In Situ Formation of MoO3 in PEDOT:PSS Matrix: A Facile Way to Produce a Smooth and Less Hygroscopic Hole Transport Layer for Highly Stable Polymer Bulk Heterojunction Solar Cells

A solution‐processed neutral hole transport layer is developed by in situ formation of MoO₃ in aqueous PEDOT:PSS dispersion (MoO₃‐PEDOT:PSS). This MoO₃‐PEDOT:PSS composite film takes advantage of both the highly conductive PEDOT:PSS and the ambient conditions stability of MoO₃; consequently it possesses a smooth surface and considerably reduced hygroscopicity. The resulting bulk heterojunction polymer solar cells (BHJ PSC) based on poly[2,3‐bis‐(3‐octyloxyphenyl)quinoxaline‐5,8‐diyl‐alt‐thiophene‐2,5‐diyl] (TQ1):[6,6]‐phenyl‐C₇₁‐butyric acid methyl ester (PC₇₀BM) blends using MoO₃‐PEDOT:PSS composite film as hole transport layer (HTL) show considerable improvement in power conversion efficiency (PCE), from 5.5% to 6.4%, compared with the reference pristine PEDOT:PSS‐based device. More importantly, the device with MoO₃‐PEDOT:PSS HTL shows considerably improved stability, with the PCE remaining at 80% of its original value when stored in ambient air in the dark for 10 days. In comparison, the reference solar cell with PEDOT:PSS layer shows complete failure within 10 days. This MoO₃‐PEDOT:PSS implies the potential for low‐cost roll‐to‐roll fabrication of high‐efficiency polymer solar cells with long‐term stability at ambient conditions.     

Overcoming Interfacial Losses in Solution‐Processed Organic Multi‐Junction Solar Cells

Organic solar cells are promising in terms of full‐solution‐processing which enables low‐cost and large‐scale fabrication. While single‐junction solar cells have seen a boost in power conversion efficiency (PCE), multi‐junction solar cells are promising to further enhance the PCE. In all‐solution‐processed multi‐junction solar cells, interfacial losses are often encountered between hole‐transporting layer (HTL) and the active layers and therefore greatly limit the application of newly developed high‐performance donor and acceptor materials in multi‐junction solar cells. Here, the authors report on a systematic study of interface losses in both single‐junction and multi‐junction solar cells based on representative polymer donors and HTLs using electron spectroscopy and time‐of‐flight secondary ion mass spectrometry. It is found that a facile mixed HTL containing poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) and MoO _x nanoparticles successfully overcomes the interfacial losses in both single‐ and multi‐junction solar cells based on various active layers by reducing interface protonation, promoting better energy‐level alignment, and forming a dense and smooth layer. Solution‐processed single‐junction solar cells are demonstrated to reach the same performance as with evaporated MoO _x (over 7%). Multi‐junction solar cells with polymers containing nitrogen atoms as the first layer and the mixed PEDOT:PSS and MoO _x nanoparticles as hole extraction layer reach fill factor (FF) of over 60%, and PCE of over 8%, while the identical stack with pristine PEDOT:PSS or MoO _x nanoparticles show FF smaller than 50% and PCE less than 5%.     

Suppressing Interfacial Dipoles to Minimize Open‐Circuit Voltage Loss in Quantum Dot Photovoltaics

