On Proton Conductivity in Porous and Dense Yttria Stabilized Zirconia at Low Temperature

The electrical conductivity of dense and nanoporous zirconia‐based thin films is compared to results obtained on bulk yttria stabilized zirconia (YSZ) ceramics. Different thin film preparation methods are used in order to vary grain size, grain shape, and porosity of the thin films. In porous films, a rather high conductivity is found at room temperature which decreases with increasing temperature to 120 °C. This conductivity is attributed to proton conduction along physisorbed water (Grotthuss mechanism) at the inner surfaces. It is highly dependent on the humidity of the surrounding atmosphere. At temperatures above 120 °C, the conductivity is thermally activated with activation energies between 0.4 and 1.1 eV. In this temperature regime the conduction is due to oxygen ions as well as protons. Proton conduction is caused by hydroxyl groups at the inner surface of the porous films. The effect vanishes above 400 °C, and pure oxygen ion conductivity with an activation energy of 0.9 to 1.3 eV prevails. The same behavior can also be observed in nanoporous bulk ceramic YSZ. In contrast to the nanoporous YSZ, fully dense nanocrystalline thin films only show oxygen ion conductivity, even down to 70 °C with an expected activation energy of 1.0 ± 0.1 eV. No proton conductivity through grain boundaries could be detected in these nanocrystalline, but dense thin films.     

低温微波水热法制备氧化钇稳定氧化锆

微波水热合成法是新型的纳米粉体材料制备方法,它与常规水热法相比,反应时间更短、反应温度更低,并且微波的非热效应影响产物晶型的形成。立方相氧化钇稳定氧化锆(YSZ)陶瓷材料是制作氧传感器、固体氧化物燃料电池及高温湿度传感器等多种功能元器件的核心原材料。采用可程序化控制的MARS-5微波消解仪实现了微波水热合成,反应温度100~120℃,反应时间1~5h,在强碱环境下制备氧化钇稳定氧化锆纳米粉体,而常规水热法制备氧化锆的温度一般为190~250℃。采用X射线衍射、热分析等方法,研究了温度、时间、pH和Y2O3含量对产物粒度和晶型的影响,使用了Rietveld方法进行定量分析、粒度计算。结果显示,与常规水热法相比,微波水热法不仅缩短了反应时间,并且影响产物的结构组成。分析表明,微波加速反应的机理可以用晶粒旋转驱动的晶粒聚合解释,而微波的介电加热效应,微波离子传导损耗等是加速化学反应的主要原因。     

Confined Transformation of UiO‐66 Nanocrystals to Yttria‐Stabilized Zirconia with Hierarchical Pore Structures for Catalytic Applications

Solid acids as a substitution for hazardous liquid acids (e.g., HF and H₂SO₄) can promote many important reactions in the industry, such as carbon cracking, to proceed in a more sustainable way. Starting from a zirconium‐based metal‐organic framework (UiO‐66 nanocrystals), herein a transformative method is reported to prepare micro/mesoporous yttria‐stabilized zirconia (YSZ) encapsulated inside a mesoporous silica shell. It is then further demonstrated that the resultant reactor‐like catalysts can be used for a wide range of catalytic reactions. The acidity of the YSZ phase is found with rich accessible Lewis acid and Brønsted acid sites and they display superior performances for esterification (acetic acid and ethanol) and Friedel‐Crafts alkylation (benzylation of toluene). After being loaded with different noble metals, furthermore, hydrogenation of CO₂ and a one‐pot cascade reaction (nitrobenzene and benzaldehyde to N‐benzylaniline) are used as model reactions to prove the versatility and stability of catalysts. Based on the findings of this work, it is believed that this class of reactor‐like catalysts can meet future challenges in the development of new catalyst technology for greener heterogeneous catalysis.     

Crystallization and Microstructure of Yttria‐Stabilized‐Zirconia Thin Films Deposited by Spray Pyrolysis

The crystallization and microstuctural evolution upon thermal treatment of yttria‐stabilized zirconia (YSZ, Zr_0.85Y_0.15O_1‐δ) thin films deposited by spray pyrolysis at 370 °C are investigated. The as‐deposited YSZ films are mainly amorphous with a few crystallites of 3 nm in diameter and crystallize in the temperature range from 400 °C to 900 °C. Fully crystalline YSZ thin films are obtained after heating to 900 °C or by isothermal dwells for at least 17 h at a temperature as low as 600 °C. Three exothermic heat releasing processes with activation energies are assigned to the crystallization and the oxidation of residuals from the precursor. Microporosity develops during crystallization and mass loss. During crystallization the microstrain decreases from 4% to less than 1%. Simultaneously, the average grain size increases from 3 nm to 10 nm. The tetragonal phase content of the YSZ thin film increases with increasing temperature and isothermal dwell time. Based on these data, gentle processing conditions can be designed for zirconia based thin films, which meet the requirements for Si‐based microfabrication of miniaturized electrochemical devices such as micro‐solid oxide fuel cells or sensors.     

