Simple hybrid dithiafulvenes-triphenylamine systems as dopant-free hole-transporting materials for efficient perovskite solar cells

Two extended hybrid conjugated systems based on a triphenylamine(TPA) core with two and three peripheral 1,4-dithiafulvenes(DTF) units coded WH-2 and WH-3 as hole-transporting materials(HTMs) applied in perovskite solar cells(PSCs) are synthesized by facile one-step reaction in good yield over 75%. DTF unit as electron donor can enhance the electron donating ability and the fusion of benzenic ring of TPA with DTF unit may lead to reinforced intermolecular interactions in the solid state. In addition,WH-2 and WH-3 exhibit a pyramid shape containing partial planarity and quasi three-dimensionality features, which is also conducive to enhancing the π-π stacking of molecules in the solid state. The above-mentioned structural characteristics make the two HTMs have good hole mobilities. As a result,WH-2 and WH-3 obtained the high intrinsic hole mobilities of 4.69 × 10^(-4)and 2.18 × 10^(-3)cm^(2)V^(-1)s^(-1)respectively. Finally, the power conversion efficiencies(PCEs) of PSCs with WH-2 and WH-3 as cost-effective dopant-free HTMs are 15.39% and 19.22% respectively and the PCE of PSC with WH-3 is on a par with that of PSC with Li-TFSI/t-BP doped Spiro-OMe TAD(19.67%).

Improvement on the performance of perovskite solar cells by doctor-blade coating under ambient condition with hole-transporting material optimization

Numerous fabrication methods have been developed for high-efficiency perovskite solar cells(PSCs). However, these are limited to spin-coating processes in a glove box and are yet to be commercialized. Therefore, there is a need to develop a controllable and scalable deposition technique that can be carried out under ambient conditions. Even though the doctor-blade coating technique has been widely used to prepare PSCs, it is yet to be applied to high-efficiency PSCs under ambient conditions(RH ~45%, RT ~25 °C). In this study, we conducted blade-coating fabrication of modified high-efficiency PSCs under such conditions. We controlled the substrate temperature to ensure phase transition of perovskite and added dimethyl sulfoxide(DMSO) to the perovskite precursor solution to delay crystallization, which can facilitate the formation of uniform perovskite films by doctor-blade coating. The as-prepared perovskite films had large crystal domains measuring up to 100 μm. Solar cells prepared from these films exhibited a current density that was enhanced from 17.22 to 19.98 m A/cm^2 and an efficiency that was increased from 10.98% to 13.83%. However, the open-circuit voltage was only 0.908 V, probably due to issues with the hole-transporting layer. Subsequently, we replaced poly(3,4-ethylenedioxythiophene) polystyrene sulfonate(PEDOT:PSS) with Ni O x as the hole-transporting material and then prepared higher-quality perovskite films by blade-coating under ambient conditions. The as-prepared perovskite films were preferably orientated and had large crystal domains measuring up to 200 μm;The open-circuit voltage of the resulting PSCs was enhanced from 0.908 to 1.123 V, while the efficiency increased from 13.83% to 15.34%.

Phenylfluorenamine-functionalized poly(N-vinylcarbazole)s as dopant-free polymer hole-transporting materials for inverted quasi-2D perovskite solar cells

