HM acknowledges funding from King Abdullah University of Science and Technology (KAUST).

NOTE: Arrays of reentrant and doubly reentrant cavities and pillars were microfabricated by adapting the multistep protocol for pillars reported by Liu and Kim27. Precautions were taken to minimize the formation of pin residues or particles on our surfaces that could interfere with wetting transitions36.
MICROFABRICATION OF CAVITIES 
Broadly, the protocols for the microfabrication of reentrant and doubly reentrant cavities (RCs and DRCs) consist of two-dimensional layout designing, photolithography, general silica etching, and specific silicon etching, depending on the final feature required37,38,39,40,41.
1. Design
<ol>
	<li>Start the microfabrication process by designing the required pattern in a layout software42. An example of such a software is listed in the Materials List.</li>
	<li>Using the software, create a new file. Draw a unit cell comprising a circle of diameter, D = 200 &#181;m. Copy and paste this circle with a center-to-center distance (pitch) of L = 212 &#181;m to create an array of circles in a square patch of area 1 cm2 (Figure 2).</li>
	<li>Draw a circle of diameter 100 mm (4 inches). Place the 1 cm2 square array inside the circle and replicate it to create a 4 x 4 grid of square arrays. Features inside the circle will be transferred onto the 4-inch wafers (Figure 2).</li>
	<li>Export the design file to the desired format for the mask writing system (e.g., the GDSII format).</li>
</ol>
2. Cleaning of Wafers
<ol>
	<li>Clean a silicon wafer 4 inches in diameter, &#60;100&#62; orientation, and with a 2.4 &#181;m thick thermal oxide layer (see the Materials List), in piranha solution for 10 min. Piranha solution comprises sulfuric acid (H2SO4, 96%): hydrogen peroxide (H2O2, 30%) in a 3:1 volumetric ratio and is maintained at T = 388 K.</li>
	<li>Rinse the wafer with deionized water and spin-dry under nitrogen (N2) environment.</li>
</ol>
3. Photolithography
<ol>
	<li>Coat the wafer with hexamethyldisilazane (HMDS) using vapor-phase deposition to improve adhesion with the photoresist. Refer to Table 1 for the process details.</li>
	<li>Mount the wafer on a 4-inch vacuum chuck in the spin coater. Cover the wafer with the AZ-5214E photoresist. Use the spin coater to spread the photoresist uniformly on the surface as a 1.6 &#181;m-thick layer. Refer to Table 2 for spin coating parameters.</li>
	<li>Bake the photoresist-coated wafer on a hot-plate maintained at 110 &#176;C for 120 s.</li>
	<li>Transfer the wafer to a direct-writing system and expose the wafer to UV radiation for 55 ms (defocus: +5). This step transfers the desired design on the AZ-5214E (used in the positive tone; see Materials List) (Figure 2).</li>
	<li>Place the UV-exposed wafer in a glass Petri dish containing the AZ-726 developer for 60 s for the features to develop. See Materials List for details.</li>
	<li>Remove the wafer from the developer solution and rinse with deionized (DI) water gently to remove excess developer. Spin dry the wafer in a N2 environment. These steps are presented in Figure 3A&#8211;C.</li>
</ol>
NOTE: At the end of this step, design patterns on the wafer can be seen under a standard optical microscope.
4. Anisotropic Etching of Silica (SiO2) Layer
NOTE: The goal of this step is to completely etch away the silica layer (2.4 &#181;m-thick) that was exposed during photolithography to expose the silicon layer underneath.
<ol>
	<li>After photolithography, transfer the wafer to an inductively coupled plasma (ICP) reactive-ion etching (RIE) system that employs a mixture of octafluorocyclobutane (C4F8) and oxygen (O2) gases to etch silica vertically downward (anisotropic etching).</li>
	<li>Run the ICP-RIE process for approximately 13 min to etch the exposed silica layer. Refer to the ICP-RIE parameters in Table 3. During this step, the photoresist layer also gets completely etched away (Figure 3C&#8211;D).</li>
	<li>To ensure that the silica layer thickness inside the desired patterns is reduced to zero, so that the silicon layer is exposed, measure the thickness of the remaining silica using a reflectometer. Adjust the duration of the subsequent etching period based on the thicknesses of the silica layers (especially in and around the patterns).</li>
</ol>
NOTE: A reflectometer was used to measure the thickness of the remaining silica layer43. Alternatively, other tools, such as ellipsometer or an interactive color chart to predict the color of SiO2 and thickness can also be used44,45.
The procedures detailed in steps 1 and 4 are common for both reentrant and doubly reentrant cavities. However, the etching protocols for the silicon layer are different and are described below:
5. Reentrant Cavities
<ol>
	<li>Anisotropic silicon etching
	<ol>
		<li>After etching the silica layer, transfer the wafer to a deep ICP-RIE system to etch silicon. The first step consists of a fluorine-based anisotropic etching method known as the Bosch process that etches silicon vertically downward, creating a straight wall. 
		NOTE: The Bosch process uses C4F8 and sulfur hexafluoride (SF6) gases in the reaction chamber: the C4F8 deposition creates a passivation layer, while the SF6 etches silicon vertically downward. Thus, the Bosch process enables the microfabrication of deep trenches in silicon with high-aspect ratios.</li>
		<li>Run this process for five cycles, which corresponds to an etching depth for silicon equivalent to &#8776; 2 &#181;m. Process parameters are listed in Table 4.</li>
		<li>Clean the wafer in piranha solution for 10 min to remove any remnants of the Bosch process. Rinse the wafer with DI water and spin-dry in a N2 environment (Figure 3E).</li>
	</ol>
	</li>
	<li>Isotropic silicon etching: In order to create the reentrant feature, perform isotropic etching that would create an undercut beneath the silica layer. A 5 &#181;m overhang can be achieved by etching the silicon layer with SF6 for 2 min 45 s (Figure 3F). Refer to Table 5 for the process parameters.</li>
	<li>Anisotropic silicon etching: Once the reentrant features are created, tune the depth of the cavities by the Bosch process (step 5.1). 