High‐Temperature Performance of Alumina–Zirconia Composite Coatings Containing Amorphous Phases

Amorphous phases are commonly found in nanostructured plasma‐sprayed coatings. Nonetheless, the role of these phases in the resulting coatings’ properties has remained uninvestigated until now. In the present work, pseudo‐eutectic coatings—based on alumina and 8 wt% yttria‐stabilized zirconia (YSZ)—containing amorphous phases are produced using a suspension‐plasma‐spray process. These composite materials are a potential choice for thermal‐barrier coating applications. The role of the amorphous phase on the performance of the coatings is investigated before and after heat treatment. Results show that, although the amorphous phases in untreated coatings reduce the thermal conductivity, they impair the mechanical properties. However, treatment above the crystallization temperature leads to better mechanical properties as well as enhanced high‐temperature stability of the resulting nanostructure. Moreover, the role of alumina as a stabilizer of high‐temperature YSZ phases (tetragonal and cubic) is confirmed and the high‐temperature phase stability of the alumina–YSZ composite is demonstrated. The amorphous phases are found to crystallize into their corresponding high‐temperature stable phases; i. e., α‐alumina and tetragonal zirconia.     

Adopting the Principles of Collagen Biomineralization for Intrafibrillar Infiltration of Yttria‐Stabilized Zirconia into Three‐Dimensional Collagen Scaffolds

In this paper, a process for generating collagen‐yttria‐stabilized amorphous zirconia hybrid scaffolds by introducing acetylacetone‐inhibited zirconia precursor nanodroplets into a poly(allylamine)‐coated collagen matrix is reported. This polyelectrolyte coating triggers intrafibrillar condensation of the precursors into amorphous zirconia, which is subsequently transformed into yttria‐stabilized zirconia after calcination. These findings represent a new paradigm in the synthesis of non‐naturally occurring collagen‐based hybrid scaffolds under alcoholic mineralizing conditions.     

Surface‐Modified Low‐Temperature Solid Oxide Fuel Cell

This paper reports both experimental and theoretical results of the role of surface modification on the oxygen reduction reaction in low‐temperature solid oxide fuel cells (LT‐SOFC). Epitaxial ultrathin films of yttria‐doped ceria (YDC) cathode interlayers (<10–130 nm) are grown by pulsed laser deposition (PLD) on single‐crystalline YSZ(100). Fuel cell current–voltage measurements and electrochemical impedance spectroscopy are performed in the temperature range of 350 °C ≈ 450 °C. Quantum mechanical simulations of oxygen incorporation energetics support the experimental results and indicate a low activation energy of only 0.07 eV for YDC, while the incorporation reaction on YSZ is activated by a significantly higher energy barrier of 0.38 eV. Due to enhanced oxygen incorporation at the modified Pt/YDC interface, the cathodic interface resistance is reduced by two‐fold, while fuel cell performance shows more than a two‐fold enhancement with the addition of an ultrathin YDC interlayer at the cathode side of an SOFC element. The results of this study open up opportunities for improving cell performance, particularly of LT‐SOFCs by adopting surface modification of YSZ surface with catalytically superior, ultrathin cathodic interlayers.     

Controllable Ceramic Green‐Body Configuration for Complex Ceramic Architectures with Fine Features

Fabrication of dense ceramic articles with intricate fine features and geometrically complex morphology by using a relatively simple and the cost‐effective process still remains a challenge. Ceramics, either in its green‐ or sintered‐form, are known for being hard yet brittle which limits further shape reconfiguration. In this work, a combinatorial process of ceramic robocasting and photopolymerization is demonstrated to produce either flexible and/or stretchable ceramic green‐body (Flex‐Body or Stretch‐Body) that can undergo a postprinting reconfiguration process. Secondary shaping may proceed through: i) self‐assembly‐assisted shaping and ii) mold‐assisted shaping process, which allows a well‐controlled ceramic structure morphology. With a proposed well‐controlled thermal heating process, the ceramic Sintered‐Body can achieve >99.0% theoretical density with good mechanical rigidity. Complex and dense ceramic articles with fine features down to 65 μm can be fabricated. When combined with a multi‐nozzle deposition process, i) self‐shaping ceramic structures can be realized through anisotropic shrinkage induced by suspensions' composition variation and ii) technical and functional multiceramic structures can be fabricated. The simplicity of the proposed technique and its inexpensive processing cost make it an attractive approach for fabricating geometrically complex ceramic articles with unique macrostructures, which complements the existing state of‐the‐art ceramic additive manufacturing techniques.     

