Abstract
Theoretical limiting efficiencies have a critical role in determining technological viability and expectations for device prototypes, as evidenced by the photovoltaics community’s focus on detailed balance. However, due to their multicomponent nature, photoelectrochemical devices do not have an equivalent analogue to detailed balance, and reported theoretical efficiency limits vary depending on the assumptions made. Here we introduce a unified framework for photoelectrochemical device performance through which all previous limiting efficiencies can be understood and contextualized. Ideal and experimentally realistic limiting efficiencies are presented, and then generalized using five representative parameters—semiconductor absorption fraction, external radiative efficiency, series resistance, shunt resistance and catalytic exchange current density—to account for imperfect light absorption, charge transport and catalysis. Finally, we discuss the origin of deviations between the limits discussed herein and reported watersplitting efficiencies. This analysis provides insight into the primary factors that determine device performance and a powerful handle to improve device efficiency.
Introduction
In the photovoltaics community, the detailed balance limit serves as a gold standard to which all device efficiencies are compared^{1}. The seminal paper written by Shockley and Queisser in 1961 presents photovoltaic limiting efficiencies as a function of a single parameter, the semiconductor bandgap, under the assumption that the only loss mechanism is radiative recombination in the semiconductor. While many corollaries to this limit exist^{2,3,4,5,6,7,8,9}, the transcendence of this analysis is enabled by its elegance, analytic simplicity and basis in the ultimate limit of semiconductor device physics.
Due to their complex, multicomponent nature, an equivalent analogue to the detailed balance limit does not exist for photoelectrochemical (PEC) devices. A number of articles have been written on the limiting efficiencies of photoelectrochemical devices^{3,10,11,12,13,14,15}, each with slightly different approaches and assumptions to arrive at different limiting efficiency values. In this article, we aim to present a unified framework for photoelectrochemical device performance through which all previous limiting efficiencies can be understood. To do so, we first present the analytic equations and solutions for the limiting efficiencies of photoelectrochemical watersplitting devices based on the ultimate limits of device physics; limiting efficiencies reported here are consistent with those presented in references^{3,13,15}. Subsequently, we examine the validity of these ideal limits and consider more realistic limits based on existing materials, similar to those presented in references^{10,11,12,14}; the realistic limits are presented and discussed as a function of five parameters: semiconductor absorption fraction, semiconductor external radiative efficiency (ERE), series resistance, shunt resistance and catalytic exchange current density. These five parameters directly correlate with the three governing physical phenomena of photoelectrochemical device operation—light absorption (absorption fraction), charge carrier transport (ERE, series resistance and shunt resistance), catalysis (catalytic exchange current density); the parameter variation study demonstrates the varying impact of each phenomenon on overall device efficiency and efficiency limits. Finally, this analysis is contextualized via a comparison of the discussed limits with reported watersplitting efficiencies.
Results
Outline
The following analysis of watersplitting device efficiencies is divided into five parts. First, we derive the analytic equation that governs a variablejunction photoelectrochemical device and its efficiency. This set of equations is generally applicable to any photoelectrochemical device. Second, we present the absolute limiting efficiencies for a photoelectrochemical device for watersplitting for both single and dual junction photodiode units. Subsequently, we present two sets of realistic limiting efficiencies based on currently available high performance (real_{1}) and Earth abundant (real_{2}) materials. Next, we consider the effects of five representative parameters on the limiting efficiency and the corresponding semiconductor bandgap(s). Finally, we contextualize this theoretical efficiency analysis via a brief discussion of reported efficiencies. This analysis provides insight into the primary factors currently limiting device efficiency and guidance to researchers on (1) the most powerful handles to improve device efficiency and (2) routes to maximize device efficiency for a given set of material and device parameters.
Analytic equation for PEC device operation and efficiency
In previous work, we derived analytic equations for a variablejunction photoelectrochemical device^{16,17}. This derivation is briefly summarized below. The characteristic currentvoltage relationship for a photoelectrochemical device lends itself to an inverse formulation, V_{PEC}(j), where V_{PEC} is the voltage generated by the device that is available for conversion into chemical energy, j is the device current density, V_{PV,i}(j) is the inverse currentvoltage relationship for the ith photodiode component, V_{cat,a}(j) and V_{cat,c}(j) are the currentdependent overpotentials of the anodic and cathodic catalysts, respectively, V_{series} is the series resistance due to electrolyte transport through solution and membrane, formulated as jR_{series}, and E_{rxn} is the electrochemical potential of the desired chemical reaction.
The photodiode voltage is described by an inverse formulation of the diode equation, where j_{0} is the reverse saturation (dark) current, n_{d} is the ideality factor, k_{B} is the Boltzmann constant and T is the device temperature.
