Showing papers by "Alex K.-Y. Jen published in 2018"

Non-fullerene acceptors for organic solar cells

Abstract: Non-fullerene acceptors (NFAs) are currently a major focus of research in the development of bulk-heterojunction organic solar cells (OSCs). In contrast to the widely used fullerene acceptors (FAs), the optical properties and electronic energy levels of NFAs can be readily tuned. NFA-based OSCs can also achieve greater thermal stability and photochemical stability, as well as longer device lifetimes, than their FA-based counterparts. Historically, the performance of NFA OSCs has lagged behind that of fullerene devices. However, recent developments have led to a rapid increase in power conversion efficiencies for NFA OSCs, with values now exceeding 13%, demonstrating the viability of using NFAs to replace FAs in next-generation high-performance OSCs. This Review discusses the important work that has led to this remarkable progress, focusing on the two most promising NFA classes to date: rylene diimide-based materials and materials based on fused aromatic cores with strong electron-accepting end groups. The key structure–property relationships, donor–acceptor matching criteria and aspects of device physics are discussed. Finally, we consider the remaining challenges and promising future directions for the NFA OSCs field. Non-fullerene acceptors have been widely used in organic solar cells over the past 3 years. This Review focuses on the two most promising classes of non-fullerene acceptors — rylene diimide-based materials and fused-ring electron acceptors — and discusses structure–property relationships, donor– acceptor matching criteria and device physics, as well as future research directions for the field.

Dithienopicenocarbazole-Based Acceptors for Efficient Organic Solar Cells with Optoelectronic Response Over 1000 nm and an Extremely Low Energy Loss.

Abstract: Two cheliform non-fullerene acceptors, DTPC-IC and DTPC-DFIC, based on a highly electron-rich core, dithienopicenocarbazole (DTPC), are synthesized, showing ultra-narrow bandgaps (as low as 1.21 eV). The two-dimensional nitrogen-containing conjugated DTPC possesses strong electron-donating capability, which induces intense intramolecular charge transfer and intermolecular π–π stacking in derived acceptors. The solar cell based on DTPC-DFIC and a spectrally complementary polymer donor, PTB7-Th, showed a high power conversion efficiency of 10.21% and an extremely low energy loss of 0.45 eV, which is the lowest among reported efficient OSCs.

Toward Perovskite Solar Cell Commercialization: A Perspective and Research Roadmap Based on Interfacial Engineering.

Abstract: High-efficiency and low-cost perovskite solar cells (PVKSCs) are an ideal candidate for addressing the scalability challenge of solar-based renewable energy. The dynamically evolving research field of PVKSCs has made immense progress in solving inherent challenges and capitalizing on their unique structure-property-processing-performance traits. This review offers a unique outlook on the paths toward commercialization of PVKSCs from the interfacial engineering perspective, relevant to both specialists and nonspecialists in the field through a brief introduction of the background of the field, current state-of-the-art evolution, and future research prospects. The multifaceted role of interfaces in facilitating PVKSC development is explained. Beneficial impacts of diverse charge-transporting materials and interfacial modifications are summarized. In addition, the role of interfaces in improving efficiency and stability for all emerging areas of PVKSC design are also evaluated. The authors' integral contributions in this area are highlighted on all fronts. Finally, future research opportunities for interfacial material development and applications along with scalability-durability-sustainability considerations pivotal for facilitating laboratory to industry translation are presented.

