Dopant‐Free Squaraine‐Based Polymeric Hole‐Transporting Materials with Comprehensive Passivation Effects for Efficient All‐Inorganic Perovskite Solar Cells

Development of high‐performance dopant‐free hole‐transporting materials (HTMs) with comprehensive passivation effects is highly desirable for all‐inorganic perovskite solar cells (PVSCs). Squaraines (SQs) could be a candidate for dopant‐free HTMs as they are natural passivators for perovskites. One major limitation of SQs is their relatively low hole mobility. Herein we demonstrate that polymerizing SQs into pseudo two dimensional (2D) p–π conjugated polymers could overcome this problem. By rationally using N,N‐diarylanilinosquaraines as the comonomers, the resulting polysquaraine HTMs not only exhibit suitable energy levels and efficient passivation effects, but also achieve very high hole mobility close to 0.01 cm^?2 V^?1 s^?1. Thus as dopant‐free HTMs for α‐CsPbI₂Br‐based all‐inorganic PVSCs, the best PCE reached is 15.5 %, outperforming those of the doped‐Spiro‐OMeTAD (14.4 %) based control devices and among the best for all‐inorganic PVSCs.     

Recent advances in the design of dopant-free hole transporting materials for highly efficient perovskite solar cells

This review gives an overview of the latest advances in dopant-free hole transporting materials (HTMs) for perovskite solar cells and discusses the new molecular design strategies towards efficient and stable dopant-free HTMs.     

Dithieno[3,2‐b:2′,3′‐d]pyrrole Cored p‐Type Semiconductors Enabling 20 % Efficiency Dopant‐Free Perovskite Solar Cells

Organic p‐type semiconductors with tunable structures offer great opportunities for hybrid perovskite solar cells (PVSCs). We report herein two dithieno[3,2‐b:2′,3′‐d]pyrrole (DTP) cored molecular semiconductors prepared through π‐conjugation extension and an N‐alkylation strategy. The as‐prepared conjugated molecules exhibit a highest occupied molecular orbital (HOMO) level of ?4.82 eV and a hole mobility up to 2.16×10^?4 cm² V^?1 s^?1. Together with excellent film‐forming and over 99 % photoluminescence quenching efficiency on perovskite, the DTP based semiconductors work efficiently as hole‐transporting materials (HTMs) for n‐i‐p structured PVSCs. Their dopant‐free MA_0.7FA_0.3PbI_2.85Br_0.15 devices exhibit a power conversion efficiency over 20 %, representing one of the highest values for un‐doped molecular HTMs based PVSCs. This work demonstrates the great potential of using a DTP core in designing efficient semiconductors for dopant‐free PVSCs.     

Engineering of dendritic dopant-free hole transport molecules:enabling ultrahigh fill factor in perovskite solar cells with optimized dendron construction

Developing dopant-free hole-transporting materials(HTMs)for high-performance perovskite solar cells(PVSCs)has been a very active research topic in recent years since HTMs play a critical role in optimizing interfacial charge carrier kinetics and in turn determining device performance.Here,a novel dendritic engineering strategy is first utilized to design HTMs with a D-A type molecular framework,and diphenylamine and/or carbazole is selected as the building block for constructing dendrons.All HTMs show good thermal stability and excellent film morphology,and the key optoelectronic properties could be fine-tuned by varying the dendron structure.Among them,MPA-Cz-BTI and MCz-Cz-BTI exhibit an improved interfacial contact with the perovskite active layer,and non-radiative recombination loss and charge transport loss can be effectively suppressed.Consequently,high power conversion efficiencies(PCEs)of 20.8%and 21.35%are achieved for MPA-Cz-BTI and MCz-Cz-BTI based devices,respectively,accompanied by excellent long-term storage stability.More encouragingly,ultrahigh fill factors of 85.2%and 83.5%are recorded for both devices,which are among the highest values reported to date.This work demonstrates the great potential of dendritic materials as a new type of dopant-free HTMs for high-performance PVSCs with excellent FF.     

