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1. Introduction
The significant research interest in the engineering of photovoltaic (PV)
structures at the nanoscale is directed toward enabling reductions in PV Harvesting sunlight with photovoltaic
(PV) cells could generate enough electrical
module fabrication and installation costs as well as improving cell
energy to meet the worlds increasing energy
power conversion efficiency (PCE). With the emergence of a multitude demand while simultaneously enabling
of nanostructured photovoltaic (nano-PV) device architectures, the a reduction in the environmental impact
question has arisen of where both the practical and the fundamental associated with present modes of electricity
limits of performance reside in these new systems. Here, the former production.[1] Scaling of PV installations
to the needed terawatt scale, however, will
is addressed a posteriori. The specific challenges associated with
require significant improvements in the
improving the electrical power conversion efficiency of various nano-PV cost-effectiveness of installed PVs, including
technologies are discussed and several approaches to reduce their improvements in their power conversion
thermal losses beyond the single bandgap limit are reviewed. Critical efficiencies (PCE) as well as reductions in
considerations related to the module lifetime and cost that are unique the cost of PV module installation through
to nano-PV architectures are also addressed. The analysis suggests that a streamlined fabrication and innovations in
rapid and lightweight PV deployment.
practical single-junction laboratory power conversion efficiency limit of
Advancements in the field of nano-
17% and a two-cell tandem power conversion efficiency limit of 24% are structured PVs (nano-PVs) have led to
possible for nano-PVs, which, when combined with operating lifetimes of rapid improvements over the past decade
10 to 15 years, could position them as a transformational technology for in the power conversion efficiencies of this
solar energy markets. broad class of solar cells,[2] in which we
include molecular, organic, polymeric, dye-
sensitized, and colloidal quantum dot
(CQD) PVs due to the similarity of the
physical processes that govern their operation and fabrication. In
general, we define nano-PVs as solar cells that 1) consist of thin
Prof. R. R. Lunt
Department of Chemical Engineering and Materials Science films (<2 m) of semiconductor material, 2) incorporate nanom-
Michigan State University eter-scale optoelectronic materials that 3) have excitonic or
East Lansing, MI 48824, USA quantum-confinement character and 4) can be fabricated entirely
E-mail: rlunt@msu.edu with low-temperature (<300 C) processing steps. The compat-
Prof. R. R. Lunt, Prof. V. Bulovic ibility of many nanostructured PV materials with the use of low-
Department of Electrical Engineering and Computer Science
Massachusetts Institute of Technology
temperature processing can enable the use of flexible, lightweight
Cambridge, MA 02139, USA substrates,[3,4] potentially leading to a lower cost of solar module
E-mail: bulovic@mit.edu fabrication and installation. A particular advantage of nanostruc-
T. P. Osedach tured materials is the tunability of their optical and electronic
School of Engineering and Applied Sciences properties, which may enable the implementation of third-
Harvard University generation approaches (i.e., strategies for reducing thermal
Cambridge, MA 02138, USA
losses) for improved PV power conversion efficiencies.[5]
P. R. Brown
Department of Physics Here, we first review the fundamental limits to the perform-
Massachusetts Institute of Technology ance of solar cells and then consider those limits in the con-
Cambridge, MA 02139, USA text of various nano-PV technologies that are currently under
J. A. Rowehl investigation. We review the state of the art for PV technologies
Department of Materials Science and Engineering in each material class and calculate practical and semiempirical
Massachusetts Institute of Technology
Cambridge, MA 02139, USA
limits to their efficiency, taking into account the prospect for
the application of third-generation concepts such as multiple
DOI: 10.1002/adma.201103404 exciton generation (MEG), singlet fission, and stacked-tandem
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device architectures. We also address critical considerations
related to cost and module lifetime that are unique to nanos- Richard R. Lunt earned
tructured PV architectures. his PhD from Princeton
University and then worked as
a post-doctoral researcher at
2. Theoretical Limits of PV Operation the Massachusetts Institute
of Technology (MIT) in the
Single-junction photovoltaic cells are typically limited by four Organic and Nanostructured
fundamental loss mechanisms:[6,7] 1) incomplete solar spec- Electronics Laboratory.
