Moderately reduced graphene oxide/PEDOT:PSS as hole transport layer to fabricate efficient perovskite hybrid solar cells

Graphene oxide (GO) with single layer was moderately reduced at 200 °C for 4 h under N₂. Then the moderately reduced graphene oxide (rGO) water solution was employed as an additive to tune the properties of conventional poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) solution. It's found that the incorporation of rGO into PEDOT:PSS nearly did not change its transparency, hydrophilic property, or the surface roughness. So, the rGO/PEDOT:PSS composite was used as a hole transport layer (HTL) to fabricate perovskite solar cells (PSCs). As a result, PSCs with rGO/PEDOT:PSS as HTL exhibit improved power conversion efficiency than that of PSCs with PEDOT:PSS as HTL. Our findings show that moderately reduced rGO/PEDOT:PSS could be an efficient HTL to improve power conversion efficiency of PSCs.     

Improved performance of perovskite solar cells with a TiO2/MoO3 core/shell nanoparticles doped PEDOT:PSS hole-transporter

We demonstrate improved performance of inverted planar heterojunction CH₃NH₃PbI_3-xCl_x perovskite solar cells with a TiO₂/MoO₃ core/shell nanoparticles (NPs) doped poly(3,4-ethylene dioxythiophene):poly(4-styrenesulfonate) (PEDOT:PSS) hole-transporting layer (HTL). TiO₂/MoO₃ Core/shell NPs with size of approximately 40 nm are successfully prepared with a simple wet solution method and are interspersed into PEDOT: PSS layer to construct the HTL. The optimized device shows a high power conversion efficiency of 13.63%, which is dramatically improved compared with the reference device with a pristine PEDOT:PSS HTL. The improvement is mainly attributed to the increased crystalline of the CH₃NH₃PbI_3-xCl_x film with large-scale domains and a compact morphology. More interesting, the cells exhibit superior stability in ambient conditions, which is attributed to the inhibited penetration of moisture due to the compact morphology of the CH₃NH₃PbI_3-xCl_x film and the reduced hygroscopicity of the PEDOT:PSS film.     

Tuning Hole Transport Layer Using Urea for High‐Performance Perovskite Solar Cells

Interface engineering is critical to the development of highly efficient perovskite solar cells. Here, urea treatment of hole transport layer (e.g., poly(3,4‐ethylene dioxythiophene):polystyrene sulfonate (PEDOT:PSS)) is reported to effectively tune its morphology, conductivity, and work function for improving the efficiency and stability of inverted MAPbI₃ perovskite solar cells (PSCs). This treatment has significantly increased MAPbI₃ photovoltaic performance to 18.8% for the urea treated PEDOT:PSS PSCs from 14.4% for pristine PEDOT:PSS devices. The use of urea controls phase separation between PEDOT and PSS segments, leading to the formation of a unique fiber‐shaped PEDOT:PSS film morphology with well‐organized charge transport pathways for improved conductivity from 0.2 S cm^?1 for pristine PEDOT:PSS to 12.75 S cm^?1 for 5 wt% urea treated PEDOT:PSS. The urea‐treatment also addresses a general challenge associated with the acidic nature of PEDOT:PSS, leading to a much improved ambient stability of PSCs. In addition, the device hysteresis is significantly minimized by optimizing the urea content in the treatment.     

An ammonia modified PEDOT: PSS for interfacial engineering in inverted planar perovskite solar cells

Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) is one of the most widely used hole transport layers (HTL) in inverted perovskite solar cells (PSCs) due to its simple solution-processed ability, high transparency, and conductivity. However, PEDOT:PSS-based devices suffer a lower open-circuit voltage (V_oc) than devices with the conventional structure. To address this issue, we fabricated ammonia-modified PEDOT:PSS films by simply doping PEDOT:PSS solution with different ratio of ammonia. The acidity of PEDOT:PSS can be neutralized by the doped ammonia, which inhibits the ion-exchange reaction between PSS-H and CH₃NH₃I, thus retarding the reduction of the work function for PEDOT:PSS to some extent. As a result, a superior power conversion efficiency (PCE) of 15.5% was obtained for the device based on the ammonia-doped PEDOT:PSS HTL than that of the pristine PEDOT:PSS-based device. We ascribe the PCE enhancement to the increased V_oc and fill factor (FF), which is attributed not only to the better energy-level alignment between the ammonia-modified PEDOT:PSS film and perovskite layer but also to the increased grain size and crystallinity of perovskite film.     

