作者衷心感谢美国空军科研办公室在协议编号 FA9550-14-1-0128 的资助。t.l.a. 还衷心感谢大卫和露西尔基金会的部分支持。

为试剂阅读 MSDS, 并按照贵机构的要求, 遵守所有化学安全措施。
1. PProDOT 和氯-PTT 的沉积
<ol><li>建立 custom-built 管状气相沉积室的结构, 如图 1所示。<ol>
<li>做一个1/4 的. (外径, 外径) 熔融石英侧入口到 2 in. (外径) 熔融石英管。用 custom-built U 形1的不锈钢管和杜瓦瓶做一个冷的陷阱。</li>
		<li>使用不锈钢 KF 连接器和快速连接接头将石英管与真空计和冷阱连接。将单体放在石英安瓿中, 并将安瓿连接到管状腔内, 通过 1/4-in. 快连接联轴器和针阀。将氧化剂放在室内的坩埚中。</li>
		<li>使用单独的加热带作为氧化剂、基质和单体的热源。在腔室的右端添加一个气体入口, 以引入额外的惰性气体, 以便在必要时控制过程压力。</li>
	</ol>
</li>
	<li>
氯 PProDOT 的沉积
	<ol>
<li>在单体安瓿中加入50毫克的 34-propylenedioxythiophene (ProDOT), 并将其连接到管状腔内。保持针阀开启。</li>
		<li>将衬底 (玻璃滑梯、布料、纸张等) 放在室内。基体的大小是 1.3 cm x 2.5 cm。</li>
		<li>添加50毫克的 FeCl3在一个5毫升的坩埚, 并把它放在会议厅。 注: 单体入口、衬底和坩埚的相对位置显示在图 1中。单体入口与坩埚之间的距离为13厘米。</li>
		<li>打开水泵。慢慢关闭右端的阀门。室压低于 525 mTorr (70 Pa) 后, 在冷阱中加入液氮。</li>
		<li>用加热带将三加热区包裹起来, 并将加热带连接到温度控制器。</li>
		<li>当压力降低到加工压力 (52.5 mTorr, 7 Pa) 时, 关闭单体容器的针阀。</li>
		<li>开始加热氧化剂, 基板和单体在170° c, 80 ° c, 和80° c 分别。在10分钟后, FeCl3被汽化, 并且红色 FeCl3实体在凉爽的区域中形成。</li>
		<li>打开单体容器的针阀。 注: 在承印物区域将形成蓝色的薄膜。典型的增长率是〜 10 nm/分钟. 确保在打开单体容器的针阀之前, 在腔室中形成 FeCl 的3蒸气。否则, 单体将与 FeCl 的3固体在坩埚中反应, 形成聚合物层, 防止氧化剂进一步汽化。</li>
		<li>当所需的厚度达到时, 关闭单体容器的针阀。关掉所有的暖气胶带, 冷却系统到室温。</li>
		<li>打开进气阀门, 关闭泵。</li>
		<li>把样品从房间里拿出来。将样品在甲醇中仔细浸泡30分钟, 除去残余氧化剂和单体。 注: 冲洗时间应随着薄膜厚度的增加而增加。30分钟冲洗是典型的薄膜薄比 100 nm 在玻璃幻灯片。当冲洗时, 厚于500纳米的薄膜可能会从基体分层。</li>
		<li>小心地用氮气吹干样品。</li>
	</ol>
</li>
	<li>
沉积的氯-PTT
	<ol>
<li>在单体安瓿中加入50毫克的 2,3-c [32-b] 噻吩 (TT), 并将其连接到管状腔内。保持针阀开启。</li>
		<li>重复步骤1.2.2。1.2.12。</li>
	</ol>
</li>
</ol>2. Br-PEDOT 的沉积
<ol><li>
沉积室设置
	<ol>
<li>添加一个额外的1/4 个. 侧向进口氧化剂的石英管, 使它8在. 除了单体入口。将液体氧化剂放置在石英安瓿中, 并将安瓿与单体 (图 2) 的方式连接到管腔。</li>
	</ol>
</li>
	<li>
Br-PEDOT 的沉积
	<ol>
<li>在单体安瓿中加入2毫升的 34-吩 (EDOT), 并将安瓿连接到管腔。保持针阀开启。</li>
		<li>将基板 (玻片、织物、纸张等) 放置在单体蒸汽入口附近的管状腔内。基体的大小是 1.3 cm x 2.5 cm。</li>
		<li>在油烟罩中, 在氧化剂安瓿中加入2毫升的 Br2 , 将安瓿连接到针阀, 并保持针阀关闭。将针阀连接至石英管。 警告:Br2是一种有害物质。在处理时使用警告。</li>
		<li>打开水泵。慢慢关闭右端的阀门。室压低于 525 mTorr (70 Pa) 后, 在冷阱中加入液氮。</li>
		<li>用加热带将单体区域包裹起来, 并将其与温度控制器连接。在室温下保持基体和氧化剂的区域。</li>
		<li>当压力降低到 52.5 mTorr (7 Pa) 的加工压力时, 打开氧化剂的针阀。 注意: 反应非常快。蓝 PEDOT 薄膜将形成接近单体入口, 因为 Br2是非常不稳定的。</li>
		<li>当所需的厚度达到时, 关闭单体和氧化剂的针阀。</li>
		<li>关闭加热胶带, 将系统冷却至室温。</li>
		<li>打开进气阀门, 关闭泵。把样品从房间里拿出来。 注: Br2掺杂聚合物不需要漂洗。</li>
	</ol>
</li>
</ol>

