Alkoxy substituted benzodithiophene-alt-fluorobenzotriazole copolymer as donor in non-fullerene polymer solar cells

A new benzodithiophene(BDT)-alt-fluorobenzotriazole(FBTA) D-A copolymer J40 was designed and synthesized by introducing 2-octyldodecyloxy side chains on its BDT units, for expanding the family of the BDT- alt-FBTA-based copolymers and investigating the side chain effect on the photovoltaic performance of the polymer in non-fullerene polymer solar cells(PSCs).J40 exhibits complementary absorption spectra and matched electronic energy levels with the n-type organic semiconductor(n-OS)(3,9-bis(2-methylene-(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)-dithieno[2,3-d:2′,3′-d′]-sindaceno[1,2-b:5,6-b′]dithiophene)(ITIC) acceptor, and was used as polymer donor in the non-fullerene PSCs with ITIC as acceptor. The power conversion efficiency(PCE) of the PSCs based on J40:ITIC(1:1, w/w) with thermal annealing at 120 °C for 10 min reached 6.48% with a higher open-circuit voltage(Voc) of 0.89 V. The high Voc of the PSCs is benefitted from the lower-lying highest occupied molecular orbital(HOMO) energy level of J40. Although the photovoltaic performance of the polymer J40 with alkoxy side chain is lower than that of J60 and J61 with alkylthio-thienyl conjugated side chains, the PCE of6.48% for the J40-based device is still a relatively higher photovoltaic efficiency in the non-fullerene PSCs reported so far. The results indicate that the family of the BDT-alt-FBTA-based D-A copolymers are high performance polymer donor materials for non-fullerene PSCs and the side chain engineering plays an important role in the design of high performance polymer donors in the non-fullerene PSCs.     

Enhanced Charge Transfer,Transport and Photovoltaic Efficiency in All‐Polymer Organic Solar Cells by Polymer Backbone Fluorination

We successfully designed and synthesized two BDT‐BT‐T (BDT=benzo[1,2‐b:4,5‐b']dithiophene, BT‐T=4,7‐dithien‐2‐yl‐2,1,3‐benzothiadiazole) based polymers as the electron donor for application in all‐polymer solar cells (all‐PSCs). By adopting N2200 as the electron acceptor, we systematically investigated the impact of fluorination on the charge transfer, transport, blend morphology and photovoltaic properties of the relevant all‐PSCs. A best power conversion efficiency (PCE) of 3.4% was obtained for fluorinated PT‐BT2F/N2200 (BT2F=difluorobenzo[c][1,2,5]thiadiazole) all‐PSCs in comparison with that of 2.7% in non‐fluorinated PT‐BT/N2200 (BT=benzothiadiazole) based device. Herein, all‐polymers blends adopting either non‐fluorinated PT‐BT or fluorinated PT‐BT2F exhibit similar morphology features. In depth optical spectrum measurements demonstrate that molecular fluorination can further enhance charge transfer between donor and acceptor polymer. Moreover, all‐polymer blends exhibit improved hole mobilities and more balanced carriers transport when adopting fluorinated donor polymer PT‐BT2F. Therefore, although the PCE is relatively low, our findings may become important in understanding how subtle changes in molecular structure impact relevant optoelectronic properties and further improve the performance of all‐PSCSs.     

Effect of furan π-bridge on the photovoltaic performance of D-A copolymers based on bi(alkylthio-thienyl)benzodithiophene and fluorobenzotriazole

The medium band gap donor-acceptor(D-A) copolymer J61 based on bi(alkylthio-thienyl)benzodithiophene as donor unit and fluorobenzotriazole as acceptor unit and thiophene as π-bridge has demonstrated excellent photovoltaic performance as donor material in nonfullerene polymer solar cells(PSCs) with narrow bandgap n-type organic semiconductor ITIC as acceptor.For studying the effect of π-bridges on the photovoltaic performance of the D-A copolymers,here we synthesized a new D-A copolymer J61-F based on the same donor and acceptor units as J61 but with furan π-bridges instead of thiophene.J61-F possesses a deeper the highest occupied molecular orbital(HOMO) level at-5.45 eV in comparison with that(-5.32 eV) of J61.The non-fullerene PSCs based on J61-F:ITIC exhibited a maximum power conversion efficiency(PCE) of 8.24%with a higher open-circuit voltage(V_(oc)) of 0.95 V,which is benefitted from the lower-lying HOMO energy level of J61-F donor material.The results indicate that main chain engineering by changing π-bridges is another effective way to tune the electronic energy levels of the conjugated D-A copolymers for the application as donor materials in non-fullerene PSCs.     

