A Conclusive View on Charge Generation,Recombination, and Extraction in As‐Prepared and Annealed P3HT:PCBM Blends: Combined Experimental and Simulation Work

Time‐delayed collection field (TDCF) and bias‐amplified charge extraction (BACE) are applied to as‐prepared and annealed poly(3‐hexylthiophene):[6,6]‐phenyl C₇₁ butyric acid methyl ester (P3HT:PCBM) blends coated from chloroform. Despite large differences in fill factor, short‐circuit current, and power conversion efficiency, both blends exhibit a negligible dependence of photogeneration on the electric field and strictly bimolecular recombination (BMR) with a weak dependence of the BMR coefficient on charge density. Drift‐diffusion simulations are performed using the measured coefficients and mobilities, taking into account bimolecular recombination and the possible effects of surface recombination. The excellent agreement between the simulation and the experimental data for an intensity range covering two orders of magnitude indicates that a field‐independent generation rate and a density‐independent recombination coefficient describe the current–voltage characteristics of the annealed P3HT:PCBM devices, while the performance of the as‐prepared blend is shown to be limited by space charge effects due to a low hole mobility. Finally, even though the bimolecular recombination coefficient is small, surface recombination is found to be a negligible loss mechanism in these solar cells.     

Identifying the Nature of Charge Recombination in Organic Solar Cells from Charge‐Transfer State Electroluminescence

Charge‐transfer (CT) state electroluminescence is investigated in several polymer:fullerene bulk heterojunction solar cells. The ideality factor of the electroluminescence reveals that the CT emission in polymer:fullerene solar cells originates from free‐carrier bimolecular recombination at the donor‐acceptor interface, rather than a charge‐trap‐mediated process. The fingerprint of the presence of nonradiative trap‐assisted recombination, a voltage‐dependent CT electroluminescence quantum efficiency, is only observed for the P3HT:PCBM system, which is explained by a reduction of the competing bimolecular recombination rate. These results are in agreement with measurements of the illumination‐intensity dependence of the open‐circuit voltage.     

Intra‐Molecular Donor–Acceptor Interaction Effects on Charge Dissociation,Charge Transport,and Charge Collection in Bulk‐Heterojunction Organic Solar Cells

This article reports experimental studies on internal charge dissociation, transport, and collection by using magnetic field effects of photocurrent (MFE_PC) and light‐assisted dielectric response (LADR) in highly‐efficient organic solar cells based on photovoltaic polymer PTB2 and PTB4 with intra‐molecular “donor–acceptor” interaction. The MFE_PC at low‐field (< 150 mT) indicates that intra‐molecular “donor‐acceptor” interaction generates charge dissociation in un‐doped PTB2 and PTB4 films, which is similar to that in lightly doped P3HT (Poly(3‐hexylthiophene)) with 5 wt% PCBM (1‐(3‐methyloxycarbonyl)‐propyl‐1‐phenyl (6,6) C₆₁). After PTB2 and PTB4 are mixed with PCBM to form bulk‐heterojunctions, the MFE_PC at high‐field (> 150 mT) reveals that the charge‐transfer complexes formed at PTB2:PCBM and PTB4:PCBM interfaces have much lower binding energies due to stronger electron‐withdrawing abilities, as compared to the P3HT:PCBM device, towards the generation of photocurrent. Furthermore, the light‐assisted dielectric response: LADR indicates that the PTB2:PCBM and PTB4:PCBM solar cells exhibit larger capacitances relative to P3HT:PCBM device under photoexcitation. This reflects that the PTB2:PCBM and PTB4:PCBM bulk heterojunctions have more effective charge transport and collection than the P3HT:PCBM counterpart. As a result, our experimental results indicate that intra‐molecular “donor‐acceptor” interaction plays an important role to enhance charge dissociation, transport, and collection in bulk‐heterojunction organic solar cells.     