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作者没有什么可透露的。

反应的机理是氧化聚合。采用相同机理的聚合物涂层方法包括聚合17和气相聚合法18。聚合需要导电衬底, 缺乏均匀和保形涂层的优势, 是一种环境不友好的解决方法19。现有的气相聚合方法与这里所报道的方法相似, 但只能聚合高挥发性单体20。我们的方法改进了现有方法的腔室设计, 不仅能聚合高挥发性单体, 而且还能不稳定的单体。用气相沉积法首次合成了一些新型导电和半导体聚合物, 如 PProDOT 和 PTT, 使用这里所报告的方法20。
协议中的一个关键步骤是引入单体蒸气 (步骤 1.2.8) 的时机。在该协议中, 在 FeCl3蒸气形成后, 应将单体蒸气引入到腔室中, 这可以通过在冷区形成红色固体来告诉。如果在有 FeCl3蒸汽之前引入单体蒸汽, 则单体蒸气将到达氧化剂坩埚, 并直接与固体氧化剂反应。这将形成一个聚合物层覆盖固体氧化剂, 防止它汽化。另一方面, 如果单体蒸气的引入太晚, 将形成一层厚的氧化剂, 从而影响聚合物薄膜的形貌。
聚合物薄膜的厚度可由反应时间控制。本文介绍的聚合物薄膜的沉积速率为 10 nm/分钟, 可由单体的流速控制。在本协议中, 通过调节单体温度和针阀来控制单体的流动速率。如果需要更精确的控制, 可以在单体安瓿和单体入口之间添加一个高温质量流量计。
我们只在这个协议中展示了三个聚合物的例子。对于其他聚合物的涂层, 反应条件需要优化。如果使用相同的氧化剂, 氧化剂的温度可以与协议保持一致。据报道, 过程压力影响了聚合物的链长度。低过程压力会导致短的共轭21。每个新单体的氧化剂的温度也应优化。一个典型的起始值是氧化剂的熔点。当单体温度增加时, 最佳衬底温度通常会增加。对于小于500纳米的聚合物薄膜, 用丰富的甲醇冲洗就足以完全去除所有残余氧化剂和单体。对于较厚的薄膜, 要完全去除残余的 FeCl3, 薄膜可以浸泡在一个1米 HCl 水溶液过夜, 然后用甲醇冲洗。
报告的沉积室的缺点是它缺乏一个原位QCM (石英晶体天平) 传感器, 因此, 沉积速率和薄膜厚度不能监测在沉积过程中。由于质量输送的横向方向, 整个衬底区的膜厚不均匀。在图 3中显示了 PProDOT 的气相聚合的横向聚合物膜厚度剖面。在单体源与氧化剂源中间形成的聚合物膜厚度最厚, 从中间到两个侧向方向逐渐减小。这证实了从两个气源到基体区域中间的质量输送的横向方向, 并揭示了厚度不仅可以通过反应时间来控制, 而且还可通过基底位置来进行调节。
由于这种方法可以在任意基底上沉积导电和半导体聚合物, 因此可以应用于非常规基板上的下一代电子学, 如可穿戴设备22,23。例如, 导电 PEDOT 或 PProDOT 可以在纺织品上进行大规模的涂层, 以制造导电纺织品, 它们可用于可穿戴的电子产品24。此外, 蒸气沉积共轭聚合物也可以作为电极或在电子纸上的活性层, 以实现轻质和低成本, 而解决涂层方法不适用于纸张基板25。
最后, 我们展示了一种反应性的气相沉积方法, 用于创建导电 PProDOT 和 PEDOT, 以及在玻片、纸张和纺织品上的半导体 PTT 薄膜。这两种聚合物都没有经过反应气相沉积合成。这种气相沉积法能在高度无序和纹理高的表面积基底上均匀地形聚合物薄膜。这一特性允许在柔性和高质感的基板上应用蒸汽沉积聚合物在电子设备上。