trum absorption, 2) thermalization of hot carriers (or excitons) Currently, he is an Assistant
in the form of excess heat, 3) chemical potential (thermody- Professor at Michigan State
namic) losses dictating that the photovoltage must be less than University where he heads
band gap (EG) for relaxed carriers, and 4) radiative recombina- the Molecular and Organic
tion. The presence of other non-radiative losses (e.g., Auger Electronics group. His research interests include organic
recombination,[8] internal or phonon conversion, surface epitaxy, excitonic photophysics, and thin-film photovoltaics.
recombination,[8,9] etc.) can further reduce cell performance.[10]
Considering only radiative losses, Shockley and Queisser (SQ) Vladimir Bulovic is a
predicted a limiting power efficiency of 30% under simulated Professor of Electrical
black body radiation,[7] that has been subsequently recalculated Engineering at MIT,
as 33% under AM 1.5 solar irradiance.[6,10] leading the Organic and
The power conversion efficiency (PCE) is defined as Nanostructured Electronics
Laboratory and co-directing
J SC VOC F F
p = (1) the MIT-ENI Solar Frontiers
P0 Center. His interests include
where VOC is the open circuit voltage, JSC is the short circuit cur- studies of physical proper-
rent, FF is the fill factor, and P0 is the incident power. Starting ties of organic and organic/
from the SQ limit, where the ideal diode equation describes the inorganic nanocrystal com-
current density (J)voltage (V) characteristics vis posites, and development
of novel optoelectronic organic and hybrid nanoscale
Rp q (V J RS ) V devices.
J = J S exp 1 + J SC (2)
RS + Rp nkT Rp
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Figure 1. Illustrated structure of nanostructured materials including a) small molecule (C60), organic (Ru-complex), and polymer (P3HT) materials
along with ligand-coated CQDs. Calculations of the SQ, practical, and various MEG characteristics of b) photocurrent (Jsc) and c) open circuit voltage
(VOC) under AM 1.5G illumination as a function of optical or excitonic gap. Note that the VOC for the M1 and M2 MEG cases are nearly identical
(the M2 line is therefore emitted for clarity). A range of measured device performance is shown for organic small molecule, dye-sensitized solar cell
(DSSC), polymer, and CQD where the gap was estimated from the photoresponse edge (0.1 eV). The maximum reported photocurrents under AM
1.5G illumination follow the curve for the practical photocurrent limit (M1) defined by 75% EQE across the spectrum to EG. M2 MEG is a two-staircase
multiplication, SF1 is a lone singlet fission material (or paired with a bandgap larger than the triplet level), and SF2 is a singlet-fission material paired
with acceptor that has an optical gap equal to the triplet level of the SF material.
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Table 1. Representative device performance of various single-junction nanostructured photovoltaic cells under 1-sun illumination.
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Table 1. Continued
DIP - di-indenoperylene; DBP - dibenzo{[f,f] - 4,4,7,7-tetraphenyl}diindeno[1,2,3-cd:1,2,3-lm]perylene; PtTPBP - platinum tetraphenylbenzoporphyrin; CuPc - copper
phthalocyanine; SubPc - boron subphthalocyanine; BP - tetrabenzoporphyrin; DCV6T - bis-(dicyanovinylen)-sexithiophene; SQ - 2,4-bis[4-(N,N-diisobutylamino)-2,6-di-
hydroxyphenyl]squaraine; ZnPc - zinc phthalocyanine; ClAlPc - chloro-aluminum phthalocyanine; SnPc - tin phthalocyanine; PT Psub - diporphyrinpyrene; PT Pfused
- pyrene-fused diporphyrin; CNT - carbon nanotube; P3HT - poly(3-hexylthiophene); APFO-3 - poly[(9,9-dioctylfluorenyl-2,7-diyl)-alt-5,5-(40,70-di-2-thienyl-20,10,30-benzothi-
adiazole)]; F8TBT - poly((9,9-dioctylfluorene)-2,7-diyl-alt-[4,7-bis(3-hexylthien-5-yl)-2,1,3-benzothiadiazole]-2,2-diyl); PBDTTT-CF - poly[4,8-bis(2-ethylhexyloxy)-benzo[1,2-
b:4,5-b]dithiophene-2,6-diyl-alt-(4-octanoyl-5-fluoro-thieno[3,4-b]thiophene-2-carboxylate)-2,6-diyl]; MDMO-PPV - poly[2-methoxy-5-(3,7-dimethyloctyloxy)-1,4-phenylene
vinylene]; PCPDTBT - poly[2,1,3-benzothiadiazole-4,7-diyl[4,4-bis(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b]dithiophene-2,6-diyl]; P3 - 6,7-diphenyl-4,9-bis-(thiophen-
2-yl)-[1,2,5]thiadiazolo[3,4-g]quinoxaline/9-triarylamino-9H-carbazole; PCBM - [6,6]-phenyl-C61-butyric acid methyl ester; spiro-OMeTAD - (2,2(,7,7(-tetrakis-(N,N-di-
pmethoxyphenylamine)9,9(-spirobifluorene); PEDOT - poly(3,4-ethylenedioxythiophene); HTL - hole transport layer.
