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Review pubs.acs.org/cm Materials Design Considerations for Charge Generation in Organic Solar Cells Stoichko D. Dimitrov
Review pubs.acs.org/cm Materials Design Considerations for Charge Generation in Organic Solar Cells Stoichko D. Dimitrov
Review

Review

Materials Design Considerations for Charge Generation in Organic Solar Cells

Stoichko D. Dimitrov and James R. Durrant *

Centre for Plastic Electronics and Department of Chemistry, Imperial College London, London SW7 2AZ, United Kingdom

ABSTRACT: This article reviews some of our recent progress on materials design guidelines for photoinduced

ABSTRACT: This article reviews some of our recent progress on materials design guidelines for photoinduced charge generation in bulk-heterojunction organic solar cells. Over the last 7 years, our group has employed transient absorption measurement to determine the relative quantum yields of long- lived polaron pairs for over 300 di erent organic Donor/ Acceptor blend lms. We have shown that this optical assay of charge separation can be a strong indicator of photocurrent generation eciency in complete devices. In this review, we consider the lessons that can be drawn from these studies concerning the parameters that determine e ciency of this photoinduced charge separation in such solar cells. We consistently nd, from studies of several materials series, that the energy oset driving charge separation is a key determinant of the eciency of this charge generation, and thereby photocurrent generation. Moreover, we nd that the magnitude of the energy oset required to drive charge separation, and the strength of this energetic dependence, varies substantially between materials classes. In particular, copolymers such as diketopyrrolopyrrole- and thiazolothiazole-based polymers are found to be capable of driving charge separation in blends with PCBM at much lower energy osets than polythiophenes, such as P3HT, while replacement of PCBM with more crystalline perylene diimide acceptors is also observed to reduce the energy oset requirement for charge separation. We go on to discuss the role of lm microstructure in also determining the eciency of charge separation, including the role of mixed and pure domains, PCBM exciton di usion limitations and the role of material crystallinity in modulating material energetics, thereby providing additional energy o sets that can stabilize the spatial separation of charges. Other factors considered include the role of Coulombically bound polaron pair or charge transfer states, device electric elds, charge carrier mobilities, triplet excitons, and photon energy. We discuss brie y a model for charge separation consistent with these and other observations. We conclude by summarizing the materials design guidelines for e cient charge photogeneration that can be drawn from these studies. KEYWORDS: polymer, fullerene, transient absorption spectroscopy, charge transfer states, photocurrent, charge separation

KEYWORDS: polymer, fullerene, transient absorption spectroscopy, charge transfer states, photocurrent, charge separation

INTRODUCTION

Organic solar cells (OSC) are showing rapid advances in eciency and potential for technological application. The most e cient single-junction polymer/fullerene OSC are now approaching 10% power conversion eciencies under labo- ratory conditions, 1 8 with increasing condence that e cien- cies of 15% or higher will be achievable at least with multi- junction devices. These advances in eciency have largely been achieved by the synthesis and testing of new materials and device architectures, including, in particular, new photoactive layer materials whose energy levels have been modulated to achieve higher output voltages and/or improved photocurrent generation due to lower optical bandgaps. 1,2,4,7,9 However, at present, our ability to predict device function from materials structure remains relatively limited. As a consequence, the vast majority of new materials tested have not performed better than the ongoing state of the art, typically achieving sig- nicantly lower device performance than that predicted by simple, energy level based, device models. 10,11 A key challenge for this eld is therefore the development of improved materials design guidelines to increase the eectiveness of materials

guidelines to increase the e ff ectiveness of materials © XXXX American Chemical Society synthesis and

© XXXX American Chemical Society

synthesis and screening programmes. In this review, we address one aspect of this materials design challenge, namely, the materials design requirements for ecient photocurrent gen- eration and, in particular, the requirements for a high quantum yield photoinduced charge separation. In practice, for most new photoactive layer materials, the quantum eciency of photocurrent generation in optimized solar cells is found to be signi cantly below unity. Identifying the cause(s) of this underperformance in photocurrent genera- tion is therefore a key consideration for materials design. The e ciency of photocurrent generation in OSC can be broken down into four factors, the eciencies of photon absorption ( η abs ), exciton di usion to the donor/acceptor (D/A) interface ( η diff ), charge separation at this interface ( η ), and charge collection by the external circuit (η coll ) (see Figure 1). 12 14 The

sep

Special Issue: Celebrating Twenty-Five Years of Chemistry of Materials

Received: July 17, 2013 Revised: September 9, 2013

A

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Chemistry of Materials Review Figure 1. Simpli fi ed illustration of the typical architecture of a

Figure 1. Simpli ed illustration of the typical architecture of a BHJ polymer/fullerene organic solar cell. The diagram depicts the four processes leading to photocurrent generation in the photoactive layer:

light absorption (by the polymer in this case), exciton di usion to D/A interface, charge separation at this interface, and charge collection at the electrodes. The diagram illustrates both nely intermixed and relatively pure polymer and fullerene domains, as well as variations in local material crystallinity; the relative proportions of these structural features are strongly dependent upon the choice of photoactive layer materials and lm processing conditions.

development of new, lower bandgap polymers has resulted in signi cant, and easily measured, improvements in η abs , although at the expense of lower energies of the resultant photoexcited states (excitons). Similarly, the bulk-heterojunction (BHJ) strategy, based on an interpenetrating blend of donor and acceptor domains, has proved, for many photoactive layers, to be remarkably e ective at enabling ecient exciton di usion to the D/A interface. In addition, for many devices and, in particular, for blends of donor polymers with reasonable hole mobilities blended with the soluble fullerene acceptor PC 60 BM ([6,6]-phenyl C 61 -butyric acid methyl ester), the charge collection eciency η coll is found to approach unity at short circuit (it should be noted that the eciency of charge col- lection is, however, a key consideration for overall device e - ciency, with the competing process of nongeminate recombi- nation limiting the voltage output, and often the ll factor,

of most devices). 11,15 20 In some cases, a tension between η coll and η abs is observed as a function of photoactive thickness, with e cient charge collection only being obtained for lm thicknesses too thin for e cient light absorption. 21 23 How- ever, in general, it appears that, for many new photoactive layers and, in particular, blends of new donor materials with PCBM, the observation of suboptimal photocurrent densities often derives neither from ine ciencies in η abs , η diff , nor η coll . Rather, as we discuss in this review, such suboptimal pho- tocurrent densities often result from limitations in charge separation eciency, η sep . As such, this review focuses upon evidence that the e ciency of charge separation indeed limits photocurrent generation in many OSC and, more importantly, upon the material parameters that determine this eciency. Understanding of the device physics of OSC has improved signi cantly in recent years, with semiempirical device models now able to reconstruct the open circuit voltage, and in some

cases the ll factor, of a device relatively well.

