Double-layered hole transport material of CuInS2/Spiro for highly efficient and stable perovskite solar cells

In this paper, double-layered hole transport material (HTM) was designed and fabricated by adding a thin CuInS₂ film between perovskite and Spiro-OMeTAD (Spiro) layers. The power conversion efficiency (PCE) of the perovskite solar cells (PSCs) with double-layered HTM of CuInS₂/Spiro was improved to 19.63% from 17.97% for the devices with pure Spiro. Moreover, the operational stability of the PSCs with double-layered HTM of CuInS₂/Spiro was enhanced. The PCE of the PSCs with CuInS₂/Spiro retains 91% of the initial value after 30 days storage in ambient atmosphere. The experimental results indicate that the improved performance could be come from the energy band match between CuInS₂ and Spiro, fast hole extraction and transport, and decreased charge recombination in the PSCs with double-layered HTM of CuInS₂/Spiro. This work provides a promising prospect to design a low-cost and high stability HTM for commercial PSCs.     

Tetrapropyl-substituted palladium phthalocyanine used as an efficient hole transport material in perovskite solar cells

This report presents two tetrapropyl-substituted metal phthalocyanines (PdPrPc and ZnPrPc) used as dopant-free hole transport materials (HTMs) for perovskite solar cells (PSCs). The substitution of Pd atom did not significantly reduce the mobility of the material but increased its lowest unoccupied molecular orbital (LUMO) level. Owing to spin-orbit coupling, the PdPrPc is thought to have a longer carrier diffusion length than that of the ZnPrPc. The higher LUMO level together with the longer carrier diffusion length of the PdPrPc reduced the hole-electron recombination, which led to a higher FF value of its PSC, giving rise to a higher PCE of 18.09% than that of the ZnPrPc-based device. Further, the PdPrPc-based PSC exhibited an increased stability compared with the ZnPrPc-based one. The result indicates the potential application of MPcs containing heavier atoms in efficient and stable PSCs.     

Fused-ring electron acceptor as an efficient interfacial material for planar and flexible perovskite solar cells

Perovskite solar cell (PSC) has attracted great attention due to its high power conversion efficiency (PCE), low cost and solution processability. The well-designed interface and the modification of electron transport layer (ETL) are critical to the PCE and long-term stability of PSCs. In this article, a fused-ring electron acceptor is employed as the interfacial material between TiO₂ and the perovskite in rigid and flexible PSCs. The modification improves the surface of TiO₂, which decreases the defects of ETL surface. Moreover, the modified surface has lower hydrophilicity, and thus is beneficial to the growth of perovskite with large grain size and high quality. As a result, the interfacial charge transfer is promoted and the interfacial charge recombination can be suppressed. The highest PCE of 19.61% is achieved for the rigid PSCs after the introduction of ITIC, and the hysteresis effect is significantly reduced. Flexible PSC with ITIC obtains a PCE of 14.87%, and the device stability is greatly improved. This study provides an efficient candidate as the interfacial modifier for PSCs, which is compatible with low-temperature solution process and has a great practical potential for the commercialization of PSCs.     

Black phosphorus doped Poly(triarylamine) as hole transport layer for highly efficient perovskite solar cells

Charge transport layer plays a critical role in high-performance perovskite solar cells (PSCs). Herein, few-layered 2D black phosphorus (BP) nanosheet doped poly(triarylamine) (PTAA) is employed as hole transport layer for PSCs. The BP:PTAA significantly improves charge extraction at perovskite/BP:PTAA interface together with the smaller energy barrier, the increased conductivity of the PTAA film, and the formation of the high-quality perovskite film with enlarged crystal gain size, which suppress the interfacial charge recombination and trap-assisted recombination. As a result, the champion device using BP:PTAA produces the higher power conversion efficiency of 20.49% than the control device of 18.26%. Moreover, the remarkable improvement in device stability has been demonstrated attributed to the more hydrophobicity of BP:PTAA and the perovskite layer with less defect states. This work provides an effective hole transport layer for PSCs, which is comparable with the commonly used 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ):PTAA.     