Mechanism of Low‐Temperature Protonic Conductivity in Bulk,High‐Density,Nanometric Titanium Oxide

Uncovering the mechanism of low‐temperature protonic conduction in highly dense nanostructured metal oxides opens the possibility to exploit the application of simple ceramic electrolytes in proton exchange fuel cells, overcoming the drawbacks related to the use of polymeric membranes. High proton conducting, highly dense (relative density 94 vol%) TiO₂ samples are prepared by a fast pressure‐assisted sintering method, which allows leaving behind an interconnected network of open nanoporosity. Solid‐state ¹H NMR is used to characterize the presence of strongly associated water confined in the nanopores and hydroxyl moieties bonded to the pores walls, providing a model to explain the unusually high protonic conductivity. At the lowest temperatures (T < 55 °C) protons hop between confined water molecules, according to a Grotthuss mechanism. The resulting conductivity values are however much higher than those of liquid water, indicating a significant increase in the charge carriers concentration. At higher temperatures (up to 450 °C) unexpected proton conduction is still present, thanks to the persistence of hydroxyl groups, derived from water chemisorption, which still produce protons by ionization. The phenomenon is strongly dependent on grain size, and not explicable by simple geometric brick‐layer models, suggesting that the enhanced ionization could rely on space charge region effects.     

An Offset‐Compensated LVDS Receiver with Low‐Temperature Poly‐Si Thin Film Transistor

The poly‐Si thin film transistor (TFT) shows large variations in its characteristics due to the grain boundary of poly‐crystalline silicon. This results in unacceptably large input offset of low‐voltage differential signaling (LVDS) receivers. To cancel the large input offset of poly‐Si TFT LVDS receivers, a full‐digital offset compensation scheme has been developed and verified to be able to keep the input offset under 15 mV which is sufficiently small for LVDS signal receiving.     

Assessment of Novel Long‐Lasting Ceria‐Stabilized Zirconia‐Based Ceramics with Different Surface Topographies as Implant Materials

The development of long‐lasting zirconia‐based ceramics for implants, which are not prone to hydrothermal aging, is not satisfactorily solved. Therefore, this study is conceived as an overall evaluation screening of novel ceria‐stabilized zirconia–alumina–aluminate composite ceramics (ZA₈Sr₈‐Ce11) with different surface topographies for use in clinical applications. Ceria‐stabilized zirconia is chosen as the matrix for the composite material, due to its lower susceptibility to aging than yttria‐stabilized zirconia (3Y‐TZP). This assessment is carried out on three preclinical investigation levels, indicating an overall biocompatibility of ceria‐stabilized zirconia‐based ceramics, both in vitro and in vivo. Long‐term attachment and mineralized extracellular matrix (ECM) deposition of primary osteoblasts are the most distinct on porous ZA₈Sr₈‐Ce11_p surfaces, while ECM attachment on 3Y‐TZP and ZA₈Sr₈‐Ce11 with compact surface texture is poor. In this regard, the animal study confirms the porous ZA₈Sr₈‐Ce11_p to be the most favorable material, showing the highest bone‐to‐implant contact values and implant stability post implantation in comparison with control groups. Moreover, the microbiological evaluation reveals no favoritism of biofilm formation on the porous ZA₈Sr₈‐Ce11_p when compared to a smooth control surface. Hence, together with the in vitro in vivo assessment analogy, the promising clinical potential of this novel ZA₈Sr₈‐Ce11 as an implant material is demonstrated.     

Bowtie‐Shaped NiCo2O4 Catalysts for Low‐Temperature Methane Combustion

Bowtie‐shaped NiCo₂O₄ nanostructures are prepared using a hydrothermal method. Variation of the synthesis parameters, including reaction time, additives, and calcination temperature, allows an understanding of the origin of the bowtie‐shaped structure to be developed. Methane oxidation experiments performed using temperature‐programed oxidation (TPO) show that the new materials, which do not contain precious metals, have excellent activity for low‐temperature methane combustion, with 100% conversion at ≈410 °C (gas hourly space velocity (GHSV): 90 000 mL (STP) g^?1 h^?1). The structure–activity relationships of the bowtie‐shaped nanostructures are explored.     

Low‐Temperature,Nontoxic Water‐Induced Metal‐Oxide Thin Films and Their Application in Thin‐Film Transistors

Here, a simple, nontoxic, and inexpensive “water‐inducement” technique for the fabrication of oxide thin films at low annealing temperatures is reported. For water‐induced (WI) precursor solution, the solvent is composed of water without additional organic additives and catalysts. The thermogravimetric analysis indicates that the annealing temperature can be lowered by prolonging the annealing time. A systematic study is carried out to reveal the annealing condition dependence on the performance of the thin‐film transistors (TFTs). The WI indium‐zinc oxide (IZO) TFT integrated on SiO₂ dielectric, annealed at 300 °C for 2 h, exhibits a saturation mobility of 3.35 cm² V^?1 s^?1 and an on‐to‐off current ratio of ≈10⁸. Interestingly, through prolonging the annealing time to 4 h, the electrical parameters of IZO TFTs annealed at 230 °C are comparable with the TFTs annealed at 300 °C. Finally, fully WI IZO TFT based on YO_x dielectric is integrated and investigated. This TFT device can be regarded as “green electronics” in a true sense, because no organic‐related additives are used during the whole device fabrication process. The as‐fabricated IZO/YO_x TFT exhibits excellent electron transport characteristics with low operating voltage (≈1.5 V), small subthreshold swing voltage of 65 mV dec^?1 and the mobility in excess of 25 cm² V^?1 s^?1.     