18,20,24 29 How-

ever, models to calculate the photocurrent density of devices from materials parameters are relatively limited. Most device e ciency prediction s assume unity e ciency of exciton diusion η diff to the D/A interface (i.e., that the domain sizes are much less than the exciton diusion length) and that unity eciency of charge separation η sep is achieved provided that the energy o set between the polymer and fullerene lowest unoccupied molecular orbitals (LUMO) is at least

B

0.3 eV. 11,30,31 Such a simplistic view of photocurrent gen- eration, however, is clearly unable to explain the large variations in photocurrent generation e ciency observed between di erent photoactive layer materials. One additional factor that has been identi ed as potentially limiting photocurrent generation is the formation of Coulombically bound charges at the D/A interface. 12,14,32 38 The low dielectric constant of organic semiconductors ( ε r = 3 4) suggests that such bound states could have coulomb binding energies of several hundred meV (k B T ). There have been extensive studies of such bound states, which we will refer to herein as bound polaron pair states (BPP). We note that such states have also been referred to as charge transfer (CT) states (due to the obser- vation of sub-bandgap optical absorption or emission) or exciplex states (due to the observation of exciplex-like emission). Several studies have provided evidence that these states can undergo relatively rapid charge recombination (on

ns), 35,36,39 42 with this

recombination pathway potentially being a key limitation on the eciency of charge separation, and thereby photocurrent generation. 12,37,38,41 59 The extent to which this charge recombination channel at the D/A interface indeed competes

with the charge separation process in OSC, and the conse- quences of this for materials design, is a subject of extensive

discussion in the current OSC

In this review, we discuss recent advances in our under- standing of charge photogeneration in polymer/fullerene OSC, with the aim of developing empirical materials design rules for e cient photocurrent generation. We start by introducing the primary experimental approach we have employed, transient absorption spectroscopy (TAS), and considering the evidence that this approach is indeed an eective assay of charge sep- aration eciency in OSC. We then focus on a key con- sideration for the thermodynamic eciency of such solar cells, namely the correlation between energetic o set driving charge separation and the quantum eciency of this charge separation process η sep . This is followed by a discussion of the role of lm microstructure and material crystallinity, again focusing upon η sep . We then discuss other factors we observe to inuence η sep . These considerations are then summarized and discussed in terms of empirical materials design guidelines for e cient charge photogeneration for OSC. Background to Photoinduced Charge Generation in OSC. Photocurrent generation in OSC is fundamentally dif- ferent from that of the standard pn junction solar cells. The origin of this di erence lies in the low permittivity of organic materials and their inherent energetic and structural disorder. Unlike most inorganic semiconductors, light absorption by polymer and fullerene lms generates localized excited states that are tightly bound electron and hole pairs. The binding energies of these so-called excitons can be more than an order of magnitude higher than the thermal energy, therefore making their separation a key issue for e cient photocurrent gen- eration. This issue was successfully addressed by Tang, who in 1986 rst used a heterojunction of two organic materials with di erent electron donor and acceptor properties to provide an energetic driving force for the dissociation of the photo- generated excitons. 64 This breakthrough device was based on a bilayer heterojunction of copper phthalocyanine and a perylene tetracarboxylic derivative sandwiched between transparent ITO and Ag electrodes, and achieved 1% power conversion e ciency (PCE).

time scales from picoseconds to 100

literature. 35,37,53,54,60 63

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The photocurrent of most organic bilayer heterojunction devices, such as that reported by Tang et al., 64 is, however, limited by the short exciton di usion length of organic materials. Polymers and fullerenes, for example, are typically reported to have exciton di usion lengths shorter than 10 nm, thus substantially limiting the thickness of the active layer and its light harvesting properties. 65 69 One approach to addressing this limitation is the use of BHJ lms; this approach has proved particularly e ective for polymer/fullerene-based devices. 70 These are typically fabricated as random bicontinuous inter- penetrating networks of a p-type polymer and n-type fullerene in which the D/A heterojunction area is very high; as a result, the likelihood of excitons reaching the D/A interface is sub- stantially increased. Figure 1 shows a standard device archi- tecture excluding hole and electron blocking layer, which are not discussed in this review. The active layer of the device is presented as a polymer/fullerene BHJ with pure and intermixed domains and variations in polymer crystallinity; the relative proportions of pure and intermixed domains, and material crystallinity, are thought to vary substantially between di erent donor and acceptor materials and lm processing conditions. OSC based on such BHJ architectures are now achieving close to 10% PCE. 1 8 Transient Absorption Assay of Charge Photogenera- tion E ciency. The primary experimental technique we have employed to assay the eciency of charge generation in D/A blend lms and solar cells is nanosecond to millisecond TAS. This is a relatively straightforward pump probe technique that monitors the transient absorption of photogenerated charge carriers, with the primary requirement being a high detection sensitivity, enabling signal magnitudes to be measured reliably with low light excitation densities, thereby avoiding nonlinear

and saturation e ects in the active layer.

Nanosecond

laser pulses are used as an excitation source, while the output of a tungsten lamp probes the changes in the optical density of the lm or device induced by the laser excitation. A Si or InGaAs photodiode, connected to an ampli er and oscilloscope is used for detecting and recording the transient absorption signals on nanosecond to millisecond time scales. On this time scale, dissociated polarons can be identi ed by their characteristic power law decay dynamics and nonlinear behavior at high excitation densities, indicative of nongeminate recombina-

tion. 72,74 In contrast, geminate recombination, for an example of Coulombically bound polaron pair states, exhibits distinct exponential (or stretched exponential) dynamics, linear behavior as a function of excitation density, and relatively fast decay times (picoseconds to a hundred nano-

seconds).

ute to the transient absorption signals on these time scales, can be often distinguished from these polaron states by their more exponential decay dynamics and quenching in the presence of molecular oxygen. 77 As such, the magnitude of the transient polaron absorption ( Δ OD = change in the optical density) can be employed as a direct, at least semiquantitative, assay of the quantum e ciency of generation of dissociated charges. There are, of course, limitations to this approach, including for ex- ample di erences in polaron absorption coecient (which means that comparison of polaron yields can only be done quantitatively when comparing blends of similar chemical composition) and the potential for some nongeminate recom- bination to occur on time scales faster than the instrument response (avoided or minimized by the use of suciently low excitation densities such that the temporal onset of

56,71 73

35 37,39,47,75,76

Triplet states, which can also contrib-

C

nongeminate recombination occurs within the resolved time

range; see, for example, ref 40). The simplicity of this approach has allowed us to undertake comparative studies of the e - ciency of charge generation for a large number of photoactive layer materials, blend compositions, and processing conditions, now comprising over 300 such distinct lm types (including 70

di erent donors and 20 dierent acceptors, as well as a range of

blend compositions and lm processing conditions). The results of many of these studies have been published previously. 7,37,40,56,78 88 This large body of data has allowed us to identify statistically signi cant empirical materials cor- relations that can be dicult to observe from smaller data sets. In this review, we aim to summarize some of the key ndings of these studies. We have reported strong evidence that our transient

absorption assay of charge generation in blend lms is indeed

a good indicator of the eciency of photocurrent generation in

devices. In particular, we have observed a clear correlation between the amplitude of our transient absorption assay of polaron yield, Δ OD, and photocurrent density J SC /maximal IQE for a broad range of polymer/PCBM blend lms over 3 orders of magnitude in signal size (Figure 2). 89 This correlation

in signal size (Figure 2). 8 9 This correlation Figure 2. Correlation between a Δ OD

Figure 2. Correlation between a Δ OD assay of the yield of dissociated polarons measured by transient absorption spectroscopy of thin blend lms and J SC ( × ) and IQE rel (squares) measured in complete devices for a series of polymer/PCBM blends as a function of polymer, blend composition, and thermal annealing. Filled circles correspond to blends with two low hole mobility polymers, where the low hole mobility results in low photocurrent due to collection losses, the open circle corresponds to the indeno uorene polymer IF8TBTT, 89 and, for this polymer, the deviation from the correlation line is assigned to eld dependent charge generation. Reprinted with permission from ref 89. Copyright 2010, WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimQ.

is clear evidence not only of the eectiveness of our empirical approach as an indicator of photocurrent generation but also that, for many such blend lms, η coll is not a key factor determining J SC . It should be noted that this correlation between ΔOD and J SC is not observed for all photoactive layers; for example, it breaks down for donor/acceptor blends employing perylene diimide acceptors and for donor poly- mers with low hole mobilities (speci cally FET mobilities of <10 4 cm 2 V 1 s 1 ), in both cases assigned to nongeminate losses during collection limiting photocurrent generation in

these blend lms. 86,89 In addition, for some, notably amorphous blend lms, the device photocurrent is observed to be sig-

ni cantly larger than that predicted from our lm Δ OD assay;

we have shown that this behavior is associated with a strong electric eld dependence of η sep , as we discuss further later. Notwithstanding these exceptions, in general, we observe a

90

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clear, at least semiquantitative, correlation between Δ OD and J SC for many photoactive layers. As such, for the rest of this review, we focus primarily upon the parameters that we observe empirically to determine the magnitude of our Δ OD assay of polaron generation. It should be noted that our transient absorption assay of polaron yield does not distinguish between trapped and free polarons. There is extensive evidence that most organic pho- toactive layers exhibit an exponential tail of states extending energetically into the bandgap of the layer, below the mobility edge of at least one material (most notably the donor polymer). Following charge separation, polarons will relax down this density of states to the lm quasi-Fermi levels. Both non- geminate recombination and transport of photogenerated charge carriers have been suggested to occur primarily through thermally driven detrapping of these energetically trapped

carriers.