Two-Dimensional Perovskite Solar Cells with 14.1% Power Conversion Efficiency and 0.68% External Radiative Efficiency

Abstract: Quasi-2D perovskites are attractive because of their improved stability compared to 3D counterparts, but they suffer from reduced performance. Here we report an efficient quasi-2D perovskite (PEA)2(MA)4Pb5I16-based optoelectronic device processed with NH4SCN and NH4Cl additives, showing a stabilized photovoltaic power conversion efficiency as high as 14.1% (average value 12.9 ± 0.8%), which is among the highest-performing quasi-2D perovskite solar cells. These additives increase the perovskite crystallinity and induce a preferred orientation with the (0k0) planes perpendicular to the substrate, resulting in improved transport properties and hence increased short-circuit current density. Furthermore, the NH4Cl treatment enriches the Cl– concentration near the PEDOT:PSS/perovskite interface, which passivates the electron traps, leading to an enhanced electroluminescence external quantum efficiency (0.68% at +2.5 V bias). As a result, high open-circuit voltages of 1.21 ± 0.01 V with a record low nonradiative...

Realizing Efficient Lead-Free Formamidinium Tin Triiodide Perovskite Solar Cells via a Sequential Deposition Route

Abstract: Recently, the evolved intermediate phase based on iodoplumbate anions that mediates perovskite crystallization has been embodied as the Lewis acid-base adduct formed by metal halides (serve as Lewis acid) and polar aprotic solvents (serve as Lewis base). Based on this principle, it is proposed to constitute efficient Lewis acid-base adduct in the SnI2 deposition step to modulate its volume expansion and fast reaction with methylammonium iodide (MAI)/formamidinium iodide (FAI) (FAI is studied hereafter). Herein, trimethylamine (TMA) is employed as the additional Lewis base in the tin halide solution to form SnY2 -TMA complexes (Y = I- , F- ) in the first-step deposition, followed by intercalating with FAI to convert into FASnI. It is shown that TMA can facilitate homogeneous film formation of a SnI2 (+SnF2 ) layer by effectively forming intermediate SnY2 -TMA complexes. Meanwhile, its relatively larger size and weaker affinity with SnI2 than FA+ ions will facilitate the intramolecular exchange with FA+ ions, thereby enabling the formation of dense and compact FASnI3 film with large crystalline domain (>1 µm). As a result, high power conversion efficiencies of 4.34% and 7.09% with decent stability are successfully accomplished in both conventional and inverted perovskite solar cells, respectively.

Highly Efficient Organic Solar Cells Based on S,N-Heteroacene Non-Fullerene Acceptors

Abstract: Two novel non-fullerene acceptors, SN6IC and SN6IC-4F, based on an S,N-heteroacene backbone were designed and synthesized. The cyclopentadiene fragments of commonly used acceptors were replaced with pyrrole rings to improve the electron-donating ability to increase the energy levels of the molecules. Both acceptors match well with the absorption and energy levels of the polymer donor PBDB-T, and PBDB-T:SN6IC-4F-based solar cells showed an excellent power conversion efficiency of 13.2%, with a relatively small VOC loss of 0.54 eV. This study proves that the introduction of a nitrogen atom to replace the sp3-hybridized carbon in the fused ring is very effective for making highly efficient NFAs to further improve the performance of organic solar cells.

Ternary non-fullerene polymer solar cells with 13.51% efficiency and a record-high fill factor of 78.13%

Abstract: Non-fullerene polymer solar cells (NF PSCs) have attracted much attention in recent years due to their rapidly increasing power conversion efficiency (PCE). In this work, two highly efficient ternary NF PSCs with FFs over 78% and PCEs up to 13.52% and 12.70% are demonstrated by adding a strongly aggregating polymer P1 into the classic PBDB-T:IT-M and PBDB-T:ITIC non-fullerene blends. The addition of P1 significantly enhances the crystallization of the blend film, while maintaining the desired morphology. The ternary devices show highly improved charge extraction and suppressed charge recombination in comparison to the binary mixture. The PCE of the PBDB-T:ITIC based NF PSC was found to increase from 10.82% to 12.70% and the FF from 71.85% to 78.07% after adding P1. For the PBDB-T:IT-M based NF PSC, the PCE increases from 11.71% to 13.52% and the FF from 72.07% to 77.83%. The high FFs and PCEs are the best results reported for ternary NF PSCs to date.

