Incorporation of silver and gold nanostructures for performance improvement in P3HT: PCBM inverted solar cell with rGO/ZnO nanocomposite as an electron transport layer

Inefficient light absorption and inefficient charge separation are considered as two major impediments for the efficiency improvement in bulk heterojunction organic solar cells (BHJ OSCs). In this work, we report the simultaneous role of modified electron transport layer (ETL) and photoactive layers on the performance of poly (3-hexylthiophene), [6, 6]-phenyl C61-butyric acid methyl ester (P3HT: PCBM) BHJ OSCs. To modify the ETL, composite of reduced graphene oxide (rGO) (0.4 wt %) and ZnO nanoparticles (NPs) was used, which resulted in efficiency enhancement from 3.13 to 3.81%, as compared to a value of 3.13% when only ZnO was used. Thereafter, to improve upon the optical absorption properties, the photoactive layer is modified by embedding nanoparticles and nanorods of Ag and Au into it. The size of Ag and Au nanoparticles were chosen to be 50 nm while the dimensions of Ag and Au nanorods were so controlled to obtain length of approx. 50 nm and width of ∼10 nm. All the devices were fabricated in inverted geometry and 20 wt% nanostructures embedded devices showed the best results. For Ag and Au NPs embedded devices, the maximum power conversion efficiency was found to be 4.21% and 4.44%, respectively. On the other hand, for Ag and Au NRs embedded devices, the maximum efficiency was 4.37% and 4.85%, respectively. For comparison, the control devices where no nanostructures were embedded, which shows efficiency of 3.81%. Therefore, an overall enhancement in efficiency was nearly 1.21 and 1.1, 1.16, 1.14, 1.27 fold after modifying ETL as well as the active layer. The reasons for performance improvement were ascribed to better charge extraction properties of ETL, enhanced light absorption due to localized surface plasmon resonance (LSPR) and efficient light scattering by the nanostructures and improved global mobilities.     

Novel brominated compounds using in binary additives based organic solar cells to achieve high efficiency over 10.3%

Solvent additives have been considered as a simple and efficient method to increase the performance of bulk-heterojunction (BHJ) organic solar cells, in which, the morphology of the active layer could obtain further improvements by using the binary solvent additives. In this paper, a series of brominated compounds, 1-Bromo-4-butylbenzene (Brbb), 1-Bromo-4-n-hexylbenzene (Brbh) and 1-Bromo-4-n-octylbenzene (Brbo), have been respectively incorporated with 1, 8-diiodooctane (DIO) and regarded as binary solvent additives to fabricate highly efficient bulk heterojunction (BHJ) organic solar cells (OSCs). Compared with the BHJ film based on single additive, the binary additives contained BHJ film shows increased optical absorption, efficient charge transport and better active layer morphology, leading to an enhancement of short-circuit current (J_SC) together with a higher achieved fill factor (FF). The conventional BHJ device using PTB7: PC₇₁BM or PTB7-th: PC₇₁BM with the binary solvent additives exhibit enhanced PCE of 8.13% and 10.31%, respectively, which is much higher than that of single additive based devices (7.04% for PTB7 and 8.73% for PTB7-th). The optimized performance of BHJ devices indicates that these brominated compounds are promising additives to improve device efficiency.     

Tailoring of the plasmonic and waveguide effect in bulk-heterojunction photovoltaic devices with ordered,nanopatterned structures

Various nano-patterned bulk-heterojunction (BHJ) films with different diameters and pitches were fabricated by a stamping method to tailor the plasmonic effect. The nanopatterned BHJ active layers exhibit regular-ordered embossing structures, which were confirmed by the surface morphological analysis with SEM and AFM. The simulation results confirm that devices with nanopatterned BHJ film with a diameter/pitch of 265/400 nm exhibit a strong improvement in E-field distribution intensity due to the combination of the plasmonic and waveguide modes compared to devices without a nanopattern, with 150/400 nm, or with 265/800 nm, which led to increased J_SC and cell efficiency in J–V curves under solar light illumination. The optimized plasmonic effect plays an important role in the light harvesting of BHJ devices.     