22,91,92

ENERGETICS OF CHARGE GENERATION

De nitions and Measurements of Energy Oset. From an e ciency viewpoint, the energy loss associated with pho- toinduced charge separation is a critical consideration. The energy dierence between the optical bandgap of the device

and the maximal free energy of the photogenerated charge carriers, as measured by its open circuit voltage, is a key measure of thermodynamic e ciency. In another viewpoint, charge separation is necessary to give the photogenerated species su cient lifetime to be collected by the external circuit as an external photocurrent; however, driving and stabilizing this charge separation requires energy losses. This balance between kinetics and energetics is a key cause of why increases in device photocurrent output are often achieved at the expense of cell voltage, or vice versa . There is currently considerable variation in the literature over how the energy dierence driving charge separation in OSC

We will

should be de ned and how it can be measured.

consider rst di erent de nitions of this energy o set and then how these can be measured. For simplicity, we will only con- sider charge separation fro m polymer excitons. Charge separation from fullerene excitons is discussed briey and fol- lows similar energetic arguments.

Figure 3 illustrates two dierent descriptions of the ener- getics of charge separation, one based on the electronic orbital energies and the other on state energies. In the electronic orbital picture, the energy oset driving charge separation is often described as the LUMO LUMO level o set ΔE LUMO . It has been widely reported that Δ E LUMO > 0.3 eV is required to drive charge separation, although we note that there is very little experimental evidence for this speci c energy oset requirement. This 0.3 eV energy oset requirement has been described as being necessary to overcome the binding energy of the excitons generated in organic semiconductor lms,

typically estimated at 0.3

This exciton binding energy

is also considered the reason for the optical bandgap ( E g ) of

most organic semiconductors being less than their elec- tronic bandgap. It should be noted that, in this viewpoint, a ΔE LUMO > 0.3 eV requirement corresponds to an approximately zero energy di erence between the exciton energy (as ap- proximated by E g ) and the blend electronic bandgap (IP EA, where IP is the electron donor ionization potential and EA is the electron acceptor electron a nity). As such, this require- ment Δ E LUMO > 0.3 eV is equivalent to requiring that the energy oset driving charge separation, after accounting for

93

eV. 11,13

charge separation, after accounting for 93 e V . 11,13 Figure 3. Energy level diagrams of

Figure 3. Energy level diagrams of a polymer/fullerene D/A interface during photocurrent generation shown as (a) an electronic orbital energy diagram illustrating material conduction and valence band energies and (b) a state energy diagram illustrating the relative energies of singlet exciton (S 1 ) and charge separated (CS) states relative to ground state (S 0 ). Both diagrams also include illustration of the energetics of bound polaron pair states. E exc b is the binding energy of the singlet exciton; E BPP b is the equivalent binding energy of the BPP states. Δ E LUMO is the donor/acceptor LUMO LUMO o set. E F and E F h are the electron and hole quasi-Fermi levels of the blend under device operation; the splitting of these levels corresponds to the free energy of photogenerated charge carriers after thermalisation to these Fermi levels (this thermally relaxed charge separated state is illustrated as CS TR in part b). At open circuit, the energy of CS TR corresponds to eV OC (in the absence of other voltage losses). Δ E CS is the enthalpy di erence driving charge separation de ned as the di erence in enthalpy between the singlet exciton energy ( E S1 ) and the enthalpy of the charge separated polarons at their respective material band edges, as given by IP EA. Δ G CS corresponds to the overall free energy di erence associated with charge photogeneration, including the enthalpy di erence Δ E CS and the entropy gain/energetic losses resulting from thermalization with the lm quasi-Fermi levels.

e

the exciton binding energy, to be greater than zero. An alternative viewpoint is to consider state energies, as illustrated

in Figure 3b. As we discuss, we use the energy di erence Δ E CS between the polymer exciton, E S1 , and the polaron energies IP and EA ΔE CS = (IP EA) E S1 , as a measure of the energy

o set driving charge

by Δ E CS = Δ E LUMO E exc b . E exc b represents the exciton binding energy. Also illustrated on both diagrams is the energy of BPP

states E BPP , with their coulomb binding energy relative to IP EA being given by E BPP b . The above discussion employs IP and EA as measures of the polaron energies. For semiconductors, these correspond to the conduction and valence band edge enthalpies. It is important to distinguish these energies from the free energies of electrons and holes in the blend, as de ned by the electron and hole quasi-Fermi levels. The splitting of the quasi-Fermi levels by light irradiation determines the voltage output of the device (often referred to, at open circuit, as eV OC , in the absence of other voltage losses) and corresponds to the energy stored by the photogenerated electrons and holes following thermal- isation with these Fermi levels (CS TR in Figure 3b). In general, the quasi-Fermi levels lie within the electronic bandgap of the lm, such that the free energy of photogenerated polaron pairs is less than the electronic bandgap of the lm. This dierence in energy between IP EA and eV OC derives most simply from the increase in entropy of the electrons and holes as they separate from the interface (readily calculated from simple degeneracy arguments to be several hundred meV), 13 as well as thermal relaxation/trapping processes as the polarons relax down the intraband density of states discussed above. The free energy lost

separation. Δ E CS is related to the Δ E LUMO

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during this overall charge separation process to polarons thermalized with the lm quasi-Fermi levels is illustrated in Figure 3b as Δ G CS . 94 We note that in our initial discussion of the energetics of charge separation, 13,56 we did not make this distinction between ΔE CS and Δ G CS . In terms of experimental measurements of the various energy osets illustrated in Figure 3 as driving charge separation, here- in, we employ ΔE CS = (IPEA) E S1 where E S1 is measured from optical spectroscopy data and IP and EA from photoelectron spectroscopy or cyclic voltammetry data. We note that these measurement techniques have the potential for signi cant systematic errors (for example due to the presence of an exponential density of tail states complicating the determination of the band edge); as such, we consider relative magnitudes of Δ E CS rather than its absolute value. An alter- native energy o set measurement used in the literature is based on electroluminescence of emissive interfacial charge transfer states, which determines the di erence in energy between the emissive exciton and CT states. 95 A third measure employs the dierence between the optical bandgap and open circuit voltage of the device (E eV OC ), this assay corresponds (at open

by

circuit) to Δ G CS , as de ned above, and di ers from Δ E CS

the energy loss associated with entropy gain and trapping. 96 We note that this latter, free energy assay of energetic oset depends upon the magnitude of the quasi-Fermi level splitting generated under solar irradiation and will therefore depend upon several additional factors, including the irradiation in- tensity and the nongeminate recombination rate constant. Exciton Quenching versus Polaron Generation: The Impact of Materials Energetics. Charge separation in donor/acceptor blend systems can be most simply described as electron transfer from donor excitons to generate positive and negative polarons (for acceptor excitons, this corresponds

to a hole transfer process). In this simple picture, the eciency of exciton quenching at the D/A interface should correlate directly with the yield of photogenerated charges. There is now extensive evidence that this correlation is not observed. In the extreme case of donor polymers with very low optical ban- dgaps, blending with PCBM does not result in strong polymer photoluminescence quenching, indicative of unfavorable energetics for exciton quenching at the D/A interface. How- ever, for almost all the donor polymers we have studied, we have observed remarkably e cient polymer photoluminescence quenching (PLQ) following blending with PCBM, typically in excess of 90%, and often >98% (in this regard, P3HT is rather anomalous, exhibiting modest PLQ (70 90%) attributed to its more complete phase segregation and the resultant exciton decay losses during di usion to the P3HT/PCBM inter-

face).