	NOTE: To microfabricate cavities with a depth of hc &#8776; 50 &#181;m, 160 cycles of the Bosch process are required (Figure 3G, Table 4).</li>
	<li>Wafer cleaning and storage
	<ol>
		<li>Clean the wafer using piranha solution as described in step 2. After this step, the wafer becomes superhydrophilic, characterized by contact angles of water, &#952;o &#8776; 0&#176;.</li>
		<li>Store the wafer in a glass Petri dish and place inside a clean vacuum oven maintained at T = 323 K and vacuum pressure PVac = 3.3 kPa for 48 h, after which the intrinsic contact angle of the silica layer stabilizes to &#952;o &#8776; 40&#176;.</li>
		<li>Store the samples in a clean cabinet equipped with an outward nitrogen (99%) flow, ready for further characterization.</li>
	</ol>
	</li>
</ol>
6. Doubly Reentrant Cavities
<ol>
	<li>Anisotropic silicon etching: To create doubly reentrant cavities, follow steps 1, 2, 3, 4, and 5.1 (see Figure 4A&#8211;E).</li>
	<li>Isotropic silicon etching 
	In order to create doubly reentrant features, reentrant features must be created first. To achieve that, perform isotropic etching to create an undercut beneath the silica layer. Etch the silicon layer with SF6 for 25 s (Figure 4F). Refer to Table 5 for the process parameters. Subsequently, clean the wafer using piranha solution as described in step 2.</li>
	<li>Thermal oxide growth
	<ol>
		<li>To achieve doubly reentrant features, grow a 500 nm layer of thermal oxide on the wafer, using a high temperature furnace system (Figure 4G).</li>
		<li>Measure the thickness of the oxide layer using a reflectometer. 
		NOTE: The oxidation was carried out by exposing the samples to an environment comprising oxygen (O2) and water vapor, leading to the wet oxidation of silicon in an enclosed environment at temperatures ranging from 800&#8211;1,200 &#176;C.</li>
	</ol>
	</li>
	<li>Silica etching: Carry out the same process as described in the step 4 to etch silica vertically downward for 3 min. As a result of the anisotropic etching, the thermal oxide (500 nm thick silica layer) is etched away from the cavity, but it leaves an &#34;overhang&#34; along the sidewalls that would form the doubly reentrant edge eventually (Figure 4H, Table 3).</li>
	<li>Anisotropic silicon etching: Repeat five cycles of the Bosch process to deepen of the cavities by &#8776; 2 &#181;m (Figure 4I, Table 5). This step is necessary to remove the silicon behind the doubly reentrant feature in the next step. Clean the wafer using piranha solution.</li>
	<li>Isotropic silicon etching: Perform the isotropic etching of silicon for 2 min and 30 s using the process parameters described in Table 4. This step creates an empty space (&#8776;2 &#181;m) behind the thermally-grown oxide at the mouth of the cavity, leading to the doubly reentrant edge (Figure 4J).</li>
	<li>Anisotropic silicon etching: Use the Bosch process recipe (step 5.1) for 160 cycles to increase the depth of the cavities to hc &#8776; 50 &#181;m, (Figure 4K, Table 5).</li>
	<li>Wafer cleaning and storage: Clean the wafer using piranha solution and store as described in step 5.4 above.</li>
</ol>
MICROFABRICATION OF PILLARS 
The design protocol for fabricating reentrant and doubly reentrant pillars and &#34;hybrids&#34; (comprising doubly reentrant pillars surrounded by walls) consists of three key steps: wafer preparation, silica etching, and specific silicon etching. Figure 5A&#8211;C show the top-view of the layout design for reentrant and doubly reentrant pillars, while Figure 5D&#8211;F represent the layout of the hybrid arrays. Select the dark-field option of the UV exposure in order to expose the whole wafer except for the pattern using the same photoresist (AZ5214E) (Figure 6A&#8211;C and Figure 7A&#8211;C). Besides these specificities, the processes for cleaning the wafer (step 2) and etching silica (step 4) are identical.
7. Reentrant Pillars
<ol>
	<li>Anisotropic silicon etching: After photolithography, UV exposure, development, and etching silica with the specificities for pillars described above (steps 1&#8211;4), transfer the wafer to a deep ICP-RIE system to etch the silicon layer using the Bosch process. This step controls the height of the pillars. Use 160 cycles of the Bosch process to achieve pillars of height, hP &#8776; 30 &#181;m (Figure 6E, Table 5). Clean the wafer as described in step 2.</li>
	<li>Isotropic silicon etching: Perform isotropic etching using SF6 for 5 min to create the reentrant edge on the pillars (Figure 6F, Table 4). The resulting length of the overhang is 5 &#181;m.</li>
	<li>Piranha cleaning and storage: Clean the wafer using piranha solution and store as described in step 5.4 above.</li>
</ol>
8. Doubly Reentrant Pillars and Hybrids
<ol>
	<li>Anisotropic silicon etching: After etching SiO2, transfer the wafer to a deep ICP-RIE system to etch the Si under the SiO2 layer. Perform five cycles of the Bosch process that corresponds to an etching depth of &#8776; 2 &#181;m (Figure 7E, Table 4). Subsequently, clean the wafer as described in step (2).</li>
	<li>Isotropic silicon etching: Carry out isotropic etching using SF6 for 16 s to create the reentrant edge (Table 5, Figure 7F). Clean the wafer as described in step 2.</li>
	<li>Thermal oxide growth: Grow 500 nm layer of thermal oxide all over the wafer using a high temperature furnace system as described in step 6.3 (Figure 7G).</li>
	<li>Silica etching: Etch the thermally-grown oxide layer (500 nm thick) for 3 min as described in step 6.4 (Figure 7H, Table 3).</li>
	<li>Anisotropic silicon etching: Repeat 160 cycles of the Bosch process (Table 4) to increase the height of the pillars (Figure 7I). Clean the wafer as described in step 2 above.</li>
	<li>Isotropic silicon etching: Perform isotropic etching of silicon for 5 min using the process parameters as described in Table 4. This step creates the doubly reentrant edge (Figure 7J). The space between pillar stem and doubly reentrant edge is &#8776;2 &#181;m.</li>
	<li>Wafer cleaning and storage: Clean the wafer using piranha solution and store as described in step 5.4 above.</li>
</ol>
Figure 8 represents the list of processes used in microfabricating reentrant and doubly reentrant cavities and pillars.

