The authors acknowledge the support of the Cambridge Overseas and Commonwealth Trust, the Rutherford Foundation of New Zealand, Girton College Cambridge. This work has been funded by ERC Advanced Investigator Grant, Novox, ERC-2009-adG247276 and by the EPSRC (under RGS3717).

1.氧化亚铜预处理。 <ol><li> 铜箔的氧化 <ol><li>切0.127毫米厚铜箔到13毫米×13平方毫米和清洁，丙酮超声处理。 </li><li>升温铜箔至1000℃，同时连续通过炉子流入Ar气。监测在整个氧化的气体分析器炉内的气体气氛。当达到1000℃的温度下，引入氧气到炉中，在一个流率以得到10,000ppm的氧气分压，并保持该至少2小时。 2小时后，关闭氧气，但保留氩气的流动。 </li><li>冷却炉至500℃（保持Ar气体流动）。通过从炉中的坩埚的迅速撤离淬灭氧化样品。浸基板去离子水中更快地冷却它们。 </li></ol></li><li> 铜2 O的蚀刻 <ol><li>通过反复施加蚀刻基片的一侧的稀硝酸滴（1:H 2 O和70％的HNO 3 1:1混合物），以从表面除去任何氧化铜。继续蚀刻直到没有灰膜是在Cu 2 O表面上是可见的。注意:此过程在一个通风柜进行。 </li><li>蚀刻后立即冲洗用去离子水各基板和异丙醇超声处理。干燥用空气枪。 </li><li>存款80纳米的黄金到铜2 O基板蚀刻的一侧通过蒸发1g的金颗粒置于钨舟的电阻蒸发器内部。使用基础压力8×10 -6毫巴和4所述的电流达到0.8埃/秒的蒸发速率。 </li><li>通过施加酸一滴到表面蚀刻在稀硝酸基板的另一侧。确保酸不蚀刻在另一侧的金膜。如第1.2.2描述冲洗，超声。 </li><li>封面用黑色绝缘漆底物（使用高温Ëngine搪瓷）使用油漆刷，留下大约为0.1 cm 2的作为太阳能电池的有源区的未掩蔽区域。覆盖上用记号笔完全背面的金电极。 </li></ol></li></ol> 2.存入锌1-X镁×○使用AP-SALD反应堆注意:存款锌1-X镁X在铜的一面暴露无遗2 O基板13在这项工作中，使用了定制的AP-SALD反应器，改编自柯达开发的原始设计O透明导电膜11,12详情在反应器的定制在参考文献中给出。 12。 <ol><li>设置对AP-SALD系统如下: <ol><li>使用二乙基锌（DEZ）作为锌前体和二（乙基环戊二烯基）镁作为镁前体。这些都是在各自的玻璃起泡每个包含液体前体。前体是自燃的，应该永远不会与空气或水接触。沉积系统是气密。 </li><li>氧化锌沉积，通过二乙基锌到25毫升/分钟，载在RT（20℃）调整氮气的鼓泡速率。锌氧化镁沉积，通过经由二乙基锌通过双（乙基环戊二烯基）镁（其被加热到55℃）6-毫升/分钟和200毫升/分钟设定鼓泡速率调整每个前体的气体馏分以控制到锌与Mg的比例在锌1-X镁点¯xO. </li><li>设置氮气载气的流速为金属前体混合物到100毫升/分钟。在通过去离子水，其中使用作为氧化剂为100ml /分钟气泡氮气。此蒸汽与氮气载气以200ml /分流动稀释。 </li><li>在500毫升/分钟到气体歧管流动氮气。在AP-SALD气体歧管，该氮气被分割至四个独立的通道。每个通道用于在空间上两个氧化剂通道从它们之间的金属前驱物混合通道中分离出来。 </li></o升&gt; </li><li>保持气体歧管在通过循环水的40℃的温度。升温阶段（移动压板），以期望的温度（50 - 150℃）。 </li><li>设置所需的样品与头部的距离，样本大小，压板速度（50毫米/秒），并振荡数（周期）与软件控制压板。该ZnO蒸镀速率为1.1纳米/秒（或每个周期）及锌1-X镁×○淀积速率是在150℃下大约0.54纳米/秒。沉积循环的典型数量是200。 </li><li>沉积在400振荡或直到一个明确的厚的均质薄膜可以看出载玻片所需的氧化物。 </li><li>放置在玻璃掩模基板，如果需要，然后将其放置在气歧管下。头部（气歧管）的高度调整至50μm的衬底的上方。 </li><li>存款锌1-X镁×○首先打开阀门的镁前体起泡，那么锌前体起泡片，然后开始MOVI通过点击在软件"开始沉积"纳克的气体歧管下压板上。只为了避免氧化亚铜表面接触而加热的氧化剂与金属前体5振荡扫描衬底之后打开轰2 O鼓泡器。 </li><li>当沉积完成时，从加热压板尽快除去所述Cu 2 O基板和关闭金属前体的起泡器阀门。清洗在歧管中的气体流路用刀片以除去任何沉积的氧化物粉末。如在2.6节开始下一个沉积周期。 </li><li>完成后，清洗系统30分钟关闭阀门氮之前。 </li></ol> 3. ITO溅射<ol><li>通过直流磁控管在下列条件下溅射20溅射氧化铟锡（ITO）的175纳米:功率20瓦，基础压力&lt;10 -9毫巴中，Ar压力为2.5帕在为35nm的溅射速率/分，溅射ITØ5分钟的175纳米厚的ITO膜。所得ITO /氧化锌/铜2 O异质结示于图3。 </li></ol> 4.整理设备的<ol><li>清洗从用丙酮金电极的标记笔，以暴露金电极。 </li><li>通过坚持2 Ag膏细线到ITO和Au电极应用电子触点。 </li></ol>