Quantum‐dot (QD) photovoltaics (PVs) offer promise as energy‐conversion devices; however, their open‐circuit‐voltage (V_OC) deficit is excessively large. Previous work has identified factors related to the QD active layer that contribute to V_OC loss, including sub‐bandgap trap states and polydispersity in QD films. This work focuses instead on layer interfaces, and reveals a critical source of V_OC loss: electron leakage at the QD/hole‐transport layer (HTL) interface. Although large‐bandgap organic materials in HTL are potentially suited to minimizing leakage current, dipoles that form at an organic/metal interface impede control over optimal band alignments. To overcome the challenge, a bilayer HTL configuration, which consists of semiconducting alpha‐sexithiophene (α‐6T) and metallic poly(3,4‐ethylenedioxythiphene) polystyrene sulfonate (PEDOT:PSS), is introduced. The introduction of the PEDOT:PSS layer between α‐6T and Au electrode suppresses the formation of undesired interfacial dipoles and a Schottky barrier for holes, and the bilayer HTL provides a high electron barrier of 1.35 eV. Using bilayer HTLs enhances the V_OC by 74 mV without compromising the J_SC compared to conventional MoO₃ control devices, leading to a best power conversion efficiency of 9.2% (>40% improvement relative to relevant controls). Wider applicability of the bilayer strategy is demonstrated by a similar structure based on shallow lowest‐unoccupied‐molecular‐orbital (LUMO) levels.     

Critical Impact of Hole Transporting Layers and Back Electrode on the Stability of Flexible Organic Photovoltaic Module

Properties of hole transporting layers (HTLs) and back electrode are very critical to the stability of inverted bulk heterojunction organic photovoltaic (OPV) modules. Here, various deposition methods for back electrodes and materials of HTLs are examined by applying to inverted organic solar cells with a structure of indium tin oxide/ZnO/photoactive layer/poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS)/Ag. The experiment is performed on encapsulated modules with flexible barrier films under accelerated conditions. The OPV modules with screen‐printed Ag electrodes are shown to be electrically unstable with a reduction of the current density under damp heat condition at 85 °C/85% RH. Optical images for the active layer/PEDOT:PSS interface reveal that a reaction between the solvent from the Ag electrode and the underlying layers is the major cause for the degradation. In comparison with materials of the HTLs, the PEDOT:PSS layer shows low stability compared to the MoO₃ layer under the accelerated conditions. Unusual chemical changes in the PEDOT:PSS film are observed through X‐ray photoelectron spectroscopy and this is further addressed by correlating the stability of the OPV devices.     

Charge Formation in Pentacene Layers During Solar‐Cell Fabrication: Direct Observation by Electron Spin Resonance

Microscopic characterization of charge carriers in solar cells is useful for high‐performance cell fabrication because the formation and accumulation of charges in cells greatly affect the device performance. Electron spin resonance (ESR) is suitable for such characterization because it can directly observe charge carriers with spins in these cells. In this work, the ESR method is applied to organic thin‐film solar cells to investigate charge formation in such devices. Heterojunction cells of indium tin oxide (ITO)/poly(3,4‐ethylenedioxythiophene):poly(4‐styrenesulfonate) (PEDOT:PSS)/pentacene/C₆₀/bathocuproine (BCP)/Al are investigated. Clear ESR signals are observed by inserting a typical PEDOT:PSS hole buffer layer. From analysis of the dependence of the ESR characteristics on the external magnetic field direction, the bias voltage, and the duration of solar‐simulated irradiation, the charges (mobile holes) in pentacene layers are successfully identified and it can be deduced that these holes are formed at the PEDOT:PSS/pentacene interface during device fabrication. This ESR analysis provides useful knowledge for understanding device operation and improving device performance at the microscopic level.     

Inverted Semi‐transparent Polymer Solar Cells with Transparency Color Rendering Indices approaching 100

Window‐ or building‐integrated semi‐transparent solar cells are particularly interesting applications for organic photovoltaic devices. In this work, we present an easy‐to‐process inverted device architecture comprising fully solution processable poly(3,4‐ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS) bilayer top‐electrodes for efficient semi‐transparent organic solar cells. By incorporating dyes with a complementary absorption to the light harvesting polymer poly[[9‐(1‐octylnonyl)‐9H‐carbazole‐2,7‐diyl]‐2,5‐thiophenediyl‐2,1,3‐benzothiadiazole‐4,7‐diyl‐2,5‐thiophenediyl] (PCDTBT) into the PEDOT:PSS electrode, we achieve fully color neutral transparency perception and a color rendering index approaching 100. This makes the devices suitable for applications such as window shadowing or the integration into overhead glazing.     