eciency of polymer PLQ, indicative that polymer excitons are indeed being quenched at polymer/fullerene interfaces, the yields of dissociated photogenerated charges, as assayed by our ΔOD measurement, are observed to vary very signicantly between blend lms. This distinction between consistently ecient PLQ and strongly varying yields of charge generation was rst reported by Ohkita et al. in a study of a series of poly- thiophene based polymers blended with PCBM, as illustrated in

Figure 4, 56 and has since been observed for several other polymer/fullerene, polymer/perylene, and polymer/quantum

dot systems.

number of reasons. First, it indicates that photoluminescence quenching is not a reliable assay of charge generation in organic blend lms. Second, as the yield of dissociated charges does not

g

46,56,79,97

Despite this remarkably ubiquitous high

40,46,80,86,98

This observation is important for a

E

high 40,46,80,86,98 This observation is important for a E Figure 4. Spectroscopic analyses of exciton quenching

Figure 4. Spectroscopic analyses of exciton quenching and charge generation yields as a function of the energy oset driving charge separation Δ E CS for a series of seven polythiophene/PCBM (19:1) blend lms. (a) Polymer photoluminescence quenching data relative to neat polymer lms, showing consistently high PLQ eciency plotted as a function of Δ E CS . (b) Transient absorption assay of the yield of dissociated charges determined from the magnitude of the Δ OD signals at 1 μ s delay time. Molecular structures of four of the polymers are included in part b. All data have been corrected for variations in the absorption at the excitation wavelength. Adapted with permission from ref 13. Copyright 2010, American Chemical Society.

correlate with the e ciency of exciton quenching, it suggests the presence of a competing pathway following exciton quenching at the interface that competes with the generation of long-lived dissociated charges. As we discuss later on, there is now extensive evidence that this competing pathway involves

the formation of interfacial BPP states. We have conducted several studies to investigate how the yield of dissociated charges varies with material ener- getics. 40,79,80,86,88 We have not observed strong correlations with either the absolute exciton or polaron pair energies, nor with the magnitudes of these energies relative to estimates of material triplet state energies (further discussion of this point is found later on). However, we have observed a strong cor- relation between our polaron quantum yield assay, Δ OD, and the di erence in energy between the exciton and polaron pairs, as dened as Δ E CS = (IPEA) E S1 . This is illustrated in Figure 4 for the data reported by Ohkita et al., 56 which shows that, for this series of donor polymers, the charge photo-

generation yields increases with 2 orders of magnitude for a 300 meV increase in Δ E CS . This observation strongly indicates that the energy o set Δ E CS is a key determinant of charge separation e ciency η sep and thereby photocurrent generation in OSC. We have since carried out studies with several series of polymer/acceptor lms to investigate the generality of the

13,35,36,41,42,47

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correlation between ΔE CS and η sep . 37,40,86,89 While clear cor- relations were not observed in all cases, indicative of other

factors inuencing η sep within the particular series studied in

addition to ΔE CS (such as dierences in lm microstructure, as

discussed later), we have successfully reproduced the clear

for six

correlation between ΔE CS and our Δ OD assay of η

distinct material series. 40,56,78 80,86,88 Typical data from three such series are shown in Figure 5, a fourth, employing PDI

sep

series are shown in Figure 5, a fourth, employing PDI sep Figure 5. Plots of the

Figure 5. Plots of the yield of dissociated charges, as determined from transient absorption signal amplitudes, against Δ E CS for three di erent series of donor polymers blended with PCBM. A strong correlation of the yields and Δ E CS is observed for the three di erent series of D/A blend lms, presented in the gure using di erent color codes. DPP-based copolymers blended with PC 70 BM at 1:2 w/w are shown with black triangles. Polythiophene-based polymers, such as P3HT, blended with PCBM at 1:1 w/w are shown with blue open squares. Thiazolothiazole-based polymers blended (1:1 w/w) with PCBM and ICBA are shown in red. For each series, the largest Δ OD signal is normalized to one to facilitate comparison between series, as di erences in polaron extinction coe cients between polymer series are possible. The electron a nities of the PC 70 BM and PC 60 BM were assumed to be 3.7 eV. Data were taken from refs 40, 86 and 88. For the polythiophene series, the Δ OD data have been extrapolated to a time delay of 100 ns to facilitate comparison with the other data series.

acceptors is discussed later (Figure 8). Based on these results, we conclude that the energy oset Δ E CS is indeed a key factor determining the charge separation yields in organic donor/ acceptor blends. Haque et al. have also recently reported a sim- ilar correlation for a series of polymer/quantum dot blends. 98 In addition, Janssen et al. have reported a similar energetic cor- relation for a series of diketopyrrolopyrrole (DPP) polymers, employing an EQE assay for charge generation and E eV OC as an assay of the energy o set driving charge separation. 96 These observations provide clear evidence that Δ E CS is, in general, a key determinant of charge separation e ciency in OSC. In addition to demonstrating the reproducibility of the correlation between ΔE CS and ΔOD within a materials series, it is also apparent from Figure 5 that the magnitudes of Δ E CS needed to achieve ecient charge photogeneration vary sub- stantially between materials series. For example, it is apparent that the DPP-based polymer/PC 70 BM blend lms (black- lled triangles in Figure 5) show ecient charge separation at energy osets almost 1 eV lower than those required to achieve comparable yields of charge separation for the polythiophene/ PCBM blend lms. We have reported a similar reduction in the energy o set required to drive charge separation for blend lms employing the donor polymer PCPDTBT relative to polythiophene polymers. 78,86,88 At present, it is unclear whether

g

F

this striking e ect derives from a reduction in coulomb binding energy of the BPP, an increase in local dielectric constant,

di erence in polymer internal dipole, 99 greater mixing of charge transfer and exciton states, or another parameter. Our observation that the energy o set required to drive

e cient charge separation may be modulated by choice of class

of donor polymers is of key signi cance for optimization of the

solar cell device e ciency. It clearly indicates that the widely used assumption that ΔE LUMO > 0.3 eV for e cient charge generation is material dependent. For the polythiophene-based polymers blended with PCBM, the energy o set Δ E CS required

to drive charge separation is 0.9 eV, almost half the photon en-

to ΔE LUMO = 1.2 eV, using ΔE LUMO =

and assuming E exc b = 0.3 eV). This energy loss is

ergy (and corresponding

a

50

Δ E CS + E exc

b

therefore the dominant energetic loss limiting device eciency in such devices. In contrast, for several of the more recently developed low bandgap copolymers such as DPP-TT-T, the energy oset Δ E CS required to drive charge separation ap- proaches 0 eV (corresponding indeed to ΔE LUMO = 0.3 eV,

assuming E exc b = 0.3 eV).

