Small Molecule Donor Research Articles

Synthesis and photovoltaic properties of organic molecules based on difluoroquinoxaline derivatives for OPVs

We designed and synthesized two novel low band gap small molecule donors (M1 and M2) that consist of benzo[1,2-b:4,5-b′]dithiophene as the electron-rich core and 6,7-difluoroquinoxaline as the electron-deficient end-group. M1 and M2 with A-D-A type structure were synthesized via Stille coupling reaction for use in OSCs. The absorption maximum of the M1 and M2 in solid thin films exhibited at 536 and 540 nm and absorption onset at 582 and 592 nm, corresponding to band gaps of 2.31 and 2.10 eV, respectively. Although the absorption of the M1 with branched alkyl chain was blue shifted as compared to M2, the branched alkyl chain in benzodithiophene core provide appropriate solubility to provide good OSC performance.

Synergy of Liquid-Crystalline Small-Molecule and Polymeric Donors Delivers Uncommon Morphology Evolution and 16.6% Efficiency Organic Photovoltaics.

Achieving an ideal morphology is an imperative avenue for enhancing key parameters toward high‐performing organic solar cells (OSCs). Among a myriad of morphological‐control methods, the strategy of incorporating a third component with structural similarity and crystallinity difference to construct ternary OSCs has emerged as an effective approach to regulate morphology. A nematic liquid‐crystalline benzodithiophene terthiophene rhodamine (BTR) molecule, which possesses the same alkylthio‐thienyl‐substituted benzo moiety but obviously stronger crystallinity compared to classical medium‐bandgap polymeric donor PM6, is employed as a third component to construct ternary OSCs based on a PM6:BTR:Y6 system. The doping of BTR (5 wt%) is found to be enough to improve the OSC morphology—significantly enhancing the crystallinity of the photoactive layer while slightly reducing the donor/acceptor phase separation scale simultaneously. Rarely is such a morphology evolution reported. It positively affects the electronic properties of the device—prolongs the carrier lifetime, shortens the photocurrent decay time, facilitates exciton dissociation, charge transport, and collection, and ultimately boosts the power conversion efficiency from 15.7% to 16.6%. This result demonstrates that the successful synergy of liquid‐crystalline small‐molecule and polymeric donors delicately adjusts the active‐layer morphology and refines device performance, which brings vibrancy to the OSC research field.

Combining chlorination and sulfuration strategies for high-performance all-small-molecule organic solar cells

Abstract Three small-molecule donors based on dithieno[2,3-d:2ʹ,3ʹ-dʹ]-benzo[1,2-b:4,5-bʹ] dithiophene (DTBDT) unit were designed and synthesized by side chain regulation with chlorinated or/and sulfurated substitutions (namely ZR1, ZR1-Cl, and ZR1-S-Cl respectively), along with a crystalline non-fullerene acceptor IDIC-4Cl with a chlorinated 1,1-dicyanomethylene-3-indanone (IC) end group. Energy levels, molar extinction coefficients and crystallinities of three donor molecules can be effectively altered by combining chlorination and sulfuration strategies. Especially, the ZR1-S-Cl exhibited the best absorption ability, lowest higher occupied molecular orbital (HOMO) energy level and highest crystallinity among three donors, resulting in the corresponding all-small-molecule organic solar cells to produce a high power conversion efficiency (PCE) of 12.05% with IDIC-4Cl as an acceptor.

All-Small-Molecule Organic Solar Cells Based on a Fluorinated Small Molecule Donor With High Open-Circuit Voltage of 1.07 V.

A new small molecule donor with an acceptor-donor-acceptor (A-D-A) structure, namely DRTB-FT, has been designed and synthesized for all-small-molecule organic solar cells (ASM-OSCs). By introducing fluorine atoms on the thienyl substituent of the central benzodithiophene unit, DRTB-FT shows a low-lying highest occupied molecular orbital (HOMO) energy level of −5.64 eV. Blending with an A-D-A type acceptor F-2Cl, DRTB-FT based ASM-OSCs gave a power conversion efficiency (PCE) of 7.66% with a high open-circuit voltage (Voc) of 1.070 V and a low energy loss of 0.47 eV. The results indicate that high Voc of ASM-OSC devices can be obtained through careful donor molecular optimization.