Solution‐Processed Hydrogen Molybdenum Bronzes as Highly Conductive Anode Interlayers in Efficient Organic Photovoltaics

Highly efficient and stable organic photovoltaic (OPV) cells are demonstrated by incorporating solution‐processed hydrogen molybdenum bronzes as anode interlayers. The bronzes are synthesized using a sol‐gel method with the critical step being the partial oxide reduction/hydrogenation using an alcohol‐based solvent. Their composition, stoichiometry, and electronic properties strongly correlate with the annealing process to which the films are subjected after spin coating. Hydrogen molybdenum bronzes with moderate degree of reduction are found to be highly advantageous when used as anode interlayers in OPVs, as they maintain a high work function similar to the fully stoichiometric metal oxide, whereas they exhibit a high density of occupied gap states, which are beneficial for charge transport. Enhanced short‐circuit current, open‐circuit voltage and, fill factor, relative to reference devices incorporating either PEDOT‐PSS or a solution processed stoichiometric molybdenum oxide, are obtained for a variety of bulk heterojunction mixtures based on different polymeric donors and fullerene acceptors. In particular, high power conversion efficiencies are obtained in devices that employed the s‐H_xMoO_2.75 as the hole extraction layer.     

Enhancing the Open‐Circuit Voltage of Perovskite Solar Cells by up to 120 mV Using π‐Extended Phosphoniumfluorene Electrolytes as Hole Blocking Layers

Four π‐extended phosphoniumfluorene electrolytes (π‐PFEs) are introduced as hole‐blocking layers (HBL) in inverted architecture planar perovskite solar cells with the structure of ITO/PEDOT:PSS/MAPbI₃/PCBM/HBL/Ag. The deep‐lying highest occupied molecular orbital energy level of the π‐PFEs effectively blocks holes, decreasing contact recombination. It is demonstrated that the incorporation of π‐PFEs introduces a dipole moment at the PCBM/Ag interface, resulting in significant enhancement of the built‐in potential of the device. This enhancement results in an increase in the open‐circuit voltage of the device by up to 120 mV, when compared to the commonly used bathocuproine HBL. The results are confirmed both experimentally and by numerical simulation. This work demonstrates that interfacial engineering of the transport layer/contact interface by small molecule electrolytes is a promising route to suppress nonradiative recombination in perovskite devices and compensates for a nonideal energetic alignment at the hole‐transport layer/perovskite interface.     

Poly(3,4‐Ethylenedioxythiophene): Methylnaphthalene Sulfonate Formaldehyde Condensate: The Effect of Work Function and Structural Homogeneity on Hole Injection/Extraction Properties

Poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) is widely used as hole injection/extraction material in organic optoelectronics. However, there still exist drawbacks for PEDOT:PSS such as low work function (WF), poor structural and electrical homogeneity. To solve these problems, methylnaphthalene sulfonate formaldehyde condensate (MNSF) is applied, which has excellent dispersion property, branched chemical structure, and low cost, as dispersant and dopant instead of linear PSS to prepare PEDOT:MNSF. The hole injection/extraction capability of PEDOT:MNSF is systematically studied in organic optoelectronic devices. PEDOT:MNSF‐1:6 exhibits unexpected high device performance with a maxima current efficiency of 33.4 cd A^?1 in blue phosphorescent organic light‐emitting diode and a power conversion efficiency of 13.1% in CH₃NH₃PbI_x Cl_3?x ‐based inverted perovskite solar cell, respectively. Compared with PEDOT:PSS, the relatively higher efficiency of PEDOT:MNSF‐1:6 is attributed mainly to its higher WF of 5.29 eV, structural and electrical homogeneity. Our research displays a promising future of MNSF as a cheap and widely available alternative of PSS. Moreover, a clear map is provided for the design of dopant for PEDOT considering the structure of dopant.     

