Hole Transport Material Research Articles

Hole-Transporting Materials Based on a Fluorene Unit for Efficient Optoelectronic Devices

Solution-processable hole-transporting materials (HTMs) that form highly soluble films and thermally stable amorphous states are essential for advancing optoelectronic devices. However, the currently commercialized HTM, N,N-bis(3-methylphenyl)-N,N0-bis(phenyl)benzidine (TPD), exhibits poor solubility and limited carrier transport when spin-coated into thin films. Herein, to address these issues, a fluorenyl group was ingeniously incorporated into a series of molecules structurally similar to TPD. The resulting compounds, namely, 2,7-di-(N,N-diphenylamino)-9,9-dimethyl-9H-fluorene (DDF), 2,7-di-p-tolyl-(N,N-diphenylamino)-9,9-dimethyl-9H-fluorene (2M-DDF), and 2,7-di-tetra-p-tolyl-(N,N-diphenylamino)-9,9-dimethyl-9H-fluorene (4M-DDF), offered tunable energy levels, carrier transport, crystallinity, and steric configuration via adjustment of the number of terminal methyl groups. Owing to its satisfactory performance, 2M-DDF can serve as an effective alternative to TPD in OLED devices as well as a guest molecule in host–guest systems for long-afterglow materials. Devices incorporating 2M-DDF as the HTM, with an Alq3 emitter, achieved a maximum CE of 4.78 cd/A and a maximum L (Lmax) of 21,412 cd m−2, with a turn-on voltage (Von) of 3.8 V. The luminous efficiency of 2M-DDF was approximately five times that of TPD (4106 cd m−2). Furthermore, when 2M-DDF and TPD were utilized as guest molecules in afterglow materials, the afterglow duration of 2M-DDF (10 s) was 2.5 times that of TPD (4 s). This study provides a theoretical basis for the development of high-performance HTMs and long-afterglow materials, establishing a framework for the application of fluorene-based compounds in emerging fields such as long-afterglow materials.

Comprehensive device simulation of perovskite solar cell with CuFeO2 as hole transport layer

Abstract Solid-state organic-inorganic halide perovskite solar cells have attracted increasing interest due to their potential as high-efficiency, low-cost photovoltaic devices. In this study, we comprehensively simulate CH₃NH₃PbI₃ perovskite-based solar cells with CuFeO₂ as the hole transport material (HTM) layer, and compare them to cells using Spiro-OMETAD and Cu₂O as HTM layers, utilizing SCAPS-1D software. The effects of absorber thickness, back contact work function, CuFeO₂ thickness, acceptor concentration, and defect density at the CH₃NH₃PbI₃/CuFeO₂ interface are analyzed. The results indicate that delafossite CuFeO₂ is a promising HTM that could significantly enhance the performance of perovskite-based solar cells. TiO₂/CH₃NH₃PbI₃/CuFeO₂ solar cells demonstrate comparable photovoltaic performance to those using traditional Spiro-OMETAD when the back contact electrode work function exceeds 4.9 eV, and superior performance compared to those with Cu₂O and Spiro-OMETAD at work functions below 4.8 eV. A high acceptor concentration exceeding 10¹⁶ cm⁻³ in CuFeO₂ is recommended to achieve optimal photovoltaic performance. These simulation results highlight the significant potential of employing CuFeO₂ as an HTM layer in CH₃NH₃PbI₃ perovskite-based solar cells as an alternative to the organic Spiro-OMETAD.

Molecular Engineering of Oxadiazole-based Small Organic-Functional Molecules as Hole Transporting Materials for Dopant-free Perovskite Solar Cells

The present investigation concerns the synthesis and characterization of new hole-transporting materials (HTMs) for dopant free perovskite solar cells (PSCs). In this work, emphasis is placed on three new HTMs, specifically materials P-H, P-OMe, and P-CN, whose center-core is 2,2'-(4,8-bis(octyloxy)benzo[1,2-b:4,5-b']dithiophene (OBDT) and combined with two donor units of substituted triphenylamine as at both ends along with oxadiazole acceptor units in between donor and OBDT. The fabrication of perovskite solar cell devices using new HTMs and compared the power conversion performance with the standard spiro-OMeTAD HTM. Several spectroscopic techniques were utilized to characterize the properties of the new HTMs, such as FESEM analysis of thin-film morphologies, time-dependent photoluminescence (PL) spectra, and mobility measurements. The HTMs P-OMe established a compressed and steady protective layer on the perovskite layer. This layer contributed to the development of open-circuit voltage (VOC) and short-circuit current density (JSC), both of which are crucial for accomplishing high power conversion efficiency (PCE) in PSCs. The PSC device integrating the P-OMe HTM displayed a superior PCE of 21.14% over an active area of 0.22 cm2. This activity was related to the standard device that utilized the standard Spiro-OMeTAD HTM, which accomplished a PCE of 17.46 %. The improved devices with the P-OMe HTM continued about 90% of their initial PCE throughout maximum power point tracking (MPPT) for 90 days. Furthermore, these devices engaged in their activity over a further 2160 hours under various temperature settings (25 °C and 35 °C), probably because of the hydrophobic property of the HTM.

