Dopant-Free Hole Transport Materials Based on a Large Conjugated Electron-Deficient Core for Efficient Perovskite Solar Cells

Hole transport materials (HTMs) play a significant role in device efficiencies and long-term stabilities of perovskite solar cells (PSCs). In this work, two simple dopant-free HTMs are designed with a large conjugated electron-deficient core. On the one hand, a large coplanar backbone endows enhanced π–π stacking and reduced hole hopping distance. On the other hand, the incorporation of electron-deficient unit can easily tune the energy levels as well as increase hole mobilities. Combining these two advantages together, 12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro[1,2,5]thiadiazole[3,4-e]thieno[2″,3″:4,5]thieno[2′,3′:4,5]pyrrolo[3,2-g]thieno[2′,3′:4,5]thieno[3,2-b]indole is chosen as the large electron-deficient core to construct two novel dopant-free HTMs, Y6-T and Y-T. Both Y6-T and Y-T behave suitable highest occupied molecular orbital levels, good hole mobilities, as well as strong hydrophobicities. After careful device optimization with a passivation agent, Y-T delivers an impressive power conversion efficiency of 20.29%, which is higher than that of Y6-T (18.82%) and doped spiro-OMeTAD (19.24%). Moreover, PSCs based on Y6-T and Y-T show much better long-term stabilities than spiro-OMeTAD due to the intrinsic hydrophobicity. Therefore, this work provides a promising candidate as well as a useful design strategy for exploring dopant-free HTMs, which may pave the way for the commercialization of PSCs.     

Boosting the performance and stability of perovskite solar cells with phthalocyanine-based dopant-free hole transporting materials through core metal and peripheral groups engineering

Three novel dopant-free hole-transporting materials (HTMs) based on phthalocyanine core containing (4-methyl formate) phenoxy or (4-butyl formate) phenoxy as the peripheral groups with cupper or zinc as the core metals (CuPcNO₂-OMFPh, CuPcNO₂-OBFPh, ZnPcNO₂-OBFPh) were designed and synthesized. All of the phthalocyanine complexes show excellent thermal stabilities, appropriate energy levels and suitable hole mobilities. The potential of three HTMs were tested in perovskite solar cells (PSCs) and ZnPcNO₂-OBFPh based PSC obtained power conversion efficiency (PCE) of 15.74% under 100 mA cm⁻² standard AM 1.5G solar illumination. Most important of all, PSC based on ZnPcNO₂-OBFPh shows better stability than that of the other two phthalocyanines and Spiro-OMeTAD under continuous light irradiation at 60 °C and maximum power point tracking in ambient air without encapsulation after 500 h. The results show that the introduction of appropriate peripheral groups and core metals can improve the performance and stability of PSCs dramatically, which provides an alternative way to develop HTMs for efficient and stable PSCs.     

Fluorinated Pentafulvalene-Fused Hole-Transporting Material Enhances the Performance of Perovskite Solar Cells with Efficiency Exceeding 23%

Organic small molecular materials with coplanar π-conjugated system as HTMs in perovskite solar cells (PSCs) have attracted considerable attention due to their high charge transport capability and thermal stability. Herein, three novel pentafulvalene-fused derivatives with or without fluorine atoms incorporated ( YSH-oF and YSH-mF and YSH-H , respectively) are designed, synthesized, and applied as hole-transporting materials (HTMs) in PSCs fabrication. The fluorinated HTMs, YSH-oF and YSH-mF , exhibited higher hole mobility and better charge extraction at the perovskite/HTM interface than non-fluorinated one do, presumably due to the closer intermolecular π–π packing interactions. As a result, small-area (0.09 cm²) PSCs made with YSH-oF and YSH-mF achieved an impressive power conversion efficiency (PCE) of 23.59% and 22.76% respectively, with negligible hysteresis, in contrast with the 20.57% for the YSH-H -based devices. Furthermore, for large-area (1.00 cm²) devices, the PSCs employing YSH-oF exhibited a PCE of 21.92%. Moreover, excellent long-term device stability is demonstrated for PSCs with F-substituted HTMs ( YSH-oF and YSH-mF ), presumably due to the higher hydrophobicity. This study shows the great potential of fluorinated pentafulvalene-fused materials as low-cost HTM for efficient and stable PSCs.     

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.     

