Tuning Energy Levels without Negatively Affecting Morphology: A Promising Approach to Achieving Optimal Energetic Match and Efficient Nonfullerene Polymer Solar Cells

One advantage of nonfullerene polymer solar cells (PSCs) is that they can yield high open‐circuit voltage (V_OC) despite their relatively low optical bandgaps. To maximize the V_OC of PSCs, it is important to fine‐tune the energy level offset between the donor and acceptor materials, but in a way not negatively affecting the morphology of the donor:acceptor (D:A) blends. Here, an effective material design rationale based on a family of D–A1–D–A2 terthiophene (T3) donor polymers is reported, which allows for the effective tuning of energy levels but without any negative impacts on the morphology of the blend. Based on a T3 donor unit combined with difluorobenzothiadiazole (ffBT) and difluorobenzoxadiazole (ffBX) acceptor units, three donor polymers are developed with highly similar morphological properties. This is particularly surprising considering that the corresponding quaterthiophene polymers based on ffBT and ffBX exhibit dramatic differences in their solubility and morphological properties. With the fine‐tuning of energy levels, the T3 polymers yield nonfullerene PSCs with a high efficiency of 9.0% for one case and with a remarkably low energy loss (0.53 V) for another polymer. This work will facilitate the development of efficient nonfullerene PSCs with optimal energy levels and favorable morphology properties.     

On the Molecular Origin of Charge Separation at the Donor–Acceptor Interface

Fullerene‐based acceptors have dominated organic solar cells for almost two decades. It is only within the last few years that alternative acceptors rival their dominance, introducing much more flexibility in the optoelectronic properties of these material blends. However, a fundamental physical understanding of the processes that drive charge separation at organic heterojunctions is still missing, but urgently needed to direct further material improvements. Here a combined experimental and theoretical approach is used to understand the intimate mechanisms by which molecular structure contributes to exciton dissociation, charge separation, and charge recombination at the donor–acceptor (D–A) interface. Model systems comprised of polythiophene‐based donor and rylene diimide‐based acceptor polymers are used and a detailed density functional theory (DFT) investigation is performed. The results point to the roles that geometric deformations and direct‐contact intermolecular polarization play in establishing a driving force (energy gradient) for the optoelectronic processes taking place at the interface. A substantial impact for this driving force is found to stem from polymer deformations at the interface, a finding that can clearly lead to new design approaches in the development of the next generation of conjugated polymers and small molecules.     

Theoretical design of donor-acceptor conjugated copolymers based on furo-, thieno-, and selenopheno[3,4-c] thiophene-4,6-dione and benzodithiophene units for organic solar cells

In this work, a series of donor-acceptor (D-A) copolymers (PBDTFPD(Pa1), PBDTTPD (Pa2) and PBDTSePD(Pa3)) were selected and theoretically investigated using O3LYP/6-31G(d), PBE0/6-31G(d), TD-O3LYP/6-31G(d)//O3LYP/6-31G(d) and periodic boundary conditions methods. The calculated results go well with the available experimental data of highest occupied and lowest unoccupied molecular orbital (HOMO/LUMO) energy levels and band gaps. A series of conjugated polymers (Pb1?~?Pb3) comprised of electron-deficient benzodithiophene and electron-rich furo-, thieno-, and selenopheno[3,4-c]thiophene-4,6-dione were further designed and studied. Compared with Pa1-Pa3, the designed polymers of Pb1?~?Pb3 show better performances with smaller band gaps, lower HOMO energy levels, red shift of absorption spectra, and larger open circuit voltage (Voc). For investigated polymers (Pa1, Pa2, Pa3, Pb1, Pb2, Pb3), the power conversion efficiencies (PCEs) of ~6.1 %, ~7.2 %, ~7.9 %, ~8.0 %, ~9.5 % and ~9.0 % are predicted by Scharber diagrams when they are used in combination with PC60BM as an acceptor. The results illustrate that these designed polymers which turn the electron-withdrawing capability in D-A conjugated polymers are expected to turn into highly efficient donor materials for organic solar cells.

