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Nonstoichiometric nickel oxide (NiOx) is one of the very few metal oxides successfully used as hole extraction layer in p-i-n type perovskite solar cells (PSCs). Its favorable optoelectronic properties and facile large-scale preparation methods are potentially relevant for future commercialization of PSCs, though currently low operational stability of PSCs is reported when a NiOx hole extraction layer is used in direct contact with the perovskite absorber. Poorly understood degradation reactions at this interface are seen as cause for the inferior stability, and a variety of interface passivation approaches have been shown to be effective in improving the overall solar cell performance. To gain a better understanding of the processes happening at this interface, we systematically passivated specific defects on NiOx with three different categories of organic/inorganic compounds. The effects on NiOx and the perovskite (MAPbI3) deposited on top were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Here, we find that the perovskite's structural stability and film formation can be significantly affected by the passivation treatment of the NiOx surface. In combination with density functional theory (DFT) calculations, a likely origin of NiOx-perovskite degradation interactions is proposed. The surface passivated NiOx layers were incorporated into MAPbI3-based PSCs, and the influence on device performance and operational stability was investigated by current-voltage (J-V) characterization, impedance spectroscopy (IS), and open circuit voltage decay (OCVD) measurements. Interestingly, we find that a superior structural stability due to interface passivation must not relate to high operational stability. The discrepancy comes from the formation of excess ions at the interface, which negatively impacts all solar cell parameters.
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Inverted NiOx-based perovskite solar cells (PSCs) exhibit considerable potential because of their low-temperature processing and outstanding excellent stability, while is challenged by the carriers transfer at buried interface owing to the inherent low carrier mobility and abundant surface defects that directly deteriorates the overall device fill factor. Present work demonstrates a chemical linker with the capability of simultaneously grasping NiOx and perovskite crystals by forming a Ni-S-Pb bridge at buried interface to significantly boost the carriers transfer, based on a rationally selected molecule of 1,3-dimethyl-benzoimidazol-2-thione (NCS). The constructed buried interface not only reduces the pinholes and needle-like residual PbI2 at the buried interface, but also deepens the work function and valence band maximum positions of NiOx, resulting in a smaller VBM offset between NiOx and perovskite film. Consequently, the modulated PSCs achieved a high fill factor up to 86.24 %, which is as far as we know the highest value in records of NiOx-based inverted PSCs. The NCS custom-tailored PSCs and minimodules (active area of 18â cm2) exhibited a champion efficiency of 25.05 % and 21.16 %, respectively. The unencapsulated devices remains over 90 % of their initial efficiency at maximum power point under continuous illumination for 1700â hours.
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The wettability of precursor solution on substrates is the critical factor for fabricating quality film. In this work, superwetting nanofluids (NFs) of non-stoichiometric nickel oxide (NiOx) nanocrystals (NCs)-CsBr solution are first utilized to fabricate quality NiOx-CsPbBr3 hybrid film with gradient-distributed NiOx NCs in the upper part for constructing hole transport ladder in carbon-based perovskite solar cells (C-PSCs). As anticipated, the crystalline properties (improved crystalline grain diameters and reduced impurity phase) and hole extraction/transport of the NiOx-CsPbBr3 hybrid film are improved after incorporating NiOx NCs into CsPbBr3. This originates from the superb wettability of NiOx-CsBr NFs on substrates and the excellent hole-transport properties of NiOx. Consequently, the C-PSCs with the structure of FTO/SnO2/NiOx-CsPbBr3/C displays a power conversion efficiency of 10.07%, resulting in a 23.6% improvement as compared with the pristine CsPbBr3 cell. This work opens up a promising strategy to improve the absorber layer in PSCs by incorporating NCs into perovskite layers through the use of the superwettability of NFs and by composition gradient engineering.