ButlerVolmer kinetics are selected to describe the current densitydependent catalytic overpotentials, V_{cat}(j); this model and the further simplified Tafel equation are commonly used to fit electrocatalyst behaviour, however, it should be noted that ButlerVolmer kinetics are only accurate for outer sphere single electron transfer reactions^{18}. Specifically, we employ an inverse formulation of the ButlerVolmer equation, found by assuming that the charge transfer coefficients of a specific catalyst in the forward and reverse directions, α_{f} and α_{r}, are equal, where R is the universal gas constant, n_{e} is the number of electrons associated with the reaction, F is Faraday’s constant and j_{0,cat} is the catalytic exchange current density. A comparison of this formulation, the more standard Tafel equation and the complete ButlerVolmer equation is provided in Supplementary Note 1 and Supplementary Fig. 1, as well as in previous work^{17}.
The reaction proceeds when the photoelectrochemical device voltage is greater than or equal to the electrochemical potential required to drive the reaction, E_{rxn}, as defined in equation (1). The maximum efficiency occurs when the voltage is precisely equal to the required electrochemical potential because this maximizes the device current density; this point is defined as the device operating point, V_{op}(j_{op})=E_{rxn} (see Supplementary Note 2 and Supplementary Fig. 2 for visualization). The device operating current density is directly proportional to the device efficiency, η_{PEC}, according to the following equation, where f_{FE} is the Faradaic efficiency and P_{in} is the incident solar power.
Absolute limiting efficiencies
To determine the absolute limiting efficiencies of single and dual junction photoelectrochemical devices for watersplitting, the following assumptions were made (and are also summarized in Table 1):

1
Illumination with the AM1.5G spectrum:
2. Complete absorption of all photons above the bandgap of the semiconductor.
3. A detailed balance model for the photodiode dark current, assuming only radiative recombination in the semiconductor:
This equation assumes a perfect antireflective coating and perfect back reflector. For the dual junction calculations, the dark current of the upper junction is multiplied by a factor of 2 to account for emission from the upper and lower surfaces. A detailed treatment of angular emission probability, more formally known as the etendue, can be found in Markvart et al.^{19}
4. Diode ideality factor, n_{d}, of 1.
5. Catalytic overpotentials are assumed to be negligible. Mathematically, this assumption corresponds to infinite catalytic exchange current densities. This condition can be approached by (1) discovery of new catalysts with very highcatalytic exchange current densities and (2) highsurface area catalyst and high catalyst loading, which increases the effective catalytic exchange current density when normalized to device area.
6. Charge transfer coefficients of 0.5.
7. No series resistance.
8. The electrochemical potential for watersplitting at standard conditions, E_{rxn}=1.23 V.
9. Unity Faradaic efficiency.
The analysis is restricted to single and dual junctions because additional junctions do not result in any efficiency gains. In fact, the maximum ideal triple junction efficiency for watersplitting is 28.3%, which is significantly lower than the maximum dual junction efficiency (40.0%). This drop in efficiency with increasing junction number (beyond 2) is contrary to photovoltaic efficiencies and occurs because additional photovoltage beyond that required to kinetically split water does not increase efficiency; furthermore, the increased number of currentmatched junctions reduces device photocurrent, which directly lowers efficiency, as shown in equation 4.
Figure 1 (blue solid line) and Fig. 2a display the limiting efficiencies as a function of semiconductor bandgap for single and dual junction photoelectrochemical devices, respectively, that result from this ideal set of assumptions. The maximum single and dual junction efficiencies are 30.6% at a bandgap of 1.59 eV, and 40.0% with bandgaps of 0.52 and 1.40 eV, respectively. The single junction efficiency trend, Fig. 1(blue solid line), strongly resembles that of the single junction photovoltaic detailed balance limit, with a few notable differences. The efficiency decreases for bandgaps smaller and larger than the maximum efficiency point due to the inverse correlation between light absorption and voltage generation. The efficiency decreases with increasing bandgap due to decreased absorption of the incident solar spectrum, but the photoelectrochemical efficiency decreases more rapidly than the photovoltaic efficiency because the voltage converted to chemical energy remains constant (E_{rxn}) despite the larger photovoltages supplied by wide bandgap semiconductors. According to equation (4), the decrease in efficiency is directly proportional to the decrease in photocurrent. For small bandgaps, the photoelectrochemical efficiency drops off sharply to zero, in contrast with the gradual decay of photovoltaic efficiency with decreasing bandgap; this sharp cutoff in efficiency occurs due to insufficient photovoltage to drive the reaction. Another critical difference is that the maximum single junction photoelectrochemical device efficiency is about 3% lower than that of a single junction photovoltaic device, despite the fact that this calculation has neglected any catalyst or solutionrelated losses. This difference exists because the output voltage of a photovoltaic device is variable, whereas the required output voltage of a watersplitting device is fixed at 1.23 V. The result of this requirement is that the maximum efficiency occurs for the semiconductor with a sufficient bandgap to generate 1.23 V of photovoltage, which is a bandgap of 1.59 eV assuming detailed balance.