聚合物导电和半导体材料具有独特的特性, 如灵活性1、拉伸2、透明3和低密度、4 , 它为创建下一代电子设备在非传统的基板上。目前, 许多研究人员正在努力利用高分子材料的独特特性来创造灵活和/或耐磨的电子产品5,6和智能纺织品7。然而, 形涂层的能力高纹理表面和 non-robust 基板, 如纸张, 织物和线程/纱线, 仍然 unmastered。最常见的是, 用溶液方法合成和涂覆在表面的聚合物。8,9,10,11,12虽然解决方法提供了聚合物涂层纤维/纺织品, 但由此获得的涂层通常不均匀, 容易受到小物理应力的破坏13,14 。由于润湿问题, 解决方法也不适用于涂布纸。
活性气相沉积可以在不同的基底上产生共形共轭聚合物膜, 无论表面化学/成分, 表面能和表面粗糙度/地形15。在这种方法中, 共轭聚合物在蒸汽相中合成, 同时将单体和氧化剂蒸气输送到表面。聚合和膜的形成发生在一个单一的, 无溶剂的步骤表面。这种方法在理论上适用于任何可以用溶液法合成的共轭聚合物。然而, 到目前为止, 只存放一组狭窄的共轭聚合物结构的协议是已知的。15
在这里, 我们演示了导电聚 (34-吩) (PEDOT) 和聚 (34-propylenedioxythiophene) (PProDOT), 和半导体聚 (2,3-c [32-b] 噻吩) (PTT) 薄膜通过反应气相沉积。两种氧化剂, 固体 FeCl3和液体 Br2, 在该过程中使用。相应的聚合物被命名为 PProDOT、cl-PTT 和 Br-PEDOT。传统的基板, 玻璃幻灯片, 和非传统的纹理基板, 如纸, 毛巾和织物, 都涂上了聚合物薄膜。
本协议描述了 custom-built 气相沉积室的设置和沉积过程的细节。它的目的是帮助新的从业者建立他们的沉积系统, 避免与气相合成相关的常见缺陷。

<table>
	<tbody>
		<tr>
			<td>3,4-Ethylenedioxythiophene, 97%</td>
			<td>Sigma Aldrich</td>
			<td>483028</td>
			<td></td>
		</tr>
		<tr>
			<td>3,4-Propylenedioxythiophene, 97%</td>
			<td>Sigma Aldrich</td>
			<td>660485</td>
			<td></td>
		</tr>
		<tr>
			<td>Thieno[3,2-b]thiophene, 95%</td>
			<td>Sigma Aldrich</td>
			<td>702668</td>
			<td></td>
		</tr>
		<tr>
			<td>FeCl3, 97%</td>
			<td>Sigma Aldrich</td>
			<td>157740</td>
			<td></td>
		</tr>
		<tr>
			<td>Br2</td>
			<td>Sigma Aldrich</td>
			<td>207888</td>
			<td></td>
		</tr>
	</tbody>
</table>

