Surface Reconstruction Engineering with Synergistic Effect of Mixed-Salt Passivation Treatment toward Efficient and Stable Perovskite Solar Cells

Surface passivation treatment is a widely used strategy to resolve trap-mediated nonradiative recombination toward high-efficiency metal-halide perovskite photovoltaics. However, a lack of passivation with mixture treatment has been investigated, as well as an in-depth understanding of its passivation mechanism. Here, a systematic study on a mixed-salt passivation strategy of formamidinium bromide (FABr) coupled with different F-substituted alkyl lengths of ammonium iodide is demonstrated. It is obtained better device performance with decreasing chain length of the F-substituted alkyl ammonium iodide in the presence of FABr. Moreover, they unraveled a synergistic passivation mechanism of the mixed-salt treatment through surface reconstruction engineering, where FABr dominates the reformation of the perovskite surface via reacting with the excess PbI₂. Meanwhile, ammonium iodide passivates the perovskite grain boundaries both on the surface and top perovskite bulk through penetration. This synergistic passivation engineer results in a high-quality perovskite surface with fewer defects and suppressed ion migration, leading to a champion efficiency of 23.5% with mixed-salt treatment. In addition, the introduction of the moisture resisted F-substituted groups presents a more hydrophobic perovskite surface, thus enabling the decorated devices with excellent long-term stability under a high humid atmosphere as well as operational conditions.     

Inhibition of the reduction of Cr(VI) at the magnetite–water interface by calcium carbonate coatings

The effect of calcium carbonate coatings on the reduction of aqueous chromate on the magnetite(1 1 1) surface has been investigated using a combination of synchrotron based X-ray photoemission spectroscopy (PES) and X-ray absorption near edge structure (XANES) spectroscopy, along with laboratory-based powder X-ray diffraction (XRD) and scanning electron microscopy (SEM). CaCO₃ coatings (dominantly calcite with minor quantities of aragonite and vaterite) of thicknesses ranging from 10 Å to 20 m were grown on magnetite(1 1 1) surfaces by exposure to supersaturated aqueous solutions followed by evaporation of the solution—a process that mimics pore-water evaporation in vadose zones leading to the formation of caliche and calcium carbonate coatings on mineral grains. Coating thicknesses were determined from attenuation of the Fe 2p photoemission signal by the carbonate coating. For coatings less than 15 Å thick, Cr 2p photoemission and Cr L_II, L_III-edge XANES spectra show that chromate is reduced by the underlying magnetite surface; however, as the minimum coating thickness increases beyond 15 Å, the magnetite surface becomes passivated and further chromate reduction ceases. Our findings suggest that carbonate coatings on natural magnetite grains can significantly reduce or eliminate their ability to reduce Cr(VI), which is a toxic and highly mobile environmental contaminant.     

载波钝化和钼酸盐后处理对不锈钢钝化膜性能的影响

一般认为交流电对金属的腐蚀过程具有加速作用,但我们发现,在直流电位基础上叠加适当波形、幅值和频率的交流电对不锈钢进行载波钝化,尔后再进行适当后处理可使钝化膜的稳定性提高,我们曾就不经后处理的载波钝化过程进行过探讨,本文着重探讨钼酸盐后处理对载波钝化膜表面状态和化学稳定性改善的作用机理。     

Adsorptive passivation of iron by organic acid anions

Studies on the iron passivation by organic acid anions in aqueous solutions are briefly reviewed. It is shown that the passivation can be caused only by their adsorption, retarding both the iron dissolution and the formation of oxide films. Earlier, it had been believed that oxide films play a dominant role in the iron passivation in neutral solutions. The recent viewpoint is that such nonoxide iron passivation can occur in solutions of salts of not only aromatic amino acids (sodium phenylantranilate and its substitutes), but other carboxylic acids as well. An important role of chemisorption and hydrophobic properties of anions for the formation of adsorption passive films is emphasized. New possibilities for inhibitor protection of iron against corrosion, which is based on adsorptive passivation, are pointed out.Translated from Elektrokhimiya, Vol. 40, No. 12, 2004, pp. 1503–1507.Original Russian Text Copyright © 2004 by Kuznetsov.     

A Polymer Defect Passivator for Efficient Hole-Conductor-Free Printable Mesoscopic Perovskite Solar Cells

Due to the low cost and excellent potential for mass production, printable mesoscopic perovskite solar cells (p-MPSCs) have drawn a lot of attention among other device structures. However, the low open-circuit voltage (V_OC) of such devices restricts their power conversion efficiency (PCE). This limitation is brought by the high defect density at perovskite grain boundaries in the mesoporous scaffold, which results in severe nonradiative recombination and is detrimental to the V_OC. To improve the perovskite crystallization process, passivate the perovskite defects, and enhance the PCE, additive engineering is an effective way. Herein, a polymeric Lewis base polysuccinimide (PSI) is added to the perovskite precursor solution as an additive. It improves the perovskite crystallinity and its carbonyl groups strongly coordinate with Pb²⁺, which can effectively passivate defects. Additionally, compared with its monomer, succinimide (SI), PSI serves as a better defect passivator because the long-chained macromolecule can be firmly anchored on those defect sites and form a stronger interaction with perovskite grains. As a result, the champion device has a PCE of 18.84%, and the V_OC rises from 973 to 1030 mV. This study offers a new strategy for fabricating efficient p-MPSCs.     