BCP Buffer Layer Enables Efficient and Stable Dopant-Free P3HT Perovskite Solar Cells.

Poly(3-hexylthiophene) (P3HT) has garnered significant attention as a novel hole transport material (HTM). Principally, its cost-effective synthesis, excellent hole conductivity, and stable film morphology make it one of the most promising HTMs for perovskite solar cells (PSCs). However, the efficiency of PSCs employing P3HT remains less than ideal, primarily due to the mismatch of energy levels and insufficient interface contact between P3HT and the perovskite film. In this work, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline (BCP) was inserted into the P3HT/perovskite interface for effectively alleviating the recombination loss. BCP could effectively anchor uncoordinated Pb2+ and establish π-π stacking interactions with P3HT. These interactions not only neutralize flaws to reduce energy depletion but also enhance the configuration of P3HT, aiding in carrier transfer. Consequently, the BCP-modified device achieved an efficiency of 19.27%, which is significantly superior to the control device (12%).

Fabrication of High-Efficiency Perovskite Solar Cells using Benzodithiophene-Based Random Copolymeric Hole Transport Material

The design of donor-acceptor based random copolymers-type hole transporting materials (HTMs) are important for achieving superior performance of perovskite solar cells (PSCs) with high durability. In this work, a 2-alkylthienyl-substituted benzodithiophene (BDTT)-based random copolymer (denoted as RCP-BDTTPD), containing 2-ethylhexylthiophene-substituted benzo[1,2-b:4,5-b′]dithiophene (BDTT as an electron-donor; M1) and two different side-chain functionalized thieno[3,4-c]-pyrrole-4,6-dione as the electron-acceptors (M2 and M3), is prepared and applied as an efficient interfacial HTM for PSCs. The optical, electrochemical, and electronic properties of RCP-BDTTPD is shown to be structurally and energetically viable to serve as HTM for PSCs. The RCP-BDTTPD has deeper highest occupied molecular orbitals (HOMO; -5.53 eV) and lowest unoccupied molecular orbitals (LUMO; -3.57 eV) energy levels. This is shown to be energetically suitable for realizing better compatibility with Cs-containing formamidinium/methylammonium (FAMA) mixed-cation perovskite as light absorber having HOMO energy level (-5.85 eV). The RCP-BDTTPD possessing gradient band alignment with perovskite, which is shown to be highly significant for the extraction of charge carriers, resulting in higher hole mobility of PSCs. RCP-BDTTPD delivered a reasonably good Voc of 1.10 V and higher Jsc of 19.01 mAcm−2 and, champion power conversion efficiency (PCE) up to 15.30% with hole mobility (1.34×10−3 cm2V−1s−1) and high durability (Encapsulated cell retention of its PCE about 98% over 16 hours under harsh environment: Temp. ∼85 °C, RH∼85%). This work demonstrating a potential application of RCP-BDTTPD based HTMs for the fabrication of high-performance PSCs with high durability as well as low cost.

Tuning anchoring groups of “Y-Type” self-assembled hole transport materials for interface passivation in inverted perovskite solar cells

Tuning anchoring groups of “Y-Type” self-assembled hole transport materials for interface passivation in inverted perovskite solar cells

Small Molecular Dibenzo[b,d]thiophene-Based Hole Transport Materials for Tin-Lead Perovskite Solar Cell.

