Suppressing Energy Loss due to Triplet Exciton Formation in Organic Solar Cells: The Role of Chemical Structures and Molecular Packing

In the most efficient solar cells based on blends of a conjugated polymer (electron donor) and a fullerene derivative (electron acceptor),ultrafast formation of charge‐transfer (CT) electronic states at the donor‐acceptor interfaces and efficient separation of these CT states into free charges, lead to internal quantum efficiencies near 100%. However, there occur substantial energy losses due to the non‐radiative recombinations of the charges, mediated by the loweset‐energy (singlet and triplet) CT states; for example, such recombinations can lead to the formation of triplet excited electronic states on the polymer chains, which do not generate free charges. This issue remains a major factor limiting the power conversion efficiencies (PCE) of these devices. The recombination rates are, however, difficult to quantify experimentally. To shed light on these issues, here, an integrated multi‐scale theoretical approach that combines molecular dynamics simulations with quantum chemistry calculations is employed in order to establish the relationships among chemical structures, molecular packing, and non‐radiative recombination losses mediated by the lowest‐energy charge‐transfer states.     

Difference picosecond spectroscopy of pigment-protein complexes of photosystem I from higher plants

Using a difference picosecond spectrophotometer with a time resolution of 10 ps, we investigated excitation energy transfer and charge separation in pigment-protein complexes of Photosystem I from bean leaves (chlorophyll/P-700 = 60). Under 20 ps excitation at 650 or 667 nm, the difference absorption spectra in the spectral region 600–720 nm were measured. They are associated with transition of antenna chlorophylls into singlet excited states and P-700 photooxidation. It was shown that the excited states in the whole inhomogeneous antenna were generated within 10 ps and deactivated with three-component kinetics, the t_1/e values being 20–45, 100–300 and over 500 ps. Formation of P-700⁺ has a rise time of 15–30 ps. The fast component of the depletion of the antenna excited states is suggested to be due to transfer of excitation energy from antenna pigments to reaction centers and its trapping. The kinetics of the fast component is independent of excitation energy and a redox state of P-700.     

Dynamics of energy conversion in reaction center core complexes of the green sulfur bacterium Prosthecochloris aestuarii at low temperature.

Excited-state and electron-transfer dynamics at cryogenic temperature in reaction center core (RCC) complexes of the photosynthetic green sulfur bacterium Prosthecochloris aestuarii were studied by means of time-resolved absorption spectroscopy, using selective excitaton of bacteriochlorophyll (BChl) a and of chlorophyll (Chl) a 670. The results indicate that the BChls a of the RCC complex form an excitonically coupled system. Relaxation of the excitation energy within the ensemble of BChl a molecules occurred within 2 ps. A time constant of about 25 ps was ascribed to charge separation. Absorption changes in the 670 nm region, where Chl a 670 absorbs, were fairly complicated. They showed various time constants and were dependent on the wavelength of excitation and they did not lead to a simple picture of the electron acceptor reaction. Energy transfer from Chl a 670 to BChl a occurred with a time constant of 1.5 ps. However, upon excitation of Chl a 670 the amount of oxidized primary electron donor, P840(+), formed relative to that of excited BChl a was considerably larger than upon direct excitation of BChl a. This indicates the existence of an alternative pathway for charge separation which does not involve excited BChl a.     

Kinetics and spectra of photo-induced changes in the absorption of pigment-protein complexes of photosystem 1 in a picosecond range

The energy transfer from the light-harvesting antenna chlorophylls to the reaction center molecules and subsequent charge separation were investigated using a difference picosecond spectrophotometer with selective excitation. The objects were the pigment-protein complexes of photosystem 1 (Chl/P700 = 60) isolated from bean leaves. The difference absorption spectra of the excited states of light-harvesting antenna chlorophylls and the P700 photooxidation were measured. It was shown that the excited states of antenna chlorophylls were generated within 10 ps and deactivated with three-component kinetics: tau 1 = 20--45 ps, tau 2 = 100--300 ps, tau 3 greater than 500 ps. The process of the P700 photooxidation induced by the 650 nm exciting pulse was approximately monoexponential with tau equal to 15--30 ps. It is established that the P700 photooxidation is due to the efficient transfer of excitation energy from antenna chlorophylls to reaction centers.     

