Seyeong Song

Conjugated polyelectrolyte hole transport layer for inverted-type perovskite solar cells

Organic–inorganic hybrid perovskite materials offer the potential for realization of low-cost and flexible next-generation solar cells fabricated by low-temperature solution processing. Although efficiencies of perovskite solar cells have dramatically improved up to 19% within the past 5 years, there is still considerable room for further improvement in device efficiency and stability through development of novel materials and device architectures. Here we demonstrate that inverted-type perovskite solar cells with pH-neutral and low-temperature solution-processable conjugated polyelectrolyte as the hole transport layer (instead of acidic PEDOT:PSS) exhibit a device efficiency of over 12% and improved device stability in air. As an alternative to PEDOT:PSS, this work is the first report on the use of an organic hole transport material that enables the formation of uniform perovskite films with complete surface coverage and the demonstration of efficient, stable perovskite/fullerene planar heterojunction solar cells.

Thienoisoindigo (TIIG)-based small molecules for the understanding of structure–property–device performance correlations

In this contribution, a series of small molecule semiconductors based on the recently conceived thienoisoindigo (TIIG) and three different end-capping moieties (benzene (Bz), naphthalene (Np), and benzofuran (Bf)) with varied electron-donating strength and conformations has been synthesized by Suzuki coupling and utilized for organic photovoltaics (OPVs). Incorporation of different end-capping blocks onto the TIIG core facilitated the tuning of optical properties and the electronic structure (HOMO/LUMO energy levels), solid-state morphology and performance in OPVs. It is apparent that the bandgaps within this series (TIIG-Bz, TIIG-Np, and TIIG-Bf) were progressively red-shifted and the absorption coefficients were enhanced by increasing the conjugation length and/or the donor ability of the end-capping units. In addition, HOMO and LUMO levels were shown to simultaneously follow changes made to the end-capping moieties. The best performing OPVs using TIIG-Np:PC71BM exhibited a power conversion efficiency (PCE) of 1.81% with Jsc = 7.15 mA cm−2, FF = 0.39, and Voc = 0.66 V. With the aim of exploring underlying structure–property relationships for this new class of molecular systems, we have quantitatively investigated various morphological structures in both the pristine small molecule films and small molecule/PC71BM blend films using a combination of grazing incidence wide angle X-ray scattering (GIWAXS) and atomic force microscopy (AFM). In this study, a correlation between the molecular structure, thin film morphology, and photovoltaic properties of these conjugated small molecules was established that provides guidance for the molecular design of new photovoltaic semiconductors based on TIIG units.

High-efficiency photovoltaic cells with wide optical band gap polymers based on fluorinated phenylene-alkoxybenzothiadiazole

A series of semi-crystalline, wide band gap (WBG) photovoltaic polymers were synthesized with varying number and topology of fluorine substituents. To decrease intramolecular charge transfer and to modulate the resulting band gap of D–A type copolymers, electron-releasing alkoxy substituents were attached to electron-deficient benzothiadiazole (A) and electron-withdrawing fluorine atoms (0–4F) were substituted onto a 1,4-bis(thiophen-2-yl)benzene unit (D). Intra- and/or interchain noncovalent Coulombic interactions were also incorporated into the polymer backbone to promote planarity and crystalline intermolecular packing. The resulting optical band gap and the valence level were tuned to 1.93–2.15 eV and −5.37 to −5.67 eV, respectively, and strong interchain organization was observed by differential scanning calorimetry, high-resolution transmission electron microscopy and grazing incidence X-ray scattering measurements. The number of fluorine atoms and their position significantly influenced the photophysical, morphological and optoelectronic properties of bulk heterojunctions (BHJs) with these polymers. BHJ photovoltaic devices showed a high power conversion efficiency (PCE) of up to 9.8% with an open-circuit voltage of 0.94–1.03 V. To our knowledge, this PCE is one of the highest values for fullerene-based single BHJ devices with WBG polymers having a band gap of over 1.90 eV. A tandem solar cell was also demonstrated successfully to show a PCE of 10.3% by combining a diketopyrrolopyrrole-based low band gap polymer.

