Selective Dye Loading at the Heterojunction in Polymer/Fullerene Solar Cells

Selective dye loading at the polymer/fullerene interface was studied for ternary blend bulk heterojunction solar cells, consisting of regioregular poly(3‐hexylthiophene) (RR‐P3HT), a fullerene derivative (PCBM), and a silicon phthalocyanine derivative (SiPc) as a light‐harvesting dye. The photocurrent density and power conversion efficiency of the ternary blend solar cells were most improved by loading SiPc with a content of 4.8 wt%. The absorption and surface energy measurements suggested that SiPc is located in the disordered P3HT domains at the RR‐P3HT/PCBM interface rather than in the PCBM and crystal P3HT domains. From the peak wavelength of SiPc absorption, the local concentration of SiPc ([SiPc]_Local) was estimated for the RR‐P3HT:PCBM:SiPc ternary blends. Even for amorphous films of regiorandom P3HT (RRa‐P3HT) blended with PCBM and SiPc, [SiPc]_Local was higher than the original content, suggesting dye segregation into the RRa‐P3HT/PCBM interface. For RR‐P3HT:PCBM:SiPc blends, [SiPc]_Local increased with the increase in the P3HT crystallinity. Such interfacial segregation of dye molecules in ternary blend films can be rationally explained in terms of the surface energy of each component and the crystallization of P3HT being enhanced by annealing. Notably, the solvent annealing effectively segregated dye molecules into the interface without the formation of PCBM clusters.     

Impact of Fullerene on the Photophysics of Ternary Small Molecule Organic Solar Cells

Ternary organic solar cells (OSCs) are among the best‐performing organic photovoltaic devices to date, largely due to the recent development of nonfullerene acceptors. However, fullerene molecules still play an important role in ternary OSC systems, since, for reasons not well understood, they often improve the device performance, despite their lack of absorption. Here, the photophysics of a prototypical ternary small‐molecule OSC blend composed of the donor DR3, the nonfullerene acceptor ICC6, and the fullerene derivative PC₇₁BM is studied by ultrafast spectroscopy. Surprisingly, it is found that after excitation of PC₇₁BM, ultrafast singlet energy transfer to ICC6 competes efficiently with charge transfer. Subsequently, singlets on ICC6 undergo hole transfer to DR3, resulting in free charge generation. Interestingly, PC₇₁BM improves indirectly the electron mobility of the ternary blend, while electrons reside predominantly in ICC6 domains as indicated by fast spectroscopy. The improved mobility facilitates charge carrier extraction, in turn leading to higher device efficiencies of the ternary compared to binary solar cells. Using the (photo)physical parameters obtained from (transient) spectroscopy and charge transport measurements, the device's current–voltage characteristics are simulated and it is demonstrated that the parameters accurately reproduce the experimentally measured device performance.     

Polymer Blend Solar Cells Based on a High‐Mobility Naphthalenediimide‐Based Polymer Acceptor: Device Physics,Photophysics and Morphology

A high electron mobility polymer, poly{[N,N’‐bis(2‐octyldodecyl)‐naphthalene‐1,4,5,8‐bis(dicarboximide)‐2,6‐diyl]‐alt‐5,5’‐(2,2’‐bithiophene) (P(NDI2OD‐T2)) is investigated for use as an electron acceptor in all‐polymer blends. Despite the high bulk electron mobility, near‐infrared absorption band and compatible energy levels, bulk heterojunction devices fabricated with poly(3‐hexylthiophene) (P3HT) as the electron donor exhibit power conversion efficiencies of only 0.2%. In order to understand this disappointing photovoltaic performance, systematic investigations of the photophysics, device physics and morphology of this system are performed. Ultra‐fast transient absorption spectroscopy reveals a two‐stage decay process with an initial rapid loss of photoinduced polarons, followed by a second slower decay. This second slower decay is similar to what is observed for efficient P3HT:PCBM ([6,6]‐phenyl C₆₁‐butyric acid methyl ester) blends, however the initial fast decay that is absent in P3HT:PCBM blends suggests rapid, geminate recombination of charge pairs shortly after charge transfer. X‐ray microscopy reveals coarse phase separation of P3HT:P(NDI2OD‐T2) blends with domains of size 0.2 to 1 micrometer. P3HT photoluminescence, however, is still found to be efficiently quenched indicating intermixing within these mesoscale domains. This hierarchy of phase separation is consistent with the transient absorption, whereby localized confinement of charges on isolated chains in the matrix of the other polymer hinders the separation of interfacial electron‐hole pairs. These results indicate that local, interfacial processes are the key factor determining the overall efficiency of this system and highlight the need for improved morphological control in order for the potential benefit of high‐mobility electron accepting polymers to be realized.     

