Dopant-free Hole-transporting Materials Research Articles

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.

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 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.

Thieno[3,2 -b]thiophene-based linear dopant-free hole transport materials for efficient perovskite solar cells

Organic hole transport materials (HTMs) are extensively studied in perovskite solar cells (PSCs). However, due to the inherently low charge carrier mobility, chemical dopants are often required to increase mobility and achieve high power conversion efficiency. Unfortunately, the use of dopants not only brings high costs, but also accelerates the degradation of perovskite, severely reducing the stability of perovskite solar cells. Therefore, developing efficient dopant-free HTMs has become a big challenge. Here, two linear molecules DTTTP-DPA and DTTTP-TPA were designed and synthesized, with diethyl 2,5-bis(thieno [3,2-b]thiophen-2-yl)terephthalate (DTTTP) as the core structure, methoxydiphenylamine/methoxytriphenylamine as the end group, respectively. Compared to diphenylamine, the triphenylamine end group endowed DTTTP-TPA with a longer conjugation length and a lower HOMO level. The longer conjugation is more conducive to charge transporting. While the lower HOMO level due to the weaker electron donating ability of triphenylamine, is potential to achieve a higher open-circuit voltage when used in PSCs. In addition, the carbonyl group in molecular structure could passivate the defect at perovskite/hole transport layer (HTL) interface. As a result, the dopant-free DTTTP-TPA device shows a high photovoltaic performance of 21.62%. At room temperature (30% relative humidity), the initial PCE of the unencapsulated device remains above 93% after 1000 h, showing excellent stability. Our work demonstrates that constructing linear type molecular structure with extended conjugation is an efficient way to enhance hole mobility and is promising to obtain dopant-free HTMs.

Two birds with one stone: dopant-free squaraine hole-transporting material for perovskite solar cell

Developing alternative dopant-free hole-transporting materials (HTM) with a passivation effect and high hole mobility is significant for enhancing the power conversion efficiency (PCE) and stability of the perovskite solar cells (PSCs) with a simplified process. In this work, we report a squaraine HTM 3,4-bis(4'-(bis(4-methoxyphenyl)amino)-[1,1′-biphenyl]-4-yl)cyclobut-3-ene-1,2-dione (D12) with a resonance central structure shuttling between electrically neutral dione and charge-separated inner salts. The donor-acceptor-donor type molecule D12 exhibits an extremely strong capacity not only for hole exaction and mobility, but also for the passivation of perovskite defects. This results in a high PCE of 22.32% for D12-based PSCs. After 30 days of aging at a high relative humidity of 65% at 30 °C, it remains 90% of its initial PCE. This work offers a strategy of designing dopant-free small-molecule HTM and enhancing the stability and PCE of PSCs.

Dopant-free hole-transporting materials featuring intramolecular π-π interactions for efficient and stable perovskite solar cells

The development of hole-transporting materials (HTMs), especially dopant-free ones, is of great significance for simultaneously improving the efficiency and stability of perovskite solar cells (PSCs). Herein, two molecularly engineered HTMs (BFM-C1 and BFM-C6) featuring intramolecular π-π interactions are designed based on the well-known spiro-OMeTAD and synthesized via simple synthetic routes. Unlike the spiro-OMeTAD with orthogonal conformation, both BFM-C1 and BFM-C6 are revealed to adopt a “face-to-face” stacking orientation with evident intramolecular π-π interactions, and display about five times higher hole mobilities (≈ 10-4 cm2V-1s−1) than pristine spiro-OMeTAD. Moreover, both the HTMs exhibit high hole extraction capacity likely owing to good electronic contact with the perovskite. Notably, the incorporated long alkyl chains endow BFM-C6 with better film morphology and superior hydrophobicity, as compared with BFM-C1, thereby resulting in enhanced charge extraction at the perovskite/HTM interface as well as the moisture stability of the perovskite underneath. Consequently, the PSCs employing BFM-C6 as HTM without dopants achieve a power conversion efficiency of 19.06%, along with preferable durability. Furthermore, BFM-C6-based PSCs also exhibit improved thermal stability as compared to the devices based on doped spiro-OMeTAD. This work not only enriches the variety of dopant-free HTMs for PSCs, but also provide a new strategy for developing high-performance dopant-free HTMs.

