Dopant-free Hole-transporting Materials Research Articles

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.

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.

Revealing the Impact of Aging on Perovskite Solar Cells Employing Nickel Phthalocyanine-Based Hole Transporting Material.

The enhancement of the photovoltaic performance upon the aging process at particular environment is often observed in perovskite solar cells (PSCs), particularly for the devices with 2,2',7,7'-tetrakis(N,N-di(4-methoxyphenyl)amino)-9,9'-spirobifluorene (spiro-OMeTAD)as hole transporting material (HTM). In this work, for the first time the effect of aging the typical n-i-p PSCs employing nickel phthalocyanine (coded as Bis-PF-Ni) solely as dopant-free HTM is investigated and as an additive in spiro-OMeTAD solution. This study reveals that the prolong aging of these devices at dry air condition (RH= 2%, 25°C) is beneficial for the improvement of their performances. Various bulk and surface characterization techniques are utilized to understand the factors behind the spontaneous efficiency enhancement of the devices after storage. As a result, the changes in properties of the Bis-PF-Ni layer are observed and at perovskite/Bis-PF-Ni interface, which ultimately improves the charge transport and reduces non-radiative recombination. In addition, the devices with Bis-PF-Ni HTM reveal enhanced long-term ambient and thermal stability compared to the PSCs based on doped spiro-OMeTAD.

Direction Modulation of Intramolecular Electric Field Boosts Hole Transport in Phthalocyanines for Perovskite Solar Cells.

Tuning the strength of intramolecular electric field (IEF) in conjugated molecules has emerged as an effective approach to boost charge transfer. While direction manipulation of IEF would be a potential way that is still unclear. Here, we leverage the control of peripheral substituents of conjugated phthalocyanines to chemically tune the spatial orientation of IEF. By analyzing the spatial swing of side chains using the Kolmogorov-Arnold representation and least squares algorithm, a comprehensive mathematical-physical model has been established. This model enables rapid evaluation of the IEF and maximum hole transport performance induced by spatial swings. The champion phthalocyanine as dopant-free hole transport material in perovskite solar cell realizes a record performance of 23.41%. Greatly device stability is also exhibited. This work affords a new way to enhance hole transport capabilities of conjugated molecules by optimizing their IEF vector for photovoltaic devices.

Chlorine-Substituent Regulation in Dopant-Free Small-Molecule Hole-Transport Materials Improves the Efficiency and Stability of Inverted Perovskite Solar Cells

Although doped hole-transport materials (HTMs) offer an efficiency benefit for perovskite solar cells (PSCs), they inevitably diminish the stability. Here, we describe the use of various chlorinated small molecules, specifically fluorenone-triphenylamine (FO-TPA)-x-Cl [x = para, meta, and ortho (p, m, and o)], with different chlorine-substituent positions, as dopant-free HTMs for PSCs. These chlorinated molecules feature a symmetrical donor–acceptor–donor structure and ideal intramolecular charge transfer properties, allowing for self-doping and the establishment of built-in potentials for improving charge extraction. Highly efficient hole-transfer interfaces are constructed between perovskites and these HTMs by strategically modifying the chlorine substitution. Thus, the chlorinated HTM-derived inverted PSCs exhibited superior efficiencies and air stabilities. Importantly, the dopant-free HTM FO-TPA-o-Cl not only attains a power conversion efficiency of 20.82% but also demonstrates exceptional stability, retaining 93.8% of its initial efficiency even after a 30-day aging test conducted under ambient air conditions in PSCs without encapsulation. These findings underscore the critical role of chlorine-substituent regulation in HTMs in ensuring the formation and maintenance of efficient and stable PSCs.