The ideal dual junction efficiency contour plot (Fig. 2a) exhibits a similar trend, but in two dimensions; it has a sharp turnon of efficiency for bandgaps just large enough to supply the watersplitting efficiency voltage and a gradual decline of efficiency beyond the peak due to decreasing light absorption. The dual junction watersplitting efficiency falls short of the dual junction photovoltaic efficiency for the same reason: fixed photovoltage.
Realistic limiting efficiencies
The absolute limiting efficiencies presented in the previous section represent theoretical limits for an ideally constructed device with ideal photodiodes and catalysts. This section presents realistic limiting efficiencies based on material and device parameters reported in literature for (1) high performance (real_{1}) and (2) Earth abundant photodiodes and catalysts (real_{2}). Five material parameters capture nonideal photodiode and catalyst performance—semiconductor absorption fraction, f_{abs}, semiconductor ERE, series resistance, R_{S}, shunt resistance, R_{Sh} and catalytic exchange current density, j_{0,cat}. Absorption fraction and catalytic exchange current density represent the efficiency of light absorption and catalysis. The efficiency of charge carrier transport is divided into three parameters, where ERE represents intrinsic semiconductor material quality in accordance with the photovoltaic community^{20}, and series and shunt resistance represent device fabrication quality. ERE serves as a straightforward, linear modification to the detailed balance limit (as shown in assumption #2, below). In the detailed balance limit, the only loss mechanism is radiative recombination, as required by black body emission of the semiconductor above its band edge. This limit implies that a photodiode at open circuit voltage will reemit all photons that were absorbed. This ideal case corresponds to an ERE of 1. In real absorbers, nonradiative recombination mechanisms exist, so that the reemitted photons at open circuit voltage are only some fraction of those absorbed; this fraction is the ERE. Additional details and tabulated values for photovoltaic materials can be found in ref. 20. For semiconductor–liquid junctions, the ERE factor can also be treated as a simple dark current modification factor (see equation 8) to align the open circuit voltage of the model to the builtin voltage of the semiconductorelectrolyte interface^{18,21}. The series and shunt resistance terms account for nonidealities in charge transport that are not captured by the ERE parameter and primarily affect the device fill factor. Series resistance reduces the fill factor and, at high values, also the short circuit current density; sources of series resistance include solution resistance to electrolyte transport, interfacial resistance at the semiconductorcatalyst interface, and resistance to majority carrier flow in the semiconductor. Shunt resistance pathways lower the fill factor and, at significantly low values of shunt resistance, can also reduce open circuit voltage; shunt resistance arises from partial shorting of diode junctions, which can occur quite readily in semiconductor—liquid junctions due to the ease with which liquid electrolyte can intercalate into pinholes in the semiconductor^{22,23,24}.
Highperformance realistic efficiencies
We first consider realistic limiting efficiencies for highperformance materials and devices. In these calculations, we include the effects of nonideal light absorption, ERE and catalytic exchange current density, but neglect the effects of series and shunt resistances because fill factors of current highperformance photodiodes are approaching their ideal values^{25}. Specifically, the following modifications to the ideal efficiency calculations in the previous section were made (also summarized in Table 1):

1
Absorption of 90% of incident photons above the bandgap of the semiconductor. Reflection and incomplete and parasitic absorption by catalyst materials or other device components contribute to this 10% loss. Analytically, we express this nonunity absorption fraction, f_{abs}, as a modification to the ideal diode equation:
2. An ERE of 3%, meaning that the detailed balance radiative recombination represents 3% of the total (radiative and nonradiative) recombination, and thus 3% of the total dark current. This value is characteristic of highperformance III–V materials^{20}. Analytically, ERE modifies the ideal photodiode dark current:
3. Catalytic exchange current densities of 1 mA cm^{−2} and 10^{−3} mA cm^{−2} for the hydrogen (cathodic) and oxygen (anodic) evolution reactions, respectively. These values are consistent with the best reported values in literature for Pt and IrO_{2}(refs 26, 27).
This analysis is limited to single and dual junction devices because triple junction maximum efficiencies are lower than that of dual junctions under these assumptions (25.4 versus 28.3%); although, the gap between dual and triple junction device efficiencies has narrowed in comparison to the ideal case.
Figure 1 (green dotted line) and Fig. 2b display the limiting efficiencies as a function of semiconductor bandgap for single and dual junction photoelectrochemical devices, respectively, under these assumptions. An identical colour scale is used for each contour plot in Fig. 2 for facile visual comparison. The maximum efficiency is 15.1% for a single junction device with a bandgap of 2.05 eV, and is 28.3% for a dual junction device with bandgaps of 0.92 and 1.59 eV. The highperformance realistic efficiency plots exhibit similar trends to the ideal efficiency plots, but the efficiencies are significantly lower and the optimum bandgaps are substantially higher. Due to the series addition of photovoltages, the inclusion of realistic experimental values in this calculation does not affect the dual junction device efficiency as dramatically as the single junction device efficiency. All three of the modifications stated above have a role in lowering the efficiency and increasing the optimum bandgaps, but as discussed in greater detail in the parameter variation section, the introduction of finite catalytic exchange current densities has the most dramatic effect.