Polymer:Nonfullerene Bulk Heterojunction Solar Cells with Exceptionally Low Recombination Rates

Organic semiconductors are in general known to have an inherently lower charge carrier mobility compared to their inorganic counterparts. Bimolecular recombination of holes and electrons is an important loss mechanism and can often be described by the Langevin recombination model. Here, the device physics of bulk heterojunction solar cells based on a nonfullerene acceptor (IDTBR) in combination with poly(3‐hexylthiophene) (P3HT) are elucidated, showing an unprecedentedly low bimolecular recombination rate. The high fill factor observed (above 65%) is attributed to non‐Langevin behavior with a Langevin prefactor (β/β_L) of 1.9 × 10^?4. The absence of parasitic recombination and high charge carrier lifetimes in P3HT:IDTBR solar cells inform an almost ideal bimolecular recombination behavior. This exceptional recombination behavior is explored to fabricate devices with layer thicknesses up to 450 nm without significant performance losses. The determination of the photoexcited carrier mobility by time‐of‐flight measurements reveals a long‐lived and nonthermalized carrier transport as the origin for the exceptional transport physics. The crystalline microstructure arrangement of both components is suggested to be decisive for this slow recombination dynamics. Further, the thickness‐independent power conversion efficiency is of utmost technological relevance for upscaling production and reiterates the importance of understanding material design in the context of low bimolecular recombination.     

A Shockley‐Type Polymer: Fullerene Solar Cell

Charge extraction rate in solar cells made of blends of electron donating/accepting organic semiconductors is typically slow due to their low charge carrier mobility. This sets a limit on the active layer thickness and has hindered the industrialization of organic solar cells (OSCs). Herein, charge transport and recombination properties of an efficient polymer (NT812):fullerene blend are investigated. This system delivers power conversion efficiency of >9% even when the junction thickness is as large as 800 nm. Experimental results indicate that this material system exhibits exceptionally low bimolecular recombination constant, 800 times smaller than the diffusion‐controlled electron and hole encounter rate. Comparing theoretical results based on a recently introduced modified Shockley model for fill factor, and experiments, clarifies that charge collection is nearly ideal in these solar cells even when the thickness is several hundreds of nanometer. This is the first realization of high‐efficiency Shockley‐type organic solar cells with junction thicknesses suitable for scaling up.     

Relation of Nanostructure and Recombination Dynamics in a Low‐Temperature Solution‐Processed CuInS2 Nanocrystalline Solar Cell

The understanding and control of nanostructures with regard to transport and recombination mechanisms is of key importance in the optimization of the power conversion efficiency (PCE) of solar cells based on inorganic nanocrystals. Here, the transport properties of solution‐processed solar cells are investigated using photo‐CELIV (photogenerated charge carrier extraction by linearly increasing voltage) and transient photovoltage techniques; the solar cells are prepared by an in‐situ formation of CuInS₂ nanocrystals (CIS NCs) at the low temperature of 270 °C. Structural and morphological analyses reveal the presence of a metastable CuIn₅S₈ phase and a disordered morphology in the CuInS₂ nanocrytalline films consisting of polycrystalline grains at the nanoscale range. Consistent with the disordered morphology of the CIS NC thin films, the CIS NC devices are characterized by a low carrier mobility. The carrier density dynamic indicates that the recombination kinetics in these devices follows the dispersive bimolecular recombination model and does not fully behave in a diffusion‐controlled manner, as expected by Langevin‐type recombination. The mobility–lifetime product of the charge carriers properly explains the performance of the thin (200 nm) CIS NC solar cell with a high fill‐factor of 64% and a PCE of over 3.5%.     

Trade‐Off between Trap Filling,Trap Creation,and Charge Recombination Results in Performance Increase at Ultralow Doping Levels in Bulk Heterojunction Solar Cells

Doping of organic bulk heterojunction solar cells has the potential to improve their power conversion efficiency (PCE). Deconvoluting the effect of doping on charge transport, recombination, and energetic disorder remains challenging. It is demonstrated that molecular doping has two competing effects: on one hand, dopant ions create additional traps while on the other hand free dopant‐induced charges fill deep states possibly leading to V _OC and mobility increases. It is shown that molar dopant concentrations as low as a few parts per million can improve the PCE of organic bulk heterojunctions. Higher concentrations degrade the performance of the cells. In doped cells where PCE is observed to increase, such improvement cannot be attributed to better charge transport. Instead, the V _OC increase in unannealed P3HT:PCBM cells upon doping is indeed due to trap filling, while for annealed P3HT:PCBM cells the change in V _OC is related to morphology changes and dopant segregation. In PCDTBT:PC70BM cells, the enhanced PCE upon doping is explained by changes in the thickness of the active layer. This study highlights the complexity of bulk doping in organic solar cells due to the generally low doping efficiency and the constraint on doping concentrations to avoid carrier recombination and adverse morphology changes.     