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The development of high-density and closely spaced frustrated Lewis pairs (FLPs) is crucial for enhancing catalyst activity and accelerating reaction rates. However, constructing efficient FLPs by breaking classical Lewis bonds poses a significant challenge. Here, this work has made a pivotal discovery regarding the Jahn-Teller effect during the formation of grain boundaries in carbon-encapsulated Ni/NiOx (Ni/NiOx@C). This effect facilitates the formation of high-density O (VO) and Ni (VNi) vacancy sites with different charge polarities, specifically FLP-VO-C basic sites and FLP-VNi-C acidic sites. The synergistic interaction between FLP-VO-C and FLP-VNi-C sites not only reduces energy barriers for water adsorption and splitting, but also induces a strong photothermal effect. This mutually reinforcing effect contributes to the exceptional performance of Ni/NiOx@C as a cocatalyst in photothermal-assisted photocatalytic hydrogen production. Notably, the Ni/NiOx@C/g-C3N4 (NOCC) composite photocatalyst exhibits remarkable hydrogen production activity with a rate of 10.7 mmol g-1 h-1, surpassing that of the Pt cocatalyst by 1.76 times. Moreover, the NOCC achieves an impressive apparent quantum yield of 40.78% at a wavelength of 380 nm. This work paves the way for designing novel defect-state multiphase cocatalysts with high-density and adjacent FLP sites, which hold promise for enhancing various catalytic reactions.
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High performance flexible all-thin-film electrochromic devices (ATF-ECDs) have been fabricated and systematically investigated by operating with different driving voltages during the electrochromic processes. The device structure (cross-section) and material properties of some main functional layers were presented and analysed. The electrochromic properties including kinetic and spectral tests were systematically investigated through combining chronoamperometry, cyclic voltammetry measurements and optical measurements. In addition, the open circuit memory measurement was also carried out. A much higher driving voltage might lead to a current leakage inside the device during coloring process. A proper driving voltage is needed for achieving high device performances. More details were widely described and deeply discussed.
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Low-cost and eco-friendly Ni/NiO heterojunctions have been theoretically proven to be the ideal candidate for stepwise electrocatalysis of alkaline hydrogen evolution reaction, attributed to the preferred OHad adsorption by incompletely filled d orbitals of NiO phase and favorable Had adsorption energy of Ni phase. Nevertheless, most Ni/NiO compounds reported so far fail to exhibit excellent catalytic activity, possibly due to the lack of efficient electron transport, limited interfacial active sites, and unregulated Nin+ ratios. To address the above bottlenecks, herein, the ultrasmall Ni/NiOx@C nanocapsules (<5 nm) are directly constructed by graphitization of four-layer Ni-based coordination polymers at record low temperatures of 400 °C. Ascribed to the accelerated electron and mass transfer by the carbon nano-onions coated around Ni/NiOx heterojunctions, the extreme rise in interfaces and Ni3+ defects with t6 2ge1 g electronic configuration owed to the ultrasmall size, the Ni/NiOx@C nanocapsules exhibit the highest catalytic activity and the lowest overpotential of η10 = 80 mV among various Ni/NiO materials (measured on the glassy carbon electrode). This work not only constructs an industrialized high-efficiency electrocatalyst toward alkaline HER, but also provides a novel strategy for the constant-scale preparation of multicomponent transition metals-based nanocrystals below 4 nm.
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Nickel oxide (NiOx) has been limited in use as a hole transport layer for its low conduction, surface defects, and redox reactions with the perovskite layer. To address these issues, the incorporation of zwitterion L-tryptophan (Trp) is proposed at the NiOx/Trp interface. The carboxyl group of Trp effectively passivates the surface positive defects of NiOx, thereby improving its optical and electrical properties. The ammonium group of Trp not only passivates negative defects but modulates the growth of the perovskite layer, resulting in an improved perovskite film quality. Furthermore, the Trp layer acts as a buffer layer, suppressing adverse interfacial reactions between the perovskite and NiOx. Consequently, perovskite solar cells with 1.56 and 1.68 eV absorbers achieve the champion power conversion efficiency (PCE) of 23.79% and 20.41%, respectively. Moreover, the unencapsulated devices demonstrate excellent long-term stability, retaining above 80% of the initial PCE value after 1600 h of storage in the air with a humidity of 50-60%.