F4TCNQ-doped DEPT-SC as hole transporting material for stable perovskite solar cells

The CH₃NH₃PbI₃-based perovskite solar cells using α, α′-diethoxyethyl-oligothiophenes (DEPT-SC) doped with 2,3,5,6-Tetrafluoro-7,7,8,8-tetracyanoquino-dimethane (F4TCNQ) as hole transport material (HTM) exhibited a power conversion efficiency of 11.52%. Compared to the pristine devices, the perovskite solar cells using the new synthesized HTM showed an increased efficiency by about 18% and exhibited better photo-stability, indicating that the organic dopant is an effective method for DEPT-SC toward stable perovskite solar cells.     

Undercoordinated Pb2+ defects passivation via tetramethoxysilane-modified for efficient and stable perovskite solar cells

Organic-inorganic hybrid perovskite solar cells (PSCs) have developed rapidly in recent years, and the instability limits its commercialization. Non-radiative recombination caused by defects and water stability affect the device stability. Here we introduce an organic silane additive, tetramethoxysilane (TMOS), which can reduce the non-radiative recombination and prevent the water erosion. The methoxy group in TMOS can combine with Pb²⁺ of perovskite to passivate undercoordinated Pb²⁺ defects and reduce non-radiative recombination. Under a certain humidity, the hydrolyzed product SiO₂ can occupy the grain boundary sites to prevent the erosion of water molecules, slow down the degradation of perovskite, and improve the crystal phase stability of perovskite. The PCE of the device increases from 17.13% to 20.12%. After 400 h at 50% relative humidity (RH), the PSC with 2% TMOS can maintain the efficiency of 90%, while the efficiency of the control group quickly dropped to only 70% of the initial.     

Moderately reduced graphene oxide/PEDOT:PSS as hole transport layer to fabricate efficient perovskite hybrid solar cells

Graphene oxide (GO) with single layer was moderately reduced at 200 °C for 4 h under N₂. Then the moderately reduced graphene oxide (rGO) water solution was employed as an additive to tune the properties of conventional poly(ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) solution. It's found that the incorporation of rGO into PEDOT:PSS nearly did not change its transparency, hydrophilic property, or the surface roughness. So, the rGO/PEDOT:PSS composite was used as a hole transport layer (HTL) to fabricate perovskite solar cells (PSCs). As a result, PSCs with rGO/PEDOT:PSS as HTL exhibit improved power conversion efficiency than that of PSCs with PEDOT:PSS as HTL. Our findings show that moderately reduced rGO/PEDOT:PSS could be an efficient HTL to improve power conversion efficiency of PSCs.     

Effect of dimethylamino substituent on tetraphenylethylene-based hole transport material in perovskite solar cells

A N,N-dimethylamino substituted tetraphenylethylene derivative (TPE-NMe) was synthesized and characterized, and was successfully applied as hole transport material (HTM) in perovskite solar cells. The methoxy-substituted analogue TPE-4DPA was also studied for comparison. The effect of replacing the para-methoxy substituent with N,N-dimethylamino on photophysical properties, energy levels, and hole transport properties is investigated. Photovoltaic performances of the corresponding devices using the two HTMs are studied. Compared to the methoxy substituent, the N,N-dimethylamino groups in TPE-NMe generates a lower V_oc (0.87 V), yet it provides higher J_sc (21.69 mA/cm²) and FF (0.73) values, resulting in an overall power conversion efficiency of 13.78%.     

