Biomaterial Improves the Stability of Perovskite Solar Cells by Passivating Defects and Inhibiting Ion Migration.

With the rapid improvement of power conversion efficiency (PCE), perovskite solar cells (PSCs) have broad application prospects and their industrialization will be the next step. Nevertheless, the performance and long-term stability of the devices are limited by the defect-induced nonradiative recombination centers and ions' migration inside the perovskite films. Here, usnic acid (UA), an easy-to-obtain and efficient natural biomaterial with a hydroxyl functional group (-OH) and four carbonyl groups (-C═O) was added to MAPbI3 perovskite precursor to regulate the crystallization process by slowing the crystallization rate, thereby expanding the crystal size and preparing perovskite films with low defect density. In addition, UA anchors the uncoordinated Pb2+ and suppresses the migration of I-ions, which enhances the stability of the perovskite film. Consequently, an impressive PCE exceeding 20% was achieved for inverted structure MAPbI3-based PSCs. More impressively, the optimized PSCs maintained 78% of the initial PCE under air with high humidity (RH ≈ 65%, 25-30 °C) for 1000 h. UA can be extracted from the plant, usnea, making it inexpensive and easy to obtain. Our work demonstrates the application of the plant material in PSCs and their industrialization, which is significant nowadays.

Synergistic Passivation on Buried Interface for Highly Efficient and Stable p-i-n Perovskite Solar Cells.

The properties of an interface at the hole transport layer (HTL)/perovskite layer are crucial for the performance and stability of perovskite solar cells (PVSCs), especially the buried interface between HTL and perovskite layer. Here, a molecular named potassium 1-trifluoroboratomethylpiperidine (3FPIP) assistant-modified perovskite bottom interface strategy is proposed to improve the charge transfer capability and balances energy level between HTL and perovskite. BF3 - in the 3FPIP molecule interacts with undercoordinated Pb2+ to passivate iodine vacancies and enhance PVSCs performance. Furthermore, the infiltration of K+ ions into perovskite molecules enhances the crystallinity and stability of perovskite. Therefore, the PVSCs with the buried interface treatment exhibit a champion performance of 24.6%. More importantly, the corresponding devices represent outstanding ambient stability, remaining at 92% of the initial efficiency after 1200 h. This work provides a new method of buried interface engineering with functional group synergy.

An MBene Modulating the Buried SnO2/Perovskite Interface in Perovskite Solar Cells.

The interface of perovskite solar cells (PSCs) plays an important role in transferring and collecting charges. Interface defects are important factors affecting the efficiency and stability of PSCs. Here, the buried interface between SnO2 and the perovskite layer is bridged by two-dimensional (2D) MBene, which improves charge transfer. MBene can deposit additional electrons on the surface of SnO2, passivate its surface defects and facilitate the charge collection. Moreover, the dipole moment formed at the interface increases the electron transfer ability in the PSCs. MBene also regulates the growth of perovskite crystals, improves the quality of perovskite films, and reduces its grain boundary defects. As a result, PSCs based on FA0.2MA0.8PbI3 and (FAPbI3)0.95(MAPbBr3)0.05 get the enhanced efficiencies of 22.34 % and 24.32 % with negligible hysteresis. Furthermore, the optimized device exhibits better stability. This work opens up the application of MBene materials in PSCs, reveals a deeper understanding of the mechanism behind using 2D materials as an interface modification layer, and shows opportunities for using MBene as potential material in photoelectric devices.

p-Toluenesulfonic Acid Modified Two-Dimensional ZrSe2 as a Hole Transport Layer for High-Performance Organic Solar Cells.