Temperature Performance of Doping‐Free Top‐Gate CNT Field‐Effect Transistors: Potential for Low‐ and High‐Temperature Electronics

High‐performance top‐gate carbon nanotube (CNT) field‐effect transistors (FETs) have been fabricated via a doping‐free fabrication process in which the polarity of the CNT FET is controlled by the injection of carriers from the electrodes, instead of using dopants. The performance of the doping‐free CNT FETs is systemically investigated over a wide temperature range, from very low temperatures of down to 4.3 K up to 573 K, and analyzed using several temperature‐dependent key device parameters including the ON/OFF state current and ratio, carrier mobility, and subthreshold swing. It is demonstrated that for ballistic and quasi‐ballistic CNT FETs, the operation of the CNT FETs is largely independent of the presence of dopant, thus avoiding detrimental effects due to dopant freeze‐out at low temperature and dopant diffusion at high temperature, and making it possible to use doping‐free CNT FETs in both low‐ and high‐temperature electronics. A new method is also proposed for extracting the band‐gap and diameter of a semiconducting CNT from the temperature dependent OFF‐state current and shown to yield results that are consistent with AFM measurements.     

Low‐Temperature Growth of SiO2 Films by Plasma‐Enhanced Atomic Layer Deposition

Silicon dioxide (SiO₂) films prepared by plasma‐enhanced atomic‐layer deposition were successfully grown at temperatures of 100 to 250 °C, showing self‐limiting characteristics. The growth rate decreases with an increasing deposition temperature. The relative dielectric constants of SiO₂ films are ranged from 4.5 to 7.7 with the decrease of growth temperature. A SiO₂ film grown at 250 °C exhibits a much lower leakage current than that grown at 100°C due to its high film density and the fact that it contains deeper electron traps.     

Room‐Temperature Metallic Fusion‐Induced Layer‐by‐Layer Assembly for Highly Flexible Electrode Applications

To fabricate flexible electrodes, conventional silver (Ag) nanomaterials have been deposited onto flexible substrates, but the formed electrodes display limited electrical conductivity due to residual bulky organic ligands, and thus postsintering processes are required to improve the electrical conductivity. Herein, an entirely different approach is introduced to produce highly flexible electrodes with bulk metal–like electrical conductivity: the room‐temperature metallic fusion of multilayered silver nanoparticles (NPs). Synthesized tetraoctylammonium thiosulfate (TOAS)‐stabilized Ag NPs are deposited onto flexible substrates by layer‐by‐layer assembly involving a perfect ligand‐exchange reaction between bulky TOAS ligands and small tris(2‐aminoethyl)amine linkers. The introduced small linkers substantially reduce the separation distance between neighboring Ag NPs. This shortened interparticle distance, combined with the low cohesive energy of Ag NPs, strongly induces metallic fusion between the close‐packed Ag NPs at room temperature without additional treatments, resulting in a high electrical conductivity of ≈1.60 × 10⁵ S cm^?1 (bulk Ag: ≈6.30 × 10⁵ S cm^?1). Furthermore, depositing the TOAS–Ag NPs onto cellulose papers through this approach can convert the insulating substrates into highly flexible and conductive papers that can be used as 3D current collectors for energy‐storage devices.     

A Facile Solution‐Doping Method to Improve a Low‐Temperature Zinc Oxide Precursor: Towards Low‐Cost Electronics on Plastic Foil

Optimization of thin‐film transistors performance is usually accompanied by an increase of the process temperature. This work presents a method to raise the field effect mobility by a factor of 3 without a change of the process parameters. The modification involves a solution doping process where an ammine zinc complex is formed in the presence of metal ions of the 13^th group, namely gallium and indium. Morphological studies, including scanning electron microscopy and atomic force microscopy, reveal the difference among the resulting films. Moreover, X‐ray diffraction results show that the doping affects the preferred orientation of the zinc oxide crystals in the resulting film. The electrical properties vary distinctly and are best for a solution doped with both gallium and indium. With a double‐layer system the performance of this new precursor exceeds field effect mobility values of 1 cm² V^?1 s^?1 after a maximum process temperature of 160 °C.