Molecular packing regulation of dopant-free hole transport polymers for efficient perovskite solar cells

Spiro-OMeTAD is a primary hole transport material (HTM) employed in most state-of-the-art regular perovskite solar cells (PSCs). The essential reliance on hygroscopic ionic dopants to enhance the conductivity and mobility of Spiro-OMeTAD has dramatically compromised the stability of PSCs. Here, we demonstrated excellent photovoltaic performance of PSCs by developing two dopant-free polymers, namely L1 and L2, using thieno[3,2-b]thiophene as a building block. It is found that the n-hexyl-modified thiophene side chains endow the polymer L2 with favorable crystallinity, unique self-assembly behavior, and a preferable face-on stacking orientation. After the addition of a small amount (10 %) of PM6 to create a polymer alloy named LPA, the above properties were further improved, and the resulting film exhibited a distinct fibrous morphology, resulting in increased hole mobility and effective defect passivation. Consequently, PSCs employing LPA as a dopant-free HTM afforded a high efficiency of 23.81 %. Importantly, LPA-based PSCs exhibit significantly enhanced operational stability with a T80 lifetime of 1572 h at 55 °C. This work provides a crucial guideline for the design of dopant-free polymers, thereby advancing the practical application of PSCs.

Trade-off effect of hydrogen-bonded dopant-free hole transport materials on performance of inverted perovskite solar cells

Benefiting from their ordered orientation and superior stability compared to traditional conjugated materials, hydrogen bonding (HB)-induced H-aggregates in organic small molecule hole-transport materials (HTMs) hold a big potential for high-performance inverted perovskite solar cells (IPSCs). However, H-aggregates can also lead to excessive face-aggregation by forming the gaps between aggregates, which is in turn unfavorable for charge mobility and thus for the overall device performance. Herein, we design and synthesize a new set of HB-containing triphenylamine-based small molecules to tailor the degree of H-aggregation, namely O1 (without HB), O2 (unilateral HB unit), and O3 (bilateral HB units). These HTMs make a clear trade-off effect on the charge mobility within the HTM and the interfacial properties of perovskite and HTM. Although the interfacial hole extraction process is promoted upon the HB-functionalized interface, the best performance of IPSCs is still achieved by O1 HTM, which is mainly influenced by the higher hole mobility without HB-induced H-aggregates. Nevertheless, the photo stability of as-fabricated devices is effectively improved upon the HB passivation effect on the interface of HTM (O2 or O3) and perovskite, as well as the better quality of atop perovskite layers with less grain boundary compared to the reference case (O1).

Fluorinated hole transport material resistant to high annealing temperature applied in inverted perovskites solar cells

A dopant-free and low-cost hole transport material (HTM) with dibenzo[b,d]thiophene as the center unit, bis(4-methoxyphenyl)amine as the terminal unit, and fluorine substitution adjacent to the methoxyl (named DBT-4F-MOP) is designed and applied in inverted organic-inorganic hybrid perovskite solar cells (OIH-PSCs). The synthetic cost of DBT-4F-MOP in the lab is just as low as 115 CNY/g, which is much lower than the benchmark HTM poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA, 2500 CNY/g). Due to the introduction of the fluorine atoms, the annealing temperature of the HTM can be increased by over 150 ℃. The highest efficiency of the inverted device based on it can reach 16.8 %, with an open circuit voltage of 1.04 V, a short circuit current of 21.57 mA cm−2, and a fill factor of 74.69 %, while the reference device based on PTAA can reach a PCE of 17.54 %. This work provides an avenue for the design of low-cost, dopant-free, and high-annealing temperature HTMs for inverted OIH-PSCs.

Dibenzo[b,d]thiophene 5,5-dioxide-based dopant-free hole-transporting material with passivation effect in inverted perovskite solar cells

For the rocket development of organic-inorganic hybrid perovskite solar cells (OIH–PSCs), the research of low-cost, dopant-free hole-transporting materials (HTMs) with high performance and stability is still an urgent problem. In this work, we synthesize organic small molecule HTM with sulfone-containing benzodithiophene (BDTOxide) as the central unit, termed BDTOxide-MTP. The synthetic cost of DBTOxide-MTP in the lab is 238 CNY/g, which is just one-fifth of the cost of the PTAA (1200 CNY/g). BDTOxide-MTP exhibits the deep highest occupied molecular orbital energy level, high hole transport mobility, and excellent passivation effect. BDTOxide-MTP is introduced into inverted OIH-PSCs as a dopant-free hole transport layer, the champion efficiency of MAPbI3-xClx-based devices reaches 18.72 % with an excellent VOC of 1.13 V, while the efficiency of the control device based on PTAA is about 18.49 %. The device based on BDTOxide-MTP exhibits comparable stability to the one based on PTAA, which can maintain over 90 % of the original efficiency after 46 days in a nitrogen environment.