Promising hole-transporting materials for perovskite solar cells: Modulation of the electron-deficient units in triphenylamine derivative-based molecules

Modulation of the electron-deficient π-bridge units in 4-methoxy-N-(4-methoxyphenyl)-N-phenylbenzenamine (MeTPA)-based hole-transporting materials (HTMs) is a significant approach to improve hole mobility of HTMs for perovskite solar cells (PSCs). In this study, a class of simple MeTPA-based HTMs (H1-H4) with different π-bridged electron-deficient units were designed for the purpose of providing a theoretical model to obtain potential MeTPA-based HTMs. The results indicated that H2 to H4 exhibit better performance, such as larger Stokes shifts, smaller exciton-binding energy, better stability, good solubility, and higher hole mobility, in comparison with the parental material H1. H2 to H4 materials with high hole mobility (5.45 × 10⁻⁴, 2.70 × 10⁻¹, and 3.99 × 10⁻³ cm² V⁻¹ second⁻¹, respectively) may embody promising HTMs to yield good performance in PSCs. Therefore, the useful information obtained regarding control of the electron-deficient π-bridge units of MeTPA-based HTMs is an effective way to obtain excellent HTMs for PSC applications.     

Tuning Hole Transport Properties via Pyrrole Derivation for High-Performance Perovskite Solar Cells

Hole transport materials (HTMs) with high hole mobility, good band alignment and ease of fabrication are highly desirable for perovskite solar cells (PSCs). Here, we designed and synthesized novel organic HTMs, named T3, which can be synthesized in high yields with commercially available materials, featuring a substituted pyrrole core and triphenylamine peripheral arms. The capability of functionalization in the final synthetic step provides an efficient way to obtain a variety of T3-based HTMs with tunable energy levels and other properties. Among them, fluorine-substituted T3 (T3-F) exhibits the best band alignment and hole extraction properties, leading to PSCs with outstanding PCEs of 24.85 % and 24.03 % (certified 23.46 %) for aperture areas of 0.1 and 1 cm², respectively. The simple structure and tunable performance of T3 can inspire further optimization for efficient PSCs.     

Porphyrin Supramolecule as Surface Carrier Modulator Imparts Hole Transporter with Enhanced Mobility for Perovskite Photovoltaics

Modulating the surface charge transport behavior of hole transport materials (HTMs) would be as an potential approach to improve their hole mobility, while yet realized for fabricating efficient photovoltaic devices. Here, an oxygen bridged dimer-based monoamine Fe^III porphyrin supramolecule is prepared and doped in HTM film. Theoretical analyses reveal that the polaron distributed on dimer can be coupled with the parallel arranged polarons on adjacent dimers. This polaron coupling at the interface of supramolecule and HTM can resonates with hole flux to increase hole transport efficiency. Mobility tests reveal that the hole mobility of doped HTM film is improved by 8-fold. Doped perovskite device exhibits an increased efficiency from 19.8 % to 23.2 %, and greatly improved stability. This work provides a new strategy to improve the mobility of HTMs by surface carrier modulation, therefore fabricating efficient photovoltaic devices.     

Low-cost Cu-based inorganic hole transporting materials in perovskite solar cells: Recent progress and state-of-art developments

Perovskite solar cells (PSCs) are rapidly approaching as promising processes toward efficient energy harvesting technologies. High cost and low environmentally stable organic hole transporting materials (HTMs) are the main hurdles in their commercial realization. Perovskite community is actively looking for inorganic HTMs which will potentially yield into a pragmatic solution. Cu-based materials, e.g. Cu-based oxides, halides, and chalcogenides exhibit features like low production cost, suitable band alignment, and high hole mobility Due to these properties, Cu-based materials are being explored as potential HTMs in PSCs. Significant efforts are contributed toward using low-cost Cu-based materials because of high chemical stability, high carrier mobility, low-cost and the possibility of developing a very simple technique. The photo-physical properties, e.g. optical electronic structure, valence band engineering, and carrier mobility are briefly discussed. Detailed insights toward understanding the development of Cu-based HTMs along with their possible pragmatic commercialization aspects are presented. This article highlights the utilization of Cu-based chalcogenide HTM and role of ternary Cu-based chalcopyrite, Pnma ternary chalcogenides, sulvanite and oxychalcogenides in the field of PSC with a brief idea about tailoring their optoelectronic properties. This article will significantly help the community toward the engineering of novel Cu-based HTMs for possible commercialization of PSC technology.     

Semi‐Locked Tetrathienylethene as a Building Block for Hole‐Transporting Materials: Toward Efficient and Stable Perovskite Solar Cells

The construction of state‐of‐the‐art hole‐transporting materials (HTMs) is challenging regarding the appropriate molecular configuration for simultaneously achieving high morphology uniformity and charge mobility, especially because of the lack of appropriate building blocks. Herein a semi‐locked tetrathienylethene (TTE) serves as a promising building block for HTMs by fine‐tuning molecular planarity. Upon incorporation of four triphenylamine groups, the resulting TTE represents the first hybrid orthogonal and planar conformation, thus leading to the desirable electronic and morphological properties in perovskite solar cells (PSCs). Owing to its high hole mobility, deep lying HOMO level, and excellent thin film quality, the dopant‐free TTE‐based PSCs exhibit a very promising efficiency of over 20 % with long‐term stability, achieving to date the best performances among dopant‐free HTM‐based planar n‐i‐p structured PSCs.     