The authors declare that they have no competing interests.

Here we discuss additional factors and design criteria to help the reader in applying these microfabrication protocols. For cavity microtextures (RCs and DRCs) the choice of pitch is crucial. Thinner walls between adjacent cavities would lead to low liquid-solid interfacial area and high liquid-vapor interfacial area, leading to high apparent contact angles34. However, thin walls could compromise the mechanical integrity of the microtexture, for instance, during handling and characterization; a little over-etching with thin walls (e.g., in step 6.6) could destroy the entire microtexture; under-etching with thin walls could also prevent the development of doubly reentrant features. If the DRC features are not fully developed, their ability to entrap air for long-term might suffer, especially if the liquid condenses inside the cavities26. For this reason, we chose the pitch in our experiments to be L = D + 12 &#956;m (i.e., the minimum wall thickness between the cavities was 12 &#181;m). We also fabricated doubly reentrant cavities with a smaller pitch of L = D + 5 &#956;m, but the resulting surfaces were not homogeneous due to structural damage during microfabrication.
During the etching of the silica layer with C4F8 and O2 in step 4, the prior history of usage or the cleanliness of the reaction chamber could give variable results, despite following the same steps, for instance, in a common user facility such as in most universities. Thus, it is recommended that this step is performed in short time periods, for instance, no more than 5 min each and monitored the thickness of the silica layer by an independent technique, such as reflectometry. For our wafers with a 2.4 &#956;m-thick silica layer, a typical etching routine took 13 min to remove silica completely from the targeted areas (Table 3). Because the photoresist was also etched during the process, this step removed 1 &#956;m of the silica layer that was initially masked by the photoresist. Furthermore, to ensure that the etching rate was as expected, and to avoid cross-contamination from previous etch processes (a common issue in multiuser facilities), silica etching was always preceded by etching a sacrificial wafer as a precautionary step. During the development of the photoresist, the exposed surface might get contaminated with the photoresist&#39;s traces/particles, which could act as (microscopic) masks leading to the formation of pin residues. To avoid this, rigorous cleaning and storage protocols should be followed throughout the microfabrication process36.
Similarly, during the Bosch process, even though the SiO2 layer acts as a mask for the Si-layer underneath, it does get etched during long etching cycles, albeit at slower rates. Thus, the depth of the cavities or the height of the pillars is limited up to the point that the reentrant features will not be compromised. The passivation and etching times during the Bosch process should be tuned to obtain smooth walls. This can be achieved by testing recipes iteratively and observing their effects on samples, for instance, using electron microscopy.
In the case of RPs and DRPs, the longer the duration of isotropic etching, the smaller the diameter of the stem. If the diameter is less than 10 &#956;m, it might lead to mechanical fragility. This limitation should inform the design at the beginning of the microfabrication procedure.
Dry-etching tools commonly available in universities do not have industrial-grade tolerances, leading to spatial non-uniformities in terms of the rate of etching inside the chamber. Thus, the features obtained in the center of the wafer might not be the same as those at the boundary. To overcome this limitation, we used four-inch wafers and concentrated only in the central region.
We also recommend using direct-writing systems instead of using hard-contact masks for photolithography, allowing for rapid changes in design parameters, including feature diameters, pitches and shapes (circular, hexagonal and square), etc.
Obviously, neither SiO2/Si wafers nor photolithography are the desired materials or processes for the mass production of omniphobic surfaces. However, they serve as an excellent model system to explore innovative microtextures for engineering omniphobic surfaces, for instance by biomimetics26,27,34,35,46,47, which can be translated to low-cost and scalable materials systems for applications. It is expected that in the near future, the design principles for GEMs might be scaled up using techniques such as 3-D printing48, additive manufacturing49, and laser micromachining50, among others. Microtextured SiO2/Si surfaces could also be used for templating soft materials29,51. Currently, we are investigating applications of our gas-entrapping surfaces for mitigating cavitation damage47, desalination46,52, and reducing hydrodynamic drag.