This reduction in the energy

o set with new donor polymers is likely to be one of the key factors behind the impressive advances in device eciency in recent years. Dependence of Charge Photogeneration Yield upon Photon Energy. The previous section discusses data where the energetics of charge separation were modulated by chang- ing the materials in the photoactive layer. We now consider data employing a complementary approach, modulating the photon energy used to excite a single material system. In this approach, we employed a low-band gap polymer/fullerene

blend with a very low Δ E CS , such that bandgap excitation

resulted in relatively low yields of separated charges. 37 The results of transient absorption experiments as a function

of excitation wavelength (shown in Figure 6) revealed that, for

this blend, the charge photogeneration yield increases with photon excitation energy above the optical bandgap. Com- plementing this observation, pump push photocurrent spec- troscopy demonstrated that this increase in the yield of dissociated charges with photon energy correlated with a reduction in the yield of interfacial BPP states. Bakulin et al. also compared directly the yield of dissociated charges vs BPP state formation in three di erent related polymer/fullerene blend lms, thereby comparing the hole (PCBM excitation) and electron (polymer excitation) transfer contributions. 36 A strong correlation between driving energy and bound state

generation was observed independent of the material excited. Experimental evidence that the photon energy can also mod- ulate the e ciency of charge separation, alongside the materials energetics discussed in the previous section, has also been reported in two other studies (although in at least one case rather controversially 60 62 ). 100,101 In our own studies, we have only observed a clear photon energy dependence for two blend systems with particularly small energy o sets. In general, such a photon energy dependency requires charge separation to proceed on a time scale faster than exciton thermal relaxation and therefore is unlikely to be observed in all systems, in agreement with our observation that, for most blend systems we have studied, we have not observed any photon energy dependence of charge separation yield. Notwithstanding this caveat, these data therefore provide further evidence that the yield of dissociated charges is strongly dependent upon the di erence in energy between the exciton initiating charge sep- aration and the dissociated polaron pairs.

1,37,88

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Chemistry of Materials Review Figure 6. (top graph) Charge photogeneration quantum yields of a BTT-DPP/PCBM blend

Figure 6. (top graph) Charge photogeneration quantum yields of a BTT-DPP/PCBM blend lm as estimated by TAS, recorded at the polymer polaron band (1150 nm) at a 0.2 μs time delay (red circles) as a function of excitation wavelength λ exc . Data was normalized for di erences in lm absorption at λ exc . IQE for photocurrent generation of the corresponding device is presented with a black line; it shows similar increases in the charge yield with excitation wavelength. Inset:

PL quenching of the BTT-DPP/PCBM blend lm plotted as a function of excitation wavelength. (bottom graph) Results of pump push photocurrent ( δ J/ J ) measurements on BTT-DPP/PCBM devices at di erent excitation wavelengths. The decays correspond to relaxed BPP state formation and recombination, thus showing that higher yields of relaxed BPP states are generated by longer wavelength excitation. Reprinted with permission from ref 37. Copyright 2012, American Chemical Society.

Model for Energetic Dependence. We turn now to discuss briey a model of charge separation based on our experimental observation that the yield of dissociated charges increases with Δ E CS . A key consideration for this model is the empirical observation that, even for blend lms with small energy osets such that the yield of dissociated polarons drops substantially, the eciency of exciton quenching at the interface can still be very high (often approaching unity). This observation clearly implies a competing loss pathway, which results in charge carrier recombination after exciton dissociation and which appears to be particularly dominant for small energy osets. For the purpose of this discussion, we will only consider charge separation across a D/A interface consisting of well- de ned polymer and fullerene phases (see the following text for discussion of more realistic interface structures). The model, as illustrated in Figure 7, is based on that originally proposed

in Ohkita et al.,

but modied to take into account recent

ultrafast spectroscopy and theoretical studies, including, in particular, those by the Friend group. 33,35,100,101 A key com-

ponent of the model is the presence of Coulombically bound polaron pair states at the D/A interface that function as a

56

G

pair states at the D/A interface that function as a 56 G Figure 7. Energy level

Figure 7. Energy level diagram depicting a model of charge photogeneration at organic D/A heterojunctions. The model is illustrated for two di erent initial exciton energies ( S A and S B ) relative to the polaron energies, corresponding for example to singlet excitons of two donor polymers with di erent optical bandgaps, or two di erent excitation wavelengths of the BTT-DPP polymer. Excitation of the higher energy exciton ( S A ) results in electron transfer ( k ET ) to the acceptor with su cient excess energy to avoid formation of a Coulombically bound interfacial polaron pair (BPP R ) but rather leads to formation of charge separated states (CS), which are subsequently stabilized ( k TR ) by charge migration away from the D/A interface, resulting in an increase in state degeneracy (entropy) and electronic relaxation into lower energy polaron states in the lm (CS TR ). In contrast, for the lower energy exciton (S B ), the injected electron does not have su cient excess energy to escape the coulomb attraction of the polymer polaron and therefore results in formation of bound polaron pair states that subsequently recombine ( k R ) radiatively or nonradiatively to ground or to lower lying polymer/acceptor triplet states.

recombination loss pathway. The model assumes that the electron is transferred adiabatically from the polymer exciton to the fullerene acceptor without an initial loss of energy (neglecting any exciton di usion processes). The electron is therefore injected with excess energy, corresponding to Δ E CS

above the bulk band edges, or Δ E CS + E g BPP above the BPP state energy (we have previously referred to this initial state with excess energy as a hot state ). There is then a competition between motion of the electron away from the D/A interface, corresponding to spatial charge separation, and loss of the excess energy through thermalisation/electronic relaxation processes. This hot electron motion versus thermalization picture is analogous to the Onsager model for autoionization in solution, as we have discussed previously. 13,102 As for Onsager, stable charge separation is only achieved if the electron escapes the coulomb attraction of the positive polaron residing on the polymer before it loses its excess energy. 102 A large energy o set Δ E CS results in injection of electrons with a large excess energy, facilitating their escape from the coulomb attraction of the polymer polaron. This increased escape probability may derive both from the longer time taken to thermalize this large excess energy and from the poten- tially greater wave function delocalization present for states well above the band edge, as has been proposed by several

For example, theoretical calculations

groups. 14,35,39,43,100,103 107

have provided evidence that higher energy BPP or CT states can be more delocalized and hence more prone to disso- ciation. 8,100,103 In contrast, for a small energy Δ E CS , the injected electron does not have su cient excess energy to escape the coulomb attraction with the positive polaron, and therefore, it becomes trapped at the interface, forming a bound interfacial BPP state. This bound BPP subsequently either decays directly to ground or, for systems with material triplet excitons lying below the BPP state in energy, undergoes intersystem crossing

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to the triplet BPP state, followed by charge recombination to triplet excitons. The model illustrated in Figure 7 suggests an inverse cor- relation between the yields of separated charges and inter- facially bound states, as evidenced by the data in Figure 6. Analogous inverse correlations have also been observed bet-

ween the intensity of CT state emission and EQE or polaron forma- tion, again consistent with a competition between generation of

bound interfacial states and free

We note, however, that there remains signi cant controversy in the literature over the nature and role of these BPP or CT states in organic solar cells, and signicantly more experimental and theoretical work is necessary to establish fully the detailed mechanism of charge separation in these devices. For example, an optimum driving energy for charge separation, consistent

with Marcus nonadiabatic electron transfer theory, has been observed for charge separation from fullerene excitons in dilute blends with donor polymers. 111 In addition, there is increasing evidence that sub-bandgap excitation of low optical density charge transfer (CT) transitions can result in e cient photo- current generation, suggesting that the states populated in such experiments do not correspond to the interfacially bound states responsible for the energetic dependencies of charge separation discussed above, as we discuss further towards the end of this

article. 53,112 115

charges. 33,35,37,41,57,76,108,109

We note that following the initial charge separation, the energy of the electron and hole is further reduced as the charge carriers thermalize to the lm quasi-Fermi levels, as also illustrated in Figure 7. For ecient solar cell materials that achieve charge separation with Δ E CS approaching 0 meV, this thermalization/trapping process is actually the dominant energy loss process associated with the overall charge pho- togeneration process 13,32 and is a key factor in stabilizing the charge separation in these devices. The magnitude of this over- all free energy loss, Δ G CS , is dependent upon device operating condition (being largest at short circuit conditions) and also depends (at open circuit conditions) upon the rate constant for nongeminate recombination. However, we do not discuss these energetic losses further in this review, as our focus is on the quantum e ciency of photocurrent generation, which is determined by e ciency of the initial charge separation, rather than by these energetic loss processes. In terms of materials design rules, the model illustrated in Figure 7 has several important implications. In addition to po- tentially explaining the origin of the energy oset dependence we observe empirically, it suggests several other parameters are likely to in uence the eciency of charge separation. These include the BPP state binding energy E g BPP , the extent of delocalization of the electron and hole wave functions after/ during charge transfer at the interface, the electron mobility, the thermalization time of the excess energy, the physical structure of the interface, including any local variations in energetics or composition, the domain structure and material composition in the blend lm, and the presence of interface or molecular dipoles. In the following sections, we consider the extent to which our studies have provided experimental evidence for the importance of some of these parameters.