Charge‐Transfer States at Organic–Organic Interfaces: Impact of Static and Dynamic Disorders

Molecular dynamics simulations are combined with density functional theory calculations to evaluate the impact of static and dynamic disorders on the energy distribution of charge‐transfer (CT) states at donor–acceptor heterojunctions, such as those found in the active layers of organic solar cells. It is shown that each of these two disorder components can be partitioned into contributions related to the energetic disorder of the transport states and to the disorder associated with the hole–electron electrostatic interaction energies. The methodology is applied to evaluate the energy distributions of the CT states in representative bulk heterojunctions based on poly‐3‐hexyl‐thiophene and phenyl‐C₆₁‐butyric‐acid methyl ester. The results indicate that the torsional fluctuations of the polymer backbones are the main source of both static and dynamic disorders for the CT states as well as for the transport levels. The impact of static and dynamic disorders on radiative and nonradiative geminate recombination processes is also discussed.     

High‐Voltage Photogeneration Exclusively via Aggregation‐Induced Triplet States in a Heavy‐Atom‐Free Nonplanar Organic Semiconductor

The electron–hole recombination kinetics of organic photovoltaics (OPVs) are known to be sensitive to the relative energies of triplet and charge‐transfer (CT) states. Yet, the role of exciton spin in systems having CT states above 1.7 eV—like those in near‐ultraviolet‐harvesting OPVs—has largely not been investigated. Here, aggregation‐induced room‐temperature intersystem crossing (ISC) to facilitate exciton harvesting in OPVs having CT states as high as 2.3 eV and open‐circuit voltages exceeding 1.6 V is reported. Triplet excimers from energy‐band splitting result in ultrafast CT and charge separation with nonradiative energy losses of <250 meV, suggesting that a 0.1 eV driving force is sufficient for charge separation, with entropic gain via CT state delocalization being the main driver for exciton dissociation and generation of free charges. This finding can inform engineering of next‐generation active materials and films for near‐ultraviolet OPVs with open‐circuit voltages exceeding 2 V. Contrary to general belief, this work reveals that exclusive and efficient ISC need not require heavy‐atom‐containing active materials. Molecular aggregation through thin‐film processing provides an alternative route to accessing 100% triplet states on photoexcitation.     

The Role of Photon Energy in Free Charge Generation in Bulk Heterojunction Solar Cells

To determine the role of photon energy on charge generation in bulk heterojunction solar cells, the bias voltage dependence of photocurrent for excitation with photon energies below and above the optical band gap is investigated in two structurally related polymer solar cells. Charges generated in (poly[2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′′]dithiophene)‐alt‐4,7‐(2,1,3‐benzothia­diazole)] (C‐PCPDTBT):[6,6]‐phenyl‐C61‐butyric acid methyl ester (PCBM) solar cells via excitation of the low‐energy charge transfer (CT) state, situated below the optical band gap, need more voltage to be extracted than charges generated with excitation above the optical band gap. This indicates a lower effective binding energy of the photogenerated electrons and holes when the excitation is above the optical band gap than when excitation is to the bottom of the CT state. In blends of PCBM with the silicon‐analogue, poly[(4,4‐bis(2‐ethylhexyl)dithieno[3,2‐b:2′,3′‐d]silole)‐2,6‐diyl‐alt‐(2,1,3‐benzothiadiazole)‐4,7‐diyl] (Si‐PCPDTBT), there is no effect of the photon energy on the electric field dependence of the dissociation efficiency of the CT state. C‐PCPDTBT and Si‐PCPDTBT have very similar electronic properties, but their blends with PCBM differ in the nanoscale phase separation. The morphology is coarser and more crystalline in Si‐PCPDTBT:PCBM blends. The results demonstrate that the nanomorphological properties of the bulk heterojunction are important for determining the effective binding energy in the generation of free charges at the heterojunction.     