Near‐Infrared Electron Acceptors with Fluorinated Regioisomeric Backbone for Highly Efficient Polymer Solar Cells

Abstract: Solar photon-to-electron conversion with polymer solar cells (PSCs) has experienced rapid development in the recent few years. Even so, the exploration of molecules and devices in efficiently converting near-infrared (NIR) photons into electrons remains critical, yet challenging. Herein presented is a family of near-infrared nonfullerene acceptors (NIR NFAs, T1-T4) with fluorinated regioisomeric A-Aπ-D-Aπ-A backbones for constructing efficient single-junction and tandem PSCs with photon response up to 1000 nm. It is found that the tuning of the regioisomeric bridge (Aπ) and fluoro (F)-substituents on a molecular skeleton strongly influences the backbone conformation and conjugation, leading to the optimized optoelectronic and stable stacking of resultant NFAs, which eventually impacts the performance of derived PSCs. In PSCs, the proximal NFAs with varied F-atoms (T1-T3) mostly outperform than that of distal NFA (T4). Notably, single-junction PSC with PTB7-Th:T2 blend can reach 10.87% power conversion efficiency (PCE), after implementing a solvent additive to improve blend morphology. Moreover, efficient tandem PSCs are fabricated through integrating such NIR cells with mediate bandgap nonfullerene-based subcells, to achieve a PCE of 14.64%. The results reveal the structural design of organic semiconductor and device with improved photovoltaic performance.

Intensive Exposure of Functional Rings of a Polymeric Hole-Transporting Material Enables Efficient Perovskite Solar Cells

Abstract: A variety of dopant-free hole-transporting materials (HTMs) is effectively applied in perovskite solar cells (PSCs); however, HTMs with the additional function of HTM/perovskite interfacial optimization that is crucial to their photovoltaic performance are really limited. In this work, the design of an HTM bearing an intensive exposure of its functional aromatic rings to perovskite layer via side-chain engineering is attempted. With an edge-on orientation and a short distance to perovskite, this HTM was expected to display an excellent ability to extract holes from and passivate defects in the perovskite layer. To demonstrate this strategy, an alternating copolymer was constructed with a 2,5-di-2-ethylhexyloxy-1,4-phenylene unit and a bithiophene unit, and the PSC based on this polymer showed an ultrahigh short-circuit current density of 25.50 mA cm-2 , which was the highest so far presented by dopant-free organic HTMs. A comparable power conversion efficiency of 19.68% (certified: 19.5%) to that of a control 2,2',7,7'-tetrakis(N,N-di-p-methoxyphenylamine)-9,9'-spirobifluorene (spiro-OMeTAD) device (19.81%) was thus obtained, which is the highest value ever reported for mesoporous PSCs based on dopant-free polymeric HTMs.

Enhancing Defect Tolerance and Phase Stability of High-Bandgap Perovskites via Guanidinium Alloying

Abstract: The open-circuit voltages (VOC) of hybrid perovskite (HP) solar cells do not increase sufficiently with increasing bandgap (for Eg > 1.70eV). We study the impact of A+ size mismatch induced lattice distortions (in ABX3 structure) on the optoelectronic quality of high-bandgap HPs and find that the highest quality films have high A-site size-mismatch, where large guanidinium (GA) compensates for small Cs to keep the tolerance factor in the range for the perovskite structure. Specifically, we find that 1.84eV bandgap (FA0.33GA0.19Cs0.47)Pb(I0.66Br0.34)3 and 1.75eV bandgap (FA0.58GA0.10Cs0.32)Pb(I0.73Br0.27)3 attain quasi-Fermi level splitting of 1.43eV and 1.35eV, respectively, which is >91% of the Shockley-Queisser limit for both cases. Films of 1.75eV bandgap (FA,GA,Cs)Pb(I,Br)3 are then used to fabricate p-i-n photovoltaic devices that have a VOC of 1.24 V. This VOC is among the highest VOC reported for any HPs with similar bandgap (1.7 to 1.8 eV) and a substantial improvement for the p-i-n architecture, ...