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the best practical device performance, upper
limits for the FF as a function of optical gap
are similarly assumed to be that of the highest
reported (i.e., FF = 0.75) across the spectrum
(Table 1). Deviations in FF from the SQ limit
generally stem from a combination of large
series resistance (RS) and low shunt resist-
ance (RP). While many empirical forms have
been proposed for the dependence of VOC as a
function of EG,[13,14] it is found that maximum
demonstrated photovoltages follow a trend
of reaching 80% of the value predicted by
the SQ limit (Equation 4); the difference can
be attributed to a number of recombination
phenomena including internal conversion,
interface recombination, and exciton binding
losses, as discussed below.[15] Nonetheless,
this threshold in VOC is consistent with the
framework of the SQ limit and can be used in
combination with the practical upper limits in
photocurrents and fill-factors to estimate the
ultimate laboratory efficiency limits of nano-
PVs, as shown in Figure 2a. We find that a
semiempirically derived maximum efficiency
of 17% is achievable for a single-junction cell
with a bandgap in the range of 1.1 eV to 1.4 eV.
This maximum efficiency is lower than that
reported in recent semitheoretical studies in
which practical considerations described above
are not taken into account and which led to
maximum exciton-limited efficiencies ranging
from 2227%.[15] Also plotted in Figure 2a are
P versus. bandgap curves calculated with Figure 3. a) Schematic of various methods relevant in nanostructured materials to reduce
thermal losses including singlet exciton fission, multiple exciton generation, and tandem
Equation 35 based on the implementation of stacking. EG,Jsc (singlet level) and EG,Voc (triplet level) are the gaps used to calculate the Jsc and
various third-generation concepts (shown in VOC in the SQ limit, respectively, for singlet fission case SF1, where there is negligable oscil-
Figure 3) that will be described in detail below; lator strength between the triplet and singlet levels for photocurrent generation. Solid arrows
for two-cell current-matched nanostructured are optical transition, red dashed arrows are electronics transistions associated with multiple
tandems, the optimal efficiency as function of exciton generation and the blue dashed line designates charge transfer exciton dissociation.
top-cell bandgap is shown in Figure 2a, where b) AM 1.5G solar photon flux as a function of energy and the representative external quantum
efficiency profiles of various cell configurations. Profiles are offset slightly from the M1 (prac-
the corresponding optimal pairing of the back-
tical) line for clarity; M2 and M3 MEG are a two-staircase and three staircase multiplication
cell gap is plotted in Figure 2b. profile, respectively; SF1 is a lone singlet fission material (or paired with an acceptor bandgap
larger than the triplet level) and SF2 is a singlet-fission material paired with acceptor that has an
optical gap equal to the triplet level of the SF material; T is the 2-cell current-matched tandem
scenario where the vertical lines indicate the two bandgaps.
