Counter-Doping Effect by Trivalent Cations in Tin-Based Perovskite Solar Cells.

Tin (Sn) -based perovskite solar cells (PSCs) normally show low open circuit voltage due to serious carrier recombination in the devices, which can be attributed to the oxidation and the resultant high p-type doping of the perovskite active layers. Considering the grand challenge to completely prohibit the oxidation of Sn-based perovskites, a feasible way to improve the device performance is to counter-dope the oxidized Sn-based perovskites by replacing Sn2+ with trivalent cations in the crystal lattice, which however is rarely reported. Here, the introduction of Sb3+, which can effectively counter-dope the oxidized perovskite layer and improve the carrier lifetime, is presented. Meanwhile, Sb3+ can passivate deep-level defects and improve carrier mobility of the perovskite layer, which are all favorable for the photovoltaic performance of the devices. Consequently, the target devices yield a relative enhancement of the power conversion efficiency (PCE) of 31.4% as well as excellent shelf-storage stability. This work provides a novel strategy to improve the performance of Sn-based PSCs, which can be developed as a universal way to compensate for the oxidation of Sn-based perovskites in optoelectronic devices.

Co-Self-Assembled Monolayers Modified NiOx for Stable Inverted Perovskite Solar Cells.

[4-(3,6-dimethyl-9H-carbazol-9yl)butyl]phosphonic acid (Me-4PACz) self-assembled molecules (SAM) are an effective method to solve the problem of the buried interface of NiOx in inverted perovskite solar cells (PSCs). However, the Me-4PACz end group (carbazole core) cannot forcefully passivate defects at the bottom of the perovskite film. Here, a Co-SAM strategy is employed to modify the buried interface of PSCs. Me-4PACz is doped with phosphorylcholine chloride (PC) to form a Co-SAM to improve the monolayer coverage and reduce leakage current. The phosphate group and chloride ions (Cl-) in PC can inhibit NiOx surface defects. Meantime, the quaternary ammonium ions and Cl- in PC can fill organic cations and halogen vacancies in the perovskite film to enable defects passivation. Moreover, Co-SAM can promote the growth of perovskite crystals, collaboratively solve the problem of buried defects, suppress nonradiative recombination, accelerate carrier transmission, and relieve the residual stress of the perovskite film. Consequently, the Co-SAM modified devices show power conversion efficiencies as high as 25.09% as well as excellent device stability with 93% initial efficiency after 1000 h of operation under one-sun illumination. This work demonstrates the novel approach for enhancing the performance and stability of PSCs by modifying Co-SAM on NiOx.

Dual-Interface Engineering in Perovskite Solar Cells with 2D Carbides.

Passivating the interfaces between the perovskite and charge transport layers is crucial for enhancing the power conversion efficiency (PCE) and stability in perovskite solar cells (PSCs). Here we report a dual-interface engineering approach to improving the performance of FA0.85 MA0.15 Pb(I0.95 Br0.05 )3 -based PSCs by incorporating Ti3 C2 Clx Nano-MXene and o-TB-GDY nanographdiyne (NanoGDY) into the electron transport layer (ETL)/perovskite and perovskite/ hole transport layer (HTL) interfaces, respectively. The dual-interface passivation simultaneously suppresses non-radiative recombination and promotes carrier extraction by forming the Pb-Cl chemical bond and strong coordination of π-electron conjugation with undercoordinated Pb defects. The resulting perovskite film has an ultralong carrier lifetime exceeding 10 µs and an enlarged crystal size exceeding 2.5 µm. A maximum PCE of 24.86 % is realized, with an open-circuit voltage of 1.20 V. Unencapsulated cells retain 92 % of their initial efficiency after 1464 hours in ambient air and 80 % after 1002 hours of thermal stability test at 85 °C.

Increasing donor-acceptor spacing for reduced voltage loss in organic solar cells.

