Molecular packing tuning via chlorinated end group enables efficient binary organic solar cells over 18.5%

Designing novel nonfullerene acceptors(NFAs)is of vital importance for the development of organic solar cells(OSC).Modification on the side chain and end group are two powerful tools to construct efficient NFAs.Here,based on the high-performance L8BO,we selected 3-ethylheptyl to substitute the inner chain of 2-ethylhexyl,obtaining the backbone of BON3.Then we introduced different halogen atoms of fluorine and chlorine on 2-(3-oxo-2,3-dihydro-1Hinden-1-ylidene)malononitrile end group(EG)to construct efficient NFAs named BON3-F and BON3-Cl,respectively.Polymer donor D18 was chosen to combine with two novel NFAs to construct OSC devices.Impressively,D18:BON3-Cl-based device shows a remarkable power conversion efficiency(PCE)of 18.57%,with a high open-circuit voltage(V_(OC))of 0.907 V and an excellent fill factor(FF)of 80.44%,which is one of the highest binary PCE of devices based on D18 as the donor.However,BON3-F-based device shows a relatively lower PCE of 17.79%with a decreased FF of 79.05%.The better photovoltaic performance is mainly attributed to the red-shifted absorption,higher electron and hole mobilities,reduced charge recombination,and enhanced molecular packing in the D18:BON3-Cl films.Also,we performed stability tests on two binary systems;the D18:BON3-Cl and D18:BON3-F devices maintain 88.1%and 85.5%of their initial efficiencies after 169 h of storage at 85°C in an N2-filled glove box,respectively.Our work demonstrates the importance of selecting halogen atoms on EG and provides an efficient binary system of D18:BON3-Cl for further improvement of PCE.

End-capped Thiophene Modulated Molecular Packing in 2,8-Dibenzothiophene-based Materials:from Face-to-face to Edge-to-face Stacking

Two new organic crystals of 2,8-bisthienyldibenzothiophene（BTDT） and 2,8-bis-dithienyldibenzothiophene（BDTDT） compounds were successfully obtained.The change of end-capped group from thiophene to dithiophene causes big differences in molecular packing and carrier-transport property.The adjacent molecules of compound BTDT adopt face-to-face π stacking and exhibit two-dimensional interchain interactions.On the contrary,BDTDT molecules are arranged in an edge-to-face motif and show mainly one-dimensional interacting character.The packing mode exerts dramatic effect on the carrier-transport property.The crystal of BTDT belongs to the orthorhombic system,space group P21212 with a = 20.1427（11）,b = 4.6016（3）,c = 8.6340（5） ,V = 800.27（8） 3,Z = 2,Dc = 1.446 g/cm3,F（000） = 360,S = 1.019,the final R = 0.0491 and wR = 0.0960 for 1605 reflections with I 2σ（I）.The crystal of BDTDT belongs to the orthorhombic system,space group P212121 with a = 7.2636（15）,b = 25.359（5）,c = 25.359 ？,V = 4670.9（14） ？3,Z = 8,Dc = 1.458 g/cm3,F（000） = 2112,S = 0.880,the final R = 0.0597 and wR = 0.1318 for 8047 reflections with I 2σ（I）.

Enhancing Photovoltaic Performance of Ladder-Type Heteroarene-Based Electron Acceptors by Modulating Molecular Packing

Comprehensive Summary,The development of novel building blocks with sp3-hybridized-carbon-free conjugated skeletons is important to further advance and enrich nonfullerene acceptors(NFAs),but this remains a challenge due to the lack of strategies to effectively modulate the aggregation behavior of resulting NFAs.Herein,two novel nitrogen-bridged octacyclic ladder-type heteroarenes end-capped with thiophene rings(BTPS)or selenophene rings(BTPSe)are designed and synthesized as the donor cores for constructing NFAs(MQX-2 and MQX-4).It is found that replacing the sulfur atoms(MQX-2)at the outer positions of the heteroarene core with selenium atoms(MQX-4)can effectively modulate the molecular packing mode of the NFAs.The incorporation of selenium atoms induces stronger O···Se noncovalent interaction than O···S,thus promoting the formation of mixed H/J-type aggregates in MQX-4.Benefiting from more electron hopping channels,MQX-4 exhibits higher electron transport(more than 1-fold enhancement)and photovoltaic properties compared to MQX-2,which forms only H-type aggregates.

