Spectral Splitting Solar Cells Consisting of a Mesoscopic Wide-Bandgap Perovskite Solar Cell and an Inverted Narrow-Bandgap Perovskite Solar Cell.

In comparison to monolithic perovskite/perovskite double-junction solar cells, a four-terminal spectrum-splitting system is a simple method to obtain a higher power conversion efficiency (PCE) because it has no constraints of unifying the structures of the top and bottom cells. In this work, utilizing the fact that low-bandgap Sn-Pb bottom cells work the best in p-i-n while Pb-based wide-bandgap top cells work better in an n-i-p architecture, a wide-bandgap (Eg = 1.61 eV) perovskite solar cell with a mesoscopic structure and a narrow-bandgap (Eg = 1.27 eV) perovskite solar cell with an inverted structure were combined to fabricate a double-junction four-terminal spectral splitting solar cell. The double-junction solar cell with the 801 nm spectral splitting with an active area of 0.18 cm2 was found to work with a PCE of 25.3%, which is the highest reported so far for a 4-T all-perovskite double-junction spectral splitting solar cell.

Effect of Chloride Incorporation on the Intermediate Phase and Film Morphology of Methylammonium Lead Halide Perovskites.

The influence of chloride integration on perovskite film deposition, encompassing both the structures of intermediate phases and the properties of the final films, was explored. Our methodology involved the fabrication of perovskite intermediate-phase films with varying concentrations of methylammonium chloride (MACl). Subsequently, we conducted an analysis employing X-ray diffraction and Rietveld refinement, incorporating the March-Dollase correction, to gain insights into how chloride-induced intermediate phases impact film morphology. Remarkably, a distinct preferred orientation was observed in the (020) lattice plane perpendicular to the substrate surface, and this orientation was found to be directly correlated to the MACl concentration. This distinctive arrangement of chloride-induced intermediate-phase complexes facilitated controlled crystallization, leading to highly oriented crystals and an improved film morphology. As a consequence, perovskite solar cell devices incorporating chloride-containing methylammonium lead iodide achieved a power conversion efficiency exceeding 20%. These findings suggest a crucial link between the preferred orientation observed in the final chlorine-derived perovskite films and the intermediate-phase structure formed during the initial stages of perovskite formation. These results suggest a profound impact of intermediate phase compositions and crystal structures on perovskite formation, emphasizing the importance of a comprehensive understanding of these factors to enable precise control over ideal structures and the subsequent transformation into high-quality perovskite films.

Impact of compact TiO2 interface modification on the crystallinity of perovskite solar cells.

The effect of TiO2 interfacial morphology on perovskite crystallinity was investigated by modifying the micro and nanoscale surface roughness of compact TiO2. While surface treatments of the compact TiO2 layer are recognized as effective strategies to enhance the photovoltaic performance of perovskite solar cells, the discussion regarding the crystallinity of perovskite atop TiO2 has been limited. In this study, we explored the impact of micro and nano scale interface morphology on perovskite crystal formation and its subsequent effects on device performance. Surprisingly, despite the absence of noticeable voids at the interface between the compact TiO2 and perovskite layers, the perovskite crystal morphology exhibited significant improvement following either micro or nanoscale interfacial modification. This enhancement ultimately led to improved photoconversion efficiency and reduced I-V hysteresis. These results emphasize the importance of underlayer surface morphology in the perovskite crystallization and suggest that the presence of grain boundaries within the perovskite layer may also contribute to I-V hysteresis in perovskite solar cells.

Crystal structure of bis-[octa-kis-(di-methyl sulfoxide-κO)-ytterbium(III)] penta-bromido-plumbate(II) tribromide di-methyl sulfoxide monosolvate: a ytterbium-doped lead halide perovskite precursor.