Effect of bulk and planar heterojunctions based charge generation layers on the performance of tandem organic light-emitting diodes

Tandem organic light-emitting diodes (OLEDs) were fabricated using organic planar and bulk heterojunctions based charge generation layers (CGLs), which were composed of cobalt phthalocyanine (CoPc) and fullerene (C₆₀). The electroluminescent (EL) characteristics of these two kinds of devices were systematically studied. The results showed that, compared to the corresponding devices with planar heterojunction (PHJ) based CGL, the tandem OLEDs with bulk heterojunction (BHJ) based CGL exhibited a dramatic improvement of performance. By investigating the electrical characteristics of CGLs, it was found that more hetero-interfaces introduced in the BHJ blend were beneficial for generating more interfacial dipoles and charge carriers, and the optimized charge transport pathways were favorable to promote both electron and hole mobilities. As a result, the improved charge carrier balance led to the efficiency enhancement of device performance. The results demonstrated the advantageous effect of BHJ blend film for the rational design of CGLs on the realization of high OLEDs performance.     

An efficient inverted organic solar cell with improved ZnO and gold contact layers

This paper presents a high efficiency (～3.8%) inverted organic photovoltaic devices based on a P3HT:PCBM bulk heterojunction (BHJ) blend with improved electron- and hole-selective contact layers. Zinc oxide (ZnO) nanoparticle films with different thicknesses are deposited on the transparent electrodes as a nano-porous electron-selective contact layer. A thin gold film is used between the BHJ photoactive layer and the poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS), which improves the wettability and significantly enhances the stability of the device (>50 days of air exposure). Photovoltaic device parameters such as power conversion efficiency (PCE) and external quantum efficiency (EQE) are systematically examined for inverted devices with different thicknesses of ZnO and gold layers in comparison to the non-inverted and reference inverted devices with no contact layers. The optimized organic devices with ZnO and Au contact layers show exceptional short circuit currents (in excess of 13 mA/cm²), in comparison to the reference devices, which is related to increased quantum efficiency of the device observed in measured EQE experiments. These results are important for development of high efficiency and stable all-printed organic solar cells and point out the role of contact layers, in particular, ZnO conductivity and morphology in the device performance.     

Does Electronic Type Matter when Single‐Walled Carbon Nanotubes are Used for Electrode Applications?

Single‐walled carbon nanotube (SWNT) electrodes that are chemically and mechanically robust are fabricated using a simple drop cast method with thermal annealing and acid treatment. An electronic‐type selective decrease in sheet resistance of SWNT electrodes with HNO₃ treatment is shown. Semiconducting SWNTs show a significantly higher affinity toward hole doping in comparison to metallic SWNTs; a ≈12‐fold and a ≈fivefold drop in sheet resistance, respectively. The results suggest the insignificance of the electronic type of the SWNTs for the film conductivity after hole doping. The SWNT films have been employed as transparent hole extracting electrodes in bulk heterojunction (BHJ) organic photovoltaics. Performances of the devices enlighten the fact that the electrode film morphology dominates over the electronic type of the doped SWNTs with similar sheet resistance and optical transmission. The power conversion efficiency (PCE) of 4.4% for the best performing device is the best carbon nanotube transparent electrode incorporated large area BHJ solar cell reported to date. This PCE is 90% in terms of PCEs achieved using indium tin oxide (ITO) based reference devices with identical film fabrication parameters indicating the potential of the SWNT electrodes as an ITO replacement toward realization of all carbon solar cells.     

Harnessing Structure–Property Relationshipsfor Poly(alkyl thiophene)–Fullerene Derivative Thin Filmsto Optimize Performance in Photovoltaic Devices

Nanoscale bulk heterojunction (BHJ) systems, consisting of fullerenes dispersed in conjugated polymers have been actively studied in order to produce high performance organic photovoltaics. How the BHJ morphology affects device efficiency, is currently ill‐understood. Neutron reflection together with grazing incidence X‐ray and neutron scattering and X‐ray photoelectron spectroscopy are utilized to gain understanding of the BHJ morphology in functional devices. For nine model systems, based on mixtures of three poly(3‐alkyl thiophenes, P3AT) (A = butyl, hexyl, octyl) blended with three different fullerene derivatives, the BHJ morphology through the film thickness is determined. It is shown that fullerene enrichment occurs at both the electrode interfaces after annealing. The degree of fullerene enrichment is found to strongly correlate with the short circuit current (J_SC ) and to a lesser degree with the fill factor. Based on these findings, it is demonstrated that by deliberately adding a fullerene layer at the electron transport layer interface, J_SC can be increased by up to 20%, resulting in an overall increase in power conversion efficiency of 5%.     