Efficient Polymer Solar Cells on Opaque Substrates with a Laminated PEDOT:PSS Top Electrode

Solution processed polymer:fullerene solar cells on opaque substrates have been fabricated in conventional and inverted device configurations. Opaque substrates, such as insulated steel and metal covered glass, require a transparent conducting top electrode. We demonstrate that a high conducting (900 S cm^?1) PEDOT:PSS layer, deposited by a stamp‐transfer lamination technique using a PDMS stamp, in combination with an Ag grid electrode provides a proficient and versatile transparent top contact. Lamination of large size PEDOT:PSS films has been achieved on variety of surfaces resulting in ITO‐free solar cells. Power conversion efficiencies of 2.1% and 3.1% have been achieved for P3HT:PCBM layers in inverted and conventional polarity configurations, respectively. The power conversion efficiency is similar to conventional glass/ITO‐based solar cells. The high fill factor (65%) and the unaffected open‐circuit voltage that are consistently obtained in thick active layer inverted geometry devices, demonstrate that the laminated PEDOT:PSS top electrodes provide no significant potential or resistive losses.     

Linking Vertical Bulk‐Heterojunction Composition and Transient Photocurrent Dynamics in Organic Solar Cells with Solution‐Processed MoOx Contact Layers

It is demonstrated that a combination of microsecond transient photocurrent measurements and film morphology characterization can be used to identify a charge‐carrier blocking layer within polymer:fullerene bulk‐heterojunction solar cells. Solution‐processed molybdenum oxide (s‐MoO_x) interlayers are used to control the morphology of the bulk‐heterojunction. By selecting either a low‐ or high‐temperature annealing (70 °C or 150 °C) for the s‐MoO_x layer, a well‐performing device is fabricated with an ideally interconnected, high‐efficiency morphology, or a device is fabricated in which the fullerene phase segregates near the hole extracting contact preventing efficient charge extraction. By probing the photocurrent dynamics of these two contrasting model systems as a function of excitation voltage and light intensity, the optoelectronic responses of the solar cells are correlated with the vertical phase composition of the polymer:fullerene active layer, which is known from dynamic secondary‐ion mass spectroscopy (DSIMS). Numerical simulations are used to verify and understand the experimental results. The result is a method to detect poor morphologies in operating organic solar cells.     

Modified PEDOT Layer Makes a 1.52 V Voc for Perovskite/PCBM Solar Cells

The work functions for charge transport layers in perovskite solar cells affect device performance significantly. In this work, the regular poly(3,4‐ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) is modified by adding a polymer electrolyte PSS‐Na to improve its HTL function in perovskite solar cells. The modified PEDOT:PSS films (called m‐PEDOT:PSS) possess higher work function than the regular one. Its energy level matches the valence band of perovskite very well, leading to enhanced V_oc and PCE (power conversion efficiency). When CH₃NH₃PbI₃ is used as the light absorber, the cell with PEDOT:PSS HTL gives a V_oc of 0.96 V and a PCE of 12.35%, while the cell with m‐PEDOT:PSS layer gives a V_oc of 1.11 V and a PCE of 15.56%. Enhanced V_oc and PCE are also achieved when CH₃NH₃PbI₂Br or CH₃NH₃PbBr₃ is used as the light absorber. The m‐PEDOT:PSS/CH₃NH₃PbBr₃/PC₆₁BM solar cells demonstrate an outstanding V_oc of 1.52 V.     

