Review of current progress in hole-transporting materials for perovskite solar cells

Recent advancements in perovskites’ application as a solar energy harvester have been astonishing. The power conversion efficiency(PCE) of perovskite solar cells(PSCs) is currently reaching parity(>25 percent), an accomplishment attained over past decades. PSCs are seen as perovskites sandwiched between an electron transporting material(ETM) and a hole transporting material(HTM). As a primary component of PSCs, HTM has been shown to have a considerable effect on solar energy harvesting, carrier extraction and transport, crystallization of perovskite, stability, and price. In PSCs, it is still necessary to use a HTM.While perovskites are capable of conducting holes, they are present in trace amounts, necessitating the use of an HTM layer for efficient charge extraction. In this review, we provide an understanding of the significant forms of HTM accessible(inorganic, polymeric and small molecule-based HTMs), to motivate further research and development of such materials. The identification of additional criteria suggests a significant challenge to high stability and affordability in PSC.

Recent advances of Cu-based hole transport materials and their interface engineering concerning different processing methods in perovskite solar cells

In recent years, perovskite solar cells (PSCs) have become a much charming photovoltaic technology and have triggered enormous studies worldwide, owing to their high efficiency, low cost and ease of preparation. The power conversion efficiency has rapidly increased by more than 6 times to the current 25.5% in the past decade. Hole transport materials (HTMs) are an indispensable part of PSCs, which great affect the efficiency, the cost and the stability of PSCs. Inorganic Cu-based p-type semiconductors are a kind of representative inorganic HTMs in PSCs due to their unique advantages of rich variety, low cost, excellent hole mobility, adjustable energy levels, good stability, low temperature and scalable processing ability. In this review, the research progress in new materials and the control of photoelectric properties of Cu-based inorganic HTMs were first summarized systematically. And then, concerning different processing methods, advances of the interface engineering of Cu-based hole transport layers (HTLs) in PSCs were detailly discussed. Finally, the challenges and future trends of Cu-based inorganic HTMs and their interface engineering in PSCs were analyzed.

Improving the performance of arylamine-based hole transporting materials in perovskite solar cells： Extending π-conjugation length or increasing the number of side groups？

In this work, we prepared three simple arylamine-based hole transporting materials from commercially available starting materials. The effect of extending z-conjugation length or increasing the number of side groups compared with reference compound on the photophysical, electrochemical, hole mobility properties and performance in perovskite solar cells were further studied. It is noted that these two kinds of molecular modifications can significantly lower the HOMO level and improve the hole mobility, thus improving the hole injection from valence band of perovskite. On the other hand, the compound with more side groups showed higher hole injection efficiency due to lower HOMO level and higher hole mo- bility compared with the compound with extending π-conjugation length. The perovskite solar cells with the modified molecules as hole transporting materials showed a higher efficiency of 15.40% and 16.95%, respectively, which is better than that of the reference compound （13.18%）. Moreover, the compound with increasing number of side groups based devices showed comparable photovoltaic performance with that of conventional spiro-OMeTAD （16.87%）.

Diketopyrrolopyrrole based D-π-A-π-D type small organic molecules as hole transporting materials for perovskite solar cells

Three novel diketopyrrolopyrrole （DPP） based small organic molecules were synthesized as hole transporting materials for perovskite solar cells. The effects of different donors and zr bridges on the performance of perovskite solar cells （PSCs） were discussed. The efficiency of TPADPP-1, TPADPP-2. PTZDPP-2 was 5.10%, 9.85% and 8.16% respectively. Compared to TPADPP-2, the voltage of PTZDPP-2 was higher. Because the electron-donatingability of phenothiazine based donor was larger than that of triphenylamine based donor, the HOMO level of PTZDPP-2 was lower than that of TPADPP-2. The results indicated that the diketopyrrolopyrrole based D-π-A-π-D type small organic molecule might be a promising hole trans- porting material in the perovskite solar cells.