A Simple Cu(II) Polyelectrolyte as a Method to Increase the Work Function of Electrodes and Form Effective p-Type Contacts in Perovskite Solar Cells

One effective strategy to improve the performance of perovskite solar cells (PSCs) is to develop new hole transport layers (HTLs). In this work, a simple polyelectrolyte HTL, copper (II) poly(styrene sulfonate) (Cu:PSS), which comprises easily reduced Cu²⁺ counter-ions with an anionic PSS polyelectrolyte backbone is investigated. Photoelectron spectroscopy reveals an increase in the work function of the anode and upward band bending effect upon incorporation of Cu:PSS in PSC devices. Cu:PSS shows a synergistic effect when mixed with polyethylenedioxythiophene: polystyrenesulfonate (PEDOT:PSS) in various proportions and results in a decrease in the acidity of PEDOT:PSS as well as reduced hysteresis in completed devices. Cu:PSS functions effectively as a HTL in PSCs, with device parameters comparable to PEDOT:PSS, while mixtures of Cu:PSS with PEDOT:PSS shows greatly improved performance compared to PEDOT:PSS alone. Optimized devices incorporating Cu:PSS/PEDOT:PSS mixtures show an improvement in efficiency from 14.35 to 19.44% using a simple CH₃NH₃PbI₃ active layer in an inverted (P-I-N) geometry, which is one of the highest values yet reported for this type of device. It is expected that this type of HTL can be employed to create p-type contacts and improve performance in other types of semiconducting devices as well.     

Interface degradation of perovskite solar cells and its modification using an annealing-free TiO2 NPs layer

Interface is one of the most important factors to influence the device stability, which directly determines the commercialization of perovskite solar cells (PSCs). The research disclosed the degradation process and mechanism of planar heterojunction (PHJ) PSCs with a structure of ITO/PEDOT:PSS/CH₃NH₃PbI₃/PCBM/Al using in-situ experiments. The degradation of PHJ-PSCs is mainly attributed to the interface decay of perovskite/cathode. Large amount of bubbles formed quickly at the interface and grew up as PHJ-PSCs exposed to air. The cathode electrode easily peeled off from the devices that led to lose the efficiency completely after only 1 h exposure to air. On the other hand, the degradation driven by intrinsic decomposition of perovskite itself under atmosphere (humidity ∼ 45 RH%) was not obvious and the power conversion efficiency (PCE) could retain almost the same when only the perovskite layer was exposed to air for 200 h. Furthermore, annealing-free TiO₂ nanocrystalline particles (TiO₂ NPs) as an interface modification layer was inserted into PHJ-PSCs and dramatically improved the stability, of which the PCEs retained over 75% of its initial values after exposure to air for 200 h. The results provide important information to understand the degradation of PSCs and the improvement of the stability, which may potentially accelerate the development and commercialization of PSCs.     

High-efficiency inverted polymer solar cells via dual effects of introducing the high boiling point solvent and the high conductive PEDOT:PSS layer

Polymer solar cells (PSCs) are of great interest in the past decade owing to their potentially low-cost in the manufacturing by the solution-based roll to roll method. In this paper, a novel inverted device structure was introduced by inserting a high conductive PEDOT:PSS (hcPEDOT:PSS) layer between the Au nanoparticles (NPs)-embedded hole transport layer (PEDOT:PSS) and the top electrode layer. Power conversion efficiency (PCE) initially reached up to 4.51%, illustrating ∼10% higher compared with the device similarly enhanced by Au NPs plasmonics where only one PEDOT:PSS layer with the embedded Au NPs was used in single bulk heterojunction inverted PSCs based on the poly(3-hexylthiophene):[6,6]-phenyl C61-butyric acid methylester (P3HT:PCBM). The PCE was further improved from 4.51% to 5.01% by adding the high-boiling point solvent of 1,8-diiodooctane (DD) into the active layer, presenting ∼20% enhancement in PCE through dual effects of introducing the high boiling point solvent and the high conductive PEDOT:PSS layer. Morphologies of the active layers were characterised by SEM and AFM separately in the paper.     

