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.     

Green-solvent Processable Dopant-free Hole Transporting Materials for Inverted Perovskite Solar Cells

The commercialization of perovskite solar cells (PVSCs) urgently requires the development of green-solvent processable dopant-free hole transporting materials (HTMs). However, strong intermolecular interactions that ensure high hole mobility always compromise the solubility and film-forming ability in green solvents. Herein, we show a simple but effective design strategy to solve this trade-off, that is, constructing star-shaped D-A-D structure. The resulting HTMs (BTP1-2) can be processed by green solvent of 2-methylanisole (2MA), a kind of food additive, and show high hole mobility and multiple defect passivation effects. An impressive efficiency of 24.34 % has been achieved for 2MA-processed BTP1 based inverted PVSCs, the highest value for green-solvent processable HTMs so far. Moreover, it is manifested that the charge separation of D-A type HTMs at the photoinduced excited state can help to passivate the defects of perovskites, indicating a new HTM design insight.     

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.     

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.     

Polycyclic Arenes Dihydrodinaphthopentacene-based Hole-Transporting Materials for Perovskite Solar Cells Application

In this paper, two D-π-D type compounds, C1 and C2 , containing dihydrodinaphthopentacene (DHDNP) as a π-bridge, p-methoxydiphenylamine and p-methoxytriphenylamine groups as the donor groups were synthesized. The four 4-hexylphenyl groups at the sp³-carbon bridges of DHDNP were acquainted with control morphology and improving solubility. The light absorption, energy level, thermal properties, and application as hole-transporting materials in perovskite solar cells of these compounds were fully investigated. The HOMO/LUMO levels and energy gaps of these DHDNP-based molecules are suitable for use as hole-transporting materials in PSCs. The best power conversion efficiencies of the PVSCs based on the C1 and C2 are 15.96% and 12.86%, respectively. The performance of C1 is comparable to that of the reference compound spiro-OMeTAD (16.38%). Compared with spiro-OMeTAD, the C1 -based PVSC device showed good stability, which was slightly decreased to 98.68% of its initial efficiency after 48 h and retained 81% of its original PCE after 334 h without encapsulation. These results reveal the potential usefulness of the DHDNP building block for further development of economical and highly efficient HTMs for PVSCs.     

Novel Push-Pull Benzodithiophene-Containing Polymers as Hole-Transport Materials for Efficient Perovskite Solar Cells

Donor-acceptor conjugated polymers are considered advanced semiconductor materials for the development of thin-film electronics. One of the most attractive families of polymeric semiconductors in terms of photovoltaic applications are benzodithiophene-based polymers owing to their highly tunable electronic and physicochemical properties, and readily scalable production. In this work, we report the synthesis of three novel push–pull benzodithiophene-based polymers with different side chains and their investigation as hole transport materials (HTM) in perovskite solar cells (PSCs). It is shown that polymer P3 that contains triisopropylsilyl side groups exhibits better film-forming ability that, along with high hole mobilities, results in increased characteristics of PSCs. Encouraging a power conversion efficiency (PCE) of 17.4% was achieved for P3-based PSCs that outperformed the efficiency of devices based on P1, P2, and benchmark PTAA polymer. These findings feature the great potential of benzodithiophene-based conjugated polymers as dopant-free HTMs for the fabrication of efficient perovskite solar cells.     

基于吡嗪空穴传输层的合成及在p-i-n型钙钛矿太阳能电池中的应用

钙钛矿太阳能电池由于具有高的光电转换效率,简单的溶液加工工艺,较低的成本等优势因而拥有广阔的应用前景。有机小分子空穴传输层材料在钙钛矿太阳能电池中扮演着极其重要的角色。在本工作中,我们设计和合成了基于吡嗪为分子中心核,三苯胺为分枝的X型空穴传输层材料PT-TPA。与Si-OMeTPA对比,吡嗪的引入不仅不会影响其结晶性,并且能够改善其电荷转移特性和分子中心共平面性,从而显著提升了PT-TPA的空穴迁移率。在非掺杂的情况之下,基于PT-TPA空穴传输层的p-i-n型钙钛矿太阳能电池展现出17.52%的光电转换效率,与相同条件下基于Si-OMeTPA空穴传输层的器件相比,效率提高了近15%。     

Benzothieno[3,2-b]thiophene-Based Noncovalent Conformational Lock Achieves Perovskite Solar Cells with Efficiency over 24 %

Organic semiconductors with noncovalently conformational locks (OSNCs) are promising building blocks for hole-transporting materials (HTMs). However, lack of satisfied neighboring building blocks negatively impacts the optoelectronic properties of OSNCs-based HTMs and imperils the stability of perovskite solar cells (PSCs). To address this limitation, we introduce the benzothieno[3,2-b]thiophene (BTT) to construct a new OSNC, and the resulting HTM ZS13 shows improved intermolecular charge extraction/transport properties, proper energy level, efficient surface passivation effect. Consequently, the champion devices based on doped ZS13 yield an efficiency of 24.39 % and 20.95 % for aperture areas of 0.1 and 1.01 cm², respectively. Furthermore, ZS13 shows good thermal stability and the capability of inhibiting I⁻ ion migration, thus, leading to enhanced device stability. The success in neighboring-group engineering can triggered a strong interest in developing thienoacene-based OSNCs toward efficient and stable PSCs.     