Spatial configuration engineering of perylenediimide-based non-fullerene electron transport materials for efficient inverted perovskite solar cells

Due to their excellent photoelectron chemical properties and suitable energy level alignment with perovskite,perylene diimide(PDI)derivatives are competitive non-fullerene electron transport material(ETM)candidates for perovskite solar cells(PSCs).However,the conjugated rigid plane structure of PDI units result in PDI-based ETMs tending to form large aggregates,limiting their application and photovoltaic performance.In this study,to restrict aggregation and further enhance the photovoltaic performance of PDI-type ETMs,two PDI-based ETMs,termed PDO-PDI2(dimer)and PDO-PDI3(trimer),were constructed by introducing a phenothiazine 5,5-dioxide(PDO)core building block.The research manifests that the optoelectronic properties and film formation property of PDO-PDI2 and PDO-PDI3 were deeply affected by the molecular spatial configuration.Applied in PSCs,PDO-PDI3 with threedimensional spiral molecular structure,exhibits superior electron extraction and transport properties,further achieving the best PCE of 18.72%and maintaining 93%of its initial efficiency after a 720-h aging test under ambient conditions.

Non-conjugated polymers as thickness-insensitive electron transport materials in high-performance inverted organic solar cells

Two non-conjugated polymers PEIE-DBO and PEIE-DCO, prepared by quaternization of polyethyleneimine ethoxylate by 1,8-dibromooctane and 1,8-dichlorooctane respectively, are developed as electron transport layer(ETL) in high-performance inverted organic solar cells(OSCs), and the effects of halide ions on polymeric photoelectric performance are fully investigated. PEIE-DBO possesses higher electron mobility(3.68×10-4 cm2 V-1s-1), higher conductivity and more efficient exciton dissociation and electron extraction, attributed to its lower work function(3.94 eV) than that of PEIE-DCO, which results in better photovoltaic performance in OSCs. The inverted OSCs with PTB7-Th: PC71BM as photoactive layer and PEIE-DBO as ETL exhibit higher PCE of 10.52%, 9.45% and 9.09% at the thickness of 9, 35 and 50 nm,respectively. To our knowledge, PEIE-DBO possesses the best thickness-insensitive performance in polymeric ETLs of inverted fullerene-based OSCs. Furthermore, PEIE-DBO was used to fabricate the inverted non-fullerene OSCs(PM6:Y6) and obtained a high PCE of 15.74%, which indicates that PEIE-DBO is effective both in fullerene-based OSCs and fullerene-free OSCs.

Toward high-efficiency perovskite solar cells with one-dimensional oriented nanostructured electron transport materials

The unique advantages of one-dimensional(1D)oriented nanostructures in light-trapping and chargetransport make them competitive candidates in photovoltaic(PV)devices.Since the emergence of perovskite solar cells(PSCs),1D nanostructured electron transport materials(ETMs)have drawn tremendous interest.However,the power conversion efficiencies(PCEs)of these devices have always significantly lagged behind their mesoscopic and planar counterparts.High-efficiency PSCs with 1D ETMs showing efficiency over 22%were just realized in the most recent studies.It yet lacks a comprehensive review covering the development of 1D ETMs and their application in PSCs.We hence timely summarize the advances in 1D ETMs-based solar cells,emphasizing on the fundamental and optimization issues of charge separation and collection ability,and their influence on PV performance.After sketching the classification and requirements for high-efficiency 1D nanostructured solar cells,we highlight the applicability of 1D TiO_(2)nanostructures in PSCs,including nanotubes,nanorods,nanocones,and nanopyramids,and carefully analyze how the electrostatic field affects cell performance.Other kinds of oriented nanostructures,e.g.,ZnO and SnO_(2)ETMs,are also described.Finally,we discuss the challenges and propose some potential strategies to further boost device performance.This review provides a broad range of valuable work in this fast-developing field,which we hope will stimulate research enthusiasm to push PSCs to an unprecedented level.