Broad Bandgap D–A Copolymer Based on Bithiazole Acceptor Unit for Application in High‐Performance Polymer Solar Cells with Lower Fullerene Content

A new broad bandgap and 2D‐conjugated D‐A copolymer, PBDTBTz‐T , based on bithienyl‐benzodithiophene donor unit and bithiazole (BTz) acceptor unit, is designed and synthesized for the application as donor material in polymer solar cells (PSCs). The polymer possesses highly coplanar and crystalline structure with a higher hole mobility and lower HOMO energy level which is beneficial to achieve higher open circuit voltage (V_oc) of the PSCs with the polymer as donor. The PSCs based on PBDTBTz‐T :PC₇₁BM blend film with a lower PC₇₁BM content of 40% demonstrate a power conversion efficiency (PCE) of 6.09% with a relatively higher V_oc of 0.92 V. These results indicate that the lower HOMO energy level of the BTz‐based D–A copolymer is beneficial to a high V_oc of the PSCs. The polymer, with highly coplanar and crystalline structure, can effectively reduce the content of fullerene acceptor in the active layer and can enhance the absorption and PCE of the PSCs.

     

Enhanced open-circuit voltage in methoxyl substituted benzodithiophene-based polymer solar cells

The open-circuit voltage (V _oc) is one of the important parameters that influence the power conversion efficiency (PCE) of polymer solar cells. Its value is mainly determined by the energy level offset between the highest occupied molecular orbital (HOMO) of the donor and the lowest unoccupied molecular orbital (LUMO) of the acceptor. Therefore, decreasing the HOMO value of the polymer could lead to a high V _oc and thus increasing the cell efficiency. Here we report a facile way to lower the polymer HOMO energy level by using methoxyl substituted-benzodithiophene (BDT) unit. The polymer with the methoxyl functionl group (POBDT(S)-T1) exhibited a HOMO value of–5.65 eV, which is deeper than that (–5.52 eV) of polymer without methoxyl unit (PBDT(S)-T1). As a result, POBDT(S)-T1-based solar cells show a high V _oc of 0.98 V and PCE of 9.2%. In contrast, PBDT(S)-T1-based devices show a relatively lower V _oc of 0.89 V and a moderate PCE of 7.4%. The results suggest that the involvement of methoxyl group into conjugated copolymers can efficiencly lower their HOMO energy levels.     

Side-chain fluorination on the pyrido[3,4-<Emphasis Type="Italic">b</Emphasis>]pyrazine unit towards efficient photovoltaic polymers

A series of new polymer donors (PT-PP, PT-2fPP and PT-4fPP) were synthesized based on alkylthiophene substituted benzodithiophene (BDT-T) and pyrido[3,4-b]pyrazine (PP) building blocks and the effects of fluorination on the polymer properties were explored. Photophysical properties, charge mobilities and morphologies of the three polymers have been intensively investigated. The results indicated that the introduction of the fluorine atom at meta-positions of phenyl substituted PP unit hardly affected their highest occupied molecular orbital (HOMO) level. More importantly, controlling the degree of side-chain fluorination in the polymers is crucial for optimizing the blend morphology. Three polymers showed different photovoltaic properties. The polymer solar cell (PSC) based on the single layer device structure of ITO/PEDOT:PSS/PT-4fPP:PC₇₁BM (1:1, w:w)/ZrAcac/Al demonstrates a high power conversion efficiency (PCE) of 7.61% under the illumination of AM 1.5G, 100 mW cm^?2, which is the highest value for PP-based PSCs.     

