, has had some success in

modeling the efﬁciency of conventional power plants

but has also been used as the starting point in a dis- The Available Work. Landsberg

cussion aiming to compare and contrast the power Efﬁciency

and energy efﬁciencies in more general terms.32 For At the fundamental level, the nature of energy supply

TS = 6000 K and To = 300 K, the efﬁciency of the to the engine is at the heart of a different model for

endoreversible engine is equal to 77.7%. solar energy conversion. The photothermal and

548 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. Volume 5, September/October 2016

WIREs Energy and Environment From steam engine to solar cells

(a) (b)

1 1

C

0 0

1 1

PT

Power efficiency

0 0

0 0.2 0.4 0.6 0.8 1 0 0.2 0.4 0.6 0.8 1

. . . .

Q1 / Qmax Q1 / Qmax

FI GU RE 3 | The energy and power efﬁciencies of the photothermal (a) and endoreversible (b) engines: ηCA denotes the energy efﬁciency of

the Curzon–Ahlborn (endoreversible) engine and ηPT the photothermal power efﬁciency. Both efﬁciencies are determined at the point where the

engine delivers maximum power. Q_ 1 denotes the rate of heat supply to the Carnot engine, with the maximum value Q_ max .

endoreversible engines consider the energy delivery Wmax can be determined by the method of thermody-

as a continuous process. One can consider an alter- namics in terms of the availability or exergy:39,i

native picture where solar radiation arrives in the

form of ﬁnite energy packets which are consumed To pS po

Wmax = US −To SS + po VS = 1− US − − To VS

when converted to useful work. Photons are trans- TS TS To

ported to Earth from the Sun as light beams, in a ð9Þ

process akin to convection or ballistic transport,

which could be compared to particle motion as where US and SS are the internal energy and entropy

described by classical mechanics,39 without the need of a radiant energy packet at temperature TS with

to employ the laws of thermodynamics. It can there- volume VS. Equation (9) has been adapted for equi-

fore be argued that statistical concepts such as librium black-body radiation with chemical potential

entropy play no part in photon transport in a clear equal to zero.

medium, and that the absorption of light differs from It is instructive to consider the different pro-

the absorption of heat by a heat engine which is asso- cesses leading to the Carnot and Landsberg efﬁcien-

ciated with a change in entropy. cies in more detail. The Carnot engine receives heat

A model can thus be perceived where, instead from a high temperature source (the Sun, at tempera-

of absorbing heat, a hot working medium in the form ture TS) and rejects heat into the surroundings at

of solar radiation at temperature TS, is injected into temperature To. Unlike the Carnot cycle, however,

the engine. Work can then be carried out by cooling the availability process is not cyclical, and the work

the medium inside the engine to a state of equilib- done by and on the engine must include the work on

rium with its surroundings at temperature To and or by the surroundings at pressure po.40 We note that

pressure po. The maximum amount of available work the input energy to the Carnot engine is heat

Volume 5, September/October 2016 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. 549

Advanced Review wires.wiley.com/energy

exchanged at temperature TS (equal to TSΔS = TSSS) incident and emitted photon ﬂuxes as well as the pro-

but the initial energy for the conversion process duction of useful work (Figure 2(c)) by an incident

described by availability (9) is the internal energy US _ in :

energy (solar) ﬂux U

at temperature TS and volume VS. Accordingly, the

conversion efﬁciency is thus deﬁned as Wmax/UTS. In

U _ out + Q

_ in = U _ +W_

mathematical terms, the efﬁciencies of the two pro-

_S = S_ out + Q=T

_ o − S_ i ð11Þ

cesses differ in the second term of the second equa- in

the subject of discussion in several parts of this where U _ out and S_ denote the energy and entropy

out

review; for brevity, it will be denoted by—Δp and ﬂuxes of the emitted photons, Q _ is the heat ﬂux

referred to simply as the pressure correction. rejected into a low-temperature reservoir at tempera-

The notion of solar energy conversion leading _ is the rate of work (electrical energy)

ture To, W

to available work was followed by Petela,41 Press,42

and Landsberg and Mallinson43 who determined the done by the converter, and S_ i is the rate of irreversi-

maximum work that can be carried out by a volume ble entropy generation. Interestingly, the application

of black-body radiation at temperature TS if cooled of Eq. (11) to the conversion of black-body radiation

to temperature To, leading to what is now usually at temperature TS by a converter at To under reversi-

called the Landsberg efﬁciency ble operation with S_ i = 0, leads again to the Lands-

berg efﬁciency (10). As already noted at the end of

the previous section, however, the energy input is

Wmax 4 To 1 To 4

ηL = = 1− + ð10Þ now the energy ﬂux U _ rather than the energy U of a

US 3 TS 3 TS

volume V of black-body radiation.

The use of Carnot and Landsberg efﬁciencies has Landsberg and Tonge47 showed that the deter-

been discussed in detail in Refs 44–46. All three efﬁ- mination of an upper bound on the efﬁciencies or

ciencies discussed above as functions of the ratio To/ coefﬁcients of performance reduces to the determina-

TS are compared in Figure 8. tion of the appropriate temperatures Tout and Texc of

As presented in this review, Eq. (10) is consid- the emitted and exciting radiation. This is a simple

ered as energy efﬁciency. In the literature, in contrast, matter for monochromatic radiation where a suitable

the Landsberg efﬁciency is usually portrayed as deﬁnition had already been provided previously by

power efﬁciency—either as a result of a derivation Landau.48 For broadband radiation, the situation is

based on energy ﬂows (see the section Energy and more complex as it is impossible to correctly match

Entropy Flows) or simply by changing the work the spectrum as well as the total radiance/energy ﬂux

Wmax into power or energy ﬂow. Notwithstanding, by using a single temperature. We shall see in Quan-

the emphasis placed in this review on the distinction tum Solar Energy Conversion section that a satisfac-

between energy and power efﬁciency requires that a tory resolution of this issue had to await a later

more rigorous argument is sought to justify the development: the introduction of a ﬁnite chemical

notion of Landsberg efﬁciency as power efﬁciency. potential of radiation.

Indeed, we shall show in the section The Maximum The deﬁnition of a satisfactory effective temper-

Efﬁciency of Solar Energy Conversion on fundamen- ature becomes particularly acute for solar radiation

tal grounds that this notion may require a on the ground where the spectrum resembles the

reappraisal. black-body spectrum but the total energy ﬂux is, of

course, much lower. This led Landsberg and Tonge

to introduce the concept of diluted black-body radia-

Energy and Entropy Flows tion16 where the energy ﬂux is reduced by a factor of

One can simply brush aside the difﬁcult process to

justify the difference between power and conversion ε = ℰin =ℰout = CωS =π ð12Þ

efﬁciencies (which bears many similarities to the dif-

ferences between the transition from classical to irre- with respect to the full black-body ﬂux, where ℰin

versible thermodynamics) and apply the laws of and ℰout are the étendues of the incident and emitted

equilibrium thermodynamics directly to energy rates beams and C is the concentration ratio. Landsberg

rather than to energy quantities themselves. This was and Tonge show that the formalism allows the deter-

the approach taken by Landsberg and Tonge47 who mination of the appropriate entropy, and hence,

used rate equations for a system not dissimilar to the gives an effective temperature of the diluted black-

Carnot heat engine, to describe the balance between body radiation which can be used to obtain an upper

550 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. Volume 5, September/October 2016