Two-dimensional (2D) materials have attracted attention due to their excellent optoelectronic properties, but their applications are limited by their defects and vacancies. Surface modification is an effective method to restore their performance. Here, ZrSe2 is modified with conductive polymer p-toluenesulfonic acid (PTSA). It is found that PTSA can obtain electrons of ZrSe2 through the combination of -SO3H and ZrSe2, thus forming interfacial dipoles, which improve the work function of ZrSe2. In addition, -OH in PTSA can effectively fill the Se vacancy in ZrSe2 to form P-type doping, thereby improving its conductivity. ZrSe2 modified by the PTSA material is first used as a hole transport layer (HTL) in organic solar cells (OSCs). The efficiency of OSCs based on the PBDB-T:ITIC and PM6:L8-BO binary active layer with ZrSe2:PTSA as the novel HTL reaches 10.66 and 18.14%, which are obviously higher than the efficiency of OSCs with pure ZrSe2 as the HTL (8.48 and 15.64%). More interestingly, the stability of the device with ZrSe2:PTSA as HTL is significantly better than that of PEDOT:PSS. This study shows that the modification of the organic material can effectively improve the photoelectric performance of ZrSe2 and explores the physical mechanism of the interaction between the organic modifier and 2D materials.

Improved Air Stability for High-Performance FACsPbI3 Perovskite Solar Cells via Bonding Engineering.

Despite the fact that perovskite solar cells (PSCs) are widely popular due to their superb power conversion efficiency (PCE), their further applications are still restricted by low stability and high-density defects. Especially, the weak binding and ion-electron properties of perovskite crystals make them susceptible to moisture attack under environmental stress. Herein, we report an overall sulfidation strategy via introduction of 1-pentanethiol (PT) into the perovskite film to inhibit bulk defects and stabilize Pb ions. It has been confirmed that the thiol groups in PT can stabilize uncoordinated Pb ions and passivate iodine vacancy defects by forming strong Pb-S bonds, thus reducing nonradiative recombination. Moreover, the favorable passivation process also optimizes the energy-level arrangement, induces better perovskite crystallization, and enhances the charge extraction in the full solar cells. Consequently, the PT-modified inverted device delivers a champion PCE of 22.46%, which is superior to that of the control device (20.21%). More importantly, the PT-modified device retains 91.5% of its initial PCE after storage in air for 1600 h and over 85% of its initial PCE after heating at 85 °C for 800 h. This work provides a new perspective to simultaneously improve the performance and stability of PSCs to satisfy their commercial applications.

Synergetic Regulation of Interface Defects and Carriers Dynamics for High-Performance Lead-Free Perovskite Solar Cells.

Severe nonradiative recombination and open-circuit voltage loss triggered by high-density interface defects greatly restrict the continuous improvement of Sn-based perovskite solar cells (Sn-PVSCs). Herein, a novel amphoteric semiconductor, O-pivaloylhydroxylammonium trifluoromethanesulfonate (PHAAT), is developed to manage interface defects and carrier dynamics of Sn-PVSCs. The amphiphilic ionic modulators containing multiple Lewis-base functional groups can synergistically passivate anionic and cationic defects while coordinating with uncoordinated Sn2+ to compensate for surface charge and alleviate the Sn2+ oxidation. Especially, the sulfonate anions raise the energy barrier of surface oxidation, relieve lattice distortion, and inhibit nonradiative recombination by passivating Sn-related and I-related deep-level defects. Furthermore, the strong coupling between PHAAT and Sn perovskite induces the transition of the surface electronic state from p-type to n-type, thus creating an extra back-surface field to accelerate electron extraction. Consequently, the PHAAT-treated device exhibits a champion efficiency of 13.94% with negligible hysteresis. The device without any encapsulation maintains 94.7% of its initial PCE after 2000 h of storage and 91.6% of its initial PCE after 1000 h of continuous illumination. This work provides a reliable strategy to passivate interface defects and construct p-n homojunction to realize efficient and stable Sn-based perovskite photovoltaic devices.

Surface-Engineered Ti3 C2 Tx with Tunable Work Functions for Highly Efficient Polymer Solar Cells.