Positional Effect of the Triphenylamine Group on the Optical and Charge‐Transfer Properties of Thiophene‐Based Hole‐Transporting Materials

Hybrid organic‐inorganic perovskite solar cells (PSCs) have shown significant potential for use in the energy field. Typically, hole‐transporting materials (HTMs) play an important role in affecting the power conversion efficiency (PCE) of PSCs. A deep understanding of the structure‐property relationship plays a vital role in developing efficient HTMs. Herein, the relationship between the structure and properties of two small organic HTMs H2,5 and H3,4 were systematically investigated in terms of the electronic and optical properties, the hole‐transporting behavior by using density functional theory (DFT) and Marcus electron transfer theory. The results demonstrated that the high power conversion efficiency of the H2,5‐ based PSC was caused by strong interactions with the perovskite material on the interface and an enhanced hole mobility in H2,5 compared with H3,4 . The strong interaction derives from the short bond length of O atom of HTM and Pb atom of perovskite material, and the highly hole mobility derives from the quasi‐planar conjugated conformation and tight packing model of neighboring molecules in H2,5 . In addition, we found that the planar structure enhances the intermolecular interaction between HTM and perovskite materials compared with the ′V′‐shaped molecule. Importantly, we also note that the HOMO level of the isolated molecule is not always proportional to the open‐circuit voltages of PSCs since the HOMO level might move toward a higher level when the interaction between HTM and interface of perovskite was included. The work gives essential information for rational designing efficient HTMs.     

3,4‐Phenylenedioxythiophene (PheDOT) Based Hole‐Transporting Materials for Perovskite Solar Cells

Two new electron‐rich molecules based on 3,4‐phenylenedioxythiophene (PheDOT) were synthesized and successfully adopted as hole‐transporting materials (HTMs) in perovskite solar cells (PSCs). X‐ray diffraction, absorption spectra, photoluminescence spectra, electrochemical properties, thermal stabilities, hole mobilities, conductivities, and photovoltaic parameters of PSCs based on these two HTMs were compared with each other. By introducing methoxy substituents into the main skeleton, the energy levels of PheDOT‐core HTM were tuned to match with the perovskite, and its hole mobility was also improved (1.33×10^?4 cm² V^?1 s^?1, being higher than that of spiro‐OMeTAD, 2.34×10^?5 cm² V^?1 s^?1). The PSC based on MeO‐PheDOT as HTM exhibits a short‐circuit current density (J_sc) of 18.31 mA cm^?2, an open‐circuit potential (V_oc) of 0.914 V, and a fill factor (FF) of 0.636, yielding an encouraging power conversion efficiency (PCE) of 10.64 % under AM 1.5G illumination. These results give some insight into how the molecular structures of HTMs affect their performances and pave the way for developing high‐efficiency and low‐cost HTMs for PSCs.     

Designing Hole Transport Materials with High Hole Mobility and Outstanding Interface Properties for Perovskite Solar Cells

Organic–inorganic halide perovskite solar cells (PSCs) have attracted much attention due to their rapid increase in power conversion efficiencies (PCEs), and many efforts are devoted to further improving the PCEs. Designing highly efficient hole transport materials (HTMs) for PSCs may be one of the effective ways. Herein we theoretically designed three new HTMs (FDT−N, FDT−O, and FDT−S) by introducing a nitrogen-phenyl group, an oxygen atom, and a sulfur atom into the spiro core of an experimentally synthesized HTM (FDT), respectively. And then we performed quantum chemical calculation to study their application potential. The results show that the devices with FDT−O and FDT−S instead of FDT may have higher open circuit voltages owing to their lower highest occupied molecular orbital (HOMO) energy levels. Moreover, FDT−S exhibits the best hole transport performance among the studied HTMs, which may be due to the significant HOMO-HOMO overlap in the hole hopping path with the largest transfer integral. Furthermore, the results on interface properties indicate that introducing oxygen and sulfur atoms can enhance the MAPbI₃/HTM interface interaction. The present work not only offers two promising HTMs (FDT−O and FDT−S) for PSCs but also provides theoretical help for subsequent research on HTMs.     