Inner alkyl chain modulation of small molecular acceptors enables molecular packing optimization and efficient organic solar cells

With the generation of Y6,organic solar cells have reached remarkable achievement of over 19%efficiency.Alkyl chain is of importance to modulate intermolecular stacking and possibly enhance optoelectronic properties of small molecule acceptors(SMAs).Three alkyl chains of 2-ethylhexyl,2-butylocyl and 3-ethylheptyl were selected to obtain G6-EH,G6-BO and G6-EHep molecules,respectively.Compared to G6-EH and G6-BO,G6-EHep was found inducing unfavourable large domain size.Furthermore,we discover that 2-butyloctyl effectively inhibits monomolecular and bimolecular recombination,improves molecular packing,generates more balanced carrier mobility and enhances exciton dissociation.The SMA with 2-butyloctyl alkyl chains(G6-BO)shows the best electrical and morphological characteristics,achieving a higher power conversion efficiency(PCE)of 17.06%,with an open circuit voltage of 0.912 V,a short-circuit current of 24.22 m A cm-2and a fill factor of 77.25%.Finally,using the ternary strategy by incorporating the G6-BO acceptor into PM6:BTP-e C9,we achieved a higher PCE of18.13%with enhanced electron transport.

Lowing the energy loss of organic solar cells by molecular packing engineering via multiple molecular conjugation extension

The central unit(benzo[c][1,2,5]thiadiazole) in Y6 series of molecules plays a determining role in their unique intermolecular packing for a three-dimensionally(3D) network, largely endowing their organic solar cells(OSCs) with so far the best power conversion efficiencies(PCEs) and also largely suppressed energy losses(Eloss). Despite its vital role in molecular packing, very few explorations for central unit have been conducted due to possibly the constructing challenge of central heterocyclic units.Herein, a highly efficient acceptor-donor-acceptor(A-D-A) type electron acceptor, CH17, has been designed and constructed,featured with a prominent π extension in both directions of the central and end units with respect to Y6 series. Such a multiple and much enhanced conjugation extension in CH17 enables a much more effective and compact 3D molecular packing compared with that of Y6 supported by X-ray single crystal and other analysis, mainly caused by a newly observed distinctive dual “end unit to central unit” packing mode. This much favorable molecular packing, also kept in its blends with donor materials, leads a larger electron and hole transfer integrals and hence much improved charge transport, and reduced energetic disorders in CH17blends. More importantly, the observed upshifted charge transfer(CT) state of CH17 blends compared with that of Y6, due to its increased molecular conjugation extension in both directions, further enhances the hybridization between its CT and local exciton(LE) states, resulting in higher luminescence efficiency, much suppressed non-radiative recombination loss and smaller Elosswith respect to that of Y6. Consequently, an excellent PCE of 17.84% is achieved with PM6 as the donor in a binary device compared with a PCE of 16.27% for the controlled Y6 device. Furthermore, a further improved PCE of 18.13% is achieved by CH17-based ternary single-junction OSCs along with a markedly reduced Elossof 0.49 e V and larger open-circuit voltage(Voc) of0.89 V, compared with that(16.27% of PCE, 0.85 V of Voc, and 0.53 e V of Eloss) of the control device using Y6. This significantly improved photovoltaic performance caused by molecular multiple conjugation extension, especially through the largely unexplored central unit, indicates that there is still much room to further enhance OSC performance by addressing the most important issue for OSC, i.e, the smaller Voccaused by larger Eloss, through engineering molecular packing by designing/tuning molecule more dedicatedly.

Multiscale description of molecular packing and electronic processes in small-molecule organic solar cells

This paper summarizes our recent works on theoretical modelling of molecular packing and electronic processes in small-molecule organic solar cells.Firstly,we used quantum-chemical calculations to illustrate exciton-dissociation and charge-recombination processes at the DTDCTB/C_（60） interface and particularly emphasized the major role of hot charge-transfer states in the exciton-dissociation processes.Then,we systematically analyzed the influence of DTDCTB surfaces with different features on the vacuum vapor deposition growth and packing morphologies of C_（60） via atomistic molecular dynamics simulations,and found that the formation of crystalline fullerene is the result of an integrated impact of stability,landscape,and molecular orientation of the substrate surfaces.Also,we investigated the impact of different film-processing conditions,such as solvent evaporation rates and thermal annealing,on molecular packing configurations in a neat small-molecule donor material,DPP（TBFu）_2,and discussed the correlation between charge mobility and molecular packing via atomistic simulations in combination with electronic-structure calculations and kinetic Monte Carlo simulations.