A mixture of PbBr2 and YbBr3·nH2O in a dimethyl sulfoxide (DMSO) solution yielded single crystals of a lead halide perovskite precursor with ytterbium, bis-[octa-kis-(di-methyl sulfoxide)-ytterbium(III)]penta-bromido-plumbate(II) tri-bromide with di-methyl sulfoxide as co-crystallite, [Yb(C2H6OS)8][PbBr5]0.5Br1.5·0.5C2H6OS. The complex ions PbBr5 3- and Yb(DMSO)8 3+ are present in the crystal together with three Br- ions and DMSO mol-ecules. X-ray crystallography revealed that the Br- ions in YbBr3 are replaced by the solvent and bound to a PbII atom or remain free. The presence of PbBr5 3- units, which are mol-ecular ions with a square-pyramidal structure, is also observed. These single crystals react with a caesium chloride solution, exhibiting near-infrared (NIR) luminescence by visible photoexcitation, suggesting the formation of Yb3+-doped lead halide perovskites (CsPbBr3-x Cl x ·Yb3+).

Phase Control of Organometal Halide Perovskites for Development of Highly Efficient Solar Cells.

To develop a highly efficient solar cell using organometal halide perovskites, its microscale structure control is one of the most important factors because the microstructural defects inside the organometal halide perovskite are harmful to charge carrier flow and, thus, degrade device performance. In this study, we confirmed the existence of large physical gaps at the grain boundary in a methylammonium iodide (MAPbI3, MA = CH3NH3) perovskite with transmission electron microscopy (TEM) analysis and revealed that the physical gap prevents charge carrier flow in the MAPbI3 perovskite. To minimize the physical gap and its negative influences, the grain size of the MAPbI3 perovskite was optimized by increasing the portion of the cubic phase via microstructural phase control using liquid nitrogen (LN2). Through microstructural phase control of the MAPbI3 perovskite, its grain boundaries and physical gap were significantly decreased, and 20.23% power conversion efficiency (PCE) was achieved with a single cation MAPbI3 perovskite solar cell.

Graphene-Like Conjugated Molecule as Hole-Selective Contact for Operationally Stable Inverted Perovskite Solar Cells and Modules.

Further enhancing the operational lifetime of inverted-structure perovskite solar cells (PSCs) is crucial for their commercialization, and the design of hole-selective contacts at the illumination side plays a key role in operational stability. In this work, the self-anchoring benzo[rst]pentaphene (SA-BPP) is developed as a new type of hole-selective contact toward long-term operationally stable inverted PSCs. The SA-BPP molecule with a graphene-like conjugated structure shows a higher photostability and mobility than that of the frequently-used triphenylamine and carbazole-based hole-selective molecules. Besides, the anchoring groups of SA-BPP promote the formation of a large-scale uniform hole contact on ITO substrate and efficiently passivate the perovskite absorbers. Benefiting from these merits, the champion efficiencies of 22.03% for the small-sized cells and 17.08% for 5 × 5 cm2 solar modules on an aperture area of 22.4 cm2 are achieved based on this SA-BPP contact. Also, the SA-BPP-based device exhibits promising operational stability, with an efficiency retention of 87.4% after 2000 h continuous operation at the maximum power point under simulated 1-sun illumination, which indicates an estimated T80 lifetime of 3175 h. This novel design concept of hole-selective contacts provides a promising strategy for further improving the PSC stability.

Ultra-Thin SnOx Buffer Layer Enables High-Efficiency Quantum Junction Photovoltaics.

Solution-processed solar cells are promising for the cost-effective, high-throughput production of photovoltaic devices. Colloidal quantum dots (CQDs) are attractive candidate materials for efficient, solution-processed solar cells, potentially realizing the broad-spectrum light utilization and multi-exciton generation effect for the future efficiency breakthrough of solar cells. The emerging quantum junction solar cells (QJSCs), constructed by n- and p-type CQDs only, open novel avenue for all-quantum-dot photovoltaics with a simplified device configuration and convenient processing technology. However, the development of high-efficiency QJSCs still faces the challenge of back carrier diffusion induced by the huge carrier density drop at the interface of CQDs and conductive glass substrate. Herein, an ultra-thin atomic layer deposited tin oxide (SnOx ) layer is employed to buffer this carrier density drop, significantly reducing the interfacial recombination and capacitance caused by the back carrier diffusion. The SnOx -modified QJSC achieves a record-high efficiency of 11.55% and a suppressed hysteresis factor of 0.04 in contrast with reference QJSC with an efficiency of 10.4% and hysteresis factor of 0.48. This work clarifies the critical effect of interfacial issues on the carrier recombination and hysteresis of QJSCs, and provides an effective pathway to design high-performance all-quantum-dot devices.