reactive vapor deposition of conjugated polymer films on arbitrary substrates

我们演示了一种形涂层共轭聚合物在任意基底上使用定制设计的低压反应室的方法。导电聚合物, 聚 (34-吩) (PEDOT) 和聚 (34-propylenedioxythiophene) (PProDOT), 和一个半导体聚合物, 聚 (2,3-c [32-b] 噻吩) (PTT), 沉积在非传统的高度无序和具有高表面积的纹理基质, 如纸、毛巾和织物。这一报告的沉积室是以前的蒸气反应堆的改进, 因为我们的系统可以同时容纳挥发性和非挥发单体, 如 34-propylenedioxythiophene 和 2,3-c [32-b] 噻吩。同时也证明了固体和液态氧化剂的利用。这种方法的一个局限性是它缺乏复杂的原位厚度监视器。通常采用的解决涂层方法 (如自旋涂层和表面接枝) 所制成的聚合物涂层通常不均匀或易受机械降解的影响。这种报告的气相沉积方法克服了这些缺点, 是一种很强的替代普通解决涂层方法。值得注意的是, 被报道的方法涂覆的聚合物薄膜在粗糙表面上是均匀和共形的, 即使在微米尺度上也是如此。这一特性允许在柔性和高质感的基板上应用蒸汽沉积聚合物在电子设备上。

在 1.3 cm x 2.5 cm 玻璃幻灯片上形成的 PProDOT 薄膜的厚度, 在沿中心管的离散侧向位置上由一个仪 (图 3) 测量。电导率是用国产四点探针测站测量的。在玻片上的 100 nm 厚的氯 PProDOT 薄膜的电导率是 106s/厘米, 这是足够的资格这部电影作为一个潜在的电极材料。图 4是在玻片上的 100 nm PProDOT 胶片的 AFM 图像。收集了在冲洗前后的玻片上的 PProDOT 薄膜的 X 射线光电子能谱 (XPS) 谱, 以证明所有剩余的 FeCl3被移除, 并证明了电导率仅从聚合物中产生 (图 5)。
在图 6中显示了 cl-PProDOT、cl-PTT 和 Br-PEDOT 的紫外/可见光吸收光谱。由于存在过量氧化剂, 在沉积后立即分离的聚合物是p掺杂的。因此, 这些薄膜是彩色的蓝色, 由于 polaronic 和 bipolaronic 吸收带在红色/近红外区域。在冲洗前后, 极化和极化子子的特性在600纳米以上的广泛的、无特征的吸收带保持不变, 这表明 cl-PProDOT 和 br-PEDOT 仍然是p掺杂冲洗后。相比之下, 在漂洗过程中, cl ptt 没有极化子或极化峰, 这表明在漂洗期间, cl ptt 是完全 de-doped 的。
在图 7中显示了显微和扫描电子显微镜 (SEM) 的纸张、灯芯绒织物和一条棉巾在与 Cl PTT 涂层前后的图像。涂布后, 洁白的基板变成暗红色, 表明存在的 Cl PTT 涂层。所有的三基板都是高度纹理和无序, 有较高的表面积。SEM 图像显示, 在所有的三基底上, 薄膜在表面上都是均匀的和共形的。
<img alt="Figure 1" class="xfigimg" src="/files/ftp_upload/56775/56775fig1.jpg"> 图1。沉积室设置.固体氧化剂气相沉积室示意图。<a href="//cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56775/56775fig1large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 2" class="xfigimg" src="/files/ftp_upload/56775/56775fig2.jpg"> 图2。沉积室设置.液体氧化剂的管状气相沉积室示意图。<a href="//cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56775/56775fig2large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 3" class="xfigimg" src="/files/ftp_upload/56775/56775fig3.jpg"> 图3。聚合物薄膜的厚度表征.PProDOT 的气相聚合的横向聚合物膜厚度剖面。
<img alt="Figure 4" class="xfigimg" src="/files/ftp_upload/56775/56775fig4.jpg"> 图4。用 AFM 进行形貌表征.100纳米氯 PProDOT 在玻片上的 AFM 图像。
<img alt="Figure 5" class="xfigimg" src="/files/ftp_upload/56775/56775fig5.jpg"> 图5。元素分析.XPS 光谱的 1.3 cm x 2.5 cm 玻璃幻灯片涂层与 100 nm 厚膜的 Cl PProDOT 后立即沉积 (黑线) 和后冲洗 (红线) 与甲醇。光谱显示, 铁盐在漂洗之后被去除。
<img alt="Figure 6" class="xfigimg" src="/files/ftp_upload/56775/56775fig6.jpg"> 图6。光学特性特性.在玻片上的 PProDOT、氯-PTT 和 Br-PEDOT 薄膜的吸收光谱。<a href="//cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56775/56775fig6large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>
<img alt="Figure 7" class="xfigimg" src="/files/ftp_upload/56775/56775fig7.jpg"> 图7。光学显微镜和扫描电子显微镜 (SEM) 的形态学表征.光学显微 (a-c) 和 PTT 涂层 (d-f) 纸, 聚酯/人造丝灯芯绒和棉毛巾。SEM 图像 (g i) 的 PTT 涂层纸, 聚酯/人造丝灯芯绒和棉毛巾。<a href="//cloudflare-jove-com.remotexs.ntu.edu.sg/files/ftp_upload/56775/56775fig7large.jpg" target="_blank">请单击此处查看此图的较大版本.</a>