4. Analysis of Performance
of Nano-PV Technologies excited states, known as Frenkel excitons.[16] These excitons
In the remainder of this article, we review the challenges asso- have a significant impact on many of the processes in photo-
ciated with each type of nano-PV device and suggest particular voltaic devices, from photocurrent generation to the character-
areas for improvement in order to approach the efficiency limits. istically pronounced absorption features.[3] For example, organic
We then discuss third-generation concepts particularly relevant to semiconductors typically exhibit static dielectric constants in the
nanostructured materials that can allow for efficiencies beyond the range of 2 to 5[16] and, accordingly, exhibit large exciton binding
single-junction limit and, finally, consider these efficiency limits energies of between 0.2 eV and 0.8 eV.
in the context of the nano-PV module cost and operating lifetime. To overcome this exciton binding energy, bilayer donor
acceptor architectures have become common to promote
exciton separation to free carriers[1719] as shown in Figure 4.
4.1. Small Molecule and Polymer PVs However, there still remains an inherent tradeoff between the
light absorption efficiency within the nano-PV device layers
One of the distinguishing features of molecular, organic, and (quantified by the absorption constant, ) and exciton diffu-
polymeric semiconductors is the presence of strongly bound sion efficiency (quantified by the exciton diffusion length,
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collection efficiencies already achieved in the
best devices. Accordingly, this will require a
combination of morphology optimization
and material engineering of molecules with
long diffusion length, high carrier mobilities,
and smaller bandgaps. Indeed, engineering
optical gaps in organic molecules into the
infrared remains a significant challenge, one
that may be overcome through the use of
hybrid material systems such as organic/col-
loidal-quantum-dot or organic/nanotube[38,39]
combinations. Stacked structures in which
each stacked cell can be optimized for a dif-
ferent wavelength range may also be key to
enabling efficient harvesting of light at longer
wavelengths.[3,36,40,41]
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reported, hence the benefit of the MEG enhancement in PVs EG (i.e., without an offset) as assumed by Beard and Nozik, then
has not yet been demonstrated. As the measurements of MEG the efficiency limit would be unchanged from the M1 case.[91]
processes are still evolving, we can assess the practical benefit An alternative device configuration utilizing SF in a PV is
of implementing the MEG process in PVs by comparing it to with a donor-acceptor pair consisting of an SF material with
equivalent processes that have been extensively studied such as large bandgap that forms a junction with a non-SF material
the impact ionization (or the reverse of the Auger recombina- whose gap is half as large (vis, same as the triplet gap). This
tion process), which to date has been demonstrated to be only case, which we refer to as SF2 in Figure 1,2, results in the
weakly present in most bulk inorganic semiconductors.[75] Like- same maximum P as the M2 MEG case. Additionally, this
wise, recent measurements show that the overall magnitude of approach would require structured absorption in the low-
MEG in CQD films is also limited, with onset thresholds and gap material so that higher energy photons are preferentially
multiplication-profiles that are far from ideal[59,7679] or overes- absorbed only within the SF layer and not thermalized in the
timated due to charging effects.[80,81] Calculations show that if non-SF layer. The SF2 pairing would therefore be less compat-
the MEG profile onset thresholds are less than M2 MEG, the ible with BHJ and DSSC architectures[90,92] where such optical
expected achievable P is nearly identical to that for PV cells engineering becomes more challenging and would result in
without MEG.[74,78] Altogether, this limits the potential for P thermal losses approaching the M1 scenario. Figure 3 outlines
enhancements through an MEG process, with the benefit of both SF1 and SF2 schemes.
MEG enhancement of PVs only present if nearly ideal MEG
process can be achieved for small gap materials.