In order to improve the efficiency and stability of inverted three-dimensional(3D) or quasi-2D perovskite solar cells(PSCs) for future commercialization, exploring high efficient dopant-free polymer holetransporting materials(HTMs) is still desired and meaningful. One simple and efficient way to achieve high performance dopant-free HTMs is to synthesize novel non-conjugated side-chain polymers via rational molecular design. In this work, N-(4-methoxyphenyl)-9,9-dimethyl-9H-fluoren-2-amine(FMeNPh) groups are introduced into the poly(N-vinylcarbazole)(PVK) side chains to afford two nonconjugated polymers PVCz-DFMeNPh and PVCz-FMeNPh as dopant-free HTMs in inverted quasi-2D PSCs. Benefited from the flexible properties of polyethylene backbone and excellent optoelectronic natures of FMeNPh side-chain groups, PVCz-DFMeNPh with more FMeNPh units exhibited excellent thermal stability, well-matched energy levels and improved charge mobility as compared to PTAA and PVCzFMeNPh. Moreover, the morphologies investigation of quasi-2D perovskite on PVCz-DFMeNPh shows more compact and homogeneous perovskite films than those on PTAA and PVCz-FMeNPh. As a result,the dopant-free PVCz-DFMeNPh based inverted quasi-2D PSCs deliver power conversion efficiency(PCE) up to 18.44% as well as negligible hysteresis and favorable long-term stability, which represents as excellent performance reported to date for inverted quasi-2D PSCs. The results demonstrate the great potentials of constructing non-conjugated side-chain polymer HTMs based on phenylfluorenamine-func tionalized PVK for the development of high efficient and stable inverted 3D or quasi-2D PSCs.

Synthesis and Characteristics of Hole-transporting Materials Based on Biphenyl Diamine Derivatives with Carbazole Groups

Two hole-transporting materials containing carbazole moieties with TPD- and NPB-like structures, 4,4′-bis [ N- （4-carbazolylphenyl） -N-phenylamino ] biphenyl （ CPB ） and 4,4′-bis [ N- （ 4-carbazolylphenyl ） -N- （ 1-naphthyl ） amino] biphenyl（ CNB）, were synthesized via a modified Ullmann reaction. The resulting compounds were thermally stable with high glass transition temperatures ranging from 145 to 147 ℃ and possessed a good electrochemical reversibility and hole-transporting properties. Typical double-layer device evaluation with the structure ITO/CPB（40 nm）/ Alq3 （60 nm）/LiF/Al demonstrated that they were promising hole-transporting materials with a current efficiency of 5.25 cd/A and a power efficiency of 2.00 lm/W.

Truxene-based Hole-transporting Materials for Perovskite Solar Cells

Three star-shaped truxene-based small molecules（namely TXH,TXM,TXO） were synthesized,characterized and used as hole-transporting materials（HTMs） for perovskite solar cells（Pv SCs）. The device based on TXO delivered a respectable power conversion efficiency（PCE） of 7.89% and a high open-circuit voltage（Voc） of 0.97 V,which far exceeded the values of the devices based on other two small molecules. The highest PCE for the device based on TXO is mainly contributed from its lowest series resistance（Rs） value and largest short-circuit current（Jsc） value under the same circumstances. All these results indicate that TXO is a promising HTM candidate for Pv SCs.

Light-Emitting Diodes Based on All-Quantum-Dot Multilayer Films and the Influence of Various Hole-Transporting Layers on the Performance

We present a systematic analysis of the exciton-recombination zone within all-quantum-dot （QD） multilayer films using sensing QD layers in QD-based light-emitting diodes （QLEDs）, and demonstrate the a11-QD multilayer films with different sequences of layers prepared by inserting a sensing blue QD layer denoted as B at various positions within four red QD multilayers denoted as R. We also use different hole transporting layers （PVK, CBP as well as poly-TPD） to prevent the formation of leakage current and to improve the luminance. The results show that the total EL emission is mostly at the fourth （60%） and fifth （40%） QD monolayers, adjacent to ITO. This presents both decreasing current density and increasing brightness with different hole transporting layers, thus resulting in more efficient performance.

An asymmetrically substituted dithieno[3,2-b:2',3'-d]pyrrole organic small-molecule hole-transporting material for high-performance perovskite solar cells

Hole-transporting materials play a vital role in terms of the performance of perovskite solar cells(PSCs).The dithieno[3,2-b:2’,3’-d]pyrrole(DTP),an S,N-heterocyclic building block,has been proved to be desirable for molecular design of hole-transporting materials in PSCs.We developed an asymmetrically substituted DTP small-molecule(JW12)and a reference compound(JW11).The asymmetrical structure of JW12 leads to different absorption properties and electron distribution.The device in a planar n-i-p architecture using JW12 shows a much higher PCE(18.07%)than that based on JW11(15.46%),which is also better than the device based on spiro-OMe TAD(17.47%).We hope our research can provide a new perspective in molecular design of organic HTMs for perovskite solar cells.