The most commonly used hole transport material (HTM) in tin-lead (Sn-Pb) perovskite solar cells (PSCs) is the aqueous poly(3,4-ethylenedioxythiophene):polystyrenesulfonate (PEDOT:PSS), and its inherent hygroscopic and acidic features greatly limit the power conversion efficiency (PCE) and stability of PSCs. Concerning this, by selecting dibenzo[b,d]thiophene 5,5-dioxide (DBTDO) as the core and engineering the donor units, 4-methoxy-N-(4-methoxyphenyl)-N-phenylaniline (TPA) and N1-(4-(bis(4-methoxyphenyl)amino)phenyl)-N4,N4-bis(4-methoxyphenyl)benzene-1,4-diamine (DTPA) as peripheral groups, two alternative HTMs are reported. Among them, the HTM TPA-DBTDO-DTPA can form a smoother film, which is conducive to the growth of dense perovskite film on it and shows the most suitable energy level. Meanwhile, the sulfonyl unit can passivate the buried defects of perovskite and improve the open-circuit voltage (VOC) of Sn-Pb mixed PSCs. Correspondingly, the TPA-DBTDO-DTPA-based PSC achieves a champion power conversion efficiency of 22.6% and maintains 75.9% of the initial PCE after aging 1000 h in a nitrogen (N2) environment, which fully outperforms the PEDOT:PSS-based control device.

Advancements in Carbazole-Based Sensitizers and Hole-Transport Materials for Enhanced Photovoltaic Performance

Carbazole-based molecules play a significant role in dye-sensitized solar cells (DSSCs) due to their advantageous properties. Carbazole derivatives are known for their thermal stability, high hole-transport capability, electron-rich (p-type) characteristics, elevated photoconductivity, excellent chemical stability, and commercial availability. This review focuses on DSSCs, including their structures, working principles, device characterization, and the photovoltaic performance of carbazole-based derivatives. Specifically, it covers compounds such as 2,7-carbazole and indolo[3,2-b]carbazole, which are combined with various acceptors like benzothiadiazole, thiazolothiazole, diketopyrrolopyrrole, and quinoxaline, as reported over the past decade. The review will also outline the relationship between molecular structure and power-conversion efficiencies. Its goal is to summarize recent research and advancements in carbazole-based dyes featuring a D-π-A architecture for DSSCs. Additionally, this review addresses the evolution of carbazole-based hole-transport materials (HTMs), which present a promising alternative to the costly spiro-OMeTAD. We explore the development of novel HTMs that leverage the unique properties of carbazole derivatives to enhance charge transport, stability, and overall device performance. By examining recent innovations and emerging trends in carbazole-based HTMs, we provide insights into their potential to reduce costs and improve the efficiency of DSSCs.

Microscopic analysis of low but stable perovskite solar cell device performance using electron spin resonance

Perovskite solar cells have attracted much attention as next-generation solar cells. However, a typical hole-transport material, spiro-OMeTAD, has associated difficulties including tedious synthesis and high cost. To overcome these shortcomings, an easily synthesized and low-cost hole-transport material has been developed: HND-2NOMe. Although HND-2NOMe has high local charge mobility because of the quasi-planar structure, its lower device performance is a weak point, the cause of which has not yet been clarified. Here, we analyse the source of the lower performance by clarifying the internal states from a microscopic viewpoint using electron spin resonance. We observe hole diffusion from perovskite to HND-2NOMe under dark conditions, indicating hole barrier formation at the perovskite/HND-2NOMe interface, leading to lower performance. Although such a barrier is formed, less hole accumulation for the HND-2NOMe-based cells under solar irradiation occurs, which is related to the stable performance. The sources of the lower but stable performance are crucially important for providing guidelines for improving the device performance.

π-Conjugation-Induced In Situ Nanoscale Ordering of Spiro-OMeTAD Boosts the Efficiency and Stability of Perovskite Solar Cells.

Spiro-OMeTAD hole transport materials typically exhibit an amorphous state in perovskite solar cells. However, the lack of structural ordering leads to weak intermolecular interaction, inferior carrier transfer, and poor stability in devices. Herein, we developed a π-conjugation-induced short-range ordering strategy to modulate the stacking order of spiro-OMeTAD during film formation. A clear molecular ordering at the nanoscale is observed, which enhances intermolecular π-π stacking in spiro-OMeTAD and enables effective carrier extraction and favorable energy level alignment. The nanoscale-ordered spiro-OMeTAD allows the achievement of perovskite solar cells with a champion efficiency of 25.37%, surpassing devices utilizing amorphous spiro-OMeTAD (23.52%). The unencapsulated device demonstrates enhanced operational stability by retaining 98% of its initial efficiency under continuous 1 sun equivalent illumination at 60 °C for 840 h. This work establishes a significant and valid modulation concept for the stacking order of organic transport materials, paving the way for the development of efficient and stable perovskite solar cells.