The effect of ruthenium on the performance of porphyrin dye and porphyrin–fullerene dyad solar cells predicted by DFT and TD-DFT calculations

The effect of ruthenium on the performance of porphyrin dye and porphyrin–fullerene (PF) dyad solar cells is investigated by using density functional theory and time-dependant density functional theory calculations. The results reveal that ruthenium facilitates rapid electron injection from porphyrin to fullerene, narrows the band gaps of porphyrin dye and PF dyad and alters the density of states near the corresponding Fermi levels. The HOMOs are localised on the donor moieties and the LUMOs on the acceptor moieties. The donor and acceptor dyads form good donor–acceptor pairs for photo-to-current conversion under the effect of ruthenium. HOMOs of porphyrin and ruthenium metalloporphyrin dyes fall within the (TiO₂)₆₀ and Ti₃₈O₇₆ gaps, and support the issue of typical interfacial electron transfer reaction. The calculated transition energies of porphyrin are almost insensitive to ethanol solvent effects. The introduction of ruthenium to the porphyrin ring leads to more active nonlinear optical performance, stronger response to the external electric field and induces higher photo-to-current conversion efficiency. Moreover, ruthenium shifts the absorption bands of porphyrin and makes it a potential candidate for harvesting light for photovoltaic applications.     

A DFT study of the effects of donor-to-acceptor ratio on the electronic properties of copolymers based on tricyclic non-classical thiophene

The geometries and electronic properties of the 1D polymers composed of thieno[3,2-b]thiophene (TT), thiophene (T), pyrrole (P), furan (F) and tricyclic non-classical thiophenes ([1,2,5]thiadiazolo[3,4-b]thieno-[3,4-e]pyrazine, TTP) are investigated systematically by the density functional theory method at the B3LYP level with 6-31G(d) basis set. The theoretical study suggests that the ratio of donor-to-acceptor (D-A ratio) plays a crucial role in the geometric and electronic properties for the alternating donor–acceptor polymers. The increase in the D-A ratio leads to an increase in the bridge bond length and an inverse change in the bond-length alternation. Furthermore, the increase in the portion of donor units can lead to an obvious reduction in band gap for these studied polymers. The TT-containing polymer possessing the D-A ratio of 2:1 (p-BTTTTP) that is predicted to have a small band gap of 0.25 eV and a relatively small effective mass of carriers is a good candidate for an intrinsic conducting polymer. Therefore, the tricyclic non-classical thiophenes (TTP) and TT are good building blocks that can lead to small band gap polymers.     

Dopant‐Free,Donor–Acceptor‐Type Polymeric Hole‐Transporting Materials for the Perovskite Solar Cells with Power Conversion Efficiencies over 20%

The rich molecular design of electron donor (D)–acceptor (A) polymers offers many valuable clues to obtain high‐efficiency hole‐transporting materials (HTMs) for use in perovskite solar cells (PVSCs). The fused aromatic or heteroaromatic units can increase the conjugation of the polymer backbone to facilitate electron delocalization, which increases the rigidity of adjacent units to prevent rotational disorder and lower the reorganization energy, leading to improved carrier mobility and optimized film morphology. In this work, fused‐ring ladder‐type indacenodithiophene and indacenodithieno[3,2‐b]thiophene are used as D units, benzodithiophene‐4,8‐dione as the A unit, and thienothiophene as a π‐bridge to form the D–A polymers PBDTT and PBTTT, respectively. Both polymers exhibit favorable properties as HTMs including suitable energy levels, high hole mobility, and excellent film quality. Both dopant‐free HTMs endow n‐i‐p PVSCs with promising performance and stability. A maximum power conversion efficiency of 20.28% is achieved for PBDTT‐based devices, which is among the highest values reported to date.     

Matrix Organization and Merit Factor Evaluation as a Method to Address the Challenge of Finding a Polymer Material for Roll Coated Polymer Solar Cells

The results presented demonstrate how the screening of 104 light‐absorbing low band gap polymers for suitability in roll coated polymer solar cells can be accomplished through rational synthesis according to a matrix where 8 donor and 13 acceptor units are organized in rows and columns. Synthesis of all the polymers corresponding to all combinations of donor and acceptor units is followed by characterization of all the materials with respect to molecular weight, electrochemical energy levels, band gaps, photochemical stability, carrier mobility, and photovoltaic parameters. The photovoltaic evaluation is carried out with specific reference to scalable manufacture, which includes large area (1 cm²), stable inverted device architecture, an indium‐tin‐oxide‐free fully printed flexible front electrode with ZnO/PEDOT:PSS (poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate), and a printed silver comb back electrode structure. The matrix organization enables fast identification of active layer materials according to a weighted merit factor that includes more than simply the power conversion efficiency and is used as a method to identify the lead candidates. Based on several characteristics included in the merit factor, it is found that 13 out of the 104 synthesized polymers outperformed poly(3‐hexylthiophene) under the chosen processing conditions and thus can be suitable for further development.     