IMPACT OF FILM MORPHOLOGY AND MATERIAL CRYSTALLINITY

There is now extensive evidence that, in addition to energetics, lm morphology and material crystallinity play key roles in de-

termining the eciency of charge separation.

34,40,85,110,116 120

H

In most text-book descriptions of polymer/fullerene bulk

heterojunction solar cells, the lm morphology is typically described as a two-component, bicontinuous blend comprising

a polymer phase and a fullerene phase. The function of such

lms is then described as light absorption in one or both phases, exciton di usion to the polymer/fullerene interface, exciton dissociation at this D/A interface to yield electrons and holes, and transport of these charges through the two phases to the device contacts. However, more detailed analyses are increasingly questioning whether this pure polymer phase/pure fullerene phase structural model is appropriate for the blend lms typically employed in BHJ OSC, with increasing evidence for the importance to device function of, for example, D/A mixing on a molecular scale, and the role of variations of material crystallinity within and between blends. 40,85,117,121 128 The former consideration, the presence of molecularly mixed regions of the lms, is important with regard to charge sep- aration, as it suggests that charge separation may be, at least in part, a molecular rather than interfacial process. Molecular mixed regions can also function as recombination centers in the lm due to the lack of spatial separation of donor and acceptor molecules. Variations in material crystallinity can impact charge separation by, for example, causing changes in wave function delocalization or material energetics (increased crystallinity typically results in smaller electronic bandgaps). In this section, we consider some insights into these dependencies derived particularly from correlations with our transient optical studies. Exciton Dynamics. Film morphology can have a major impact on the eciency of exciton di usion to D/A junctions. In this regard, a particularly important parameter for excitons is their diusion length; this is the average distance that an exciton can migrate during its lifetime. Typically this parameter is assessed by quantifying PLQ of bilayers as a function of a layer thickness using time-resolved or steady-state photo- luminescence spectroscopy. 65,129 133 For example, measure-

ments of this type have yielded exciton di usion lengths of

3 9 nm for P3HT and 5 nm

eral, achieving a high eciency for diusion of photogenerated

excitons to the charge separation interface, η diff , requires do- main sizes smaller than these di usion lengths. We note that the exciton di usion length will depend not only on the exciton

di usion constant but also on its lifetime, with shorter exciton

lifetimes likely to result in more severe exciton di usion re- quirements. For many of the polymer/PCBM blends discussed in this review, polymer photoluminescence quenching is remarkably high (often >95%), indicating that polymer excitons do not need to di use signi cant distances to reach a PCBM acceptor. Indeed, this high PLQ is indicative of the presence of signi cant molecular mixing of PCBM into the donor polymer on the length scale of the exciton wave function size (we note there is currently some discussion over the extent of exciton wave function delocalization at early times). 85,137,138 Such molecular scale mixing is consistent with several recent reports of PCBM miscibility with, and diusion into, donor polymers domains, includ- ing, in particular. relatively amorphous polymers. 122,124,128,139 143 More modest polymer PLQ, indicative of signi cant polymer exciton di usion on length scales approaching the exciton dif- fusion lengths, is only observed for highly crystalline polymers such as P3HT and DPP-TT-T, consistent with the formation of relatively pure crystalline polymer domains for these materials. This photoluminescence quenching has been most extensively studied for P3HT, which has PLQ, and therefore exciton

for PC 60 BM. 66,68,134 136

In gen-

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dissociation yields, sensitive to changes in lm morphology, for example, thermal annealing, which increases phase segregation

in the P3HT/PCBM

In general, polymer photoluminescence quenching following blending with PCBM can derive from either electron or energy transfer to PCBM. 67,145,146 In most cases, electron transfer appears to be the dominant pathway. We have observed e - cient energy transfer from donor polymer excitons to PCBM, but only for highly uorescent, high bandgap uorene-based polymers, where the strong uorescence e ciency and good spectral overlap between polymer emission and fullerene ab- sorption results in a suciently high energy transfer rate con- stant to enable ecient energy transfer. 81,87 In this case, this

energy transfer can result in a loss of charge photogeneration, as the resultant PCBM excitons can be too low in energy to drive e cient charge generation. In contrast to the typically very e cient quenching of poly- mer photoluminescence in blend lms, the quenching of fuller-

ene photoluminescence is often less ecient.

cannot, in general, be attributed to unfavorable energetics, as often the PCBM exciton has a higher energy than the polymer exciton. Rather, this eciency loss appears to derive from the tendency of both PC 60 BM and PC 70 BM to form aggregates on the length scale or larger than their exciton di usion lengths, as we have recently reported in a study of photocurrent generation from PC 70 BM excitons in blends with a low-bandgap DPP- based polymer. 83 In this case, clear correlations were observed between photocurrent density, PC 70 BM photoluminescence

quenching, and PC 70 BM domain size, indicative of exciton dif- fusion limitations. This result suggests that fullerene aggre- gation and its miscibility with the polymer are a key con- sideration for optimization of photocurrent generation from fullerene excitons. Exciton Separation and Charge Carrier Mobility/ Delocalization. The molecular scale structure of the D/A junction can be expected to have a profound impact on the e - ciency and dynamics of exciton separation. One consideration attracting particular interest is the potential for increased wave

function delocalization and/or high carrier mobility to facilitate escape of charge carriers from the D/A junction (see proposed model in Figure 7). Several studies have reported both experi-

mental and theoretical analyses of this issue.

8,22,26 28,51,110,150

Our own studies comparing the charge separation e ciency of polymer/PCBM and polymer/PDI (perylene diimide) blends

are particularly relevant to this.

replacement of PCBM in blend lms with crystalline PDIs results in a large reduction in the energy o set dependence of charge separation (Figure 8). An analogous observation has also been made for polymer/CdS nanocrystals blends, where an increase in CdS crystallinity was also observed to reduce the energy o set dependence of charge separation. 98 In both cases,

the improved charge separation e ciency was assigned to increases in electron delocalization/mobility in the acceptor material facilitating the escape of the charge carriers from their mutual coulomb attraction. We have also observed that decreasing the fullerene content in the blend lm increases the energy oset dependence of charge separation, attributed to more nely dispersed PCBM molecules within the blend making it more di cult for photogenerated electrons and holes

to move away from each other.

observed a strong correlation between donor polymer hole mobility/crystallinity and charge separation eciency, at least for charge separation from polymer excitons, 56,86,89 suggesting

blends. 79,97,144

83,118,147

149 This

40,86

We have observed that

80

Interestingly, we have not

40,86 We have observed that 80 Interestingly, we have not Figure 8. Comparison of the Δ