Carbon Dangling Bonds in Photodegraded Polymer:Fullerene Solar Cells

Intrinsic photodegradation of organic solar cells, theoretically attributed to C? H bond rearrangement/breaking, remains a key commercialization barrier. This work presents, via dark electron paramagnetic resonance (EPR), the first experimental evidence for metastable C dangling bonds (DBs) formed by blue/UV irradiation of polymer:fullerene blend films in nitrogen. The DB density increases with irradiation and decreases ≈4‐fold after 2 weeks in the dark. The dark EPR also shows increased densities of other spin‐active sites in photodegraded polymer, fullerene, and polymer:fullerene blend films, consistent with broad electronic measurements of fundamental properties, including defect/gap state densities. The EPR and electronic measurements enable identification of defect states, whether in the polymer, fullerene, or at the donor/acceptor (D/A) interface. Importantly, the EPR results indicate that the DBs are at the D/A interface, as they were present only in the blend films. The role of polarons in interface DB formation is also discussed.     

The Impact of Device Polarity on the Performance of Polymer–Fullerene Solar Cells

Diketopyrrolopyrrole (DPP)‐conjugated polymers are a versatile class of semiconductors for application in organic solar cells because of their tunable optoelectronic properties. A record power conversion efficiency (PCE) of 9.4% was recently achieved for DPP polymers, but further improvements are required to reach true efficiency limits. Using five DPP polymers with different chemical structures and molecular weights, the device performance of polymer:fullerene solar cells is systematically optimized by considering device polarity, morphology, and light absorption. The polymer solubility is found to have a significant effect on the optimal device polarity. Soluble polymers show a 10–25% increase in PCE in inverted device configurations, while the device performance is independent of device polarity for less soluble DPP derivatives. The difference seems related to the polymer to fullerene weight ratio at the ZnO interface in inverted devices, which is higher for more soluble DPP polymers. Optimization of the nature of the cosolvent to narrow the fibril width of polymers in the blends toward the exciton diffusion length enhances charge generation. Additionally, the use of a retroreflective foil increases absorption of light. Combined, the effects afford a PCE of 9.6%, among the highest for DPP‐based polymer solar cells.     

Improved Performance of Ternary Polymer Solar Cells Based on A Nonfullerene Electron Cascade Acceptor

Efficient ternary polymer solar cells are constructed by incorporating an electron‐deficient chromophore (5Z,5′Z)‐5,5′‐((7,7′‐(4,4,9,9‐tetrakis(4‐hexylphenyl)‐4,9‐dihydro‐s‐indaceno[1,2‐b:5,6‐b′]dithiophene‐2,7‐diyl)bis(6‐fluorobenzo[c][1,2,5]thiadiazole‐7,4‐diyl))bis(methanylylidene))bis(3‐ethyl‐2‐thioxothiazolidin‐4‐one) (IFBR) as an additional component into the bulk‐heterojunction film that consists of a wide‐bandgap conjugated benzodithiophene‐alt‐difluorobenzo[1,2,3]triazole based copolymer and a fullerene acceptor. With respect to the binary blend films, the incorporation of a certain amount of IFBR leads to simultaneously enhanced absorption coefficient, obviously extended absorption band, and improved open‐circuit voltage. Of particular interest is that devices based on ternary blend film exhibit much higher short‐circuit current densities than the binary counterparts, which can be attributed to the extended absorption profiles, enhanced absorption coefficient, favorable film morphology, as well as formation of cascade energy level alignment that is favorable for charge transfer. Further investigation indicates that the ternary blend device exhibits much shorter charge carrier extraction time, obviously reduced trap density and suppressed trap‐assisted recombination, which is favorable for achieving high short‐circuit current. The combination of these beneficial aspects leads to a significantly improved power conversion efficiency of 8.11% for the ternary device, which is much higher than those obtained from the binary counterparts. These findings demonstrate that IFBR can be a promising electron‐accepting material for the construction of ternary blend films toward high‐performance polymer solar cells.     