Application of phenonaphthazine derivatives as hole-transporting materials for perovskite solar cells

Two electron-rich, solution-processable phenonaphthazine derivatives, 5,12-bis(N-[4,4'-bis-(phenyl) aminophen-4 ''-yl]}-phenonaphthazine (BPZTPA) and 5,12-bis{N-[4,4'-bis(methoxy-phenyl)aminophen-4'-phenonaphthazine (MeO-BPZTPA) have been designed and employed in the fabrication of perovskite solar cells. BPZTPA and MeO-BPZTPA exhibit excellent thermal stabilities, hole mobilities (similar to 10(-4) cm(2)/(V.s)) and suitable HOMO levels (-5.34 and-5.29 eV, respectively) relative to the valence band of the CH3NH3PbI3 and Au work function, showing their potential as alternative hole-transporting materials (HTMs). Meanwhile, the corresponding mesoporous TiO2/CH3NH3PbI3/HTM/Au devices are investigated, and the best power conversion efficiency of 10.36% has been achieved for MeO-BPZTPA without using p-type dopant. (C) 2016 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by Elsevier B.V. and Science Press. All rights reserved.

The donor-dependent methoxy effects on the performance of hole-transporting materials for perovskite solar cells

In this work, a comprehensive study on the deliberate molecular design and modifications of electron donors is carried out to elucidate correlations between the methoxy effects and donor configuration of hole-transporting materials(HTMs). Our initial findings demonstrate the donor-dependent methoxy effects. Photovoltaic performance of the HTM with twisted donor highly depends on the methoxy substituent. In contrast, efficiency’s reliance on methoxy is insignificant for the HTM with planar donor. The HTM(M123) featuring the methoxy–substituted carbazole shows a decent power conversion efficiency of 19.33% due to synergistic effects from both planar structure and methoxy. This work gives a guideline to access HTMs reaching both high-performance and good stability.

Carbon-based perovskite solar cells with electron and hole-transporting/-blocking layers

Towards commercialization of perovskite solar cells(PSCs),further reducing the cost and increasing the stability of PSCs have been the most important tasks of researchers,as the efficiency of single-junction PSCs has reached a competitive level among all kinds of single-junction solar cells.Carbon-electrode-based PSCs(CPSCs),as one of the most promising constructions for achieving stable economical PSCs,now attract enormous attention for their cost-effectiveness and stability.Here,we briefly review the development of CPSCs and reveal the importance of n-i-p architecture for state-of-the-art CPSCs.However,despite their promising potential,challenges still exist in CPSCs in the n-i-p architecture,which mainly stem from the incompact contact of the hole-transporting layer(HTL)/carbon electrode.Thus,new carbon materials and/or novel manufacturing methods should be proposed.In addition,HTL is yet to be appropriate for state-of-the-art CPSCs because the fabrication of carbon electrode could result in the destruction of the underlayer.To further enhance the performance of CPSCs,both the HTL and electron transport layer as well as their interfaces with perovskite active layer need to be improved.We recommend that the perovskite active layer,with its long carrier lifetime,strong carrier transport capability,and long-term stability,is necessary as well for improved performance of CPSCs.We also highlight current researches on CPSCs and provide a systematic review of various types of regulation tools.