Inorganic p-type semiconductors and carbon materials based hole transport materials for perovskite solar cells

Incorporation of proper inorganic p-type semiconductors as hole transport layer has great potential to increase long-term stability while maintaining high power conversion efficiency of perovskite solar cells with low material cost.     

Indeno[1,2‐b]carbazole as Methoxy‐Free Donor Group: Constructing Efficient and Stable Hole‐Transporting Materials for Perovskite Solar Cells

With perovskite‐based solar cells (PSCs) now reaching efficiencies of greater than 20 %, the stability of PSC devices has become a critical challenge for commercialization. However, most efficient hole‐transporting materials (HTMs) thus far still rely on the state‐of‐the‐art methoxy triphenylamine (MOTPA) donor unit in which methoxy groups usually reduce the device stability. Herein, a carbazole‐fluorene hybrid has been employed as a methoxy‐free donor to construct organic HTMs. The indeno[1,2‐b]carbazole group not only inherits the characteristics of carbazole and fluorene, but also exhibits additional advantages arising from the bulky planar structure. Consequently, M129, endowed with indeno[1,2‐b]carbazole simultaneously exhibits a promising efficiency of over 20 % and superior long‐term stability. The hybrid strategy toward the methoxy‐free donor opens a new avenue for developing efficient and stable HTMs.     

Recent studies on small molecular and polymeric hole-transporting materials for high-performance perovskite solar cells

A decade of significant research has led to the emergence of photovoltaic solar cells based on perovskites that have achieved an exceptionally high-power conversion efficiency of 26.08%. A key breakthrough in perovskite solar cells (PSCs) occurred when solid hole-transporting materials (HTMs) replaced liquid electrolytes in dye-sensitized solar cells (DSSCs), because HTMs play a crucial role in improving photovoltaic performance as well as cell stability. This review is mainly focused on the HTMs that are responsible for hole transport and extraction in PSCs, which is one of the crucial components for efficient devices. Here, we have reviewed small molecular as well as polymeric HTMs that have been reported in the last two years and discussed their performance based on the analysis of their molecular architectures. Finally, we include a perspective on the molecular engineering of new functional HTMs for highly efficient stable PSCs.     

Structurally-tuned benzo[1,2-b:4,5:b']dithiophene-based polymer as a dopant-free hole transport material for perovskite solar cells

For highly efficient and stable perovskite solar cells (PSCs), hole transport material (HTM) should be designed and synthesized to afford suitable energy levels, high charge transport, efficient passivation ability, and high device stability. Here, we systematically modulated benzo[1,2-b:4,5:b']dithiophene-based polymer by finely controlling the thienyl and pyridyl contents within the conjugated backbone in order to develop a high performance dopant-free HTM for PSCs. We found that the optimized copolymer with 25% of pyridine content exhibits improved energy level, charge transport, and morphology compared with control homopolymers. As a result, remarkably high power conversion efficiencies up to 21.1% were achieved by employing the optimized polymer as a dopant-free HTM in 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.     

Hexaazatrinaphthylene Derivatives: Efficient Electron‐Transporting Materials with Tunable Energy Levels for Inverted Perovskite Solar Cells

Hexaazatrinaphthylene (HATNA) derivatives have been successfully shown to function as efficient electron‐transporting materials (ETMs) for perovskite solar cells (PVSCs). The cells demonstrate a superior power conversion efficiency (PCE) of 17.6 % with negligible hysteresis. This study provides one of the first nonfullerene small‐molecule‐based ETMs for high‐performance p–i–n PVSCs.     

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.     

Dopant-free NiOx Nanocrystals: A Low-cost and Stable Hole Transport Material for Commercializing Perovskite Optoelectronics

Advancing inverted (p-i-n) perovskite solar cells (PSCs) is critical for commercial applications given their compatibility with different bottom cells for tandem photovoltaics, low-temperature processability (≤100 °C), and promising operational stability. Although inverted PSCs have achieved an efficiency of over 25 % using doped or expensive organic hole transport materials (HTMs), their synthesis cost and stability still cannot meet the requirements for their commercialization. Recently, dopant-free and low-cost non-stoichiometric nickel oxide nanocrystals (NiO_x NCs) have been extensively studied as a low-cost and effective HTM in perovskite optoelectronics. In this minireview, we summarize the synthesis and surface-functionalization methods of NiO_x NCs. Then, the applications of NiO_x NCs in other perovskite optoelectronics beyond photovoltaics are discussed. Finally, we provide a perspective for the future development of NiO_x NCs for the commercialization of perovskite optoelectronics.     