Electrochemical Design of Nanostructured ZnO Charge Carrier Layers for Efficient Solid‐State Perovskite‐Sensitized Solar Cells

The preparation of ZnO structured films designed to act as electron transport layers in efficient ZnO/perovskite CH₃NH₃PbI₃/spirobifluorene (spiro‐OMeTAD) solid‐state solar cells by electrochemical deposition is reported. Well‐conducting ZnO layers are deposited in chloride medium and grown with tailored (nano)structures ranging from arrays of nanowires to a compact, well‐covering film. Moreover, the effect of a thin intermediate overlayer of ZnO conformally electrodeposited in nitrate medium and with a low n‐type doping (i‐ZnO) is discussed. The results show higher power conversion efficiencies for the nanostructured oxide layers compared to the dense one. Moreover, the presence of the i‐ZnO layer is shown to markedly improve the cell short‐circuit current and the open‐circuit voltage due to charge recombination reduction. For the best cells, the active layers efficiently absorb light over a large spectral range from near‐UV to near infrared region and exhibit excellent charge collection efficiencies. Solar cells based on an optimized design generate a very large photocurrent and the power conversion efficiency at one sun is as high as 10.28%.     

Tail State‐Assisted Charge Injection and Recombination at the Electron‐Collecting Interface of P3HT:PCBM Bulk‐Heterojunction Polymer Solar Cells

The systematic insertion of thin films of P3HT and PCBM at the electron‐ and hole‐collecting interfaces, respectively, in bulk‐heterojunction polymer solar cells results in different extents of reduction in device characteristics, with the insertion of P3HT at the electron‐collecting interface being less disruptive to the output currents compared to the insertion of PCBM at the hole‐collecting interface. This asymmetry is attributed to differences in the tail state‐assisted charge injection and recombination at the active layer‐electrode interfaces. P3HT exhibits a higher density of tail states compared to PCBM; holes in these tail states can thus easily recombine with electrons at the electron‐collection interface during device operation. This process is subsequently compensated by the injection of holes from the cathode into these tail states, which collectively enables net current flow through the polymer solar cell. The study presented herein thus provides a plausible explanation for why preferential segregation of P3HT to the cathode interface is inconsequential to device characteristics in P3HT:PCBM bulk‐heterojunction solar cells.     

Morphology‐Limited Free Carrier Generation in Donor/Acceptor Polymer Blend Solar Cells Composed of Poly(3‐hexylthiophene) and Fluorene‐Based Copolymer

The charge generation and recombination dynamics in polymer/polymer blend solar cells composed of poly(3‐hexylthiophene) (P3HT, electron donor) and poly[2,7‐(9,9‐didodecylfluorene)‐alt‐5,5‐(4′,7′‐bis(2‐thienyl)‐2′,1′,3′‐benzothiadiazole)] (PF12TBT, electron acceptor) are studied by transient absorption measurements. In the unannealed blend film, charge carriers are efficiently generated from polymer excitons, but some of them recombine geminately. In the blend film annealed at 160 °C, on the other hand, the geminate recombination loss is suppressed and hence free carrier generation efficiency increases up to 74%. These findings suggest that P3HT and PF12TBT are intermixed within a few nanometers, resulting in impure PF12TBT and disordered P3HT domains. The geminate recombination is likely due to charge carriers generated on isolated polymer chains in the matrix of the other polymer and at the domain interface with disordered P3HT. The undesired charge loss by geminate recombination is reduced by both the purification of the PF12TBT‐rich domain and crystallization of the P3HT chains. These results show that efficient free carrier generation is not inherent to the polymer/fullerene domain interface, but is possible with polymer/polymer systems composed of crystalline donor and amorphous acceptor polymers, opening up a new potential method for the improvement of solar cell materials.     