The electronic properties of poly(p-phenylenevinylene) derivatives and their monomers and oligomers

The electronic structures of monomers, oligomers and polymers of poly(p-phenylenevinylene) (PPV) derivatives are calculated and analysed based on density functional theory (DFT) methods. The influences of different substituent groups on the band gaps are discussed. Strong relationships are found between band-gap and bond length alternation (BLA) of polymers, and between band-gap and Wiberg bond index (WBI). Analysis of nuclear independent chemical shift (NICS) reveals that oligomers with similar energy gaps have close values of NICS.     

Quantum chemical investigations aimed at modeling highly efficient zinc porphyrin dye sensitized solar cells

Zinc tetraphenylporphyrin (ZnTPP) was modified by a push-pull strategy and then density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations were performed for the resulting derivatives. The smallest HOMO-LUMO energy gaps were found in ZnTPP-6 and ZnTPP-7, which had nitro substituents and a conjugated chain, while the largest was observed for ZnTPP-5. The energy gaps of all of the systems designed in this work were smaller than that of ZnTPP. Clear intramolecular charge transfer was observed from donor to acceptor in ZnTPP-6 and ZnTPP-7, which had nitro groups at positions R8, R9, and R10, as well as in ZnTPP-3 and ZnTPP-4, which had cyano groups at those positions. The narrow band gaps (compared to that of ZnTPP) of these designed systems, where the LUMO is above the conduction band of TiO(2) and the HOMO is below the redox couple, indicate that they are efficient sensitizers. The B bands of these newly designed derivatives, except for ZnTPP-5, are redshifted compared with the B band of ZnTPP.     

Ternary Organic Solar Cells with Minimum Voltage Losses

A new strategy for designing ternary solar cells is reported in this paper. A low‐bandgap polymer named PTB7‐Th and a high‐bandgap polymer named PBDTTS‐FTAZ sharing the same bulk ionization potential and interface positive integer charge transfer energy while featuring complementary absorption spectra are selected. They are used to fabricate efficient ternary solar cells, where the hole can be transported freely between the two donor polymers and collected by the electrode as in one broadband low bandgap polymer. Furthermore, the fullerene acceptor is chosen so that the energy of the positive integer charge transfer state of the two donor polymers is equal to the energy of negative integer charge transfer state of the fullerene, enabling enhanced dissociation of all polymer donor and fullerene acceptor excitons and suppressed bimolecular and trap assistant recombination. The two donor polymers feature good miscibility and energy transfer from high‐bandgap polymer of PBDTTS‐FTAZ to low‐bandgap polymer of PTB7‐Th, which contribute to enhanced performance of the ternary solar cell.     

Designing 1,5‐Naphthyridine‐2,6‐dione‐Based Conjugated Polymers for Higher Crystallinity and Enhanced Light Absorption to Achieve 9.63% Efficiency Polymer Solar Cells