Comparison of excitation energy transfer in cyanobacterial photosystem I in solution and immobilized on conducting glass

Excitation energy transfer in monomeric and trimeric forms of photosystem I (PSI) from the cyanobacterium Synechocystis sp. PCC 6803 in solution or immobilized on FTO conducting glass was compared using time-resolved fluorescence. Deposition of PSI on glass preserves bi-exponential excitation decay of ~4–7 and ~21–25 ps lifetimes characteristic of PSI in solution. The faster phase was assigned in part to photochemical quenching (charge separation) of excited bulk chlorophylls and in part to energy transfer from bulk to low-energy (red) chlorophylls. The slower phase was assigned to photochemical quenching of the excitation equilibrated over bulk and red chlorophylls. The main differences between dissolved and immobilized PSI (iPSI) are: (1) the average excitation decay in iPSI is about 11 ps, which is faster by a few ps than for PSI in solution due to significantly faster excitation quenching of bulk chlorophylls by charge separation (~10 ps instead of ~15 ps) accompanied by slightly weaker coupling of bulk and red chlorophylls; (2) the number of red chlorophylls in monomeric PSI increases twice—from 3 in solution to 6 after immobilization—as a result of interaction with neighboring monomers and conducting glass; despite the increased number of red chlorophylls, the excitation decay accelerates in iPSI; (3) the number of red chlorophylls in trimeric PSI is 4 (per monomer) and remains unchanged after immobilization; (4) in all the samples under study, the free energy gap between mean red (emission at ~710 nm) and mean bulk (emission at ~686 nm) emitting states of chlorophylls was estimated at a similar level of 17–27 meV. All these observations indicate that despite slight modifications, dried PSI complexes adsorbed on the FTO surface remain fully functional in terms of excitation energy transfer and primary charge separation that is particularly important in the view of photovoltaic applications of this photosystem.     

Cofactors involved in light-driven charge separation in photosystem I identified by subpicosecond infrared spectroscopy

Photosystem I is one of the key players in the conversion of solar energy into chemical energy. While the chlorophyll dimer P(700) has long been identified as the primary electron donor, the components involved in the primary charge separation process in PSI remain undetermined. Here, we have studied the charge separation dynamics in Photosystem I trimers from Synechococcus elongatus by femtosecond vis-pump/mid-infrared-probe spectroscopy upon excitation at 700, 710, and 715 nm. Because of the high specificity of the infrared region for the redox state and small differences in the molecular structure of pigments, we were able to clearly identify specific marker bands indicating chlorophyll (Chl) oxidation. Magnitudes of chlorophyll cation signals are observed to increase faster than the time resolution of the experiment (~0.2 ps) upon both excitation conditions: 700 nm and selective red excitation. Two models, involving either ultrafast charge separation or charge transfer character of the red pigments in PSI, are discussed to explain this observation. A further increase in the magnitudes of cation signals on a subpicosecond time scale (0.8-1 ps) indicates the formation of the primary radical pair. Evolution in the cation region with time constants of 7 and 40 ps reveals the formation of the secondary radical pair, involving a secondary electron donor. Modeling of the data allows us to extract the spectra of the two radical pairs, which have IR signatures consistent with A+A?- and P???+A?-. We conclude that the cofactor chlorophyll A acts as the primary donor in PSI. The existence of an equilibrium between the two radical pairs we interpret as concerted hole/electron transfer between the pairs of electron donors and acceptors, until after 40 ps, relaxation leads to a full population of the P???+A?. radical pair.     