Dual-Strategy Tailoring Molecular Structures of Dopant-Free Hole Transport Materials for Efficient and Stable Perovskite Solar Cells.

Dopant-free hole transport materials (HTMs) are ideal materials for highly efficient and stable n-i-p perovskite solar cells (PSCs), but most current design strategies for tailoring the molecular structures of HTMs are limited to single strategy. Herein, four HTMs based on dithienothiophenepyrrole (DTTP) core are devised through dual-strategy methods combining conjugate engineering and side chain engineering. DTTP-ThSO with ester alkyl chain that can form six-membered ring by the S⋅⋅⋅O noncovalent conformation lock with thiophene in the backbone shows good planarity, high-quality film, matching energy level and high hole mobility, as well as strong defect passivation ability. Consequently, a remarkable power conversion efficiency (PCE) of 23.3 % with a nice long-term stability is achieved by dopant-free DTTP-ThSO-based PSCs, representing one of the highest values for un-doped organic HTMs based PSCs. Especially, the fill factor (FF) of 82.3 % is the highest value for dopant-free small molecular HTMs-based n-i-p PSCs to date. Moreover, DTTP-ThSO-based devices have achieved an excellent PCE of 20.9 % in large-area (1.01 cm2) devices. This work clearly elucidates the structure-performance relationships of HTMs and offers a practical dual-strategy approach to designing dopant-free HTMs for high-performance PSCs.

The dopant-free hole transport material based on benzo[1,2-b:4,5-b']dithiophene with high efficiency in inverted perovskite solar cells

In the commercialization process of organic-inorganic hybrid perovskite solar cells (OIH–PSCs), the research of dopant-free hole transport materials (HTMs) with high efficiency is still an urgent problem. In this work, we synthesize two organic small molecule HTMs with well-known benzodithiophene (BDT) as the central unit, abbreviated as BDTO-MTP and BDTT-PMTP. Compared with BDTO-MTP (with oxygen-substituted alkyl chain and diphenylamine derivatives as the terminal group), BDTT-PMTP introduces thiophene to replace oxygen beside the central group, triphenylamine to replace diphenylamine derivatives as the terminal group. Both BDTO-MTP and BDTT-PMTP exhibit high hole mobility without doping. It is worth noting that two new materials are introduced into inverted OIH-PSCs as a doped-free hole transport layer, the champion efficiency of MAPbI3-based devices based on BDTT-PMTP reaches 21.08%, and the highest efficiency of BDTO-MTP-based devices can also reach 19.54%. The results show that the planar building blocks with the similarity of BDT will be an excellent and universal choice for the future design of dopant-free small molecule HTMs with high efficiency.

Dopant-Free Pyrene-Based Hole Transporting Material Enables Efficient and Stable Perovskite Solar Cells.

Dopant-free hole transporting materials (HTMs) is significant to the stability of perovskite solar cells (PSCs). Here, we developed a novel star-shape arylamine HTM, termed Py-DB, with a pyrene core and carbon-carbon double bonds as the bridge units. Compared to the reference HTM (termed Py-C), the extension of the planar conjugation backbone endows Py-DB with typical intermolecular π-π stacking interactions and excellent solubility, resulting in improved hole mobility and film morphology. In addition, the lower HOMO energy level of the Py-DB HTM provides efficient hole extraction with reduced energy loss at the perovskite/HTM interface. Consequently, an impressive power conversion efficiency (PCE) of 24.33 % was achieved for dopant-free Py-DB-based PSCs, which is the highest PCE for dopant-free small molecular HTMs in n-i-p configured PSCs. The dopant-free Py-DB-based device also exhibits improved long-term stability, retaining over 90 % of its initial efficiency after 1000 h exposure to 25 % humidity at 60 °C. These findings provide valuable insights and approaches for the further development of dopant-free HTMs for efficient and reliable PSCs.