Balanced Carrier Mobilities: Not a Necessary Condition for High‐Efficiency Thin Organic Solar Cells as Determined by MIS‐CELIV

A novel technique based upon injection‐charge extraction by linearly increasing voltage (i‐CELIV) in a metal‐insulator‐semiconductor (MIS) diode structure is described for studying charge transport in organic semiconductors. The technique (MIS‐CELIV) allows selective measurement of both electron and hole mobilities of organic solar cells with active layers thicknesses representative of operational devices. The method is used to study the model high efficiency bulk heterojunction combination poly[N‐9′′‐heptadecanyl‐2,7‐carbazole‐alt‐5,5‐(4′,7′‐di‐2‐thienyl‐2′,1′,3′‐benzothiadiazole)] (PCDTBT) and [6,6]‐phenyl C70‐butyric acid methyl ester (PC70BM) at various blend ratios. The absence of bipolar transport in PCDTBT‐and‐PC70BM‐only diodes is shown and strongly imbalanced carrier mobility is found in the most efficient “optimized” blend ratios. The mobility measurements are correlated with overall device performance and it is found that balanced and high charge carrier mobility are not necessarily required for high efficiencies in thin film organic solar cells.     

Effects of Solvent Additives on Morphology,Charge Generation,Transport, and Recombination in Solution‐Processed Small‐Molecule Solar Cells

The effects of solvent additive (1,8‐diiodooctane (DIO)) on the morphology, charge generation, transport, and recombination in solution‐processed small‐molecule solar cells are studied and these parameters are correlated with device performance. In the optimum nanoscale morphology, which is processed with 0.4% DIO, the phase separation is large enough to create a percolating pathway for carrier transport, yet still small enough to form large interfacial area for efficient charge separation. Complete phase separation in this film reduces the interfacial defects, which occurs without DIO, and hence suppresses the monomolecular recombination. Moreover, balanced charge transport and weak bimolecular recombination lead to a high fill factor (72%). On the other hand, an excess amount of DIO (0.8%) in the solvent results in the over‐aggregation of the donor phase, which disturbs the percolating pathway of the acceptor phase and reduces the electron mobility. The over‐aggregation of the donor phase also shrinks the interfacial area for charge separation and consequently reduces the photocurrent generation.     

Electric Field and Mobility Dependent First‐Order Recombination Losses in Organic Solar Cells

The origin of photocurrent losses in the power‐generating regime of organic solar cells (OSCs) remains a controversial topic, although recent literature suggests that the competition between bimolecular recombination and charge extraction determines the bias dependence of the photocurrent. Here the steady‐state recombination dynamics is studied in bulk‐heterojunction OSCs with different hole mobilities from short‐circuit to maximum power point. It is shown that in this regime, in contrast to previous transient extracted charge and absorption spectroscopy studies, first‐order recombination outweighs bimolecular recombination of photogenerated charge carriers. This study demonstrates that the first‐order losses increase with decreasing slower carrier mobility, and attributes them to either mobilization of charges trapped at the donor:acceptor interface through the Poole–Frenkel effect, and/or recombination of photogenerated and injected charges. The dependence of both first‐order and higher‐order losses on the slower carrier mobility explains why the field dependence of OSC efficiencies has historically been attributed to charge‐extraction losses.     