Heterogeneous FASnI3 Absorber with Enhanced Electric Field for High-Performance Lead-Free Perovskite Solar Cells.

Lead-free tin perovskite solar cells (PSCs) have undergone rapid development in recent years and are regarded as a promising eco-friendly photovoltaic technology. However, a strategy to suppress charge recombination via a built-in electric field inside a tin perovskite crystal is still lacking. In the present study, a formamidinium tin iodide (FASnI3) perovskite absorber with a vertical Sn2+ gradient was fabricated using a Lewis base-assisted recrystallization method to enhance the built-in electric field and minimize the bulk recombination loss inside the tin perovskites. Depth-dependent X-ray photoelectron spectroscopy revealed that the Fermi level upshifts with an increase in Sn2+ content from the bottom to the top in this heterogeneous FASnI3 film, which generates an additional electric field to prevent the trapping of photo-induced electrons and holes. Consequently, the Sn2+-gradient FASnI3 absorber exhibits a promising efficiency of 13.82% for inverted tin PSCs with an open-circuit voltage increase of 130 mV, and the optimized cell maintains over 13% efficiency after continuous operation under 1-sun illumination for 1,000 h.

Enhancing the Electronic Properties and Stability of High-Efficiency Tin-Lead Mixed Halide Perovskite Solar Cells via Doping Engineering.

Overcoming Voc loss to increase the efficiency of perovskite solar cells (PSCs) has been aggressively studied. In this work, we introduce and compare rubidium iodide (RbI) and potassium iodide (KI) alkali metal halides (AMHs) as dopants in a tin-lead (SnPb)-based perovskite system to improve the performance of PSCs by enhancing their Voc. Improvement in terms of surface morphology, crystallinity, charge transfer, and carrier transport in the SnPb perovskites was observed with the addition of AMH dopants. Significant power conversion efficiency improvement has been achieved with the incorporation of either dopant, and the highest efficiency was 21.04% in SnPb mixed halide PSCs when the RbI dopant was employed. In conclusion, we can outline the enhancement strategy that yields a remarkable efficiency of >20% with a smaller Voc loss and improved storage, light, and thermal stability in SnPb PSCs via doping engineering.

Emission Spectroscopy Investigation of the Enhancement of Carrier Collection Efficiency in AgBiS2-Nanocrystal/ZnO-Nanowire Heterojunction Solar Cells.

Eco-friendly solar cells were fabricated using interdigitated layers comprising ZnO nanowires (NWs) and infrared absorbing AgBiS2 nanocrystals (ITO/ZnO NWs/AgBiS2/P3HT/Au). The quality of ZnO NWs was studied using photoluminescence and Raman spectroscopy to identify the defects in ZnO NWs influencing solar cell performance. Oxygen vacancies and Zn interstitial sites, among various recombination sites, were observed to be the main sites for carrier recombination, which hinders the carrier collection in the solar cells. Accordingly, the power conversion efficiency of AgBiS2 solar cells exhibited a good correlation with the number of oxygen vacancies. The structural order and electron-phonon interaction in ZnO NWs were also investigated via Raman scattering spectroscopy. A lower concentration of oxygen vacancies and zinc interstitials (Zni) resulted in a higher structural order as well as a weaker electron-phonon interaction in ZnO NWs. When ZnO NWs were treated at 500 °C in oxygen with the lowest oxygen vacancy concentration, the solar cells (500-O2 solar cell (SC)) demonstrated an external quantum efficiency of approximately 70% in the visible region and a corresponding internal quantum efficiency of more than 80%. The 500-O2 SC exhibited a power conversion efficiency of 5.41% (JSC = 22.21 mA/cm2, VOC = 0.41 V, and FF = 60%) under quasi one-sun illumination. New methods that can efficiently reduce oxygen vacancies and Zni without affecting the structural order of ZnO NWs would further enhance the carrier collection efficiency. Moreover, since ZnO is a key electron transport material for constructing not only colloidal quantum dot solar cells but also other emerging solar cells, such as organic thin-film solar cells, the present findings provide significant information for improving their performance.