Solid surfaces that exhibit apparent contact angles, &#952;r &#62; 90&#176; for polar and nonpolar liquids, such as water and hexadecane, are referred to as omniphobic1. These surfaces serve numerous practical applications, including water desalination2,3, oil-water separation4,5, antibiofouling6, and reducing hydrodynamic drag7. Typically, omniphobicity necessitates perfluorinated chemicals and random topographies8,9,10,11,12. However, the cost, non-biodegradability, and vulnerability of those materials/coatings pose a myriad of constraints, e.g., perfluorinated desalination membranes degrade as the feed-side temperatures are raised, leading to pore-wetting13,14, and perfluorinated/hydrocarbon coatings also get abraded15,16 and degraded by silt particles in the flow streams and cleaning protocols. Thus, there is a need for alternative strategies for achieving the functions of perfluorinated coatings (i.e., entrapping air on immersion in liquids without using water repellent coatings). Therefore, researchers have proposed surface topographies comprised of overhanging (reentrant) features that could entrap air on immersion by microtexturing alone17,18,19,20,21,22,23,24,25. These microtextures come in three types: cavities26, pillars27, and fibrous mats8. Hereafter, we will refer to reentrant features with simple overhangs as reentrant (Figure 1A&#8211;B and Figure 1E&#8211;F) and reentrant features with overhangs that make a 90&#176;-turn towards the base as doubly reentrant (Figure 1C&#8211;D and Figure 1G&#8211;H).
In their pioneering work, Werner et al.22,28,29,30,31 characterized cuticles of springtails (Collembola), soil-dwelling arthropods, and explained the significance of mushroom-shaped (reentrant) features in the context of wetting. Others have also investigated the role of mushroom-shaped hairs in sea-skaters32,33 towards facilitating extreme water repellence. Werner and coworkers demonstrated the omniphobicity of intrinsically wetting polymeric surfaces by carving biomimetic structures through reverse imprint lithography29. Liu and Kim reported on silica surfaces adorned with arrays of doubly reentrant pillars that could repel drops of liquids with surface tensions as low as &#947;LV = 10 mN/m, characterized by apparent contact angles, &#952;r &#8776; 150&#176; and extremely low contact angle hysteresis27. Inspired by these amazing developments, we followed the recipes of Liu and Kim to reproduce their results. However, we discovered that those microtextures would catastrophically lose their superomniphobicity, i.e. &#952;r &#8594; 0&#176;, if wetting liquid drops touched the edge of the microtexture or if there was localized physical damage34. These findings demonstrated that pillar-based microtextures were unfit for applications that required omniphobicity on immersion, and they also questioned the criteria for assessing omniphobicity (i.e., should they be limited to contact angles alone, or if additional criteria are needed).
In response, using the SiO2/Si wafers, we prepared arrays of microscale cavities with doubly reentrant inlets and, and using water and hexadecane as the representative polar and nonpolar liquids, we demonstrated that (i) these microtextures prevent liquids from entering them by entrapping air, and (ii) the compartmentalized architecture of the cavities prevents the loss of the entrapped air by localized defects34. Thus, we have termed these microtextures as &#34;gas-entrapping microtextures&#34; (GEMs). As the next step, we microfabricated GEMs with varying shapes (circular, square, hexagonal) and profiles (simple, reentrant, and doubly reentrant) to systematically compare their performance under immersion in wetting liquids26. We also created a hybrid microtexture comprising arrays of doubly reentrant pillars surrounded by walls with doubly reentrant profiles, which prevented liquids from touching the stems of the pillars and robustly entrapped air on immersion35. Below, we present detailed protocols for manufacturing GEMs on SiO2/Si surfaces through photolithography and etching techniques along with design parameters. We also present representative results of characterizing their wetting by contact angle goniometry (advancing/receding/as-placed angles) and immersion in hexadecane and water.