WIREs Energy and Environment From steam engine to solar cells

bound on the conversion efﬁciency with the use The Shockley—Queisser Model of

of (10). Detailed Balance

The model of Landsberg and Tonge built on We have already noted that the origins of modern

the previous work by Weinstein17 who used rate photovoltaics are anchored in semiconductor tech-

equations to study the conversion of work into opti- nology. A satisfactory understanding of the funda-

cal emission excited by the injection of electrical cur- mental limits on solar cell operation, however, relies

rent where the energy of the emitted photon can on an insight from a different branch of science. This

exceed the electrostatic energy of the applied bias,49 came with a description of the solar cell solely in

in a model based on a heat engine (Figure 2(d)). Chu- terms of the characteristics of the incident and

kova18 later extended Weinstein’s result to photolu- emitted energy beams of light, in a breakthrough

minescence (Figure 2(e)). More recently, a similar paper by William Shockley and Hans-Joachim Queis-

line of work has been pursued in connection with ser51 in the early 1960’s.

laser cooling.50 Based on what might now seem a simple strat-

egy, Shockley and Queisser called their method

‘detailed balance’. Indeed, certain similarities will be

QUANTUM SOLAR ENERGY recognized with the balance between absorption and

CONVERSION. KINETIC ASPECTS emission as summarized in Kirchhoff’s law in the

Foundation Pillars section. What Shockley and

The focus of our review so far has been what could Queisser had in mind was to equate the incident (and

be called the classical approach to the thermody- completely absorbed) ﬂux Φin of photons with energy

namics of solar energy conversion: the conversion of above the bandgap Eg at temperature TS to the ﬂux

the incident energy ﬂux in terms of equilibrium ther- Φout in the same energy range at temperature To

modynamics, with no attempt to describe the quan- emitted by the cell, allowing for a fraction of photons

tum nature of solar radiation as a stream of which are used for conversion to electrical current I:

photons. The theoretical foundations of modern

photovoltaics, accompanied by an improved under- Φin = Φout + I=q ð13Þ

standing of photochemical energy conversion in pho-

tosynthesis, are underpinned by the quantum nature A model for the incident ﬂux was at hand in the form

of solar energy conversion where photons play a of black-body radiation emitted by the Sun (see the

primary role. Foundation Pillars section) but no universally

A brief glance at the output of a solar cell along accepted view was available to describe the photon

the current voltage characteristic will illustrate the ﬂux emitted by a semiconductor under electrical exci-

main features of the conversion process. The energy tation. Shockley and Queisser made an approxima-

generated by a photon is directly related to the volt- tion which turned out to be surprisingly accurate: to

age at the solar cell terminals, or to energy content of multiply the equilibrium photon ﬂux at the ambient

the molecular product. Near the open circuit, the temperature by a factor equal to the rate of increase

solar cell is an energy converter where each photon of radiative recombination at a semiconductor junc-

produces energy qV, under conditions similar to clas- tion under applied voltage V:

sical thermodynamics because the ‘turnover rate’ I/q

(represented here by the extraction of charge carriers) ωS

Φin = C Φo ðTS Þ

is low. Near the short circuit, on the other hand, the π ð14Þ

solar cell resembles a kinetic device, converting Φout = e qV=kB To

Φo ðTo Þ

photons into electrons in an electrical circuit, at a

rate given by the turnover rate I/q. When extended to where ωS is the solid angle subtended by the Sun,

produce the complete current–voltage characteristic C is the concentration ratio (C = 1 for one sun illu-

both viewpoints are, of course, equivalent. As we mination and C = π/ωS for maximum concentration),

shall see in the next sections, each aspect provides a and the photon ﬂuxes refer to the range of photon

different aspect on the device operation and a differ- energies hv > Eg, where Eg is the bandgap of the

ent description of losses in conversion. We begin our semiconductor. Combining Eqs. (13) and (14) gives

discussion with a review of the more traditional the current voltage characteristic of an ideal

approach, the kinetics, based on currents and photon solar cell:

ﬂows. We will return to consider the energy aspects

and thermodynamics in the section Thermodynamics I = Iℓ −Io e qV=kB To −1 ð15Þ

of Photovoltaic Conversion.

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Advanced Review wires.wiley.com/energy

CulnSe2 cSi GaAs

statistics56

40% aSi

Ultimate efficiency 1

ρν ðT, μÞ = ð17Þ

Efficiency

30%

InP CdTe Maximum eðhν−μÞ=kB T −1

concentration

20%

One sun

The chemical potential μ in (17) is set equal to the

10% electrostatic energy qV corresponding to the voltage

produced by the solar cell. Numerically, the differ-

0% ence between the original and ‘corrected’ I-V charac-

0 1 2 3 4 5

teristics has little signiﬁcance except under a very

Bandgap (eV)

high concentration of incident sunlight. The basic

F I G U R E 4 | The Shockley–Queisser ideal efﬁciency of a single- structure, however, completes the foundation of pho-

junction solar cell as a function of the semiconductor bandgap, tovoltaics, and could be later built on to describe

together with the bandgaps of a number semiconductor with solar cell operation in terms of an ‘engine’ operating

photovoltaic applications. The incident and emitted light beams have between two equilibrium reservoirs of the

the black-body spectrum at temperatures 6000 and 300 K, photon gas.

respectively.

Although the open-circuit voltage cannot be

calculated analytically, a useful approximation exists

for weak to moderate illumination intensities:57

where Iℓ and Io are the photogenerated and dark sat- To TS ℰout

qVoc = 1− Eg + kB To ln −kB To ln

uration currents, TS To ℰin

ð18Þ

Io = qΦo ðTo Þ

ωS ð16Þ Additional corrections can be applied to improve the

Iℓ + Io = qC Φo ðTS Þ

π accuracy of this formula to bring it to a useful form

for practical applications.8 Equation (18) will form the

Figure 4 shows the ideal efﬁciencies as functions of starting point for the discussion of solar cell voltage in

the bandgap Eg under one-sun illumination, under thermodynamic terms in the section Thermodynamics

maximum concentration of sunlight, and what of Photovoltaic Conversion, where we will identify the

Shockley and Queisser called the ‘ultimate efﬁ- origin of each term in this equation.

ciency’—a result obtained earlier by Trivich and

Flinn52 and Müser53 who approximated the open-

circuit voltage by the voltage Eg/q corresponding to

the bandgap of the semiconductor. Photochemical Energy Conversion in

A key element of the Shockley–Queisser result Photosynthesis

was to show that efﬁciency limit for solar cell oper- An early application of thermodynamics to quantum

ation is described completely by the characteristics solar energy conversion was to describe one of the

of the incident and emitted light beams. most ancient energy conversion processes on Earth:

Equations (14) and (15) describe the well-known photosynthesis. Photosynthesis usually evokes the

current voltage characteristic of an ideal solar cell picture of a complex set of chemical reactions where

which has enjoyed much success since the early sunlight converts water and carbon dioxide into car-

days of photovoltaics. From a more fundamental bohydrates and oxygen. The energy producing part

point of view, however, a correction is required to of the photosynthetic reaction, however, bears a

put the emitted photon ﬂux on a more rigorous remarkable similarity to solid state photovoltaics.

footing. This correction became apparent from the The key feature that underlines this similarity is that

photoluminescence studies which indicated that the the primary reaction consists of a sequence of

photon ﬂuxes emitted as ﬂuorescence or phospho- oxidation–reduction reactions: in other words, elec-

rescence are described well by the Bose–Einstein tron transfer. Energy is collected in a light-harvesting

distribution with a non-zero chemical poten- unit and transferred to the photochemical reaction

tial.54,55 The emitted photon ﬂux Φout than takes center (trap) by exciton transport (Figure 5). The

the form of a ‘generalized Planck’s law,’ where the complex of energy conversion reactions (sometimes

occupation probability (3) is replaced by a value called storage) then follows, initiated by charge

552 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. Volume 5, September/October 2016