Photosensitized Protein Damage by DiethyleneglycoxyP(V)tetrakis(p-n-butoxyphenyl)porphyrin Through Electron Transfer: Activity Control Through Self-aggregation and Dissociation.

DiethyleneglycoxyP(V)tetrakis(p-n-butoxyphenyl)porphyrin (EGP(V)TBPP) forms a self-aggregation in an aqueous solution, and the photoexcited state of this molecule was effectively deactivated. Association with human serum albumin (HSA), a water-soluble protein, causes dissociation of the self-aggregation, resulting in recovery of the photosensitizer activity of EGP(V)TBPP. Under visible light irradiation, EGP(V)TBPP photosensitized HSA oxidation. The photosensitized singlet oxygen-generating activity of EGP(V)TBPP was confirmed by near-infrared emission measurement. A singlet oxygen quencher, sodium azide, partially inhibited the HSA photodamage; however, the quenching effect was estimated to be 57%. Another 43% of the HSA photodamage could be explained by the electron transfer mechanism. The redox potential of EGP(V)TBPP and the calculated Gibbs energy of electron transfer from tryptophan to photoexcited EGP(V)TBPP demonstrated the possibility of HSA oxidation through electron extraction. Fluorescence lifetime measurements of EGP(V)TBPP verified the electron transfer from HSA. The photosensitizer activity of EGP(V)TBPP can be controlled through an association with biomolecules, such as protein, and the electron transfer-mediated biomolecule photooxidation plays an important role in photodynamic therapy under hypoxia.

Reduction of Nonradiative Loss in Inverted Perovskite Solar Cells by Donor-π-Acceptor Dipoles.

Inverted perovskite solar cells (IPSCs) attract growing interest because of their simple configuration, reliable stability, and compatibility with tandem applications. However, the power conversion efficiency (PCE) of IPSCs still lags behind their regular counterparts, mainly due to the more serious nonradiative loss. Here, we design three donor-π-acceptor (D-π-A) dipoles with various dipole moments to introduce extra electric fields at the interface of perovskites and electron transport materials via the binding between the carboxylate end group and under-coordinated divalent Pb. The chemical binding reduces the recombination centers, while the superposition of the built-in electric field facilitates the electron collection and the hole blocking. As a result, the nonradiative loss is diminished as the dipole moments of D-π-A dipoles increase, which contributes to a PCE of 21.4% with enhancement in both the open-circuit voltage and fill factor. The stability for an unencapsulated device is also improved due to the hydrophobic property of D-π-A dipoles.

The Main Progress of Perovskite Solar Cells in 2020-2021.

Perovskite solar cells (PSCs) emerging as a promising photovoltaic technology with high efficiency and low manufacturing cost have attracted the attention from all over the world. Both the efficiency and stability of PSCs have increased steadily in recent years, and the research on reducing lead leakage and developing eco-friendly lead-free perovskites pushes forward the commercialization of PSCs step by step. This review summarizes the main progress of PSCs in 2020 and 2021 from the aspects of efficiency, stability, perovskite-based tandem devices, and lead-free PSCs. Moreover, a brief discussion on the development of PSC modules and its challenges toward practical application is provided.

A Sodium Chloride Modification of SnO2 Electron Transport Layers to Enhance the Performance of Perovskite Solar Cells.

A sodium chloride modification was applied where different amounts of sodium chloride was physically blended in a tin oxide colloid solution to passivate the interface between the electron transport layer (ETL) and perovskite layer and improve the performance of perovskite solar cells. Sodium chloride-modified tin oxide was utilized as the electron transport material to fabricate perovskite solar cells. It was found that sodium chloride-modified tin oxide as an ETL could considerably enhance the performance of the device compared to pristine tin oxide. The power conversion efficiency of the perovskite solar cell displayed 8.8% remarkable improvement from 18.7 ± 0.4% to 20.3 ± 0.3% on average and 9.5% improvement from 18.9 to 20.7% in champion devices because of the considerable enhancement of the fill factor when 25 mM sodium chloride-modified tin oxide as the ETL was used in comparison with pristine tin oxide.