<table><tbody><tr><td>AZ-5214 E photoresist</td><td>Merck</td><td>DEAA070796-0W59</td><td>Photoresist, flammable liquid</td></tr><tr><td>AZ-726 MIF developer</td><td>Merck</td><td>10055824960</td><td>To develop photoresist</td></tr><tr><td>Confocal microscopy</td><td>Zeiss</td><td>Zeiss LSM710</td><td>Upright confocal microscope to visualize liquid meniscus shape</td></tr><tr><td>Deep ICP-RIE</td><td>Oxford Instruments</td><td>Plasmalab system100</td><td>Silicon etching tool</td></tr><tr><td>Direct writer</td><td>Heidelberg Instruments</td><td>&amp;micro;PG501</td><td>Direct-writing system</td></tr><tr><td>Drop shape analyzer</td><td>KRUSS</td><td>DSA100</td><td>To measure contact angle</td></tr><tr><td>Hexadecane</td><td>Alfa Aesar</td><td>544-76-3</td><td>Test liquid</td></tr><tr><td>Highspeed imaging camera</td><td>Phantom vision research</td><td>v1212</td><td>To image droplet bouncing</td></tr><tr><td>HMDS vapor prime</td><td>Yield Engineering systems</td><td></td><td></td></tr><tr><td>Hot plate</td><td>Cost effective equipments</td><td>Model 1300</td><td></td></tr><tr><td>Hydrogen peroxide 30%</td><td>Sigma Aldrich</td><td>7722-84-1</td><td>To prepare piranha solution</td></tr><tr><td>Imaris software</td><td>Bitplane</td><td>Version 8</td><td>Post process confocal microscopy images</td></tr><tr><td>Nile Red</td><td>Sigma Aldrich</td><td>7385-67-3</td><td>Fluorescent dye for hexadecane</td></tr><tr><td>Nitrogen gas</td><td>KAUST lab supply</td><td></td><td>To dry the wafer</td></tr><tr><td>Petri dish</td><td>VWR</td><td>HECH41042036</td><td></td></tr><tr><td>Reactive-Ion Etching (RIE)</td><td>Oxford Instruments</td><td>Plasmalab system100</td><td>Silica etching tool</td></tr><tr><td>Reflectometer</td><td>Nanometrics</td><td>Nanospec 6100</td><td>To check remaining oxide layer thickness</td></tr><tr><td>Rhodamine B (Acros)</td><td>Fisher scientific</td><td>81-88-9</td><td>Fluorescent dye for water</td></tr><tr><td>SEM stub</td><td>Electron Microscopy Sciences</td><td>75923-19</td><td></td></tr><tr><td>SEM-Quanta 3D</td><td>FEI</td><td>Quanta 3D FEG Dual Beam</td><td></td></tr><tr><td>Silicon wafer</td><td>Silicon Valley Microelectronics</td><td></td><td>Single side polished, 4&quot; diameter, 500 &amp;micro;m thickness, 2.4 &amp;micro;m thick oxide layer</td></tr><tr><td>Spin coater</td><td>Headway Research,Inc</td><td>PWM32</td><td></td></tr><tr><td>Spin rinse dryer</td><td>MicroProcess technology</td><td>Avenger Ultra -Pure 6</td><td>Dry the wafers after piranha clean</td></tr><tr><td>Sulfuric acid 96%</td><td>Technic</td><td>764-93-9</td><td>To prepare piranha solution</td></tr><tr><td>Tanner EDA L-Edit software</td><td>Tanner EDA, Inc.</td><td>version15</td><td>Layout design</td></tr><tr><td>Thermal oxide growth</td><td>Tystar furnace</td><td></td><td>To grow thermal oxide in patterned silicon wafer</td></tr><tr><td>Tweezers</td><td>Excelta</td><td>490-SA-PI</td><td>Wafer tweezer</td></tr><tr><td>Vacuum oven</td><td>Thermo Scientific</td><td>13-258-13</td><td></td></tr><tr><td>Water</td><td>Milli-Q</td><td>Advantage A10</td><td>Test liquid</td></tr></tbody></table>

rendering sio2/si surfaces omniphobic by carving gas-entrapping microtextures comprising reentrant and doubly reentrant cavities or pillars