2,2-dimethyl-2H-benzimidazole based small molecules for organic solar cells

We report the small molecules utilizing new electron-deficient unit, 2,2-dimethyl-2H-benzimidazole (MBI) and phenanthro[9,10-c][1,2,5]thiadiazole (PT), for the photovoltaic application. Donor-acceptor-donor (D-A-D) types of conjugated small molecules containing benzo[1,2-b;3,4-b′]dithiophene (BDT) as electron rich unit and MBI and PT as electron deficient units (SM1 and SM2) were synthesized. D-A-D type of small molecules has the abilities of increasing intramolecular charge transfer (ICT) inducing long wavelength absorption and lowering the HOMO level for the improvement of open-circuit voltage (VOC). SM1 was synthesized by coupling BDT and PT units by Stille coupling reaction with Pd(0)-catalyst. By using same type of Pd(0)-catalized reaction, BDT unit and MBI unit linked with two thiophenes were coupled to provide SM2. The spectrum of SM2 in the solid thin film shows absorption band with maximum peak at 601 nm and the absorption onset at 756 nm, corresponding to band gap of 1.64 eV. The device comprising SM2 with PCBM (3:7) showed a VOC of 0.62 V, a JSC of 1.69 mA/cm2, and a fill factor (FF) of 0.27, giving a power conversion efficiency of 0.28%.

Medium bandgap copolymers based on carbazole and quinoxaline exceeding 1.0 V open-circuit voltages

Open-circuit voltage (VOC) is an important parameter in determining the performance of polymer solar cells (PSCs). Given the desire for superior VOC values in PSCs, we have designed and synthesized a series of ‘medium bandgap’ donor–acceptor (D–A) copolymers containing carbazole (Cz) and quinoxaline (Qx) (PCzDT-Qx, PCzDT-fQx, and PCzDT-ffQx). As a result of their deep-lying HOMO levels (−5.45 to −5.61 eV), high VOC values are achieved in PSCs with the resulting copolymers, despite the expense of short-circuit current density (JSC) and fill factor (FF) parameters. In this study, in addition to the best power-conversion efficiency (PCE) of up to 4.03% from PCzDT-fQx-based on PSCs, we have demonstrated a VOC value exceeding 1.0 V with PSCs of PCzDT-ffQx, which is among the highest VOC values achieved to date. Moreover, a comprehensive investigation on the mechanism of charge recombination and transport characteristics can determine a clear structure–property correlation in this class of molecules, which is helpful for designing better materials with maximum VOC without scarifying other key photovoltaic parameters.

Formamidinium-based planar heterojunction perovskite solar cells with alkali carbonate-doped zinc oxide layer

We herein demonstrate n-i-p-type planar heterojunction perovskite solar cells employing spin-coated ZnO nanoparticles modified with various alkali metal carbonates including Li2CO3, Na2CO3, K2CO3 and Cs2CO3, which can tune the energy band structure of ZnO ETLs. Since these metal carbonates doped on ZnO ETLs lead to deeper conduction bands in the ZnO ETLs, electrons are easily transported from the perovskite active layer to the cathode electrode. The power conversion efficiency of about 27% is improved due to the incorporation of alkali carbonates in ETLs. As alternatives to TiO2 and n-type metal oxides, electron transport materials consisting of doped ZnO nanoparticles are viable ETLs for efficient n-i-p planar heterojunction solar cells, and they can be used on flexible substrates via roll-to-roll processing.

Twisted Linker Effect on Naphthalene Diimide-Based Dimer Electron Acceptors for Non-fullerene Organic Solar Cells

Naphthalene diimide (NDI) dimers, NDI-Ph-NDI with a phenyl linker and NDI-Xy-NDI with a xylene linker, are designed and synthesized. The influence of the xylene and phenyl linkers on optical properties, electrochemical properties, morphology, and device performance is systematically investigated. Non-fullerene organic solar cells (OSCs) with NDI-Ph-NDI show poor device efficiency due to aggregation of polymer chains and/or NDI dimers caused by the highly planar structure of NDI-Ph-NDI. Although NDI-Xy-NDI is a non-planar structure, uniform surface morphology and weak bimolecular recombination lead to high power conversion efficiencies of 3.11%, which is the highest value in non-fullerene OSCs with NDI small molecules.