Dopamine Semiquinone Radical Doped PEDOT:PSS: Enhanced Conductivity,Work Function and Performance in Organic Solar Cells

Poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) has been is applied as hole transport material in organic electronic devices for more than 20 years. However, the redundant sulfonic acid group of PEDOT:PSS has often been overlooked. Herein, PEDOT:PSS‐DA is prepared via a facile doping of PEDOT:PSS with dopamine hydrochloride (DA·HCl) which reacts with the redundant sulfonic acid of PSS. The PEDOT:PSS‐DA film exhibits enhanced work function and conductivity compared to those of PEDOT:PSS. PEDOT:PSS‐DA‐based devices show a power conversion efficiency of 16.55% which is the highest in organic solar cells (OSCs) with (poly[(2,6‐(4,8‐bis(5‐(2‐ethylhexyl)‐4‐fluorothiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithio‐phene))‐co‐(1,3‐di(5‐thiophene‐2‐yl)‐5,7‐bis(2‐ethylhexyl)‐benzo[1,2‐c:4,5‐c′]dithiophene‐4,8‐dione))] (PM6):(2,2′‐((2Z,2′Z)‐((12,13‐bis(2‐ethylhexyl)‐3,9‐diundecyl‐12,13‐dihydro‐[1,2,5]thiadiazolo[3,4‐e]thieno[2′′,3′:4′,5′]thieno[2′,3′:4,5]pyrrolo[3,2‐g]thieno[2′,3′:4,5]thieno[3,2‐b]indole‐2,10‐diyl)bis(methanylylidene))bis(5,6‐difluoro‐3‐oxo‐2,3‐dihydro‐1H‐indene‐2,1‐diylidene))dimalononitrile) (Y6) as the active layer. Furthermore, PEDOT:PSS‐DA also exhibits enhanced performance in three other donor/acceptor systems, exhibiting high compatibility in OSCs. This work demonstrates that doping PEDOT:PSS with various amino derivatives is a potentially efficient strategy to enhance the performance of PEDOT:PSS in organic electronic devices.     

Dual Functional Electron‐Selective Contacts Based on Silicon Oxide/Magnesium: Tailoring Heterointerface Band Structures while Maintaining Surface Passivation

Silicon (Si)‐based dopant‐free heterojunction solar cells (SCs) featuring carrier‐selective contacts (CSCs) have attracted considerable interest due to the extreme simplifications in their device structure and manufacturing procedure. However, these SCs are limited by the unsatisfactory contact properties on both sides of the junction, and their efficiencies are not comparable with those of commercially available Si SCs. In this report, a high‐performance silicon‐oxide/magnesium (SiO_x/Mg) electron‐selective contact (ESC) design is described. Combining an ultrathin SiO_x and a low work function Mg layer, the novel ESC simultaneously yields low recombinative and resistive losses. In addition, deposition of Mg on SiO_x relaxes the restriction on the threshold thickness of the SiO_x for electron tunneling and therefore broadens the optimization space for rear‐sided passivation. Meanwhile, hole‐selective contact with boosted light harvesting and suppressed interfacial recombination is achieved by forming a fully conformal contact between the conducting poly(3,4‐ethylene dioxythiophene): poly(styrenesulfonate) (PEDOT: PSS) and periodic Si pyramid arrays. With the double‐sided carrier‐selective contact designs, PEDOT: PSS/Si/SiO_x/Mg SCs with efficiency of 15% are finally obtained via a totally dopant‐free processing. Subsequent calculations further indicate a pathway for the improvement of these contacts toward an efficiency that is competitive with conventionally diffused pn junction SCs.     

A New Interconnecting Layer of Metal Oxide/Dipole Layer/Metal Oxide for Efficient Tandem Organic Solar Cells