Ionic liquid induced surface trap-state passivation for efficient perovskite hybrid solar cells

The highly crystalline methylammonium lead halides (MALHs) perovskite has large carrier diffusion length and thus minimal charge loss within the MALHs layers. But the charge extraction from the perovskite to the charge extraction layers can be significantly influenced by the interfacial contact. Since the fast-crystalized MALHs usually have a rough surface with numerous trap-states and crystal grain boundaries near the top surface, which will deteriorate the electrical coherence and physical contact with the top electron extraction layer (EEL) in the conventional device structure. In this study, we introduced an ionic liquid methyltrioctylammonium trifluoromethanesulfonate (MATS) to passivate the traps and boundaries at the interface of the i-n junction. The photoluminance results demonstrated an improved electron extraction upon the MATS surface treatment. And the impedance measurements also showed a reduced charge transfer resistance within the MATS treated device. Consequently, the conventional planar heterojunction solar cells based on the MALHs perovskite treated by MATS, showed an enhanced device efficiency of 16.10%. Moreover, after heating at elevated temperatures under 2 V forward bias and cooling down to room temperature, we found the MATS modified solar cell devices exhibit a further efficiency improvement to 17.51%.     

Novel D-A-D type small-molecular hole transport materials for stable inverted perovskite solar cells

Hole transport materials (HTMs), as a critical role in the hole extraction and transportation processes, highly influence the efficiency and stability of perovskite solar cells (PSCs). Despite that several efficient dopant-free HTMs have been reported, there is still no clear structure-property relationship that could give instructions for the rational molecular design of efficient HTMs. Thus, in this work, a series of donor–acceptor-donor (D–A–D) type carbazole-based small molecules, TM-1 to TM-4, have been carefully designed and synthesized. By varing the electron acceptor unit from benzene to pyridine, pyrazine and diazine, their packing structure in single crystals, optical and electronic properties have shown a great difference. While as dopant-free HTM in p-i-n type PSCs, TM-2 improved the device photovoltaic performance with a power conversion efficiency from 15.02% (based on PEDOT:PSS) to 16.13%. Moreover, the unencapsulated device based on TM-2 retains about 80% of its initial efficiency after 500 h storage in ambient environment, showing the superior stability.     

Benzodithiophene-based small molecules with various termini as hole transporting materials in efficient planar perovskite solar cells

In this study we prepared four benzodithiophene (BDT)-based small organic molecules presenting bithiophene (TT), thiophene (FT), carbazole (CB), and triphenylamine (TPA) units, respectively, as termini, and used them as hole transporting materials for perovskite solar cells (PSCs). The high degrees of planarity of these BDT-based small molecules imparted them with high degrees of stacking and charge transport. These small molecules had suitable optical properties and energy level alignments for use in PSCs based on MAPbI₃, with compact-TiO₂ as the electron transporting layer and a BDT-based material as the hole transporting layer, in a n–i–p structure. Among our tested BDT-based materials, the PSC incorporating BDT-TT had the best performance, with an average power conversion efficiency of 13.63%.     

In-situ synthesis of metal nanoparticle-polymer composites and their application as efficient interfacial materials for both polymer and planar heterojunction perovskite solar cells

A new approach for the synthesis of gold nanoparticles (Au NPs) via a simple and fast in-situ generation method using an amine-containing polymer (PN4N) as both stabilizer and reducing agent is reported. The application of the Au NPs-PN4N hybrid material as efficient interfacial layer in different types of solar cells was also explored. The synthesized Au NPs show good uniformity in size and shape and the Au NPs doped PN4N hybrid composites exhibit high stability. Amine-containing polymers are good cathode interfacial materials (CIMs) in polymer solar cells (PSCs) and planar heterojunction perovskite solar cells (PVKSCs). The performance of the PSCs with Au NPs doped PN4N CIMs is largely improved when compares to devices with pristine PN4N CIM due to the enhanced electronic properties of the doped PN4N. Furthermore, by incorporating larger Au NPs into PEDOT:PSS to enhance absorption of the light harvesting layer, power conversion efficiencies (PCEs) of 6.82% and 13.7% are achieved for PSC with PCDTBT/PC₇₁BM as the light harvesting materials and PVKSC with a ∼280 nm-thick CH₃NH₃PbI_3−xCl_x perovskite layer, respectively. These results indicate that Au NPs doped into both PEDOT:PSS and PN4N interlayers exhibited a synergistic effect in performance improvement of PSCs and PVKSCs.     