Watch this Scientific Journal Video about Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates at JoVE.com

Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

任意基底上共轭聚合物薄膜的反应气相沉积

本文介绍了在玻片和粗糙衬底上的聚 (34-吩)、聚 (34-propylenedioxythiophene) 和聚 (2,3-c [32-b] 噻吩) 薄膜的活性气相沉积的协议, 如纺织品和纸张。

We demonstrate a method of conformally coating conjugated polymers on arbitrary substrates using a custom-designed, low-pressure reaction chamber. ...

reactive-vapor-deposition-conjugated-polymer-films-on-arbitrary

Nanyang Technological University

Research

JoVE Journal

Chemistry

33.4K 次观看.  University of Wisconsin-Madison. 本文介绍了在玻片和粗糙衬底上的聚 (34-吩)、聚 (34-propylenedioxythiophene) 和聚 (2,3-c [32-b] 噻吩) 薄膜的活性气相沉积的协议, 如纺织品和纸张。

视频: Reactive Vapor Deposition of Conjugated Polymer Films on Arbitrary Substrates

Preparation of Hydrophobic Metal-Organic Frameworks via Plasma Enhanced Chemical Vapor Deposition of Perfluoroalkanes for the Removal of Ammonia

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high surface area microporous materials, such as metal-organic frameworks (MOFs), unique challenges present themselves for PECVD treatments. Herein the protocol for development of a MOF that was previously unstable to humid conditions is presented. The protocol describes the synthesis of Cu-BTC (also known as HKUST-1), the treatment of Cu-BTC with PECVD of perfluoroalkanes, the aging of materials under humid conditions, and the subsequent ammonia microbreakthrough experiments on milligram quantities of microporous materials. Cu-BTC has an extremely high surface area (~1,800 m2/g) when compared to most materials or surfaces that have been previously treated by PECVD methods. Parameters such as chamber pressure and treatment time are extremely important to ensure the perfluoroalkane plasma penetrates to and reacts with the inner MOF surfaces. Furthermore, the protocol for ammonia microbreakthrough experiments set forth here can be utilized for a variety of test gases and microporous materials.

Herein the procedures for plasma enhanced chemical vapor deposition of perfluoroalkanes on microporous materials such as metal-organic frameworks to enhance their stability and hydrophobicity are described. Furthermore, breakthrough testing of milligram quantities of samples is described in detail.

增强型氟烷烃的化学气相沉积等离子通过疏水金属 - 有机骨架的制备氨的去除

Plasma enhanced chemical vapor deposition (PECVD) of perfluoroalkanes has long been studied for tuning the wetting properties of surfaces. For high ...