The calculation of D-A-π-A-D hole transfer materials containing fluoranthene core for efficient perovskite solar cells

In this work, an inexpensive, effective, and dopant-free hole transport material (HTM) of D-A-π-A-D (D=donor, A=acceptor) molecular configuration, called DTB-FL was selected as the basis and then different substitutes were introduced (SO3H, SiCl3, PO3H2, OC2F3, F, CO2H, CH2OH and H) on its central five-membered ring to replace C8H17 alkyl groups. These materials were applied as HTMs for ammonium-free Cs0.05FA0.95PbI3 perovskite solar cells (PSCs). Several properties of the designed HTMs were explored by density functional theory (DFT) and time-dependent DFT (TD-DFT) computations combined with Marcus theory for electron transfer, such as absorption and emission spectra, solubility, stability, reorganization energy, and hole mobility. Results showed that each designed HTM had a higher HOMO level than the perovskite valence band, allowing holes to be successfully injected into the HTM from perovskite. Moreover, theoretical results proved that all HTMs had LUMO energies very upper compared to perovskite conduction band, guaranteeing blocked electron flow effect from CsPbI3−xBrx towards cathode. In terms of VOC amounts, DTB-PO3H2 and DTB-SO3H were found to have the highest power conversion efficiency (PCE), open-circuit voltage (VOC), and fill factor (FF) amounts, which verified they were promising HTMs for the fabrication of PSC devices. Overall, it could be concluded that the designed HTMs had great potentials for PSC fabrication.

Multifunctional Narrow Band Gap Terpolymer-Enabled High-Performance Dopant-Free Perovskite and Additive-Free Organic Solar Cells with Long-Term Stability.

The optoelectronic devices endowing multifunctionality while utilizing a single low-cost material have always been challenging. For this purpose, we adopted a random ternary copolymerization strategy for designing two terpolymers, namely TP-0.8-EG and TP-0.8-TEG comprising a benzothiadiazole (BT)-benzo[1,2-b:4,5-b']dithiophene-diketopyrrolo[3,4-c]pyrrole (A1-π-D-π-A2) backbone. The figure of merits of the narrow band gap TP-0.8-EG terpolymer include deepened frontier energy levels, high hole mobility, better film formability, enriched multifunctionality, and passivation capability. Accordingly, the suitable electronic properties of TP-0.8-EG revealed that it can function as a dopant-free hole-transporting material in perovskite solar cells (PSCs) as well as the third component in organic solar cells (OSCs). Remarkably, TP-0.8-EG outperforms by exhibiting a higher power conversion efficiency (PCE) of 20.9% over TP-0.8-TEG (PCE of 18.3%) and BT-UF (PCE of 14.6%) in dopant-free PSCs. Interestingly, TP-0.8-EG fabricated along with PM6:Y7 displayed a high PCE of 16.52% in ternary OSCs. Also, TP-0.8-EG established good device storage stabilities (85 and 83% of their initial PCEs for 1200 and 500 h) in dopant-free PSC as well as OSC devices. Notably, the devices with TP-0.8-EG showed excellent thermal and moisture stabilities. To the best of our knowledge, A1-π-D-π-A2 terpolymer performing both in PSCs and OSCs with decent efficiencies and good device stabilities is a rare scenario.

Heterocyclic Functionalized Donor-Acceptor Hole-Transporting Materials for Inverted Perovskite Solar Cells.

Hole transport materials (HTMs) with appropriate energy levels and comprehensive passivation effects help to obtain highly efficient and stable perovskite solar cells (PSCs). Electron-deficient character-induced HTMs can generate varying energy level alignments near the HTM/perovskite interface. Herein, we report the synthesis and investigation of two new dipolar HTMs, WWC103 and WWC105, based on 2-(1,1-dicyanomethylene)rhodamine and 4-cynophenylacetonitrile acceptors, enabling high-efficiency mixed-cation mixed-halide perovskite solar cells. Apart from having different acceptors, these HTMs are built on a heterocyclic frame, which can provide passivation effects and improve the morphology of the perovskite layer. As a result, these dopant-free HTM-based solar cells show a high open-circuit voltage and good power conversion efficiency. Among both, the solar cell based on the HTM with 2-(1,1-dicyanomethylene)rhodamine exhibits a high open-circuit voltage of 1.09 V with a champion power conversion efficiency of over 20.51%. The improved performance of WWC103 over WWC105 (19.74%) is attributed to the new acceptor, which, in addition to providing good energy-level alignments and hole mobility, also holds the ability to passivate the defects. The findings suggest a new acceptor unit for constructing dopant-free HTMs for efficient PSCs.