A new metal‐oxide‐based interconnecting layer (ICL) structure of all‐solution processed metal oxide/dipole layer/metal oxide for efficient tandem organic solar cell (OSC) is demonstrated. The dipole layer modifies the work function (WF) of molybdenum oxide (MoO _x ) to eliminate preexisted counter diode between MoO _x and TiO₂. Three different amino functionalized water/alcohol soluble conjugated polymers (WSCPs) are studied to show that the WF tuning of MoO _x is controllable. Importantly, the results show that S‐shape current density versus voltage (J–V) characteristics form when operation temperature decreases. This implies that thermionic emission within the dipole layer plays critical role for helping recombination of electrons and holes. Meanwhile, the insignificant homotandem open‐circuit voltage (V _oc) loss dependence on dipole layer thickness shows that the quantum tunneling effect is weak for efficient electron and hole recombination. Based on this ICL, poly(3‐hexylthiophene) (P3HT)‐based homotandem OSC with 1.20 V V _oc and 3.29% power conversion efficiency (PCE) is achieved. Furthermore, high efficiency poly(4,8‐bis(5‐(2‐ethylhexyl)‐thiophene‐2‐yl)‐benzo[1,2‐b54,5‐b9]dithiophene‐alt alkylcarbonylthieno[3,4‐b]thiophene) (PBDTTT‐C‐T)‐based homotandem OSC with 1.54 V V _oc and 8.11% PCE is achieved, with almost 15.53% enhancement compared to its single cell. This metal oxide/dipole layer/metal oxide ICL provides a new strategy to develop other qualified ICL with different hole transporting layer and electron transporting layer in tandem OSCs.     

Semi‐Transparent Tandem Organic Solar Cells with 90% Internal Quantum Efficiency

Semi‐transparent (ST) organic solar cells with potential application as power generating windows are studied. The main challenge is to find proper transparent electrodes with desired electrical and optical properties. In this work, this is addressed by employing an amphiphilic conjugated polymer PFPA‐1 modified ITO coated glass substrate as the ohmic electron‐collecting cathode and PEDOT:PSS PH1000 as the hole‐collecting anode. For active layers based on different donor polymers, considerably lower reflection and parasitic absorption are found in the ST solar cells as compared to solar cells in the standard geometry with an ITO/PEDOT:PSS anode and a LiF/Al cathode. The ST solar cells have remarkably high internal quantum efficiency at short circuit condition (～90%) and high transmittance (～50%). Hence, efficient ST tandem solar cells with enhanced power conversion efficiency (PCE) compared to a single ST solar cell can be constructed by connecting the stacked two ST sub‐cells in parallel. The total loss of photons by reflection, parasitic absorption and transmission in the ST tandem solar cell can be smaller than the loss in a standard solar cell based on the same active materials. We demonstrate this by stacking five separately prepared ST cells on top of each other, to obtain a higher photocurrent than in an optimized standard solar cell.     

Photochemical Transformations in Fullerene and Molybdenum Oxide Affect the Stability of Bilayer Organic Solar Cells

Thin films of fullerene C₆₀ and molybdenum oxide (MoO₃) are ubiquitously used as the electron acceptor material and hole extraction interfacial layer for the fabrication of organic photovoltaic (OPV) cells. It is well known that light exposure induces color changes in MoO₃ (photochromism) and the formation of intermolecular bonds between C₆₀ molecules (photopolymerization). The influence of these photoinduced reactions on the long‐term stability of OPV cells, however, has not previously been studied in detail. Here, a study and discussion of the early (<5 days) aging mechanisms occurring in illuminated ITO/MoO₃/organic cyanine dye/C₆₀/Alq₃/Ag bilayer solar cells under nitrogen atmosphere is presented. A degradation process at the organic heterojunction is identified and the formation of Mo⁵⁺ species during illumination is found to adversely affect cell behavior. For these widely used materials, the results suggest that light processing is a first necessary step before OPV characteristics can be meaningfully rated.     