Low-cost dopant-free fluoranthene-based branched hole transporting materials for efficient and stable n-i-p perovskite solar cells

It has been widely recognized that hole transporting materials (HTMs) play a key role in the rapid progress of perovskite solar cells (PVSCs). However, common organic HTMs such as spiro-OMeTAD not only suffer from high synthetic costs, but also usually require the additional chemical doping process to improve their hole transport ability, which unfortunately induces the terrible stability issue. Therefore, it is urgent to develop low-cost dopant-free HTMs for efficient and stable PVSCs. In this work, we have successfully developed a new class of efficient dopant-free fluoranthene-based HTMs (TPF1–5) with quite low lab synthetic costs by combining donor-acceptor and branched structure designs. The detailed structure-property study revealed that tuning the twisted arms at different substitution sites would regulate the intermolecular interactions and film-forming ability, thereby significantly affecting the performance of the HTMs. By applying these HTMs in conventional PVSCs, the dopant-free TPF1-based devices not only achieved the best efficiency of 21.76%, which is comparable to that of the doped spiro-OMeTAD control devices, but also showed much better operational stability, which maintained over 87% of the initial efficiency under maximum power point tracking after 1038 h.

Non-Equivalent Donor-Acceptor Type Polymers as Dopant-Free Hole-Transporting Materials for Perovskite Solar Cells.

Electron donor (D)-electron acceptor (A) type conjugated polymers present bright prospects as dopant-free hole-transporting materials (HTMs) for perovskite solar cells (PVSCs). Most of the reported D-A polymeric HTMs contain equivalent amounts of D and A units, while the appropriate excess proportion of D units could optimize the aggregation state of polymer chains and improve the hole transport properties of the polymers. Herein, a non-equivalent D-A copolymerization strategy was utilized to develop three indacenodithiophene-benzotriazole-based polymeric HTMs for PVSCs, named as F-10, F-15, and F-20, and the equivalent D-A polymer F-00 was studied in parallel. Effects of D : A ratio on the hole transport properties of these D-A type polymeric HTMs, including energy level, molecular stacking, hole mobility, and surface morphology, were investigated by theoretical simulation and test analysis. F-15 performed best due to the appropriate D : A ratio, endowing the PVSCs a champion power conversion efficiency of 20.37 % with high stability, which confirms the fine-tuning D : A ratio via non-equivalent D-A copolymerization strategy is very helpful to construct D-A type polymeric HTMs for high-performance PVSCs.

Investigating the impact of end-capped acceptor alterations to dimethyl fluorene-based hole transporting material for perovskite solar cells

Hole-transporting materials (HTMs) could boost the proficiency of third generation-perovskite solar cells since they have ultrafast charge mobility that improves optoelectronic and photovoltaic attributes. Five new H-shaped molecules were sketched using thiophene bridged, end-capped acceptor alteration on a dimethyl fluorene core-based molecule. Planarity measurements, absorption spectra, frontier molecular orbitals (FMOs), excitation energy (Ex), density of states (DOS), molecular electrostatic potentials (MEPs), transition density matrix (TDM), exciton binding energy, interaction coefficient, hole-electron overlap, open circuit voltage, fill factor, and power conversion efficiency were analyzed via DFT/MPW1P9W1/6-31G (d,p) for evaluating performance of perovskite solar cells. All newly sketched molecules with an A-π-D-π-A skeleton exhibited outstanding optoelectronic properties, including broader absorbance (563–740 nm) in chlorobenzene, indicating better solution processing. Lower band gaps (2.08–2.72 eV) than reference (3.78 eV) indicated efficient electron density transfer. Increased open-circuit voltage (1.55–2.02 eV) along with lower reorganization energies of the electron (0.043249–0.122527 eV) and hole (0.108105–0.148322 eV) lead to effective charge transport capabilities. Higher dipole moments indicated suitable film fabrication. A higher fill factor (0.9166–0.9325) and power conversion efficiency (34.31–45.49 %) led to an improved performance. Concisely, all the newly sketched molecules showed redshifted absorbance, narrower band gaps, deeper HOMO energies, improved charge transfer, higher softness, and smaller hardness values when compared to ZR, which confirms their superiority as future dopant-free HTM for PSCs.