Pathways of energy transformation in antenna reaction center complexes of Heliobacillus mobilis

The conversion of excitation energy in the antenna reaction center complex of Heliobacillus mobilis was investigated at 10 K as well as at 275 K by means of time-resolved absorbance difference spectroscopy of isolated membranes in the (sub)picosecond time range. Selective excitation of the primary electron acceptor, chlorophyll (Chl) a 670, and of the different spectral pools of bacteriochlorophyll (BChl) g (BChl g 778, BChl g 793, and BChl g 808) was applied. At 10 K, excitation at 770 or 793 nm resulted on the one hand in rapid energy transfer to BChl g 808 and on the other hand in fast charge separation from excited BChl g 793 ( approximately 1 ps). Once the excitations were on BChl g 808, the bleaching band shifted gradually to the red, from 806 to 813 nm, and charge separation from excited BChl g 808 occurred by a very slow process ( approximately 500 ps). The main purpose of our experiments was to answer the question whether an "alternative" pathway for charge separation exists upon excitation of Chl a 670. Our measurements showed that the amount of oxidized primary donor (P798(+)) relative to that of excited BChl g produced by excitation of Chl a 670 was considerably larger than upon direct excitation of BChl g. This indicates the existence of an alternative pathway for charge separation that does not involve excited antenna BChl g. This effect occurred at 10 K as well as at 275 K. The mechanism for this process is discussed in relation to different trapping models; it is concluded that charge separation occurs directly from excited Chl a 670.     

Pathways and timescales of primary charge separation in the photosystem II reaction center as revealed by a simultaneous fit of time-resolved fluorescence and transient absorption

We model the dynamics of energy transfer and primary charge separation in isolated photosystem II (PSII) reaction centers. Different exciton models with specific site energies of the six core pigments and two peripheral chlorophylls (Chls) in combination with different charge transfer schemes have been compared using a simultaneous fit of the absorption, linear dichroism, circular dichroism, steady-state fluorescence, transient absorption upon different excitation wavelengths, and time-resolved fluorescence. To obtain a quantitative fit of the data we use the modified Redfield theory, with the experimental spectral density including coupling to low-frequency phonons and 48 high-frequency vibrations. The best fit has been obtained with a model implying that the final charge separation occurs via an intermediate state with charge separation within the special pair (RP(1)). This state is weakly dipole-allowed, due to mixing with the exciton states, and can be populated directly or via 100-fs energy transfer from the core-pigments. The RP(1) and next two radical pairs with the electron transfer to the accessory Chl (RP(2)) and to the pheophytin (RP(3)) are characterized by increased electron-phonon coupling and energetic disorder. In the RP(3) state, the hole is delocalized within the special pair, with a predominant localization at the inactive-branch Chl. The intrinsic time constants of electron transfer between the three radical pairs vary from subpicoseconds to several picoseconds (depending on the realization of the disorder). The equilibration between RP(1) and RP(2) is reached within 5 ps at room temperature. During the 5-100-ps period the equilibrated core pigments and radical pairs RP(1) and RP(2) are slowly populated from peripheral chlorophylls and depopulated due to the formation of the third radical pair, RP(3). The effective time constant of the RP(3) formation is 7.5 ps. The calculated dynamics of the pheophytin absorption at 545 nm displays an instantaneous bleach (30% of the total amplitude) followed by a slow increase of the bleaching amplitude with time constants of 15 and 12 ps for blue (662 nm) and red (695 nm) excitation, respectively.     

Multistep Photoluminescence Decay Reveals Dissociation of Geminate Charge Pairs in Organolead Trihalide Perovskites

Charge carrier dynamics in organolead iodide perovskites is analyzed by employing time‐resolved photoluminescence spectroscopy with several ps time resolution. The measurements performed by varying photoexcitation intensity over five orders of magnitude enable separation of photoluminescence components related to geminate and nongeminate charge carrier recombination and to address the dynamics of an isolated geminate electron–hole pair. Geminate recombination dominates at low excitation fluence and determines the initial photoluminescence decay. This decay component is remarkably independent of the material structure and experimental conditions. It is demonstrated that dependences of the geminate and nongeminate radiative recombination components on excitation intensity, repetition rate, and temperature, are hardly compatible with carrier trapping and exciton dissociation models. On the basis of semiclassical and quantum mechanical numerical calculation results, it is argued that the fast photoluminescence decay originates from gradual spatial separation of photogenerated weakly bound geminate charge pairs.     