Detailed analysis and contact properties of low-voltage organic thin-film transistors based on dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene (DNTT) and its didecyl and diphenyl derivatives

Low-voltage organic thin-film transistors (TFTs) based on four different small-molecule semiconductors (pentacene, DNTT (dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene), C₁₀-DNTT and DPh-DNTT) were fabricated, and a detailed comparison of the semiconductor thin-film morphology, of the current-voltage characteristics of transistors with channel lengths ranging from 100 to 1 μm, and of the contact resistances is provided. The three thienoacene derivatives DNTT, C₁₀-DNTT and DPh-DNTT all have significantly larger charge-carrier mobilities and smaller contact resistances than pentacene. In terms of the intrinsic channel mobility (determined using the transmission line method), C₁₀-DNTT and DPh-DNTT perform quite similarly and notably better than DNTT, suggesting that the decyl substituents in C₁₀-DNTT and the phenyl substituents in DPh-DNTT provide a similar level of enhancement of the charge-transport characteristics over DNTT. However, the DPh-DNTT TFTs have a substantially smaller contact resistance than both the DNTT and the C₁₀-DNTT TFTs, resulting in notably larger effective mobilities, especially in transistors with very small channel lengths. For DPh-DNTT TFTs with a channel length of 1 μm, an effective mobility of 0.68 cm²/V was determined, together with an on/off ratio of 10⁸ and a subthreshold swing of 100 mV/decade.     

Dithieno[3,2‐b:2′,3′‐d]pyrrol‐Cored Hole Transport Material Enabling Over 21% Efficiency Dopant‐Free Perovskite Solar Cells

Dopant‐free hole transport materials (HTMs) are essential for commercialization of perovskite solar cells (PSCs). However, power conversion efficiencies (PCEs) of the state‐of‐the‐art PSCs with small molecule dopant‐free HTMs are below 20%. Herein, a simple dithieno[3,2‐b:2′,3′‐d]pyrrol‐cored small molecule, DTP‐C6Th, is reported as a promising dopant‐free HTM. Compared with commonly used spiro‐OMeTAD, DTP‐C6Th exhibits a similar energy level, a better hole mobility of 4.18 × 10^?4 cm² V^?1 s^?1, and more efficient hole extraction, enabling efficient and stable PSCs with a dopant‐free HTM. With the addition of an ultrathin poly(methyl methacrylate) passivation layer and properly tuning the composition of the perovskite absorber layer, a champion PCE of 21.04% is achieved, which is the highest value for small molecule dopant‐free HTM based PSCs to date. Additionally, PSCs using the DTP‐C6Th HTM exhibit significantly improved long‐term stability compared with the conventional cells with the metal additive doped spiro‐OMeTAD HTM. Therefore, this work provides a new candidate and effective device engineering strategy for achieving high PCEs with dopant‐free HTMs.     

Pyrite‐Based Bi‐Functional Layer for Long‐Term Stability and High‐Performance of Organo‐Lead Halide Perovskite Solar Cells

Organo‐lead halide perovskite solar cells (PSCs) have received great attention because of their optimized optical and electrical properties for solar cell applications. Recently, a dramatic increase in the photovoltaic performance of PSCs with organic hole transport materials (HTMs) has been reported. However, as of now, future commercialization can be hampered because the stability of PSCs with organic HTM has not been guaranteed for long periods under conventional working conditions, including moist conditions. Furthermore, conventional organic HTMs are normally expensive because material synthesis and purification are complicated. It is herein reported, for the first time, octadecylamine‐capped pyrite nanoparticles (ODA‐FeS₂ NPs) as a bi‐functional layer (charge extraction layer and moisture‐proof layer) for organo‐lead halide PSCs. FeS₂ is a promising candidate for the HTM of PSCs because of its high conductivity and suitable energy levels for hole extraction. A bi‐functional layer based on ODA‐FeS₂ NPs shows excellent hole transport ability and moisture‐proof performance. Through this approach, the best‐performing device with ODA‐FeS₂ NPs‐based bi‐functional layer shows a power conversion efficiency of 12.6% and maintains stable photovoltaic performance in 50% relative humidity for 1000 h. As a result, this study has the potential to break through the barriers for the commercialization of PSCs.     