Effect of Fluorination on the Photovoltaic Properties of Medium Bandgap Polymers for Polymer Solar Cells

Fluorination of conjugated polymers is one of the effective strategies to tune the molecular energy levels and morphology for high efficient polymer solar cells (PSCs). Herein, two novel donor‐acceptor conjugated polymers, PffBT and PBT, based on bis(3,5‐bis(hexyloxy)phenyl)benzo[1,2‐ b:4,5‐b']dithiophene and benzo[c][1,2,5]thiadiazole (BT) with or without fluorination, respectively, were synthesized, and their photovoltaic properties were compared. The polymer PffBT based on fluorinated BT showed lower frontier energy levels, improved polymer ordering, and a well‐developed fibril structure in the blend with PC₇₁BM. As a result, the PSCs based on PffBT/PC₇₁BM exhibit a superior power conversion efficiency (PCE) of 8.6% versus 4.4% for PBT‐based devices, due to a high space charge limit current (SCLC) hole mobility, mixed orientation of polymer crystals in the active layer, and low bimolecular recombination.     

13.34 % Efficiency Non‐Fullerene All‐Small‐Molecule Organic Solar Cells Enabled by Modulating the Crystallinity of Donors via a Fluorination Strategy

Non‐fullerene all‐small‐molecule organic solar cells (NFSM‐OSCs) have shown potential as OSCs, owing to their high purity, easy synthesis and good reproducibility. However, challenges in the modulation of phase separation morphology have limited their development. Herein, two novel small molecular donors, BTEC‐1F and BTEC‐2F, derived from the small molecule DCAO3TBDTT, are synthesized. Using Y6 as the acceptor, devices based on non‐fluorinated DCAO3TBDTT showed an open circuit voltage (V_oc) of 0.804 V and a power conversion efficiency (PCE) of 10.64 %. Mono‐fluorinated BTEC‐1F showed an increased V_oc of 0.870 V and a PCE of 11.33 %. The fill factor (FF) of di‐fluorinated BTEC‐2F‐based NFSM‐OSC was improved to 72.35 % resulting in a PCE of 13.34 %, which is higher than that of BTEC‐1F (61.35 %) and DCAO3TBDTT (60.95 %). To our knowledge, this is the highest PCE for NFSM‐OSCs. BTEC‐2F had a more compact molecular stacking and a lower crystallinity which enhanced phase separation and carrier transport.     

Synthesis of D-A copolymers based on thiadiazole and thiazolothiazole acceptor units and their applications in ternary polymer solar cells

We have designed and synthesized two wide bandgap new donor-acceptor (D-A) copolymers consisting of the same alkylthiazole-substituted benzo[1,2-b;4,5-b′]dithiophene (BDTTz) donor unit and but different acceptor units, i.e., thiazolo[5,4-d]thiazole (TT_Z) ( P122 ) and 1,3,-4 thiadiazole (TDz) ( P123 ) and investigated their optical and electrochemical properties. We have employed these copolymers as donor and fullerene (PC ₇₁ BM) and narrow bandgap non-fullerene (Y6) as acceptor, to fabricate binary and ternary bulk heterojunction polymer solar cells (PSCs). The overall power conversion efficiency (PCE) of optimized binary bulk heterojunction PSCs based on P122 :Y6 and P123 :Y6 is 12.60% and 13.16%, respectively. The higher PCE for PSCs based on P123 than P122 counterparts may be associated with the broader absorption profile of the P123 and more charge carrier mobilities than that for the P122 active layer. With the incorporation of small amount of PC₇₁BM into either P122 :Y6 or P123 :Y6 binary blend, the corresponding ternary PSCs showed an overall PCE of 14.89% and 15.52%, respectively, which is higher than the binary counterparts using either Y6 or PC₇₁BM as acceptor. Incorporating the PC₇₁BM in the binary host blend increases the absorption in the 300–500 nm wavelength region, generating more excitons in the active ternary layer and helping to dissociate the excitons into free charge carriers more effectively. The more appropriate nanoscale phase separation in the active ternary layer than the binary counterpart may be one of the reasons for higher PCE.     