5.3. Tandem PVs
5.2. Singlet Exciton Fission in PVs The tried method for simultaneously reducing thermalization
and absorption losses is to stack multiple cells with varying
The singlet exciton fission (SF) in organic semiconductors is a bandgaps, so that each cell absorbs a different part of the solar
nearly equivalent analog of MEG in CQDs. In the SF process, spectrum. Indeed, this approach has led to record PV efficien-
one high energy singlet exciton at the band edge spontane- cies of 42.3% with GaInP/GaInAs/Ge two-terminal, triple junc-
ously separates to form two triplet excitons, each with 1/2 tion cells.[2] While tandem stacking of high efficiency inorganic
(singlet energy) kT. While this process has been observed for cells is limited by epitaxial growth considerations (i.e., lattice
a range of polyacene crystals,[8285] the quantum mechanical matching) and can add substantial cost to PV fabrication,
mechanism has only recently been explored.[86] Ideal SF can nanostructured materials do not have such restrictions. This
result in a doubling of the photogenerated current at a given makes tandem growth of nano-PVs feasible on arbitrary sub-
bandgap[87] and has been suggested as a method for slightly strates and with arbitrary combinations of subcells, as already
increasing multijunction PV efficiencies through improved cur- demonstrated for molecular PV structures.[93]
rent matching.[6,88] Moreover, it has been speculated that access Tandem stacking of multiple cells requires matching the
to the triplet state could lead to enhanced diffusion lengths and photocurrents (for series connection) or photovoltages (for
bridge the gap between experimentally observed and theoreti- parallel connection) of the stacked subcells (i.e., matching max-
cally predicted maximum photocurrents.[87,89] Although triplet imum power points). Series matching generally leads to higher
diffusions lengths can sometimes exceed those of the singlet efficiencies since cells in parallel are limited by the voltage of
exciton,[24,25] triplet formation in the absence of singlet fission the lowest gap cell.[72] However, parallel tandem junctions can
results in additional thermalization losses that lower the max- also exhibit better light-shading stability where the photovoltage
imum efficiency below the practical limit calculated here. This is logarithmic with light intensity and therefore could be useful
is highlighted in a recent report of IQE > 100% for SF in a pen- under highly variable illumination conditions.[94] Therefore, in
tacene-C60 and tetracene-C60 bilayer architectures where overall contrast to the MEG and SF approaches, excess thermal energy
EQE at zero bias and power efficiency still remain lower than in tandem structures can be utilized to build either current (in
other combinations of similar optical gap.[87,90] parallel integration) or voltage (in series stacking). Utilizing the
The triplet states have negligible oscillator strength (even assumptions of SQ, the maximum efficiency for series two-cell,
smaller than the MEG process) and there are rarely other opti- three-cell, and infinite number of tandem cells are 43%, 48%,
cally absorptive states between the lowest singlet and triplet and 67%, respectively.[74] However, assuming a non-idealized
levels. Therefore, for our analysis EG = ES is used as the optical PV performance (discussed before for the M1 case in Figure 2),
gap in Equation 3 to determine the photocurrent resulting we calculate a maximum practical laboratory power conver-
from the absorbed incident light, while EG = ET = 1/2ES is used sion efficiency of 24% for a stacked, current-matched, two-cell
in Equation 5 to determine the carrier level or VOC for spon- nano-PV tandem structure (compared to the predicted 43.4%
taneous fission. In Figure 1,2 we refer to this case as SF1. in the SQ limit). This performance is slightly better than the
We note that while the ideal MEG process in CQD films acts maximum P for M2 MEG or SF2.
similarly to stacking tandem PV cells (as discussed below), While tandem architectures for small-molecule and polymer
singlet fission in a single organic thin film layer does not. In PVs have been demonstrated, full optimization of such struc-
the SF1 case the maximum achievable P is lower than for the tures will require subcells with responsivity deeper into the
single junction cells that do not exhibit singlet fission because near IR (NIR). Accordingly, tandem PVs could be designed
the decrease in the open circuit voltage is more severe than the from a combination of CQD and organic containing subcells,
gain in the photocurrent (Figure 1). If the VOC scaled exactly as where the infrared responsivity of CQD layers can complement
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Figure 7. Estimated levelized energy cost ($ kW1 h1) as a function of both module efficiency and lifetime for various cost scenarios: a) Scenario of
an intermediate BOS cost (75 $ m2) (estimated for rooftop mounting) and a conservative module cost (75 $ m2). b) Scenario of lower-limit module
cost (20 $ m2). c) Best-case scenario with lower-limit module costs and also a reduced financing rate (i = 6%). Note that a laboratory efficiency has
to be scaled by roughly 0.75 to estimate the losses in scaling to a module efficiency.