3,7-Bis((E)-2-oxoindolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]dithiophene-2,6-dione (IBDT) based polymer with balanced ambipolar charge transport performance

A novel acceptor building block, 3,7-bis((E)-2-oxoindolin-3-ylidene)-3,7-dihydrobenzo[1,2-b:4,5-b′]dithiophene-2,6-dione (IBDT), is developed to construct a donor-acceptor polymer PIBDTBT-40. This polymer has favorable highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels for balanced ambipolar charge transport. Organic thin film transistors (OTFTs) based on this polymer shows well-balanced ambipolar characteristics with electron mobility of 0.14 cm² V⁻¹ s⁻¹ and hole mobility of 0.10 cm² V⁻¹ s⁻¹ in bottom-gate bottom-contact devices. This polymer is a promising semiconductor for solution processable organic electronics such as CMOS-like logic circuits.     

Dopant-Free Polymer HTM-Based CsPbI2Br Solar Cells with Efficiency Over 17% in Sunlight and 34% in Indoor Light

To abate the issue of moisture-assisted phase transition of CsPbI₂Br, caused by hygroscopic dopants used in the hole-transporting material (HTM), developing dopant-free HTMs is necessary. In this work, a new polymer, PDTDT, is developed as a dopant-free HTM for CsPbI₂Br solar cells, and the device performance and stability are systematically compared with cells employing dopant-free P3HT. CsPbI₂Br solar cells using PDTDT show an efficiency of 17.36% with V_OC of 1.42 V and FF of 81.29%, which is one of the highest values for CsPbI₂Br cells. Moreover, a record-high efficiency of 34.20% with V_OC of 1.14 V under 200 lux indoor light illumination and efficiency of 14.54% (certified efficiency of 13.86%) for a 1 cm² device under one sun are accomplished. Importantly, PDTDT shows superior/comparable device stability to P3HT, promising its potential to be an alternative to popular doped Spiro-OMeTAD and P3HT HTM.     

Mobility enhancement of DNTT and BTBT derivative organic thin-film transistors by triptycene molecule modification

Interface modification with a particular triptycene molecule that spontaneously forms a highly uniform molecule layer is a promising technique for realizing high-performance flexible organic thin-film transistors (OTFTs). Previous studies have shown that the triptycene-modified polymer surface enhances the crystallinity of the small-molecule organic semiconductor (OSC), DNTT (dinaphtho[2,3-b:2′,3′-f]thieno[3,2-b]thiophene), resulting in improved mobility. However, to date, the effectiveness of triptycene modification for the other OSCs has not been confirmed. Here, we report on the positive effect of triptycene layers on four different thienoacene-based OSCs (C₁₀-DNTT, DPh-DNTT, C₈-BTBT ([1]benzothieno[3,2-b][1]benzothiophene), and DPh-BTBT) in OTFTs. Regardless of the OSC type, triptycene-modified OTFTs are found to improve the field-effect mobility. A maximum effective mobility enhancement of 20-fold was obtained for C₁₀-DNTT OTFTs. Furthermore, detailed observations of the surface morphology of the OSCs via scanning electron microscopy revealed that the crystal grain size of the OSC thin films can be increased when triptycene modification is conducted.     

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.     

Recent progress of dopant-free organic hole-transporting materials in perovskite solar cells

Organic-inorganic hybrid perovskite solar cells have undergone especially intense research and transformation over the past seven years due to their enormous progress in conversion efficiencies. In this perspective, we review the latest developments of conventional perovskite solar cells with a main focus on dopant-free organic hole transporting materials (HTMs). Regarding the rapid progress of perovskite solar cells, stability of devices using dopant-free HTMs are also discussed to help readers understand the challenges and opportunities in high performance and stable perovskite solar cells.     

Annealing-free multi-thermal techniques comprising aging,cycling and seeding to enhance performance of thick P3HT:PCBM photovoltaic cells via developing hairy crystals