Donor‐Acceptor Interfacial Interactions Dominate Device Performance in Hybrid P3HT‐ZnO Nanowire‐Array Solar Cells

The adsorption of self‐assembled monolayers (SAMs) on metal oxide surfaces is a promising route to control electronic characteristics and surface wettability. Here, arylphosphonic acid derivatives are used to modulate the surface properties of vertically oriented ZnO nanowire arrays. Arylphosphonate‐functionalized ZnO nanowires are incorporated into hybrid organic‐inorganic solar cells in which infiltrated poly(3‐hexylthiophene) (P3HT) serves as the polymer donor. Strong correlations between device short‐circuit current density (J _sc) and power conversion efficiencies (PCEs) with ZnO surface functionalization species are observed and a weak correlation in the open‐circuit voltage (V _oc) is observed. Inverted solar cells fabricated with these treated interfaces exhibit PCEs as high as 2.1%, primarily due to improvements in J _sc. Analogous devices using untreated ZnO arrays having efficiencies of 1.6%. The enhancement in J _sc is attributed to surface passivation of ZnO by SAMs and enhanced wettability from P3HT, which improve charge transfer and reduce carrier recombination at the organic‐inorganic interface in the solar cells.     

Photo‐Carrier Recombination in Polymer Solar Cells Based on P3HT and Silole‐Based Copolymer

Photo‐current loss in donor‐acceptor (DA) polymer‐fullerene bulk heterojunction solar cells was studied via carrier transport and recombination measurements. Focusing on the DA polymer poly((4,4‐dioctyldithieno (3,2‐b:2',3'‐d) silole)‐2,6‐diyl‐alt‐(2,1,3‐benzothiadiazole)‐4,7‐diyl) (DTS‐BTD) we found that the carrier transport is well‐balanced and attribute the loss mechanism in DTS‐BTD solar cells to carrier recombination. Using carrier extraction with linear increasing voltage (photo‐CELIV) and transient photo‐voltage (TPV), we show that carrier recombination plays an important role in photo‐current extraction at open circuit conditions due to increase in photo‐excited carrier concentration. Delay time dependent photo‐CELIV and temperature dependent transport studies suggest that the recombination rate is related to the degree of energetic disorder in the polymer: fullerene blends.     

Inverted Current–Voltage Hysteresis in Mixed Perovskite Solar Cells: Polarization,Energy Barriers,and Defect Recombination

Organic‐inorganic metal halide perovskite solar cells show hysteresis in their current–voltage curve measured at a certain voltage sweep rate. Coinciding with a slow transient current response, the hysteresis is attributed to a slow voltage‐driven (ionic) charge redistribution in the perovskite solar cell. Thus, the electric field profile and in turn the electron/hole collection efficiency become dependent on the biasing history. Commonly, a positive prebias is beneficial for a high power‐conversion efficiency. Fill factor and open‐circuit voltage increase because the prebias removes the driving force for charge to pile‐up at the electrodes, which screen the electric field. Here, it is shown that the piled‐up charge can also be beneficial. It increases the probability for electron extraction in case of extraction barriers due to an enhanced electric field allowing for tunneling or dipole formation at the perovskite/electrode interface. In that case, an inverted hysteresis is observed, resulting in higher performance metrics for a voltage sweep starting at low prebias. This inverted hysteresis is particularly pronounced in mixed‐cation mixed‐halide systems which comprise a new generation of perovskite solar cells that makes it possible to reach power‐conversion efficiencies beyond 20%.     

Charge Transport and Recombination in Low‐Bandgap Bulk Heterojunction Solar Cell using Bis‐adduct Fullerene

Charge transport and recombination are studied for organic solar cells fabricated using blends of polymer poly[(4,4′‐bis(2‐ethylhexyl)dithieno[3,2‐b:2′,3′‐d]silole)‐2,6‐diyl‐alt‐(4,7‐bis(2‐thienyl)‐2,1,3‐benzothiadiazole)‐5,5′‐diyl] (Si‐PCPDTBT) with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (mono‐PCBM) and the bis‐adduct analogue of mono‐PCBM (bis‐PCBM). The photocurrent of Si‐PCPDTBT:bis‐PCBM devices shows a strong square root dependence on the effective applied voltage. From the relationship between the photocurrent and the light intensity, we found that the square‐root dependence of the photocurrent is governed by the mobility‐lifetime (μτ) product of charge carriers while space‐charge field effects are insignificant. The fill factor (FF) and short circuit current density (J_sc) of bis‐PCBM solar cells show a considerable increase with temperature as compared to mono‐PCBM solar cells. SCLC analysis of single carrier devices proofs that the mobility of both electrons and holes is significantly lowered when replacing mono‐PCBM with bis‐PCBM. The increased recombination in Si‐PCPDTBT:bis‐PCBM solar cells is therefore attributed to the low carrier mobilities, as the transient photovoltage measurements show that the carrier lifetime of devices are not significantly altered by using bis‐PCBM instead of mono‐PCBM.     