The introduction of a perovskite seed layer for high performance perovskite solar cells

Processing for obtaining compact and uniform perovskite photoactive layers has been intensively studied over the last few years to achieve high power conversion efficiencies (PCEs) in solar cells. Particularly, high quality crystal growth of perovskite layers is critical to enhance device performance. We demonstrate an easy and effective new process for high efficiency p–i–n planar heterojunction structures of perovskite solar cells (PeSCs) by using a compact seed perovskite layer (CSPL). The CSPL assists vertical growth of perovskite crystals and obtains the highly crystalline perovskite photoactive layer, which leads to the reduction in the charge transfer resistance and a longer photoluminescence lifetime. The PeSC device with a CSPL shows a remarkably improved PCE, from 15.07% to 19.25%, with a record open circuit voltage (VOC) of 1.16 V in the p–i–n structure with pure crystal perovskite and negligible current density–voltage hysteresis. Additionally, a PCE of 20.37% was achieved in CSPL assisted n–i–p structure PeSCs.

Semi-crystalline photovoltaic polymers with siloxane-terminated hybrid side-chains

Three types of semi-crystalline photovoltaic polymers were synthesized by incorporating a siloxane-terminated organic/inorganic hybrid side-chain and changing the number of fluorine substituents. A branch point away from a polymer main backbone in the siloxane-containing side-chains and the intra- and/or interchain noncovalent coulombic interactions enhance a chain planarity and facile interchain organization. The resulting polymers formed strongly agglomerated films with high roughness, suggesting strong intermolecular interactions. The optical band gap of ca. 1.7 eV was measured for all polymers with a pronounced shoulder peak due to tight π-π stacking. With increasing the fluorine substituents, the frontier energy levels decreased and preferential face-on orientation was observed. The siloxane-terminated side-chains and fluorine substitution promoted the intermolecular packing, showing well resolved lamellar scatterings up to (300) for this series of polymers in the grazing incidence wide angle X-ray scattering measurements. The PPsiDTBT, PPsiDTFBT and PPsiDT2FBT devices showed a power conversion efficiency of 3.16%, 4.40% and 5.65%, respectively, by blending with PC71BM. Langevin-type bimolecular charge recombination was similar for three polymeric solar cells. The main loss in the photocurrent generation for PPsiDTBT:PC71BM was interpreted to originate from the trap assisted charge recombination by measuring light-intensity dependent short-circuit current density (Jsc) and open-circuit voltage (Voc). Our results provide a new insight into the rational selection of solubilizing substituents for optimizing crystalline interchain packing with appropriate miscibility with PC71BM for further optimizing polymer solar cells.

Synthesis and photovoltaic properties of three different types of terpolymers

Three types of photoactive terpolymers (Random, Regular and Block) were synthesized by incorporating two electron-deficient moieties and one electron-rich moiety based on two parent donor polymers, poly[(2,5-bis(2-decyltetradecyloxy)phenylene)-alt-(5,6-difluoro-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2FBTDT) and poly[(2,5-bis(2-decyltetradecyloxy)phenylene)-alt-(5,6-dicyano-4,7-di(thiophen-2-yl)benzo[c][1,2,5]thiadiazole)] (PPDT2CNBT). All three terpolymers showed broad light absorption in the range of 300–850 nm covering the absorption of two parent polymers. Their optical, electrochemical, morphological and photovoltaic properties were compared and investigated in detail. Power conversion efficiencies (PCEs) of 5.63, 4.45 and 3.13% were obtained for PPDT2FBTDT-random-PPDT2CNBT, PPDT2FBTDT-regular-PPDT2CNBT and PPDT2FBTDT-block-PPDT2CNBT based photovoltaic devices, respectively. Through intensive investigation on charge carrier mobility, photocurrent and light intensity dependence of JSC, the random structure was proved to be the most effective molecular design in this series of terpolymers, showing weaker charge recombination and enhanced charge transport/extraction with well-distributed blend morphology. The fine modulation of different arrangements and compositions of the three monomers in a main chain is crucial for optimizing the terpolymeric structures as efficient photoactive materials.