Molecular Structure of (1-Benzyl-4-phenyl-1H-1,2,3-triazol-5-yl)(4-bromophenyl) methanone: A Combined Experimental and Theoretical Study

One-pot three component reaction was used to synthesize 1,4,5-trisubstituted 1,2,3-triazole(A) from the corresponding acid chloride, benzyl azide and 1-copper(I) phenylethyne. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the orthorhombic space group Pbca, a = 14.9815(14), b = 9.6496(10), c = 25.528(2) A, Z = 8. Furthermore, crystal packing demonstrated a molecular wall-like structure based on supramolecular chains of A, stabilized by CH···O, CH···Br, N···C and CH···π interactions. Molecular geometry in the ground state has been determined by density functional theory(DFT) by B3LYP/6-311G* basis set and compared with the experimental data. The computed vibrational frequencies are compared with the experimental FT-IR data and frontier molecular orbital analyses were performed at the same level of theory. Theoretical parameters are in good agreement with the corresponding X-ray diffraction values.

Impact of regio-isomeric monochlorinated end groups on packing mode,miscibility,and photovoltaic performance of asymmetric selenophene-fused M-series acceptors

Optimal bulk-heterojunction(BHJ)morphology is crucial for efficient charge transport and good photovoltaic performance in organic solar cells(OSCs).Yet,the correlation between chemical structures of nonfullerene acceptors(NFAs)and molecular interaction in the BHJ blends remains opaque.Herein,we study three isomeric NFAs referred to as MQ1-x(x=β,y,or 8)that shared an asymmetric selenophene-fused heteroheptacene backbone end-capped by two monochlorinated end groups.Remarkably,miscibility between the polymer donor of PM6 and MQ1-x successively elevates as the chlorine atoms move fromβ-,to y-,to 8-position of terminals.Combined with the varied molecular crystallinity of these NFAs,diverse BHJ morphologies are observed in their blend films.As a result,the MQ1-8-based devices present the highest PCE of 12.08%owing to the efficient charge dissociation and transport induced by the compact molecular packing and optimal BHJ morphology.Our investigation provides a new insight in the material design that has a good balance in molecular packing and film morphology for high-performance OSCs.

基于雷洛昔芬的多重刺激响应性单组分室温磷光分子晶体

Simultaneously achieving room-temperature phosphorescence(RTP) and multiple-stimuli responsiveness in a single-component system is of significance but remains challenging. Crystallization has been recognized to be a workable strategy to fulfill the above task. However, how the molecular packing mode affects the intersystem crossing and RTP lifetime concurrently remains unclear so far. Herein, four economic small-molecular compounds, analogues of the famous drug raloxifene(RALO), are facilely synthesized and further explored as neat single-component and stimuli-responsive RTP emitters via crystallization engineering. Thanks to their simple structures and high ease to crystallize, these raloxifene analogues function as models to clarify the important role of molecular packing in the RTP and stimuliresponsiveness properties. Thorough combination of the single-crystal structure analysis and theoretical calculations clearly manifests that the tight antiparallel molecular packing mode is the key point to their RTP behaviors. Interestingly, harnessing the controllable and reversible phase transitions of the two polymorphs of RALO-OAc driven by mechanical force, solvent vapor, and heat, a single-component multilevel stimuli-responsive platform with tunable emission color is established and further exploited for optical information encryption. This work would shed light on the rational design of multi-stimuli responsive RTP systems based on single-component organics.

Delicate chemical structure regulation of nonfullerene acceptor for efficient and large thickness organic solar cells

Inspired by the success of CH-series acceptors, a small-molecular acceptor, CH-Tz was reported by adopting a new conjugationextended electron-deficient unit([1,2,5]thiadiazolo[3,4-b]pyrazine) on the central core. Owing to the enhanced inter-/intramolecular interactions, CH-Tz exhibited near-infrared absorption and an effective three-dimensional molecular packing network in its single crystal. When blended with polymer donor PM6, the binary device achieved a high power conversion efficiency(PCE) of 18.54%, with a notable short-circuit current density(J_(sc)) of 27.54 m A cm-2and an excellent fill factor(FF) over 80%,which can be partly ascribed to the balanced charge transport properties in the blend film. After employing D18-Cl as the third component, an enhanced PCE of 18.85% was achieved due to a more obvious fiber network. Impressively, the CH-Tz-based OSC devices show excellent thermal stability and thickness insensitivity. Record-breaking Jscof 28.92 m A cm-2was reached for PM6:D18-Cl:CH-Tz ternary device with a thickness of 560 nm. Besides, CH-Tz shows potential in fabricating multicomponent high-performance organic solar cells, where over 19% efficiency could be realized in the quaternary device. Our work advances the strong influence of electron-deficient central units on molecular photovoltaic properties and guides the design of acceptors for stable and large-thickness organic solar cells.