Earth abundant realistic efficiencies
Next, we consider realistic limiting efficiencies for Earth abundant materials and devices that currently have less than optimal performance characteristics. In these calculations, we include the effects of all five parameters—nonideal light absorption, ERE, series resistance, shunt resistance and catalytic exchange current density. Specifically, the following modifications to the ideal efficiency calculations in the previous section were made (and are also summarized in Table 1):

1
Absorption of 90% of incident photons above semiconductor bandgap.

2
An ERE of 10^{−6}, consistent with reported values for Earth abundant materials^{20}.

3
Catalytic exchange current densities of 1 mA cm^{−2} and 10^{−5} mA cm^{−2} for the hydrogen (cathodic) and oxygen (anodic) evolution reactions, respectively. These values are consistent with reported values for Earth abundant catalysts in literature, such as NiMo for hydrogen evolution, and NiZn, CoFe and NiMoFe for oxygen evolution^{28}.

4
Normalized series and shunt resistance values of 0.1 and 10, respectively, which each result in approximately a 10% reduction in fill factor. Series and shunt resistances are normalized to the characteristic resistance of an ideal photodiode, which is the ratio of the open circuit voltage to the short circuit current density. This normalization results in an approximately bandgapindependent reduction in fill factor. A more detailed explanation and discussion of these parameters can be found in Supplementary Note 3. Analytically, incorporation of the shunt and series resistance terms results in a transcendental equation for the photodiode currentvoltage equation, where R_{S} and R_{Sh} are the absolute (nonnormalized) series and shunt resistances, respectively:
This analysis includes single, dual and triple junction devices because the additional assumed reductions in material and device parameters lead to a maximum triple junction maximum efficiency that exceeds that of a dual junction (17.3 versus 16.2%).
Figure 1(red dotted line), Fig. 2c, and Fig. 3 display the Earth abundant limiting efficiencies as a function of semiconductor bandgap for single, dual and triple junction photoelectrochemical devices that result from the above specified set of assumptions. Figure 3 displays the triple junction efficiency as a function of its upper two bandgaps for three values of the lower bandgap (0.73, 0.93 and 1.13 eV), and uses a colour scale identical to that of Fig. 2 for facile value comparison. The maximum efficiency is 5.4% for a single junction device with a bandgap of 2.53 eV, 16.2% for a dual junction device with bandgaps of 1.38 and 1.93 eV, and 17.3% for a triple junction device with bandgaps of 1.91, 1.36 and 0.93 eV (contained in the middle contour of Fig. 3). As expected, the Earth abundant realistic (real_{2}) efficiency plots also exhibit similar trends to the ideal efficiency and highperformance realistic (real_{1}) efficiency plots, but efficiencies are significantly lower and the optimum bandgaps are substantially higher; the dual and triple junction devices are also affected significantly less than the single junction devices by nonideal charge carrier transport. Additionally, the inclusion of series and shunt resistance terms that affect the fill factor result in a softening of the efficiency ‘turnon’ with increasing bandgap, which is most evident in the single junction device trend (Fig. 1, red dotted line). It is also important to note that the maximum triple junction device efficiency exceeds that of a dual junction device due to nonideal charge carrier transport and large catalyst overpotentials, indicating that use of Earth abundant materials may (presently) necessitate the use of three or more junctions to maximize device efficiency.
Effect of parameter variation on device efficiency
A detailed analysis of the dependence of device efficiency on key parameters provides insight into the most powerful handles to improve device performance. To this end, we present the dependence of the maximum achievable device efficiency and the corresponding semiconductor bandgap(s) on the aforementioned parameters for single (Fig. 4) and dual (Fig. 5) junction devices; specifically, parameter variations are performed around the three base cases presented in the previous sections (ideal, highperformance realistic—real_{1}, and Earth abundant realistic—real_{2}). The absorption fraction is varied between 0.7 and 1.0 (Figs 4a and 5a), the ERE between 10^{−6} and 1 (Figs 4b and 5b), the catalytic exchange current density between 10^{−4} and 10^{2} mA cm^{−2} (Figs 4c and 5c); the normalized series resistance between 0 and 0.2 (Figs 4d and 5d), and the normalized shunt resistance between 5 and 10^{3} (Figs 4e and 5e). The maximum device efficiency for a given set of parameters is plotted on the y axis and colour is used to display the corresponding bandgap(s); for the dual junction devices, the coloured line is a double band, where the upper component represents the wider bandgap, E_{g,1}, as indicated in the figure legends. The colour variation representation of the optimum bandgaps is designed to illustrate trends; for easier extraction of the precise numeric bandgap values, plots of bandgap versus parameter corresponding to Figs 4 and 5 can be found in Supplementary Figs 3, 4 and 5. The maximum efficiency points corresponding to the ideal, highperformance realistic (real_{1}) and Earth abundant realistic (real_{2}) cases presented in previous sections are marked on Figs 4 and 5; each point on Figs 4 and 5 originates from a calculation analogous to those in the previous sections with one modified parameter. Note that the ideal, real_{1} and real_{2} points are omitted from the j_{0,cat} variation plots because the anodic and cathodic exchange currents were lumped into a single parameter for simplicity. An animation is provided in Supplementary Movie 1 to visualize the connection between Fig. 3b and Fig. 1.