Influence of the surface treatment of PEDOT:PSS layer with high boiling point solvent on the performance of inverted planar perovskite solar cells

Since perovskite precursor solution is typically prepared from high boiling point solvents, understanding the effect of high boiling point solvent treatment of the PEDOT:PSS layer on the performance of perovskite solar cells is important for device processing optimization. In this paper, influence of the surface treatment of the PEDOT:PSS layer with high boiling point solvent, including N,N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), and ethylene glycol (EG), on the device performance of the perovskite solar cells was investigated. Increased conductivity was measured for the PEDOT:PSS film after solvent treatments, which was ascribed to the partial removal of PSS component from the PEDOT:PSS layer, as evidenced by the UV–vis absorption spectroscopy and XPS spectroscopy. In comparison with the reference cell, poorer device performance was obtained for the perovskite solar cells directly deposited on the solvent washed PEDOT:PSS film, which was ascribed to the increased pin hole density of the perovskite films. However, insertion of a thin PSSNa layer between the PEDOT:PSS layer and the perovskite layer greatly improved device performance, demonstrating that PSS-rich surface is favorite for the crystal growth of the perovskite film. Increased external quantum efficiency over 600–750 nm was measured for the cells based on solvent treated PEDOT:PSS layer, leading to a short circuit current and the consequent performance enhancement.     

Efficient and Stable Perovskite Solar Cells via Dual Functionalization of Dopamine Semiquinone Radical with Improved Trap Passivation Capabilities

Highly efficient planar heterojunction perovskite solar cells (PVSCs) with dopamine (DA) semiquinone radical modified poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) (DA‐PEDOT:PSS) as a hole transporting layer (HTL) were fabricated. A combination of characterization techniques were employed to investigate the effects of DA doping on the electron donating capability of DA‐PEDOT:PSS, perovskite film quality and charge recombination kinetics in the solar cells. Our study shows that DA doping endows the DA‐PEDOT:PSS‐modified PVSCs with a higher radical content and greater perovskite to HTL charge extraction capability. In addition, the DA doping also improves work function of the HTL, increases perovskite film crystallinity, and the amino and hydroxyl groups in DA can interact with the undercoordinated Pb atoms on the perovskite crystal, reducing charge‐recombination rate and increasing charge‐extraction efficiency. Therefore, the DA‐PEDOT:PSS‐modified solar cells outperform those based on PEDOT:PSS, increasing open‐circuit voltage (V _oc) and power conversion efficiency (PCE) to 1.08 V and 18.5%, respectively. Even more importantly, the efficiency of the unencapsulated DA‐PEDOT:PSS‐based PVSCs are well retained with only 20% PCE loss after exposure to air for 250 hours. These in‐depth insights into structure and performance provide clear and novel guidelines for the design of effective HTLs to facilitate the practical application of inverted planar heterojunction PVSCs.     

Pre-buried Interface Strategy for Stable Inverted Perovskite Solar Cells Based on Ordered Nucleation Crystallization

The buried interface has important effect on carrier extraction and nonradiative recombination of perovksite solar cells (PSCs). Herein, to inactivate the buried interfacial defects of perovskite and boost the crystallization quality of perovskite film, 3-amino-1-adamantanol (AAD) serves as a pre-buried interface modifier on nickel oxide (NiO_x) surface to regulate the nucleation and crystallization process of perovskite precursor. The amino and hydroxyl groups in AAD molecule can synchronously coordinate with nickel ion (Ni³⁺) in NiO_x and lead ion in perovskite, respectively. The dual action favors the ordered arrangement of AAD molecules between NiO_x and perovskite, which not only enhances hole extraction in hole transport layer, but also provides active sites for homogeneous nucleation. Furthermore, AAD modifier blocks the unfavorable reaction between Ni³⁺ and perovskite, and effectively passivates the buried interfacial defects. The optimal inverted PSCs achieve a champion power conversion efficiency of 22.21% with negligible hysteresis, favorable thermal, optical, and long-term stability. Thus, this strategy of modulating perovskite nucleation and crystallization by pre-buried modifier is feasible for achieving efficient and stable inverted perovskite solar cells.     