科研

化学

Fabrication of Large-area Free-standing Ultrathin Polymer Films

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films. Typically, ultrathin films are prepared using either sacrificial layers, which may damage the film or affect its mechanical properties, or they are made on freshly cleaved mica, a substrate that is difficult to scale. Further, the size of ultrathin film is typically limited to a few square millimeters. In this method, we modify a surface with a polyelectrolyte that alters the strength of adhesion between polymer and deposition substrate. The polyelectrolyte can be shown to remain on the wafer using spectroscopy, and a treated wafer can be used to produce multiple films, indicating that at best minimal amounts of the polyelectrolyte are added to the film. The process has thus far been shown to be limited in scalability only by the size of the coating equipment, and is expected to be readily scalable to industrial processes. In this study, the protocol for making the solutions, preparing the deposition surface, and producing the films is described.

We describe a method for the fabrication of large-area (up to 13 cm diameter) and ultrathin (as thin as 8 nm) polymer films. Instead of using a sacrificial interlayer to delaminate the film from its substrate, we use a self-limiting surface treatment suitable for arbitrarily large areas.

大面积的制造自立性的超薄聚合物薄膜

This procedure describes a method for the fabrication of large-area and ultrathin free-standing polymer films.  Typically, ultrathin films are prepared ...

Chemical Vapor Deposition of an Organic Magnet, Vanadium Tetracyanoethylene

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in traditional materials, including low cost and mechanical flexibility. In a similar vein, it would be advantageous to expand the use of organics into high frequency electronics and spin-based electronics. This work presents a synthetic process for the growth of thin films of the room temperature organic ferrimagnet, vanadium tetracyanoethylene (V[TCNE]x, x~2) by low temperature chemical vapor deposition (CVD). The thin film is grown at &#60;60 &#176;C, and can accommodate a wide variety of substrates including, but not limited to, silicon, glass, Teflon and flexible substrates. The conformal deposition is conducive to pre-patterned and three-dimensional structures as well. Additionally this technique can yield films with thicknesses ranging from 30 nm to several microns. Recent progress in optimization of film growth creates a film whose qualities, such as higher Curie temperature (600 K), improved magnetic homogeneity, and narrow ferromagnetic resonance line-width (1.5 G) show promise for a variety of applications in spintronics and microwave electronics.

We present the synthesis of the organic-based ferrimagnet vanadium tetracyanoethylene (V[TCNE]x, x~2) via low temperature chemical vapor deposition (CVD). This optimized recipe yields an increase in Curie temperature from 400 K to over 600 K and a dramatic improvement in magnetic resonance properties.

化学气相沉积的有机磁体，钒四氰

Recent progress in the field of organic materials has yielded devices such as organic light emitting diodes (OLEDs) which have advantages not found in ...

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 ...

Preparation of Macroporous Epitaxial Quartz Films on Silicon by Chemical Solution Deposition

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step process based on the preparation of a sol in a one-pot synthesis which is followed by the deposition of a gel film on Si(100) substrates by evaporation induced self-assembly using the dip-coating technique and ends with a thermal treatment of the material to induce the gel crystallization and the growth of the quartz film. The formation of a silica gel is based on the reaction of a tetraethyl orthosilicate and water, catalyzed by HCl, in ethanol. However, the solution contains two additional components that are essential for preparing mesoporous epitaxial quartz films from these silica gels dip-coated on Si. Alkaline earth ions, like Sr2+ act as glass melting agents that facilitate the crystallization of silica and in combination with cetyl trimethylammonium bromide (CTAB) amphiphilic template form a phase separation responsible of the macroporosity of the films. The good matching between the quartz and silicon cell parameters is also essential in the stabilization of quartz over other SiO2 polymorphs and is at the origin of the epitaxial growth.

A protocol is presented for the preparation of piezoelectric macroporous epitaxial films of quartz on silicon by solution chemistry using dip-coating and thermal treatments in air.