This sensitivity analysis reveals that the efficiency of a single junction device is predominantly controlled by catalyst performance (catalytic exchange current density—j_{0,cat}), whereas the maximum efficiency of a dual junction device is strongly affected by the optoelectronic performance of the semiconductor photodiodes in addition to catalyst performance (all five parameters—j_{0,cat}, f_{abs}, ERE, r_{s} and r_{sh}).
For single junction devices, variation of the catalytic exchange current density around all three cases (ideal, real_{1}, real_{2}) results in the largest modulation in device efficiency and semiconductor bandgap (Fig. 4c). As the catalytic exchange current density decreases and, thus, kinetic overpotential increases, the semiconductor bandgap required to drive the watersplitting reaction increases, which leads to a precipitous drop in efficiency due to reduced solar spectrum conversion, as illustrated in Fig. 1 and previously discussed. Series resistance (Fig. 4d) also has a distinct effect on single junction device efficiency because, even at moderate values, series resistance shifts the maximum power point to lower voltages and thus significantly lowers the photocurrent near the maximum power point, thereby lowering the efficiency for a given bandgap and pushing the bandgap for maximum efficiency to higher values. Variation of the ERE (Fig. 4b), absorption fraction (Fig. 4a) and shunt resistance (Fig. 4e) have significantly less influence than catalytic exchange current density and series resistance on the single device efficiency. Unlike series resistance, shunt resistance primarily lowers the photocurrent, but, at moderate values, does not significantly shift the voltage at maximum power; therefore, shunt resistance lowers the efficiency due to photocurrent, but the effect is more moderate because the optimum bandgap remains relatively constant. The dependence of device efficiency on absorption fraction is almost linear, and the bandgap corresponding to maximum efficiency is nearly unaffected due to the weak logarithmic dependence of photovoltage on photocurrent (equations (2) and (7)). The ERE exhibits a similar, nearly loglinear correlation with device efficiency; however, the semiconductor bandgap and device efficiency are more strongly correlated with ERE than with absorption fraction because a lower ERE translates to a lower photovoltage and, therefore, a large bandgap semiconductor is required to generate an equivalent photovoltage. The optimum bandgap trends provide guidance to experimentalists for (i) initial semiconductor selection in device design given known achievable material parameters, and (ii) when a redesign of their device would be beneficial to its performance. For instance, a significant improvement in catalytic exchange current density significantly shifts the optimum bandgap for maximum device efficiency and may suggest the use of a different semiconductor material with a lower bandgap whereas improvements in semiconductor absorption do not.
Unlike single junction devices, all five parameters have a significant effect on the overall dual junction device efficiency (Fig. 5). The effect of poor catalyst performance on dual junction device efficiency is mitigated due to the series addition of two photovoltages. Similar to the single junction device, an increase in photovoltage is needed to compensate for the increase in kinetic overpotential, but in a dual junction device, this photovoltage increase is split between two semiconductors, which translates to a smaller increase in required bandgaps and, consequently, less overall effect on device efficiency. Conversely, variation of the charge transport parameters (ERE, series resistance and shunt resistance) and absorption fraction affect the performance of each semiconductor individually and, therefore, the effect of these four parameters on overall efficiency is largely the same across single and dual junction devices. The kinks in the efficiency curves for ERE and catalyst exchange current density variations are a direct product of the AM1.5G spectrum; dips in atmospheric transparency translate to quick jumps in the ideal semiconductor bandgap, and thus, the efficiency. These kinks are not observed in all curves because the ideal bandgaps do not cross these values.
Theoretical limits versus reported efficiencies
To place the above theoretical analysis into context, this final section contains a brief consideration of discrepancies between theoretical and experimental efficiencies, based on three exemplary watersplitting devices—(1) a minimally integrated, dual junction Pt_{black}SiAlGaAsRuO_{2} device with 18.3% efficiency from Licht et al. in 2000 (ref. 29); (2) an integrated dual junction RhGaInPGaInAsRuO_{2} device with 14% efficiency from May et al. in 2015 (ref. 30); and (3) a triple junction CoPiBVOaSincSiPt device with 5.2% efficiency from Han et al. in 2014 (ref. 31). A recent review paper from Ager et al.^{32} provides a more comprehensive summary of record watersplitting efficiencies as a function of time and device subtype. These three devices were selected because they mimic our three cases (ideal, high performance and Earth abundant) and highlight the varying limiting factors in different device design strategies. In the device by Licht et al., a high efficiency, dual junction photodiode component is wired to large surface area, highperformance catalyst components. The device by May et al. also uses a highperformance dual junction photodiode, but is monolithically integrated with a highperformance catalyst and fully immersed in solution. The device by Han et al. takes a very different tact by employing all Earth abundant materials and sacrificing performance.