WIREs Energy and Environment From steam engine to solar cells

Light

absorption Exciton Storage

Light harvesting Trap

units Transport (yield chem)

Fluorescence

(yield f)

Nonradiative losses

F I G U R E 5 | A schematic diagram of the primary photosynthetic energy conversion process (after Refs 58 and 59).

separation across the photosynthetic membrane. Since Teff ≤ TS, this term expresses both the second

Research into the primary steps in photosynthesis law of thermodynamics and the reduction in efﬁ-

has contributed much to the understanding of ther- ciency due to ‘dilution’ of solar radiation on Earth.

modynamic concepts by linking energy production The second term represents a correction for nonra-

with luminescence. diative transitions when the ﬂuorescence yield φf is

A discussion of the photosynthetic primary less than unity. The last term which includes the

energy conversion in thermodynamic terms was probability of chemical reaction (the ‘chemical yield’

initiated by Duysens 60 who proposed, on an intui- φchem) links the energy production per electron

tive basis, that the efﬁciency of the conversion proc- (as expressed by Δμ) to the ‘power’ production dis-

ess could be described by the Carnot efﬁciency (6). cussed already in the Light, Heat, and Work section,

Similarly to the discussion in the section Light, Heat, and indicates that if energy is to be produced at a

And Work, the dilution of solar radiation was ﬁnite rate, Δμ must decrease from its maximum value

allowed by using an effective temperature Teff instead at ‘open circuit’ (or ‘static head’ 66) where the overall

of the true black-body temperature of solar radiation rate of chemical reaction is zero.

TS. This effective temperature was determined by

equating the observed photoexcitation rate to the

rate of photon absorption from a black-body radia-

tion at temperature Teff. A more detailed description THERMODYNAMICS OF

on molecular basis was provided by Ross and Cal- PHOTOVOLTAIC CONVERSION.

vin61 (see also Ross,62,63 Bolton,64 and Lavergne and SOLAR CELL AS A HEAT ENGINE

Joliot65) who introduced the chemical potential of

the reaction products, linked to the concentration P* An alternative view to the detailed balance method

of the excited state of the primary electron donor P: discussed in The Shockley—Queisser Model can be

obtained by combining the energy aspects of the con-

version process with the quantum nature of sunlight

P*

Δμ = kB To ln ð19Þ and of the energy produced. The key parameter is

P*o

then the useful work per photon—in thermodynam-

ics terms, the free energy, or chemical potential:

where P*o is the concentration of P*in thermal equi-

librium in the dark at ambient temperature To.

μ = u −Ts ð21Þ

The ﬁeld was reviewed, in a particularly clear

form, by Knox58,59 who showed that

where u and s are the energy and entropy per

photon.67,j The thermodynamic approach with focus

To

Δμ = 1 − ΔE + kB To ln φf + kB To lnðφchem Þ on energy parameters bears the promise of shedding

Teff a new light on the fundamental losses in the conver-

ð20Þ sion process, and providing a theoretical basis for

novel devices and structures aiming to exceed the

Equation (20) generalizes Duysen’s result which is Shockley–Queisser limit68–72 or constructing a ther-

represented by the ﬁrst term on the right-hand side. modynamic cycle for a solar cell.45,73

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Since a solar cell emits light as well as produces generation σ i. Since the entropy-generation term σ i

power in the external circuit, the analysis may be depends on the current produced by the solar cell,

simpliﬁed by considering the solar cell simply as a Eq. (24) demonstrate a close link between the energy

light emitting device (Figure 2(f )).k Since, under opti- efﬁciency of a solar cell and its current–voltage char-

mum operation, the emitted photons are in equilib- acteristic, expressed in the form of voltage as a func-

rium with the electron-hole system which performs tion of current.

work, the energy produced by the solar cell can be To be of practical use, Eq. (23) has to be sup-

determined by equating the work to the chemical plemented by a formula for the entropy balance

potential of the emitted beam.19 We can then follow

a similar philosophy as in Light, Heat, and Work To σ i = Δu −To Δs ð25Þ

section to write down the required energy–entropy

balance, but this time per incident photon: where the Δ denotes a difference between quantities

pertaining to the incident and emitted beam.

uin = uout + Q Equation (25) provides a recipe for how the irreversi-

ð22Þ

sin = sout + Q=To − σ i ble losses can be determined using, for example,

standard results from the statistical mechanics of

where the subscripts in and out refer to incident and radiation,13,22 In keeping with an earlier remark con-

emitted beams with étendues ℰin and ℰout at temper- cerning Eq. (21), we note that the expression on the

ature TS and To, respectively, Q is the heat rejected right-hand side of (25) resembles the availability/

into a low-temperature reservoir at temperature To exergy of one photon, without the pressure

and σ i is the irreversible entropy generated in the correction—in other words, describing a process at

conversion process. A simple transformation of Eq constant volume. We shall return to this point in the

(22) now yields: section The Maximum Efﬁciency of Solar Energy

Conversion.

To The use of Eqs. (23) and (25) will now be illus-

qV = μout = 1 − uin − To σ i ð23Þ

TS trated on the examples of two speciﬁc conversion

devices: a monochromatic, or two-level, converter

giving the energy efﬁciency of conversion in the form and a single-junction solar cell, providing a parallel

(see Table 1) to the Shockley–Queisser treatment in the

section Quantum Solar Energy Conversion.

ηe = qV=uin = ηC − To σ i =uin ð24Þ

Equations (23) and (24) express the work pro- The analysis of a two-level converter which converts

duced by a quantum of solar radiation in terms photons in a monochromatic beam (more precisely,

which are familiar from classical thermodynamics. quasi-monochromatic radiation with frequencies

Sometimes referred to as the Guy–Stodola ν!ν + δν) into useful work or electricity has been of

theorem,74,75 the work that can be carried out by a interest as a prototype model for a solar cell since the

thermal source is equal to the input energy (in this early days of photovoltaics. It provides a clear link to

instance, radiation originating from a black-body thermodynamics and the Carnot efﬁciency, by effec-

source with μin = 0) converted with the Carnot efﬁ- tively generalizing the Einstein’s balance between

ciency, less losses due to irreversible entropy absorption and emission by introducing photon

Efﬁciency Deﬁnition Remarks

ηe ηe = qV/uin Energy (voltage) efﬁciency

ηP ηP = ΦIin ηe = iηe Power efﬁciency, within the spectral

range of the converter

η η = scf ηP = scf iηe Usual solar cell conversion efﬁciency

uin is the average incident photon energy and Φin is the incident photon ﬂux, both within the absorption range of the converter / solar cell. The spectral cover-

_ ðhν > Eg Þ =U

age factor is given by scf = U _ o , where the energy ﬂuxes in the numerator and denominator refer to the spectral range absorbed by the semiconductor

o

and the full spectrum, respectively.

