This work was partially funded by a PEPS project of Cellule Energie INSIS-CNRS (1D-RENOX) to ACG and the Spanish Government (MAT2012-35324 and PIE-201460I004).

1. Preparation of the Sol
<ol>
	<li>Prepare a solution of prehydrolyzed tetraethyl orthosilicate (TEOS) the day before the preparation of the gel films in a fume hood in which a lab balance and a magnetic stirrer are placed. In this step and throughout the protocol wear a lab coat, gloves and safety goggles.
	<ol>
		<li>In a 50 ml beaker containing a Teflon coated magnetic stirring bar weigh 1.68 g of CTAB, add 48.13 ml of ethanol and 3.00 ml of HCl 35%, cover the beaker with a watch glass and stir until the CTAB is co...

<ol>
	<li>Esser, A. T., Smith, K. C., Gowrishankar, T. R., Vasilkoski, Z., Weaver, J. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mechanisms+for+the+intracellular+manipulation+of+organelles+by+conventional+electroportation.">Mechanisms for the intracellular manipulation of organelles by conventional electroportation.</a> Biophys. J. 98 (11), 2506-2514 (2010).</li><li>Stava, E., Yu, M., Shin, H. C., Shin, H., Kreft, D. J., Blick, R. H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Rapid+fabrication+and+piezoelectric+tuning+of+micro-+and+nanopores+in+single+crystal+quartz.">Rapid fabrication and piezoelectric tuning of micro- and nanopores in single crystal quartz.</a> Lab Chip. 13 (1), 156-160 (2013).</li><li>Varshneya, A. K. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=.">.</a> Fundamentals of Inorganic Glasses. , (1994).</li><li>Christov, M., Kirov, G. C. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=The+ratio+of+dissolving+surface+area/growing+surface+area+in+the+hydrothermal+growth+of+quartz.">The ratio of dissolving surface area/growing surface area in the hydrothermal growth of quartz.</a> J. Cryst. Growth. 131 (3-4), 560-564 (1993).</li><li>Bertone, J. F., Cizeron, J., Wahi, R. K., Bosworth, J. K., Colvin, V. L. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrothermal+synthesis+of+quartz+nanocrystals.">Hydrothermal synthesis of quartz nanocrystals.</a> Nano Lett. 3, 655-659 (2003).</li><li>Jiang, Y., Brinker, C. J. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Hydrothermal+synthesis+of+monodisperse+single-crystalline+alpha-quartz+nanospheres.">Hydrothermal synthesis of monodisperse single-crystalline alpha-quartz nanospheres.</a> Chem. Comm. 47 (26), 7524-7526 (2011).</li><li>Okabayashi, M., Miyazaki, K., Kono, T., Tanaka, M., Toda, Y. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Preparation+of+Spherical+Particles+with+Quartz+Single.">Preparation of Spherical Particles with Quartz Single.</a> Chem. Lett. 34 (1), 58-59 (2005).</li><li>Carretero-Genevrier, 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=Soft-Chemistry-Based+Routes+to+Epitaxial+&#945;-Quartz+Thin+Films+with+Tunable+Textures.">Soft-Chemistry-Based Routes to Epitaxial &#945;-Quartz Thin Films with Tunable Textures.</a> Science. 340 (6134), 827-831 (2013).</li><li>Brinker, C. J., Clem, P. G. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Quartz+on+Silicon.">Quartz on Silicon.</a> Science. 340 (6134), 818-819 (2013).</li><li>Brinker, C. J., Lu, Y., Sellinger, A., Fan, H. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Evaporation-Induced+Self-Assembly:+Nanostructures+Made+Easy.">Evaporation-Induced Self-Assembly: Nanostructures Made Easy.</a> Adv. Mater. 11 (7), 579-585 (1999).</li><li>Griffith, C. S., Sizgek, G. D., Sizgek, E., Scales, N., Yee, P. J., Luca, V. <a target="_blank" href="http://www.ncbi.nlm.nih.gov/entrez/query.fcgi?db=PubMed&cmd=Search&doptcmdl=Citation&defaultField=Title+Word&term=Mesoporous+Zirconium+Titanium+Oxides.+Part+1:+Porosity+Modulation+and+Adsorption+Properties+of+Xerogels.">Mesoporous Zirconium Titanium Oxides. Part 1: Porosity Modulation and Adsorption Properties of Xerogels.</a> Langmuir. 24 (21), 12312-12322 (2008).</li><li>Lu, Y., 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=Continuous+formation+of+supported+cubic+and+hexagonal+mesoporous+films+by+sol-gel+dip-coating.">Continuous formation of supported cubic and hexagonal mesoporous films by sol-gel dip-coating.</a> Nature. 389 (6649), 364-368 (1997).</li><li>Drisko, G. L., 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=Water-Induced+Phase+Separation+Forming+Macrostructured+Epitaxial+Quartz+Films+on+Silicon.">Water-Induced Phase Separation Forming Macrostructured Epitaxial Quartz Films on Silicon.</a> Adv. Funct. Mater. 24 (35), 5494-5502 (2014).</li></ol>

The authors have nothing to disclose.