Determination of the excitation migration time in Photosystem II consequences for the membrane organization and charge separation parameters

The fluorescence decay kinetics of Photosystem II (PSII) membranes from spinach with open reaction centers (RCs), were compared after exciting at 420 and 484 nm. These wavelengths lead to preferential excitation of chlorophyll (Chl) a and Chl b, respectively, which causes different initial excited-state populations in the inner and outer antenna system. The non-exponential fluorescence decay appears to be 4.3+/-1.8 ps slower upon 484 nm excitation for preparations that contain on average 2.45 LHCII (light-harvesting complex II) trimers per reaction center. Using a recently introduced coarse-grained model it can be concluded that the average migration time of an electronic excitation towards the RC contributes approximately 23% to the overall average trapping time. The migration time appears to be approximately two times faster than expected based on previous ultrafast transient absorption and fluorescence measurements. It is concluded that excitation energy transfer in PSII follows specific energy transfer pathways that require an optimized organization of the antenna complexes with respect to each other. Within the context of the coarse-grained model it can be calculated that the rate of primary charge separation of the RC is (5.5+/-0.4 ps)(-1), the rate of secondary charge separation is (137+/-5 ps)(-1) and the drop in free energy upon primary charge separation is 826+/-30 cm(-1). These parameters are in rather good agreement with recently published results on isolated core complexes [Y. Miloslavina, M. Szczepaniak, M.G. Muller, J. Sander, M. Nowaczyk, M. R?gner, A.R. Holzwarth, Charge separation kinetics in intact Photosystem II core particles is trap-limited. A picosecond fluorescence study, Biochemistry 45 (2006) 2436-2442].     

Trapping and annihilation in the antenna system of Photosystem I

The primary charge separation in Photosystem I of pea chloroplasts was measured as a photovoltage in the pico- and nanosecond time range by applying laser flashes at 532 nm of variable energy and different duration (12 ns and 30 ps, respectively). Contributions to the photovoltage from Photosystem II was eliminated by addition of 3-(3,4-dichlorophenyl)-1,1-dimethylurea and preillumination. The dependence of the photovoltage amplitude on the excitation energy could be described by an exponential saturation law when the excitation flash had a duration of 12 ns. Nearly the same dependence was found when the excitation source was the train of a mode-locked laser (approx. ten 30-ps flashes spaced by 7 ns; highest energy of a single flash, 80 μJ / cm⁻²). Even with single 30-ps flashes the photovoltage was only slightly smaller than the one elicited by 12-ns flashes of the same energy. These findings demonstrate that trapping of excitation energy by the reaction center of Photosystem I is much more effective than losses by annihilation and other loss processes. The photovoltage yield was nearly independent of the fraction of closed traps, thus demonstrating that the absorption cross section of Photosystem I is not altered by the closing of its reaction centers. By recording the rise time of the photovoltage with our highest time resolution we found that the trapping rate of the excitation energy in Photosystem I depended on the energy of the 30-ps flashes: at low excitation energies (less than 10¹⁴ photons / cm² per pulse) trapping occurred within 90 ± 15 ps and at high excitation energy (10¹⁵ photons / cm² per pulse) trapping and charge stabilization occurred within the time resolution of the apparatus, i.e., up to 50 ps. The trapping rate at low energies is in agreement with the one determined by fluorescence decay kinetics. Up to 50 ns there was no further detectable electrogenic phase (neither forward nor backward reactions). This demonstrates that all the electrogenicity, produced by the charge separation, takes place in less than 50 ps.     