<ol>
	<li>Meyer, B. K., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Binary+copper+oxide+semiconductors:+From+materials+towards+devices.">Binary copper oxide semiconductors: From materials towards devices.</a> Phys. Status Solidi (B). 249 (8), 1487-1509 (2012).</li><li>Mittiga, A., Salza, E., Sarto, F., Tucci, M., Vasanthi, R. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Heterojunction+solar+cell+with+2%+efficiency+based+on+a+Cu2O+substrate.">Heterojunction solar cell with 2% efficiency based on a Cu2O substrate.</a> Appl. Phys. Lett. 88 (16), 163502 (2006).</li><li>Minami, T., Miyata, T., Nishi, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Cu2O-based+heterojunction+solar+cells+with+an+Al-doped+ZnO/oxide+semiconductor/thermally+oxidized+Cu2O+sheet+structure.">Cu2O-based heterojunction solar cells with an Al-doped ZnO/oxide semiconductor/thermally oxidized Cu2O sheet structure.</a> Solar Energy. 105, 206-217 (2014).</li><li>Duan, Z., Du Pasquier, A., Lu, Y., Xu, Y., Garfunkel, E. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Effects+of+Mg+composition+on+open+circuit+voltage+of+Cu2O-MgxZn1&#8722;xO+heterojunction+solar+cells.">Effects of Mg composition on open circuit voltage of Cu2O-MgxZn1&#8722;xO heterojunction solar cells.</a> Sol. Energ. Mat. Sol. C. 96, 1-6 (2011).</li><li>Minami, T., Nishi, Y., Miyata, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=High-efficiency+Cu2O-based+heterojunction+solar+cells+fabricated+using+a+Ga2O3+thin+film+as+n-type+layer.">High-efficiency Cu2O-based heterojunction solar cells fabricated using a Ga2O3 thin film as n-type layer.</a> Appl. Phys. Express. 6 (4), 044101 (2013).</li><li>Lee, Y. S., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Atomic+layer+deposited+gallium+oxide+buffer+layer+enables+1.2+v+open-circuit+voltage+in+cuprous+oxide+solar+cells.">Atomic layer deposited gallium oxide buffer layer enables 1.2 v open-circuit voltage in cuprous oxide solar cells.</a> Adv. Mater. 26 (27), 4704-4710 (2014).</li><li>Pavan, M., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=TiO2/Cu2O+all-oxide+heterojunction+solar+cells+produced+by+spray+pyrolysis.">TiO2/Cu2O all-oxide heterojunction solar cells produced by spray pyrolysis.</a> Sol. Energ. Mat. Sol. C. 132, 549-556 (2015).</li><li>Ievskaya, Y., Hoye, R. L. Z., Sadhanala, A., Musselman, K. P., MacManus-Driscoll, J. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Fabrication+of+ZnO/Cu2O+heterojunctions+in+atmospheric+conditions:+Improved+interface+quality+and+solar+cell+performance.">Fabrication of ZnO/Cu2O heterojunctions in atmospheric conditions: Improved interface quality and solar cell performance.</a> Sol. Energ. Mat. Sol. C. 135, 43-48 (2015).</li><li>Minami, T., Nishi, Y., Miyata, T. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Heterojunction+solar+cell+with+6%+efficiency+based+on+an+n-type+aluminum-gallium-oxide+thin+film+and+p-type+sodium-doped+Cu2O+sheet.">Heterojunction solar cell with 6% efficiency based on an n-type aluminum-gallium-oxide thin film and p-type sodium-doped Cu2O sheet.</a> Appl. Phys. Express. 8, 022301 (2015).</li><li>Munoz-Rojas, D., MacManus-Driscoll, J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Spatial+Atmospheric+Atomic+Layer+Deposition:+A+new+laboratory+and+industrial+tool+for+low-cost+photovoltaics.">Spatial Atmospheric Atomic Layer Deposition: A new laboratory and industrial tool for low-cost photovoltaics.</a> Mater. Horiz. , (2014).</li><li>Hoye, R. L. Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Research+Update:+Atmospheric+pressure+spatial+atomic+layer+deposition+of+ZnO+thin+films:+Reactors,+doping,+and+devices.">Research Update: Atmospheric pressure spatial atomic layer deposition of ZnO thin films: Reactors, doping, and devices.</a> APL Mat. 3 (4), 040701 (2015).</li><li>Hoye, R. L. Z., Mu&#241;oz-Rojas, D., Musselman, K. P., Vaynzof, Y., MacManus-Driscoll, J. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Synthesis+and+Modeling+of+Uniform+Complex+Metal+Oxides+by+Close-Proximity+Atmospheric+Pressure+Chemical+Vapor+Deposition.">Synthesis and Modeling of Uniform Complex Metal Oxides by Close-Proximity Atmospheric Pressure Chemical Vapor Deposition.</a> ACS Appl. Mater. Interfaces. 7, 10684-10694 (2015).</li><li>Hoye, R. L. Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Improved+open-circuit+voltage+in+ZnO-PbSe+quantum+dot+solar+cells+by+understanding+and+reducing+losses+arising+from+the+ZnO+conduction+band+tail.">Improved open-circuit voltage in ZnO-PbSe quantum dot solar cells by understanding and reducing losses arising from the ZnO conduction band tail.</a> Adv. Energy Mat. 4 (8), 1301544 (2014).</li><li>Hoye, R. L. Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Enhanced+Performance+in+Fluorene-Free+Organometal+Halide+Perovskite+Light-Emitting+Diodes+using+Tunable,+Low+Electron+Affinity+Oxide+Electron+Injectors.">Enhanced Performance in Fluorene-Free Organometal Halide Perovskite Light-Emitting Diodes using Tunable, Low Electron Affinity Oxide Electron Injectors.</a> Adv. Mater. 27, 1414-1419 (2014).</li><li>Hoye, R. L. Z., Musselman, K. P., MacManus-Driscoll, J. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Research+Update:+Doping+ZnO+and+TiO2+for+solar+cells.">Research Update: Doping ZnO and TiO2 for solar cells.</a> APL Mat. 1 (6), 060701 (2013).</li><li>Ohtomo, A., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=MgxZn1-xO+as+a+II-VI+widegap+semiconductor+alloy.">MgxZn1-xO as a II-VI widegap semiconductor alloy.</a> Appl. Phys. Lett. 72 (19), 2466-2468 (1998).</li><li>Su, S. C., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Valence+band+offset+of+ZnO4H-SiC+heterojunction+measured+by+x-ray+photoelectron+spectroscopy.">Valence band offset of ZnO4H-SiC heterojunction measured by x-ray photoelectron spectroscopy.</a> Appl. Phys. Lett. 92 (19), 1-4 (2008).</li><li>Lee, S. W., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Improved+Cu2O-based+solar+cells+using+atomic+layer+deposition+to+control+the+Cu+oxidation+state+at+the+p-n+junction.">Improved Cu2O-based solar cells using atomic layer deposition to control the Cu oxidation state at the p-n junction.</a> Adv. Energy Mat. 4 (11), 1301916 (2014).</li><li>Brandt, R. E., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Band+offsets+of+n-type+electron-selective+contacts+on+cuprous+oxide+(Cu2O)+for+photovoltaics.">Band offsets of n-type electron-selective contacts on cuprous oxide (Cu2O) for photovoltaics.</a> Appl. Phys. Lett. 105 (26), 263901 (2014).</li><li>Hakimi, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Magnetism and spin transport studies on indium tin oxide. , (2011).</li><li>Biccari, F. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Defects and doping in Cu2O. , (2009).</li><li>Schmidt-Whitley, R., Martinez-Clemente, M., Revcolevschi, A. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Growth+and+microstructural+control+of+single+crystal+cuprous+oxide+Cu2O.">Growth and microstructural control of single crystal cuprous oxide Cu2O.</a> J. Cryst. Growth. 23 (2), 113-120 (1974).</li><li>Laughlin, D. E., Hono, K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Predominance+phase+diagram+for+the+Cu-O2+system.">Predominance phase diagram for the Cu-O2 system.</a> Physical Metallurgy. 1, 219 (2014).</li><li>Kronemeijer, A. J., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Two-dimensional+carrier+distribution+in+top-gate+polymer+field-effect+transistors:+correlation+between+width+of+density+of+localized+states+and+Urbach+energy.">Two-dimensional carrier distribution in top-gate polymer field-effect transistors: correlation between width of density of localized states and Urbach energy.</a> Adv. Mater. 26 (5), 728-733 (2014).</li><li>Hoye, R. L. Z., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Perspective:+Maintaining+surface-phase+purity+is+key+to+efficient+open+air+fabricated+cuprous+oxide+solar+cells.">Perspective: Maintaining surface-phase purity is key to efficient open air fabricated cuprous oxide solar cells.</a> APL Mat. 3, 020901 (2015).</li><li>Poodt, P., et al. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Spatial+atomic+layer+deposition:+A+route+towards+further+industrialization+of+atomic+layer+deposition.">Spatial atomic layer deposition: A route towards further industrialization of atomic layer deposition.</a> J. Vac. Sci. Technol., A. 30 (1), 010802 (2012).</li></ol>