Mapping Nonfullerene Acceptors with a Novel Wide Bandgap Polymer for High Performance Polymer Solar Cells

A new weak electron‐deficient building block, bis(2‐ethylhexyl) 2,5‐bis(5‐bromothiophen‐2‐yl) thieno[3,2‐b]thiophene‐3,6‐dicarboxylate ( TT‐Th ), is incorporated to construct a wide‐bandgap (1.88 eV) polymer PBDT‐TT for nonfullerene polymer solar cells (NF‐PSCs). PBDT‐TT possesses suitable energy levels and complementary absorption when blended with both ITIC analogues ( ITIC and IT‐M ) and a near‐infrared (NIR) acceptor ( 6TIC ). Moreover, PBDT‐TT exhibits good conjugated planarity and preferable face‐on orientation in the blended thin film, which are beneficial for charge transfer and carrier transport. The PSCs based on PBDT‐TT : IT‐M and PBDT‐TT : 6TIC blend films yield high power conversion efficiencies of 11.38% and 11.03%, respectively. To the best of the authors' knowledge, the PCE of 11.03% for PBDT‐TT : 6TIC‐ based device is one of the highest values reported for NIR NF‐PSCs. This work demonstrates that TT‐Th is a useful new electron‐accepting building block for making p‐type wide bandgap polymers for efficient NIR NF‐PSCs.     

Efficient Ternary Polymer Solar Cells with Two Well‐Compatible Donors and One Ultranarrow Bandgap Nonfullerene Acceptor

Nonfullerene polymer solar cells (PSCs) are fabricated by using one wide bandgap donor PBDB‐T and one ultranarrow bandgap acceptor IEICO‐4F as the active layers. One medium bandgap donor PTB7‐Th is selected as the third component due to the similar highest occupied molecular orbital level compared to that of PBDB‐T and their complementary absorption spectra. The champion power conversion efficiency (PCE) of PSCs is increased from 10.25% to 11.62% via incorporating 20 wt% PTB7‐Th in donors, with enhanced short‐circuit current (J_SC) of 24.14 mA cm^?2 and fill factor (FF) of 65.03%. The 11.62% PCE should be the highest value for ternary nonfullerene PSCs. The main contribution of PTB7‐Th can be summarized as the improved photon harvesting and enhanced exciton utilization of PBDB‐T due to the efficient energy transfer from PBDB‐T to PTB7‐Th. Meanwhile, PTB7‐Th can also act as a regulator to adjust PBDB‐T molecular arrangement for optimizing charge transport, resulting in the enhanced FF of ternary PSCs. This experimental result may provide new insight for developing high‐performance ternary nonfullerene PSCs by selecting two well‐compatible donors with different bandgap and one ultranarrow bandgap acceptor.     