The high voltage losses ([Formula: see text]), originating from inevitable electron-phonon coupling in organic materials, limit the power conversion efficiency of organic solar cells to lower values than that of inorganic or perovskite solar cells. In this work, we demonstrate that this [Formula: see text] can in fact be suppressed by controlling the spacing between the donor (D) and the acceptor (A) materials (DA spacing). We show that in typical organic solar cells, the DA spacing is generally too small, being the origin of the too-fast non-radiative decay of charge carriers ([Formula: see text]), and it can be increased by engineering the non-conjugated groups, i.e., alkyl chain spacers in single component DA systems and side chains in high-efficiency bulk-heterojunction systems. Increasing DA spacing allows us to realize significantly reduced [Formula: see text] and improved device voltage. This points out a new research direction for breaking the performance bottleneck of organic solar cells.

Revealing the Side-Chain-Dependent Ordering Transition of Highly Crystalline Double-Cable Conjugated Polymers.

We developed a series of highly crystalline double-cable conjugated polymers for application in single-component organic solar cells (SCOSCs). These polymers contain conjugated backbones as electron donor and pendant perylene bisimide units (PBIs) as electron acceptor. PBIs are connected to the backbone via alkyl units varying from hexyl (C6 H12 ) to eicosyl (C20 H40 ) as flexible linkers. For double-cable polymers with short linkers, the PBIs tend to stack in a head-to-head fashion, resulting in large d-spacings (e.g. 64 Šfor the polymer P12 with C12 H24 linker) along the lamellar stacking direction. When the length of the linker groups is longer than a certain length, the PBIs instead adopt a more ordered packing likely via H-aggregation, resulting in short d-spacings (e.g. 50 Šfor the polymer P16 with C16 H32 linker). This work highlights the importance of linker length on the molecular packing of the acceptor units and the influences on the photovoltaic performance of SCOSCs.

End Group Engineering on the Side Chains of Conjugated Polymers toward Efficient Non-Fullerene Organic Solar Cells.

Side chains properties of conjugated polymers, such as the length, branching point, and heteroatom, have been widely studied for application in organic solar cells (OSCs), but the end groups of side chains have been rarely reported. In this work, we systematically explored a series of new conjugated polymers with distinct side-chain end groups for high performance non-fullerene OSCs. The key components for the polymers contained functionalized units as the end groups of side chains, such as Br, alkyloxy (OMe), and alkylthienyl (T) groups. We found that the new conjugated polymers have similar absorption spectra and crystallinity with the polymer without substitution, but they showed distinct photovoltaic performance in solar cells. When the polymer without functionalized units had a power conversion efficiency (PCE) of 9.94%, the modified conjugated polymers provided high PCEs of over 13% with significantly enhanced photocurrent and fill factors. In addition, they also show additive-free and highly stable characteristics. These results demonstrate that end group engineering on side chains is a promising strategy to design new conjugated polymers toward efficient OSCs.

Lateral Photodetectors Based on Double-Cable Polymer/Two-Dimensional Perovskite Heterojunction.

Double-cable conjugated polymers and two-dimensional (2D) perovskites are both promising materials for next-generation photodetectors (PDs) due to their solution processibility and tunable optoelectronic properties. In this work, a lateral PD is designed by layering a double-cable conjugated polymer film atop a 2D Ruddlesden-Popper perovskite film. Compared to the corresponding single-layer polymer and perovskite PDs, the heterojunction device exhibits greatly improved performance with a high responsivity of 27.06 A W-1, an on/off ratio of 1379, and a short rise/decay time of 3.53/3.78 ms. In addition, a flexible device using polyimide as the substrate is successfully fabricated and exhibits comparable performance with the device on glass. This work demonstrates the great potential of double-cable polymer/2D perovskite heterojunctions in future flexible optoelectronics.

Crystalline Cooperativity of Donor and Acceptor Segments in Double-Cable Conjugated Polymers toward Efficient Single-Component Organic Solar Cells.