consider in Figure 7b the impact of realizing the full low-cost a greater amenability to integration with existing infrastructure
potential of nano-PV by calculating the LEC assuming the lowest (building-integrated photovoltaics), which could significantly
estimated module cost of 20 $ m2. Finally, Figure 7c shows the reduce the amount of dedicated framing/support required for
same calculations from Figure 7b, but with the interest rate installation. Such optimization and integration is expected to
lowered from i = 10% to i = 6% (the best-case cost scenario). substantially lower BOS costs.[107,110]
For each of the plots in Figure 7 we find that the LEC flattens
out as the module efficiency or lifetime increases suggesting
that the steepest gains in LEC occur with improvements of
7. Operating Lifetime of Nano PVs
relatively low module efficiencies and lifetimes. For the most
conservative assumptions of module and BOS cost utilized The inherently nanostructured forms of DSSCs, molecular
(Figure 7a), modules with lifetimes n 15 years and P 15% and polymeric organic PVs (OPVs), and CQD PVs can lead to
result in the cost-competitive LEC 0.12 $ kW1 h1, enabling instabilities in their operation under thermal and optical stress,
their market penetration. By lowering the module cost from which do not affect conventional monolithic inorganic PVs. For
75 $ m2 to 20 $ m2 (as in Figure 7b), nano-PVs can reach cost- example, DSSCs could suffer electrolyte leakage under thermal
competitive LEC with a 10 year lifetime and P 12%, a power expansion and bleaching or desorption of the photopactive
conversion efficiency achievable within the practical efficiency dye;[111] OPVs could undergo morphological change to the active
limits estimated above. Reduction in the financing interest layer and photo-oxidation under environmental exposure;[112,113]
(as in Figure 7c) would further reduce the requirements for and CQD PVs are often subject to loss of ligands that passivate
nano-PVs with cost-competitive LEC to P 10% and 10 year the QD surface and can undergo rapid oxidation of the semi-
lifetime. In this case, if nano-PV modules are realized close to conductor shell/core.[114] Additional degradation mechanisms
our estimated practical efficiency limits and with lifetimes of include indium diffusion from the indium tin oxide (ITO) elec-
between 10 and 20 years, LECs for M1 single and two-junction trode[115] and delamination or oxidation of the low-work-func-
tandem cells of between 0.10 and 0.06 $ kW1 h1 and between tion cathode.[116] Nonetheless, some of these challenges have
0.07 and 0.04 $ kW1 h1 are possible, respectively (we take the already been overcome in the similar field of organic light-emit-
practical laboratory efficiency limits of 17% and 24% for single- ting diodes, where long lifetimes (>10 years)[117,118] have been
and tandem-junction cells, respectively, and multiple by 0.75 to demonstrated and commercialization is well underway.
estimate the practical module efficiency limits).[109] Thus, the Plots in Figure 7 shows us that in an assessment of a nano-
degree of market penetration will be highly dependent on the PV technology in terms of $ kW1 h1, the useful lifetime of
ability to fully realize the low-cost manufacturing of nano-PVs the device, typically reported as T80 (the time for the device to
as well as advances in both efficiency and cell lifetime. decay to 80% of its initial performance under standard oper-
Manufacturing cost structures required to reach these LECs ating conditions), is as important as the initial efficiency. Stand-
may be enabled by processing active layers with low-temperature ardized conditions and procedures for lifetime testing are thus
vapor-phase or solution processing techniques, often employed necessary for the effective comparison of different device archi-
in the fabrication of nano-PVs. While the ultimate and relative tectures and encapsulation methods. A frequently employed
cost advantages of these two processing techniques remain accelerated lifetime testing method consists of a 1000 hour
unclear, the ability to process active layers at low temperatures light soak under constant AM1.5G illumination (100 mW cm2)
and onto inexpensive flexible substrates should enable a reduc- and elevated temperature (5060 C) with continual moni-
tion in the manufacturing as well as infrastructure costs. For toring of the photovoltaic operational parameters (JSC, VOC, FF,
example, flexible and light-weight PV modules will likely have and PCE).[111,119] This submits the device to roughly the same
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ciency with time, but are often characterized P3HT:PCBM Polymer BHJ 4.0 4400 Light soak 74 [121]
by a burn-in period involving a relatively PCDTBT:PCBM Polymer BHJ 5.5 4400 Light soak 69 [121]
rapid increase or decay of the initial perform- Undisclosed Small-molecule 6.07 5000 Light soak 100 [36]
ance, followed by a period of slow, linear BHJ (tandem)
decay.[119,121] Because of O2 and H2O sensi-
tivity[120] of many of the active layers to deg-
radation, packaging technology will be crucial.[121] Accordingly, Table 4. CO2 emission factors (EF) for organic photovoltaic modules.