Alkyl Chain Length Effects of Polymer Donors on the Morphology and Device Performance of Polymer Solar Cells with Different Acceptors

The development of nonfullerene acceptors has brought polymer solar cells into a new era. Maximizing the performance of nonfullerene solar cells needs appropriate polymer donors that match with the acceptors in both electrical and morphological properties. So far, the design rationales for polymer donors are mainly borrowed from fullerene‐based solar cells, which are not necessarily applicable to nonfullerene solar cells. In this work, the influence of side chain length of polymer donors based on a set of random terpolymers PTAZ‐TPD10‐Cn on the device performance of polymer solar cells is investigated with three different acceptor materials, i.e., a fullerene acceptor [70]PCBM, a polymer acceptor N2200, and a fused‐ring molecular acceptor ITIC. Shortening the side chains of polymer donors improves the device performance of [70]PCBM‐based devices, but deteriorates the N2200‐ and ITIC‐based devices. Morphology studies unveil that the miscibility between donor and acceptor in blend films depends on the side chain length of polymer donors. Upon shortening the side chains of the polymer donors, the miscibility between the donor and acceptor increases for the [70]PCBM‐based blends, but decreases for the N2200‐ and ITIC‐based blends. These findings provide new guidelines for the development of polymer donors to match with emerging nonfullerene acceptors.     

Improved Tandem All‐Polymer Solar Cells Performance by Using Spectrally Matched Subcells

All‐polymer solar cells (all‐PSCs) are attractive as alternatives to fabricate thermally and mechanically stable solar cells, especially with recent improvements in their power conversion efficiency (PCE). In this work, efficient all‐PSCs with near‐infrared response (up to 850 nm) are developed using newly designed regioregular polymer donors with relatively narrow optical gap. These all‐PSCs systems achieve PCEs up to 6.0% after incorporating fluorine into the polymer backbone. More importantly, these polymers exhibit absorbance that is complementary to previously reported wide bandgap polymer donors. Thus, the superior properties of the newly designed polymers afford opportunities to fabricate the first spectrally matched all‐polymer tandem solar cells with high performance. A PCE of 8.3% is then demonstrated which is the highest efficiency so far for all‐polymer tandem solar cells. The design of narrow bandgap polymers provides new directions to enhance the PCE of emerging single‐junction and tandem all polymer solar cells.     

Benzotriazole-Based Polymer Acceptor for High-Efficiency All-Polymer Solar Cells with High Photocurrent and Low Voltage Loss

The power conversion efficiencies (PCEs) of all-polymer solar cells (all-PSCs) have already exceeded 17%. However, the limited absorption range of an all-polymer system results in significantly reduced short-circuit current density (J_sc), which eventually influences the PCE improvement. To broaden the light absorption of polymer acceptors, herein, benzotriazole is introduced in the core unit of small molecule acceptors and thus two narrow-bandgap polymer acceptors named PTz-BO and PTz-C11 featuring the same molecular backbone and different side-chain length are synthesized. Compared with PTz-C11, the PTz-BO based-all PSCs deliver a slightly reduced J_sc, a large open-circuit voltage (V_oc) and a low voltage loss below 0.50 V. Moreover, ternary all-PSCs are constructed by introducing PTz-C11 as a guest component. Benefiting from the reduced recombination, improved exciton generation and dissociation, and balanced charge transport, a high efficiency of 16.58% is obtained for the ternary all-PSCs, with a high J_sc over 25 mA cm⁻² without sacrificing the V_oc. Such result represents the highest efficiency reported for benzotriazole-based all-PSCs in the literature thus far. This work demonstrates the great potential of benzotriazole for the synthesis of efficient narrow-bandgap polymer acceptors.     