Increasing open circuit voltage by adjusting work function of hole-transporting materials in perovskite solar cells

A series of conductive polymers, i.e., poly（3-methylthiophene） （PMT）, poly（thiophene） （PT）, poly（3-bromothiophene） （PBT） and poly（3-chlorothiophene） （PCT）, were prepared via the electrochemical polymerization process. Subse- quently, their application as hole-transporting materials （HTMs） in CHBNI-I3Pb｜3 perovskite solar cells was explored. It was found that rationally increasing the work function of HTMs proves beneficial in improving the open circuit voltage （Voc） of the devices with an ITO/conductive-polymer/CHBNHBPbIg/C60/BCP/Ag structure. In addition, the higher-Voc devices with a higher-work-function HTM exhibited higher recombination resistances. The highest open circuit voltage of 1.04 V was obtained from devices with PCT, with a work function of -5.4 eV, as the hole-transporting layer. Its power conversion efficiency attained a value of approximately 16.5%, with a high fill factor of 0.764, an appreciable open voltage of 1.01 V and a short circuit current density of 21.4 mA.cm-2. This simple, controllable and low-cost manner of preparing HTMs will be beneficial to the production of large-area perovskite solar cells with a hole-transportin~ laver.

New advances in small molecule hole-transporting materials for perovskite solar cells

Organic π-functional molecules are the foundation and basic component of organic optoelectronic devices.For example,for ideal carrier transporting materials,extended π-conjugation and ordered π-πstacking are necessary to enhance the charge mobility and achieve desirable results.As a promising way to convert sunlight into electricity,organometal halide perovskite solar cells（PSCs） have captured a lot of attention due to its predominant merits especially in the aspect of remarkable photovoltaic performance and much potentially low production cost.For conventional planar PSC structure,hole-transporting layer which typically consists of organic π-functional materials plays a key role in suppressing holeelectron pair recombination,promoting charge transporting and ensuring ohmic contact of back electrode.Considering the key roles of HTMs and its soaring progress in recent years,here,we will summarize recent progress in small organic π-functional materials from its diverse functions in PSCs.Besides,aiming to further promote the development of organic π-functional molecules and HTMs,a promising direction toward highly efficient HTMs will also be discussed.

Efficient perovskite solar cells employing a solution-processable copper phthalocyanine as a hole-transporting material

The development of alternative low-cost and high-performing hole-transporting materials(HTMs) is of great significance for the potential large-scale application of perovskite solar cells(PSCs) in the future.Here,a facilely synthesized solution-processable copper tetra-(2,4-dimethyl-3-pentoxy) phthalocyanine(CuPc-DMP) via only two simple steps,has been incorporated as a hole-transporting material(HTM) in mesoscopic perovskite solar cells(PSCs).The optimized devices based on such a HTM afford a very competitive power conversion efficiency(PCE) of up to 17.1%measured at 100 mW cm^(-2) AM 1.5G irradiation,which is on par with that of the well-known 2,2',7,7'-tetrakis(N'N'-di-p-methoxyphenylamine)-9,9'-spirobifluorene(spiro-OMeTAD)(16.7%) under equivalent conditions.This is,to the best of our knowledge,the highest value reported so far for metal organic complex-based HTMs in PSCs.The advantages of this HTM observed,such as facile synthetic procedure,superior hole transport characteristic,high photovoltaic performance together with the feasibility of tailoring the molecular structure would make solution-processable copper phthalocyanines as a class of promising HTM that can be further explored in PSCs.The present finding highlights the potential application of solution processed metal organic complexes as HTMs for cost-effective and high-performing PSCs.

Recent progress in organic hole-transporting materials with 4-anisylamino-based end caps for efficient perovskite solar cells

Perovskite solar cells(PVSCs)have emerged as a promising photovoltaic technology and have attracted wide research interest due to their outstanding photovoltaic performance,low cost,and the ability to fabricate largearea devices.An impressive certified power conversion efficiency(PCE)of 25.2%has been achieved,demonstrating the excellent potential of PVSCs for future applications.Hole-transporting materials play a key role in improving the device performance of PVSCs by facilitating the extraction of photogenerated holes and their transport from the perovskite layer to the anode.This review provides a brief introduction to PVSCs and summarizes the recent progress in small molecule hole-transporting materials(SM-HTMs)bearing various cores and different4-anisylamino-based end caps.We classify the end caps into N,N-di-4-anisylamino(DAA),4-(N,N-di-4-anisylamino)benzo(DAB),and N3,N6(or N2,N7)-bis(di-4-anisylamino)-9 H-carbazole(3,6-DAC or 2,7-DAC)groups.We also review the core type,end cap position and number,how these affect the overall properties of the SM-HTMs,and the resultant PVSC device performances.Finally,the challenges and perspectives for the future development of SM-HTMs are presented.