Intermolecular electronic coupling of 9-methyl-9H-dibenzo[a,c]carbazole for strong emission in aggregated state by substituent effect

Bright emission of organic luminogens at aggregated state has attracted increasing attention for their potential applications in opto-electronic devices and bio-/chemo-sensors.In this article,upon the introduction of different substituents(Br,Ph and TPh)to the large conjugated core of 9-methyl-9H-dibenzo[a,c]carbazole(DBC)moiety,the resultant luminogens demonstrated PL quantum yields in solid state ranging from 4.81%to 47.39%.Through the systematic investigation of molecular packing,together with theory calculation,the strong intermolecular electronic coupling in the dimers is proved as the main factor to the bright emission in the solid state.The results afforded a new avenue to investigate the intrinsic relationship among the molecular structures,packing modes and emission properties.

A gated strategy stabilizes room-temperature phosphorescence

Room-temperature phosphorescence(RTP)of purely organic materials is easily quenched with unexpected purposes because the excited triplet state is extremely susceptible to external stimuli.How to stabilize the RTP property of purely organic luminogens is still challenging and considered as the bottleneck in the further advancement of the bottom-up approach.Here,we describe a gated strategy that can effectively harness RTP by employing complexation/dissociation with proton.Due to the order-disorder transition orientation of intermolecular packing,the RTP of organic molecules 2,4,6-tris(4′-bromo-[1,1′-biphenyl]-4-yl)-1,3,5-triazine(Br-TRZ)will easily vanish upon mechanical force.Impressively,by enhancing its intramolec-ular charge transfer effect,the protonated Br-TRZ stubbornly possesses an obvious RTP under external grinding,whatever in the ordered or disordered intermolec-ular arrangement state.Consequently,the“Lock”gate of RTP was achieved in the protonated Br-TRZ molecule.Combined with theoretical calculation analy-sis,the enhanced charge transfer effect can narrow the energy gap singlet-tripletsignificantly,and stabilize the RTP property of triazine derivative sequentially.Fur-thermore,the locked RTP can be tuned via proton and counterions repeatedly and show excellent reversibility.This gated RTP concept provides an effective strategy for stabilizing the RTP emission of purely organic systems.

Improving the Performance of TIPS-pentacene Thin Film Transistors via Interface Modification

Understanding the structure-performance relationship is crucial for optimizing the performance of organic thin film transistors. Here, two interface modification methods wereapplied to modulate the thin film morphology of the organic semiconductor, 6,13-bis（triisopropylsilylethynyl）pentacene（TIPS-pentacene）. The resulting different film morphologies and packing structures led to distinct charge transport abilities. A substantial 40-fold increase in charge carrier mobility was observed on the octadecyltrichlorosilane（OTS）-modified sample compared to that of the transistor on the bare substrate. A better charge mobility greater than 1 cm^2· V^-1· s^-1 is realized on the p-sexiphenyl（p-6P）- modified transistors due to the large grain size, good continuity and, importantly, the intimate π-π packing in each domain.

Ultralong Room-Temperature Phosphorescence of Silicon-Based Pure Organic Crystal for Oxygen Sensing

Quantitative oxygen detection is of great importance in biological fields,complex environments,and chemical process engineering.Due to the high sensitivity and rapid response of long-lived phosphorescence to oxygen,pure organic room-temperature phosphorescence(RTP)for oxygen detection has recently attracted considerable interest.However,to simultaneously achieve ultralong phosphorescence at room temperature and quantitative oxygen detection from pure organic crystals is difficult.Tight packing to restrict nonradiative decay is not apt to allow oxygen diffusion for sensing.Reported herein is an exceptional example,that is,a crystal of simple carbazole molecules that bridges with an ethoxysilane(DCzC2OSi)and is capable of oxygen sensing with remarkable sensitivity.Photophysical studies and single-crystal structure analysis reveal that DCzC2OSi crystals display ultralong RTP and suitable oxygen diffusion channels from its butterfly-like tetrahedron geometry.Further comparisons with the crystals of CzC2OH and DCzSi verify the important roles of silicon and ethoxy groups of DCzC2OSi for both enhanced phosphorescence lifetime and oxygen sensitivity.When the crystals of DCzC2OSi were doped into polymer,the lifetime-based oxygen sensor exhibited high KSV(5.308 kPa^(−1))with full reversibility,which is attractive for the development of practical oxygen sensors from pure organic crystals.