Progress in hole-transporting materials for perovskite solar cells

In recent years the photovoltaic community has witnessed the unprecedented development of perovskite solar cells（PSCs） as they have taken the lead in emergent photovoltaic technologies. The power conversion efficiency of this new class of solar cells has been increased to a point where they are beginning to compete with more established technologies. Although PSCs have evolved a variety of structures, the use of hole-transporting materials（HTMs） remains indispensable. Here, an overview of the various types of available HTMs is presented. This includes organic and inorganic HTMs and is presented alongside recent progress in associated aspects of PSCs, including device architectures and fabrication techniques to produce high-quality perovskite films. The structure, electrochemistry, and physical properties of a variety of HTMs are discussed, highlighting considerations for those designing new HTMs. Finally, an outlook is presented to provide more concrete direction for the development and optimization of HTMs for highefficiency PSCs.

Heat transport in low-dimensional materials: A review and perspective

Heat transport is a key energetic process in materials and devices. The reduced sample size, low dimension of the problem and the rich spectrum of material imperfections introduce fruitful phenomena at nanoscale. In this review, we summarize recent progresses in the understanding of heat transport process in low-dimensional materials, with focus on the roles of defects, disorder, interfaces, and the quantum- mechanical effect. New physics uncovered from computational simulations, experimental studies, and predictable models will be reviewed, followed by a perspective on open challenges.

Heteroatom engineering on spiro-type hole transporting materials for perovskite solar cells

A series of spiro-type hole transporting materials, spiro-OMe TAD, spiro-SMe TAD and spiro-OSMe TAD,with methoxy, methylsulfanyl or half methoxy and half methylsulfanyl terminal groups are designed and prepared. The impact of varied terminal groups on bulk properties, such as photophysical, electrochemical, thermal, hole extraction, and photovoltaic performance in perovskite solar cells is investigated.It is noted that the terminal groups of the hole transporting material with half methoxy and half methylsulfanyl exhibit a better device performance and decreased hysteresis compared with all methoxy or methylsulfanyl counterparts due to better film-forming ability and improved hole extraction capability.Promisingly, the spiro-OSMe TAD also shows comparable performance than high-purity commercial spiro-OMe TAD. Moreover, the highest power conversion efficiency of the optimized device employing spiro-OSMe TAD exceeding 20% has been achieved.

C≡N-based carbazole-arylamine hole transporting materials for perovskite solar cells: Substitution position matters

Hole transporting materials(HTMs)containing passivating groups for perovskite materials have attracted much attention for efficient and stable perovskite solar cells(PSCs).Among them,C≡N-based molecules have been proved as efficient HTMs.Herein,a series of novel C≡N functionalized carbazole-arylamine derivatives with variable C≡N substitution positions(para,meta,and ortho)on benzene-carbazole skeleton(on the adjacent benzene of carbazole)were synthesized(p-HTM,m-HTM and o-HTM).The experimental results exhibit that the substitution positions of the Ctriple bondN unit on HTMs have minor difference on the HOMO energy level and hydrophobicity.m-HTM has a relatively lower glass transition temperature compared with that of p-HTM and o-HTM.The functional theory calculations show that the C≡N located on meta position exposed very well,and the exposure direction is also the same with the methoxy.Upon applying these molecules as HTMs in PSCs,their device performance is found to sensitively depend on the substitution position of the C≡N unit on the molecule skeleton.The devices using m-HTM and o-HTM exhibit better performance than that of p-HTM.Moreover,m-HTM-based devices exhibit better light-soaking performance and long-term stability,which could be resulted from better interaction with the perovskite according to DFT results.Moreover,we further prepared a HTM with two C≡N units on the symmetrical meta position of molecular skeleton(2m-HTM).Interestingly,2m-HTM-based devices exhibit relatively inferior performance compared with that of the m-HTM,which could be resulted from weak negative electrical character of C≡N unit on 2m-HTM.The results give some new insights for designing ideal HTM for efficient and stable PSCs.