Significant influence of doping effect on photovoltaic performance of efficient fullerene-free polymer solar cells

The modification mechanism of the water/alcohol cathode interlayer is one of the most complicated problems in the field of organic photovoltaics,which has not been clearly elucidated yet;this greatly restricts the further enhancement of the PCE for polymer solar cells.Herein,we clarified the different effects of PFN and its derivatives,namely,poly[(9,9-bis(3'-((N,N-dimethyl)-N-ethylammonium)-propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)](PFN-Br) in modifying fullerene-free PSCs.It is found for the first time that doping on IT-4F by the amino group of PFN leads to the unfavorable charge accumulation,and hence,forms a dense layer of electronegative molecule due to the poor electron transport capacity of the non-fullerene acceptor IT-4F.The electronegative molecular layer can block the electron transfer from the active layer to the interlayer and cause serious charge recombination at the active layer/cathode interface.This mechanism could be verified by the ESR measurement and electron-only devices.By replacing PFN with PFN-Br,the excessive doping effect between the cathode interlayer and IT-4F is eliminated,by which the charge transport and collection can be greatly improved.As a result,a high PCE of 13.5%was achieved in the fullerene-free PSCs.     

Fluorination of aromatic compounds with xenon difluoride in the presence of boron trifluoride etherate

Fluorination of benzene with the XeF₂—BF₃?Et₂O system in acetonitrile at low temperatures affords fluorobenzene in 18% yield, the conversion of benzene being 92%. The rest products are di-, tri-, tetra-, and polyphenyls with different fluorination pattern. Toluene and chloro- and bromobenzenes are fluorinated predominantly at the ortho and para positions. Fluorination of 4-nitroanisole affords 2-fluoro-4-nitroanisole in 73% yield.     

Reduced‐bandgap triphenylamine‐alt‐benzo[1,2‐b:4,5‐b′]dithiophene copolymers pending benzothiadiazole or diketopyrrolopyrrole units for efficient polymer solar cells

Two new side‐chain donor–acceptor (D‐A)‐based triphenylamine‐alt‐benzo[1,2‐b:4,5‐b′]dithiophene (TPA‐alt‐BDT) copolymers ( P1 and P2 ) with pendant benzothiadiazole (BT)/diketopyrrolopyrrole (DPP) in TPA unit were synthesized by Stille coupling polymerization. Their thermal, photophysical, electrochemical, blend film morphology and photovoltaic properties were investigated. Efficient bulk heterojunction polymer solar cells (PSCs) were obtained by solution process using both copolymers as donor materials and PC₇₁BM as acceptor. The maximum power conversion efficiency (PCE) of 3.17% with a highest open‐circuit voltage (V_oc) of 0.86V was observed in the P1 ‐based PSCs, while the maximum short‐circuit current (J_sc) of 10.77 mA cm^?2 was exhibited in the P2 ‐based PSCs under the illumination of AM 1.5, 100 mW cm^?2. The alternating binary donor units and pending acceptor groups played a significant role in tuning photovoltaic properties for this class of the side‐chain D–A‐based copolymers. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4103–4110     

Steric structure of alkyl 2-aryl(hetaryl)hydrazono-3-fluoroalkyl-3-oxopropionates

Steric structure of fluorinated 2-arylhydrazono-3-oxo esters was studied by ¹H, ¹⁹F, and ¹³C NMR spectroscopy and X-ray analysis. It was found that these compounds in the crystalline state and in solutions in acetone-d ₆, DMSO-d ₆, and CDCl₃ exist as Z isomers with the ester fragment involved in intramolecular hydrogen bond with the hydrazone NH proton. Exceptions are alkyl 2-arylhydrazono-4,4-difluoro-3-oxobutanoates which exist in acetone-d ₆ as mixtures of Z and E isomers, the former prevailing. Unlike fluorinated analogs, ethyl 2-(4-methylphenyl)hydrazono-3-oxobutanoate in crystal has the structure of E isomer in which intramolecular hydrogen bond is formed between the NH proton and acetyl carbonyl group. The same compound in acetone-d ₆, DMSO-d ₆, and CDCl₃ gives rise to a mixture of Z and E isomers, the latter prevailing.     

Developing Wide Bandgap Polymers Based on Sole Benzodithiophene Units for Efficient Polymer Solar Cells