Structure-fluorescence relationships in pyrrole appended o-carborane crystalline materials

Based on three rationally designed pyrrole-appended o-carborane derivatives,we present that fluores-cence properties of crystalline materials are highly dependent on intermolecular interaction and steric hinderance.Though the three molecules are similar in structure,single crystals of the three compounds showed obvious difference in molecular stacking and fluorescence behavior.Systematic studies indicate that fluorescence quantum yields,thermo-response as well as mechano-response are highly dependent on intermolecular interaction and steric hindrance.In the three crystalline materials,the CB-NMe crys-tals with weaker intermolecular interaction and looser molecular packing showed superior fluorescence quantum yield and temperature sensitivity.Accordingly,surface temperature detection strip with favor-able reversibility is prepared by doping CB-NMe into the polymer.In addition,the CB-NMe aggregates can be used for monitoring bovine serum albumin(BSA)denaturation,as temperature response of the aggregates can be reversed when co-assembled with BSA.

Progress in mechanochromic luminescence of gold(Ⅰ) complexes

Photophysical properties of organic and organometallic luminophors are closely related with their molecular packings, enabling the exploitation of stimuli-responsive functional luminescent molecules.Mechanochromic molecules, which can change their luminescence characteristics after mechanical stimulus, have received an increasing interest due to their promising applications in multifunctional sensors and molecular switches. During the past two decades, the development of gold(Ⅰ) chemistry has been attracting the attention of plenty of researchers. Indeed, a variety of gold(I) complexes with fascinating photophysical behaviors have been discovered. This review focuses on the research progress in the different types of mechanoluminochromic gold(Ⅰ) complexes, including mono-, bi-and multi-nuclear gold(Ⅰ)systems. Their interesting luminescence behaviors of these gold(Ⅰ)-containing luminogens upon mechanical stimulus and the proposed mechanisms of their observed mechanochromic luminescence are summarized systematacially. Moreover, this review will put forward an outlook about the possible opportunities and challenges in this significative scientific field.

Subtle Alignment of Organic Semiconductors at the Donor/Acceptor Heterojunction Facilitates the Photoelectric Conversion Process

The aligned molecular packing structure is vital to the anisotropic charge transport in conjugated polymer and small molecule thin films.However,how this molecular packing motif influences the photoelectric conversion process at the donor/acceptor heterojunction is still mysterious.Herein,we employed a PM6/Y6 bilayer model to investigate the long-range alignment of molecular packing induced photoelectric conversion process.Both PM6 and Y6 layers were properly controlled to exhibit the uniaxially oriented molecular packing compared to their as-cast counterparts,as revealed by the polarized absorption spectra and transmission electron microscopy.After analyzing the photovoltaic performance of bilayer devices,the smaller energy loss,lower energetic disorder,and longer charge carrier lifetime can be observed in the bilayer devices with aligned Y6 molecules,which contribute to a higher power conversion efficiency(PCE)than the as-cast devices.While the molecular packing structure of PM6 layer exhibited negligible influence on the device performance,probably resulting from the intrinsic semicrystalline nature of PM6 molecules.Our results indicate that the alignment of small molecular acceptor at the donor/acceptor interfaces should be a powerful strategy to facilitate the photoelectric conversion process,which will definitely pave the way to highly efficient bulk heterojunction photovoltaic device.

Effect of Aggregation Structure on Thermal Expansion Behavior of Polyimide Films with Different Thickness

Polyimide films derived from representative PMDA/ODA were prepared with thickness ranging from 5 μm to 25 μm,and the effect of aggregation structure on thermal expansion behavior along different directions was studied.Both in-plane and out-of-plane linear thermal expansion(CTEand CTE) were respectively characterized by thermal mechanical analysis and FT-near-IR interference method.Volumetric and anisotropic behavior of thermal expan sion were also investigated.With increasing film thickness,CTEgradually increased from 32.2 ppm/℃ to46.1 ppm/℃ while CTEdecreased from 149.7 ppm/℃ to 128.2 ppm/℃.Volumetric thermal expansion of polyimide films was less sensitive to the va ried thickness,but anisotropy of thermal expansion was reduced.Polyimide film of 5 μm thickness showed large birefringence,indicating more considerable in-plane chain orientation anisotropy.Besides,molecular chains were more densely packed along in-plane direction when film thickness increased,while became loosely stacked in the out-of-plane direction.In contrast to the enhanced lateral chain packing for thicker film s,higher vertical chain packing order was found in thinner films.The variation of aggregation structure during thermal expansion procedure was analyzed by temperature-dependent WAXD.It is proved that thermal expansion behavior of thinner films could be largely attributed to molecular chain packing,whereas that may be influenced by many factors for thicker films in addition to the effect of chain packing.The results revealed that thermal expansion of films with thickness variation is closely related to molecular chain orientation and packing,which is associated with both chemistry and morphological structure of polyimide.