π-Conjugated Polymer with Pendant Side Chains as a Dopant-Free Hole Transport Material for High-Performance Perovskite Solar Cells.

Dopant-free polymeric hole transport materials (HTMs) have attracted considerable attention in perovskite solar cells (PSCs) due to their high carrier mobilities and excellent hydrophobicity. They are considered promising candidates for HTMs to replace commercial Spiro-OMeTAD to achieve long-term stability and high efficiency in PSCs. In this study, we developed BDT-TA-BTASi, a conjugated donor-π-acceptor polymeric HTM. The donor benzo[1,2-b:4,5-b']dithiophene (BDT) and acceptor benzotriazole (BTA) incorporated pendant siloxane, and alkyl side chains led to high hole mobility and solubility. In addition, BDT-TA-BTASi can effectively passivate the perovskite layer and markedly decrease the trap density. Based on these advantages, dopant-free BDT-TA-BTASi-based PSCs achieved an efficiency of over 21.5%. Furthermore, dopant-free BDT-TA-BTASi-based devices not only exhibited good stability in N2 (retaining 92% of the initial efficiency after 1000 h) but also showed good stability at high-temperature (60 °C) and -humidity conditions (80 ± 10%) (retaining 92 and 82% of the initial efficiency after 400 h). These results demonstrate that BDT-TA-BTASi is a promising HTM, and the study provides guidance on dopant-free polymeric HTMs to achieve high-performance PSCs.

Cross-linkable fluorene-based hole transporting materials for perovskite solar cells

Cross-linkable hole transporting materials (HTMs) based on fluorene core containing vinyl groups were synthesized and analyzed. It has been demonstrated that these HTMs are cross-linkable at temperatures above 200 °C and they are thermally stable at up to 400 °C. Cross-linking has little effect on energy level (HOMO) and causes only slight changes in the hole drift mobility values at room temperature, due to changes in spatial and energetic disorder. While employing cross-linked fluorene-diphenylamine derivative (V1145) as an HTM layer between perovskite and indium-tin oxide (ITO) in inverted perovskite solar cells (PSCs), the power conversion efficiency (PCE) of the cell was 11.42% (under AM 1.5G 100 mW cm−2 illumination), demonstrating the potential of the presented class of dopant-free organic HTMs.

A machine learning approach for in silico prediction of the photovoltaic properties of perovskite solar cells based on dopant-free hole-transport materials

Machine learning approaches for building robust autoQSPR models for the prediction of the photovoltaic properties of PSCs based on dopant free hole transport materials.

A review on conventional perovskite solar cells with organic dopant-free hole-transport materials: roles of chemical structures and interfacial materials in efficient devices

Efficient conventional perovskite solar cells with organic dopant-free HTMs are collected. It is showed that both the chemical structure of HTMs and interfacial materials play significant roles in efficiency, and their effects are discussed.

Hole and electron transport materials: A review on recent progress in organic charge transport materials for efficient, stable, and scalable perovskite solar cells

Charge transporting materials are essential for fabricating stable and efficient perovskite solar cells. The high-temperature processing, surface defects, and low mobility are common issues in inorganic charge transport materials which can hinder the fabrication of low-cost, efficient, and stable perovskite solar cells. Dopants increase the processing cost of the hole transport materials. Surface defects are observed in the high-temperature processed inorganic electron transport materials. There is a need to develop organic compounds for charge transportation in perovskite solar cells. Herein, the advancements in the organic materials for charge transport in the perovskite solar cells are reviewed. The low-cost processing, better solubility, efficient charge mobility, tunable molecular orbitals, and better stability of organic compounds are some properties for their utilization as charge transport materials in perovskite solar cells. Organic small molecules, polymers, and phthalocyanine compounds can be utilized as dopant-free hole transport materials. Fullerene and non-fullerene derivatives like C60, C70, azaacenes, indacenodithiophene, polymers, and rylene diimides are promising electron transport materials. The functionality, engineering, charge transport properties, and device characteristics of different organic materials are discussed. The review will offer a forecast for improving device stability and efficiency in terms of architecture, engineering, and materials to realize the commercialization of perovskite solar cells soon.