Emerging Non-Noble-Metal Atomic Layer Deposited Copper as Seeds for Electroless Copper Deposition.

Copper metal catalyst seeds have recently triggered much research interest for the development of low-cost and high-performance metallic catalysts with industrial applications. Herein, we present metallic Cu catalyst seeds deposited by an atomic layer deposition method on polymer substrates. The atomic layer deposited Cu (ALD-Cu) can ideally substitute noble metals Ag, Au, and Pd to catalyze Cu electroless deposition. The optimized deposition temperature and growth cycles of an ALD-Cu catalyzed seed layer have been obtained to achieve a flexible printed circuit (FPC) with a high performance electroless plating deposited Cu (ELD-Cu) film. The ELD-Cu films on the ALD-Cu catalyst seeds grown display a uniform and dense deposition with a low resistivity of 1.74 µΩ·cm, even in the through via and trench of substates. Furthermore, the ALD-Cu-catalyzed ELD-Cu circuits and LED devices fabricated on treated PI also demonstrate excellent conductive and mechanical features. The remarkable conductive and mechanical characteristics of the ALD-Cu seed catalyzed ELD-Cu process demonstrate its tremendous potential in high-density integrated FPC applications.

Homogeneous and Nanogranular Prussian Blue to Enable Long-Term-Stable Electrochromic Devices.

The increasing demand for the state-of-the-art electrochromic devices has received great interest in synthesizing Prussian blue (PB) nanoparticles with a uniform diameter that exhibit excellent electrochromism, electrochemistry, and cyclability. Herein, we report the controllable synthesis of sub-100 nm PB nanoparticles via the coprecipitation method. The diameter of PB nanoparticles can be modulated by adjusting the reactant concentration, the selection of a chelator, and their purification. The self-assembled nanogranular thin films, homogeneously fabricated by using optimized PB nanoparticles with an average diameter of 50 nm as building blocks via the blade coating technique enable excellent performance with a large optical modulation of 80% and a high coloration efficiency of 417.79 cm2 C-1. It is also demonstrated by in situ and ex situ observations that the nanogranular PB thin films possess outstanding structural and electrochemical reversibility. Furthermore, such nanogranular PB thin films can enjoy the enhanced long-term cycling stability of the PB-WO3 complementary electrochromic devices having a 91.4% optical contrast retention after 16,000 consecutive cycles. This work provides a newly and industrially compatible approach to producing a complementary electrochromic device with extraordinary durability for various practical applications.

Improved Electrical Resistivity of Atomic-Layer-Deposited Copper Thin Films on Polyimide Substrates by an In Situ ZnO Interlayer.

The low-temperature atomic layer deposition of metal on polymer surfaces is often challenging owing to the deficiency of functional groups and reactivity. Here, the deposition of ALD-Cu employing Cu(hfac)2 and Et2Zn at a low temperature (120 °C) on polyimide (PI) substrates is improved by the utilization of an in situ ultrathin ALD-ZnO buffer layer. A conformal and continuous ALD-Cu thin film with low resistivity (6.07 µΩ cm) is fabricated on an ALD-ZnO/PI substrate. The findings demonstrate that the ALD-ZnO buffer layer provides chemisorption and a nucleation site for the initial growth of ALD-Cu. Transmission electron microscopy and energy-dispersive X-ray analysis reveal that the ALD-ZnO layer plays a buffer role in the fitness of ALD-Cu on PI substrates and its ability to elicit the formation of an ALD-ZnO nanocluster and polar surface. ALD-ZnO can be effectively utilized as a buffer layer for polymer-based ALD-metal processes, showing potential in flexible electronic applications.

Apoptosis related genes mediated molecular subtypes depict the hallmarks of the tumor microenvironment and guide immunotherapy in bladder cancer.

Apoptosis has been discovered as a mechanism of cell death. The purpose of this study is to identify the diagnostic signature factors related to bladder cancer (BLCA) through apoptosis related genes (ARGs). Clinicopathological parameters and transcriptomics data of 1,440 BLCA patients were obtained from 7 datasets (GSE13507, GSE31684, GSE32548, GSE32894, GSE48075, TCGA-BLCA, and IMvigor210). We first identified prognosis-related ARGs in BLCA and used them to construct two ARGs molecular subtypes by using consensus clustering algorithm. By using principal component analysis algorithms, a ARGscore was constructed to quantify the index of individualized patient. High ARGscore correlated with progressive malignancy and poor outcomes in BLCA patients. High ARGscore was associated with higher immune cell, higher estimate scores, higher stromal scores, higher immune scores, higher immune checkpoint, and lower tumor purity, which was consistent with the "immunity tidal model theory". Preclinically, BLCA immunotherapy cohorts confirmed patients with low ARGscore demonstrated significant therapeutic advantages and clinical benefits. These findings contribute to our understanding of ARGs and immunotherapy in BLCA. The ARGscore is a potentially useful tool to predict the prognosis and immunotherapy in BLCA.