554 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. Volume 5, September/October 2016

WIREs Energy and Environment From steam engine to solar cells

ﬂuxes at different temperatures76,77 (see also Ref 78). thermodynamics, σ i can only be positive. This also

The key relation which underpins the thermodynamic follows from the application of the detailed balance

analysis is the expression for the monochromatic (13) to the monochromatic converter. Use of the gen-

photon entropy:13 eralized Planck law (15) then shows that, for I > 0,

the chemical potential μ must be smaller than at open

Gν circuit. Since the energy hν is constant, (21) implies

sν = kB ln 1 + ℰ ð26Þ

Φν an increase of entropy on account of irreversible

nature of the conversion process. The voltage pro-

where Gν = 2ν2δν/c2 and Φν is the photon ﬂux in a duced by the two-level converter qV = qVoc − Toσ i

small frequency range δν at frequency ν. We note must therefore decrease from the open-circuit value

that entropy per photon increases with increasing as current is extracted from the converter. We can

étendue ℰ and decreases with increasing photon ﬂux. draw a parallel between entropy generation resulting

For monochromatic radiation uin = uout = hν. from non-zero current (to be denoted by σ kin) and

The conversion process therefore proceeds with no the losses in photothermal and endoreversible engines

photon energy losses between absorption and emis- due to a ﬁnite rate of turnover of the heat engine.

sion, the ﬁrst term on the right-hand side of For the two-level converter, the entropy generation

(25) vanishes and the irreversible entropy generation can be written down in a closed form by

σ i is determined solely by the entropy balance using Eq. (26)

between the incident and emitted photons of mono-

chromatic light at frequency ν. 1− ie −xS

σ i = sout −sin = kB ln ð28Þ

We shall consider ﬁrst the conversion process 1− i

under maximum concentration of sunlight. The

Landsberg–Tonge dilution factor ϵ (12) is then equal where i = I/(qΦin), with Φin the incident black-body

to unity and the open-circuit voltage corresponds to photon ﬂux in the frequency range δν, denotes the

the photon energy converted with the Carnot normalized current produced by the converter, and

efﬁciency: xS = hν/kBTS.

The energy efﬁciency ηe is a useful characteristic

To of a heat engine but, as in the analysis of thermody-

qVoc = 1 − hν ð27Þ

TS namic engines in the section Light, Heat, and Work,

the key parameter of solar cells is the power efﬁ-

Comparison with (23) shows that entropy generation ciency ηP (see Table 1) which takes into account the

σ i vanishes at open circuit indicating a reversible kinetic nature of the conversion process. As deﬁned

energy transformation as implied, of course, by the here, the power efﬁciency ηP refers only to the mono-

thermodynamic nature of the Carnot engine. chromatic radiation which is absorbed by the solar

As ﬁnite current is extracted from the converter, cell. In comparison with the energy efﬁciency ηe, the

the irreversible entropy generation σ i becomes non- power efﬁciency ηP contains an additional loss (1

zero—in fact, as a consequence of the second law of −i)ηe due to the (free) energy carried away by

1.0

C

Energy or power efficiency

e

Kinetic entropy

(1 – i)e generation

0.5 P

Photon

re-emission

0.0

0 0.2 0.4 0.6 0.8 1

i

FI GU RE 6 | The I-V characteristic of a two-level converter as energy efﬁciency. (a) The energy efﬁciency (blue line) showing the Carnot energy

not available for conversion (shaded by blue) and the loss on account of irreversible entropy generation on account of current extraction. The power

efﬁciency (red line) includes additionally the power loss by photon emission (1 − i)ηe. The inset in (b) shows losses at the maximum power point.

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photons emitted by the solar cell. It highlights the look at the ideal single-junction solar cell. As already

fact that, while the principal loss channel for power indicated, this analysis parallels the Shockley–

at short circuit is the irreversible entropy generation Queisser treatment but focuses on voltage rather than

σ i contained in ηe, losses near the open circuit are current as the principal variable. In the present termi-

dominated by photon emission (Figure 6). nology, we consider a converter that absorbs all radi-

The interplay between the thermodynamic and ation with photon energy above a certain threshold

kinetic losses is usually summarized by the ﬁll factor: deﬁned by the semiconductor bandgap Eg, and con-

ratio of the maximum power divided by the product verts an incident beam with photon ﬂux Φin, étendue

of open-circuit voltage and short-circuit current. The ℰin at temperature TS, into a beam with parameters

ﬁll factor provides a ‘conversion factor’ between the Φout, ℰout, and To, while producing useful work w =

power efﬁciency and the energy efﬁciency at short μout = qV per photon.

circuit, including losses by both kinetic entropy gen- The voltage of such a converter can again be

eration and photon re-emission:l obtained from Eq. (23). In comparison with the mon-

ochromatic converter, the conversion of broadband

ηP = ff ηe ðocÞ ð29Þ solar radiation results in an additional loss through

entropy generation and heat rejection into the low-

For the ideal monochromatic converter under maxi- temperature reservoir. The new entropy-generation

mum concentration ηe(oc) is equal to the Carnot efﬁ- term σ cool describes ‘photon cooling’ due to the ther-

ciency. We note that (29) can be written in a form malization of photogenerated electron-hole pairs

familiar from standards solar cell theory: (and thus also of the emitted photons with which

they are in equilibrium) by the interaction with lattice

Pν = ff Isc Voc ð30Þ vibrations. σ cool can be determined from Eq. (25),

allowing for the fact that photons emitted at the

where Pv is the power produced by the monochro- ambient temperature To now have a lower energy

matic converter at the maximum power point. than the incident photons at temperature TS. The

We are now in position to analyze the conver- analysis is particularly simple in the limit of weak to

sion process under one-sun illumination. The moderate illuminationm when the photon statistics

Landsberg–Tonge dilution factor then becomes ε = resembles an ideal two-dimensional gas:

π/ωS < 1. The concomitant étendue expansion results

in entropy generation (to be denoted by σ exp ), in a

TS TS

process analogous to the expansion of gas into vac- σ cool ﬃ kB −1 − ln ð33Þ

To To

uum, resulting in an additional further voltage loss

Toσ exp/q. This has a further consequence that a mon-

ochromatic converter can only meaningfully convert Although present in all current-generation solar cells,

a part of the solar spectrum under one-sun illumina- the thermalization loss expressed by σ cool is not, in

tion as low energy photons cannot produce a positive principle, unavoidable. A hypothetical device where

chemical potential, or voltage. At frequencies above this loss is avoided—a hot-carrier solar cell—is dis-

this threshold, the entropy generation can be writ- cussed further in the section The Model of Ross and

ten as Nozik.

Combining all three irreversible losses gives the

σ i = σ exp + σ kin ð31Þ total entropy generation σ i = σ exp + σ kin + σ cool and

evaluating the resulting expression for voltage

where σ kin is the entropy (28) and (23) conﬁrms the result (18), obtained by the

Shockley–Quiesser detailed balance. The present

−xS π − xS π treatment, however, distinguishes the different contri-

σ exp = kB ln e − ð1 − e Þ ﬃ kB ln ð32Þ butions to the fundamental losses, as shown by the

ωS ωS

different processes that make up the energy efﬁciency

where the approximate expression holds at sufﬁ- (24) in Figure 7(a).

ciently high-photon frequencies. We can now approach the key attribute of solar

cell operation: power conversion. The power efﬁ-

ciency ηP (29) was deﬁned for monochromatic radia-

The Single-junction Solar Cell tion. In a similar fashion, we can consider the power

No discussion of the thermodynamics of photovoltaic efﬁciency for a broadband converter for radiation

conversion would be complete without at least a brief which is actually absorbed by an ideal solar cell—in

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WIREs Energy and Environment From steam engine to solar cells

(b) 1.2

Reversible (Carnot) extraction) 1.0

1.0

Energy and power efficiency

0.8

Photon cooling

P

Efficiency

0.6

0.5 Etendue expansion

Spectral

e coverage

Photon 0.4 losses

re-emission P

0.0 0.2

0 0.2 0.4 0.6 0.8 1

Normalized current i

0.0

0.5 1.5 2.5 3.5

Eg

FI GU RE 7 | The fundamental losses in an ideal single-junction solar cell. (a) The energy (ηe) and power (ηP) efﬁciencies (heavy full and dashed

lines, respectively) plotted against the normalized current i = I / (qΦin). The dotted vertical dashed line shows the maximum power point. The

graph corresponds to the room temperature bandgap 1.12 eV of crystalline silicon. (b) The solar cell conversion efﬁciency under one-sun

illumination and losses at the maximum power point, plotted against the bandgap Eg of the solar cell material. The colors indicating

thermodynamic losses correspond to those in part (a). Spectral coverage losses are equal to 1—scf. The dotted line shows the bandgap used in

the graph of energy and power efﬁciencies in part (a).