An ammonia modified PEDOT: PSS for interfacial engineering in inverted planar perovskite solar cells

Poly(3,4-ethylenedioxythiophene)-poly(styrene sulfonate) (PEDOT:PSS) is one of the most widely used hole transport layers (HTL) in inverted perovskite solar cells (PSCs) due to its simple solution-processed ability, high transparency, and conductivity. However, PEDOT:PSS-based devices suffer a lower open-circuit voltage (V_oc) than devices with the conventional structure. To address this issue, we fabricated ammonia-modified PEDOT:PSS films by simply doping PEDOT:PSS solution with different ratio of ammonia. The acidity of PEDOT:PSS can be neutralized by the doped ammonia, which inhibits the ion-exchange reaction between PSS-H and CH₃NH₃I, thus retarding the reduction of the work function for PEDOT:PSS to some extent. As a result, a superior power conversion efficiency (PCE) of 15.5% was obtained for the device based on the ammonia-doped PEDOT:PSS HTL than that of the pristine PEDOT:PSS-based device. We ascribe the PCE enhancement to the increased V_oc and fill factor (FF), which is attributed not only to the better energy-level alignment between the ammonia-modified PEDOT:PSS film and perovskite layer but also to the increased grain size and crystallinity of perovskite film.     

Design new hole transport materials for efficient perovskite solar cells by suitable combination of donor and core groups

The electronic, optical, and hole transporting mobility of three organic hole transporting materials (HTMs), X59, X59-P, and X59-T, are investigated by combination of first principle and molecular dynamics associated with Marcus theory and Einstein equation. As compared with the experimental reported X59, the new designed X59-P has more stable HOMO energy level. Moreover, the latter has smaller reorganization energy and larger hole transfer integral resulting in the larger hole transporting mobility. Besides the hole transporting mobility, the solubility and stability of two designed molecules are also evaluated by comparison with X59, which are two important items to determine the cost and performance in real application of solar cell. More importantly, they would be synthesized in a benign condition without expensive materials. Our studies introduce a possible pathway to explore the efficient HTMs by suitable combination mode rather than development of new groups.     

A rapid annealing technique for efficient perovskite solar cells fabricated in air condition under high humidity

A rapid annealing technique for fabricating perovskite materials via microwave radiation in air condition is presented. A planar-heterojunction perovskite device via microwave radiation within 6 min exhibits an efficiency of 10.29%, compared to 11.08% for a 90 min heating-annealed device in inert atmosphere, which is higher than that (8.04%) of a heating-annealed device in air condition under high humidity (∼60%). We believe that the microwave annealing technique provides a fast and less energy-intensive process for fabricating ideal perovskite active layers for high performance solar cells.     

Solution-processed vanadium oxide thin film as the hole extraction layer for efficient hysteresis-free perovskite hybrid solar cells

In this study, we report a simple way to fabricate VO_x thin film from pure-water solution, as the hole extraction layer (HEL) for perovskite hybrid solar cells (pero-HSCs). Furthermore, an aminopropanoic acid (APPA) interfacial layer is used to modify VO_x thin film for reducing the charge carrier recombination rate. As a result, the pero-HSCs with the VO_x/APPA HEL exhibits better device performance than that of the pero-HSCs with the VO_x HEL and the pero-HSCs with poly(3,4-ethylenedioxythiophene):poly-(styrenesulfonate) HEL. Moreover, the pero-HSCs with the VO_x/APPA HEL exhibits hysteresis-free characteristics. All these results indicate that we report a simple approach to realize high performance of perovskite hybrid solar cells.     