Despite the use of highperformance materials and large catalyst areas, the 18.3% efficiency device by Licht et al., recognized as the current record watersplitting efficiency by Ager et al. as of February 2015, falls far short of the ideal and highperformance realistic (real_{1}) limiting efficiencies (40.0% and 28.3%, respectively). The primary reason for this efficiency gap is nonideal bandgap selection. The ideal (real_{1}) efficiency limits for the bandgap combinations in the Licht device, 1.1 and 1.6 eV, and the May device, 1.26 and 1.78 eV, are 27.2% (24.5%) and 22.8% (20.5%), respectively. The ideal (real_{2}) efficiency limit for the bandgap combinations in the Han device, 2.4, 1.7, and 1.1 eV, is 9.2% (4.2%). The integration of ideal bandgap materials for multijunction devices is a challenge that also faces the photovoltaics community. For highperformance materials, the principal issue is that highquality material, which translates to high ERE, requires latticematched materials, and the latticematching requirement restricts the available bandgap combinations^{33}. Latticemismatched multijunction photovoltaics are the subject of much ongoing research, including strategies such as inverted metamorphic and pseudomorphic designs, to name a few, and progress in this area will be instrumental for waterspitting device efficiency improvement^{34,35}. In the realm of Earth abundant materials, the challenge is identification and optimization of a material with the appropriate bandgap, and for liquid junctions in the photoelectrochemistry community, also the appropriate band alignment and stability. When their nonideal bandgap combinations are taken into account, both the Licht and the May devices are within roughly 6% of the adjusted highperformance realistic (real_{1}) efficiency limits; and the Han device is within 4% of the ideal limit and actually exceeds the Earth abundant realistic (real_{2}) limit, clearly illustrating the primary limitation in Earth abundant devices—photoelectrode bandgap.
The factors accounting for the remaining 6% discrepancy between realized and theoretical efficiency are different for the Licht and May devices. The Licht device uses large area electrodes consisting of highperformance catalysts that are positioned in such a way as to not interact with light incident on the photodiode unit. Therefore, the majority of the losses in this device are due to less than ideal photodiode performance. An examination of the J–V curve of their photodiode reveals that both incomplete light absorption, nonideal EREs and shunt and series resistances have a role in the reduced efficiency; most notably, their fill factor is only 77% (∼10% below the ideal). The highperformance real efficiency limit trend with shunt resistance (Fig. 5e) shows that a 10% drop in fill factor (to r_{sh} of 10) results in a ∼5% drop in maximum efficiency; this value agrees well with the observation that the Licht device operating current was ∼5% below their short circuit current and wellaligned with their maximum power point. The May device faces different, and additional challenges due to the direct integration of catalyst on the photodiode surface. As illustrated in the supplementary information of May et al. and discussed theoretically in ref. 16, the loading of catalyst on the light incident side of the device has a tradeoff^{30}; low catalyst loading results in slow catalyst turnon and highcatalyst loading blocks light transmission. As a result, the May device loses significant current density (∼4 mA cm^{−2}) due to parasitic catalyst light absorption. May et al. also cite surface resistance and recombination at the semiconductor catalyst interface as sources of loss, indicating nonideal EREs and series resistance. Conversely, the primary factor limiting the Han device is the BVO performance; despite the use of gradient Wdoping, the high resistivity of BVO drastically reduces the device fill factor, and thus, its efficiency. Ultimately, these three exemplary devices illustrate that there is room for improvement both in individual component performance, particularly for Earth abundant materials, as well as their integration into watersplitting devices.
Discussion
In summary, we presented limiting efficiencies of watersplitting photoelectrochemical devices under ideal and realistic conditions, and arbitrary intermediate conditions through parameter variation studies. We first defined the general analytic equation that governs the currentvoltage characteristic of a variablejunction photoelectrochemical device and its efficiency. Second, we presented the limiting efficiencies (both ideal and experimentally realistic) of a watersplitting photoelectrochemical device for both single and dual junction photodiode units. Subsequently, we considered the effects of five parameters—semiconductor absorption fraction, semiconductor ERE, series resistance, shunt resistance and catalytic exchange current density—on the limiting efficiency and the corresponding semiconductor bandgap(s) and, thus, illustrated the varying impacts of the three main phenomena (light absorption, charge carrier transport and catalysis) on device performance. Finally, we contextualize this theoretical efficiency analysis by examining reported experimental results for three exemplary watersplitting devices. This analysis provides a framework through which one can understand all previous reported limiting efficiencies with various assumed values and also provides insight into the primary factors limiting device performance and the most powerful handles to improve device efficiency.