Distinct multi-thermal treatments comprising cycling, aging, and seeding were introduced to prepare very thick bulk heterojunction (BHJ) active layers (ca. 800 nm) of poly(3-hexylthiophene) (P3HT):phenyl-C71-butyric acid methyl ester (PC71BM) photovoltaic cells. To this end, various P3HT₄₈₈₀₀-based rod-coil block copolymers having the coily blocks of polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(ethylene glycol) (PEG) were synthesized. The grazing incidence X-ray scattering, field emission scanning electron microscopy (FESEM), and transmission electron microscopy (TEM) analyses proved that the dielectric coily blocks, which were excluded from the P3HT crystalline structure, accumulated on the crystals surface without decreasing the crystal quality and formed hairy crystals. The multi-thermal techniques facilitated stacking of the growth planes in π-π direction for the P3HT crystals, thereby, this dimension was improved from 5 to 27 nm for conventionally prepared BHJs to 53–265 nm for multi-thermally developed ones. The hydrophobic coily blocks were capable of neutralizing the influence of the PCBM molecules presence in the growth environment, which resulted in the larger P3HT crystals in a similar condition. By switching the conventional spin coating approach to the cycling, aging, and seeding methods, the P3HT crystals and the PCBM clusters were gradually coarsened and the respective d-spacings decreased. This trend enhanced the hole mobility (=8.8×10⁻⁵ cm²/Vs), electron mobility (=2.5×10⁻³ cm²/Vs), short circuit current density (J_sc=12.02 mA/cm²), fill factor (FF=69%), and power conversion efficiency (PCE=4.39%) up to the maximum values for seeding approach. Moreover, the higher percentages of face-on orientation were detected in the BHJs with lower d-spacings in the hexyl side chain direction. Hairy P3HT₄₈₈₀₀-b-PS crystals developed by seeding method possessed the highest face-on orientation (~5.5%).     

Methylated conjugated polymers based on diketopyrrolopyrrole and dithienothiophene for high performance field-effect transistors

In this work, a series of conjugated polymers based on diketopyrrolopyrrole (DPP) and dithienothiophene were designed for application in field-effect transistors (FETs). Owing to the synthetic nature of DPP units, the DPP polymers here contain different aromatic linkers with thiophene and methylthiophene, resulting in non-methylated and methylated DPP polymers. Methylated DPP polymers were found to show good crystalline properties and provide high hole mobilties up to 5.32 cm² V⁻¹ s⁻¹ in FETs, while non-methylated polymer exhibits a hole mobility of 3.16 cm² V⁻¹ s⁻¹. Especially, the polymer containing asymmetric linkers presents “face-on” orientation in thin films but provides the highest mobility. Our results reveal that the polymers incorporating methyl units as side chains can be used to realize high carrier mobility in FETs.     

Hole Transport Materials Based on 6,12‐Dihydroindeno[1,2‐b]fluorine with Different Periphery Groups: A New Strategy for Dopant‐Free Perovskite Solar Cells

Although several hole‐transporting materials (HTMs) have been designed to obtain perovskite solar cells (PSCs) devices with high performance, the dopant‐free HTMs for efficient and stable PSCs remain rare. Herein, a rigid planar 6,12‐dihydroindeno[1,2‐b]fluorine (IDF) core with different numbers of bulky periphery groups to construct dopant‐free HTMs of IDF‐SFXPh, IDF‐DiDPA, and IDF‐TeDPA is modified. Thanks to the contributions of the planar IDF core and the twisted SFX periphery groups, the dopant‐free IDF‐SFXPh‐based PSCs device achieves a device performance of 17.6%, comparable to the doped 2,2′,7,7′‐tetrakis(N,N‐di‐p‐methoxyphenylamine)‐9,9′‐spirobifluorene (spiro‐OMeTAD)‐based device (17.6%), with much enhanced device stability under glovebox and ambient conditions.     

A carbazole-based dopant-free hole-transport material for perovskite solar cells by increasing the molecular conjugation

Dopant-free hole-transport material (HTM) is essential to the long-term stability of the perovskite solar cells (PSCs). This study has introduced a novel carbazole-based dopant-free HTM via the simple ring-closing reaction without using the expensive catalyst. It has found that the merger of a higher rigid conjugated ring into the molecular geometry of HTM is an effective way to improve its charge extraction ability, hole mobility and phase thermal stability. Consequently, a power conversion efficiency (PCE) of 16.4% as well as a much-improved long-term stability have been achieved based on the as-prepared C302 dopant-free HTM.     