Improved Charge‐Transfer Doping in Crystalline Polymer for Efficient and Stable Perovskite Solar Cells

AbstractPerovskite solar cells (PSCs) have significant potential for next‐generation photovoltaic technology applications. However, the instability of hole transport layers (HTLs) becomes the major obstacle to long‐term operational devices, which are affected by the intrinsic thermal instability and loose structure of hole transport materials, as well as the hygroscopicity and migration of dopants. Here, poly(3‐hexylthiophene‐2,5‐diyl) (P3HT) is used as a model crystalline polymer to thoroughly investigate effective p‐type doping strategies and the underlying mechanism. According to Hard–Soft‐Acid–Base theory, the soft base P3HT is more likely to form a stable Lewis acid–base adduct with the reactive soft acid radical, resulting in a strong charge‐transfer interaction, thereby enhancing conductivity and regulating the energy band of the HTL. Meanwhile, the radical cation salt can promote pre‐nucleation to optimize the crystallization orientation of P3HT. The resulting PSCs exhibited the efficiency of 25.16%, which is the highest efficiency reported so far based on doped P3HT. In addition, the resulting devices demonstrated excellent stability, maintaining 96.5%, 96%, and 91% of their initial efficiency after aging under continuous illumination for 2028 h, at 85 °C for 1080 h, and at maximum power point (MPP) tracking under continuous 1 Sun illumination at 85 °C for 528 h, respectively.

Tailored Polymer Hole-Transporting Materials with Multisite Passivation Functions for Effective Buried-Interface Engineering of Inverted Quasi-2D Perovskite Solar Cells.

Although quasi-2D Ruddlesden‒Popper (RP) perovskite exhibits advantages in stability, their photovoltaic performance are still inferior to 3D counterparts. Optimizing the buried interface of RP perovskite and suppress energetic losses can be a promising approach for enhancing efficiency and stability of inverted quasi-2D RP perovskite solar cells (PSCs). Among which, constructing polymer hole-transporting materials (HTMs) with defect passivation functions is of great significance for buried-interface engineering of inverted quasi-2D RP PSCs. Herein, by employing side-chain tailoring strategy to extend the π-conjugation and regulate functionality of side-chain groups, target polymer HTMs (PVCz-ThSMeTPA and PVCz-ThOMeTPA) with high mobility and multisite passivation functions are achieved. The presence of more sulfur atom-containing groups in side-chain endows PVCz-ThSMeTPA with increased intra/intermolecular interaction, appropriate energy level, and enhanced buried interfacial interactions with quasi-2D RP perovskite. The hole mobility of PVCz-ThSMeTPA is up to 9.20×10-4 cm2 V-1 S-1. Furthermore, PVCz-ThSMeTPA as multifunctional polymer HTM with multiple chemical anchor sites for buried-interface engineering of quasi-2D PSCs can enable effective charge extraction, defects passivation, and perovskite crystallization modulation. Eventually, the PVCz-ThSMeTPA-based inverted quasi-2D PSC achieves a champion power conversion efficiency of 22.37%, which represents one of the highest power conversion efficiencies reported to date for quasi-2D RP PSCs.

Halogen-Bonded Hole-Transport Material Enhances Open-Circuit Voltage of Inverted Perovskite Solar Cells.

Interfacial properties of a hole-transport material (HTM) and a perovskite layer are of high importance, which can influence the interfacial charge transfer dynamics as well as the growth of perovskite bulk crystals particularly in inverted structure. The halogen bonding (XB) has been recognized as a powerful functional group to be integrated with new small molecule HTMs. Herein, a carbazole-based halo (iodine)-functional HTM (O1), is synthesized for the first time, demonstrating a high hole mobility and suitable energy levels that align well with those of perovskites. The strong interaction between O1 and perovskite, i.e., I···I-, induces the formation of an ordered interlayer, which are verified by both theoretical and experimental studies. Compared to the reference HTM (O2) without any halo-function, the XB-induced interlayer effectively enhances the interfacial charge extraction efficiency, while significantly hindering the non-radiative charge recombination by reducing the surface traps upon the strong passivation effect. This is reflected as a big increase in the open-circuit voltage by up to 114mV in the fabrication of inverted devices with the highest power conversion efficiency of 22.34%. Moreover, the ordered XB-driven interlayer at the interface of O1 and perovskite is mainly responsible for the extended lifespan under the operational conditions.

Dopant-Free Hole Transport Material Based on Non-Covalent Interaction for Efficient Perovskite Solar Cells.