High efficient and stable Tin-based perovskite solar cells via short-chain ligand modification

Sn-based perovskite material has been selected as a strong contender for perovskite solar cells (PSCs) application compared with Pb-based perovskite, due to its more suitable bandgap and excellent optoelectronic characteristics. However, the poor quality of Sn-based perovskite film and the oxidation of Sn²⁺ still lead to the unsatisfactory efficiency and instability of PSCs. In our work, a type of ligand “Trifluoroethylamine iodide (3FEAI)” was developed to achieve the crystallization regulation of FASnI₃ perovskite films, which could effectively improve the film quality while restricting the film defects. Moreover, it is found that the short-chain 3FEAI exhibited the better assistance of charge transport effect compared with the conventional ligand PEAI, which further contributed to the efficiency of PSCs. At last, with the introduction of 3FEAI, the prepared device shows the considerable efficiency (9.34%) and long-term stability (~10% PCE loss after 500 h of aging).     

Synergistic effect of MACl and DMF towards efficient perovskite solar cells

The performance of perovskite solar cells (PSCs) is extremely dependent on morphology and crystallinity of perovskite film. One of the most effective methods to achieve high performance perovskite solar cells has been to introduce additives that serve as dopants, crystallization or passivation agents. Herein a facile strategy by introducing methylammonium chloride (MACl) and polar solvent N,N-Dimethylformamide (DMF) as co-additives in two-step sequential method is proposed to realize high quality perovskite film. It is demonstrated that DMF facilitates methylammonium iodide (MAI) penetrating easily into PbI₂ layer to form highly crystalized perovskite film with uniform morphology which is essential to achieve high V_OC. While MACl induces MAPbI₃ to crystallize in a pure α-phase and suppress non-photovoltaic phase, which guarantees high FF. Pure α-phase perovskite film with uniform morphology can be achieved by adopting MACl and DMF together and the corresponding solar cell illustrates a power conversion efficiency (PCE) of 19.02% with substantially promoted durability. Moreover, A V_OC as high as 1.181 V is succeeded for MAPbI₃ based solar cell benefiting from the synergistic effect.     

Performance enhancement of perovskite solar cell by controlling deposition temperature of copper phthalocyanine as a dopant-free hole transporting layer

In this study, an efficient perovskite solar cell is introduced using dopant-free and needle-like copper phthalocyanine (CuPc) in role of a hole selective layer. The needle-like structure was obtained by controlling the substrate temperature during deposition of CuPc. The photovoltaic cell power conversion efficiency was 14.89%, which is approximately similar to that of devices using a conventional doped 2,2′,7,7′-tetrakis(N,N′-di-p-methoxyphenylamine)-9, 9′-spirobifluorene (Spiro-OMeTAD) hole transport material under the same conditions. This study demonstrates thermally evaporated CuPc can be used independently with no additive materials, and it can be an efficient hole selective material to fabricate low-cost perovskite solar cells.     

Anti-solvent engineering via potassium bromide additive for highly efficient and stable perovskite solar cells

Anti-solvent assisted crystallization is commonly employed method to achieve high-quality perovskites attributed to its great operability. Herein, we report an anti-solvent engineering approach via simply using potassium bromide (KBr) additive with commonly used chlorobenzene (CB) in triple-cation perovskite solar cells (PSCs). We show that the KBr additive in the CB anti-solvent not only increases the crystallinity and passivates the perovskite top surface defects, but also leads to suppressed nonradiative recombination and facilitates charge extraction at interfaces. Interestingly, due to the halide vacancies filling with K⁺ ions, hysteresis behavior in the treated perovskite layer was suppressed. Consequently, a champion power conversion efficiency (PCE) of 18.29% was yielded for anti-solvent engineering employing KBr (an 20% improvement in PCE compared to the CB-only anti-solvent device). Furthermore, the optimized device based on KBr demonstrated improved stability, maintaining 80% of its original efficiency after aging in an environment with a relative humidity of 30–50% for 1080 h. Our study reports the significant role of anti-solvent engineering in improving perovskite's quality for efficient PSCs and develops the potential for PSC commercialization.