catastrophic failures in packaging may also rapidly degrade the Data adapted from ref. [36] where the embodied CO2 and energy input
performance at any point during the test. Given the unpredict- from module production is estimated to be 110 kg m2 and 2800 MJ m2,
respectively, and the average irradiance is taken to be 5 kW h m2 d.
able nature of device degradation, extended lifetime tests under
conditions approximating those expected under normal opera-
Module efficiency Lifetime Generated power CO2 EF
tion, either in an outdoor environment or under repeated illu- [yr] [kW h] [g CO2 kW1 h1]
mination and heating cycles, are particularly relevant. A sample
5% 5 340 330
of extended lifetime testing results for DSSCs and OPVs is com-
piled in Table 3 and indicates that, with effective encapsulation 5% 10 680 165
strategies, the lifetime of these nanostructured PVs can be rela- 10% 10 1360 83
tively long. Toyoda et al. report a relative degradation of only 16% 13% 20 3536 32
for a DSSC after 2.5 years of outdoor testing,[122] and Pfeiffer et 18% 20 4896 23
al. observe no significant degradation of a 6% tandem OPV after
European Wall (2006) 411
5000 hours of constant 1.5 sun illumination under open-circuit
conditions.[95] Ultimately, addressing lifetime and efficiency
simultaneously will be critical in determining the adequacy of
nano-PV technologies for electricity production. Device efficiency Beyond commercial viability, PV cell lifetime is acute in the
and lifetime are not necessarily independent. Sensitivity to UV lifecycle analysis and carbon footprint. To have any impact on
photons, for instance, may contribute to a slightly higher initial reducing carbon emission, solar cells require lifetimes longer
PV cell efficiency, but at the expense of a faster cell degradation. than the energy payback time; since the present PV cells will be
produced by using electricity that is primarily generated through
Table 2. 1000 hour constant-illumination nanostructured PV testing. burning of the fossil fuels, the CO2 emission factor of PVs is
then inversely proportional to the cell lifetime and efficiency. For
Active Device architecture Initial p After 1000 h Temperature Ref. example, one recent study calcuated that the energy payback time
material [%] light soak [C]
is 4 and 2 years for a 5% and 10% OPV, respectively.[123] For a life-
[% of initial]
time of 15 years, the carbon emission factors for 5% and 10% effi-
DSSC cient modules are 110 and 55 kg CO2 kWP1, respectively, which
Z907 Polymer gel electrode 6.1 96 55 [169] compares favorably to, for example, the average 2006 European
K77 Nonvolatile electrode 9 99 60 [170] electricity CO2 emission factor of 400 kg CO2 kW1 (Table 4).[123,124]
C103 Ionic liquid electrode 8.5 94 60 [171] A reduction in the lifetime to 5 years would significantly diminish
the carbon footprint advantage of nano-PVs, particularly if P
CYC-B11 Low-volatility liquid 8.2 93 60 [172]
electrode
remain below 10%. While the cell lifetime has only a small impact
on overall cost for n > 10 years (Figure 7), extending lifetimes well
C217 Ionic liquid electrode 8.1 96 60 [173]
beyond this range will have a significant role in the ability to pro-
(Ru-free)
duce and promote clean renewable energy. Nonetheless, with
OPV widespread adoption of solar and other renewable energy gen-
P3HT:PCBM BHJ (flexible) 3 85 65 [174] eration, carbon emission factors in PV production can be further
ZnPc:C60 Planar heterojunction 2.8 84 50 [175] reduced to approach near-zero carbon footprints.
ZnPc:C60 Tandem (same 4.1 100 50 [95]
subcells)
QDPV 8. Conclusions
PbS ZnO/PbS np 3 95 20 [64] We have reviewed the limits to the performance of molecular,
heterojunction
organic, polymeric, dye-sensitized, and CQD-based solar cells.
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