Hole transport materials (HTMs) have a critical impact on the performance of perovskite solar cells (PSCs). Especially, the dopant-free HTMs could avoid the usage of hygroscopic dopants and reduce costs, which are important for device stability. Most of the current organic dopant-free HTMs are polycyclic aromatic hydrocarbons-based planar conjugated structures. Yet, the synthesis of conjugated fused heterocycles is often complicated. In this work, intramolecular non-covalent interaction is introduced to construct two organic HTMs (DCT and DTC), which can be facilely obtained through simple reactions. Compared to DTC with hexyl chain on the central benzene ring, DCT with hexyloxy chains shows better planarity in the core structure, as a result of the intramolecular non-covalent interactions between oxygen on hexyloxy and sulfur atom on the adjacent thiophene, as reflected from its single crystal structure. Moreover, DCT in a pristine state shows a decent hole mobility comparable to the doped Spiro-OMeTAD. Ultimately, conventional devices using dopant-free DCT as HTM show a high efficiency of 22.50%, with excellent long-term stability, and light and thermal stability. The results show that the noncovalent interaction is a useful and simple design strategy for dopant-free HTMs, that can effectively improve the efficiency and stability of PSCs.

Understanding the Role of Organic Hole Transport Layers on Pinhole Blocking and Performance Improvement in Sb2Se3 Solar Cells

AbstractSb2Se3 is an emerging semiconductor which has shown promise for low‐cost photovoltaic applications. After successive record‐efficiencies using a range of device structures, spiro‐OMeTAD has emerged as the default hole transport material (HTM), however, the function of HTM layers remains poorly understood. Here, thin‐film Sb2Se3 solar cells are fabricated with which three organic HTM layers ‐ namely P3HT, PCDTBT, and spiro‐OMeTAD are investigated. By comparing these against one another, and to a reference device, their role in the device stack are clarified. These organic HTM layers are found to serve a dual purpose, increasing both the average and peak efficiency by simultaneously blocking pinholes and improving the band alignment at the back contact, with marginal differences in performance between the different HTMs. This produced a champion device of 7.44% using P3HT, resulting from an improvement in all performance parameters. A more complex processing route, run‐to‐run variability, and lower overall device performance compared to the other organics challenge the assumption that spiro‐OMeTAD is the optimal HTM for Sb2Se3 devices. A Schottky barrier at the Au‐Sb2Se3 contact despite the deep work function of gold implies Fermi level pinning due to a defective interface, which each of the organic HTMs are equally capable of alleviating.

Structurally Compact Penta(N,N-diphenylamino)corannulene as Dopant-free Hole Transport Materials for Stable and Efficient Perovskite Solar Cells.

Hole transport materials (HTMs) are essential for improving the stability and efficiency of perovskite solar cells (PSCs). In this study, we have designed and synthesized a novel organic small molecule HTM, cor-(DPA)5, characterized by a bowl-shaped core with symmetric five diphenylamine groups. Compared to already-known HTMs, the bowl-shaped and relatively compact structure of cor-(DPA)5 facilitates intermolecular π-π interactions, promotes film formations, and enhances charge transport. Consequently, the cor-[DPA(2)]5 HTM exhibits high charge mobility, exceptional hydrophobicity, and a significantly elevated glass transition temperature. Superior to previously reported HTMs such as spiro-OMeTAD and cor-OMePTPA, our newly synthesized cor-(DPA)5 HTM is free from any ionic dopants. As a result, the dopant-free cor-[DPA(2)]5-based PSC demonstrates an impressive efficiency of 24.01%, and exhibits outstanding operational stability. It retains 96% after continuous exposure to 1 sun irradiation for 800 hours under MPP (maximum power point) tracking in ambient air. These findings present a structurally compact novel HTM and exemplify a new approach to the molecular design of HTM for the development of stable and effective PSCs.

Structurally Compact Penta(N,N‐diphenylamino)corannulene as Dopant‐free Hole Transport Materials for Stable and Efficient Perovskite Solar Cells

Hole transport materials (HTMs) are essential for improving the stability and efficiency of perovskite solar cells (PSCs). In this study, we have designed and synthesized a novel organic small molecule HTM, cor‐(DPA)5, characterized by a bowl‐shaped core with symmetric five diphenylamine groups. Compared to already‐known HTMs, the bowl‐shaped and relatively compact structure of cor‐(DPA)5 facilitates intermolecular π–π interactions, promotes film formations, and enhances charge transport. Consequently, the cor‐[DPA(2)]5 HTM exhibits high charge mobility, exceptional hydrophobicity, and a significantly elevated glass transition temperature. Superior to previously reported HTMs such as spiro‐OMeTAD and cor‐OMePTPA, our newly synthesized cor‐(DPA)5 HTM is free from any ionic dopants. As a result, the dopant‐free cor‐[DPA(2)]5‐based PSC demonstrates an impressive efficiency of 24.01%, and exhibits outstanding operational stability. It retains 96% after continuous exposure to 1 sun irradiation for 800 hours under MPP (maximum power point) tracking in ambient air. These findings present a structurally compact novel HTM and exemplify a new approach to the molecular design of HTM for the development of stable and effective PSCs.