Figure 8. Comparison of the Δ OD signal amplitudes of polymer/ PCBM and polymer/PDI blend lms. The substitution of PCBM with highly crystalline PDI acceptors reduces the dependence of charge photogeneration yields on energy o set driving charge separation. Adapted with permission from ref 86. Copyright 2010, American Chemical Society.

that it is the mobility/delocalization of charge carrier that is moving during exciton separation (e.g., the electron for LUMO to LUMO transfer), which is most important. Domain Energetics, Material Crystallinity, and the

Spatial Separation of Charges. As discussed above, there is increasing evidence that, for many polymer/fullerene blends, there is extensive mixing of polymer and fullerene on a molec- ular scale, depending upon the details of lm processing. This is particularly the case where the polymer is highly miscible with PCBM, either through formation of a mixed cocrystal or the

formation of amorphous, mixed regions of lm. However, there is also strong evidence that molecularly mixed

lms, in the absence of any pure domains, exhibit very rapid charge recombination, as charge carriers generated by exciton

separation are not spatially well separated.

have, for example, observed that replacing PCBM with a more miscible fullerene in blends with P3HT results in appearance of rapid ( 100 ns) recombination and, consequently, negligible photocurrent generation. 40,154 Similarly, fast recombination has been observed in lms comprising covalently attached donor and acceptor. 158 As such, it appears likely that molecularly mixed polymer/fullerene domains, while being eective at enabling ecient exciton quenching, can also function as recombination centers for photogenerated charge carriers. In this regard, it is striking that some of the highest device eciencies reported to date have been achieved with relatively amorphous polymers (for example PTB7) that show evidence for rather high miscibility with PCBM and, consequently, signicant polymer/PCBM mixing on a molecular scale. 2,4,5,122,151

We recently undertook a number of studies to address this apparent contradiction namely, that, for some blend lms, the presence of signicant fractions of molecular mixed material does not result in rapid electron/hole recombination and con- sequently poor device performance. 40,85 The key to answering this conundrum appears to come from consideration of relative energetics of pure and mixed domains. In particular, we have observed that neat PCBM lms exhibit an electron a nity approximately 100 meV greater than PCBM dispersed in a polymer matrix. 85 In lms comprising both molecularly mixed

polymer/PCBM and pure PCBM domains, this energy

di erence provides an energy oset to localize electrons in the pure PCBM domains, thereby spatially separating the charges and enabling ecient charge collection, as illustrated in Figure 9c. A similar eect is likely for blend lms exhibiting

85,122,128,151 153

39,54,90,153 157 We

Chemistry of Materials

Review

Chemistry of Materials Review Figure 9. Illustration of charge separation in blend fi lms comprising relatively

Figure 9. Illustration of charge separation in blend lms comprising relatively an amorphous, intimately mixed polymer/fullerene phase as well as relatively chemical pure, more crystalline phases. The crystalline/aggregated domains exhibit a smaller IP (for donor materials) and larger EA (fo r acceptor materials). The interface between the mixed and more crystalline domains thereby provides an energy o set that can stabilize the spatial separation of charge carriers. The model is illustrated for blend lms comprising a relatively crystalline donor polymer (a), relatively crystalline acceptor fullerene (c), or where neither polymer nor fullerene exhibit signi cant crystallinity (b). In part b, the absence of a well-de ned interface to separate spatially the polarons results in relatively rapid ( 100 ns) charge carrier recombination, preventing ecient photocurrent generation. Reprinted with permission from ref 40. Copyright 2010, Wiley-VCH Verlag GmbH & Co. KGaA.

signi cant fractions of pure, crystalline donor polymer; in general, increased polymer crystallinity reduces its ionization potential, again providing an energy oset to stabilize charge separation. 79 Appreciation that di erences in carrier energetics within a blend lm deriving from di erences in material crystallinity/ aggregation state can impact directly photovoltaic device performance has important implications for materials design. For example, the requirement of relatively pure, aggregated PCBM domains to stabilize charge separation is likely to be one origin of high PCBM weight fractions often required to achieve ecient device performance, and the reason this requirement is less pronounced for crystalline polymers (due to their typically lower immiscibility with PCBM). We have also recently shown that this additional energy oset requirement can explain empirical observations that the low electron a nity acceptor ICBA works well with some crystalline donor poly- mers but not with amorphous donor polymers. 40 ICBA appears not to exhibit a di erence in electron a nity between neat and molecularly dispersed lms, attributed to its low tendency to aggregation/crystallization. As such, the energy o set between mixed and pure fullerene domains present in blends with PCBM is not present in blends with ICBA, such that the presence of molecularly mixed domains are more likely to result in rapid electron hole recombination (Figure 9b), as evidenced by observation of a rapid (100 ns) recombination decay phase in blends of amorphous donor polymers with ICBA. 40,155 This is, however, avoided in blends with more crystalline donor poly- mers, which reduce the presence of molecular mixing, and results in the formation of pure polymer domains capable of stabilizing charge separation (Figure 9a); such blends do not exhibit this 100 ns recombination phase. A key consideration in the above discussion is that, for many blend lms, we need to consider two distinct interfaces that drive charge separation. In many cases, and particularly for more amorphous donor polymers, the initial exciton quenching may occur primarily in rather molecularly mixed domains, without the presence of a well-de ned physical D/A interface.

However, the lifetime of charge carriers in such molecular mixed domains is relatively short (100 ns). As such, stabi- lization of this charge separation requires the presence of relatively pure domains, with a favorable energy oset between the mixed and pure domains being essential to drive this sta- bilization. The presence of such mixed domains is likely to be less important for polymers that show lower miscibility with PCBM, in particular, for more crystalline polymers. However, even for these polymers, it has been suggested that the interface between polymer and PCBM domains may be relatively amorphous and molecularly mixed, with the higher bandgap in this interface region helping to drive and stabilize charge

Relating to this, recent studies have

suggested that relaxation into lower energy states resulting

from local inhomogeneities may also be a key factor helping to separate polarons away from the donor/acceptor inter-

face. 162,163

separation. 85,119,121,159 161

The presence of at least two charge separation interfaces, and realization that crystalline and amorphous regions of the lm may exhibit di erent energetics, clearly complicates both energetic and kinetic analyses of charge separation in blend lms. We have, for example, suggested that photocurrent generation may be limited both by geminate recombination of tightly BPP (or CT) states and, for some systems that lack secondary charge separation interfaces to stabilize the spatial separation of charges, by recombination of more loosely bound polaron pair states, as illustrated in Figure 9. 86 However, in general, experimental data on these issues are relatively limited to date.

OTHER FACTORS INFLUENCING CHARGE GENERATION

J

In the previous sections, we focused on the roles of energetics and lm microstructure/crystallinity in determining the e - ciency of charge photogeneration. In this section, we consider the extent to which we observe empirical correlations between our Δ OD assay of charge generation and other potential