Highly crystalline conjugated polymers represent a key material for producing high‐performance thick‐active‐layer polymer solar cells (PSCs). However, despite their potential, a limited number of crystalline polymers are used in PSCs because of the lack of highly coplanar acceptor building blocks and insufficient light absorptivity (α < 10⁵) of most donor (D)–acceptor (A)‐type polymers. This study reports a series of novel 3,7‐di(thiophen‐2‐yl)‐1,5‐naphthyridine‐2,6‐dione (NTDT) acceptor‐based conjugated polymers, PNTDT‐2T, PNTDT‐TT, and PNTDT‐2F2T, synthesized with 2,2′‐bithiophene (2T), thieno[3,2‐b]thiophene (TT), and 3,3′‐difluoro‐2,2′‐bithiophene (2F2T) donor units, respectively. PNTDT‐2F2T exhibits superior polymer crystallinity and a much higher absorption coefficient than those of PNTDT‐2T or PNTDT‐TT because of adequate matching between highly coplanar A (NTDT) and D (2F2T) building blocks. A bulk heterojunction solar cell based on PNTDT‐2F2T exhibits a power conversion efficiency of up to 9.63%, with a high short circuit current of 18.80 mA cm^?2 and fill factor of 0.70, when a thick active layer (>200 nm) is used, without postfabrication hot processing. The findings demonstrate that the polymer crystallinity and absorption coefficient can be effectively controlled by selecting appropriate D and A building blocks, and that NTDT is a novel and versatile A building block for highly efficient thick‐active‐layer PSCs.     

Manipulating Backbone Structure to Enhance Low Band Gap Polymer Photovoltaic Performance

A pair of polymers, PBDTBT and PBDTDTBT , was synthesized for application in polymer solar cells (PSCs). Although these two polymers have similar absorption bands and molecular energy levels, PBDTDTBT exhibits much better photovoltaic performance in polymer solar cell (PSC) devices with power conversion efficiency (PCE) of 7.4%. To understand the differences between PBDTDTBT and PBDTBT , we have investigated the correlations of the molecular structure, morphology, dynamics and efficiency of these two polymers. A theoretical investigation using density functional theory (DFT) and time‐dependent DFT (TDDFT) has been employed to investigate the electron density and electron delocalization extent of the unimers. TEM data showed that PBDTDTBT phase separates from PC₇₁BM, while PBDTBT suffers from having a proper morphology on different processing conditions. Grazing incidence wide angle X‐ray diffraction (GIWAXD) was used to probe the crystal structure of the polymers in thin film. A polymorph crystal structure was observed for PBDTBT . Grazing incidence small angle X‐ray scattering (GISAXS) was used to probe the size scale of phase separation, with an optimized 25 nm feature size observed for PBDTDTBT /PC₇₁BM blends, which agrees well with TEM results. Femtosecond transient absorption (TA) spectroscopy was used to probe the dynamics of the fundamental processes in organic photovoltaic (OPV) materials, such as charge separation and recombination. The enhanced absorption coefficient, good charge separation, optimal phase separation and higher charge mobility all contribute to the high PCE of the PBDTDTBT /PC₇₁BM devices.     

High‐Performance and Stable All‐Polymer Solar Cells Using Donor and Acceptor Polymers with Complementary Absorption

To explore the advantages of emerging all‐polymer solar cells (all‐PSCs), growing efforts have been devoted to developing matched donor and acceptor polymers to outperform fullerene‐based PSCs. In this work, a detailed characterization and comparison of all‐PSCs using a set of donor and acceptor polymers with both conventional and inverted device structures is performed. A simple method to quantify the actual composition and light harvesting contributions from the individual donor and acceptor is described. Detailed study on the exciton dissociation and charge recombination is carried out by a set of measurements to understand the photocurrent loss. It is unraveled that fine‐tuned crystallinity of the acceptor, matched donor and acceptor with complementary absorption and desired energy levels, and device architecture engineering can synergistically boost the performance of all‐PSCs. As expected, the PBDTTS‐FTAZ:PNDI‐T10 all‐PSC attains a high and stable power conversion efficiency of 6.9% without obvious efficiency decay in 60 d. This work demonstrates that PNDI‐T10 can be a potential alternative acceptor polymer to the widely used acceptor N2200 for high‐performance and stable all‐PSCs.     

Theoretical design of organic-inorganic hybrids based on hexamolybdate toward high performance dye-sensitized solar cells

The electronic structures, absorption spectra and photovoltaic (PV) performance of four dyes based on triphenylamine and polyoxometalate (POM) organic–inorganic hybrids for p-type dye-sensitised solar cells have been discussed by density functional theory (DFT) and time-dependent DFT calculations. In the four designed dyes, the triarylamine and carbazole take the role of the electron donor and the POMs act as the electron acceptor. It was found that introduction of electron donating groups (diphenylamine group and carbazole) into the triarylamine unit enabled better PV performance. This work is expected to be helpful for designing triarylamine–POM hybrid dyes with target properties.     