Dopant-Free Hole-Transporting Material Based on Poly(2,7-(9,9-bis(N,N-di-p-methoxylphenylamine)-4-phenyl))-fluorene for High-Performance Air-Processed Inverted Perovskite Solar Cells.

It is a great challenge to develop low-cost and dopant-free polymer hole-transporting materials (HTM) for PSCs, especially for efficient air-processed inverted (p-i-n) planar PSCs. A new homopolymer HTM, poly(2,7-(9,9-bis(N,N-di-p-methoxylphenyl amine)-4-phenyl))-fluorene (denoted as PFTPA), with appropriate photo-electrochemical, opto-electronic and thermal stability, was designed and synthesized in two steps to meet this challenge. By employing PFTPA as dopant-free hole-transport layer in air-processed inverted PSCs, a champion power conversion efficiency (PCE) of up to 16.82% (0.1 cm2) was achieved, much superior to that of commercial HTM PEDOT:PSS (13.8%) under the same conditions. Such a superiority is attributed to the well-aligned energy levels, improved morphology, and efficient hole-transporting, as well as hole-extraction characteristics at the perovskite/HTM interface. In particular, these PFTPA-based PSCs fabricated in the air atmosphere maintain a long-term stability of 91% under ambient air conditions for 1000 h. Finally, PFTPA as the dopant-free HTM was also fabricated the slot-die coated perovskite device through the same fabrication condition, and a maximum PCE of 13.84% was obtained. Our study demonstrated that the low-cost and facile homopolymer PFTPA as the dopant-free HTM are potential candidates for large-scale production perovskite solar cell.

Star-like, dopant-free, corannulene-cored hole transporting materials for efficient inverted perovskite solar cells

Hole transporting materials (HTMs), owing to their unique bottom position in inverted perovskite solar cells (PSCs), exert a considerable influence on the hole-transporting process and the morphology/performance of the perovskite layers. Considering the well-known interfacial problems associated with commonly-used NiOx and poly(triarylamine) HTMs in traditional inverted PSCs, there is an urgent need for exploring efficient HTMs exhibiting good film formability/processability and interfacial contact to meet the specific requirements of high-performance and stable inverted PSCs. Herein, we fabricated inverted PSCs involving two star-like, dopant-free, corannulene-cored HTMs with O-terminals (sym-penta(N, N-bis(4-methoxyphenyl)aniline)corannulene, namely Cor-OMePTPA) and S-terminals (sym-penta(N, N-bis(4-(methylthio)phenyl)aniline)corannulene, namely Cor-SMePTPA) for the first time. The Cor-SMePTPA HTM exhibited a stronger hole-transporting ability and a better interfacial chemical linkage when compared to the Cor-OMePTPA HTM. The device containing Cor-SMePTPA HTM delivered a power conversion efficiency of 21.70%, which was the highest among inverted PSCs based on methylthio (SMe)-terminated HTMs. Furthermore, comprehensive experimental and theoretical characterizations clearly showed that the core and outer terminals (O or S) affected the optoelectric and chemical properties of the HTMs as well as the photovoltaic performance and stability of the corresponding PSCs, highlighting the superiority of the design involving a corannulene core and SMe groups in HTMs for inverted PSCs. We believe that such dopant-free corannulene-cored HTMs can have considerable potential for realizing highly efficient and stable PSCs in the future.

Triphenylimidazole substituted D-π-D porphyrin based dopant-free hole transport materials for perovskite solar cells

Hole-transport materials (HTMs) contribute an important function in perovskite solar cells (PSCs) for achieving favourable photovoltaic performance with durability. In this work, we designed and synthesized a series of porphyrin based hydrophobic HTMs based on donor-π-donor (D-π-D) tactic in which triphenylimidazole as donor and either free-base porphyrin (H2LD) or metalloporphyrin (Cu, CuLD or Zn, ZnLD) as π-spacer for PSCs. All three HTMs were characterized by a variety of spectroscopic and electrochemical methods. Optical and electrochemical properties propose that the highest occupied molecular orbital (HOMO) energy levels were healthily aligned with the valence band of MAPbI3 perovskite. Among these HTMs, CuLD exhibited higher hole mobility of 7.39 × 10-5 cm2V-1s-1, when compared to ZnLD 5.77 × 10-5 cm2V-1s-1, and H2LD 2.7 × 10-5 cm2V-1s-1. We fabricated PSCs with these HTMs and among them the CuLD based PSCs showed highest power conversion efficiency of 12.44%. The better PCE for the PSCs fabricated with CuLD could be attributed to the higher conductivity and better hole mobility which could be correlated to the better film formation.