We present microfabrication protocols for rendering intrinsically wetting materials repellent to liquids (omniphobic) by creating gas-entrapping microtextures (GEMs) on them comprising cavities and pillars with reentrant and doubly reentrant features. Specifically, we use SiO2/Si as the model system and share protocols for two-dimensional (2D) designing, photolithography, isotropic/anisotropic etching techniques, thermal oxide growth, piranha cleaning, and storage towards achieving those microtextures. Even though the conventional wisdom indicates that roughening intrinsically wetting surfaces (&#952;o &#60; 90&#176;) renders them even more wetting (&#952;r &#60; &#952;o &#60; 90&#176;), GEMs demonstrate liquid repellence despite the intrinsic wettability of the substrate. For instance, despite the intrinsic wettability of silica &#952;o &#8776; 40&#176; for the water/air system, and &#952;o &#8776; 20&#176; for the hexadecane/air system, GEMs comprising cavities entrap air robustly on immersion in those liquids, and the apparent contact angles for the droplets are &#952;r &#62; 90&#176;. The reentrant and doubly reentrant features in the GEMs stabilize the intruding liquid meniscus thereby trapping the liquid-solid-vapor system in metastable air-filled states (Cassie states) and delaying wetting transitions to the thermodynamically-stable fully-filled state (Wenzel state) by, for instance, hours to months. Similarly, SiO2/Si surfaces with arrays of reentrant and doubly reentrant micropillars demonstrate extremely high contact angles (&#952;r &#8776; 150&#176;&#8211;160&#176;) and low contact angle hysteresis for the probe liquids, thus characterized as superomniphobic. However, on immersion in the same liquids, those surfaces dramatically lose their superomniphobicity and get fully-filled within &#60;1 s. To address this challenge, we present protocols for hybrid designs that comprise arrays of doubly reentrant pillars surrounded by walls with doubly reentrant profiles. Indeed, hybrid microtextures entrap air on immersion in the probe liquids. To summarize, the protocols described here should enable the investigation of GEMs in the context of achieving omniphobicity without chemical coatings, such as perfluorocarbons, which might unlock the scope of inexpensive common materials for applications as omniphobic materials. Silica microtextures could also serve as templates for soft materials.

Watch this Scientific Journal Video about Rendering SiO2/Si Surfaces Omniphobic by Carving Gas-Entrapping Microtextures Comprising Reentrant and Doubly Reentrant Cavities or Pillars at JoVE.com

Rendering SiO2/Si Surfaces Omniphobic by Carving Gas-Entrapping Microtextures Comprising Reentrant and Doubly Reentrant Cavities or Pillars

This work presents microfabrication protocols for achieving cavities and pillars with reentrant and doubly reentrant profiles on SiO2/Si wafers using photolithography and dry etching. Resulting microtextured surfaces demonstrate remarkable liquid repellence, characterized by robust long-term entrapment of air under wetting liquids, despite the intrinsic wettability of silica.

Rendering SiO2/Si Surfaces Omniphobic by Carving Gas-Entrapping Microtextures Comprising Reentrant and Doubly Reentrant Cavities or Pillars

We present microfabrication protocols for rendering intrinsically wetting materials repellent to liquids (omniphobic) by creating gas-entrapping ...

rendering-sio2si-surfaces-omniphobic-carving-gas-entrapping

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JoVE Journal

Engineering

8.9K Views.  King Abdullah University of Science and Technology (KAUST). Onze gas-entrapping microtextured oppervlakken, of GEMS, kunnen ze dan vangen lucht op emulsie en vloeistoffen, ongeacht hun oppervlakte chemie. Daarom denken we dat deze aanpak een enorm potentieel heeft voor toepassingen die anders geperfluoreerde coatings vereisen. In tegenstelling tot 3D-printen en andere conventionele productietechnieken, fotolithografie en droge etsen stelt ons in staat om complexe, micro-schaal, overhangende re-nieuwkomer en dubbel re-nieuwkomer topografie te fabricere...

Video: Rendering SiO2/Si Surfaces Omniphobic by Carving Gas-Entrapping Microtextures Comprising Reentrant and Doubly Reentrant Cavities or Pillars

Fabrication of Uniform Nanoscale Cavities via Silicon Direct Wafer Bonding

Measurements of the heat capacity and superfluid fraction of confined 4He have been performed near the lambda transition using lithographically patterned and bonded silicon wafers. Unlike confinements in porous materials often used for these types of experiments3, bonded wafers provide predesigned uniform spaces for confinement. The geometry of each cell is well known, which removes a large source of ambiguity in the interpretation of data.
Exceptionally flat, 5 cm diameter, 375 &#181;m thick Si wafers with about 1 &#181;m variation over the entire wafer can be obtained commercially (from Semiconductor Processing Company, for example). Thermal oxide is grown on the wafers to define the confinement dimension in the z-direction. A pattern is then etched in the oxide using lithographic techniques so as to create a desired enclosure upon bonding. A hole is drilled in one of the wafers (the top) to allow for the introduction of the liquid to be measured. The wafers are cleaned2 in RCA solutions and then put in a microclean chamber where they are rinsed with deionized water4. The wafers are bonded at RT and then annealed at ~1,100 &#176;C. This forms a strong and permanent bond. This process can be used to make uniform enclosures for measuring thermal and hydrodynamic properties of confined liquids from the nanometer to the micrometer scale.

A method for permanently bonding two silicon wafers so as to realize a uniform enclosure is described. This includes wafer preparation, cleaning, RT bonding, and annealing processes. The resulting bonded wafers (cells) have uniformity of enclosure ~1%1,2. The resulting geometry allows for measurements of confined liquids and gasses.