Asymmetric phthalocyanine-based hole-transporting materials: evaluating the role of heterocyclic units and PMMA additive.

Two novel asymmetric phthalocyanine derivatives, ZnPc-1 and ZnPc-2, are synthesized to enhance charge transfer properties and mitigate deep-level traps on the perovskite surface using electron-rich nitrogen atoms. PSCs with ZnPc-1 and ZnPc-2 as hole-transporting materials (HTMs) achieved power conversion efficiencies (PCEs) of 12.11% and 8.98%, respectively. Incorporating a small amount of PMMA into the HTM solution significantly improved performance, resulting in PCEs of 16.2% and 12.5% for ZnPc-1 and ZnPc-2, respectively. The addition of PMMA enhances conductivity and prevents moisture intrusion, boosting both the efficiency and stability of PSCs.

Efficient and Stable Inverted Perovskite Solar Cells Enabled by a Fullerene‐Based Hole Transport Molecule

AbstractDesigning an efficient modification molecule to mitigate non‐radiative recombination at the NiOx/perovskite interface and improve perovskite quality represents a challenging yet crucial endeavor for achieving high‐performance inverted perovskite solar cells (PSCs). Herein, we synthesized a novel fullerene‐based hole transport molecule, designated as FHTM, by integrating C60 with 12 carbazole‐based moieties, and applied it as a modification molecule at the NiOx/perovskite interface. The in situ self‐doping effect, triggered by electron transfer between carbazole‐based moiety and C60 within the FHTM molecule, along with the extended π conjugated moiety of carbazole groups, significantly enhances FHTM's hole mobility. Coupled with optimized energy level alignment and enhanced interface interactions, the FHTM significantly enhances hole extraction and transport in corresponding devices. Additionally, the introduced FHTM efficiently promotes homogeneous nucleation of perovskite, resulting in high‐quality perovskite films. These combined improvements led to the FHTM‐based PSCs yielding a champion efficiency of 25.58 % (Certified: 25.04 %), notably surpassing that of the control device (20.91 %). Furthermore, the unencapsulated device maintained 93 % of its initial efficiency after 1000 hours of maximum power point tracking under continuous one‐sun illumination. This study highlights the potential of functionalized fullerenes as hole transport materials, opening up new avenues for their application in the field of PSCs.

Towards device stability of perovskite solar cells through low-cost alkyl-terminated SFX-based hole transporting materials and carbon electrodes

Developing cost-effective, high-efficiency, and stable hole transporting materials (HTMs) is crucial for replacing traditional spiro-OMeTAD in perovskite solar cells (PSCs) and achieving sustainable solar energy solutions. This work presents two novel air-stable HTMs based on a spiro[fluorene-9,9′-xanthene] (SFX) core functionalized with N-methylcarbazole (XC2-M) and N-hexylcarbazole (XC2-H) rings. These HTMs were synthesized via a straightforward, three-step process with good overall yields (∼40%) and low production costs. To further reduce device cost, carbon back electrodes were employed. The resulting PSCs, with a structure of FTO/SnO2/Cs0.05FA0.73MA0.22Pb(I0.77Br0.23)3/HTM/C achieved power conversion efficiencies (PCEs) of 13.5% (XC2-M) and 10.2% (XC2-H), comparable to the reference spiro-OMeTAD device (12.2%). The choice of alkyl chain on the HTM significantly impacts film morphology and device stability. The XC2-H device exhibited exceptional long-term stability, retaining approximately 90% of its initial PCE after 720 h of storage in 30–40% humidity air without encapsulation. This surpasses the performance of both the spiro-OMeTAD (55% retention) and XC2-M (68% retention) devices. The superior stability of XC2-H is attributed to its highly hydrophobic nature and the formation of a compact, smooth film due to interdigitation of the hexyl chains. The straightforward synthesis of XC2-H from commercially available materials offers a promising approach for large-scale PSC production.