Data availability
The AM1.5G spectrum data used for the efficiency calculations was derived from the public domain resource, NRELRREDC: http://rredc.nrel.gov/solar/spectra/am1.5/. Additional data that support the findings of this study, including source code, are available from the corresponding author upon request.
Additional information
How to cite this article: Fountaine, K. T. et al. Efficiency limits for photoelectrochemical watersplitting. Nat. Commun. 7, 13706 doi: 10.1038/ncomms13706 (2016).
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
References
 1
Shockley, W. & Queisser, H. J. Detailed balance limit of efficiency of PN junction solar cells. J. Appl. Phys. 32, 510–519 (1961).
 2
Atwater, H. et al. in Nobel Symposium 153: Nanoscale Energy Converters, Vol. 1519. AIP Conference Proceedings eds Linke H.et al. 17–21American Institute of Physics (2013).
 3
Hanna, M. C. & Nozik, A. J. Solar conversion efficiency of photovoltaic and photoelectrolysis cells with carrier multiplication absorbers. J. Appl. Phys. 100, 074510 (2006).
 4
Marti, A. & Araujo, G. L. Limiting efficiencies for photovoltaic energy conversion in multigap systems. Sol. Energy Mater. Sol. Cells 43, 203–222 (1996).
 5
Munday, J. N. The effect of photonic bandgap materials on the ShockleyQueisser limit. J. Appl. Phys. 112, 064501 (2012).
 6
Trupke, T., Green, M. A. & Wurfel, P. Improving solar cell efficiencies by upconversion of subbandgap light. J. Appl. Phys. 92, 4117–4122 (2002).
 7
Trupke, T., Green, M. A. & Wurfel, P. Improving solar cell efficiencies by downconversion of highenergy photons. J. Appl. Phys. 92, 1668–1674 (2002).
 8
Yu, Z. F., Raman, A. & Fan, S. H. Fundamental limit of nanophotonic light trapping in solar cells. Proc. Natl Acad. Sci. USA 107, 17491–17496 (2010).
 9
Henry, C. H. Limiting efficiencies of ideal single and multiple energy gap terrestrial solar cells. J. Appl. Phys. 51, 4494–4500 (1980).
 10
Haussener, S., Hu, S., Xiang, C. X., Weber, A. Z. & Lewis, N. S. Simulations of the irradiation and temperature dependence of the efficiency of tandem photoelectrochemical watersplitting systems. Energy Environ. Sci. 6, 3605–3618 (2013).
 11
Haussener, S. et al. Modeling, simulation, and design criteria for photoelectrochemical watersplitting systems. Energy Environ. Sci. 5, 9922–9935 (2012).
 12
Hu, S., Xiang, C. X., Haussener, S., Berger, A. D. & Lewis, N. S. An analysis of the optimal band gaps of light absorbers in integrated tandem photoelectrochemical watersplitting systems. Energy Environ. Sci. 6, 2984–2993 (2013).
 13
Bolton, J. R., Strickler, S. J. & Connolly, J. S. Limiting and realizable efficiencies of solar photolysis of water. Nature 316, 495–500 (1985).
 14
Seitz, L. C. et al. Modeling practical performance limits of photoelectrochemical water splitting based on the current state of materials research. ChemSusChem 7, 1372–1385 (2014).
 15
Doscher, H., Geisz, J. F., Deutsch, T. G. & Turner, J. A. Sunlight absorption in water  efficiency and design implications for photoelectrochemical devices. Energy Environ. Sci. 7, 2951–2956 (2014).
 16
Fountaine, K. T., Lewerenz, H. J. & Atwater, H. A. Interplay of light transmission and catalytic exchange current in photoelectrochemical systems. Appl. Phys. Lett. 105, 173901 (2014).
 17
Shaner, M. R., Fountaine, K. T. & Lewerenz, H.J. Currentvoltage characteristics of coupled photodiodeelectrocatalyst devices. Appl. Phys. Lett. 103, 143905 (2013).
 18
Bard, A. J. & Faulkner, L. R. Electrochemical Methods: Fundamentals and Applications Wiley (2000).
 19
Markvart, T. The thermodynamics of optical etendue. J. Opt. APure Appl. Opt. 10, 015008 (2008).
 20
Green, M. A. Radiative efficiency of stateoftheart photovoltaic cells. Prog. Photovoltaics 20, 472–476 (2012).
 21
Sze, S. M. & Ng, K. K. Physics of Semiconductor Devices Wiley (2006).
 22
Wilson, R. H. Model for currentvoltage curve of photoexcited semiconductor electrodes. J. Appl. Phys. 48, 4292–4297 (1977).