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Inverted flexible perovskite cells (fPSCs) have attracted much attention for their high efficiency and power per weight. Still, the steady-state output is one of the critical factors for their commercialization. In this paper, it is found that the steady-state current of inverted fPSCs based on nickel oxide nanoparticles (n-NiOx) continuously decreases under light illumination. Conversely, those based on magnetron-sputtered NiOx (sp-NiOx) exhibit the opposite result. Based on visualization of ion migration in the photoluminescence (PL) imaging microscopy tests, the discrepancies in the buried surfaces lead to the differences in ion migration in perovskite films, which triggers the temporary instability of the output current of devices during operation. The DFT theoretical calculation and experimental results reveal that NiOx films with different contents of Ni vacancies can modulate the crystallization of the perovskite films on the NiOx surfaces. Tuning the crystallization of the perovskite films is essential to stabilize the output current of fPSCs at a steady state. To demonstrate that, capsaicin is doped into the perovskite solutions to improve the quality of the perovskite buried interface. Finally, the corresponding fPSCs exhibit outstanding efficiency and stability during operation. These results provide valuable scientific guidance for fabricating fPSCs with stable operation under illumination conditions.
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Perovskite solar cells (PSCs) based on sputtered nickel oxide (NiOx) hole transport layer have emerged as promising configuration due to their good stability, cost-effectiveness, and scalability. However, the adverse chemical redox reaction at the NiOx/perovskite interface remains an ever-present problem that has not yet been well solved. To address this issue before, the problems that cation deprotonation and iodide oxidation that occurred in precursor solution easily result in the interfacial chemical reaction should be prevented. Hence, we report an efficient strategy to simultaneously suppress the interfacial reaction and stabilize the precursor solution by incorporating a reducing and weakly acidic stabilizer, l-ascorbic acid (l-AA). l-AA can reduce I2 generated in the precursor solution and during the interfacial reaction to I-. Furthermore, the protons ionized by adjacent enol hydroxyl groups in l-AA effectively impede the deprotonation of organic cations in the precursor solution as well as at the NiOx/perovskite interface resulting from the chemical reaction. Attributing to the improved crystallization of the perovskite film and the suppression of the interfacial reaction by l-AA, the inverted PSC based on such good light absorber achieves an impressive power conversion efficiency (PCE) of 22.72% along with a high open-circuit voltage of 1.19 V. Notably, further introducing l-AA into the large-area solar modules by the slot-die coating method in air enables a remarkable PCE of 19.17%, which reaches one of the highest PCEs reported for inverted perovskite solar modules (PSMs) (active area >50 cm2) to date. l-AA located at the buried interface also forms a barrier layer that can prevent undesirable chemical reactions at the NiOx/perovskite interface, significantly enhancing the device stability of solar cells and PSMs. These findings in our work provide important guidance for improving the NiOx/perovskite interface and the fabrication of highly efficient, low-cost, and large-area PSMs.
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The imbalance of charge injection is considered to be a major factor that limits the device performance of cadmium-free quantum-dot light-emitting diodes (QLEDs). In this work, high-performance cadmium-free CuâInâZnâS(CIZS)-based QLEDs are designed and fabricated through tailoring interfacial energy level alignment and improving the balance of charge injection. This is achieved by introducing a bilayered hole-injection layer (HIL) of Cu-doped NiOx (CuâNiOx )/Poly(3,4-ethylenedioxythiophene): poly (styrene sulfonate) (PEDOT:PSS). High-quality CuâNiOx film is prepared through a novel and straightforward sol-gel procedure. Multiple experimental characterizations and theoretical calculations show that the incorporation of Cu2+ ions can regulate the energy level structure of NiOx and enhance the hole mobility. The state-of-art CIZS-based QLEDs with CuâNiOx /PEDOT:PSS bilayered HIL exhibit the maximum external quantum efficiency of 6.04% and half-life time of 48 min, which is 1.3 times and four times of the device with only PEDOT:PSS HIL. The work provides a new pathway for developing high-performance cadmium-free QLEDs.