Solution-processed CuOx as an efficient hole-extraction layer for inverted planar heterojunction perovskite solar cells

A solution-processed CuO_x film has been successfully integrated as the hole-transporting layer (HTL) for inverted planar heterojunction perovskite solar cells (PVSCs). The CuO_x layer is fabricated by simply spin-coating a copper acetylacetonate (Cu(acac)₂) chloroform solution onto ITO glass with high transparency in the visible range. The compact and pinhole-free perovskite film with large grain domains is grown on the CuO_x film. The inverted PVSCs with the structure of ITO/CuO_x/MAPbI₃/PC₆₁BM/ZnO/Al are fabricated and show a best PCE of 17.43% under standard AM 1.5G simulated solar irradiation with a V_OC of 1.03 V, a J_SC of 22.42 mA cm^-2, and a fill factor of 0.76, which is significantly higher and more stable than that fabricated from the often used hole-transporting material PEDOT:PSS (11.98%) under the same experimental conditions. The enhanced performance is attributed to the efficient hole extraction through the CuO_x layer as well as the high-quality CH₃NH₃PbI₃ films grown on the CuO_x. Our results indicate that low-cost and solution-processed CuO_x film is a promising HTL for high performance PVSCs with better stability.     

有机空穴传输材料在钙钛矿太阳电池中的应用

有机-无机杂化钙钛矿太阳电池(PSCs)由于其诸多优点得到广泛关注,而有机固态空穴传输材料(HTMs)代替液体电解质使其得到飞速的发展,提升了电池的效率和稳定性,已经成为PSCs的重要组成部分。目前应用于PSCs的空穴传输材料分为有机空穴传输材料和无机空穴传输材料两大类。无机空穴传输材料的可选择范围较窄,对应器件的光电转换效率相对较低。开发各类能级匹配、空穴迁移率高的有机空穴传输材料是提高器件效率和稳定性的有效手段,成为相关领域的研究热点。本文依据相对分子质量的大小,将应用于PSCs中的有机空穴传输材料分为小分子类和聚合物类空穴传输材料,详细评述了有机空穴传输材料分子结构对PSCs光电转换效率、填充因子、开路电压、短路电流和稳定性的影响,并对其能级、空穴迁移率的高低、添加剂的使用等进行了讨论。最后详细论述了有机空穴传输材料未来的研究重点和发展趋势。     

Helicenes as All‐in‐One Organic Materials for Application in OLEDs: Synthesis and Diverse Applications of Carbo‐ and Aza[5]helical Diamines

A set of eight helical diamines were designed and synthesized to demonstrate their relevance as all‐in‐one materials for multifarious applications in organic light‐emitting diodes (OLEDs), that is, as hole‐transporting materials (HTMs), EMs, bifunctional hole transporting + emissive materials, and host materials. Azahelical diamines function very well as HTMs. Indeed, with high T_g values (127–214 °C), they are superior alternatives to popular N,N′‐di(1‐naphthyl)‐N,N′‐diphenyl‐(1,1′‐biphenyl)‐4,4′‐diamine (NPB). All the helical diamines exhibit emissive properties when employed in nondoped as well as doped devices, the performance characteristics being superior in the latter. One of the carbohelical diamines (CHTPA) serves the dual function of hole transport as well as emission in simple double‐layer devices; the efficiencies observed were better by quite some margin than those of other emissive helicenes reported. The twisting endows helical diamines with significantly high triplet energies such that they also function as host materials for red and green phosphors, that is, [Ir(btp)₂acac] (btp=2‐(2′‐benzothienyl)pyridine; acac=acetylacetonate) and [Ir(ppy)₃] (ppy=2‐phenylpyridine), respectively. The results of device fabrications demonstrate how helicity/ helical scaffold may be diligently exploited to create molecular systems for maneuvering diverse applications in OLEDs.     

Minimization of Carrier Losses for Efficient Perovskite Solar Cells through Structural Modification of Triphenylamine Derivatives

Three hole transport materials (HTMs) based on a substituted triphenylamine moiety have been synthesized and successfully employed in triple‐cation mixed‐halide PSCs, reaching efficiencies of 19.4 %. The efficiencies, comparable to those obtained using spiro‐OMeTAD, point them out as promising candidates for easily attainable and cost‐effective alternatives for PSCs, given their facile synthesis from commercially available materials. Interestingly, although all these HTMs show similar chemical and physical properties, they provide different carrier recombination kinetics. Our results demonstrate that is feasible through the molecular design of the HTM to minimize carrier losses and, thus, increase the solar cell efficiencies.     