化学溶液沉积在硅外延大孔石英薄膜的制备

This work describes the detailed protocol for preparing piezoelectric macroporous epitaxial quartz films on silicon(100) substrates. This is a three-step ...

Capillary Electrophoresis to Monitor Peptide Grafting onto Chitosan Films in Real Time

Free-solution capillary electrophoresis (CE) separates analytes, generally charged compounds in solution through the application of an electric field. Compared to other analytical separation techniques, such as chromatography, CE is cheap, robust and effectively requires no sample preparation (for a number of complex natural matrices or polymeric samples). CE is fast and can be used to follow the evolution of mixtures in real time (e.g., chemical reaction kinetics), as the signals observed for the separated compounds are directly proportional to their quantity in solution.
Here, the efficiency of CE is demonstrated for monitoring the covalent grafting of peptides onto chitosan films for subsequent biomedical applications. Chitosan&#39;s antimicrobial and biocompatible properties make it an attractive material for biomedical applications such as cell growth substrates. Covalently grafting the peptide RGDS (arginine - glycine - aspartic acid - serine) onto the surface of chitosan films aims at improving cell attachment. Historically, chromatography and amino acid analysis have been used to provide a direct measurement of the amount of grafted peptide. However, the fast separation and absence of sample preparation provided by CE enables equally accurate yet real-time monitoring of the peptide grafting process. CE is able to separate and quantify the different components of the reaction mixture: the (non-grafted) peptide and the chemical coupling agents. In this way the use of CE results in improved films for downstream applications.
The chitosan films were characterized through solid-state NMR (nuclear magnetic resonance) spectroscopy. This technique is more time-consuming and cannot be applied in real time, but yields a direct measurement of the peptide and thus validates the CE technique.

Free solution capillary electrophoresis is a fast, cheap and robust analytical method that enables the quantitative monitoring of chemical reactions in real time. Its utility for rapid, convenient and precise analysis is demonstrated here through analysis of covalent peptide grafting onto chitosan films for improved cell adhesion.

毛细管电泳监视肽接枝壳聚糖膜实时

Free-solution capillary electrophoresis (CE) separates analytes, generally charged compounds in solution through the application of an electric field. ...

Low Pressure Vapor-assisted Solution Process for Tunable Band Gap Pinhole-free Methylammonium Lead Halide Perovskite Films

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, we present a protocol for the fabrication of this material via the low-pressure vapor assisted solution process (LP-VASP) method, which yields ~19% power conversion efficiency in planar heterojunction perovskite solar cells. First, we report the synthesis of methylammonium iodide (CH3NH3I) and methylammonium bromide (CH3NH3Br) from methylamine and the corresponding halide acid (HI or HBr). Then, we describe the fabrication of pinhole-free, continuous methylammonium-lead halide perovskite (CH3NH3PbX3 with X = I, Br, Cl and their mixture) films with the LP-VASP. This process is based on two steps: i) spin-coating of a homogenous layer of lead halide precursor onto a substrate, and ii) conversion of this layer to CH3NH3PbI3-xBrx by exposing the substrate to vapors of a mixture of CH3NH3I and CH3NH3Br at reduced pressure and 120 &#176;C. Through slow diffusion of the methylammonium halide vapor into the lead halide precursor, we achieve slow and controlled growth of a continuous, pinhole-free perovskite film. The LP-VASP allows synthetic access to the full halide composition space in CH3NH3PbI3-xBrx with 0&#160;&#8804; x&#160;&#8804; 3. Depending on the composition of the vapor phase, the bandgap can be tuned between 1.6 eV&#160;&#8804; Eg&#160;&#8804; 2.3 eV. In addition, by varying the composition of the halide precursor and of the vapor phase, we can also obtain CH3NH3PbI3-xClx. Films obtained from the LP-VASP are reproducible, phase pure as confirmed by X-ray diffraction measurements, and show high photoluminescence quantum yield. The process does not require the use of a glovebox.

Here, we present a protocol for the synthesis of CH3NH3I and CH3NH3Br precursors and the subsequent formation of pinhole-free, continuous CH3NH3PbI3-xBrx thin films for the application in high efficiency solar cells and other optoelectronic devices.