Optimization of Low-Cost Ti-35421 Titanium Alloy: Phase Transformation, Bimodal Microstructure, and Combinatorial Mechanical Properties.

A sophisticated understanding of phase transformations and microstructure evolution is crucial in mechanical property optimization for the newly developed low-cost Ti-35421 (Ti-3Al-5Mo-4Cr-2Zr-1Fe wt.%) titanium alloy. The phase transformations in dual-phase Ti-35421 were studied by experiments and thermo-kinetic modeling. The phase transformation reactions and temperature ranges were determined as ß→αlamellar [410-660 °C], αlamellarâ†’ß [660-740 °C], αlathâ†’ß [740-825 °C]. The Gibbs-Thomson effect and multicomponent diffusivities were proven to be responsible for the distinguishing behaviors of growth and dissolution between two α phases. The aging temperature of 540 °C was optimized based on calculations. It introduced a bimodal microstructure containing stubby α lamellae and ß matrix. The mechanical properties of bimodal Ti-35421 were tested and compared with baseline alloy Ti-B19 and other near-ß titanium alloys. The 540 °C aged alloy exhibits an optimal combination of mechanical properties with tensile strength of 1313 MPa, yield strength of 1240 MPa, elongation of 8.62%, and fracture toughness of 75.8 MPa·m1/2. The bimodal Ti-35421 shows comparable performance to Ti-B19 but has lower cost in raw materials and processing. The results also demonstrate that thermo-kinetic modeling can effectively be utilized in tailoring microstructure and enhancing mechanical properties.

Diffusivities and Atomic Mobilities in bcc Ti-Mo-Zr Alloys.

ß-type (with bcc structure) titanium alloys have been widely used as artificial implants in the medical field due to their favorable properties. Among them, Ti-Mo alloy attracted numerous interests as metallic biomaterials. Understanding of kinetic characteristics of Ti alloys is critical to understand and manipulate the phase transformation and microstructure evolution during homogenization and precipitation. In this work, diffusion couple technique was employed to investigate the diffusion behaviors in bcc Ti-Mo-Zr alloys. The diffusion couples were prepared and annealed at 1373 K for 72 h and 1473 K for 48 h, respectively. The composition-distance profiles were obtained via electron probe micro-analysis (EPMA). The chemical diffusion coefficients and impurity diffusion coefficients were extracted via the Whittle-Green method and Hall method. The obtained diffusion coefficients were assessed to develop a self-consistent atomic mobility database of bcc phase in Ti-Mo-Zr system. The calculated diffusion coefficients were compared with the experimental results. They showed good agreement. Simulations were implemented by Dictra Module in Thermo-Calc software. The predicted composition-distance profiles, inter-diffusion flux, and diffusion paths are consistent with experimental data, confirming the accuracy of the database.

The formation mechanism of eutectic microstructures in NiAl-Cr composites.

NiAl-based eutectic alloys, consisting of an ordered bcc matrix (B2) and disordered bcc fibers (A2), have been a subject of intensive efforts aimed at tailoring the properties of many of the currently used nickel-based superalloys. A thermodynamic phase field model was developed on a thermodynamic foundation and fully integrated with a thermo-kinetic database of the Ni-Al-Cr ternary system to elucidate the resulting peculiar eutectic microstructure. Invoking a variation of the liquid/solid interfacial thickness with temperature, we simulated the characteristic sunflower-like eutectic microstructures in the NiAl-Cr composites, consistent with experimental observations. The mechanism that governs the formation of the peculiar eutectic morphology was envisioned from the modeled evolutions associated with six sequential steps. Our calculations show that the conditional spinodal decomposition occurring in sequence could further trim and revise the microstructure of the eutectics by generating fine-domain structures, thereby providing an additional method to explore the novel NiAl-based eutectic composites with tunable properties at elevated temperatures.