In this work, a series of sole benzodithiophene-based wide band gap polymer donors, namely PBDTT, PBDTS, PBDTF and PBDTCl, were developed for efficient polymer solar cells (PSCs) by varying the heteroatoms into the conjugated side chains. The effects of sulfuration, fluorination and chlorination were also investigated systematically on the overall properties of these BDT-based polymers. The HOMO levels could be lowered gradually by introducing sulfur, fluorine and chlorine atoms into the side chains, which contributed to the stepwise increased V_oc (from 0.78 V to 0.84 V) in the related PSCs using Y6 as the electron acceptor. This side-chain engineering strategy could promote the polymer chain interactions and fine-tune the phase separation of active blends, leading to enhanced absorption, ordered molecular packing and crystallinity. Among them, the chlorinated PBDTCl exhibited not only high level absorption and crystallinity, but also the most balanced hole/electron charge transport and the most optimized morphology, giving rise to the best PCE of 13.46 % with a V_oc of 0.84 V, a J_sc of 23.16 mA cm⁻² and an FF of 69.2 %. The chlorination strategy afforded PBDTCl synthetic simplicity but high efficiency, showing its promising photovoltaic applications for realizing low-cost practical PSCs in near future.     

Ladder-Type Heteroheptacenes with Different Heterocycles for Nonfullerene Acceptors

The design, synthesis, and characterization of two novel nonfullerene acceptors (M8 and M34) based on ladder-type heteroheptacenes with different heterocycles are reported. Replacing the furan heterocycles with the thiophene heterocycles in the heteroheptacene backbone leads to a hypsochromically shifted absorption band and greatly improved carrier transport for the resulting nonfullerene acceptor (M34) although the π–π-stacking distances are barely affected. Bulk-heterojunction polymer solar cells fabricated from M34 and a wide band gap polymer (PM6) as the donor showed a best power conversion efficiency (PCE) of 15.24 % with an open circuit voltage (V_OC) of 0.91 V, much higher than a PCE of 4.21 % and a V_OC of 0.83 V for the counterparts based on M8:PM6. These results highlight the importance of key atoms in the construction of high-performance nonfullerene acceptors.     

Enhanced Performance of Organic Photovoltaic Cells Fabricated with a Methyl Thiophene‐3‐Carboxylate‐Containing Alternating Conjugated Copolymer

A new donor‐acceptor copolymer, containing benzodithiophene (BDT) and methyl thiophene‐3‐carboxylate (3MT) units, is designed and synthesized for polymer solar cells (PSCs). The 3MT unit is used as an electron acceptor unit in this copolymer to provide a lower highest occupied molecular orbital (HOMO) level for obtaining polymer solar cells with a higher open‐circuit voltage (V_OC). The resulting bulk heterojunction PSC made of the copolymer and [6,6]‐phenyl‐C71‐butyric acid methyl ester (PC₇₁BM) exhibits a power conversion efficiency (PCE) up to 4.52%, a short circuit current (J_SC) of 10.5 mA·cm‐², and a V_OC of 0.86 V.     

The mutual influence between <Emphasis Type="Italic">π</Emphasis>-hole pnicogen bonds and <Emphasis Type="Italic">σ</Emphasis>-hole halogen bonds in complexes of PO<Subscript>2</Subscript>Cl and XCN/C<Subscript>6</Subscript>H<Subscript>6</Subscript> (X = F,Cl, Br)

The bimolecular and termolecular complexes involving PO₂Cl and XCN/C₆H₆ (X = F, Cl, Br) were designed to form the π-hole pnicogen bonds and σ-hole halogen bonds, to compare the two types of interactions and investigate the mutual influences between them. PO₂Cl was used as simultaneous π-hole and σ-hole donor; it can interact with electron donor to form π-hole pnicogen bond and σ-hole halogen bond. The π-hole interactions are stronger than the σ-hole interactions, in both the bimolecular and the termolecular complexes. Comparing the mutual effects of the π-hole interactions and σ-hole interactions, the π-hole interaction has a greater influence on the σ-hole interaction than vice versa. With the addition of σ-hole halogen bond, the V _S,max value outside the π-hole region of PO₂Cl becomes decreasingly positive, resulting in a weaker π-hole interaction. With the addition of π-hole pnicogen bond, the V _S,max value outside the σ-hole region of PO₂Cl becomes small, also resulting in a weaker σ-hole interaction. The π-hole pnicogen bond and σ-hole halogen bond weaken each other, i.e., there is a negative cooperative effect in the termolecular complexes.     