Effect of Photogenerated Dipoles in the Hole Transport Layer on Photovoltaic Performance of Organic–Inorganic Perovskite Solar Cells

Judicious choice of transport layer in organic–inorganic halide perovskite solar cells can be one of the essential parameters in photovoltaic design and fabrication techniques. This article reports the effect of optically generated dipoles in transport layer on the photovoltaic actions in active layer in perovskite solar cells with the architecture of indium tin oxide (ITO)/TiO _x /CH₃NH₃PbI_3–x Cl _x /hole transport layer (HTL)/Au. Here, PTB7‐thieno[3,4‐b]thiophene‐alt‐benzodithiophene and P3HT‐poly(3‐hexylthiophene) are separately used as the HTL with significant and negligible photoinduced dipoles, respectively. Electric field‐induced photoluminescence quenching provides the first‐hand evidence to indicate that the photoinduced dipoles are partially aligned in the amorphous PTB7 layer under the influence of device built‐in field. By monitoring the recombination process through magneto‐photocurrent measurements under device operation condition, it is shown that the photoinduced dipoles in PTB7 layer can decrease the recombination of photogenerated carriers in the active layer in perovskite solar cells. Furthermore, the capacitance measurements suggest that the photoinduced dipoles in PTB7 can decrease charge accumulation at the electrode interface. Therefore, the studies indicate the important role of photoinduced dipoles in the HTL on charge recombination dynamics and provide a fundamental insight on how the polarization in transport layer can influence the device performance in perovskite solar cells.     

Enhanced Efficiency and Stability of Perovskite Solar Cells Through Nd‐Doping of Mesostructured TiO2

Block‐copolymer templated chemical solution deposition is used to prepare mesoporous Nd‐doped TiO₂ electrodes for perovskite‐based solar cells. X‐ray diffraction and photothermal deflection spectroscopy show substitutional incorporation into the TiO₂ crystal lattice for low Nd concentration, and increasing interstitial doping for higher concentrations. Substitutional Nd‐doping leads to an increase in stability and performance of perovskite solar cells by eliminating defects and thus increasing electron transport and reducing charge recombination in the mesoporous TiO₂. The optimized doping concentration of 0.3% Nd enables the preparation of perovskite solar cells with stabilized power conversion efficiency of >18%.     

A Thieno[3,2‐c]Isoquinolin‐5(4H)‐One Building Block for Efficient Thick‐Film Solar Cells

An aromatic lactam acceptor unit, thieno[3,2‐c]isoquinolin‐5(4H)‐one (TIQ), is developed. Compared with its analogues, dithieno[3,2‐b:2′,3′‐d]pyridin‐5(4H)‐one (DTP) and phenanthridin‐6(5H)‐one (PN), TIQ shows its advantage in constructing donor–acceptor (D–A) copolymers for efficient solar cells. TIQ‐based D–A copolymer PTIQ4TFBT delivers a power conversion efficiency (PCE) of 10.16% in polymer:fullerene solar cells, while those based on DTP and PN copolymers, PDTP4TFBT and PPN4TFBT, afford PCEs around 8.5%. The higher performance of PTIQ4TFBT:PC₇₁BM solar cells originates from enhanced short‐circuit current density (J_sc) and fill factor (FF), because of favorable morphology, less bimolecular recombination, and balanced charge transport in the active layer. Moreover, the performance for PTIQ4TFBT:PC₇₁BM solar cells is less sensitive to active layer thickness than PDTP4TFBT:PC₇₁BM and PPN4TFBT:PC₇₁BM solar cells. Over 8% PCEs can be obtained from PTIQ4TFBT:PC₇₁BM solar cells when the active layer thickness is over 500 nm.