A Self-Assembled Vertical-Gradient and Well-Dispersed MXene Structure for Flexible Large-Area Perovskite Modules

Advancing hole transport layers (HTL) to realize large-area, flexible, and high-performance perovskite solar cells (PSCs) is one of the most challenging issues for its commercialization. Here, a self-assembled gradient Ti₃C₂T_x MXene incorporated PEDOT:PSS HTL is demonstrated to achieve high-performance large-area PSCs by establishing half-caramelization-based glucose-induced MXene redistribution. Through this process, the Ti₃C₂T_x MXene nanosheets are spontaneously dispersed and redistributed at the top region of HTL to form the unique gradient distribution structure composed of MXene:Glucose:PEDOT:PSS (MG-PEDOT). These results show that the MG-PEDOT HTL not only offers favorable energy level alignment and efficient charge extraction, but also improves the film quality of perovskite layer featuring enlarged grain size, lower trap density, and longer carrier lifetime. Consequently, the power conversion efficiency (PCE) of the flexible device based on MG-PEDOT HTL is increased by 36% compared to that of pristine PEDOT:PSS HTL. Meanwhile, the flexible perovskite solar minimodule (15 cm² area) using MG-PEDOT HTL achieve a PCE of 17.06%. The encapsulated modules show remarkable long-term storage stability at 85 °C in ambient air (≈90% efficiency retention after 1200 h) and enhanced operational lifetime (≈90% efficiency retention after 200 h). This new approach shows a promising future of the self-assembled HTLs for developing optoelectronic devices.     

Boosting Performance of Non‐Fullerene Organic Solar Cells by 2D g‐C3N4 Doped PEDOT:PSS

The power‐conversion efficiency (PCE) of single‐junction organic solar cells (OSCs) has exceeded 16% thanks to the development of non‐fullerene acceptor materials and morphological optimization of active layer. In addition, interfacial engineering always plays a crucial role in further improving the performance of OSCs based on a well‐established active‐layer system. Doping of graphitic carbon nitride (g‐C₃N₄) into poly(3,4‐ethylene‐dioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as a hole transport layer (HTL) for PM6:Y6‐based OSCs is reported, boosting the PCE to almost 16.4%. After being added into the PEDOT:PSS, the g‐C₃N₄ as a Bronsted base can be protonated, weakening the shield effect of insulating PSS on conductive PEDOT, which enables exposures of more PEDOT chains on the surface of PEDOT:PSS core‐shell structure, and thus increasing the conductivity. Therefore, at the interface between g‐C₃N₄ doped HTL and PM6:Y6 layer, the charge transport is improved and the charge recombination is suppressed, leading to the increases of fill factor and short‐circuit current density of devices. This work demonstrates that doping g‐C₃N₄ into PEDOT:PSS is an efficient strategy to increase the conductivity of HTL, resulting in higher OSC performance.     

Printable and Homogeneous NiOx Hole Transport Layers Prepared by a Polymer-Network Gel Method for Large-Area and Flexible Perovskite Solar Cells

As one of the most promising hole transport layers (HTLs), nickel oxide (NiO_x) has received extensive attention due to its application in flexible large-area perovskite solar cells (PSCs). However, the poor interface contact caused by inherent easy-agglomeration phenomenon of NiO_x nanoparticles (NPs) is still the bottleneck for achieving high-performance devices. Herein, a general strategy to synthesize NiO_x NPs with high crystallinity and good dispersibility via the polymer network micro-precipitation method is reported. Promisingly, this approach realizes the flow-division of precipitant and the restraint of the NPs motion, thereby effectively alleviating the coagulation phenomenon caused by excessive local concentration and secondary movement adsorption. Furthermore, the addition of ionic liquid not only inhibits the secondary aggregation of NiO_x NPs during the dispersion process, but also significantly enhances the properties of the colloidal solution. Ultimately, the 1.01 cm² PSCs based on the optimized NiO_x HTLs achieve the champion power conversion efficiency of 20.91% and 19.17% on rigid and flexible substrates, respectively. Moreover, the reproducibility and stability of PSCs are also significantly improved, especially for flexible devices. Overall, this strategy provides the possibility for flexible, large-area fabrication of high-quality NiO_x HTLs to promote the development of stable and efficient perovskite devices.     