Rational Design of Star-shaped Molecules with Benzene Core and Naphthalimide Derivatives End Groups as Organic Light-emitting Materials

A series of star-shaped molecules with benzene core and naphthalimides derivatives end groups have been designed to explore their optical,electronic,and charge transport properties as charge transport and/or luminescent materials for organic light-emitting diodes（OLEDs）. The frontier molecular orbitals（FMOs） analysis has turned out that the vertical electronic transitions of absorption and emission are characterized as intramolecular charge transfer（ICT）. The calculated results show that the optical and electronic properties of star-shaped molecules are affected by the substituent groups in N-position of 1,8-naphthalimide ring. Our results suggest that star-shaped molecules with n-butyl（1）,benzene（2）,thiophene（3）,thiophene S？,S？-dioxide（4）,benzo[c][1,2,5]thiadiazole（5）,and 2,7a-dihydrobenzo[d]thiazole（6） fragments are expected to be promising candidates for luminescent and electron transport materials for OLEDs. This study should be helpful in further theoretical investigations on such kind of systems and also to the experimental study for charge transport and/or luminescent materials for OLEDs.

Anisotropic Transport and Magnetic Properties of Charge-Density-Wave Materials RSeTe2（R=La,Ce,Pr,Nd）

Single crystals of RSeTe2 （R =La, Ce, Pr, Nd） are synthesized using LiC1/RbCI flux. Transport and magnetic properties in the directions parallel and perpendicular to the a-c plane are investigated. We find that the resistivity anisotropy P⊥/P∥ lies in the range 486-615 for different compounds at 2K, indicating the highly two-dimensional character. In both the orientations, the charge-density-wave transitions start near Tcow = 284（3）K, 316（3）K, 359（3）K for NdSeTe2, PrSeTe2, CeSeTe2, respectively, with a considerable increase in dc resistivity. While for LaSeTe2, no obvious resistivity anomaly is observed up to 380K. The value of TCDW increases monotonically with the increasing lattice parameters. Below TCDW, slight anomalies can be observed in NdSeTe2, PrSeTe2 and CeSeTe2 with onset temperature at 193（3）K, 161（3）K, 108（3）K, respectively, decreasing as lattice parameters increase. Magnetic susceptibility measurements show that the valence state of rare earth ions are trivalenee in these compounds. Antiferromagnetie-type magnetic order is formed in CeSeTe2 at 2.1 K, while no magnetic transition is observed in PrSeTe2 and NdSeTe2 down to 1.8 K.

Bithiophene-based cost-effective hole transport materials for efficient n-i-p perovskite solar cells

Charge transport materials constitute a relatively large portion of the cost in the production of perovskite solar cells(PSCs).Therefore,developing cheap and efficient charge transport materials is of great significance for the commercialization of PSCs.In this study,three low-cost hole transport materials(HTMs),specifically 4,4'-(3,3'-bis(4-methoxy-2,6-dimethylphenyl)-[2,2'-bithiophene]-5,5'-diyl)bis(N,N-bis(4-methoxyphenyl)aniline)(TP-H),4,4'-(3,3'-bis(4-methoxy-2,6-dimethylphenyl)-[2,2'-bithiophene]-5,5'-diyl)bis(3-methoxy-N,N-bis(4-methoxy-phenyl)aniline)(TP-OMe),and 4,4'-(3,3'-bis(4-methoxy-2,6-dimethylphenyl)-[2,2'-bithiophene]-5,5'-diyl)bis(3-fluoro-N,N-bis(4-methoxyphenyl)aniline)(TP-F),were designed and synthesized using a bulky group-substi-tuted 2,2'-bithiophene core and methoxy-or F-functionalized triphenylamine derivatives.Compared to the HTMs without F atoms,TP-F using F substitution exhibited enhanced intermolecular packing,a lower highest occupied molecular orbital energy level,and increased hole mobility and conductivity.The PSC incorporating the doped TP-F as the hole transport layer achieved the highest power conversion efficiency(over 24%)among the three devices.The high performance of TP-F can be attributed to the passivation effect of S and F atoms on uncoordinated Pb2+within the perovskite(PVSK)film,which significantly reduces the density of defect states and the incidence of trap-mediated recombination in PSCs.This study demonstrates the effec-tiveness of the 3,3'-bis(4-methoxy-2,6-dimethylphenyl)-2,2'-bithiophene building block for constructing cost-effective HTMs and highlights the impact of F substitution on enhancing the photovoltaic performance of PSCs.