Tackling Energy Loss for High-Efficiency Organic Solar Cells with Integrated Multiple Strategies.

Abstract: Limited by the various inherent energy losses from multiple channels, organic solar cells show inferior device performance compared to traditional inorganic photovoltaic techniques, such as silicon and CuInGaSe. To alleviate these fundamental limitations, an integrated multiple strategy is implemented including molecular design, interfacial engineering, optical manipulation, and tandem device construction into one cell. Considering the close correlation among these loss channels, a sophisticated quantification of energy-loss reduction is tracked along with each strategy in a perspective to reach rational overall optimum. A novel nonfullerene acceptor, 6TBA, is synthesized to resolve the thermalization and VOC loss, and another small bandgap nonfullerene acceptor, 4TIC, is used in the back sub-cell to alleviate transmission loss. Tandem architecture design significantly reduces the light absorption loss, and compensates carrier dynamics and thermalization loss. Interfacial engineering further reduces energy loss from carrier dynamics in the tandem architecture. As a result of this concerted effort, a very high power conversion efficiency (13.20%) is obtained. A detailed quantitative analysis on the energy losses confirms that the improved device performance stems from these multiple strategies. The results provide a rational way to explore the ultimate device performance through molecular design and device engineering.

Terthieno[3,2-b ]Thiophene (6T) Based Low Bandgap Fused-Ring Electron Acceptor for Highly Efficient Solar Cells with a High Short-Circuit Current Density and Low Open-Circuit Voltage Loss

Abstract: A terthieno[3,2-b]thiophene (6T) based fused-ring low bandgap electron acceptor, 6TIC, is designed and synthesized for highly efficient nonfullerene solar cells The chemical, optical, and physical properties, device characteristics, and film morphology of 6TIC are intensively studied 6TIC shows a narrow bandgap with band edge reaching 905 nm due to the electron-rich π-conjugated 6T core and reduced resonance stabilization energy The rigid, π-conjugated 6T also offers lower reorganization energy to facilitate very low VOC loss in the 6TIC system The analysis of film morphology shows that PTB7-Th and 6TIC can form crystalline domains and a bicontinuous network These domains are enlarged when thermal annealing is applied Consequently, the device based on PTB7-Th:6TIC exhibits a high power conversion efficiency (PCE) of 1107% with a high JSC > 20 mA cm−2 and a high VOC of 083 V with a relatively low VOC loss (≈055 V) Moreover, a semitransparent solar cell based on PTB7-Th:6TIC exhibits a relatively high PCE (762%) The device can have combined high PCE and high JSC is quite rare for organic solar cells

Overcoming the Photovoltage Plateau in Large Bandgap Perovskite Photovoltaics.

Abstract: Development of large bandgap (1.80–1.85 eV Eg) perovskite is crucial for perovskite–perovskite tandem solar cells. However, the performance of 1.80–1.85 eV Eg perovskite solar cells (PVKSCs) are significantly lagging their counterparts in the 1.60–1.75 eV Eg range. This is because the photovoltage (Voc) does not proportionally increase with Eg due to lower optoelectronic quality of conventional (MA,FA,Cs)Pb(I,Br)3 and results in a photovoltage plateau (Voc limited to 80% of the theoretical limit for ∼1.8 eV Eg). Here, we incorporate phenylethylammonium (PEA) in a mixed-halide perovskite composition to solve the inherent material-level challenges in 1.80–1.85 eV Eg perovskites. The amount of PEA incorporation governs the topography and optoelectronic properties of resultant films. Detailed structural and spectroscopic characterization reveal the characteristic trends in crystalline size, orientation, and charge carrier recombination dynamics and rationalize the origin of improved material quality with high...