The crystalline cooperativity of the donor and acceptor segment in double-cable conjugated polymers plays an important role in the nanophase separation and photovoltaic performance in single-component organic solar cells (SCOSCs). Two double-cable conjugated polymers with the same conjugated backbone and perylene bisimide (PBI) side units were designed in which PBIs were positioned symmetrically and perpendicularly (P1) and asymmetrically and slantingly (P2) along the conjugated backbones. After thermal annealing, both conjugated backbones and PBI side units in P1 tend to form ordered nanostructures, while PBI side units in P2 dominated the crystallization and hamper the crystallization of conjugated backbones. P1 showed good crystalline cooperativity between conjugated backbones and PBI side units, resulting in improved power conversion efficiencies (PCEs) up to 3.43 % in SCOSCs, while P2 with poor crystalline cooperativity exhibited PCEs below 2.42 %.

Multifunctional Diketopyrrolopyrrole-Based Conjugated Polymers with Perylene Bisimide Side Chains.

Two conjugated polymers based on diketopyrrolopyrrole (DPP) in the main chain with different content of perylene bisimide (PBI) side chains are developed. The influence of PBI side chain on the photovoltaic performance of these DPP-based conjugated polymers is systematically investigated. This study suggests that the PBI side chains can not only alter the absorption spectrum and energy level but also enhance the crystallinity of conjugated polymers. As a result, such polymers can act as electron donor, electron acceptor, and single-component active layer in organic solar cells. These findings provide a new guideline for the future molecular design of multifunctional conjugated polymers.

"Double-Cable" Conjugated Polymers with Linear Backbone toward High Quantum Efficiencies in Single-Component Polymer Solar Cells.

A series of "double-cable" conjugated polymers were developed for application in efficient single-component polymer solar cells, in which high quantum efficiencies could be achieved due to the optimized nanophase separation between donor and acceptor parts. The new double-cable polymers contain electron-donating poly(benzodithiophene) (BDT) as linear conjugated backbone for hole transport and pendant electron-deficient perylene bisimide (PBI) units for electron transport, connected via a dodecyl linker. Sulfur and fluorine substituents were introduced to tune the energy levels and crystallinity of the conjugated polymers. The double-cable polymers adopt a "face-on" orientation in which the conjugated BDT backbone and the pendant PBI units have a preferential π-π stacking direction perpendicular to the substrate, favorable for interchain charge transport normal to the plane. The linear conjugated backbone acts as a scaffold for the crystallization of the PBI groups, to provide a double-cable nanophase separation of donor and acceptor phases. The optimized nanophase separation enables efficient exciton dissociation as well as charge transport as evidenced from the high-up to 80%-internal quantum efficiency for photon-to-electron conversion. In single-component organic solar cells, the double-cable polymers provide power conversion efficiency up to 4.18%. This is one of the highest performances in single-component organic solar cells. The nanophase-separated design can likely be used to achieve high-performance single-component organic solar cells.

Non-fullerene organic solar cells based on diketopyrrolopyrrole polymers as electron donors and ITIC as an electron acceptor.

In this work, we provide systematic studies on the non-fullerene solar cells based on diketopyrrolopyrrole (DPP) polymers as electron donors and a well-known electron acceptor ITIC. ITIC has been widely reported in non-fullerene solar cells with high power conversion efficiencies (PCEs) above 10%, when it is combined with a wide band gap conjugated polymer, while its application in small band gap DPP polymers has never been reported. Herein, we select four DPP polymers containing different thienyl linkers, resulting in distinct absorption spectra, energy levels and crystalline properties. Non-fullerene solar cells based on DPP polymers as donors and ITIC as an acceptor show PCEs of 1.9-4.1% and energy loss of 0.55-0.82 eV. The PCEs are much lower than those of cells based on fullerene derivatives due to the poor miscibility between the DPP polymers and ITIC, as confirmed by the morphology and charge transport investigation. The results indicate that it is important to tune the miscibility between the donor and acceptor in order to realize optimized micro-phase separation, which can further enhance the performance of DPP polymer based non-fullerene solar cells.