other words, by considering only the spectral region similar plot of Ref 79 to include a full classiﬁcation

with photon energy in excess of the semiconductor of losses in thermodynamic terms.

bandgap Eg. Similarly to the two-level converter, ηP

is obtained from the energy (or voltage) efﬁciency by

including an additional loss due to photon re-emis- FUTURE DIRECTIONS: BEYOND

sion, giving rise to the ﬁll factor as discussed in the THE SHOCKLEY–QUEISSER LIMIT

section The Single-Junction Solar Cell (see Thermodynamics is particularly useful in mapping

Figure 7(a)). out the potential of new conversion devices and

The power efﬁciency ηP is not the usual conver- schemes. It has also proved to be a valuable tool in

sion efﬁciency used in the textbooks on photovolta- identifying ideas which violate the fundamental

ics. This efﬁciency—which we shall simply denote by physics—usually the second law of thermodynamics

η—includes, as a loss, photons with energies below (see, e.g., the suggestion70 and the arguments71,72,80

the bandgap Eg which cannot be absorbed by the which demonstrated the internal inconsistency of the

cell. From the thermodynamic viewpoint, this loss is proposed device).

clearly of a different nature than losses considered so The number of ideas and proposed structures

far and should be considered on a different footing. that employ a reasoning based at least in part on

We shall include this loss in terms of a spectral cover- thermodynamics is now too large to cover in a

age factor scf which describes the fraction of below- review of this size. We shall focus here on two well-

bandgap light in the black-body spectrum (see known areas of photovoltaics research where ther-

Table 1). modynamics plays an indispensable role.

The expression for solar cell efﬁciency as a

product of the spectral coverage factor, the normal-

ized rate of energy extraction i, and the energy efﬁ- The Maximum Efﬁciency of Solar Energy

ciency summarizes the thermodynamic view of Conversion

fundamental losses in solar cells. The solar cell efﬁ- Arguably, the quest to determine the maximum

ciency η as a function of the bandgap Eg is plotted in attainable efﬁciency for any solar energy converter

Figure 7(b) which extends, corrects and reﬁnes a has provided one of the grand challenges to

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theoreticians since the early days of research in this the total pressure correction Δp in (9)—in other

ﬁeld. Two limits that have been prominent in this dis- words, wν/q and the open-circuit voltage (27) for the

cussion include the Landsberg efﬁciency and the efﬁ- monochromatic converter are linked in an analogous

ciency of the so-called inﬁnite tandem,81,82 identical manner as the Landsberg and Carnot efﬁciencies

to a combination of an inﬁnite set of monochromatic (10) and (6) for the full spectrum of solar radiation.

converters discussed in the section Monochromatic To complete the parallel with a solar cell, we

Photon Gas and to be discussed below, which would use the Planck relation (4) between photon density

cover the full solar spectrum. Below, we review a and hemispherical ﬂux which corresponds to the

recent uniﬁed framework85 which elucidates the link photogenerated current ðqc=4Þnv ! Jνℓ . Finally, we set

between these two limits and proposes a new limit (c/4)Wmax ! PL, where PL is the power produced by

that combines the two. a converter obtained by combining all the spectral

To this end, we note that the argument used to contributions to obtain

obtain the Landsberg efﬁciency was based on the

maximum work determined in terms of availability. ð

∞

An identical result can be obtained from the maxi- PL = _ ðT S Þ

Vνoc Jνℓ dv = ηL U ð35Þ

mum work (wν, say) per photon at a frequency ν,

0

and the results weighted by the number of photons

and integrated over the full spectrum:

A comparison of Eq. (35) and the result based on

standard solar cell theory (30) now reveals the differ-

ð

∞

ence between work obtained the energy and power

Wmax = wν nv ðTS Þdv = ηL UðTS Þ ð34Þ

efﬁciencies obtained using the availability argument:

0 the power PL (35) obtained using the availability

argument does not contain the ﬁll factor—in other

where wν = hν(1−To/TS)—δp, and δp is the pressure words, it does not include losses described by the

correction per photon. When integrated, (34) gives kinetic entropy generation σ kin. We have argued in

this review that this loss is unavoidable by virtue of

the second law of thermodynamics: as the entropy is

1

Carnot

a decreasing function of the number of photons in

0.8 Landsberg

the beam and the number of emitted photons is less

than the number of incident and absorbed photons,

Energy efficiency

Endothermal

0.6 the extraction of current from each elemental solar

must necessarily leads to entropy generation (see also

0.4 Monochromatic Photon Gas section). This argument

shows that the suggestion in Ref 31 that σ kin can be

0.2 made to vanish with the use of nonreciprocal struc-

tures would violate the second law of

0 thermodynamics.

1

Infinite tandem: deVos

We can now progress to obtain the maximum

Infinite tandem: with pressure correction

conversion efﬁciency allowed by thermodynamics.

0.8

Photothermal

The elementary work wν, and hence Vνoc , can be

Power efficiency

0.6

cal mechanics, giving also σ kin and the ﬁll factor.85

Inserting the ﬁll factor into (35), we obtain the maxi-

0.4

mum efﬁciency ηmax attainable by any solar energy

converter, which makes allowance for pressure cor-

0.2

rection as expressed in the Landsberg efﬁciency:

0

0 0.2 0.4 0.6 0.8 1 ð

∞

To/TS Pmax = _ ðT S Þ

Vνoc Jνℓ ffν dv = ηmax U ð36Þ

F I G U R E 8 | The various energy (a) and power (b) efﬁciencies 0

of the cold and hot reservoirs. The dashed line corresponds to the The efﬁciency ηmax as a function of the ratio To/TS is

temperatures TS = 6000 K and To = 300 K. shown in Figure 8; for TS = 6000 K, ηmax = 85.0%.n

558 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. Volume 5, September/October 2016

WIREs Energy and Environment From steam engine to solar cells

A previous widely used result for the maximum Hot-Carrier Solar Cell. The Model of

overall efﬁciency was obtained by deVos81,82 by a Ross and Nozik

detailed balance argument for the efﬁciency of an inﬁ- In an attempt to increase the solar cell efﬁciency

nite stack of tandem solar cells which, for TS = 6000 K, above the Shockley–Queisser limit, Ross and Nozik89

comes out as 86.8%. A thermodynamic argument87 proposed a model which aims to eliminate the ther-

later showed that that the resulting efﬁciency is equiva- malization loss due to entropy generation (33) on

lent to the method of Monochromatic Photon Gas— photon cooling. In such a hot-carrier solar cell,

in other words, setting the open circuit voltage of each photogenerated electron-hole pairs created by light

elemental converter equal to the energy hν converted come to a mutual thermal equilibrium by electron–

with the Carnot efﬁciency (1−To/TS) but neglecting the electron interaction alone, without interaction with

pressure correction of the Landsberg efﬁciency. The lattice vibrations, and do not therefore incur the

deVos efﬁciency is plotted as a function of the ratio To/ associated energy loss. In their model, the interaction

TS in Figure 8. Interestingly, this graph is very close to of carriers in the absorber/hot reservoir with carriers

the graph of the photothermal efﬁciency, as noted at contacts at ambient temperature occurs via ‘selec-

already in Ref 31 (see also Ref 88). The relationship tive energy contacts’: only and holes in a very narrow

between different efﬁciencies that have been suggested energy range are extracted in the charge separation

as representing the maximum achievable efﬁciency of process (Figure 10). The optimum energy ΔEuse

solar energy conversion discussed in this review are which was transferred between the two reservoirs

shown in Figure 9. was to be determined by an optimization of the over-

all conversion process. Ross and Nozik assumed that

this limited interaction between the two reservoirs

does not disrupt the thermal equilibrium, and that

work in the form of electrochemical potential is thus

Power Energy

carried reversibly, without any entropy generation.