Fluorinated Organic A-Cation Enabling High-Performance Hysteresis-Free 2D/3D Hybrid Tin Perovskite Transistors

2D tin-based perovskites have gained considerable attention for use in diverse optoelectronic applications, such as solar cells, lasers, and thin-film transistors (TFTs), owing to their good stability and optoelectronic properties. However, their intrinsic charge-transport properties are limited, and the insulating bulky organic ligands hinder the achievement of high-mobility electronics. Blending 3D counterparts into 2D perovskites to form 2D/3D hybrid structures is a synergistic approach that combine the high mobility and stability of 3D and 2D perovskites, respectively. In this study, reliable p-channel 2D/3D tin-based hybrid perovskite TFTs comprising 3D formamidinium tin iodide (FASnI₃) and 2D fluorinated 4-fluoro-phenethylammonium tin iodide ((4-FPEA)₂SnI₄) are reported. The optimized FPEA-incorporated TFTs show a high hole mobility of 12 cm² V⁻¹ s⁻¹, an on/off current ratio of over 10⁸, and a subthreshold swing of 0.09 V dec⁻¹ with negligible hysteresis. This excellent p-type characteristic is compatible with n-type metal-oxide TFT for constructing complementary electronics. Two procedures of antisolvent engineering and device patterning are further proposed to address the key concern of low-performance reproducibility of perovskite TFTs. This study provides an alternative A-cation engineering method for achieving high-performance and reliable tin-halide perovskite electronics.     

A Large Bandgap Organic Salt Dopant for Sn-Based Perovskite Thin-Film Transistor

Metal halide perovskite optoelectronic devices have made significant progress over the past few years, but precise control of charge carrier density through doping is essential for optimizing these devices. In this study, the potential of using an organic salt, N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate, as a dopant for Sn-based perovskite devices, is explored. Under optimized conditions, the thin film transistors based on the doped 2D/3D perovskite PEAFASnI₃ demonstrate remarkable improvement in hole mobility, reaching 7.45 cm²V⁻¹s⁻¹ with a low subthreshold swing and the smallest sweep hysteresis (ΔV_hysteresis = 2.27 V) and exceptional bias stability with the lowest contact resistance (2.2 kΩ cm). The bulky chemical structure of the dopant prevents it from penetrating the perovskite lattice and also surface passivation against Sn oxidation due to its hydrophobic nature surface. This improvement is attributed to the bifunctional effect of the dopant, which simultaneously passivates defects and improves crystal orientation. These findings provide new insights into potential molecular dopants that can be used in metal halide perovskite devices.     

Organic Ionic Plastic Crystals as Hole Transporting Layer for Stable and Efficient Perovskite Solar Cells

Organic ionic plastic crystals (OIPCs) are synthesized through a simple metal‐free, cost‐effective approach. The strategized synchronization of electron‐rich phenoxazine with benzimidazolium iodide (OIPC‐I) and bromide (OIPC‐Br) salts lead to enhanced hole mobility and conductivity of OIPCs which is suitable for an efficient alternative to conventional organic hole transporting materials (HTMs) for stable perovskite solar cells (PSCs). The fabricated PSCs with OIPC‐I as hole transporting layer yielded a power conversion efficiency of 15.0% and 18.1% without and with additive (Li salt) respectively, which are comparable with spiro‐OMeTAD based devices prepared under similar conditions. Furthermore, the PSCs with OIPCs show good stability compared to the spiro‐OMeTAD with or without additives. Here, first time benzimidazolium‐based OIPCs have been used as an alternative organic HTM for perovskite solar cells, which opens a window for the design of effective OIPCs for highly efficient PSCs with long‐term stability.     

Graphene-oxide doped PEDOT:PSS as a superior hole transport material for high-efficiency perovskite solar cell

Inverted perovskite solar cells have attracted a great deal of attention due to its high power conversion efficiency, simple configuration, and low-cost processing. The hole transport material (HTM) is a crucial factor in high performance inverted perovskite solar cell. However, the hole mobility for most common of HTM is too low to matching perovskite materials. Herein, we report a superior HTM with high hole mobility to significantly improve solar cell efficiency. Upon doing the commonly used PEDOT:PSS HTM by graphene oxide (GO), its hole mobility is increased from 5.55 × 10⁻⁵ to 1.57 × 10⁻⁴ cm² V⁻¹ s⁻¹, leading to efficient hole extraction and low current leakage, therefore 20% higher power conversion efficiency comparing to the control device without the GO doping. The development open the opportunities for efficient HTMs based on the two-dimensional materials in the perovskite solar cells.