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.     

A new strategy for constructing a dispiro-based dopant-free hole-transporting material: spatial configuration of spiro-bifluorene changes from a perpendicular to parallel arrangement

Due to the low intrinsic hole mobility caused by the orthogonal conformation of two fluorene units in Spiro-OMeTAD which is a classic hole-transporting material (HTM) in perovskite solar cells (PSCs), Spiro-OMeTAD based PSCs generally can only obtain high performances through a sophisticated doping process with dopants/additives, which adds to the cost and complicacy of device fabrication, and also adversely affects the stability of PSC devices. Herein, a novel dispiro-based HTM, WH-1, is designed by cleverly replacing the central carbon atom of Spiro-OMeTAD with cyclohexane, and the spatial configuration of the HTM is changed from vertical orthogonality of the two fluorene units to a parallel arrangement, which is beneficial for the formation of a homogeneous and compact HTM film on the surface of the perovskite film, improvement of intermolecular electronic coupling and intrinsic hole mobility. WH-1 is obtained by two-step facile synthesis with a high yield from commercially available materials. WH-1 is used in PSCs as a dopant-free HTM, which is the first time that the dispiro-based molecule has been applied as a dopant-free HTM, and a power conversion efficiency (PCE) of 19.57% is obtained, rivaling Li-TFSI/t-BP doped Spiro-OMeTAD in PCE (20.29%), and showing obvious superior long-term stability.

A dispiro-based HTM with a parallel arrangement of two fluorenes was designed by replacing the central carbon atom of Spiro-OMeTAD with cyclohexane. The PCE of a PSC based on dopant-free WH-1 is 19.57%, rivaling that of doped Spiro-OMeTAD (20.29%).     

Solid-state electropolymerization and doping of triphenylamine as a route for electroactive thin films

Solid-state electropolymerization could be a way to produce organic semiconductors with potential application as Hole Transporting Materials (HTMs) in hybrid organic-inorganic devices. Thereby, thin solid films of triphenylamine (TPA) deposited by spin coating on conducting glass substrates have been electrochemically treated by performing multiple voltammetric cycles between -0.4 V and 1.0 V vs. Ag/AgCl in a 0.5 M sodium perchlorate aqueous electrolyte. Subsequent characterization by means of in situ UV-Vis spectroscopy, in situ Electrochemical Quartz Crystal Microbalance, Atomic Force Microscopy, Contact Angle analysis, and Open Circuit Potential measurements reveals cross-linking of the monomeric units in the thin film. Such polymerized films are characterized by a high electroactivity linked to doping/undoping, a reversible electrochromic behavior under potentiodynamic conditions and fast changes of the open circuit potential upon illumination, indicating efficient charge transport throughout the film. While extensive polymerization has been demonstrated for TPA, this process is negligible in the case of tri-p-tolylamine, which is linked to the para substitution of the phenyl rings. In more general vein, the feasibility of solid-state electropolymerization is illustrated as well as the potential advantages of this methodology for the preparation of hybrid inorganic/organic materials based on nanoporous oxide matrices.     

Defect passivation of CsPbI_2Br perovskites through Zn(Ⅱ) doping:toward efficient and stable solar cells

Defect passivation is an important strategy to achieve perovskite solar cells(PVSCs) with enhanced power conversion efficiencies(PCEs) and improved stability because the trap states induced by defects in the interfaces and grain boundaries of perovskites are harmful to both large open circuit voltage and high photocurrent of devices. Here, zinc cations(Zn~(2+)) were used as a dopant to passivate defects of the CsPbI_2Br perovskite leading to Zn~(2+)-doped CsPbI_2Br film with fewer trap states, improved charge transportation, and enhanced light-harvesting ability. Thus, the best-performance PVSC based on CsPbI2 Br with the optimal Zn~(2+)doping shows a higher PCE of 12.16% with a larger open-circuit voltage(V_(OC)) of 1.236 V, an improved shortcircuit current(J_(SC)) of 15.61 mA cm~(-2) in comparison with the control device based on the pure CsPbI_2Br which exhibits a PCE of 10.21% with a V_(OC)of 1.123 V, a J_(SC)of 13.27 mA cm~(-2). Time-resolved photoluminescence results show that the Zn~(2+)doping leads to perovskite film with extended photoluminescence lifetime which means a longer diffusion length and subsequently enhanced photocurrent and open circuit voltage. This work provides a simple strategy to boost the performance of PVSCs through Zn~(2+)doping.