Grain size composition and transport of sedimentary organic carbon in the Changjiang River(Yangtze River) Estuary and Hangzhou Bay and their adjacent waters

Surface sediments from the Changjiang River （Yangtze River） Estuary, Hangzhou Bay, and their adjacent waters were analyzed for their grain size distribution, organic carbon （OC） concentration, and stable carbon isotope composition （δ13C）. Based on this analysis, about 36 surface sediment samples were selected from various environments and separated into sand （〉0.250 ram, 0.125-0.250 ram, 0.063-0.125 mm） and silt （0.025-0.063 mm） fractions by wet-sieving fractionation methods, and further into silt- （0.004-0.025 mm） and clay-sized （〈0.004 mm） fractions by centrifugal fractionation. Sediments of six grain size categories were analyzed for their OC and 613C contents to explore the grain size composition and transport paths of sedimentary OC in the study area. From fine to coarse fractions, the OC content was 1.18%, 0.51%, 0.46%, 0.42%, 0.99%, and 0.48%, respectively, while the δ13C was -21.64‰, -22.03‰, -22.52‰, -22.46‰, -22.36‰, and -22.28%0, respectively. In each size category, the OC contribution was 42.96%, 26.06%, 9.82%, 5.75%, 7.09%, and 8.33%, respectively. The OC content in clay and fine silt fractions （〈0.025 ram） was about 69.02%. High OC concentrations were mainly found in offshore modern sediments in the northeast of the Changjiang River Estuary, in modern sediments in the lower estuary of the Changjiang River and Hangzhou Bay, and in Cyclonic Eddy modern sediments to the southwest of the Cheju Island. Integrating the distribution of terrestrial OC content of each grain size category with the δ13C of the bulk sediment indicated that the terrestrial organic material in the Changjiang River Estuary was transported seaward and dispersed to the Cyclonic Eddy modern sediments to the southwest of the Cheju Island via two pathways： one was a result of the Changjiang River Diluted Water （CDW） northeastward extending branch driven by the North Jiangsu Coastal Current and the Yellow Sea Coastal Current, while the other one was the result of the CDW southward extending branch driven by the Taiwan Warm Current.

Effective Improvement of the Photovoltaic Performance of Carbon-Based Perovskite Solar Cells by Additional Solvents

A solvent-assisted methodology has been developed to synthesize CH_3NH_3 PbI_3perovskite absorber layers.It involved the use of a mixed solvent of CH_3NH_3 I,PbI_2,c-butyrolactone,and dimethyl sulfoxide(DMSO) followed by the addition of chlorobenzene(CB).The method produced ultra-flat and dense perovskite capping layers atop mesoporous TiO_2 films,enabling a remarkable improvement in the performance of free hole transport material(HTM) carbon electrode-based perovskite solar cells(PSCs).Toluene(TO) was also studied as an additional solvent for comparison.At the annealing temperature of 100 °C,the fabricated HTM-free PSCs based on drop-casting CB demonstrated power conversion efficiency(PCE) of 9.73 %,which is 36 and 71 % higher than those fabricated from the perovskite films using TO or without adding an extra solvent,respectively.The interaction between the PbI_2–DMSO–CH_3NH_3I intermediate phase and the additional solvent was discussed.Furthermore,the influence of the annealing temperature on the absorber film formation,morphology,and crystalline structure was investigated and correlated with the photovoltaic performance.Highly efficient,simple,and stable HTM-free solar cells with a PCE of 11.44 % were prepared utilizing the optimum perovskite absorbers annealed at 120 °C.