High‐Surface‐Area Porous Platinum Electrodes for Enhanced Charge Transfer

Cobalt‐based electrolytes are highly tunable and have pushed the limits of dye‐sensitized solar cells, enabling higher open‐circuit voltages and new record efficiencies. However, the performance of these electrolytes and a range of other electrolytes suffer from slow electron transfer at platinum counter electrodes. High surface area platinum would enhance catalysis, but pure platinum structures are too expensive in practice. Here, a material‐efficient host‐guest architecture is developed that uses an ultrathin layer of platinum deposited upon an electrically conductive scaffold, niobium‐doped tin oxide (NTO). This nanostructured composite enhances the counter electrode performance of dye‐sensitized solar cells (DSCs) using a Co^(II/III)BPY₃ electrolyte with an increased fill factor and power conversion efficiency (11.26%), compared to analogous flat films. The modular strategy is elaborated by integrating a light scattering layer onto the counter electrode to reflect unabsorbed light back to the photoanode to improve the short‐circuit current density and power conversion efficiency.     

High‐Performance Tandem Organic Solar Cells Using HSolar as the Interconnecting Layer

Tandem structure provides a practical way to realize high efficiency organic photovoltaic cells, it can be used to extend the wavelength coverage for light harvesting. The interconnecting layer (ICL) between subcells plays a critical role in the reproducibility and performance of tandem solar cells, yet the processability of the ICL has been a challenge. In this work the fabrication of highly reproducible and efficient tandem solar cells by employing a commercially available material, PEDOT:PSS HTL Solar (HSolar), as the hole transporting material used for the ICL is reported. Comparing with the conventional PEDOT:PSS Al 4083 (c‐PEDOT), HSolar offers a better wettability on the underlying nonfullerene photoactive layers, resulting in better charge extraction properties of the ICL. When FTAZ:IT‐M and PTB7‐Th:IEICO‐4F are used as the subcells, a power conversion efficiency (PCE) of 14.7% is achieved in the tandem solar cell. To validate the processability of these tandem solar cells, three other research groups have successfully fabricated tandem devices using the same recipe and the highest PCE obtained is 16.1%. With further development of donor polymers and device optimization, the device simulation results show that a PCE > 22% can be realized in tandem cells in the near future.     

Stability of Nonfullerene Organic Solar Cells: from Built‐in Potential and Interfacial Passivation Perspectives

Remarkable progress has been made in the development of high‐efficiency solution‐processable nonfullerene organic solar cells (OSCs). However, the effect of the vertical stratification of bulk heterojunction (BHJ) on the efficiency and stability of nonfullerene OSCs is not fully understood yet. In this work, we report our effort to understand the stability of nonfullerene OSCs, made with the binary blend poly[(2,6‐(4, 8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)‐benzo[1,2‐b:4,5‐b′]dithiophene))‐alt‐(5,5‐(1′,3′‐di‐2‐thienyl‐5′,7′‐bis(2‐ethylhexyl)benzo[1′,2′‐c:4′,5′‐c′] dithiophene‐4,8‐dione)] (PBDB‐T):3,9‐ bis(2‐methylene‐(3‐(1,1‐dicyanomethylene)‐indanone))‐5,5,11,11‐tetrakis(4‐hexylphenyl)‐ dithieno[2,3‐d:2′,3′‐d′]‐s‐indaceno[1,2‐b:5,6‐b′] dithiophene (ITIC) system. It shows that a continuous vertical phase separation process occurs, forming a PBDB‐T‐rich top surface and an ITIC‐rich bottom surface in PBDB‐T:ITIC BHJ during the aging period. A gradual decrease in the built‐in potential (V₀) in the regular configuration PBDB‐T:ITIC OSCs, due to the interfacial reaction between the poly(3,4‐ethylenedioxythiophene)‐poly(styrenesulfonate) (PEDOT:PSS) hole transporting layer and ITIC acceptor, is one of the reasons responsible for the performance deterioration. The reduction in V₀, caused by an inevitable reaction at the ITIC/PEDOT:PSS interface in the OSCs, can be suppressed by introducing a MoO₃ interfacial passivation layer. Retaining a stable and high V₀ across the BHJ through interfacial modification and device engineering, e.g., as seen in the inverted PBDB‐T:ITIC OSCs, is a prerequisite for efficient and stable operation of nonfullerene OSCs.