Measurements of the heat capacity and superfluid fraction of confined 4He have been performed near the lambda transition using lithographically patterned ...

Soft Lithographic Functionalization and Patterning Oxide-free Silicon and Germanium

The development of hybrid electronic devices relies in large part on the integration of (bio)organic materials and inorganic semiconductors through a stable interface that permits efficient electron transport and protects underlying substrates from oxidative degradation. Group IV semiconductors can be effectively protected with highly-ordered self-assembled monolayers (SAMs) composed of simple alkyl chains that act as impervious barriers to both organic and aqueous solutions. Simple alkyl SAMs, however, are inert and not amenable to traditional patterning techniques. The motivation for immobilizing organic molecular systems on semiconductors is to impart new functionality to the surface that can provide optical, electronic, and mechanical function, as well as chemical and biological activity. 
Microcontact printing (&mu;CP) is a soft-lithographic technique for patterning SAMs on myriad surfaces.1-9 Despite its simplicity and versatility, the approach has been largely limited to noble metal surfaces and has not been well developed for pattern transfer to technologically important substrates such as oxide-free silicon and germanium. Furthermore, because this technique relies on the ink diffusion to transfer pattern from the elastomer to substrate, the resolution of such traditional printing is essentially limited to near 1 &mu;m.10-16
In contrast to traditional printing, inkless &mu;CP patterning relies on a specific reaction between a surface-immobilized substrate and a stamp-bound catalyst. Because the technique does not rely on diffusive SAM formation, it significantly expands the diversity of patternable surfaces. In addition, the inkless technique obviates the feature size limitations imposed by molecular diffusion, facilitating replication of very small (&lt;200 nm) features.17-23 However, up till now, inkless &mu;CP has been mainly used for patterning relatively disordered molecular systems, which do not protect underlying surfaces from degradation.
Here, we report a simple, reliable high-throughput method for patterning passivated silicon and germanium with reactive organic monolayers and demonstrate selective functionalization of the patterned substrates with both small molecules and proteins. The technique utilizes a preformed NHS-reactive bilayered system on oxide-free silicon and germanium. The NHS moiety is hydrolyzed in a pattern-specific manner with a sulfonic acid-modified acrylate stamp to produce chemically distinct patterns of NHS-activated and free carboxylic acids. A significant limitation to the resolution of many &mu;CP techniques is the use of PDMS material which lacks the mechanical rigidity necessary for high fidelity transfer. To alleviate this limitation we utilized a polyurethane acrylate polymer, a relatively rigid material that can be easily functionalized with different organic moieties. Our patterning approach completely protects both silicon and germanium from chemical oxidation, provides precise control over the shape and size of the patterned features, and gives ready access to chemically discriminated patterns that can be further functionalized with both organic and biological molecules. The approach is general and applicable to other technologically-relevant surfaces.

Here we describe a simple method for patterning oxide-free silicon and germanium with reactive organic monolayers and demonstrate functionalization of the patterned substrates with small molecules and proteins. The approach completely protects surfaces from chemical oxidation, provides precise control over feature morphology, and provides ready access to chemically discriminated patterns.

The development of hybrid electronic devices relies in large part on the integration of (bio)organic materials and inorganic semiconductors through a ...

Bioengineering

Micro-masonry for 3D Additive Micromanufacturing

Transfer printing is a method to transfer solid micro/nanoscale materials (herein called &#8216;inks&#8217;) from a substrate where they are generated to a different substrate by utilizing elastomeric stamps. Transfer printing enables the integration of heterogeneous materials to fabricate unexampled structures or functional systems that are found in recent advanced devices such as flexible and stretchable solar cells and LED arrays. While transfer printing exhibits unique features in material assembly capability, the use of adhesive layers or the surface modification such as deposition of self-assembled monolayer (SAM) on substrates for enhancing printing processes hinders its wide adaptation in microassembly of microelectromechanical system (MEMS) structures and devices. To overcome this shortcoming, we developed an advanced mode of transfer printing which deterministically assembles individual microscale objects solely through controlling surface contact area without any surface alteration. The absence of an adhesive layer or other modification and the subsequent material bonding processes ensure not only mechanical bonding, but also thermal and electrical connection between assembled materials, which further opens various applications in adaptation in building unusual MEMS devices.

This paper introduces a 3D additive micromanufacturing strategy (termed &#8216;micro-masonry&#8217;) for the flexible fabrication of microelectromechanical system (MEMS) structures and devices. This approach involves transfer printing-based assembly of micro/nanoscale materials in conjunction with rapid thermal annealing-enabled material bonding techniques.

Transfer printing is a method to transfer solid micro/nanoscale materials (herein called &#8216;inks&#8217;) from a substrate where they are generated to ...