The presented method is a bottom-up approach to produce macroporous quartz films on Si. Compared to the standard method of production of quartz films, a top down technology based on cutting and polishing of large hydrothermally grown crystals, the method described in the protocol allows obtaining much thinner films with thicknesses between 150 and 450 nm which can be controlled with the withdrawal rate. All experimental details regarding the control of quartz films thickness, and piezoelectric response are reported in re...

When a piezoelectric material like &#945;-quartz is submitted to a voltage bias it undergoes a mechanical deformation. If this material is porous, these volume changes can lead to pore expansion or contraction, creating a responsive system similar to what may be observed in living biological organelles.1 Deformable porous &#945;-quartz has been produced using microfabrication,2 but such techniques cannot yet produce 3-D pore structures, and pore diameters are on the order of hundreds of nanometers. Crystallization of structured amorphous silica has been hindered by inhomogeneous nucleation caused by high surface energies and architectural deformation due to coarsening and melting. Moreover, since all forms of silica are built upon extremely stable SiO4 tetrahedral networks, the free energies of formation of amorphous silica, &#945;-quartz and other SiO2 polymorphs are nearly equal in a wide range of temperatures, making it difficult to produce &#945;-quartz as a single polymorph from the crystallization of an amorphous silica gel.3 Another aspect that makes harder the controlled crystallization of structured amorphous silica is that quartz presents a relatively slow nucleation rate but an extremely fast growth rate, reported between 10-94 nm/sec.4,5 Slow nucleation coupled with fast growth tends to generate crystals much larger than the original nanoporous structure, thus the original morphology is lost. Alkali metals, such as Na+ and Li+, have been used to crystallize &#945;-quartz, frequently in combination with hydrothermal treatment.5,6 Also, a Ti4+/Ca2+ combination was employed to crystallize spherical particles of silica into quartz by a soft chemistry route using silicon alcoxides.7 However, the controlled crystallization of a structured amorphous silica film into quartz remained a challenge.
Recently, strontium has been found to catalyze the nucleation and growth of crystalline SiO2 under ambient pressure and relatively low temperatures.8,9 Epitaxy, arises from the favorable mismatch between &#945;-quartz and the &#60;100&#62; silicon substrate, producing oriented piezoelectric thin films. Evaporation-induced self-assembly to produce mesoporous silica films has been used since 1999.10 This technique has been studied and applied to a multitude of templating agents under various conditions to produce pores of variable sizes and mesophases. It has been found that subnanometric changes in mesopore size can have a dramatic effect on solute diffusion through porous systems11, validating this extensive attention to pore structure. Moreover, accessibility to the internal silica pore system can be obtained by controlling the micellar phase of the template.12
Here, the synthesis route that allows unprecedented control over the thickness and pore size of amorphous silica layers using a novel phase separation is demonstrated.13 These films are infiltrated with Sr(II) salts and crystallized to &#945;-quartz at 1,000 &#176;C under air at ambient pressure. The pore size retainable using this crystallization process is determined, and the effect of wall thickness and film thickness is studied. Finally the piezoelectricity and the deformability of the pore system are studied.

<table border="0" cellpadding="0" cellspacing="0" width="714">
	<tbody>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">Dip coater</td>
			<td style="width:281px;">Nadetech&#160;</td>
			<td style="width:173px;">ND-DC 11/150&#160;</td>
			<td style="width:80px;"></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">Furnace</td>
			<td style="width:281px;">Nabertherm&#160;</td>
			<td>R 50/250/12</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">Atomic Force Microscope</td>
			<td style="width:281px;">Agilent&#160;</td>
			<td>5500 LS</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">Materials and Reagents&#160;</td>
			<td style="width:281px;"></td>
			<td></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">Silicon wafers</td>
			<td style="width:281px;">SHE Europe Ltd.</td>
			<td></td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">SrCl2&#183;6H2O</td>
			<td style="width:281px;">Aldrich</td>
			<td>13909</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">CTAB</td>
			<td style="width:281px;">Aldrich</td>
			<td>H5582</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">Ethanol Absolute&#160;</td>
			<td style="width:281px;">Aldrich</td>
			<td>161086</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">HCl 35% solution</td>
			<td style="width:281px;">PanReac</td>
			<td>721019</td>
			<td></td>
		</tr>
		<tr height="21">
			<td height="21" style="height:21px;width:180px;">TEOS</td>
			<td style="width:281px;">Aldrich</td>
			<td>131903</td>
			<td></td>
		</tr>
	</tbody>
</table>

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.

The progress of the material synthesis was controlled by monitoring different aspects. After the dip-coating process one can observe the aspect of the films, the eventual appearance of diffraction structures in the reflected spot of a green laser and the Scanning Electron Microscopy (SEM) images in backscattered electrons mode (Figure 1A-B). After the crystallization process it is important to record Atomic Force Microscopy (AFM) topographic images (Figure 1C</str...

Watch this Scientific Journal Video about Preparation of Macroporous Epitaxial Quartz Films on Silicon by Chemical Solution Deposition at JoVE.com

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

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.

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

preparation-macroporous-epitaxial-quartz-films-on-silicon-chemical

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9.2K ビュー.  CNRS-École Centrale de Lyon. 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. 