The authors declare that they have no competing financial interests.

该协议中的关键步骤是由铜2 O与CuO基材表面氧化的规定。这些包括在稀硝酸衬底蚀刻氧化之后以及金电极的蒸发后，以除去任何的CuO，最小化时基板在露天耗费锌1-X镁×○沉积之前，最后的沉积锌1-X镁×○对Cu 2 O基板由AP-SALD。 相比于常规的ALD AP-SALD的优点是膜可以与生长速率是幅度较高的一个到两个数量真空外生长。然而，这意味着，在Cu 2 O底物具有在温度至少刚刚沉积，这足以对一个薄的CuO层形成在表面上之前，升高被暴露于氧化剂中的空气。这看似限制对AP-SALD方法的某些氧化敏感本草应用LS。然而，通过优化的AP-SALD条件如温度和时间，以及减少的Cu 2 O暴露于空气和水分，用AP-SALD以ZnO /铜2 O设备的转换效率的六倍制成达到。改善来自于理解的Cu 2 O与CuO氧化为氧化铜作为异质结太阳能电池的材料，并相应地修改制造协议的主要限制因素。 为了完全避免氧化亚铜的氧化，基板必须保持在惰性气氛或真空中所有的时间，采用露天沉积技术如AP-SALD时它可以是具有挑战性的。而避免在基于真空的技术3,18，用于大规模生产的Cu 2 O的氧化，它是重要的，这个问题可以在大气制造工艺被最小化。在AP-SALD，衬底表面可以暴露于还原剂之前异质的形成，并通过由n型氧化物的沉积过程中使用成型气体与CuO的还原平衡的Cu 2 O的氧化。25还原剂在AP-SALD使用可能是一个与还原气体（ 例如，N 2 + 5％的H 2 25），或一个周期数与之前沉积的还原前体， 即，不含水的循环，以减少的CuO回的惰性气体的混合物铜2 O之前的氧化锌氧化物开始在其表面上生长。 在这项工作中，一个标准的协议已经开发出来，最大限度地减少形成氧化铜由AP-SALD露天优化制造步骤从铜2 O处理和蚀刻PN结的形成。这项工作的成功表明AP-SALD的作为在廉价和可扩展的光电器件应用一种很有前途的方法的潜力。可用于快速depos的技术的各种n型和p型半导体金属氧化物的银行足球比赛以及阻断，缓冲液和在热敏基材包括塑料太阳能电池的阻挡层。

氧化亚铜（铜2 O）是一个地球丰富无毒p型半导体材料1。与2电子伏特的带隙，氧化亚铜可以实现光吸收剂在异质结或串联型太阳能电池的作用。在异质结太阳能电池，铜2 O已知与多种n型大的带隙的半导体，例如ZnO 2和其掺杂变体3,4， 的 Ga 2 O 3 5,6和TiO 2 7配对（对于更对Cu 2 O光伏详细概述见参考文献8）。的Cu 2 O的异质结太阳能电池的开发是示于图1，其中，靠近每个数据点被指示合成该异质结的方法。可以注意的是基于真空的方法，如脉冲激光沉积（PLD）或允许更高的功率转换效率的原子层沉积（ALD）来实现（高达6.1％9）。在合作ntrast，对于非真空合成方法如电化学沉积（ECD）的效率仍然很低。然而，对于低成本光伏最好是合成的真空外异质结。而异质结形成一个自由真空，可扩展的技术是更合适的选择，它仍然具有挑战性由这种方法生产的高品质的接口。在这项工作中，我们利用一个露天，称为大气压力的空间的原子层沉积（AP-SALD）可伸缩的薄膜沉积工艺生长的n型氧化物对Cu 2 O类太阳能电池。 AP-SALD比传统的ALD的进步是，在前者中，前体在空间，而不是在时间10分离。在沉积过程中，衬底振荡上来回含有由惰性气体通道分开，前体气体通道， 如图2中的气体歧管下一个加热压板。携带precurs氮气ORS通过气体歧管向下朝横向移动压板垂直流动。由于压板的振荡，在基片上的每个点被顺序地暴露于氧化剂和金属前体，如在图2中示出。这使得金属氧化物膜由层成长层。 AP-SALD反应器的设计和操作的详细说明，可以在其他地方被发现。11,12这种方法允许沉积比传统的ALD和外部真空，这与卷对卷工艺兼容更快的发生数量级一到两个数量。通过AP-SALD生产高质量保形氧化物膜可以在低温下在各种基底上，包括塑料，这使得AP-SALD薄膜被应用到低成本功能器件如太阳能电池13被沉积（&lt;150℃） ，发光二极管14和薄膜晶体管15。 该定制的AP-SALD气歧管在这项工作中使用的是机械性地保持放置在原稿台上的基片上。这使得基板 - 歧管间距独立于气体流量的控​​制。为50微米的大的间隔被使用，这导致在气相中的金属前体与氧化剂之间的混合。因此，AP-SALD反应器中的化学汽相沉积（CVD）模式下操作。这被认为是超过在ALD模式操作有利的，因为膜在更高的速率高的厚度均匀性增加，但仍和当在相同的温度下ALD薄膜沉积是结晶的。12在这里，我们仍然参阅反应器中作为的AP-SALD反应器，因为它具有相同的基本设计原理的其它的AP-SALD反应器。11 我们使用我们的反应器中，为我们的太阳能电池沉积在n型层，特别是氧化锌和氧化锌镁（锌1-X镁×○16,17）。结合镁INTÒ的ZnO允许待调整的导带，这是用于减少由于带尾热化13和界面重组损失重要的。18,19 这里，我们显示如何调整为要获得关于允许改进的界面质量的热氧化的氧化亚铜衬底并因此更好的太阳能电池的性能上沉积的氧化锌和锌镁氧化物膜的条件。重组在异质结界面由于氧化亚铜表面上形成的过度氧化铜（CuO的）的:这个改善是通过铜2 O基础的太阳能电池识别的主要限制因素成为可能。