efficiencies efficiencies On further analysis, Würfel et al. 86 concluded

that the Ross and Nozik model contained serious

inconsistencies. The extraction of electron-hole pairs

Carnot (95.0)

95% at a single energy other than the average energy

would make it impossible for the system to achieve

Landsberg steady-state operation upon illumination. A further

(93.3)

objection can be raised with respect to the elective

energy contacts which remove carriers within a very

90% narrow energy range from the hot reservoir and

inject a monoenergetic jet of hot carriers into the

Efficiency

IT (86.8)

HC (86.4) on the grounds of equilibrium thermodynamics, how

PT (85.4) this mechanism provides a thermodynamically revers-

85%

IT-PC (85.0) ible pathway for the exchange of electron-hole pairs

between two reservoirs at different temperatures

while carrying out the maximum amount of work.

Notwithstanding, a consistent model of hot-

80% carrier converter can be reconstructed based on ele-

ments of the Ross and Nozik scheme, in search of the

maximum efﬁciency which can be attained by elimi-

ER (77.7)

nating the entropy generation by photon cooling. To

FI GU RE 9 | The efﬁciencies discussed under the maximum this end, we assume, in keeping with Ross and

concentration of sunlight in this paper for TS = 6000 K and Nozik, that electron-hole pairs reach an equilibrium

To = 300 K. PT, Photothermal; ER, Endoreversible (both discussed in without energy loss to phonons. The hot carriers are

the Light Heat and Work section); IT, Inﬁnite tandem; IT-PC, Inﬁnite then cooled to ambient temperature and perform

tandem with pressure correction; HC, Hot-carrier (the last three work in a Carnot engine, details of which we leave

discussed in the Future Directions section). The four efﬁciencies in the unspeciﬁed.

Carnot—Landsberg scheme are linked by dashed gray arrows to The model to be consider here, summarized in

indicate the insertion of the ﬁll factor/kinetic entropy generation and Figure 11, considers incident photons in a beam with

by full arrows to show the pressure correction.

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μH) will therefore be lower than in the incident beam

of black-body radiation, and must be therefore nega-

Contacts

tive. In general, the étendue expansion will also result

in a lower absorber temperature (to be denoted by

me

TH) since the full-spectrum black-body radiation is

Euse not an ideal gas, unlike the moderate-intensity radia-

mH Eg

tion with an energy threshold considered in Quan-

mh tum Solar Energy Conversion section. The emitted

photons are in equilibrium with the hot electron-hole

pairs, at temperature TH and chemical potential μH

which are now cooled to the ambient temperature

whilst carrying out reversible work (Figure 11)

The model can be readily analyzed for an ideal

hot-carrier converter operating under one-sun illumi-

F I G U R E 10 | A schematic representations of the band structure nation.90 The analysis is similar to the single-junction

and relevant energies in a hot-carrier solar cell. In an optimum solar cell although differences arise in detail as an

structure, the bandgap Eg would be close to zero. optimum hot-carrier solar cell absorbs the full solar

spectrum which implies that, unlike in conventional

TS, S = 0, in

TH, H É 0, out solar cells, the ideal bandgap is close to zero. The ﬁrst

steps in the conversion process—photon absorption

and subsequent equilibration of the hot-carrier reser-

voir at temperature TH and chemical potential μH are

conveniently considered together. Under one-sun

operation, the étendue expansion results in a chemi-

TH, µH cal potential which is negative and large in magni-

tude. The analysis can be carried out analytically

with the results, at open circuit,

π4

TH = TS = 5402 K

90ζð3Þ (

) ð37Þ

i = 0 ωS TS 3

μH = kB TH ln ζ ð3Þ = − 4:76 eV

w=µ π TH

A similar model was considered by Parrott 91 as a

representation of solar radiation by black-body spec-

trum. When ﬁnite current is extracted from the cell

To

and fewer photons are emitted by the cell, the tem-

perature TH remains constant along the current–

F I G U R E 11 | A schematic representation of the modiﬁed Ross voltage characteristic but chemical potential μH

and Nozik model. Photons absorbed in a hot absorber acquire decreases (Figure 12(a) and (b)).

temperature TH and chemical potential μH. Some photons are emitted The work carried out by the hot electron-hole

and some are converted to electricity in a Carnot engine, with pairs is now set equal to the chemical potential at

maximum efﬁciency. Entropy is generated only in the absorption/ T = To, and can be found from the energy/entropy

emission process.

balance equations (22) by setting uin ! uH, sin !

sH = (uH − μH)/TH and μout ! uout − Tosout, giving

étendue ℰin that are absorbed in an absorber. Photons

which are not converted into electrical current are To To

μ = uH −To sH = 1 − uH + μ ð38Þ

emitted, in a beam with étendue ℰout, in such a way TH TH H

that the energy per photon is conserved. The entropy

of photons in the emitted beam will be higher than in analogous to the Ross and Nozik result with the

the incident beam since ℰout ≥ ℰin. The chemical replacement ΔEuse!uH = uS. The ﬁnal output from

560 © 2016 The Authors. WIREs Energy and Environment published by John Wiley & Sons, Ltd. Volume 5, September/October 2016

WIREs Energy and Environment From steam engine to solar cells

ventional current—voltage characteristic of an ideal

–5

single-junction solar cell with Voc = 1.055 V,

µH / kBTH

(c)). The resulting conversion efﬁciency of 67.0% can

–10 be compared with the Ross and Nozik result 65.7%

(obtained, however, under a different spectrum) and

–15 the efﬁciency 68.2% for an inﬁnite tandem under

one-sun illumination.

(b) The operation of a hot-carrier solar cell under

6000

maximum concentration is similar in principle. At

open circuit, the temperature of emitted photons and

excited electron-hole pairs is equal to the temperature

TH, K

potential is zero. The open-circuit voltage corre-

sponds to the average photon energy uS in the full

5000 solar spectrum equal to 1.397 eV, converted with the

(c) 1.5 Carnot efﬁciency: qVoc = uS*(1−To/TS) = 1.327 eV.

As ﬁnite current is extracted from the cell, the tem-

perature TH, and chemical potential μH both decrease

Voltage V, or power, rel. u.

erated current corresponds to the full photon ﬂux of

52.6 × 106 A/m2.

0.5

LIGHT TRAPPING

0

0 1 Not all energy aspects of radiation with relevance to

Current (rel. units) photovoltaics involve temperature or heat, or are

directly concerned with energy conversion. One such

FI GU RE 12 | The thermodynamic parameters of the hot-carrier area is the capture of solar radiation and the phe-

solar cell. Red lines correspond to maximum concentration; blue lines nomenon of light trapping.

to one-sun illumination. (a) The ratio μH/kBTH of the chemical to

The fundamental nature of this concept can be

thermal energy for the absorber. (b) The temperature TH of the hot

understood by considering the balance of energy and

absorber. (c) The current–voltage and power characteristics (full and

dashed lines, respectively).

photon ﬂow near the interface between two media

with different refractive indices (Figure 13(a) and

(b)). As the photon density per unit volume in a

modes

c nph

nph ~ n31 f ext = –– ––––– ~ n21

n1 4p

c nph

nph ~ n32 f ext = –– ––––– ~ n22

n2 4p

Trapped/

internal

modes

Medium 2: refractive index n2

FI GU RE 13 | The energy densities (a) and photon ﬂuxes (b) at the interface between two media with different refractive indices. (c) The

radiation and trapped modes in a medium with a higher refractive index, separated by the ‘escape cone’ with critical angle θc, deﬁned by the

Snell’s law.