In‐Plane Alignment in Organic Solar Cells to Probe the Morphological Dependence of Charge Recombination

Bulk heterojunction (BHJ) organic solar cells are fabricated with the polymer semiconductor aligned in the plane of the film to probe charge recombination losses associated with aggregates characterized by varying degrees of local order. 100% uniaxial strain is applied on ductile poly(3‐hexylthiophene):phenyl‐C61‐butyric acid methyl ester (P3HT:PCBM) BHJ films and characterize the resulting morphology with ultraviolet‐visible absorption spectroscopy and grazing incidence X‐ray diffraction. It is found that the strained films result in strong alignment of the highly ordered polymer aggregates. Polymer aggregates with lower order and amorphous regions also align but with a much broader orientation distribution. The solar cells are then tested under linearly polarized light where the light is selectively absorbed by the appropriately oriented polymer, while maintaining a common local environment for the sweep out of photogenerated charge carriers. Results show that charge collection losses associated with a disordered BHJ film are circumvented, and the internal quantum efficiency is independent of P3HT local aggregate order near the heterojunction interface. Uniquely, this experimental approach allows for selective excitation of distinct morphological features of a conjugated polymer within a single BHJ film, providing insight into the morphological origin of recombination losses.     

Towards Efficient Integrated Perovskite/Organic Bulk Heterojunction Solar Cells: Interfacial Energetic Requirement to Reduce Charge Carrier Recombination Losses

Integrated perovskite/organic bulk heterojunction (BHJ) solar cells have the potential to enhance the efficiency of perovskite solar cells by a simple one‐step deposition of an organic BHJ blend photoactive layer on top of the perovskite absorber. It is found that inverted structure integrated solar cells show significantly increased short‐circuit current (J_sc) gained from the complementary absorption of the organic BHJ layer compared to the reference perovskite‐only devices. However, this increase in J_sc is not directly reflected as an increase in power conversion efficiency of the devices due to a loss of fill factor. Herein, the origin of this efficiency loss is investigated. It is found that a significant energetic barrier (≈250 meV) exists at the perovskite/organic BHJ interface. This interfacial barrier prevents efficient transport of photogenerated charge carriers (holes) from the BHJ layer to the perovskite layer, leading to charge accumulation at the perovskite/BHJ interface. Such accumulation is found to cause undesirable recombination of charge carriers, lowering surface photovoltage of the photoactive layers and device efficiency via fill factor loss. The results highlight a critical role of the interfacial energetics in such integrated cells and provide useful guidelines for photoactive materials (both perovskite and organic semiconductors) required for high‐performance devices.     

CuPc/C60 bulk heterojunction photovoltaic cells with evidence of phase segregation

This work presents organic photovoltaic (OPV) device study based on cupper phthalocyanine (CuPc) and fullerene (C60) bulk heterojunction (BHJ) structure. By varying blend composition, the optimized performances were obtained in 75%-CuPc containing devices with anode buffer of either CuPc or HPCzI (1,3,4,5,6,7-hexaphenyl-2-{3′-(9-ethylcarbazolyl)}-isoindole). It was discovered by scanning electron microscopy that 75%-CuPc containing film possessed phase separation, which is beneficial to charge transport via percolation process. Additionally, electronic absorption measurement and hole only device study showed that, depending on the mixing ratio, the absorption and the hole transport ability were different. The blend film containing 75% CuPc had the largest integrated absorption with the most CuPc dimmer aggregate and the least C60 aggregate. Moreover, the 75% CuPc blend film also possessed the highest hole transport ability. Thus, the best performance of the 75% CuPc BHJ device is mainly attributed to its good carrier transport originating from phase segregation. The present work highlights the phase separation in CuPc:C60 mixing film with optimized ratio, as well as its corresponding electronic absorption and carrier transport properties, which are essential for OPV device performance. Hence, insights are inferred for further engineering of BHJ OPV devices based on small molecules.     