可调谐带隙无针孔 Methylammonium 铅卤化物钙钛矿薄膜的低压蒸气辅助解决工艺

Organo-lead halide perovskites have recently attracted great interest for potential applications in thin-film photovoltaics and optoelectronics. Herein, ...

Aerosol-assisted Chemical Vapor Deposition of Metal Oxide Structures: Zinc Oxide Rods

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, their high cost production and/or incompatibility with microfabrication technologies, due to the use of pre-deposited catalyst-seeds and/or high processing temperatures exceeding 900 &#176;C, represent a drawback for a widespread use of these methods. Here, however, we report the synthesis of ZnO rods via a non-catalyzed vapor-solid mechanism enabled by using an aerosol-assisted chemical vapor deposition (CVD) method at 400 &#176;C with zinc chloride (ZnCl2) as the precursor and ethanol as the carrier solvent. This method provides both single-step formation of ZnO rods and the possibility of their direct integration with various substrate types, including silicon, silicon-based micromachined platforms, quartz, or high heat resistant polymers. This potentially facilitates the use of this method at a large-scale, due to its compatibility with state-of-the-art microfabrication processes for device manufacture. This report also describes the properties of these structures (e.g., morphology, crystalline phase, optical band gap, chemical composition, electrical resistance) and validates its gas sensing functionality towards carbon monoxide.

Columnar zinc oxide structures in the form of rods are synthesized via aerosol-assisted chemical vapor deposition without the use of pre-deposited catalyst-seed particles. This method is scalable and compatible with various substrates based on either silicon, quartz or polymers.

金属氧化物结构的气溶胶辅助化学气相沉积: 氧化锌棒

Whilst columnar zinc oxide (ZnO) structures in the form of rods or wires have been synthesized previously by different liquid- or vapor-phase routes, ...

Monitoring the Effects of Illumination on the Structure of Conjugated Polymer Gels Using Neutron Scattering

We demonstrate a protocol to effectively monitor the gelation process of a high concentration solution of conjugated polymer both in the presence and absence of white light exposure. By instituting a controlled temperature ramp, the gelation of these materials can be precisely monitored as they proceed through this structural evolution, which effectively mirrors the conditions experienced during the solution deposition phase of organic electronic device fabrication. Using small angle neutron scattering (SANS) and ultra-small angle neutron scattering (USANS) along with appropriate fitting protocols we quantify the evolution of select structural parameters throughout this process. Thorough analysis indicates that continued light exposure throughout the gelation process significantly alters the structure of the ultimately formed gel. Specifically, the aggregation process of poly(3-hexylthiophene-2,5-diyl) (P3HT) nano-scale aggregates is negatively affected by the presence of illumination, ultimately resulting in the retardation of growth in conjugated polymer microstructures and the formation of smaller scale macro-aggregate clusters.

A protocol for the analysis of gels formed from the optoelectronic conjugated polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) using small and ultra-small angle neutron scattering in both the presence and absence of illumination is presented.

利用中子散射监测光照对共轭高分子凝胶结构的影响

We demonstrate a protocol to effectively monitor the gelation process of a high concentration solution of conjugated polymer both in the presence and ...

Raman and IR Spectroelectrochemical Methods as Tools to Analyze Conjugated Organic Compounds

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule on the vibrational level of energy. Raman and IR spectroelectrochemistry can be used for advanced characterization of the structural changes in the organic electroactive compounds. Here, the step-by-step analysis by means of Raman and IR spectroelectrochemistry is shown. Raman and IR spectroelectrochemical techniques provide complementary information about structural changes occurring during an electrochemical process, i.e. allows for the investigation of redox processes and their products. The examples of IR and Raman spectroelectrochemical analysis are presented, in which the products of the redox reactions, both in solution and solid state, are identified.

A protocol of step-by-step Raman and IR spectroelectrochemical analysis is presented.

拉曼光谱和红外光谱电化学法作为分析共轭有机化合物的工具

In the presented work, two spectroelectrochemical techniques are discussed as tools for the analysis of the structural changes occurring in the molecule ...