<table border="0" cellpadding="0" cellspacing="0" width="942">
	<colgroup>
		<col />
		<col />
		<col />
		<col />
	</colgroup>
	<tbody>
		<tr height="42">
			<td height="42" style="height:42px;width:320px;">Copper foil</td>
			<td style="width:336px;">AVOCADO RESEARCH CHEMICALS LTD T/A ALFA AESAR</td>
			<td align="right" style="width:119px;">13380</td>
			<td style="width:167px;">0.127 mm thick, annealed, 99.9% (metals basis), annealed</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:320px;">Rapidox Oxygen analyzer</td>
			<td style="width:336px;">Rapidox</td>
			<td>&#160;Model 2100</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:320px;">Alumina boat</td>
			<td style="width:336px;">ALMATH CRUCIBLES LTD</td>
			<td align="right" style="width:119px;">6121203</td>
			<td>Dimensions 20 mm x 50 mm x 5 mm</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:320px;">GOLD PELLETS</td>
			<td style="width:336px;">KJLC</td>
			<td style="width:119px;">EVMAUXX40G</td>
			<td>99.99% PURE 1/8&#34; X 1/8&#34;, SOLD BY THE GRAM</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:320px;">Diethylzinc</td>
			<td style="width:336px;">ALDRICH</td>
			<td style="width:119px;">256781&#160;</td>
			<td style="width:167px;">&#8805;52 wt. % Zn basis</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:320px;">Bis(ethylcyclopentadienyl)magnesium</td>
			<td style="width:336px;">Strem Chemicals UK</td>
			<td style="width:119px;">12-0510</td>
			<td>5g</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:320px;">ITO target</td>
			<td style="width:336px;">GoodFellow Cambridge Limited</td>
			<td style="width:119px;">LS 427438</td>
			<td>Indium Oxide/Tin Oxide target (In2O3 90 / SnO2 10), Condition : Hot-pressed, Thickness : 2.0mm +/-0.5mm, Size : 35.5mm x 55.5mm +/-0.5mm</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:320px;">VHT engine enamel paint</td>
			<td style="width:336px;">Halfords</td>
			<td align="right" style="width:119px;">325019</td>
			<td>very high temperature engine enamel black paint</td>
		</tr>
		<tr height="25">
			<td height="25" style="height:25px;width:320px;">Nitric acid HNO3, ACS reagent 70%&#160;</td>
			<td style="width:336px;">Sigma-Aldrich Co Ltd</td>
			<td style="width:119px;">438073-2.5L</td>
			<td>Harmful, irritant</td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:320px;">2 % Oxygen/Argon 200 bar</td>
			<td style="width:336px;">BOC Limited</td>
			<td style="width:119px;">225757-L</td>
			<td>gas mixture for Cu foil oxidation, to be diluted with Ar</td>
		</tr>
	</tbody>
</table>

improved heterojunction quality in cu2o-based solar cells through the optimization of atmospheric pressure spatial atomic layer deposited zn1-xmgxo

Atmospheric pressure spatial atomic layer deposition (AP-SALD) was used to deposit n-type ZnO and Zn1-xMgxO thin films onto p-type thermally oxidized Cu2O substrates outside vacuum at low temperature. The performance of photovoltaic devices featuring atmospherically fabricated ZnO/Cu2O heterojunction was dependent on the conditions of AP-SALD film deposition, namely, the substrate temperature and deposition time, as well as on the Cu2O substrate exposure to oxidizing agents prior to and during the ZnO deposition. Superficial Cu2O to CuO oxidation was identified as a limiting factor to heterojunction quality due to recombination at the ZnO/Cu2O interface. Optimization of AP-SALD conditions as well as keeping Cu2O away from air and moisture in order to minimize Cu2O surface oxidation led to improved device performance. A three-fold increase in the open-circuit voltage (up to 0.65 V) and a two-fold increase in the short-circuit current density produced solar cells with a record 2.2% power conversion efficiency (PCE). This PCE is the highest reported for a Zn1-xMgxO/Cu2O heterojunction formed outside vacuum, which highlights atmospheric pressure spatial ALD as a promising technique for inexpensive and scalable fabrication of Cu2O-based photovoltaics.