Determination of diffusion lengths in organic semiconductors: Correlation with solar cell performances

Organic semiconductors are promising candidates for future applications in solar energy conversion. Recent investigations of bulk heterojunction (BHJ) semiconductors have suggested a density of states and transport mechanisms by multiple trapping close to those observed in disordered inorganic thin films. That is why we have applied to BHJ thin films experiments that are currently used for disordered semiconductors. In addition to the steady state photoconductivity we have tested the ability of the steady state photocarrier grating (SSPG) technique to provide information on the minority carrier diffusion length. We found that SSPG can be applied to P3HT:PCBM thin films leading, for the best sample, to a diffusion length of the order of 125 nm. From the comparison of the transport parameters obtained on thin films with the performances of the devices integrating the latter, we conclude that SSPG is a very powerful tool for optimizing the BHJ thin film properties before their incorporation in solar devices.     

A plasmonically enhanced polymer solar cell with gold–silica core–shell nanorods

We report the use of chemically synthesized gold (Au)–silica core–shell nanorods with the length of 92.5 ± 8.0 nm and diameter of 34.3 ± 4.0 nm for the efficiency enhancement of bulk heterojunction (BHJ) polymer solar cells. Silica coated Au nanorods were randomly blended into the BHJ layers of these solar cells. This architecture inhibits the carrier recombination at the metal/polymer interface and effectively exploits light absorption at the surface plasmon resonance wavelengths of the Au–silica nanorods. To match the two plasmon resonant peaks of the Au–silica nanorods, we employed a low bandgap polymer, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′] dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) to construct a solar cell. The absorption spectrum of PCPDTBT:[6,6]-phenyl-C₇₁-butyric acid methyl ester (PC₇₀BM) is relatively wide and matches the two plasmon resonance peaks of Au–silica nanorods, which leads to greater plasmonic effects. We also constructed the poly(3-hexylthiophene):[6,6]-phenyl-C₆₁-butyric acid methyl ester (P3HT:PC₆₀BM) cells for comparison. The absorption spectrum of P3HT:PC₆₀BM only overlaps one of the plasmon resonance peak of Au–silica nanorods. The efficiency of the P3HT:PC₆₀BM device incorporating optimized Au–silica nanorods is enhanced by 12.9% from 3.17% to 3.58%, which is due to the enhanced light absorption. Compared with the P3HT:PC₆₀BM device with Au–silica nanorods, the PCPDTBT:PC₇₀BM device with 1 wt% Au–silica nanorods concentration has a higher efficiency of 4.4% with an increase of 26%.     

Incorporating Graphitic Carbon Nitride (g‐C3N4) Quantum Dots into Bulk‐Heterojunction Polymer Solar Cells Leads to Efficiency Enhancement

Graphitic carbon nitride (g‐C₃N₄) has been commonly used as photocatalyst with promising applications in visible‐light photocatalytic water‐splitting. Rare studies are reported in applying g‐C₃N₄ in polymer solar cells. Here g‐C₃N₄ is applied in bulk heterojunction (BHJ) polymer solar cells (PSCs) for the first time by doping solution‐processable g‐C₃N₄ quantum dots (C₃N₄ QDs) in the active layer, leading to a dramatic efficiency enhancement. Upon C₃N₄ QDs doping, power conversion efficiencies (PCEs) of the inverted BHJ‐PSC devices based on different active layers including poly(3‐hexylthiophene‐2,5‐diyl):[6,6]‐phenyl‐C61‐butyric acid methyl ester (P3HT:PC₆₁BM), poly(4,8‐bis‐alkyloxybenzo(l,2‐b:4,5‐b′)dithiophene‐2,6‐diylalt‐(alkyl thieno(3,4‐b)thiophene‐2‐carboxylate)‐2,6‐diyl):[6,6]‐phenyl C₇₁‐butyric acid methyl ester (PBDTTT‐C:PC₇₁BM), and poly[4,8‐bis(5‐(2‐ethylhexyl)thiophen‐2‐yl)benzo[1,2‐b:4,5‐b′]dithiophene‐co‐3‐fluorothieno [3,4‐b]thiophene‐2‐carboxylate] (PTB7‐Th):PC₇₁BM reach 4.23%, 6.36%, and 9.18%, which are enhanced by ≈17.5%, 11.6%, and 11.8%, respectively, compared to that of the reference (undoped) devices. The PCE enhancement of the C₃N₄ QDs doped BHJ‐PSC device is found to be primarily attributed to the increase of short‐circuit current (J_sc), and this is confirmed by external quantum efficiency (EQE) measurements. The effects of C₃N₄ QDs on the surface morphology, optical absorption and photoluminescence (PL) properties of the active layer film as well as the charge transport property of the device are investigated, revealing that the efficiency enhancement of the BHJ‐PSC devices upon C₃N₄ QDs doping is due to the conjunct effects including the improved interfacial contact between the active layer and the hole transport layer due to the increase of the roughness of the active layer film, the facilitated photoinduced electron transfer from the conducting polymer donor to fullerene acceptor, the improved conductivity of the active layer, and the improved charge (hole and electron) transport.     