Enhanced efficiency and stability of polymer solar cells with TiO2 nanoparticles buffer layer

TiO₂ sols synthesized with a facile solution-based method were used as a buffer layer between the active layer and the cathode Al in conventional structure polymer solar cells (PSCs). Using transmission electron microscopy (TEM), selected area electron diffraction (SAED), X-ray diffraction (XRD) and atomic force microscopy (AFM), the morphological and crystallographic properties of synthesized TiO₂ nanoparticles (TiO₂ NPs) as well as the buffer layer were studied in detail. It was observed that by increasing H₂O in the process of peptization both the crystallinity and particle size of TiO₂ NPs were enhanced, while the particles in sol showed a narrower size distribution conformed by dynamic light scattering. Inserting TiO₂ NPs as a buffer layer in conventional structure PSCs, both the power conversion efficiency (PCE) and stability were improved dramatically. PSCs based on the structure of ITO/PEDOT:PSS/P3HT:PCBM/TiO₂ NPs/Al showed the short-circuit current (J_sc) of 12.83 mA/cm² and the PCE of 4.24%, which were improved by 31% and 37%, respectively comparing with the reference devices without a TiO₂ buffer layer. The stability measurement showed that PSC devices with a TiO₂ NPs buffer layer could retain 80% of the original PCEs after exposed in air for 200 h, much better than the devices without such a buffer layer. The effect can be attributed to the protection by the buffer layer against oxygen and H₂O diffusion into the active layers. The observations indicate that TiO₂ NPs synthesized by facile solution-based method have great potential applications in PSCs, especially for large-area printed PSCs.     

Enhanced carrier mobility and photon-harvesting property by introducing Au nano-particles in bulk heterojunction photovoltaic cells

In this study, polymer solar cells (PSCs) doped with Au nanoparticles (Au NPs) were successfully fabricated to maximize the photon-harvesting properties on the photoactive layer. In addition, a conductivity-enhanced hybrid buffer layer was introduced to improve the photon absorption properties and effectively separate the generated charges by adding Au NPs and dimethylsulfoxide (DMSO) to the PH 500 as a buffer layer. The PSC performance was optimized with a 88% improvement over the conventional PSCs (photoactive area: 225 mm², power conversion efficiency (PCE): 3.2%) by the introduction to the buffer layer of Au NPs and DMSO at 10 wt% and 1.0 wt%, respectively, and with 15 wt% Au NP doping in the photoactive layer. The internal resistance was decreased due to the increased photocurrent caused by the localized surface plasmon resonance (LSPR) effect of the Au NPs in the photoactive layer and by the improvement of carrier mobility induced by the DMSO doping of the buffer layer. As a result, the series resistance (R_S) deceased from 42.3 to 19.7 Ω cm² while the shunt resistance (R_SH) increased from 339 to 487 Ω cm².     

Achieving a Record Fill Factor for Silicon–Organic Hybrid Heterojunction Solar Cells by Using a Full‐Area Metal Polymer Nanocomposite Top Electrode

Carrier collection in conventional n‐type Si (n‐Si)/organic hybrid heterojunction solar cells (HHSCs) is mainly limited by the nonoptimized top grid‐electrode and inadequate work function (WF) of the PH1000‐type poly(3,4‐ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS). Here, a novel modified metal polymer nanocomposite top electrode (M‐MPNTE) is designed to achieve a full‐area carrier collection in n‐Si/PEDOT:PSS HHSCs. The carrier collection in both lateral and vertical directions is significantly improved by the introduction of an ultrathin Au/MoO_x modified layer between 6 nm ultrathin Ag film and AI4083‐type PEDOT:PSS layer. In addition, the carrier separation is boosted by the enhanced built‐in potential owing to a high WF of M‐MPNTE, which also suppresses the carrier recombination at the surface of n‐Si. Due to these collaborative improvements, a record fill factor of 80.21% is obtained, which is even comparable to the best value of the traditional Si‐based solar cells. With the addition of a MoO_x antireflective coating layer on top of M‐MPNTE, the short‐circuit current density and open‐circuit voltage are finally increased to 23.13 mA cm^?2 and 621.07 mV, respectively, yielding a power conversion efficiency of 10.82%. The finding suggests a novel strategy for the development of highly efficient HHSCs with ideal carrier transport mechanism.     