 23
Reichman, J. The currentvoltage characteristics of semiconductorelectrolyte junction photovoltaic cells. Appl. Phys. Lett. 36, 574–577 (1980).
 24
Reiss, H. Photocharacteristics for electrolytesemiconductor junctions. J. Electrochem. Soc. 125, 937–949 (1978).
 25
Polman, A., Knight, M., Garnett, E. C., Ehrler, B. & Sinke, W. C. Photovoltaic materials: present efficiencies and future challenges. Science 352, 6283 (2016).
 26
Trasatti, S. Work function, electronegativity, and electrochemical behavior of metals: III. Electrolytic hydrogen evolution in acid solutions. J. Electroanal. Chem. 39, 163–184 (1972).
 27
Blouin, M. & Guay, D. Activation of ruthenium oxide, iridium oxide, and mixed RuxIr1x oxide electrodes during cathodic polarization and hydrogen evolution. J. Electrochem. Soc. 144, 573–581 (1997).
 28
McCrory, C. C. L. et al. Benchmarking hydrogen evolving reaction and oxygen evolving reaction electrocatalysts for solar water splitting devices. J. Am. Chem. Soc. 137, 4347–4357 (2015).
 29
Licht, S. et al. Efficient solar water splitting, exemplified by RuO2catalyzed AlGaAs/Si photoelectrolysis. J. Phys. Chem. B 104, 8920–8924 (2000).
 30
May, M. M., Lewerenz, H.J., Lackner, D., Dimroth, F. & Hannappel, T. Efficient direct solartohydrogen conversion by in situ interface transformation of a tandem structure. Nat. Commun. 6, 8286 (2015).
 31
Han, L. H. et al. Efficient watersplitting device based on a bismuth vanadate photoanode and thinfilm silicon solar cells. ChemSusChem 7, 2832–2838 (2014).
 32
Ager, J. W., Shaner, M. R., Walczak, K. A., Sharp, I. D. & Ardo, S. Experimental demonstrations of spontaneous, solardriven photoelectrochemical water splitting. Energy Environ. Sci. 8, 2811–2824 (2015).
 33
Ertekin, E., Greaney, P. A., Chrzan, D. C. & Sands, T. D. Equilibrium limits of coherency in strained nanowire heterostructures. J. Appl. Phys. 97, 114325 (2005).
 34
Geisz, J. F. et al. 40.8% efficient inverted triplejunction solar cell with two independently metamorphic junctions. Appl. Phys. Lett. 93, 123505 (2008).
 35
Wojtczuk, S. et al. Bifacial growth InGaP/GaAs/InGaAs concentrator solar cells. IEEE J. Photovolt. 2, 371–376 (2012).
Acknowledgements
This material is based upon work performed by the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, supported through the Office of Science of the U.S. Department of Energy under Award No. DESC0004993. We are grateful to Dr E. Warmann for useful discussions regarding the impact of external radiative efficiency on photodiode efficiency.
Author information
Affiliations
Contributions
K.T.F. and H.J.L. designed the study and wrote the paper, K.T.F. executed the calculations and analysis, and H.J.L. and H.A.A. advised. All authors reviewed and commented on the manuscript.
Corresponding author
Ethics declarations
Competing interests
The authors declare no competing financial interests.
Supplementary information
Supplementary Information
Supplementary Figures 15, Supplementary Notes 13 and Supplementary References. (PDF 490 kb)
Supplementary Movie 1
Evolution of the single junction limiting efficiency vs. bandgap as a function of ERE. Left panel contains the ideal line from Fig. 4b of the main text and right panel is Fig. 1 (blue line) of main text for varying values of ERE (evolves in time from 106 to 1). Right panel marker indicates maximum efficiency value at a given ERE, which corresponds to the point plotted (and marked) on the left panel. (MOV 582 kb)
Rights and permissions
This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/
About this article
Cite this article
Fountaine, K., Lewerenz, H. & Atwater, H. Efficiency limits for photoelectrochemical watersplitting. Nat Commun 7, 13706 (2016). https://doi.org/10.1038/ncomms13706
Received:
Accepted:
Published:
Further reading

Research Progress on Catalytic Water Splitting Based on Polyoxometalate/Semiconductor Composites
Catalysts (2021)

Emerging Energy Harvesting Technology for Electro/PhotoCatalytic Water Splitting Application
Catalysts (2021)

An Unassisted Tandem Photoelectrochemical Cell Based on p and nCu2O Photoelectrodes
Catalysis Letters (2021)

Quantifying and Comparing Fundamental Loss Mechanisms to Enable Solar‐to‐Hydrogen Conversion Efficiencies above 20% Using Perovskite–Silicon Tandem Absorbers
Advanced Energy and Sustainability Research (2021)

Photoelectrochemical water splitting by hybrid organicinorganic systems: Setting the path from 2% to 20% solartohydrogen conversion efficiency
iScience (2021)
Comments
By submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.