Effects of ZnO fabricating process on the performance of inverted organic solar cells

The effects of zinc oxide (ZnO) fabricating process on the performance of the inverted bulk heterojunction (BHJ) solar cells were explored in this study. The ZnO layers were prepared by either sputtering or solution-processed method. These ZnO films on the indium tin oxide (ITO) substrates were used as the cathode of the inverted solar cells. It was found that the topography of the ZnO films played a leading role on the device performance. The devices based on solution-processed ZnO films displayed better electric output compared with that of sputtered ones. The measurement of capacitance against bias voltage indicated that ZnO film with certain degree of roughness exhibited high charge extraction efficiency, which resulted in improved device performance. The measurement of ultraviolet photoelectron spectroscopy revealed that a shift of work function was observed due to the fabricating process of ZnO films.     

Chemically Recyclable Conjugated Polymer and One-Shot Preparation of Thermally Stable and Efficient Bulk-Heterojunction from Recycled Monomer

Recyclable conjugated polymers are important for realizing eco-friendly electronics with advantages of solution processability and flexibility. A recyclable conjugated polymer, PY-TIP is developed, of which a key monomer is successfully extracted via a mild depolymerization process and is reused for the synthesis of novel conjugated polymers. One-shot preparation of polymer acceptor and its bulk-heterojunction (BHJ) is demonstrated from the recycled monomer, Y5-TA, for the first time and the resulting BHJ film shows optimal nanoscale morphology for efficient charge generation and transport. As a result, the solar cells prepared using the BHJ film show a higher efficiency of 13.08% and much improved thermal and mechanical stability compared with those based on the small molecular acceptor. These results are important in that the various polymers can be prepared from the recycled monomer in a solid state without organic solvents and purification step and this strategy is effective for improving the thermal and mechanical stability of the BHJ film as well as achieving high photovoltaic performance. PY-TIP is exemplary in that it can reproduce its monomer which can be used to synthesize conjugated polymers with novel chemical structures and physical properties. This work provides a design guideline for developing recyclable conjugated polymers with dynamic covalent bonds.     

Efficiency and stability enhancement of polymer solar cells using multi-stacks of C60/LiF as cathode buffer layer

We report on the improved performance and stability of bulk heterojunction (BHJ) polymer solar cells using five stacks of C₆₀/LiF as cathode buffer layer, which was prepared by alternating deposition of C₆₀ and LiF layers. The five-stacked C₆₀/LiF film, even with a large thickness ratio of LiF to C₆₀, exhibits good electrical conductivity. The devices with five stacks of C₆₀/LiF buffer layer show a peak power conversion efficiency (PCE) which is 19% higher than that of the conventional devices with only LiF interlayer, primarily due to the improvement in fill factor (FF) of the device. Moreover, the high efficiency of five-stacked C₆₀/LiF based devices is insensitive to changes in the thickness ratio between C₆₀ and LiF layers. Since much thicker LiF can be used in five-stacked C₆₀/LiF film, these devices also show superior air stability as compared to the devices with only LiF interlayer. Therefore, five-stacked C₆₀/LiF is a promising alternative to pristine LiF as a cathode buffer layer in polymer solar cells.     

Crystallization‐Induced Phase Separation in Solution‐Processed Small Molecule Bulk Heterojunction Organic Solar Cells

The driving forces and processes associated with the development of phase separation upon thermal annealing are investigated in solution‐processed small molecule bulk heterojunction (BHJ) organic solar cells utilizing a diketopyrrolopyrrole‐based donor molecule and a fullerene acceptor (PCBM). In‐situ thermal annealing X‐ray scattering is used to monitor the development of thin film crystallization and phase separation and reveals that the development of blend phase separation strongly correlates with the nucleation of donor crystallites. Additionally, these morphological changes lead to dramatic increases in blend electron mobility and solar cell figures of merit. These results indicate that donor crystallization is the driving force for blend phase separation. It is hypothesized that donor crystallization from an as‐cast homogeneous donor:acceptor blend simultaneously produces donor‐rich domains, consisting largely of donor crystallites, and acceptor‐rich domains, formed from previously mixed regions of the film that have been enriched with acceptor during donor crystallization. Control of donor crystallization in solution‐processed small molecule BHJ solar cells employing PCBM is thus emphasized as an important strategy for the engineering of the nanoscale phase separated, bicontinuous morphology necessary for the fabrication of efficient BHJ photovoltaic devices.     