Density functional theory study on electron and hole transport properties of organic pentacene derivatives with electron-withdrawing substituent

Attaching electron-withdrawing substituent to organic conjugated molecules is considered as an effective method to produce n-type and ambipolar transport materials. In this work, we use density functional theory calculations to investigate the electron and hole transport properties of pentacene (PENT) derivatives after substituent and simulate the angular resolution anisotropic mobility for both electron and hole transport. Our results show that adding electron-withdrawing substituents can lower the energy level of lowest unoccupied molecular orbital (LUMO) and increase electron affinity, which are beneficial to the electron injection and ambient stability of the material. Also the LUMO electronic couplings for electron transport in these pentacene derivatives can achieve up to a hundred meV which promises good electron transport mobility, although adding electron-withdrawing groups will introduce the increase of electron transfer reorganization energy. The final results of our angular resolution anisotropic mobility simulations show that the electron mobility of these pentacene derivatives can get to several cm(2) V(-1) s(-1), but it is important to control the orientation of the organic material relative to the device channel to obtain the highest electron mobility. Our investigation provide detailed information to assist in the design of n-type and ambipolar organic electronic materials with high mobility performance.     

Efficient Hole‐Transporting Materials with Triazole Core for High‐Efficiency Perovskite Solar Cells

Efficient hole‐transporting materials (HTMs), TAZ‐[MeOTPA]₂ and TAZ‐[MeOTPATh]₂ incorporating two electron‐rich diphenylamino side arms, through direct linkage or thiophen bridges, respectively, on the C3‐ and C5‐positions of a 4‐phenyl‐1,2,4‐triazole core were synthesized. These synthetic HTMs with donor–acceptor type molecular structures exhibited effective intramolecular charge transfer for improving the hole‐transporting properties. The structural modification of HTMs by thiophene bridging might increase intermolecular π–π stacking in the solid state and afford a better spectral response because of their increased π‐conjugation length. Perovskite‐based cells using TAZ‐[MeOTPA]₂ and TAZ‐[MeOTPATh]₂ as HTMs afforded high power conversion efficiencies of 10.9 % and 14.4 %, respectively, showing a photovoltaic performance comparable to that obtained using spiro‐OMeTAD. These synthetically simple and inexpensive HTMs hold promise for replacing the more expensive spiro‐OMeTAD in high‐efficiency perovskite solar cells.     

Metallated Macrocyclic Derivatives as a Hole – Transporting Materials for Perovskite Solar Cells

Spiro‐OMeTAD is widely used as thehole‐transporting material (HTM) in perovskite solar cells (PSC), which extracts positive charges and protects the perovskite materials from metal electrode, setting a new world‐record efficiency of more than 20 %. Spiro‐OMeTAD layer engross moisture leading to the degradation of perovskite, and therefore, has poor air stability. It is also expensive therefore limiting scale‐up, so macrocyclic metal complex derivatives (MMDs) could be a suitable replacement. Our review covers low‐cost, high yield hydrophobic materials with minimal steps required for synthesis of efficient HTMs for planar/mesostructured PSCs. The MMDs based devices demonstrated PCEs around 19 % and showed stability for a longer duration, indicating that MMDs are a promising alternative to spiro‐OMeTAD and also easy to scale‐up via solution approach. Additionally, this review describes how optical and electrical properties of MMDs change with chemical structure, allowing for the design of novel hole‐mobility materials to achieve negligible hysteresis and act as effective functional barriers against moisture which results in a significant increase in the stability of the device. We provide an overview of the apt green‐synthesis, characterization, stability and implementation of the various classes of macrocyclic metal complex derivatives as HTM for photovoltaic applications.     

Highly efficient perovskite solar cells based on symmetric hole transport material constructed with indaceno[1,2-b:5,6-b']dithiophene core building block

Two novel hole transport materials (HTMs) with indaceno[1,2-b:5,6-b']dithiophene (IDT) as core building blocks,termed IDT1 and IDT2,were designed and synthesized.The side alkyl chains were introduced to regulate and control the morphology and stacking behavior of HTMs,and the peripheral triarylamine arms were introduced to adjust the energy levels and to facilitate efficient hole transport.Applied in mesoporous structured perovskite solar cells (PSCs),HTM IDT1 achieved higher power conversion efficiency (PCE,19.55%) and better stability than Spiro-OMeTAD (19.25%) and IDT2 (15.77%) based PSC.These results suggest the potential of IDTl as a promising HTM for PSCs.