Excitation energy transfer and charge separation in photosystem II membranes revisited

We have performed time-resolved fluorescence measurements on photosystem II (PSII) containing membranes (BBY particles) from spinach with open reaction centers. The decay kinetics can be fitted with two main decay components with an average decay time of 150 ps. Comparison with recent kinetic exciton annihilation data on the major light-harvesting complex of PSII (LHCII) suggests that excitation diffusion within the antenna contributes significantly to the overall charge separation time in PSII, which disagrees with previously proposed trap-limited models. To establish to which extent excitation diffusion contributes to the overall charge separation time, we propose a simple coarse-grained method, based on the supramolecular organization of PSII and LHCII in grana membranes, to model the energy migration and charge separation processes in PSII simultaneously in a transparent way. All simulations have in common that the charge separation is fast and nearly irreversible, corresponding to a significant drop in free energy upon primary charge separation, and that in PSII membranes energy migration imposes a larger kinetic barrier for the overall process than primary charge separation.     

Low‐Temperature Behaviour of Charge Transfer Excitons in Narrow‐Bandgap Polymer‐Based Bulk Heterojunctions

Photoluminescence studies of the charge transfer exciton emission from a narrow‐bandgap polymer‐based bulk heterojunction are reported. The quantum yield of this emission is as high as 0.03%. Low temperature measurements reveal that while the dynamics of the singlet exciton is slower at low temperature, the dynamics of the charge transfer exciton emission is temperature independent. This behavior rules out any diffusion process of the charge transfer excitons and energy transfer from these interfacial states toward lower lying states. Photoluminescence measurements performed on the device under bias show a reduction (but not the total suppression) of the charge transfer exciton recombination. Finally, based on the low temperature results the role of the charge transfer excitons and the possible pathways to populate them are identified.     

Charge separation and energy transfer in a caroteno-C60 dyad: photoinduced electron transfer from the carotenoid excited states.

We have designed and synthesized a molecular dyad comprising a carotenoid pigment linked to a fullerene derivative (C-C(60)) in which the carotenoid acts both as an antenna for the fullerene and as an electron transfer partner. Ultrafast transient absorption spectroscopy was carried out on the dyad in order to investigate energy transfer and charge separation pathways and efficiencies upon excitation of the carotenoid moiety. When the dyad is dissolved in hexane energy transfer from the carotenoid S(2) state to the fullerene takes place on an ultrafast (sub 100 fs) timescale and no intramolecular electron transfer was detected. When the dyad is dissolved in toluene, the excited carotenoid decays from its excited states both by transferring energy to the fullerene and by forming a charge-separated C.+ -C(60).- . The charge-separated state is also formed from the excited fullerene following energy transfer from the carotenoid. These pathways lead to charge separation on the subpicosecond time scale (possibly from the S(2) state and the vibrationally excited S(1) state of the carotenoid), on the ps time scale (5.5 ps) from the relaxed S(1) state of the carotenoid, and from the excited state of C(60) in 23.5 ps. The charge-separated state lives for 1.3 ns and recombines to populate both the low-lying carotenoid triplet state and the dyad ground state.     