The effect of water on colloidal quantum dot solar cells.

Almost all surfaces sensitive to the ambient environment are covered by water, whereas the impacts of water on surface-dominated colloidal quantum dot (CQD) semiconductor electronics have rarely been explored. Here, strongly hydrogen-bonded water on hydroxylated lead sulfide (PbS) CQD is identified. The water could pilot the thermally induced evolution of surface chemical environment, which significantly influences the nanostructures, carrier dynamics, and trap behaviors in CQD solar cells. The aggravation of surface hydroxylation and water adsorption triggers epitaxial CQD fusion during device fabrication under humid ambient, giving rise to the inter-band traps and deficiency in solar cells. To address this problem, meniscus-guided-coating technique is introduced to achieve dense-packed CQD solids and extrude ambient water, improving device performance and thermal stability. Our works not only elucidate the water involved PbS CQD surface chemistry, but may also achieve a comprehensive understanding of the impact of ambient water on CQD based electronics.

Inversion of Circular Dichroism Signals in Chiral Polythiophene Films Induced by End-On-Oriented Surface-Segregated Monolayers.

A chiral polythiophene surfactant based on poly(3-(S)-2-methylbutylthiophene) ((S)-P3MBT) with a semifluoroalkyl group at one end of the main chain was synthesized and used to form surface-segregated monolayers (SSMs). Films of pure (S)-P3MBT mainly adopted the edge-on orientation, whereas (S)-P3MBT films with a SSM of the polymer surfactant (S)-P3MBT-F17 contained a large proportion of end-on-oriented polythiophene, both at the surface and inside the films. The thin films with the SSM showed circular dichroism signals, with the sign opposite to those observed in (S)-P3MBT films. These findings suggest that the orientation-controlled SSM layers induced changes in the packing of the polymer aggregates in the films, resulting in a dramatic change in the excitonic interactions of the chiral semiconducting polymers.

Eco-Friendly AgBiS2 Nanocrystal/ZnO Nanowire Heterojunction Solar Cells with Enhanced Carrier Collection Efficiency.

AgBiS2 nanocrystals (NCs) are nontoxic, lead-free, and near-infrared absorbing materials. Eco-friendly solar cells were constructed using interdigitated layers of ZnO nanowires (NWs) and AgBiS2 NCs, with the aim of elongating the otherwise short carrier diffusion length of the AgBiS2 NC assembly. AgBiS2 NCs were uniformly infiltrated into the ZnO NW layers using a low-cost and easily scalable dip coating method. The resulting ZnO NW/AgBiS2 NC interdigitated structures provided efficient carrier pathways in constructed nanowire solar cells (NWSCs), composed of a transparent electrode/ZnO NW/AgBiS2 NC interdigitated layer/P3HT hole transport layer/Au. The photocurrent external quantum efficiency (EQE) in the visible to near-infrared regions was enhanced compared to those of the control solar cells made with ZnO/AgBiS2 tandem layered structures. The maximum EQE for the NWSCs reached 82% in the visible region, which is higher than the EQE values previously reported for solar cells fabricated with ZnO/AgBiS2 NCs. Air stability tests on unsealed NWSCs demonstrated that 90% or more of the initial power conversion efficiency was maintained even after 6 months.

Efficient and stable tin perovskite solar cells enabled by amorphous-polycrystalline structure.

Tin perovskite solar cells (TPSCs) have triggered intensive research as a promising candidate for lead-free perovskite solar cells. However, it is still challenging to obtain efficient and stable TPSCs because of the low defects formation energy and the oxidation of bivalent tin; Here, we report a TPSC with a stable amorphous-polycrystalline structure, which is composed of a tin triple-halide amorphous layer and cesium-formamidinium tin iodide polycrystals. This structure effectively blocks the outside oxygen, moisture and also suppresses the ion diffusion inside the devices. In addition, its energy level benefits the charge extraction and transport in TPSCs. This design enabled us to obtain the certified quasi-steady-state efficiency over 10% for TPSCs from an accredited certification institute. The cell was stable, maintaining 95% of the initial PCE after operation at the maximum power point under AM 1.5 G simulated solar light (100 mWcm-2) for 1000 hours.