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parameters, including polymer hole mobility, macroscopic electric elds, and population of triplet states. Hole mobility is one property of polymers that is often cited in the literature in relation to good device performance. It has indeed been shown that excessively low hole mobilities can limit device performance due to poor charge extraction and resultant space charge accumulation. However, relating to the eciency of charge photogeneration, our investigations have not observed any signi cant correlation between hole mobility and charge separation from polymer excitons, at least in blends with PCBM and with FET hole mobilities >10 4 cm 2 V 1 s 1 , 89 in agreement with other studies. 19 Similarly, we have not ob- served any correlation between charge photogeneration and polymer crystallinity, beyond the impact of polymer crystal- linity upon ionization potential and miscibility with PCBM, as we have discussed above and in more detail elsewhere. 40 In this regard, it should be noted that charge photogeneration from polymer excitons corresponds to an electron rather than hole transfer process. As such, it is plausible that electron mobilities rather than hole mobilities might be the more relevant pa- rameter related to charge separation. Indeed, our comparison of fullerene and PDI acceptors, and of blends as a function of fullerene composition support this argument, as we discuss above. Hole mobilities, on the other hand, may be important for charge separation mediated via fullerene exciton dissociation (hole transfer); however, to the best of our knowledge, evi- dence for the importance of polymer hole mobility to this process is not present to date. Another factor widely discussed in terms of its impact upon charge separation is the macroscopic electric elds generated by the di erence in work function of the device electro-

des. 41,76,112,164 166 There is extensive evidence that these elec- tric elds play a key role in sweeping out photogenerated charge carriers, and thereby ensuring a high collection eciency η coll . However, our own transient absorption data on devices as function of applied bias, as well as transient optoelectronic device analyses, 16,74,84 have indicated that, for most photoactive layers, the impact of these macroscopic electric elds on the eciency of charge separation η sep is relatively insigni cant, at least under normal device operating conditions within the fourth quadrant of the device JV curve. 166 In some cases, we have observed signi cant increases in the e ciency of charge separation between open circuit and short circuit and assigned these to the e ect of macroscopic electric elds; so far, we have only observed this eld dependence in very amorphous blend lms where the morphology of the active layer is most probably dominated by well-mixed polymer/fullerene phases. 90,167 This correlation between eld-dependent generation and blend crystallinity/morphology has also been observed in elegant studies employing time-delayed collection eld measurements

by Neher et al.

dependence and crystallinity/morphology is unclear, but it is plausible that electric elds may be particularly helpful in spa- tially separating charges generated in molecular mixed domains, which would otherwise undergo relatively rapid recombination. There have been several studies in the literature, which con- sider the role of low lying triplet states in accelerating charge

recombination in OSC.

that BPP state formation may result in high yields of polymer or

fullerene triplet states, through intersystem crossing between singlet

and triplet BPP states, as illustrated in Figure 10. This polaron pair mediated triplet mechanism is analogous to that observed in for example photosynthetic reaction centers.

165

The origin of this correlation between eld

168

171 Both we and others have shown

29,41,56,75,77,169,172

In addition, from spin statistics well established in the organic light emitting diode eld, nongeminate recombination of dissociated charges is likely to lead to high yields of triplets states (Figure 10). However, our studies to date have indicated

(Figure 10). However, our studies to date have indicated Figure 10. Illustration of the charge separation

Figure 10. Illustration of the charge separation and recombination processes in organic solar cells, analogous to the model shown in Figure 7, but including the presence of triplet BPP and exciton states. Adapted with permission from ref 56. Copyright 2008, American Chemical Society.

that while triplet states may indeed be formed by such recombination processes when these triplet states lie energeti- cally below the relevant BPP or CS states, the presence of such low lying triplet states does not necessarily prevent charge gen- eration. For example, charge recombination in PTB7/PCBM blend lms appears to result in e cient PTB7 triplet gen- eration, indicative of the presence of a lower energy triplet state; yet under short-circuit conditions, photocurrent gen- eration can be remarkably e cient. 75 Work on this topic is ongoing and will be presented in more detail elsewhere. Finally, we note that there is currently extensive discussion in the literature over whether interfacial BPP or CT states may undergo thermally activated dissociation. 76,150,173 175 Our studies indicate that low energy osets result in low charge generation yields due to the presence of a competing loss path- way after exciton separation, which prevents ecient charge dissociation. The formation and recombination of Coulombi- cally bound polaron pairs are the most likely candidate for this loss pathway. Whether these Coulombically bound states are the same states as those involved in studies of CT state

emission and sub-bandgap absorption is not fully resolved. In this context, it is important to note the presence of both molecular mixed and phase segregated domains in many blend lms, as well as modulation to the energetic landscape from variations in material crystallinity, such that it is possible that such CT stateabsorption and electroluminescence studies may be probing states formed at di erent interfaces to those associated with photoinduced charge separation, as we have

It has, for example, been noted that

discussed elsewhere.

studies of CT state photoluminescence and electrolumines- cence often reveal rather distinct emission peaks, 46 indicating the presence of di erent CT states in the lm populated dif- ferently by optical or electrical generation and suggested to be associated with CT states located within molecular mixed domains and at domain interfaces, respectively. 153 Also relevant

to this discussion, Zhou et al. have considered a similar model for donor/acceptor pairs in solution and concluded that charge separation following sub-bandgap excitation in such systems can derive primarily from direct excitation of loosely bound polaron ion pairs.

40

176

CONCLUSIONS

The focus of this review is on identifying materials design guidelines that may facilitate the development of new

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photoactive layer materials or processing procedures to max- imize the quantum e ciency of photoinduced charge sep- aration η sep and thus photocurrent generation in OSC. These guidelines can be summarized as follows:

(1) A key determinant for high η sep is a su ciently large energy oset between the D and A material optical ban- dgaps, and the blend electronic bandgap IP EA, Δ E CS . However, a large value of Δ E CS corresponds to a large loss of energy per photon; therefore, a key challenge for OSC is to achieve a high quantum eciency for charge separation with as small a value for Δ E CS as possible. Em- pirically, we have observed that materials design strat- egies to achieve this include

a. the use of donor copolymers with a high degree of D Acharacter. This has proved to be remarkably e ective at reducing the energy o set requirement for charge separation and is likely to be a key factor behind recent advances in OSC device eciencies.

b. the use (for charge separation from polymer exci-

tons) of acceptors with increased electron mobility/ delocalization (e.g.: by increasing acceptor crys- tallinity). We note, however, that excessive accep- tor crystallinity may result in lower collection e ciency. (2) The generation of suciently long-lived charge carriers to enable e cient charge collection requires the spatial separation of charges into di erent domains. This typi- cally requires the presence in the blend of reasonably pure domains of either donor or acceptor (or both). For such pure domains to stabilize charge separation, there must be an energy oset (of the order of 100 meV or greater) driving one charge carrier from mixed domains into these pure domains. This energy o set can derive from di erences in crystallinity/aggregation between pure and mixed domains. (3) For most polymer/fullerene blends, the miscibility of PCBM with many donor polymers results in ecient polymer exciton quenching, with negligible exciton dif- fusion requirements. In contrast, PCBM exciton di usion limitations can result in signicant photocurrent losses. We note that, for many OSC blends, and particularly those with more amorphous donor polymers with PCBM, ecient device performance requires the for- mation of relatively pure PCBM domains, for reason 2 above. This can be achieved by appropriate lm pro- cessing (e.g., by use of cosolvent additives) or the addi- tion of excess PCBM to the blend. However, this formation of aggregated PCBM domains can also reduce the e ciency of PCBM exciton utilization. (4) Device macroscopic electric elds do not signicantly impact upon photocurrent generation in most OSC (except at strong reverse biases), apart from in blend lms employing highly amorphous donors. We also do not observe a signi cant correlation of charge separation e ciency with polymer hole mobility (for charge separation from polymer excitons). Clearly these materials design guidelines are limited both in scope and detail. However, we hope that they provide some insights that may aid synthetic chemists, materials scientists, and device physicists in their drive toward more ecient OSC materials and devices.

AUTHOR INFORMATION

Corresponding Author

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS

We gratefully acknowledge the EPSRC projects EP/J500021/1 and EP/G037515/1 for funding. We thank our many colleagues and co-workers who have contributed to these studies over the last 8 years, and in particular Safa Shoaee, Eliza Collado Fregoso, and Yvonne Soon, who helped with the preparation of some gures in this manuscript, and Christian Nielsen, Hugo Bronstein, Jenny Nelson, and Dieter Neher for helpful discussions and comments. We also thank colleagues, and particularly Peter Würfel for discussions regarding ΔE CS vs Δ G CS terminology.

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