A Mini Review: Can Graphene Be a Novel Material for Perovskite Solar Cell Applications?

Perovskite solar cells(PSCs) have raised research interest in scientific community because their power conversion efficiency is comparable to that of traditional commercial solar cells(i.e., amorphous Si, GaAs,and CdTe). Apart from that, PSCs are lightweight, are flexible, and have low production costs. Recently, graphene has been used as a novel material for PSC applications due to its excellent optical, electrical, and mechanical properties. The hydrophobic nature of graphene surface can provide protection against air moisture from the surrounding medium, which can improve the lifetime of devices. Herein, we review recent developments in the use of graphene for PSC applications as a conductive electrode,carrier transporting material, and stabilizer material. By exploring the application of graphene in PSCs, a new class of strategies can be developed to improve the device performance and stability before it can be commercialized in the photovoltaic market in the near future.

High performance perovskite solar cells using TiO2 nanospindles as ultrathin mesoporous layer

Single crystal anatase TiO2 nanospindles （NSs） with highly exposed {101} facets were synthesized and employed as electron transport materials （ETMs） in perovskite solar cells （PSCs）. Time-resolved photoluminescence （TRPL） spectra revealed that the TiO2 NSs are more effective than TiO2 nanoparticles in accepting electrons from perovskite. Moreover. the TiO2 nanospindles further endowed the PSCs with good reproducibility and suppressed hysteresis. The best device with TiO2 NSs as ETMs yielded power conversion efficiency （PCE） of 19.6%, demonstrating that the home-made TiO2 NSs is a good ETM for PSCs.

A facile solution processed ZnO@ZnS core–shell nanorods arrays for high-efficiency perovskite solar cells with boosted stability

Zinc Oxide(ZnO)has been extensively applied as electron transport material(ETM)in perovskite solar cells(PSCs)since the emergence of PSCs.However,some chemisorbed oxygen species on the surface of ZnO can cause the degradation of CH3NH3+(MA^(+))based perovskite.To avoid the destructive effect of ZnO,a facile solution strategy was proposed to produce a ZnS shell around the ZnO nanorods arrays(ZnO-NRs),i.e.ZnO@ZnS core-shell nanorods(ZnO-NRs@ZnS).The ZnO-NRs@ZnS cascade structure can not only facilitate carrier transport,but also enhance the stability of ZnO based PSCs.A power conversion efficiency(PCE)of 20.6%was finally yielded,which is the-state-of-the-art efficiency for PSCs with one-dimensional(1 D)ZnO electron transport materials(ETMs).Moreover,over 90%of the initial efficiency was retained for the unencapsulated device with ZnO-NRs@ZnS ETMs at 85℃for 500 h,demonstrating excellent stability.This work provides a simple and efficient avenue to simultaneously enhance the photovoltaic(PV)performance and stability of 1 D ZnO nanostructure-based PSCs.

Ratios of Closely Related Elements in Soil and Their Implications

This paper has investigated the ratios of closely related elements such as Mn,Cr,V,Ni,Co,Cu,Pb,Cd,Ba,Sr,La and Ce in the major soils of China,and the factors affecting them,and explored their use as indicators in soil formation,material transport and environmental pollution.Results show that the effect of soil-forming processes on the ratios of closely related elements varied with different elements,and became greater in the sequence of Ce/La <V/Cr≈Ni/Co<Zn/Cu≈Zn/Pb<Zn/Cd<Mn/Cr<Ba/Sr.The magnitude of the variation in the ratios of closely related elements depended on the chemical properties of the elements themselves,on the one hand,and the parent material and climatic conditions on the other.The ratio of Ba/Sr showed a distinct zonality,decreasing gradually in the sequence:cool temperate zone acid soils>grassland soils>desert soils and increasing gradually from the semi-arid subhumid zone soils>the temperate zone neutral soils>the north subtropic zone soils>tropical and subtropical acid soils.