Tunable Band Gap and Long Carrier Recombination Lifetime of Stable Mixed CH3NH3PbxSn1–xBr3 Single Crystals

Abstract: The mixed metal Pb/Sn halide perovskites have drawn significant attentions in perovskite photovoltaics due to their broad absorption spectra and tunable band gaps. To obtain a deeper understanding of these materials properties, single crystals are regarded as the best platform among various building blocks for fundamental study. Here, we report the mixed-metal MAPbxSn1–xBr3 (MA = CH3NH3) perovskite single crystals grown by top seeded solution growth (TSSG) method. Systematical characterizations were applied to investigating their structures and optoelectronic properties. These single crystals kept higher stability even exposed to air over one month than that of MASnBr3. The outstanding electrical properties, such as lower trap-state density and higher carrier mobility, were investigated by space charge-limited current (SCLC) and the Hall Effect measurements. More importantly, these perovskite single crystals exhibited much narrower optical band gap (1.77 eV) and longer carrier lifetime (∼2 μs) than those ...

Quantifying Efficiency Loss of Perovskite Solar Cells by a Modified Detailed Balance Model

Abstract: A modified detailed balance model is built to understand and quantify efficiency loss of perovskite solar cells. The modified model captures the light-absorption-dependent short-circuit current, contact and transport-layer-modified carrier transport, as well as recombination and photon-recycling-influenced open-circuit voltage. The theoretical and experimental results show that for experimentally optimized perovskite solar cells with the power conversion efficiency of 19%, optical loss of 25%, nonradiative recombination loss of 35%, and ohmic loss of 35% are the three dominant loss factors for approaching the 31% efficiency limit of perovskite solar cells. It is also found that the optical loss climbs up to 40% for a thin-active-layer design. Moreover, a misconfigured transport layer introduces above 15% of energy loss. Finally, the perovskite-interface-induced surface recombination, ohmic loss, and current leakage should be further reduced to upgrade device efficiency and eliminate hysteresis effect. This work contributes to fundamental understanding of device physics of perovskite solar cells. The developed model offers a systematic design and analysis tool to photovoltaic science and technology.

Long-Lived, Non-Geminate, Radiative Recombination of Photogenerated Charges in a Polymer/Small-Molecule Acceptor Photovoltaic Blend.

Abstract: Minimization of open-circuit-voltage ( VOC) loss is required to transcend the efficiency limitations on the performance of organic photovoltaics (OPV). We study charge recombination in an OPV blend comprising a polymer donor with a small molecule nonfullerene acceptor that exhibits both high photovoltaic internal quantum efficiency and relatively high external electroluminescence quantum efficiency. Notably, this donor/acceptor blend, consisting of the donor polymer commonly referred to as PCE10 with a pseudoplanar small molecule acceptor (referred to as FIDTT-2PDI) exhibits relatively bright delayed photoluminescence on the microsecond time scale beyond that observed in the neat material. We study the photoluminescence decay kinetics of the blend in detail and conclude that this long-lived photoluminescence arises from radiative nongeminate recombination of charge carriers, which we propose occurs via a donor/acceptor CT state located close in energy to the singlet state of the polymer donor. Additionally, crystallographic and spectroscopic studies point toward low subgap disorder, which could be beneficial for low radiative and nonradiative losses. These results provide an important demonstration of photoluminescence due to nongeminate charge recombination in an efficient OPV blend, a key step in identifying new OPV materials and materials-screening criteria if OPV is to approach the theoretical limits to efficiency.