Domain Compositions and Fullerene Aggregation Govern Charge Photogeneration in Polymer/Fullerene Solar Cells

The complex microstructure of organic semiconductor mixtures continues to obscure the connection between the active layer morphology and photovoltaic device performance. For example, the ubiquitous presence of mixed phases in the active layer of polymer/fullerene solar cells creates multiple morphologically distinct interfaces which are capable of exciton dissociation or charge recombination. Here, it is shown that domain compositions and fullerene aggregation can strongly modulate charge photogeneration at ultrafast timescales through studies of a model system, mixtures of a low band‐gap polymer, poly[(4,4′‐bis(2‐ethylhexyl)dithieno[3,2‐b:2′,3′‐d]germole)‐2,6‐diyl‐alt‐(2,1,3‐benzothia‐diazole)‐4,7‐diyl], and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester. Structural characterization using energy‐filtered transmission electron microscopy (EFTEM) and resonant soft X‐ray scattering shows similar microstructures even with changes in the overall film composition. Composition maps generated from EFTEM, however, demonstrate that compositions of mixed domains vary significantly with overall film composition. Furthermore, the amount of polymer in the mixed domains is inversely correlated with device performance. Photoinduced absorption studies using ultrafast infrared spectroscopy demonstrate that polaron concentrations are highest when mixed domains contain the least polymer. Grazing‐incidence X‐ray scattering results show that larger fullerene coherence lengths are correlated to higher polaron yields. Thus, the purity of the mixed domains is critical for efficient charge photogeneration because purity modulates fullerene aggregation and electron delocalization.     

Polymer/Small Molecule/Fullerene Based Ternary Solar Cells

Polymer/small molecule/fullerene based ternary solar cells have made great progress and have attracted considerable attention in recent years. The addition of small molecules can effectively compensate for the disadvantages of polymer solar cells, such as increasing the light‐harvesting ability, providing cascade energy levels, and tuning the morphology. Thus, polymer/small molecule/fullerene based ternary solar cells are promising candidates to obtain further improvements in photovoltaic performance for organic solar cells. This article summarizes the developments of ternary solar cells with small molecules as third components, and represents the possible photo‐physics process in the ternary blends. In addition, the challenges and perspectives for ternary solar cells are discussed.     

Molecular Understanding of the Open‐Circuit Voltage of Polymer:Fullerene Solar Cells

The origin of open‐circuit voltage (V_OC) was studied for polymer solar cells based on a blend of poly(3‐hexylthiophene) (P3HT) and seven fullerene derivatives with different LUMO energy levels and side chains. The temperature dependence of J–V characteristics was analyzed by an equivalent circuit model. As a result, V_OC increased with the decrease in the saturation current density J₀ of the device. Furthermore, J₀ was dependent on the activation energy E_A for J₀, which is related to the HOMO–LUMO energy gap between P3HT and fullerene. Interestingly, the pre‐exponential term J₀₀ for J₀ was larger for pristine fullerenes than for substituted fullerene derivatives, suggesting that the electronic coupling between molecules also has substantial impact on V_OC. This is probably because the recombination is non‐diffusion‐lmilited reaction depending on electron transfer at the P3HT/fullerene interface. In summary, the origin of V_OC is ascribed not only to the relative HOMO–LUMO energy gap but also to the electronic couplings between fullerene/fullerene and polymer/fullerene.     

Highly Efficient Polymer Tandem Cells and Semitransparent Cells for Solar Energy

Highly efficient tandem and semitransparent (ST) polymer solar cells utilizing the same donor polymer blended with [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PC₆₁BM) and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₁BM) as active layers are demonstrated. A high power conversion efficiency (PCE) of 8.5% and a record high open‐circuit voltage of 1.71 V are achieved for a tandem cell based on a medium bandgap polymer poly(indacenodithiophene‐co‐phananthrene‐quinoxaline) (PIDT‐phanQ). In addition, this approach can also be applied to a low bandgap polymer poly[2,6‐(4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b;3,4‐b′]dithiophene)‐alt‐4,7‐(5‐fluoro‐2,1,3‐benzothia‐diazole)] (PCPDTFBT), and PCEs up to 7.9% are achieved. Due to the very thin total active layer thickness, a highly efficient ST tandem cell based on PIDT‐phanQ exhibits a high PCE of 7.4%, which is the highest value reported to date for a ST solar cell. The ST device also possesses a desirable average visible transmittance (≈40%) and an excellent color rendering index (≈100), permitting its use in power‐generating window applications.