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Nickel oxide (NiOx) nanocrystals have been widely used in inverted (p-i-n) flexible perovskite solar cells (fPSCs) due to their remarkable advantages of low cost and outstanding stability. However, anion and cation impurities such as NO3- widely exist in the NiOx nanocrystals obtained from calcinated nickel hydroxide (Ni(OH)2). The impurities impair the photovoltaic performance of fPSCs. In this work, we report a facile but effective way to reduce the impurities within the NiOx nanocrystals by regulating the Ni(OH)2 crystal phase. We add different alkalis, such as organic ammonium hydroxide and alkali metal hydroxides, to nickel nitrate solutions to precipitate layered Ni(OH)2 with different crystalline phase compositions (α and ß mixtures). Especially, Ni(OH)2 with a high ß-phase content (such as from KOH) has a narrower crystal plane spacing, resulting in fewer residual impurity ions. Thus, the NiOx nanocrystals, by calcinating the Ni(OH)x with excess ß phase from KOH, show improved performance in inverted fPSCs. A champion power conversion efficiency (PCE) of 20.42% has been achieved, which is among the state-of-art inverted fPSCs based on the NiOx hole transport material. Moreover, the reduced impurities are beneficial for enhancing the fPSCs' stability. This work provides an essential but facile strategy for developing high-performance inverted fPSCs.
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The development of stable materials, processable on a large area, is a prerequisite for perovskite industrialization. Beyond the perovskite absorber itself, this should also guide the development of all other layers in the solar cell. In this regard, the use of NiOx as a hole transport material (HTM) offers several advantages, as it can be deposited with high throughput on large areas and on flat or textured surfaces via sputtering, a well-established industrial method. However, NiOx may trigger the degradation of perovskite solar cells (PSCs) when exposed to environmental stressors. Already after 100 h of damp heat stressing, a strong fill factor (FF) loss appears in conjunction with a characteristic S-shaped J-V curve. By performing a wide range of analysis on cells and materials, completed by device simulation, the cause of the degradation is pinpointed and mitigation strategies are proposed. When NiOx is heated in an air-tight environment, its free charge carrier density drops, resulting in a band misalignment at the NiOx/perovskite interface and in the formation of a barrier impeding hole extraction. Adding an organic layer between the NiOx and the perovskite enables higher performances but not long-term thermal stability, for which reducing the NiOx thickness is necessary.
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NiOx-based inverted perovskite solar cells (PSCs) have presented great potential toward low-cost, highly efficient and stable next-generation photovoltaics. However, the presence of energy-level mismatch and contact-interface defects between hole-selective contacts (HSCs) and perovskite-active layer (PAL) still limits device efficiency improvement. Here, we report a graded configuration based on both interface-cascaded structures and p-type molecule-doped composites with two-/three-dimensional formamidinium-based triple-halide perovskites. We find that the interface defects-induced non-radiative recombination presented at HSCs/PAL interfaces is remarkably suppressed because of efficient hole extraction and transport. Moreover, a strong chemical interaction, halogen bonding and coordination bonding are found in the molecule-doped perovskite composites, which significantly suppress the formation of halide vacancy and parasitic metallic lead. As a result, NiOx-based inverted PSCs present a power-conversion-efficiency over 23% with a high fill factor of 0.84 and open-circuit voltage of 1.162 V, which are comparable to the best reported around 1.56-electron volt bandgap perovskites. Furthermore, devices with encapsulation present high operational stability over 1,200 h during T90 lifetime measurement (the time as a function of PCE decreases to 90% of its initial value) under 1-sun illumination in ambient-air conditions.