Quantifying Efficiency Loss of Perovskite Solar Cells by a Modified Detailed Balance Model

Abstract: A modified detailed balance model is built to understand and quantify efficiency loss of perovskite solar cells. The modified model captures the light-absorption dependent short-circuit current, contact and transport-layer modified carrier transport, as well as recombination and photon-recycling influenced open-circuit voltage. Our theoretical and experimental results show that for experimentally optimized perovskite solar cells with the power conversion efficiency of 19%, optical loss of 25%, non-radiative recombination loss of 35%, and ohmic loss of 35% are the three dominant loss factors for approaching the 31% efficiency limit of perovskite solar cells. We also find that the optical loss will climb up to 40% for a thin-active-layer design. Moreover, a misconfigured transport layer will introduce above 15% of energy loss. Finally, the perovskite-interface induced surface recombination, ohmic loss, and current leakage should be further reduced to upgrade device efficiency and eliminate hysteresis effect. The work contributes to fundamental understanding of device physics of perovskite solar cells. The developed model offers a systematic design and analysis tool to photovoltaic science and technology.

Thick TiO2-Based Top Electron Transport Layer on Perovskite for Highly Efficient and Stable Solar Cells

Abstract: Simultaneously achieving high efficiency, long-term stability, and robust fabrication with good reproducibility in perovskite solar cells (PVSCs) is essential for their practical applications. Herein, we first demonstrate a thick TiO2 backbone film directly on top of a perovskite film through a simple room-temperature solution process. Through the strategy of decorating the TiO2 film with fullerene for passivating traps and filling voids, we achieve a fullerene-decorated TiO2 electron transport layer (ETL) in inverted PVSCs. Because of the suppressed monomolecular Shockley–Read–Hall recombination and ion diffusion of the fullerene-decorated TiO2 ETL, stabilized efficiencies of ∼20% and shelf life stability remaining over 98% of initial efficiency after aging in ambient conditions or 16 months are achieved. Remarkably, the PVSCs are insensitive to TiO2 thickness from 50 to 250 nm, which contributes significantly to the robust fabrication and high reproducibility of the PVSCs. This work provides an ETL desi...

Nonhalogen Solvent‐Processed Asymmetric Wide‐Bandgap Polymers for Nonfullerene Organic Solar Cells with Over 10% Efficiency

Abstract: New wide‐bandgap D–A–π copolymers based on an asymmetric bithiophene with one carboxylate substituent were synthesized. The asymmetric structure unit is flexible and versatile, which allows the absorption, energy levels and morphology of the blend films to be adjusted easily. D‐A‐p copolymers produced a high power conversion efficiency of 10.0% for halogen solvent‐processed OSCs and 9.55% for non‐halogen solvent‐processed devices.

Bis-Tridentate Iridium(III) Phosphors with Very High Photostability and Fabrication of Blue-Emitting OLEDs.

Abstract: Sky-blue and blue-emitting, carbazolyl functionalized, bis-tridentate Ir(III) phosphors Cz-1-Cz-3 with bright emission and short radiative lifetime are successfully synthesized in a one-pot manner. They exhibit very high photostability against UV-vis irradiation in degassed toluene, versus both green and true-blue-emitting reference compounds, i.e., fac-[Ir(ppy)3] and mer-[Ir(pmp)3]. Organic light-emitting diodes (OLEDs) based on Cz-2 exhibit maximum external quantum efficiency (EQE) of 21.6%, EQE of 15.1% at 100 cd m-2, and with CIE x,y coordinates of (0.17, 0.25). This study provides a conceptual solution to the exceedingly stable and efficient blue phosphor. It is promising that long lifespan blue OLED based on these emitters can be attained with further engineering of devices suitable for commercial application.

Unexpectedly Slow Yet Efficient Picosecond to Nanosecond Photoinduced Hole-Transfer Occurs in a Polymer/Nonfullerene Acceptor Organic Photovoltaic Blend