热力学，氧化铜是在RT在空气中氧化铜的唯一稳定的阶段，由于在Cu-O系的相稳定性图揭示21 - 23。为了验证CuO的存在的Cu 2 O的蚀刻的吸收光谱的表面上和未腐蚀热氧化铜2 O基材采取光热偏转谱（PDS） -一个高度敏感的技术，它允许用于子带隙吸收测量24（ 图4）。两个谱表明吸收上述1.4电子伏特，这与CuO的带隙重合，在2电子伏特（ 氧化亚铜带隙）饱和之前。未蚀刻衬底具有低于2电子伏特一个较高的吸收，未腐蚀的Cu 2 O比蚀刻基板上的表面上暗示CuO的较厚的层。 图4中的插图显示CuO的作为氧化（未蚀刻）的Cu 2 O基板上的灰层。而无灰膜可以直​​观地蚀刻基板上被检测到，一些氧化铜仍存在其表面上，作为PDS测量表明。的非常薄的氧化铜薄膜的铜2 O基板的表面上存在还证实用X射线光电子能谱（XPS）19,25。本在Cu 2 O的表面上的氧化铜在异质结界面，可以作为复合中心，因此，氧化铜存在下，在pn结是不希望的引入深能级陷阱态（铜离子 ）18。 加热的Cu 2 O底物中的氧化剂（ 例如 ，空气和水分）的存在有利于的Cu 2 O和CuO的氧化。为了通过AP-SALD以获得多晶氧化锌，基片被加热到150℃。当衬底在升高的温度在露天或氧化剂气体下的沉积期间保持，CuO的迅速形成在Cu <suB&gt; 2 O的表面上。 图5显示了之前和在150℃的氮气的气流下在AP-SALD压板花费3分钟后扫描的蚀刻铜2 O基片的电子显微镜（SEM）图像。多个的CuO副产物可以看出退火基板上，与他们的组合物是接近的CuO如通过能量色散X射线光谱（EDX）验证。 光电器件，用在150℃下由AP-SALD沉积为400秒的蚀刻热氧化铜2 O基板的顶部的ZnO制成。 图6A示出该标准设备的表面上。可以注意到许多棒状和花状的副产物存在于设备。如先前使用EDX和PDS证实，这些副产物是氧化铜和发生由于铜2 O暴露于空气和氧化剂。 表1和图7（&#39;的ZnO /铜2 O标准&#39;Curve）证明该设备的性能相对较差。 为了避免在Cu 2 O的表面上的CuO的形成，用于通过在蚀刻热氧化铜2 O底物AP-SALD沉积的ZnO的条件进行了优化。采取了以下措施，以最小化的CuO生长:还原沉积温度（ 图8A）;减少的沉积时间（ 图8B）;扫描衬底表面的几个振荡不暴露于氧化剂气体， 即只用金属前体和惰性通道开放（ 图8C）;最后，在空气中裸铜2 O基板的不必要的加热避免刚沉积的开始之前。发现在Cu 2 O ZnO蒸镀的最优参数为100℃，100秒和5不含水的循环。优化的装置的表面是自由的CuO outgrowt的HS，如展示于图6B。优化的ZnO /铜2 O装置的电流密度-电压（JV）特性与图7中的标准设备进行比较。这两个标准和优化的ZnO /铜2 O设备的光伏性能在表1中提出，它可以可以看出，由以下四个上述措施，在器件的功率转换效率的六倍达到了。 为了进一步阐明的AP-SALD条件的优化对CuO的还原和异质结质量的影响，外部量子效率（EQE）测量在沉积在150℃和100℃（ 图9）与氧化锌设备执行。两个设备的EQE谱，而在高于475纳米的波长相近，在波长显著差异低于475纳米，这是波长的范围<html>小号吸收附近的接口。对于较短波长辐射，使用ZnO器件在更高的温度下进行的EQE为小于一半，与氧化锌器件在较低温度下进行的。这表明，更多的氧化铜存在于在较高温度下进行的氧化锌/铜2 O接口，从而减少了电荷收集从接近异质由于增加重组的区域。 毫克被并入的AP-SALD ZnO薄膜为了提高氧化锌的导带和以减少重组进一步15。锌1-X镁×○/铜2 O太阳能电池用优化锌0.8镁0.2 O薄膜制成，造成2.2％的设备PCE -基于O型最高迄今为止对Cu 2太阳能电池的露天制作异质结（参见图7和表1中的设备的性能）。 内容"FO:保together.within页="1"&gt; <img alt="图1" src="/files/ftp_upload/53501/53501fig1.jpg" /> 图1 的Cu 2-O基太阳电池出版年份效率（该图已被从价修饰8）。标记表明是否在真空或大气（非真空）形成界面和标签指示的方法异质结的形成。 MSP -磁控溅射，IBS -离子束溅射，VAPE -真空电弧等离子体蒸发。 <a href="https://www.jove.com/files/ftp_upload/53501/53501fig1large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图2" src="/files/ftp_upload/53501/53501fig2.jpg" /> 图2 AP-SALD沉积工艺的示意图（与常规的ALD相比），设置用于产生多组分金属牛集成开发环境（ 一 ）传统ALD（Δ-掺杂）各前体和净化步骤的顺序曝光（这个数字已经从文献再现。11）。在本手稿的上下文中，M1为二乙基锌蒸气，M2双（乙基环戊二烯基）镁蒸气，并O1和O2的水蒸汽。 （B）的在AP-SALD金属前体的混合物（共注入），惰性气体通道（等同于"吹洗"工序）和氧化剂顺序曝光（该图已被从参考再现11）。 （C）的一般AP-SALD反应器，示出了由惰性气体通道空间分离的前体，与振荡的不同信道下方的衬底的示意图（此图是从参考文献11，这是从一个在参考文献的变形再现。 26）。 （D）与原子力显微镜的AP-SALD体系的重要组成部分的原理概述（AFM）图像显示的形态基板前后锌1-X镁×○沉积（这个数字已经从文献再现。13）。 <a href="https://www.jove.com/files/ftp_upload/53501/53501fig2large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图3" src="/files/ftp_upload/53501/53501fig3.jpg" /> 铜2 O与ZnO和ITO薄膜基板可观察到的ITO的图3.截面SEM图像/氧化锌/铜2 O异质结（这个数字已经从8参考转载）。保形涂料。 <a href="https://www.jove.com/files/ftp_upload/53501/53501fig3large.jpg" target="_blank">请点击这里查看一个更大的版本这个数字。</a> <img alt="图4" src="/files/ftp_upload/53501/53501fig4.jpg" /> 图4. PDS蚀刻和未腐蚀（如-OXI的光谱<html> dized）的Cu 2 O基板（这个数字已经从参考修改。8）。该插图显示蚀刻和未蚀刻氧化亚铜基板的照片。 <a href="https://www.jove.com/files/ftp_upload/53501/53501fig4large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图5" src="/files/ftp_upload/53501/53501fig5.jpg" /> 图5.为3分钟新鲜蚀刻退火后，在150℃的空气中的Cu 2 O基板时（A）和（B）的表面的SEM图像（该图已被从参考再现8）。插图显示面与EDX获取的构图。 <a href="https://www.jove.com/files/ftp_upload/53501/53501fig5large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <html> 501 / 53501fig6.jpg"/&gt; 图6.氧化锌/铜2 O太阳能电池的使用（A）的标准条件和（B）的AP-SALD的ZnO优化条件下（此图是从参考再现。8）方面的表面的SEM图像，各种副产物可在标准的设备看到。 <a href="https://www.jove.com/files/ftp_upload/53501/53501fig6large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图7" src="/files/ftp_upload/53501/53501fig7.jpg" /> 图7.光JV特性锌1-X镁×○/铜2 O的标准和优化的AP-SALD条件（这个数字已经从参考修改。8）。该合资公司的曲线展示太阳能电池性能的改善，当制造太阳能电池锌的组合物和AP-SALD条件1-X镁×○膜被优化。小号://www.jove.com/files/ftp_upload/53501/53501fig7large.jpg"目标="_空白"&gt;点击此处查看该图的放大版本。 <img alt="图8" src="/files/ftp_upload/53501/53501fig8.jpg" /> 图8的AP-SALD参数对ZnO /铜2 O太阳能电池的性能的影响。水的（A）和（B）的AP-SALD ZnO蒸镀时间和温度上的装置的开路电压（V OC）的影响（该图已被从参考再现。8），（C）的相关与器件的开路电压空闲周期。 <a href="https://www.jove.com/files/ftp_upload/53501/53501fig8large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <img alt="图9" src="/files/ftp_upload/53501/53501fig9.jpg" /> 图9. EQE SPECTR的ZnO /铜2 O太阳能电池的ZnO沉积在100℃和150℃。 （这个数字已经从文献转载8）。该器件的开路电压在图例中表示。 <a href="https://www.jove.com/files/ftp_upload/53501/53501fig9large.jpg" target="_blank">请点击此处查看该图的放大版本。</a> <table fo:keep-together.within-page="1"><tbody><tr><td> 太阳能电池 </td><td> 沉积温度，℃， </td><td> 沉积时间，秒 </td><td> ĴSC， 毫安 /平方厘米 </td><td> 开路电压，V </td><td> FF，％ </td><td> PCE，％ </td></tr><tr><td>氧化锌/铜2 O标准</td><td> 150 </td><td> 400 </td><td> 3.7 </td><td> 0.18 </td><td> 35 </td><td> 0.23 </td></tr><tr><td>氧化锌/铜2 O优化</td><td> 100 </td><td> 100 &lt;/ TD&gt; <td> 7.5 </td><td> 0.49 </td><td> 40 </td><td> 1.46 </td></tr><tr><td>锌镁0.8 0.2 /铜2 O优化</td><td> 150 </td><td> 100 </td><td> 6.9 </td><td> 0.65 </td><td> 49 </td><td> 2.20 </td></tr></tbody></table> 表1. 标准和优化的AP-SALD锌 1-X 镁 ×○沉积参数和最佳相应的ITO的性能/锌 1-X 镁 ×○/铜 2 O太阳能电池（该表已被修改的参考8） 。ĴSC -短路电流密度，FF -填充因子。