Passivating Defects of Perovskite Solar Cells with Functional Donor-Acceptor–Donor Type Hole Transporting Materials

In this study, a series of donor–acceptor–donor (D-A-D) type small molecules based on the fluorene and diphenylethenyl enamine units, which are distinguished by different acceptors, as holetransporting materials (HTMs) for perovskite solar cells is presented. The incorporation of the malononitrile acceptor units is found to be beneficial for not only carrier transportation but also defects passivation via Pb–N interactions. The highest power conversion efficiency of over 22% is achieved on cells based on V1359, which is higher than that of spiro-OMeTAD under identical conditions. This st shows that HTMs prepared via simplified synthetic routes are not only a low-cost alternative to spiro-OMeTAD but also outperform in efficiency and stability state-of-art materials obtained via expensive cross-coupling methods.     

流动注射区域采样法测定镀锌钝化液中高浓度锌

本文建立了流动注射二甲酚橙光度法测定镀锌纯化液中Ｚｎ￣２＋的自动分析方法。利用区域采样技术和调整管路参数自动完成对样品的上千倍稀释，确定了最佳分析条件并研究了干扰离子的影响及消除办法。所建方法仪器简单，分析速度为８４次／小时，变异系数（Ｚｎ￣２＋１６．０ｇ／Ｌ，ｎ＝２０）为１．Ｏ％，用于实际钝化液分析，相对误差小于±１０％。     

Bulk micromachining of silicon in TMAH-based etchants for aluminum passivation and smooth surface

The fabrication of silicon based micromechanical sensors often requires bulk silicon etching after aluminum metallization. All wet silicon etchants including ordinary undoped tetramethyl ammonium hydroxide (TMAH)-water solution attack the overlaying aluminum metal interconnect during the anisotropic etching of (100) silicon. This paper presents a TMAH-water based etching recipe to achieve high silicon etch rate, a smooth etched surface and almost total protection of the exposed aluminum metallization. The etch rate measurements of (100) silicon, silicon dioxide and aluminum along with the morphology studies of etched surfaces are performed on both n-type and p-type silicon wafers at different concentrations (2, 5, 10 and 15%) for undoped TMAH treated at various temperatures as well as for TMAH solution doped separately and simultaneously with silicic acid and ammonium peroxodisulphate (AP). It is established through a detailed study that 5% TMAH-water solution dual doped with 38 gm/l silicic acid and 7 gm/l AP yields a reasonably high (100) silicon etch rate of 70 μm/h at 80 °C, very small etch rates of SiO₂ and pure aluminum (around 80 Å/h and 50 Å/h, respectively), and a smooth surface (±7 nm) at a bath temperature of 80 °C. The etchant has been successfully used for fabricating several MEMS structures like piezoresistive accelerometer, vaporizing liquid micro-thruster and flow sensor. In all cases, the bulk micromachining is carried out after the formation of aluminum interconnects which is found to remain unaffected during the prolonged etching process at 80 °C. The TMAH based etchant may be attractive in industry due to its compatibility with standard CMOS process.     

Efficient polymer passivation of ligand‐stripped nanocrystal surfaces

Water‐dispersible, polymer‐wrapped nanocrystals are highly sought after for use in biology and chemistry, from nanomedicine to catalysis. The hydrophobicity of their native ligand shell, however, is a significant barrier to their aqueous transfer as single particles. Ligand exchange with hydrophilic small molecules or, alternatively, wrapping over native ligands with amphiphilic polymers is widely employed for aqueous transfer; however, purification can be quite cumbersome. We report here a general two‐step method whereby reactive stripping of native ligands is first carried out using trialkyloxonium salts to reveal a bare nanocrystal surface. This is followed by chemically directed immobilization of a hydrophilic polymer coating. Polyacrylic acids, with side‐chain grafts or functional end groups, were found to be extremely versatile in this regard. The resulting polymer‐wrapped nanocrystal dispersions retained much of the compact size of their bare nanocrystal precursors, highlighting the unique role of monomer side‐chain functionality to serve as effective, conformal ligation motifs. As such, they are well poised for applications where tailored chemical functionality at the nanocrystal's periphery or improved access to their surfaces is desirable. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Comparative studies of normally-off Al0.26Ga0.74N/AlN/GaN/Si high electron mobility transistors with different gate structures

Systematic designs to achieve normally-off operation and improved device performance for Al_0.26Ga_0.74N/AlN/GaN high electron mobility transistors (HEMTs) grown on a Si substrate are investigated in this work. The step-by-step approach includes: (1) devising a thin AlGaN/AlN composite barrier, (2) introducing fluoride ions within the active region by using CF₄ plasma treatment, (3) growing the Al₂O₃ oxide passivation layers within gate-drain/source regions by using a cost-effective ozone water oxidization technique, and (4) integrating a metal-oxide-semiconductor gate (MOS-gate) design with high-k Al₂O₃ gate dielectric. Devices with four different evolutionary gate structures have been compared and studied. Variations of threshold voltage (V_th), Hooge coefficients (α_H), maximum drain-source current density (I_{DS, max}), maximum extrinsic transconductance (g_{m, max}), gate-voltage swing (GVS) linearity, two-terminal gate-drain breakdown/turn-on voltages (BV_GD/V_on), on/off current ratio (I_on/I_off), and high-temperature characteristics up to 450 K are also investigated.