Abstract: We study photoinduced charge generation in a model polymer/nonfullerene acceptor (NFA) organic photovoltaic (OPV) blend. Specifically, we focus on hole-transfer kinetics from the photoexcited NFA thiophene-thieno[3,2-b]thiophene-thiophene-3-(dicyanomethylidene)indan-1-one (4TIC) to the conjugated polymer donor poly[(4,4′-bis(2-butyloctoxycarbonyl-[2,2′-bithiophene]-5,5-diyl)-alt-(2,2′-bithiophene-5,5′-diyl)] (PDCBT) using ultrafast transient absorption spectroscopy by selectively exciting the 4TIC electron acceptor and monitoring the bleach of the PDCBT ground-state population. In the blend, the 4TIC excitons decay with an average lifetime of 7 ps, accompanied by a concomitant rise in the ground-state bleach of the polymer with a comparable average lifetime that is 60% complete by 8 ps and 95% complete by 100 ps, occurring roughly an order of magnitude slower than that in most previously reported polymer/NFA blends. Notably, the ground-state bleach of the polymer continues to grow, not reaching its maximu...

Silicon-Organic Hybrid (SOH) Mach-Zehnder Modulators for 100 Gbit/s on-off Keying

Abstract: Electro-optic modulators for high-speed on-off keying (OOK) are key components of short- and medium-reach interconnects in data-center networks. Small footprint, cost-efficient large-scale production, small drive voltages and ultra-low power consumption are of paramount importance for such devices. Here we demonstrate that the concept of silicon-organic hybrid (SOH) integration perfectly meets these challenges. The approach combines the unique processing advantages of large-scale silicon photonics with unrivalled electro-optic (EO) coefficients obtained by molecular engineering of organic materials. Our proof-of-concept experiments demonstrate generation and transmission of OOK signals at line rates of up to 100 Gbit/s using a 1.1 mm-long SOH Mach-Zehnder modulator (MZM) featuring a π-voltage of only 0.9 V. The experiment represents the first demonstration of 100 Gbit/s OOK on the silicon photonic platform, featuring the lowest drive voltage and energy consumption ever demonstrated for a semiconductor-based device at this data rate. We support our results by a theoretical analysis showing that the nonlinear transfer characteristic of the MZM can help to overcome bandwidth limitations of the modulator and the electric driver circuitry. We expect that high-speed, power-efficient SOH modulators may have transformative impact on short-reach networks, enabling compact transceivers with unprecedented efficiency, thus building the base of future interfaces with Tbit/s data rates.

Ultra-efficient and stable electro-optic dendrimers containing supramolecular homodimers of semifluorinated dipolar aromatics

Abstract: In organic electro-optic (EO) materials, strong dipole–dipole interactions hinder the highly efficient poling of nonlinear optical chromophores. Supramolecular self-assembly through π–π stacking of fluoroaromatics was proved to be one of the most effective strategies to simultaneously achieve high chromophore loading density and highly efficient poling. Herein, we demonstrated a new strategy of supramolecular homodimerization to self-assemble EO dendritic films, in which two dendritic units with semifluorinated dipolar 1,2,3-trifluorobenzene (TFB) moieties were attached to the donor end and the π-bridge centre of push–pull tetraene chromophores. In these new dendrimers, the use of monolithic and semifluorinated TFB rings to replace the heterodimers of phenyl and pentafluorophenyl moieties has greatly simplified the synthesis of dendrimers and their intermixing, and can further potentially enable more efficient and rapid intermixing of interacting moieties in the solid states than those in binary and ternary systems. Photophysical property analysis and DFT calculations were carried out to understand the macroscopic supramolecular self-assembly and microscopic polarizability of new TFB-based EO dendrimers. The poled films of these self-assembled dendritic EO films exhibited very large EO coefficients up to 248 pm V−1 at a wavelength of 1310 nm and excellent temporal stability at room temperature with a very minimal change of ∼5% for over 1000 hours. Our study therefore illustrates that homodimer stacking of TFB rings through dipole–dipole coupling provides stabilization energy similar to that of quadrupolar interaction of phenyl and pentafluorophenyl heterodimeric pairs. Due to the highly efficient poling and excellent temporal EO stability, TFB self-assembled EO dendrimers show great potential for application in photonic devices.