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dielectric with a refractive index n is n3 times higher emission rate within the volume described by

than in vacuum, Planck’s relation (4) predicts differ- Planck’s law:

ent photon ﬂuxes directed from opposite sides

toward an interface between two media of different eν ℰ = ð1 − rν Þε=ν V ð39Þ

optical density. The equilibrium balance of ﬂows

across the interface is established by virtue of geome- where eν and ε=ν are the Kirchhoff’s surface emissivity

try and Snell’s law: only photons within the ‘escape and Plank’s volume emission coefﬁcient (see Balance

cone’ are allowed to escape, creating a directional between Absorption and Emission of Radiation sec-

barrier for photon ﬂow from the optically denser tion). For full generality, we have assumed that pho-

medium (Figure 13(c)). This constraint makes it more ton emission or absorption from the volume is

difﬁcult for photons to escape, trapping photons in constrained to a beam with any étendue ℰ. By virtue

the optically denser medium. of equilibrium, we could assume the photon density

An range of ingenious ways have been pro- per unit volume in the medium to be constant both

posed how this situation can be exploited to improve with respect to position and orientation.

the capture of solar radiation (see Ref 92 for a recent Equation (39) expresses the fact that all

comprehensive review of this ﬁeld). In this chapter, photons emitted inside a volume will be emitted to

we conﬁne ourselves to statistical techniques that the exterior unless reabsorbed. It introduces a new

have proved most successful in practical applications. quantity rν: 93,o the average probability that a pho-

The key feature of statistical light trapping is ton, created in the interior of the medium, is reab-

that the photon gas achieves completely random sorbed before being emitted from the volume. From

orientations. We may recall that such concept was an alternative viewpoint, rν complements Kirchhoff’s

already considered by Kirchhoff and Planck (see absorptivity aν for photons arriving from the interior

Black Body Radiation section). The randomness in of the medium.

orientations in black-body radiation occurs by virtue Equation (39) can be transformed into an

of strong absorption and re-emission. In contrast, absorption balance with the use of the relevant Kirchh-

light trapping is considered for weakly absorbing off’s and Planck’s laws, relating, at the same time,

media where random orientations of photon direc- photon ﬂuxes inside and outside the medium with the

tions are caused by scattering. The maximum permit- use of the brightness theorem (Balance between

ted occupation of the trapped photon states is then Absorption and Emission of Radiation section):

reached under a full directional equilibrium, resulting

in the highest enhancement of absorption. aν ℰ = 4π ð1−rν Þαν n2 V ð40Þ

Let us consider a volume V of such optically

random medium with a refractive index n, in equilib- Equation (40) can easily be solved for strongly scat-

rium with a surrounding medium with a refractive tering media where the stochastic mature of photon

index of unity (Figure 14). The requirement that the paths ensures that the probability of photon absorp-

absorption and emission of external radiation be bal- tion is the same, regardless whether photons origi-

anced by photon creation and annihilation in the nate inside or outside the medium. This makes it

bulk then gives the fundamental condition for statis- possible to set aν = rν, giving:

tical light trapping. This is expressed in mathematical

terms by linking the Kirchhoff’s law for emission

ℓopt α

from the surface of the medium with the total rν = ð41Þ

1 + ℓopt α

av where

Incident: Φvinc

ℓopt = ð42Þ

dV ℰ

Emitted 4pev dV

denotes the mean path length that photons traverse

Emitted: Φvem before escape. Result (42) can also be obtained

1 – rv

directly based on the stochastic nature of radiation

F I G U R E 14 | The Kirchhoff and Planck relations between the by using an argument analogous to the escape of gas

absorption and emission of radiation by a volume dV (to be compared through a hole94 if augmented by a factor due to the

with Figure 1). directional barrier to photon escape.

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WIREs Energy and Environment From steam engine to solar cells

tions, this has made it possible to manufacture com-

mercial or near-commercial crystalline silicon solar

cell of thickness 20–30 μm—a signiﬁcant saving in

material over traditional solar cells several 100 μm

thick. The ultimate objective, however, must be to

achieve a good efﬁciency with a cell thickness of the

order of a micrometer or less, comparable with thin

(b) ﬁlm or organic-based devices.

Understandably, there is currently much research

in this direction. A considerable effort is devoted, in

p+

particular, to studies of light trapping in ultra-thin

layers where scattering is generated by plasmon modes

n at metallic nanoparticles deposited on the surface.101

n+ oxide

p-silicon p+ The trapped modes then form a discrete set, and a full

p+ rear contact p+ oxide

understanding is needed of the relationship between

the optical path length (42) and the density of trapped

modes in the thin layer or waveguide (see, e.g., Refs

(c) Light 102 and 103). The gains through increased absorption

in speciﬁc spectral regions may be offset against dissi-

pative losses in the metal particles and a reduced

entropic advantage of fewer trapped modes.104 The

Electron use of molecular dipoles for a similar purpose has also

injection been suggested.105 Whatever the ﬁnal outcome, ideas

Dye based on thermodynamics are already being used to

Electrolyte advantage. An example of recent developments can

serve the recent clariﬁcation106 based on the reciproc-

ity between absorption and emission, that the increase

in short-circuit current due to light trapping is miti-

TiO2 gated by an increase in the dark saturation current,

nanocrystals lowering the open-circuit voltage. Whatever the

FI GU RE 15 | Examples of light trapping schemes in several enhancement, light trapping by itself cannot therefore

current types of solar cells. (a) Light trapping in the form of small be used to surpass the Shockley–Quisser limit, as has

pyramids etched in the top surface as implemented in, for example, recently been suggested.107

the COMSAT ‘black’ solar cell.97 (b) A more sophisticated form of Other suggestion to enhance light trapping is

surface texturing in the form of inverted pyramids on the UNSW PERL based on expanding the thermodynamic analysis into

cell.98 (c) Structure of the dye-sensitized (Grätzel) cell with light the frequency domain. This is easily achieved by the

trapping by scattering from titanium oxide nanoparticles.96 management of photon directions as well as frequency

using photon absorption and re-emission as ﬂuores-

cence (Figure 16). In thermodynamic terms, the ﬂuo-

Equation (42) can be written in a number of rescent medium then effectively exchanges energy with

modiﬁed but similar forms, and has been used to dis- the photon ﬁeld which no longer represents as an iso-

cuss light trapping in a wide variety of solar cell lated system. This energy loss can then be traded for

structures95–98 (Figure 15). Applied to a thin layer of an extension of the path length through solar cell

thickness d, Eq. (42), simpliﬁes to beyond the monochromatic limit (42), or for an éten-

due reduction in a device that emits light.108 These

ℓopt = 4n2 d ð43Þ two applications are brieﬂy discussed below.