Ti3 C2 Tx , as a newly investigated 2D material, has gained great attention owing to its metallic conductivity, tunable work function (WF ), and unique electrical property. However, its WF can be further adjusted to meet the needs of optoelectronic devices. Here, surface-engineered Ti3 C2 Tx is fabricated with tunable WF by treating with ethanolamine and rhodium chloride (RhCl3 ). Ethanolamine treated Ti3 C2 Tx can induce the chemical adsorption of NH2 on Ti3 C2 Tx with hydrogen-bonding, which causes the decreased WF , while chemical doping with RhCl3 leads to the improvement of WF , which is achieved by the downshift of Femi level of Ti3 C2 Tx . Moreover, the ethanolamine and RhCl3 can effectively passivate the vacancies of Ti. As such, the surface-engineered Ti3 C2 Tx is more suitable as buffer layer for polymer solar cells (PSCs) by enhancing the interfacing characteristics of the Ti3 C2 Tx /active layer. The PSCs with engineered Ti3 C2 Tx for electron or hole transport layers can exhibit a power conversion efficiency of 15.88% or 15.54%. These efficiencies can be compared with those of devices with a conventional transport layer. This work provides a facile strategy to realize the work function tunability of Ti3 C2 Tx , and also shows that the tuned Ti3 C2 Tx has a certain application prospect in photovoltaic devices.

Several Triazine-Based Small Molecules Assisted in the Preparation of High-Performance and Stable Perovskite Solar Cells by Trap Passivation and Heterojunction Engineering.

The functional group is the main body in modifying the perovskite film, and different functional groups lead to different modification effects. Here, several conjugated triazine-based small molecules such as melamine (Cy-NH2), cyanuric acid (Cy-OH), cyanuric fluoride (Cy-F), cyanuric chloride (Cy-Cl), and thiocyanuric acid (Cy-SH) are used to modify perovskite films by mixing in antisolvent. The crystallizations of perovskites are optimized by these molecules, and the perovskite films with low trap density are obtained by forming Lewis adducts with these molecules (Pb2+ and electron-donating groups including -NH2, C═N-, and C═O; I- and electron-withdrawing groups including F, Cl, N-H, and O-H). Especially for the Cy-F and Cy-Cl, the heterojunction structure is formed in the perovskite layer by p-type modification, which is conducive to charge transfer and collection in PSCs. Compared with that of control devices, the performance of devices with trap passivation and heterojunction engineering is obviously improved from 18.49 to 20.71% for MAPbI3 and 19.27 to 21.11% for FA0.85Cs0.15PbI3. Notably, the excellent moisture (retaining 67%, RH: 50% for 20 days) and thermal (retaining 64%, 85 °C for 72 h) stability of PSCs are obtained by a kind of second modification (Cy-F/Cy-SH)─spin-coating a few Cy-SH on the Cy-F-modified perovskite film surface. It also reduces Pb pollution because Cy-SH is a highly potent chelating agent. Therefore, this work also provides an effective method to obtain high-performance, stable, and low-lead pollution PSCs, combining trap passivation, heterojunction engineering, and surface treatment.

Efficient Ternary Polymer Solar Cells with Tunable Crystallinity and Phase Separation of Active Layers via Incorporating GHK-Cu.

