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??? 金屬納米晶粒是制備光電子器件的重要原料。但金屬納米晶?；钚愿?、極易被氧化，制備過(guò)程往往需要溶液、真空或惰性氣氛保護(hù)，因此制造工藝復(fù)雜，難以大規(guī)模應(yīng)用。武漢大學(xué)化學(xué)與分子科學(xué)學(xué)院鄧鶴翔教授與工業(yè)科學(xué)研究院程佳瑞教授團(tuán)隊(duì)合作，采用金屬有機(jī)框架材料作為原料，利用激光成功的制備了顆粒大小均一的金屬納米晶粒。通過(guò)程序控制激光的開(kāi)閉和光斑的移動(dòng)實(shí)現(xiàn)了圖案的制備，僅數(shù)十秒即可打印出由金屬納米晶粒構(gòu)成的晶圓級(jí)別大小的芯片，整個(gè)過(guò)程完全在空氣中進(jìn)行，所需激光功率不到5瓦（圖一），非常適合規(guī)?；a(chǎn)。

金屬有機(jī)框架材料（Metal-organic Framework, MOF）由金屬與含碳有機(jī)配體構(gòu)筑。目前大部分研究集中在MOF中有機(jī)成分上，而結(jié)構(gòu)中豐富的金屬離子尚未充分利用。此項(xiàng)工作提出了激光納米金屬冶煉及圖案化方法（Nanoscale Laser Metallurgy and Patterning, 簡(jiǎn)稱nano-LaMP），以MOF為原料的實(shí)現(xiàn)了空氣環(huán)境下的金屬納米顆粒制備和同步圖案打印。在反應(yīng)過(guò)程中， MOF晶體內(nèi)有序排列的金屬離子和有機(jī)配體分別作為金屬源和還原劑。納秒脈沖激光器則負(fù)責(zé)將能量精準(zhǔn)地投送到指定位置，為金屬還原提供能量。MOF晶體高效吸收激光后產(chǎn)生局域高溫，金屬離子被迅速還原并從MOF豐富的孔道中噴射出來(lái)，在基底上沉積并迅速冷卻形成金屬納米晶粒。nano-LaMP方法展現(xiàn)出較好的普適性，能夠基于含有不同金屬離子的MOF晶體制備出鐵，鈷，鎳，銅，鋅，鎘，銦，鉛和鉍九種金屬納米晶粒及其圖案。其中，基于銅納米晶粒的表面增強(qiáng)拉曼效應(yīng)芯片在對(duì)多種生物分子的檢測(cè)中提供極低的檢測(cè)限（10^-12 M）。

nano-LaMP結(jié)合了激光和MOF材料的優(yōu)點(diǎn)，為芯片制造提供了節(jié)能，環(huán)保，快速以及靈活的新方法。該工作在美國(guó)化學(xué)會(huì)志(Journal of the American Chemical Society，JACS)上發(fā)表，論文題目為“Nanoscale Laser Metallurgy and Patterning in Air Using MOFs”，并被選中為雜志封面。江浩慶博士后為該論文的第一作者。該工作獲得了國(guó)家自然科學(xué)基金，國(guó)家重點(diǎn)研發(fā)計(jì)劃，和武漢大學(xué)創(chuàng)新團(tuán)隊(duì)項(xiàng)目的資助，以及上海光源（SSRF），武漢大學(xué)大型儀器共享平臺(tái)以及武漢大學(xué)測(cè)試中心的支持。課題組網(wǎng)站：http://hdeng.whu.edu.cn/。

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圖一：激光照射金屬有機(jī)框架材料（MOF）產(chǎn)生金屬納米晶粒及芯片打印

English Version：

Fast printing of nano-devices by laser metallurgy of MOF

Metal nanoparticles (MNPs) are critical ingredient for the fabrication of devices on nanoscale. However, solvent, vacuum or inert atmosphere are usually used for the preparation of MNPs, due to their sensitivity to oxygen in air, which limit their application in large scale. A team led by Hexiang Deng in College of Chemistry and Molecular Sciences and Gary J. Cheng in the Institute of Technological Sciences, both from Wuhan University, reported a new method for the production of uniform metal nanoparticles in air using metal-organic frameworks (MOFs) as precursor with laser as the energy source. This method, named as Nanoscale Laser Metallurgy and Patterning (nano-LaMP), allows for the printing of MNP patterns in wafer-scale size within tens of seconds, consuming only 5-Watt power (Figure 1), ideally suited for large scale fabrication.

MOFs are constructed by orderly spaced metal ions and carbonaceous linkers. The metal ions in the structure remain underdeveloped, albeit extensive research on the organic component. In this study, the orderly spaced metal ions and organic linkers in MOF function as metal source and reductant, respectively. The nanosecond pulsed laser precisely deliver patches of energy to MOF crystals. High temperature was generated instantly at local position due to the efficient light absorption by MOFs, where metal ions were reduced and sputtered out from the porous structure, followed by condensed as metal nanoparticles. Nanoparticles of nine different metals, Fe, Co, Ni, Cu, Zn, Cd, In, Pb and Bi, and patterns were successfully produced from the corresponding MOF crystals by nano-LaMP. Surface enhanced Raman scattering (SERS) chips constructed by Cu nanoparticle patterns on glass using this method exhibited exceptionally low detection limit (10^-12 M) for biomolecules.

The nano-LaMP method combines the advantages of laser and MOFs, offering new choice for the fabrication of nano-devices in a fast, economic, efficient and flexible manner. This work, with the title “Nanoscale Laser Metallurgy and Patterning in Air Using MOFs”, was recently published on the Journal of the American Chemical Society and selected as one of the cover story, with Haoqing Jiang being the first author. This research supported by National Key R&D Program of China), Natural Science Foundation of China and the Innovation Team of Wuhan University. Shanghai Synchrotron Radiation Facility (SSRF), the Sharing Platform for Large-scale Instruments and the Test Center of Wuhan University provide help in material characterizations.

Article link：https://pubs.acs.org.ccindex.cn/doi/10.1021/jacs.9b00355

Group website：http://hdeng.whu.edu.cn/

通訊員：江浩慶?? 日期：2019年4月1日