Highly Efficient All-Small-Molecule Organic Solar Cells with Appropriate Active Layer Morphology by Side Chain Engineering of Donor Molecules and Thermal Annealing.

It is very important to fine-tune the nanoscale morphology of donor:acceptor blend active layers for improving the photovoltaic performance of all-small-molecule organic solar cells (SM-OSCs). In this work, two new small molecule donor materials are synthesized with different substituents on their thiophene conjugated side chains, including SM1-S with alkylthio and SM1-F with fluorine and alkyl substituents, and the previously reported donor molecule SM1 with an alkyl substituent, for investigating the effect of different conjugated side chains on the molecular aggregation and the photophysical, and photovoltaic properties of the donor molecules. As a result, an SM1-F-based SM-OSC with Y6 as the acceptor, and with thermal annealing (TA) at 120 °C for 10 min, demonstrates the highest power conversion efficiency value of 14.07%, which is one of the best values for SM-OSCs reported so far. Besides, these results also reveal that different side chains of the small molecules can distinctly influence the crystallinity characteristics and aggregation features, and TA treatment can effectively fine-tune the phase separation to form suitable donor-acceptor interpenetrating networks, which is beneficial for exciton dissociation and charge transportation, leading to highly efficient photovoltaic performance.

Progress of the key materials for organic solar cells

Organic solar cells have attracted academic and industrial interests due to the advantages like lightweight, flexibility and roll-to-roll fabrication. Nowadays, 18% power conversion efficiency has been achieved in the state-of-the-art organic solar cells. The recent rapid progress in organic solar cells relies on the continuously emerging new materials, device fabrication technologies, and the deep understanding on film morphology, molecular packing and device physics. Donor and acceptor materials are the key materials for organic solar cells since they determine the device performance. The past 25 years have witnessed an odyssey in developing high-performance donors and acceptors. In this review, we focus on those star materials and milestone work, and introduce the molecular structure evolution of the key materials. These key materials include homopolymer donors, D-A copolymer donors, A-D-A small molecule donors, fullerene acceptors and nonfullerene acceptors. At last, we outlook the challenges and very important directions in key materials development.

Recent Progress in Chlorinated Organic Photovoltaic Materials.

ConspectusOver the past few years, the development of new materials has contributed to rapid increases in the power conversion efficiencies (PCEs) of organic photovoltaic (OPV) cells to over 17%, showing great potential for the commercialization of this technology in the near future. At this stage, designing new materials with superior performance and low cost simultaneously is of crucial importance. Chlorinated materials are emerging as new stars with very high PCEs, creating a molecular design trend to replace the most popular fluorinated materials. For example, by using chlorinated non-fullerene acceptors, we recently got a record PCE of 17% for single-junction OPV cells. Firmly based on recent advances, herein we focus on the topic of chlorinated OPV materials, aiming to provide a guideline for further molecular design.In this Account, first, on the basis of most fundamental features of the Cl atom, we highlight the features of chlorinated materials compared with their fluorinated counterparts: (1) Chlorination is more efficient than fluorination in modulating the optical and electrical properties of OPV materials. In many cases, chlorinated materials show lower energy levels and broader absorption spectra than their fluorinated counterparts, which contribute higher output voltages and current densities in the resulting photovoltaic devices. (2) Cl has a large atomic size than F. On one hand, enhanced overlap of π electrons is beneficial for enhancing the intermolecular packing and crystalline property and thus improving the charge transport. On the other hand, if Cl is introduced inappropriately in the backbone or side chain, this feature will cause a more twisted π plane and larger steric hindrance, having negative impacts on the photovoltaic performance of the corresponding materials. (3) Importantly, chlorination is usually chemically cheaper in synthesis, which has the potential to decrease the material cost of OPV cells. Then, we provide a concise review of chlorinated OPV materials, including polymeric and small-molecule donors and non-fullerene acceptors. The photovoltaic performance in various types of OPV cells using chlorinated materials, such as single-junction, tandem, semitransparent, and indoor-light photovoltaic cells is also discussed. For instance, ultranarrow-band-gap chlorinated acceptors can be used to construct highly efficient color-semitransparent OPV cells, and the wide-band-gap chlorinated materials show great potential for fabricating indoor-light photovoltaic devices. Finally, we briefly discuss current questions related to chlorinated OPV materials and highlight the significance of chlorination in future development.