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Carbon-based all-inorganic perovskite solar cells (C-IPSCs) are stable, upscalable and have low CO2-footprint to fabricate. However, they are inefficient in converting light to electricity due to poor hole extraction at perovskite/carbon interface. Here we enable an efficient hole extraction in C-IPSCs with the aid of inorganic p-type nickel oxide nanoparticles (NiOx-NPs) at the interface and in carbon. By tailoring the work function (WF) of carbon, and reducing the energy-level misalignment at the perovskite/carbon interface, NiOx-NPs enable efficient hole transfer, reduce charge recombination and minimize energy loss. As a result, we report 15.01% and 11.02% efficiencies for CsPbI2Br and CsPbIBr2 C-IPSCs, respectively, with a high open-circuit voltage of â¼1.3 V. Unencapsulated interface-modified CsPbI2Br devices maintained 92.8% of their initial efficiency at ambient conditions after nearly 2,000 h; and 94.6% after heating at 60 °C for 170 h. This strategy to tailor carbon interface with perovskite offers an important knob in improving C-IPSCs performance.
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In this study, we positioned three quaternary ammonium halide-containing cellulose derivatives (PQF, PQCl, PQBr) as interfacial modification layers between the nickel oxide (NiOx) and methylammonium lead iodide (MAPbI3) layers of inverted perovskite solar cells (PVSCs). Inserting PQCl between the NiOx and MAPbI3 layers improved the interfacial contact, promoted the crystal growth, and passivated the interface and crystal defects, thereby resulting in MAPbI3 layers having larger crystal grains, better crystal quality, and lower surface roughness. Accordingly, the photovoltaic (PV) properties of PVSCs fabricated with PQCl-modified NiOx layers were improved when compared with those of the pristine sample. Furthermore, the PV properties of the PQCl-based PVSCs were much better than those of their PQF- and PQBr-based counterparts. A PVSC fabricated with PQCl-modified NiOx (fluorine-doped tin oxide/NiOx/PQCl-0.05/MAPbI3/PC61BM/bathocuproine/Ag) exhibited the best PV performance, with a photoconversion efficiency (PCE) of 14.40%, an open-circuit voltage of 1.06 V, a short-circuit current density of 18.35 mA/cm3, and a fill factor of 74.0%. Moreover, the PV parameters of the PVSC incorporating the PQCl-modified NiOx were further enhanced when blending MAPbI3 with PQCl. We obtained a PCE of 16.53% for this MAPbI3:PQCl-based PVSC. This PQCl-based PVSC retained 80% of its initial PCE after 900 h of storage under ambient conditions (30 °C; 60% relative humidity).
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Power conversion efficiency (PCE) and long-term stability are two vital issues for perovskite solar cells (PSCs). However, there is still a lack of suitable hole transport layers (HTLs) to endow PSCs with both high efficiency and stability. Here, NiOx nanoparticles are promoted as an efficient and 85 °C/85%-stable inorganic HTL for high-performance n-i-p PSCs, with the introduction of perovskite quantum dots (QDs) between perovskite and NiOx as systematic interfacial engineering. The QD intercalation enhances film morphology and assembly regulation of NiOx HTLs . Due to structure-function correlations, hole mobility within NiOx HTL is improved. And the hole extraction from perovskite to NiOx is also facilitated, resulting from reduced trap states and optimized energy level alignments. Hence, the promoted NiOx -based n-i-p PSCs exhibit high PCE (21.59%) and excellent stability (sustaining 85 °C aging in air without encapsulation). Furthermore, encapsulated solar modules with QDs-promoted NiOx HTLs show impressive stability during 85 °C/85% aging test for 1000 hours. With high transparency, QDs-promoted NiOx is also demonstrated to be an advanced HTL for semitransparent PSCs. This work develops promising NiOx inorganic HTL in n-i-p PSCs for manufacturing next-generation photovoltaic devices.