All-polymer solar cells with perylenediimide polymer acceptors

Four polymers based on perylenediimide co-polymerized with thiophene, bithiophene, selenophone and thieno[3,2-b]thiophene were investigated as the acceptor materials in all-polymer solar cells. Two different donor polymers, poly[4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b;4,5-b′]dithiophene-2,6-diyl-alt-(4-(2-ethylhexyl)-3-fluorothieno[3,4-b]thiophene)-2-carboxylate-2,6-diyl](PTB7-Th) and poly[(5,6-difluoro-2,1,3-benzothiadiazol-4,7-diyl)-alt-(3,3′′′-di(2-dodecyltetradecyl)-2,2′;5′,2″;5″,2′′′-quaterthiophen-5,5′′′-diyl)](Pff BT4T-2DT), with suitably complementary absorption spectra and energy levels were applied and examined. Among all different donor-acceptor pairs studied here, the combination of PTB7-Th:poly[N,N′-bis(1-hexylheptyl)-3,4,9,10-perylenediimide-1,6/1,7-diyl-alt-2,5-thiophene](PDI-Th) exhibited the best power conversion efficiency(PCE) of 5.13%, with open-circuit voltage(V_(oc)) = 0.79 V, short-circuit current density(J_(sc)) = 12.35 mA·cm~(-2) and fill-factor(FF) = 0.52. The polymer of PDI-Th acceptor used here had a regio-irregular backbone, conveniently prepared from a mixture of 1,6- and 1,7-dibromo-PDI. It is also noteworthy that neither additive nor posttreatment is required for obtaining such a cell performance.     

Effects of spin-coating speed on the morphology and photovoltaic performance of the diketopyrrolopyrrole-based terpolymer

Polymer solar cells（PSCs） were fabricated by combining a diketopyrrolopyrrole-based terpolymer（PTBT-HTID-DPP） as the electron donor, and [6,6]-phenyl C₆₁ butyric acid methyl ester(PC₆₁BM) as the electron acceptor, and the power conversion efficiency（PCE） of 4.31% has been achieved under AM 1.5 G(100 m W cm^-2) illumination condition via optimizing the polymer/PC₆₁BM ratio, the variety of solvent and the spin-coating speed. The impact of the spin-coating speed on the photovoltaic performance of the PSCs has been investigated by revealing the effects of the spin-coating speed on the morphology and the absorption spectra of the polymer/PC₆₁BM blend films. When the thickness of the blend films are adjusted by spin-coating a fixed concentration with different spin-coating speeds, the blend film prepared at a lower spin-coating speed shows a stronger absorption per unit thickness, and the correspond device shows higher IPCE value in the longer-wavelength region. Under the conditions of similar thickness, the blend film prepared at a lower spin-coating speed forms a more uniform microphase separation and smaller domain size which leads to a higher absorption intensity per unit thickness of the blend film in long wavenumber band, a larger short-circuit current density(J_sc) and a higher power conversion efficiency（PCE） of the PSC device. Noteworthily, it was found that spin-coating speed is not only a way to control the thickness of active layer but also an influencing factor on morphology and photovoltaic performance for the diketopyrrolopyrrole-based terpolymer.     

High-performance fullerene-free polymer solar cells with solution-processed conjugated polymers as anode interfacial layer

A series of conjugated polymers based on PFS derivatives with π-conjugated 5-(9H-fluoren-2-yl)-2,2′-bithiophene(fluorene-alt-bithiophene) backbones, namely PFS-3C, PFS-4C and PFS-6C, were synthesized for their use as the anode interfacial layers(AILs) in the efficient fullerene-free polymer solar cells(PSCs). Alkyl sulfonate pendants with different lengths of alkyl side chains were introduced in the three polymers in order to investigate the effect of the alkyl chain length on the anode modification. The obtained three polymers exhibited similar absorption bands and energy levels, indicating that changing the length of the alkyl side chains did not affect the optoelectronic properties of the conjugated polymers. Based on the PBDB-T:ITIC active layer, we fabricated the fullerene-free PSCs using the three polymers as the AILs. The superior performance of the fullerene-free PSC device was achieved when PFS-4C was used as the AIL, showing a power conversion efficiency(PCE) of 10.54%. The high performance of the PFS-4C-modified device could be ascribed to the high transmittance, suitable work-function(WF) and smooth surface of PFS-4C. To the best of our knowledge, the PCE obtained in the PFS-4C-modified device is among the highest PCE values in the fullerene-free PSCs at present. These results demonstrate that the PFS derivatives are promising candidates in serving as the AIL materials for high-performance fullerene-free PSCs.