Alkyl side-chain dependent self-organization of small molecule and its application in high-performance organic and perovskite solar cells

Abstract The molecular self-organization of organic semiconductors, which is mainly determined by the structural design, film processing, and device configuration, is one of the crucial factors for achieving high-performance organic photovoltaics (OPVs) and perovskite solar cells (PvSCs). In this study, we newly synthesized and developed strongly self-organized small molecules via alkyl side-chain engineering. Replacing “H” to “C6H13” on the thienyl group, SM2 showed a well-ordered face-on orientation. Due to favorable self-organization leading to effective charge carrier dynamics, including enhanced charge transfer/transport and suppressed recombination, SM2-based OPVs and PvSCs exhibited improved device performance compared to the devices based on SM1 without an additional hexyl side-chain. The best fullerene-based OPV and planar PvSC with SM2 as a small-molecule donor and as a hole transport layer (HTL) achieved an unprecedentedly high efficiency of 9.38% and 20.56%, in contrast with SM1-based devices showing lower efficiency of 8.70% and 15.37%. Furthermore, the planar PvSCs based on undoped-SM2 HTL exhibited comparable efficiency but provided excellent heat and humidity stability compared with doped spiro-OMeTAD-based devices. These results clearly indicated that SM2 with highly-ordered and favorable self-organization is a promising organic semiconductor for future applications of high-performance organic and inorganic-organic hybrid electronics.

Small molecule donor based on alkoxylated benzothiadiazole unit: Synthesis and photovoltaics properties

Two small molecule donors (namely BTRO and BTCN) based on the benzothiadiazole unit were synthesized in this study. In comparison to BTRO, BTCN has a narrower absorption spectrum, however, BTCN has better crystallinity, higher carrier mobility, and better light absorption that is complementary to IDIC-4F. Non-fullerene all small molecule organic solar cells (SM-OSCs) based on BTCN: IDIC-4F exhibited a power conversion efficiency (PCE) of 4.62% with short circuit current density (Jsc) of 11.46 mA/cm2, open-circuit voltage (Voc) of 0.89 V, and fill factor (FF) of 0.45. In contrast, non-fullerene SM-OSCs based on BTRO: IDIC-4F showed PCE, Jsc, Voc, and FF values of 4.08%, 11.04 mA/cm2, 0.91 V, and 0.41, respectively. Our results show that benzothiadiazole is a very good acceptor unit for regulating the absorption and energy levels of non-fullerene SM-OSCs.

Three-Dimensional Spirothienoquinoline-Based Small Molecules for Organic Photovoltaic and Organic Resistive Memory Applications.

A new electron-rich spirothienoquinoline unit, tBuSAF-Th, has been developed via incorporation of a thienyl unit instead of a phenyl unit into the six-membered ring of the spiroacridine (SAF) and utilized for the first time as a building block for constructing small-molecule electron donors in organic solar cells (OSCs) and as active layers in organic resistive memory devices. The resulting three-dimensional spirothienoquinoline-containing 1-4 exhibit high-lying highest occupied molecular orbital (HOMO) energy levels. By the introduction of electron-deficient benzochalcogenodiazole linkers, with the chalcogen atoms being varied from O to S and Se, a progressively lower lowest unoccupied molecular orbital (LUMO) energy level has been achieved while keeping the HOMO energy levels similar. This strategy has allowed an enhanced light-harvesting ability without compromising open-circuit voltage (Voc) in vacuum-deposited bulk heterojunction OSCs using 1-4 as donors and C70 as the acceptor. Good photovoltaic performances with power conversion efficiencies (PCEs) of up to 3.86% and high short-circuit current densities (Jsc) of up to 10.84 mA cm-2 have been achieved. In addition, organic resistive memory devices fabricated with these donor-acceptor small molecules exhibit binary logic memory behaviors with long retention times and high on/off current ratios. This work indicates that the spirothienoquinoline moiety is a potential building block for constructing multifunctional organic electronic materials.