The crystallinity of a nonfullerene small-molecule acceptor plays an important function in the bimolecular recombination and carrier transfer of polymer solar cells (PSCs). However, because of the competition between the donor (PBDB-T) and acceptor (ITIC) in processes of phase separation and crystallization, the PBDB-T preferentially forms a crystalline network, which limits the molecular diffusion of ITIC and leads to the weak crystallinity of ITIC, eventually restricting the photoelectric conversion efficiency (PCE) of PSCs. Therefore, in our work, a small-molecule biomaterial, Gly-His-Lys-Cu (SMBM GHK-Cu), is incorporated into binary PBDB-T:ITIC to construct a PBDB-T:ITIC:GHK-Cu ternary system. The addition of GHK-Cu increases ITIC crystallinity and promotes the formation in continuous single-phase domains of PBDB-T and ITIC, which creates an optimized bicontinuous network path to increase and balance charge transmission in PSCs. Meanwhile, GHK-Cu makes energy transfer from GHK-Cu to PBDB-T appreciably efficient, improving the photon capture and exciton-generation rate of PBDB-T. Moreover, it can form a complementary absorption spectrum with PBDB-T and ITIC, which enhances the PCE of ternary devices. Excitingly, the PCE of PSC-based PBDB-T:ITIC is enhanced from 10.28% to 12.07% via incorporating 0.1 wt % GHK-Cu into PBDB-T:ITIC, in which the enhanced open voltage (VOC) is 0.92 V, the short-circuit current (JSC) is 17.87 mA/cm2, and the fill factor (FF) is 73.4%. Meanwhile, the PCE of PSC-based PM6:Y6 is also enhanced from 15.21% for a binary PSC to 17.11% for ternary PSC-based PM6:Y6:0.1 wt % GHK-Cu. This work shows that the cheap and environmentally friendly GHK-Cu has great potential for application in tuning the crystallinity and phase separation of the active layer.

High-efficiency ternary polymer solar cells with optimized morphology of active layers enabled by few-layered ß-InSe nanosheets.

Due to the excellent electrical and optical properties, few-layered ß-indium selenide (InSe) nanosheets are successfully introduced into the active layer of polymer solar cells (PSCs) as the third component for the first time. The addition of few-layered ß-InSe nanosheets optimizes the absorption, crystallinity and vertical component distribution of the active layer. Compared with the binary devices, the ternary devices exhibit optimized bulk morphology and reduced charge recombination. The power conversion efficiency (PCE) of PSCs based on the PM6 : Y6 system is obviously improved from 15.02% to 16.56% due to the increasing short-circuit current and fill factor. The mechanism accounting for the morphological change in the ternary active layer is investigated in depth. Moreover, the efficacy of ß-InSe in long-term stability and other active layer systems of PSCs is confirmed. Therefore, this work demonstrates that few-layered ß-InSe has bright prospects in photovoltaic devices.

Solution-Processable PEDOT:PSS:α-In2Se3 with Enhanced Conductivity as a Hole Transport Layer for High-Performance Polymer Solar Cells.

Two-dimensional (2D) nanosheets have attracted significant attention in photovoltaic devices in recent years owing to their outstanding photoelectric properties. Herein, 2D α-In2Se3 nanosheets with high conductivity and suitable work function are synthesized by liquid-phase exfoliation method. To ameliorate the low conductivity of poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) (2.21 × 10-3 S cm-1), α-In2Se3 nanosheets are directly added into PEDOT:PSS to obtain the PEDOT:PSS:α-In2Se3 composite film. The composite film exhibits excellent optical transmittance, suitable work function, and enhanced conductivity (1.54 × 10-2 S cm-1). To profoundly investigate the mechanism of conductivity improvement, X-ray photoelectron spectroscopy, Raman spectroscopy, electron paramagnetic resonance, and atomic force microscopy are conducted. The results show that the synergistic effect of 2D α-In2Se3 nanosheets and isopropyl alcohol/deionized water cosolvent screens the Coulombic attraction among PEDOT and PSS. The screening effect results in the partial removal of PSS and the benzoid-quinoid transition of PEDOT. In addition, α-In2Se3 nanosheets may serve as physical linkers for PEDOT chains. Both these effects are beneficial to increase the interfacial contact area between PEDOT chains and form a larger conductive network of PEDOT, leading to an enhanced conductivity. The composite film is first employed as a hole transport layer (HTL) in polymer solar cells (PSCs). The power conversion efficiency (PCE) of the poly[2,6-(4,8-bis(5-(2-ethylhexyl)thiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene)-co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl)benzo[1,2-c:4,5-c']dithiophene-4,8-dione)] (PBDB-T):3,9-bis(2-methylene(3-(1,1-dicyanomethylene)-indanone))-5,5,11,11-tetrakis(4-hexylphenyl)dithieno-[2,3-d:2',3'-d']-s-indaceno[1,2-b:5,6-b']dithiophene (ITIC)-based device with composite HTL is 10% higher than that of the unmodified PBDB-T:ITIC-based device, and the maximum PCE of 15.89% is achieved in the (poly[(2,6-(4,8-bis(5-(2-ethylhexyl)-4-fluorothiophen-2-yl)benzo[1,2-b:4,5-b']dithiophene))-co-(1,3-di(5-thiophene-2-yl)-5,7-bis(2-ethylhexyl)-benzo[1,2-c:4,5-c']dithiophene-4,8-dione))] (PM6):(2,2'-((2Z,2Z)-((12,13-bis(2-ethylhexyl)-3,9-diundecyl-12,13-dihydro-[1,2,5]thiadiazolo[3,4-e]thieno[2,″3″:4',50]thieno[2',3':4,5]pyrrolo[3,2-g]thieno[2',3':4,5]thieno[3,2-b]indole-2,10-diyl)bis(methanylylidene))bis(5,6-difluoro-3-oxo-2,3-dihydro-1H-indene-2,1-diylidene))dimalononitrile) (Y6) system. More interestingly, the stability of devices with composite HTL is improved owing to the partial removal of PSS. Thus, the PEDOT:PSS:α-In2Se3 composite can be a potential HTL material in PSCs.