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.     

Bis(Naphthalene Imide)diphenylanthrazolines: A New Class of Electron Acceptors for Efficient Nonfullerene Organic Solar Cells and Applicable to Multiple Donor Polymers

Unlike universally applicable fullerene derivatives, current nonfullerene electron acceptors are rarely effective with more than one donor polymer in bulk heterojunction (BHJ) solar cells. A novel class of nonfullerene electron acceptors, bis(naphthalene imide)‐3,6‐diphenyl‐trans‐anthrazolines (BNIDPAs), that is applicable and yields efficient photovoltaic devices with multiple donor polymers, including a thiazolothiazole–dithienosilole copolymer (PSEHTT) and benzodithiophene copolymers (PBDTT‐FTTE and PTB7) is reported. Photovoltaic devices composed of the BNIDPA‐butyloctyl (BO) acceptor with PSEHTT, PBDTT‐FTTE, and PTB7, respectively, have power conversion efficiencies of 3.0%–3.1% with high open‐circuit voltages of ≈1.0 V. In contrast, BHJ devices composed of BNIDPA‐DT acceptor with larger 2‐decyltetradecyl chains and the same donor polymers have substantially reduced bulk electron mobility and reduced photovoltaic efficiencies of 1.3%–1.7%, which highlight the critical role of the size of alkyl chains appended onto nonfullerene electron acceptors. The present results provide a rare example of nonfullerene electron acceptors that are capable of pairing with multiple donor polymers to achieve efficient BHJ solar cells.     

Impact of Noncovalent Sulfur–Fluorine Interaction Position on Properties,Structures, and Photovoltaic Performance in Naphthobisthiadiazole‐Based Semiconducting Polymers

Controlling the energetics and backbone order of semiconducting polymers is essential for the performance improvement of polymer‐based solar cells. The use of fluorine as the substituent for the backbone is known to effectively deepen the molecular orbital energy levels and coplanarize the backbone by noncovalent interactions with sulfur of the thiophene ring. In this work, novel semiconducting polymers are designed and synthesized based on difluoronaphthobisthiadiazole (FNTz) as a new family of naphthobisthiadiazole (NTz)–quaterthiophene copolymer systems, which are one of the highest performing polymers in solar cells. The effect of the fluorination position on the energetics and backbone order is systematically studied. It is found that the dependence of the solar cell fill factor on the active layer thickness is very sensitive to the fluorination position. It is thus further investigated and discussed how the structural features of the polymers influence the photovoltaic parameters as well as the diode characteristics and bimolecular recombination. Further, the polymer with fluorine on both the naphthobisthiadiazole and quaterthiophene moieties exhibits a quite high power conversion efficiency of 10.8% in solar cells in combination with a fullerene. It is believed that the results would offer new insights into the development of semiconducting polymers.     

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.     

Thermally Stable All‐Polymer Solar Cells with High Tolerance on Blend Ratios

Tuning the blend composition is an essential step to optimize the power conversion efficiency (PCE) of organic bulk heterojunction (BHJ) solar cells. PCEs from devices of unoptimized donor:acceptor (D:A) weight ratio are generally significantly lower than optimized devices. Here, two high‐performance organic nonfullerene BHJ blends PBDB‐T:ITIC and PBDB‐T:N2200 are adopted to investigate the effect of blend ratio on device performance. It is found that the PCEs of polymer‐polymer (PBDB‐T:N2200) blend are more tolerant to composition changes, relative to polymer‐molecule (PBDB‐T:ITIC) devices. In both systems, short‐circuit current density (J_sc) is tracked closely with PCE, indicating that exciton dissociation and transport strongly influence PCEs. With dilute acceptor concentrations, polymer‐polymer blends maintain high electron mobility relative to the polymer‐molecule blends, which explains the dramatic difference in PCEs between them as a function of D:A blend ratio. In addition, polymer‐polymer solar cells, especially at high D:A blend ratio, are stable (less than 5% relative loss) over 70 d under continuous heating at 80 °C in a glovebox without encapsulation. This work demonstrates that all‐polymer solar cells show advantage in operational lifetime under thermal stress and blend‐ratio resilience, which indicates their high potential for designing of stable and scalable solar cells.     

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.