Extension of π-conjugation and enhancement of electron-withdrawing ability at terminal indenedione for A-π-D-π-A small molecules for application in organic solar cells

A class of A-π-D-π-A type organic small-molecule (SM) donor materials used in heterojunction solar cell has been designed and investigated by means of quantum chemical calculations. The structural modification of the end-capped 1,3-indenedione (IND) by expanding the π-conjugation and enhancing the electron-withdrawing ability are expected to improve the photovoltaic performance. To gain a better understanding of the effects of such structural modulation of IND on the electronic and photophysical properties of SM donor materials, the geometrical and electronic structures, absorption spectra, energy loss, intramolecular charge transfer (ICT), and exciton dissociation and charge recombination rates at the interface have been analyzed in detail to establish structure-property relationships for the investigated A-π-D-π-A molecules. This work demonstrates that why such terminal structural modification could increase open circuit voltages, enhance light-absorption ability and ICT properties, reduce energy loss, facilitate exciton dissociation, and suppress charge recombination, thus leading to improved photovoltaic performance as predicted by Scharber diagram. This study could give the theoretical guidelines for molecular design and shed a light on the exploration of high-performance A-π-D-π-A type SM donor materials.

Mediated Non-geminate Recombination in Ternary Organic Solar Cells Through a Liquid Crystal Guest Donor.

The approach via ternary blends prompts the increase of absorbed photon density and resultant photocurrent enhancement in organic solar cells (OSCs). In contrast to actively reported high efficiency ternary OSCs, little is known about charge recombination properties and carrier loss mechanisms in these emerging devices. Here, through introducing a small molecule donor BTR as a guest component to the PCE-10:PC71BM binary system, we show that photocarrier losses via recombination are mitigated with respect the binary OSCs, owing to a reduced bimolecular recombination. The gain of the fill factor in ternary devices are reconciled by the change in equilibrium between charge exaction and recombination in the presence of BTR toward the former process. With these modifications, the power conversion efficiency in ternary solar cells receives a boost from 8.8 (PCE-10:PC71BM) to 10.88%. We further found that the voltage losses in the ternary cell are slightly suppressed, related to the rising charge transfer-state energy. These benefits brought by the third guest donor are important for attaining improvements on key photophysical processes governing the photovoltaic efficiencies in organic ternary solar cells.

Synthesis and Photophysical Properties of Small Molecule Donor Materials Based on Indacenodithieno[3, 2-b]Thiophene Core for Organic Solar Cells

We synthesized a small molecule donor material based on IDTT for solar cells, named C6S2ThBSeIDTT, which was obtained by IDTT-2SnMe3 and a capping fragment by a simple Stiller coupling reaction. Its structure and properties were HNMR. C6S2ThBSeIDTT was confirmed that it exhibited good solubility in conventional organic solvent. It can be found that strong intermolecular charge transfer (ICT) exists in the D-A-D-A-D conformation. It has been found to have broad and strong absorption by absorption spectroscopy with a medium wide band gap of 1.70 eV, and will well agree with fullerene acceptors such as PC60BM and PC71BM for efficient bulk heterojunction solar cells.

Weak Makes It Powerful: The Role of Cognate Small Molecules as an Alloy Donor in 2D/1A Ternary Fullerene Solar Cells for Finely Tuned Hierarchical Morphology in Thick Active Layers

AbstractHerein, a novel small molecule donor is first developed, FSM6, which is a cognate molecule to BTR possessing similar molecular structure with comparable optical absorption but different crystallinity. The efficient fullerene‐type ternary small molecular solar cells (SMSCs) based on an alloy donor of BTR and FSM6 in a thick film of 250 nm reveal the improved hierarchical phase separation morphology and molecular structural order of ternary active layers with improved crystallinity of the key donor component BTR. Furthermore, FSM6 as the key third component also plays a role of charge transfer accelerator in ternary SMSCs. As a result, the optimal ternary SMSCs based on BTR:FSM6:PC71BM achieve a high power conversion efficiency (PCE) up to 10.21% with the synergistically improved open‐circuit voltage of 0.950 V, short‐circuit current density of 13.85 mA cm−2, and fill factor of 77.6%, in comparison with either the binary SMSCs of BTR:PC71BM (PCE = 9.37%) or FSM6:PC71BM (PCE = 8.00%). This work provides a promising methodology to optimize device morphology for high‐performance ternary SMSCs by combining two cognate small molecules with similar absorption spectra but different crystallinity as an alloy donor.