A device which transforms the entropy change

known as the Yablonovitch limit. 99,100 on photon cooling into an étendue reduction is called

Light trapping has been successful in improving a ﬂuorescent concentrator/collector. It usually repre-

the operation of commercial devices, particularly sents a ﬂuorescent plate that absorbs light from the

crystalline silicon solar cells. Equation (43) predicts a large face and emits the ﬂuorescent light through the

theoretical enhancement in path length by a factor of edge, making it possible to employ signiﬁcantly smaller

about 50 in comparison with a single passage solar cells. Studied since the late 1970s,109–112 the

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(a) (c)

Emission

Photonic filter / Incident solar

mirror

PV cell

Frequency

management

mirror

Photon energy

(b)

hDv

Reflectance

Photonic filter /

mirror

Frequency

management

PV cell

Photon energy

mirror Semiconductor Photonic

bandgap bandgap

F I G U R E 16 | Principles of photonic frequency management based on thermodynamics. (a) The ﬂuorescent concentrator/collector, where a

photonic bandstop helps to guide emitted light toward a solar cell at the edge. (b) The photonic bandgap solar cell where a photonic bandstop

traps assists the trapping of light emitted by the highly absorbing photon management layer inside a poorly absorbing solar cell. (c) The

reﬂectance of the photonic bandstop in (a) and (b) compared with the spectrum of the incident and ﬂuorescent radiation.

interest in ﬂuorescent collectors has recently been the spectrum but for an optimum value which trans-

revived due to the availability of a wider range of dyes mits a sufﬁcient part of the solar spectrum while

and the developments in photonics. There is much ensuring a substantial enhancement in light trapping,

optimism for a substantial increase over the current as illustrated on the example of a predicted quantum

overall efﬁciencies (solar cell plus collector) of efﬁciency that can be reached by a solar cells116

7–8%113,114 Particularly, fruitful direction appears to (Figure 17).

be the application of photonic structures to trap the

narrow-band ﬂuorescent light while allowing most of

the incident broadband solar ﬂux to be absorbed by

the collector (Figure 16(c)). Such structures can limit 1.2

photon losses to less than about 10% of the incident

light, leading to overall efﬁciencies of 18–20% with a 1.0

500µm,

good crystalline silicon solar cell.115

Quantum efficiency

BSR

0.8 1µm, geom.

This ‘thermodynamic squeezing’ of light which 1µm, BSR

light trapping

lies in the heart of operation of the ﬂuorescent collec- 0.6

tors can also be used to advantage to improve the 1µm, photonic

capture of weakly absorbed light. The use of a photo- 0.4 light trapping

nic ﬁlter in combination with frequency management

extends the photon path length by a factor equal to 0.2

an inverse of the Boltzmann factor appropriate to the 0.0

frequency bandwidth of the trapped light:115 300 500 700 900 1100

Wavelength (nm)

ℓopt ﬃ 4n2 de hΔν=kB To ð44Þ F I G U R E 1 7 | The internal quantum efﬁciencies of solar cells with

geometric and photonic light trapping, compared with a conventional

If the width of the frequency band stop Δν is large, (thickness 500 μm) and thin (1 μm) crystalline silicon solar cells. BSR

the photonic structure would block a large part of indicates Back Surface Reﬂector (after Ref 116).

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WIREs Energy and Environment From steam engine to solar cells

TABLE 2 | Efﬁciencies of Solar Cells with Quantum Efﬁciencies can operate as quantum ampliﬁers or refrigera-

Shown in Figure 17 tors119—can a similar approach (possibly based on

500 μm c-Si cell 30.3%

rectifying antennas)120,121 be exploited to beneﬁt

solar energy conversion?

1 μm cell (BSR only) 15.6%

These are just a few, almost random thoughts.

1 μm cell (geometric light trapping) 26.0% Few persons alive during the age of the steam engine

1 μm cell (photonic light trapping) 30.7% would have predicted the success of thermodynamics

in the design of modern aircraft, rockets, automo-

biles, and energy equipment that we enjoy today. It is

The predicted power conversion efﬁciencies are likely that the ‘thermodynamics of light’ will see

shown in Table 2. Remarkably, the cell efﬁciency of many years of further development, with application

a cell with thickness merely 1 μm is now comparable to new devices that are yet to be discovered. Its true

with (and even slightly exceeds!) the efﬁciency of the moment of success may well be ahead of us.

500 μm cell.

NOTES

CONCLUSION AND OUTLOOK a

The possibility to excite photons with energy higher than

Solar radiation can be represented as high- the corresponding applied voltage. See Ref 1.

temperature heat and its conversion into useful work b

A comprehensive review of efﬁciencies that have been

or electricity is described well by the laws of thermo- considered for solar energy conversion can be found in

dynamics. It is therefore not surprising that thermo- Ref 4.

dynamics now forms a routine part of the modeling c

Although the name appears to be fairly recent, similar

toolset for both the current and future generations of concepts have been associated much earlier with such dis-

solar cells, and our thinking should not be about if tinguished names as Poincaré, Lagrange, and Helmholtz.

d

but how thermodynamics can guide us to make bet- A clear exposition of the optical ideas behind the concept

ter solar cells. of étendue can be found in Ref 6.

e

The theoretical framework of thermodynamic The ﬁrst paper that appears to have drawn attention to

applications to solar energy conversion has witnessed the link between étendue and a volume on the phase space

steady development but a number of theoretical ques- appears to be in Ref 7.

f

tions and problem areas remain. How can thermody- A particularly clear discussion of this point can be found

namics be used to increase the solar cell efﬁciency? in Ref 11.

g

Several ideas have been discussed (for example, hot- In photon terminology that will be used throughout this

carrier solar cells, reviewed in the Model of Ross and paper, the balance between absorption and emission was

Nozik section) but the theory still requires develop- formulated for semiconductors (but can be easily

ment to reach a satisfactory level of understanding. generalized).23

h

Questions remain about the relationship between the This subject is reviewed in a particularly clear form in

application of classical thermodynamics to kinetic Ref 32.

i

processes and the issues of reciprocity or microscopic See, for example, Section 20 in Ref 13 or Chapter 7 in

reversibility. Can nonreciprocal structures lead to Ref 14.

j

higher efﬁciencies than those that were discussed in More rigorously, the internal energy u, entropy s as well

this review? as the chemical potential μ refer to adding or removing a

photon at constant volume rather than at constant pres-

What clues can thermodynamics provide as to

sure, as in the usual analysis of chemical reactions. We

new mechanisms and materials? With increasing use shall return to this assumption later in Thermodynamics of

of nanotechnology and a drive toward ever thinner Photovoltaic Conversion section.

devices, effective capture of sunlight is key to the efﬁ- k

A full treatment in terms of rate of photon emission and

cient new solar cells. A classical approach to light work (as depicted in Figure 2(c)) is described in Ref 67,

trapping was reviewed in the Light Trapping section, leading to identical results.

but there is a need to extend the theory to ultrathin l

In our analysis, the ﬁll factor contains the current corre-

solar cells in the form of wave guides or photonic sponding to the full photon ﬂux qΦin rather than the more

structures that trap or concentrate sunlight. Quan- usual photogenerated current Iℓ. In practical applications,

tum heat engines have been proposed based on the the difference between the two—equal to the dark satura-

thermodynamic description of masers and tion current Io—is very small and can be safely neglected.

lasers117,118 involving coherent transitions between m

In practical terms, this implies a concentration ratio of

quantum levels coupled to heat baths. These engines less than about a hundred for a silicon solar cell.

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n o

This value was obtained by a more accurate numerical Detailed discussions of reabsorption (also called photon

procedure than in Ref 85, and is slightly lower than the recycling) with application to solar cells can be found in

result 85.2% reported there. Refs 83, 84 and 93.

ACKNOWLEDGMENTS

The author’s initial stimulus to embark into research in this ﬁeld came from many frequent conversations and

debates with the late Peter Landsberg without whom this article would not have seen the light of day. Over

many years, many topics in this review have been enriched by stimulating discussions with Gottfried Bauer,

Philip Davies, Jeffrey Gordon, Martin Green, Marius Peters, Dieter Meissner, and Peter Würfel, as well as with

my colleagues and students at Southampton Solar Energy Laboratory. Although the full agreement about many

aspects is still to be reached, I hope that these debates have helped to convey the rich tapestry of science being

woven into a picture which may, one day, reﬂect a satisfactory and thorough understanding.

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