Quantum-dot light-emitting diodes with Fermi-level pinning at the hole-injection/hole-transporting interfaces

Quantum-dot light-emitting diodes(QLEDs)are multilayer electroluminescent devices promising for next-generation display and solid-state-lighting technologies.In the state-of-the-art QLEDs,hole-injection layers(HILs)with high work functions are generally used to achieve efficient hole injection.In these devices,Fermi-level pinning,a phenomenon often observed in heterojunctions involving organic semiconductors,can take place in the hole-injection/hole-transporting interfaces.However,an in-depth understanding of the impacts of Fermi-level pinning at the hole-injection/hole-transporting interfaces on the operation and performance of QLEDs is still lacking.Here,we develop a set of NiOx HILs with controlled work functions of 5.2–5.9 eV to investigate QLEDs with Fermi-level pinning at the hole-injection/hole-transporting interfaces.The results show that despite that Fermi-level pinning induces identical apparent hole-injection barriers,the red QLEDs using HILs with higher work functions show improved efficiency roll-off and better operational stability.Remarkably,the devices using the NiOx HILs with a work function of 5.9 eV demonstrate a peak external quantum efficiency of~18.0%and a long T95 operational lifetime of 8,800 h at 1,000 cd·m^(−2),representing the best-performing QLEDs with inorganic HILs.Our work provides a key design principle for future developments of the hole-injection/hole-transporting interfaces of QLEDs.

Hole-transporting layer-free inverted planar mixed lead-tin perovskite-based solar cells

Mixed lead-tin （Pb-Sn） perovskites present a promising strategy to extend the light-harvesting range of perovskite-based solar cells （PSCs）. The use of electron- transporting layer or hole-transporting layer （HTL） is critical to achieve high device efficiency. This strategy, however, requires tedious layer-by-layer fabrication as well as high-temperature annealing for certain oxides. In this work, we fabricated HTL-free planar FAPb0.5Sn0.5I3 PSCs with the highest efficiency of 7.94%. High short- circuit current density of 23.13 mA/cm2 was attained, indicating effective charge extraction at the ITO/ FAPb0.5Sn0.5I3 interface. This finding provides an alter- native strategy to simplify the manufacture of single- junction or tandem PSCs.

Sulfonyldibenzene-based hole-transporting materials for efficient n-i-p perovskite solar cells

Organic hole-transporting materials(HTMs)are an essential component in conventional perovskite solar cells(PSCs).In this work,two sulfonyldibenzene-based molecules,named CS-04 and CS-05,are synthesized and employed as HTMs in n-i-p PSCs.In comparison with CS-04,the carbazole-substituted methoxytriphenylamine(Cz MOTPA)group in CS-05 exhibits an increased degree of molecular distortion,thus endowing CS-05 with excellent solvent solubility and film-formation ability.Moreover,CS-05 shows a high hole mobility,superior hole extraction and hole transporting properties.As a result,CS-05 yields impressive device performances with a high power conversion efficiency(PCE)of 20.15%,while that of CS-04 based device is 19.50%,which is comparable to that of the Spiro-OMe TAD based control device(19.59%).This finding illustrates the potential of sulfonyldibenzene-based molecules for the applications in PSCs,and also provides a novel avenue to improve the performances and stability of PSCs by tailoring the sulfonyldibenzene-based molecules.