Watch this Scientific Journal Video about Improved Heterojunction Quality in Cu2O-based Solar Cells Through the Optimization of Atmospheric Pressure Spatial Atomic Layer Deposited Zn1-xMgxO at JoVE.co

Improved Heterojunction Quality in Cu2O-based Solar Cells Through the Optimization of Atmospheric Pressure Spatial Atomic Layer Deposited Zn1-xMgxO

在这里，我们提出了一个协议，用于合成锌1-X镁×○/铜2 O异质结在露天时，透过大气压力的空间原子层沉积（AP-SALD）锌1-X镁×○对氧化亚铜的低温。这样的高品质的共形金属氧化物可以在各种基材上，包括由这种廉价和可扩展的方法塑料的生长。

在铜改善异质结质量<sub&gt; 2</sub&gt; O型的太阳能电池通过大气压力的空间原子层沉积的优化<br /&gt;锌<sub&gt; 1-X</sub&gt;镁<sub系列&gt; X</sub&gt; 0

Atmospheric pressure spatial atomic layer deposition (AP-SALD) was used to deposit n-type ZnO and Zn1-xMgxO thin films onto p-type thermally oxidized Cu2O ...

improved-heterojunction-quality-cu2o-based-solar-cells-through

Research

JoVE Journal

Chemistry

Improved Heterojunction Quality in Cu2O-based Solar Cells Through the Optimization of Atmospheric Pressure Spatial Atomic Layer Deposited Zn1-xMgxO

12.1K 次观看.  University of Cambridge. 在这里，我们提出了一个协议，用于合成锌1-X镁×○/铜2 O异质结在露天时，透过大气压力的空间原子层沉积（AP-SALD）锌1-X镁×○对氧化亚铜的低温。这样的高品质的共形金属氧化物可以在各种基材上，包括由这种廉价和可扩展的方法塑料的生长。 

视频: Improved Heterojunction Quality in Cu2O-based Solar Cells Through the Optimization of Atmospheric Pressure Spatial Atomic Layer Deposited Zn1-xMgxO

Optimization of Synthetic Proteins: Identification of Interpositional Dependencies Indicating Structurally and/or Functionally Linked Residues

Protein alignments are commonly used to evaluate the similarity of protein residues, and the derived consensus sequence used for identifying functional units (e.g., domains). Traditional consensus-building models fail to account for interpositional dependencies &#8211; functionally required covariation of residues that tend to appear simultaneously throughout evolution and across the phylogentic tree. These relationships can reveal important clues about the processes of protein folding, thermostability, and the formation of functional sites, which in turn can be used to inform the engineering of synthetic proteins. Unfortunately, these relationships essentially form sub-motifs which cannot be predicted by simple &#8220;majority rule&#8221; or even HMM-based consensus models, and the result can be a biologically invalid &#8220;consensus&#8221; which is not only never seen in nature but is less viable than any extant protein. We have developed a visual analytics tool, StickWRLD, which creates an interactive 3D representation of a protein alignment and clearly displays covarying residues. The user has the ability to pan and zoom, as well as dynamically change the statistical threshold underlying the identification of covariants. StickWRLD has previously been successfully used to identify functionally-required covarying residues in proteins such as Adenylate Kinase and in DNA sequences such as endonuclease target sites.

Synthetic protein sequences based on consensus motifs typically ignore co-evolving residues, that imply interpositional dependencies (IPDs). IPDs can be essential to activity, and designs that disregard them may result in suboptimal results. This protocol uses StickWRLD to identify IPDs and help inform rational protein design, resulting in more efficient results.

优化合成蛋白质:Interpositional依赖性的鉴定指示在结构和/或功能性连接的残留

Protein alignments are commonly used to evaluate the similarity of protein residues, and the derived consensus sequence used for identifying functional ...

科研

化学

Layer-by-layer Synthesis and Transfer of Freestanding Conjugated Microporous Polymer Nanomembranes

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in combination with their outstanding thermal and chemical stability, and low densities. However, their insoluble nature causes problems in their processing since usually applied techniques such as spin coating are not available. Especially for membrane applications, where the processing of CMP as thin films is desirable, the processing problems have hindered their commercial application.
Here we describe the interfacial synthesis of CMP thin films on functionalized substrates via molecular layer-by-layer (l-b-l) synthesis. This process allows the preparation of films with desired thickness and composition and even desired composition gradients.
The use of sacrificial supports allows the preparation of freestanding membranes by dissolution of the support after the synthesis. To handle such ultra-thin freestanding membranes the protection with sacrificial coatings showed great promise, to avoid rupture of the nanomembranes. To transfer the nanomembranes to the desired substrate, the coated membranes are upfloated at the air-liquid interface and then transferred via dip coating.

In this paper we describe the interfacial synthesis of conjugated microporous polymers (CMP) on sacrificial substrates, and the dissolution of the substrate for the preparation of freestanding CMP nanomembranes. In addition, we will describe how the fragile nanomembranes can be transferred to other substrates.