Electron-beam-induced reduced graphene oxide as an alternative hole-transporting interfacial layer for high-performance and reliable polymer solar cells

We demonstrate an eco-friendly, simple, and cost-effective method for manufacturing reduced graphene oxide (GO) induced with electron-beam irradiation, and we investigate the feasibility of the electron-beam-induced reduced GO (ERGO) as a hole-transporting interfacial layer in polymer solar cells (PSCs). In addition, the chemical composition, conductivity, work-function, and morphology of ERGOs with various absorbed doses were systematically investigated. The analytical results revealed that the reduced GO (RGO) was successfully prepared using electron-beam irradiation, and the electrical conductivity of ERGO was increased (up to 18.3 S/cm) with increasing the amount of absorbed dose. The PSCs with the ERGO as a hole-transporting interfacial layer exhibited comparable cell performance (3.52 ± 0.08% of power conversion efficiency) to that of the conventional PSCs with the poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS), and they had better stability than the PEDOT:PSS-based PSCs. From the results, we confirmed that electron-beam irradiation is an effective approach to prepare the RGO, and the ERGO was preferable to the PEDOT:PSS for high-performance and stable PSCs.     

High performance thermal-treatment-free tandem polymer solar cells with high fill factors

It is an effective way to enhance device performance of polymer solar cells (PSCs) by using a tandem structure that combines two or more solar cells. For tandem PSCs, the buffer layer plays an important role in determining the device performance. The most commonly used buffer layers, such as PEDOT:PSS, TiO_x, and ZnO, need thermal treatments that are not beneficial for reducing the fabrication complexity and cost of tandem PSCs. It is necessary to develop tandem PSCs fabricated by a thermal-treatment-free process. In this paper, we report high performance thermal-treatment-free tandem PSCs by developing PFN as buffer layers for both subcells. A power conversion efficiency (PCE) of 10.50% and a high fill factor of 72.44% were achieved by stacking two identical PTB7:PC₇₁BM subcells. When adopting a rear PTB7-Th:PC₇₁BM subcell, the highest PCE of 10.79% was further obtained for the tandem devices. The thermal-treatment-free process is especially applicable to flexible devices, in which plastic substrates are usually used.     

Bottom-contact passivation for high-performance perovskite solar cells using TaCl5-doped SnO2 as electron-transporting layer

Organic-inorganic hybrid perovskite solar cells (PSCs) possess the promising potential to substitute photovoltaic technologies in the traditional model. The modified SnO₂ as an electron-transporting layer (ETL) has been studied extensively because of its excellent properties. Herein, we implemented the TaCl₅ doped SnO₂ ETL in the n-i-p structure perovskite solar cells. The doped SnO₂ solution was demonstrated the characterization of neutral power of value and hydrophobicity. The conduction band of changed ETLs shifted downward by 0.26 eV resulting in the efficient electron transfer. Furthermore, the doped SnO₂ films affect the perovskite crystallite size with passivated traps and reduced nonradiative recombination loss. After employing TaCl₅-doped SnO₂ ETL, the open-circuit voltage enhances from 0.97 to 1.08 V and a united power conversion efficiency increases from 16.38% to 18.23% achieved when adopted 1.0 wt% doped TaCl₅–SnO₂ TEL. The developed doping method provides an effective method to passivate SnO₂ for fabricating high-performance perovskite solar cells.     

Conjugated Small Molecule for Efficient Hole Transport in High‐Performance p‐i‐n Type Perovskite Solar Cells

The π‐conjugated organic small molecule 4,4′‐cyclohexylidenebis[N,N‐bis(4‐methylphenyl) benzenamine] (TAPC) has been explored as an efficient hole transport material to replace poly(3,4‐ethylenedio‐xythiophene):poly(styrenesulfonate) (PEDOT:PSS) in the preparation of p‐i‐n type CH₃NH₃PbI₃ perovskite solar cells. Smooth, uniform, and hydrophobic TAPC hole transport layers can be facilely deposited through solution casting without the need for any dopants. The power conversion efficiency of perovskite solar cells shows very weak TAPC layer thickness dependence across the range from 5 to 90 nm. Thermal annealing enables improved hole conductivity and efficient charge transport through an increase in TAPC crystallinity. The perovskite photoactive layer cast onto thermally annealed TAPC displays large grains and low residual PbI₂, leading to a high charge recombination resistance. After optimization, a stabilized power conversion efficiency of 18.80% is achieved with marginal hysteresis, much higher than the value of 12.90% achieved using PEDOT:PSS. The TAPC‐based devices also demonstrate superior stability compared with the PEDOT:PSS‐based devices when stored in ambient circumstances, with a relatively high humidity ranging from 50 to 85%.