A Universal Method to Enhance Flexibility and Stability of Organic Solar Cells by Constructing Insulating Matrices in Active Layers

With the rapid development of power conversion efficiency (PCE), flexibility–stability of organic solar cells (OSCs) are becoming one of the primary barriers for commercialization. This work shows that insulating poly(aryl ether) (PAE) resins have highly twisted‐stiff backbones without any side chains, which possess excellent mechanical stability, thermal stability, and good compatibility with organic photovoltaic materials. After introducing 5 wt% PAE resin as supporting matrices into the bulk heterojunction (BHJ) layer, the device yields a high PCE of 16.13%. Importantly, the devices show impressive flexibility and improved stability with passivated morphology, such as PM6/Y6‐based devices with 30 wt% PAE retains the PCE of 15.17% and exhibits enhanced 4.4‐fold elongation at break (25.07%). This is the recorded stretchability of the BHJ layer for OSCs with PCE > 8%, and morphological changes during tensile deformation are first investigated by in situ wide‐angle X‐ray scattering measurements. The PAE matrices strategy exhibits good universality in the other four photovoltaic systems. These results demonstrate that heat‐resistant PAE resins serve as supporting matrices with a tunneling effect into OSCs without sacrificing photovoltaic performance and simultaneously improve the flexibility and stability of devices, which can play an important role in promoting the development of stable and wearable electronics.     

Three‐Dimensional Bulk Heterojunction Morphology for Achieving High Internal Quantum Efficiency in Polymer Solar Cells

Here, an investigation of three‐dimensional (3D) morphologies for bulk heterojunction (BHJ) films based on regioregular poly(3‐hexylthiophene) (P3HT) and [6,6]‐phenyl‐C₆₁‐butyric acid methyl ester (PCBM) is reported. Based on the results, it is demonstrated that optimized post‐treatment, such as solvent annealing, forces the PCBM molecules to migrate or diffuse toward the top surface of the BHJ composite films, which induces a new vertical component distribution favorable for enhancing the internal quantum efficiency (η_IQE ) of the devices. To investigate the 3D BHJ morphology, novel time‐of‐flight secondary‐ion mass spectroscopy studies are employed along with conventional methods, such as UV‐vis absorption, X‐ray diffraction, and high‐resolution transmission electron microscopy studies. The η_IQE of the devices are also compared after solvent annealing for different times, which clearly shows the effect of the vertical component distribution on the performance of BHJ polymer solar cells. In addition, the fabrication of high‐performance P3HT:PCBM solar cells using the optimized solvent‐annealing method is reported, and these cells show a mean power‐conversion efficiency of 4.12% under AM 1.5G illumination conditions at an intensity of 100 mW cm^?2.     

Printable and Large‐Area Organic Solar Cells Enabled by a Ternary Pseudo‐Planar Heterojunction Strategy

Bulk heterojunction (BHJ) processing technology has had an irreplaceable role in the development of organic solar cells (OSCs) in the past decades due to the significant advantages in achieving high‐power conversion efficiency (PCE). However, the difficulty in exploring and regulating morphology makes it inadequate for upscaling large‐area OSCs. In this work, printable high‐performance ternary devices are fabricated by a pseudo‐planar heterojunction (PPHJ) strategy. The fullerene derivative indene‐C₆₀ bisadduct (ICBA) is incorporated into PM6/IT‐4F system to expand the vertical phase separation and facilitate an obvious PPHJ structure. After the addition of ICBA, the IT‐4F enriches on the surface of active layer, while PM6 is accumulated underneath. Furthermore, it increases the crystallinity of PM6, which facilitates exciton dissociation and charge transfer. Accordingly, 1.05 cm² devices are fabricated by blade‐coating with an enhanced PCE of 14.25% as compared to the BHJ devices (13.73%). The ternary PPHJ strategy provides an effective way to optimize the vertical phase separation of organic semiconductor during scalable printing methods.