层 - 层的合成和独立式共轭微孔聚合物纳米薄膜的转移

CMP as large surface area materials have attracted growing interest recently, due to their high variability in the incorporation of functional groups in ...

Epitaxial Growth of Perovskite Strontium Titanate on Germanium via Atomic Layer Deposition

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and conformality by taking advantage of self-limiting reactions between vapor-phase precursors and the growing film. Perovskite oxides present potential for next-generation electronic materials, but to-date have mostly been deposited by physical methods. This work outlines a method for depositing SrTiO3 (STO) on germanium using ALD. Germanium has higher carrier mobilities than silicon and therefore offers an alternative semiconductor material with faster device operation. This method takes advantage of the instability of germanium's native oxide by using thermal deoxidation to clean and reconstruct the Ge (001) surface to the 2&#215;1 structure. 2-nm thick, amorphous STO is then deposited by ALD. The STO film is annealed under ultra-high vacuum and crystallizes on the reconstructed Ge surface. Reflection high-energy electron diffraction (RHEED) is used during this annealing step to monitor the STO crystallization. The thin, crystalline layer of STO acts as a template for subsequent growth of STO that is crystalline as-grown, as confirmed by RHEED. In situ X-ray photoelectron spectroscopy is used to verify film stoichiometry before and after the annealing step, as well as after subsequent STO growth. This procedure provides framework for additional perovskite oxides to be deposited on semiconductors via chemical methods in addition to the integration of more sophisticated heterostructures already achievable by physical methods.

This work details the procedures for the growth and characterization of crystalline SrTiO3 directly on germanium substrates by atomic layer deposition. The procedure illustrates the ability of an all-chemical growth method to integrate oxides monolithically onto semiconductors for metal-oxide semiconductor devices.

锗通过原子层沉积钙钛矿型钛酸锶的外延生长

Atomic layer deposition (ALD) is a commercially utilized deposition method for electronic materials. ALD growth of thin films offers thickness control and ...

An Optimized Protocol for the Efficient Radiolabeling of Gold Nanoparticles by Using a 125I-labeled Azide Prosthetic Group

Here, we demonstrate a detailed protocol for the radiosynthesis of a 125I-labeled azide prosthetic group and its application to the efficient radiolabeling of DBCO-group-functionalized gold nanoparticles using a copper-free click reaction. Radioiodination of the stannylated precursor (2) was carried out by using [125I]NaI and chloramine T as an oxidant at room temperature for 15 min. After HPLC purification of the crude product, the purified 125I-labeled azide (1) was obtained with high radiochemical yield (75 &plusmn; 10%, n = 8) and excellent radiochemical purity (&gt;99%). For the synthesis of radiolabeled 13-nm-sized gold nanoparticles, the DBCO-functionalized gold nanoparticles (3) were prepared by using a thiolated polyethylene glycol polymer. A copper-free click reaction between 1 and 3 gave the 125I-labeled gold nanoparticles (4) with more than 95% of radiochemical yield as determined by radio-thin-layer chromatography (radio-TLC). These results clearly indicate that the present radiolabeling method using a strain-promoted copper-free click reaction will be useful for the efficient and convenient radiolabeling of DBCO-group-containing nanomaterials.

An Optimized Protocol for the Efficient Radiolabeling of Gold Nanoparticles by Using a 125I-labeled Azide Prosthetic Group

A detailed procedure for the synthesis of a 125I-labeled azide and the radiolabeling of dibenzocyclooctyne (DBCO)-group-conjugated, 13-nm-sized gold nanoparticles using a copper-free click reaction is described.

一个优化的协议通过使用金纳米粒子的放射性标记效率<sup&gt; 125</sup&gt;我标记的叠氮辅基

Here, we demonstrate a detailed protocol for the radiosynthesis of a 125I-labeled azide prosthetic group and its application to the efficient ...

Fizzy Extraction of Volatile Organic Compounds Combined with Atmospheric Pressure Chemical Ionization Quadrupole Mass Spectrometry

Chemical analysis of volatile and semivolatile compounds dissolved in liquid samples can be challenging. The dissolved components need to be brought to the gas phase, and efficiently transferred to a detection system. Fizzy extraction takes advantage of the effervescence phenomenon. First, a carrier gas (here, carbon dioxide) is dissolved in the sample by applying overpressure and stirring the sample. Second, the sample chamber is decompressed abruptly. Decompression leads to the formation of numerous carrier gas bubbles in the sample liquid. These bubbles assist the release of the dissolved analyte species from the liquid to the gas phase. The released analytes are immediately transferred to the atmospheric pressure chemical ionization interface of a triple quadrupole mass spectrometer. The ionizable analyte species give rise to mass spectrometric signals in the time domain. Because the release of the analyte species occurs over short periods of time (a few seconds), the temporal signals have high amplitudes and high signal-to-noise ratios. The amplitudes and areas of the temporal peaks can then be correlated with concentrations of the analytes in the liquid samples subjected to fizzy extraction, which enables quantitative analysis. The advantages of fizzy extraction include: simplicity, speed, and limited use of chemicals (solvents).

Fizzy extraction is a new laboratory technique for analysis of volatile and semivolatile compounds. A carrier gas is dissolved in the liquid sample by applying overpressure and stirring the sample. The sample chamber is then decompressed. The analyte species are liberated to the gas phase due to effervescence.

挥发性有机化合物与大气压化学电离四极杆质谱联用

Chemical analysis of volatile and semivolatile compounds dissolved in liquid samples can be challenging. The dissolved components need to be brought to ...

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven effective in gas adsorption, separations, and catalysis. MOFs are most commonly synthesized as bulk powder, requiring additional processes to adhere them to functional devices and fabrics that risk decreasing the powder porosity and adsorption capacity. Here, we demonstrate a method of first coating fabrics with metal oxide films using atomic layer deposition (ALD). This process creates conformal films of controllable thickness on each fiber, while providing a more reactive surface for MOF nucleation. By submerging the ALD coated fabric in solution during solvothermal MOF synthesis, the MOFs create a conformal, well-adhered coating on the fibers, resulting in a MOF-functionalized fabric, without additional adhesion materials that may block MOF pores and functional sites. Here we demonstrate two solvothermal synthesis methods. First, we form a MIL-96(Al) layer on polypropylene fibers using synthetic conditions that convert the metal oxide to MOF. Using initial inorganic films of varying thicknesses, diffusion of the organic linker into the inorganic allows us to control the extent of MOF loading on the fabric. Second, we perform a solvothermal synthesis of UiO-66-NH2 in which the MOF nucleates on the conformal metal oxide coating on polyamide-6 (PA-6) fibers, thereby producing a uniform and conformal thin film of MOF on the fabric. The resulting materials can be directly incorporated into filter devices or protective clothing and eliminate the maladroit qualities of loose powder.