Two-Dimensional Bi2O2Se with High Mobility for High-Performance Polymer Solar Cells.

Carrier mobility is a critical factor for power conversion efficiency (PCE) of polymer solar cells (PSCs), and the low charge carrier mobility still limits the performance improvement of PSCs. Adding high-mobility material into the active layer is one of the better ways to enhance the PCE of PSCs. Two-dimensional (2D) Bi2O2Se can be an ideal additive material for improving the carrier mobility of PSCs because of its ultrahigh mobility and high thermal stability. In this work, the Bi2O2Se few-layer 2D nanoflakes are fabricated by combining lithium intercalation with shear force-assisted liquid phase exfoliation and applied as an additive to promote charge transport in PSCs for the first time. The 2D Bi2O2Se nanoflakes, when introduced into the active layer, not only provide a new interface between a donor and an acceptor and efficient charge transfer pathways but also induce crystallization of the photosensitive layer and form continuous interpenetrating networks, which promotes the exciton separation and charge transfer in the photosensitive layer. As a result, the PCE of a device based on PBDB-T/ITIC is increased from 10.09% (0 wt %) to 12.22% (2 wt %). Meanwhile, the PCE of a device based on PM6/Y6 is also increased from 14.59% for a binary device to 16.28% for an optimized ternary device (2 wt %). Moreover, the optimized ternary device shows excellent air stability by suppressing the mixing of the two phases. This work provides a good method to enhance the PCE of PSCs and also shows that the Bi2O2Se material has a good prospect in photovoltaic devices.

Size-tunable near-infrared PbS nanoparticles synthesized from lead carboxylate and sulfur with oleylamine as stabilizer.

High quality PbS nanocrystals are synthesized reproducibly through lead stearate and sulfur stabilized by oleylamine in a non-coordinating solvent. The morphology, crystalline form and phase composition of PbS nanocrystals are examined by transmission electron microscopy (TEM), high-resolution TEM, x-ray diffraction (XRD), energy-dispersive x-ray spectroscopy (EDS) and x-ray photoelectron spectroscopy (XPS). The as-synthesized PbS nanocrystals have strong absorption and photoluminescence emissions in the near-infrared region. The size of PbS nanocrystals from 5 to 13 nm can be adjusted through the optimization of the synthesis conditions. The smaller PbS nanoparticles are obtained at the lower reaction temperature, lower precursor concentration, larger oleylamine quantity and larger lead precursor/sulfur ratio. The basic oleylamine enhances the reactivity of both lead stearate precursor and sulfur precursor in the reaction.