Anthradithiophene based hole-transport material for efficient and stable perovskite solar cells

A novel hole-transport material(HTM)based on an anthradithiophene central bridge named BTPA-7 is developed.In comparison to spiro-OMeTAD(2,2’,7,7’-tetrakis-(N,N-di-p-methoxyphenylamine)-9,9’-spirobifluorene),the synthetic steps of BTPA-7 are greatly reduced from 6 to 3 and the synthetic cost of BTPA-7 is nearly a half that of spiro-OMeTAD.Moreover,BTPA-7 exhibits a relatively lower conductivity but higher hole mobility and higher glass transition temperature(Tg)than spiro-OMeTAD.Compared with the photovolatic performance for spiro-OMeTAD,FA0.85MA0.15PbI3 and MAPbI3 PSC devices based on BTPA-7 exhibit slightly lower PCEs with the values of 17.58%(18.88%for spiro-OMeTAD)and 11.90%(13.25%for spiro-OMeTAD),respectively.Nevertheless,a dramatically higher JSC of PSC based on BTPA-7is achieved,which arises from the higher hole mobility of BTPA-7.In addition,the relatively hydrophobic character of BTPA-7 eventually enhances the PSC device stability.Lower cost,higher hole mobility,higher Tg,satisfactory photovoltaic performance,and superior device stability of BTPA-7 can be utilized as a substitute for spiro-OMeTAD in PSCs.

A crosslinked polymer as dopant-free hole-transport material for efficient n-i-p type perovskite solar cells

A new crosslinked polymer,called P65,with appropriate photo-electrochemical,opto-electronic,and thermal properties,has been designed and synthesized as an efficient,dopant-free,hole-transport material(HTM)for n-i-p type planar perovskite solar cells(PSCs).P65 is obtained from a low-cost and easily synthesized spiro[fluorene-9,90-xanthene]-30,60-diol(SFX-OH)-based monomer X65 through a freeradical polymerization reaction.The combination of a three-dimensional(3 D)SFX core unit,holetransport methoxydiphenylamine group,and crosslinked polyvinyl network provides P65 with good solubility and excellent film-forming properties.By employing P65 as a dopant-free hole-transport layer in conventional n-i-p type PSCs,a power conversion efficiency(PCE)of up to 17.7%is achieved.To the best of our knowledge,this is the first time a 3 D,crosslinked,polymeric dopant-free HTM has been reported for use in conventional n-i-p type PSCs.This study provides a new strategy for the future development of a 3 D crosslinked polymeric dopant-free HTM with a simple synthetic route and low-cost for commercial,large-scale applications in future PSCs.

Hole‑Transport Management Enables 23%‑Efficient and Stable Inverted Perovskite Solar Cells with 84%Fill Factor

NiO_(x)-based inverted perovskite solar cells(PSCs)havepresented great potential toward low-cost,highly efficient and stablenext-generation photovoltaics.However,the presence of energy-levelmismatch and contact-interface defects between hole-selective contacts(HSCs)and perovskite-active layer(PAL)still limits device efficiencyimprovement.Here,we report a graded configuration based on bothinterface-cascaded structures and p-type molecule-doped compositeswith two-/three-dimensional formamidinium-based triple-halideperovskites.We find that the interface defects-induced non-radiativerecombination presented at HSCs/PAL interfaces is remarkably suppressedbecause of efficient hole extraction and transport.Moreover,astrong chemical interaction,halogen bonding and coordination bondingare found in the molecule-doped perovskite composites,whichsignificantly suppress the formation of halide vacancy and parasitic metallic lead.As a result,NiO_(x)-based inverted PSCs present a power-conversion-efficiency over 23%with a high fill factor of 0.84 and open-circuit voltage of 1.162 V,which are comparable to the best reported around 1.56-electron volt bandgap perovskites.Furthermore,devices with encapsulation present high operational stability over 1,200 h during T_(90) lifetime measurement(the time as a function of PCE decreases to 90%of its initial value)under 1-sun illumination in ambient-air conditions.