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks are effective in gas storage and heterogeneous catalysis, but typical synthesis methods result in loose powders that are difficult to incorporate into smart materials. We demonstrate a method of first coating fabrics with ALD metal oxides, resulting in conformal films of MOF on the fabrics during solvothermal synthesis.

溶剂热合成 MIL-96 和 UiO-66-NH2在纤维垫上原子层沉积金属氧化物涂层上的合成

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven ...

Surface Functionalization of Metal-Organic Frameworks for Improved Moisture Resistance

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. However, the main issue limiting their applicability is their poor stability in humid conditions. The common methods to overcome this problem involve the formation of strong metal-linker bonds by using highly charged metals, which is limited to a number of structures, the introduction of alkylic groups to the framework by post-synthetic modification (PSM) or chemical vapour deposition (CVD) to enhance overall hydrophobicity of the framework. These last two usually provoke a drastic reduction of the porosity of the material. These strategies do not permit to exploit the properties of the MOF already available and it is imperative to find new methods to enhance the stability of MOFs in water while keeping their properties intact. Herein, we report a novel method to enhance the water stability of MOF crystals featuring Cu2(O2C)4&#160;paddle-wheel units, such as HKUST (where HKUST stands for Hong Kong University of Science &#38; Technology), with the catechols functionalized with alkyl and fluoro-alkyl chains. By taking advantage of the unsaturated metal sites and the catalytic catecholase-like activity of CuII ions, we are able to create robust hydrophobic coatings through the oxidation and subsequent polymerization of the catechol units on the surface of the crystals under anaerobic and water-free conditions without disrupting the underlying structure of the framework. This approach not only affords the material with improved water stability but also provides control over the function of the protective coating, which enables the development of functional coatings for the adsorption and separations of volatile organic compounds. We are confident that this approach could also be extended to other unstable MOFs featuring open metal sites.

Robust functional catechol coatings were produced in one step by direct reaction of the material known as HKUST with synthetic catechols under anaerobic conditions. The formation of homogeneous coatings surrounding the entire crystal is ascribed to the biomimetic catalytic activity of Cu(II) dimers on the external surface of the crystals.

金属-有机框架的表面功能化改善防潮性能

Metal-organic frameworks (MOFs) are a class of porous inorganic materials with promising properties in gas storage and separation, catalysis and sensing. ...

Key Factors Affecting the Performance of Sb2S3-sensitized Solar Cells During an Sb2S3 Deposition via SbCl3-thiourea Complex Solution-processing

Sb2S3 is considered as one of the emerging light absorbers that can be applied to next-generation solar cells because of its unique optical and electrical properties. Recently, we demonstrated its potential as next-generation solar cells by achieving a high photovoltaic efficiency of &#62; 6% in Sb2S3-sensitized solar cells using a simple thiourea (TU)-based complex solution method. Here, we describe the key experimental procedures for the deposition of Sb2S3 on a mesoporous TiO2 (mp-TiO2) layer using a SbCl3-TU complex solution in the fabrication of solar cells. First, the SbCl3-TU solution is synthesized by dissolving SbCl3 and TU in N,N-dimethylformamide at different molar ratios of SbCl3:TU. Then, the solution is deposited on as-prepared substrates consisting of mp-TiO2/TiO2-blocking layer/F-doped SnO2 glass by spin coating. Finally, to form crystalline Sb2S3, the samples are annealed in an N2-filled glove box at 300 &#176;C. The effects of the experimental parameters on the photovoltaic device performance are also discussed.

Key Factors Affecting the Performance of Sb2S3-sensitized Solar Cells During an Sb2S3 Deposition via SbCl3-thiourea Complex Solution-processing

This work provides a detailed experimental procedure for the deposition of Sb2S3 on a mesoporous TiO2 layer using a SbCl3-thiourea complex solution for applications in Sb2S3-sensitized solar cells. This article also determines key factors governing the deposition process.

利用SbCl3-硫脲复合溶液处理锑23沉积物对锑2S3敏化太阳能电池性能影响的关键因素

Sb2S3 is considered as one of the emerging light absorbers that can be applied to next-generation solar cells because of its unique optical and electrical ...

Molten-Salt Synthesis of Complex Metal Oxide Nanoparticles

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. Here, we introduce the molten-salt synthesis (MSS) method for making metal oxide nanomaterials. Advantages over other methods include its simplicity, greenness, reliability, scalability, and generalizability. Using pyrochlore lanthanum hafnium oxide (La2Hf2O7) as a representative, we describe the MSS protocol for the successful synthesis of complex metal oxide nanoparticles (NPs). Furthermore, this method has the unique ability to produce NPs with different material features by changing various synthesis parameters such as pH, temperature, duration, and post-annealing. By fine-tuning these parameters, we are able to synthesize highly uniform, non-agglomerated, and highly crystalline NPs. As a specific example, we vary the particle size of the La2Hf2O7&#160;NPs by changing the concentration of the ammonium hydroxide solution used in the MSS process, which allows us to further explore the effect of particle size on various properties. It is expected that the MSS method will become a more popular synthesis method for nanomaterials and more widely employed in the nanoscience and nanotechnology community in the upcoming years.

Here, we demonstrate a unique, relatively low-temperature, molten-salt synthesis method for preparing uniform complex metal oxide lanthanum hafnate nanoparticles.

复合金属氧化物纳米粒子的熔融盐合成

The development of feasible synthesis methods is critical for the successful exploration of novel properties and potential applications of nanomaterials. ...

Niobium Oxide Films Deposited by Reactive Sputtering: Effect of Oxygen Flow Rate

Reactive sputtering is a versatile technique used to form compact films with excellent homogeneity. In addition, it allows easy control over deposition parameters such as gas flow rate that results in changes on composition and thus in the film required properties. In this report, reactive sputtering is used to deposit niobium oxide films. A niobium target is used as metal source and different oxygen flow rates to deposit niobium oxide films. The oxygen flow rate was changed from 3 to 10 sccm. The films deposited under low oxygen flow rates show higher electrical conductivity and provide better perovskite solar cells when used as electron transport layer.

Here, we present a protocol for niobium oxide films deposition by reactive sputtering with different oxygen flow rates for use as an electron transport layer in perovskite solar cells.

活性溅射沉积的氧化氮薄膜:氧气流速效应

Reactive sputtering is a versatile technique used to form compact films with excellent homogeneity. In addition, it allows easy control over deposition ...

在铜改善异质结质量

摘要

探索更多视频

此视频中的章节