Crystal-structure of active layers of small molecule organic photovoltaics before and after solvent vapor annealing

Abstract It is demonstrated by a detailed structural analysis that the crystallinity and the efficiency of small molecule based organic photovoltaics can be tuned by solvent vapor annealing (SVA). Blends made of the small molecule donor 2,2′-[(3,3′″,3″″,4′-tetraoctyl[2,2′:5′,2″:5″,2′″:5′″,2″″-quinquethiophene]-5,5″″-diyl)bis[(Z)-methylidyne(3-ethyl-4-oxo-5,2-thiazolidinediylidene)]]bis-propanedinitrile (DRCN5T) and the acceptor [6,6]-phenyl C71 butyric acid methyl ester (PC71BM) were annealed using solvent vapors with either a high solubility for the donor (tetrahydrofuran), the acceptor (carbon disulfide) or both (chloroform). The samples were analyzed by grazing-incidence wide-angle X-ray scattering (GIWAXS), electron diffraction, X-ray pole figures, and time-of-flight secondary ion mass spectrometry (ToF-SIMS). A phase separation of DRCN5T and PC71BM is induced by SVA leading to a crystallization of DRCN5T and the formation of a DRCN5T enriched layer. The DRCN5T crystallites possess the two dimensional oblique crystal system with the lattice parameters a = 19.2 Å, c = 27.1 Å, and β = 111.1° for the chloroform case. No major differences in the crystal structure for the other solvent vapors were observed. However, the solvent choice strongly influences the size of the DRCN5T enriched layer. Missing periodicity in the [010]-direction leads to the extinction of all Bragg reflections with k ≠ 0. The annealed samples are randomly orientated with respect to the normal of the substrate (fiber texture).

Organic solar cells based on small molecule donors and polymer acceptors operating at 150 °C

An organic solar cell based on a small molecule donor and a polymer acceptor exhibits a PCE of 9.5% and can operate at high temperature. It retains 84% of its PCE after thermal treatment at 150 °C for three days.

A novel wide-bandgap small molecule donor for high efficiency all-small-molecule organic solar cells with small non-radiative energy losses

A novel small molecule donor based on thiazolo[5,4-d]thiazole (TTz) unit is developed for OSCs application with 13.9% power conversion efficiency and a small non-radiative energy loss of 0.18 eV.

The influence of the terminal acceptor and oligomer length on the photovoltaic properties of A–D–A small molecule donors

The influence of CPDTV-oligomer length and terminal acceptor units in the efficiency of OSCs with PC71BM is studied.

Co-assembly of functionalized donor-acceptor molecules within block copolymer microdomains via the supramolecular assembly approach with an improved charge carrier mobility.

Here, we demonstrate the three-component self-assembly of functionalized small molecules (donor and acceptor) and a polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer using the supramolecular approach. The introduction of functional groups on both the donor (1-pyrenebutyric acid, PBA) and acceptor (functionalized naphthalene diimide, FNDI) molecules can form stable charge-transfer (CT) complexes within the block copolymer domains and these supramolecules exhibited a charge carrier mobility of around 1.01 × 10-4 cm2 (V s)-1. In this case, both the molecules can form H-bonding with P4VP chains, and as well as π-π stacking between the PBA and FNDI molecules is also possible within the block copolymer domains. These noncovalent interactions lead to the formation of stable hierarchical structures and CT complexes between PBA and FNDI, where bilayer donor-acceptor (D-A) stacks formed within the block copolymer microdomains. Overall, the organization of both functionalized donor and acceptor molecules within the block copolymer domain exhibits an enhanced charge carrier mobility, which is potentially useful in the fabrication of organic photovoltaic cells and organic light-emitting diodes.

All-small-molecule organic solar cells with over 14% efficiency by optimizing hierarchical morphologies

The high efficiency all-small-molecule organic solar cells (OSCs) normally require optimized morphology in their bulk heterojunction active layers. Herein, a small-molecule donor is designed and synthesized, and single-crystal structural analyses reveal its explicit molecular planarity and compact intermolecular packing. A promising narrow bandgap small-molecule with absorption edge of more than 930 nm along with our home-designed small molecule is selected as electron acceptors. To the best of our knowledge, the binary all-small-molecule OSCs achieve the highest efficiency of 14.34% by optimizing their hierarchical morphologies, in which the donor or acceptor rich domains with size up to ca. 70 nm, and the donor crystals of tens of nanometers, together with the donor-acceptor blending, are proved coexisting in the hierarchical large domain. All-small-molecule photovoltaic system shows its promising for high performance OSCs, and our study is likely to lead to insights in relations between bulk heterojunction structure and photovoltaic performance.