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The effect of substitutional metal dopants in NiOx on the structural and electronic structures is of great interest, particularly for increasing the p-type conductivities as a hole transport layer (HTL) applied in perovskite solar cells (PSCs). In this paper, experimental fabrications and density functional theory calculations have been carried out on Cd-doped NiOx films to examine the effect of divalent doping on the electronic and geometric structures of NiOx. The results indicate that divalent Cd dopants reduced the formation energy of the Ni vacancy (VNi) and created more VNi in the films, which enhanced the p-type conductivity of the NiOx films. In addition, Cd doping also deepened the valence band edge, reduced the monomolecular Shockley-Read-Hall (SRH) recombination losses, and promoted hole extraction and transport. Hence, the PSCs with Cd:NiOx HTLs manifest a high efficiency of 20.47%, a high photocurrent density of 23.00 mA cm-2, and a high fill factor of 79.62%, as well as negligible hysteresis and excellent stability. This work illustrates that divalent elements such as Cd, Zn, Co, etc. may be potential dopants to improve the p-type conductivity of the NiOx films for applications in highly efficient and stabilized PSCs.
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High crystallization and conductivity are always required for inorganic carrier transport materials for cheap and high-performance inverted perovskite solar cells (PSCs). High temperature and external doping are inevitably introduced and thus greatly hamper the applications of inorganic materials for mass production of flexible and tandem devices. Here, an amorphous and dopant-free inorganic material, Ni3+ -rich NiOx , is reported to be fabricated by a novel UV irradiation strategy, which is facile, easily scaled-up, and energy-saving because all the processing temperatures are below 82 â. The as-prepared NiOx film shows highly improved conductivity and hole extraction ability. The rigid and flexible PSCs present the champion efficiencies of 22.45% and 19.7%, respectively. This work fills the gap of preparing metal oxide films at the temperature below 150 °C for inverted PSCs with the high efficiency of >22%. More importantly, this work upgrades the substantial understanding about inorganic materials to function well as efficient carrier transport layers without external doping and high crystallization.
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Photoelectrochemical (PEC) water splitting is an attractive strategy to convert and store of intermittent solar power into fuel energy. However, the detrimental charge recombination of photogenerated electrons and holes severely limits its efficiency. Despite electrocatalyst loading can obviously improve the PEC conversion efficiency, current systems still suffer from high recombination owing to the surface states. Herein, an interface "repairing" strategy is proposed to suppress the recombination at the semiconductor/electrocatalyst interface. NiOx layer acts as an interfacial repairing layer to efficiently extract photogenerated charge carriers and eliminate the surface states via high hole-transfer kinetics rather than as a traditional electrocatalyst. As expected, the resulting repaired system yields an impressive photocurrent density of 4.58 mA cm-2 at 1.23 V (vs. RHE), corresponding to a more than three-fold increase compared to BiVO4 (1.40 mA cm-2). Our work offers an appealing maneuver to improve the water oxidation performance for the semiconductor/electrocatalyst coupling system.
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The development of robust, low-cost and efficient oxygen evolution reaction (OER) electrocatalysts, especially non-noble-metal-based OER catalysts, is of great significance and imperative to address the energy crisis, but remain challenging. Herein, a biomass-derived three-dimensional (3D) porous carbon/cobalt silicate (C/Co2SiO4) architecture is developed as a support for loading nickel oxide (NiOx) species to prepare an earth-abundant and non-noble-metal-based NiOx/C/Co2SiO4 electrocatalyst. The NiOx nanoparticles are dispersed on 3D C/Co2SiO4 support and the introduction of NiOx species improves the OER active sites and shows the bimetal (Co, Ni) synergetic effect. The NiOx/C/Co2SiO4 electrocatalyst exhibits the overpotential with 355 mV at 10 mA cm-2, Tafel slope with 40 mV dec-1 and large electrochemical active surface areas (ECSA), which are superior to C/Co2SiO4 support and NiOx. The catalytic properties achieved herein are superior or comparable to most transition metal oxides/hydroxides. The findings reveal that the introduction of NiOx nanoparticles can greatly boost the OER property of C/Co2SiO4 support. This work not only develops a non-noble-metal-based NiOx/C/Co2SiO4 catalyst, but also verifies that the introduction of metal oxide species on biomass-derived 3D C/Co2SiO4 provides a new horizon to explore economical, high-efficient and robust OER catalysts.