Excitation Dynamics in Low Band Gap Donor–Acceptor Copolymers and Blends

Donor–acceptor (D–A) type copolymers show great potential for the application in the active layer of organic solar cells. Nevertheless the nature of the excited states, the coupling mechanism and the relaxation pathways following photoexcitation are yet to be clarified. We carried out comparative measurements of the steady state absorption and photoluminescence (PL) on the copolymer poly[N‐(1‐octylnonyl)‐2,7‐carbazole]‐alt‐5,5‐[4′,7′‐di(thien‐2‐yl)‐2′,1′,3′‐benzothiadiazole] (PCDTBT), its building blocks as well as on the newly synthesized N‐(1‐octylnonyl)‐2,7‐bis‐[(5‐phenyl)thien‐2‐yl)carbazole (BPT‐carbazole). The high‐energy absorption band (HEB) of PCDTBT was identified with absorption of carbazoles with adjacent thiophene rings while the low‐energy band (LEB) originates instead from the charge transfer (CT) state delocalized over the aforementioned unit with adjacent benzothiadiazole group. Photoexcitation of the HEB is followed by internal relaxation prior the radiative decay to the ground state. Adding PC₇₀BM results in the efficient PL quenching within the first 50 ps after excitation. From the PL excitation experiments no evidence for a direct electron transfer from the HEB of PCDTBT towards the fullerene acceptor was found, therefore the internal relaxation mechanisms within PCDTBT can be assumed to precede. Our findings indicate that effective coupling between copolymer building blocks governs the photovoltaic performance of the blends.     

PSI-SMALP,a Detergent-free Cyanobacterial Photosystem I,Reveals Faster Femtosecond Photochemistry

Cyanobacterial photosystem I (PSI) functions as a light-driven cyt c₆-ferredoxin/oxidoreductase located in the thylakoid membrane. In this work, the energy and charge transfer processes in PSI complexes isolated from Thermosynechococcus elongatus via conventional n-dodecyl-β-D-maltoside solubilization (DM-PSI) and a, to our knowledge, new detergent-free method using styrene-maleic acid copolymers (SMA-PSI) have been investigated by pump-to-probe femtosecond laser spectroscopy. In DM-PSI preparations excited at 740 nm, the excitation remained localized on the long-wavelength chlorophyll forms within 0.1–20 ps and revealed little or no charge separation and oxidation of the special pair, P700. The formation of ion-radical pair P700⁺A1⁻ occurred with a characteristic time of 36 ps, being kinetically controlled by energy transfer from the long-wavelength chlorophyll to P₇₀₀. Quite surprisingly, the detergent-free SMA-PSI complexes upon excitation by these long-wave pulses undergo an ultrafast (<100 fs) charge separation in ∼45% of particles. In the remaining complexes (∼55%), the energy transfer to P₇₀₀ occurred at ∼36 ps, similar to the DM-PSI. Both isolation methods result in a trimeric form of PSI, yet the SMA-PSI complexes display a heterogenous kinetic behavior. The much faster rate of charge separation suggests the existence of an ultrafast pathway for charge separation in the SMA-PSI that may be disrupted during detergent isolation.     

Local Intermolecular Order Controls Photoinduced Charge Separation at Donor/Acceptor Interfaces in Organic Semiconductors

How free charge is generated at organic donor–acceptor interfaces is an important question, as the binding energy of the lowest energy (localized) charge transfer states should be too high for the electron and hole to escape each other. Recently, it has been proposed that delocalization of the electronic states participating in charge transfer is crucial, and aggregated or otherwise locally ordered structures of the donor or the acceptor are the precondition for this electronic characteristic. The effect of intermolecular aggregation of both the polymer donor and fullerene acceptor on charge separation is studied. In the first case, the dilute electron acceptor triethylsilylhydroxy‐1,4,8,11,15,18,22,25‐octabutoxyphthalocyaninatosilicon(IV) (SiPc) is used to eliminate the influence of acceptor aggregation, and control polymer order through side‐chain regioregularity, comparing charge generation in 96% regioregular (RR‐) poly(3‐hexylthiophene) (P3HT) with its regiorandom (RRa‐) counterpart. In the second case, ordered phases in the polymer are eliminated by using RRa‐P3HT, and phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) is used as the acceptor, varying its concentration to control aggregation. Time‐resolved microwave conductivity, time‐resolved photoluminescence, and transient absorption spectroscopy measurements show that while ultrafast charge transfer occurs in all samples, long‐lived charge carriers are only produced in films with intermolecular aggregates of either RR‐P3HT or PC₆₁BM, and that polymer aggregates are just as effective in this regard as those of fullerenes.