Microbubble Fabrication of Concave-porosity PDMS Beads

Microbubble fabrication (by use of a fine emulsion) provides a means of increasing the surface-area-to-volume (SAV) ratio of polymer materials, which is particularly useful for separations applications. Porous polydimethylsiloxane (PDMS) beads can be produced by heat-curing such an emulsion, allowing the interface between the aqueous and aliphatic phases to mold the morphology of the polymer. In the procedures described here, both polymer and crosslinker (triethoxysilane) are sonicated together in a cold-bath sonicator. Following a period of cross-linking, emulsions are added dropwise to a hot surfactant solution, allowing the aqueous phase of the emulsion to separate, and forming porous polymer beads. We demonstrate that this method can be tuned, and the SAV ratio optimized, by adjusting the electrolyte content of the aqueous phase in the emulsion. Beads produced in this way are imaged with scanning electron microscopy, and representative SAV ratios are determined using Brunauer&#8211;Emmett&#8211;Teller (BET) analysis. Considerable variability with the electrolyte identity is observed, but the general trend is consistent: there is a maximum in SAV obtained at a specific concentration, after which porosity decreases markedly.

Procedures used to generate microstructured concave-porosity polydimethylsiloxane beads are presented. Effects of electrolyte concentration and identity within the aqueous phase are particularly emphasized.

Microbubble fabrication (by use of a fine emulsion) provides a means of increasing the surface-area-to-volume (SAV) ratio of polymer materials, which is ...

Chemistry

TiO2-coated Hollow Glass Microspheres with Superhydrophobic and High IR-reflective Properties Synthesized by a Soft-chemistry Method

This manuscript proposes a soft-chemistry method to develop superhydrophobic and highly IR-reflective hollow glass microspheres (HGM). The anatase TiO2 and a superhydrophobic agent were coated on the HGM surface in one step. TBT and PFOTES were selected as the Ti source and the superhydrophobic agent, respectively. They were both coated on the HGM, and after the hydrothermal process, the TBT turned to anatase TiO2. In this way, a PFOTES/TiO2-coated HGM (MCHGM) was prepared. For comparison, PFOTES single-coated HGM (F-SCHGM) and TiO2 single-coated HGM (Ti-SCHGM) were synthesized as well. The PFOTES and TiO2 coatings on the HGM surface were demonstrated through X-ray diffraction (XRD), scanning electron microscopy (SEM), and energy-dispersive detector (EDS) characterizations. The MCHGM showed a higher contact angle (153&#176;) but a lower sliding angle (16&#176;) than F-SCHGM, with a contact angle of 141.2&#176; and a sliding angle of 67&#176;. In addition, both Ti-SCHGM and MCHGM displayed similar IR reflectivity values, which were about 5.8% higher than the original HGM and F-SCHGM. Also, the PFOTES coating barely changed the thermal conductivity. Therefore, F-SCHGM, with a thermal conductivity of 0.0479 W/(m&#183;K), was quite like the original HGM, which was 0.0475 W/(m&#183;K). MCHGM and Ti-SCHGM were also similar. Their thermal conductivity values were 0.0543 W/(m&#183;K) and 0.0543 W/(m&#183;K), respectively. The TiO2 coating slightly increased the thermal conductivity, but with the increase in reflectivity, the overall heat-insulation property was enhanced. Finally, since the IR-reflecting property is provided by the HGM coating, if the coating is fouled, the reflectivity decreases. Therefore, with the superhydrophobic coating, the surface is protected from fouling, and its lifetime is also prolonged.

TiO2-coated Hollow Glass Microspheres with Superhydrophobic and High IR-reflective Properties Synthesized by a Soft-chemistry Method

This manuscript proposes a soft-chemistry method to synthesize superhydrophobic, TiO2-coated hollow glass microspheres (HGM) with high IR-reflective properties.

This manuscript proposes a soft-chemistry method to develop superhydrophobic and highly IR-reflective hollow glass microspheres (HGM). The anatase TiO2 ...

Experimental Methods for Trapping Ions Using Microfabricated Surface Ion Traps

Ions trapped in a quadrupole Paul trap have been considered one of the strong physical candidates to implement quantum information processing. This is due to their long coherence time and their capability to manipulate and detect individual quantum bits (qubits). In more recent years, microfabricated surface ion traps have received more attention for large-scale integrated qubit platforms. This paper presents a microfabrication methodology for ion traps using micro-electro-mechanical system (MEMS) technology, including the fabrication method for a 14 &#181;m-thick dielectric layer and metal overhang structures atop the dielectric layer. In addition, an experimental procedure for trapping ytterbium (Yb) ions of isotope 174 (174Yb+) using 369.5 nm, 399 nm, and 935 nm diode lasers is described. These methodologies and procedures involve many scientific and engineering disciplines, and this paper first presents the detailed experimental procedures. The methods discussed in this paper can easily be extended to the trapping of Yb ions of isotope 171 (171Yb+) and to the manipulation of qubits.

This paper presents a microfabrication methodology for surface ion traps, as well as a detailed experimental procedure for trapping ytterbium ions in a room-temperature environment.

Ions trapped in a quadrupole Paul trap have been considered one of the strong physical candidates to implement quantum information processing. This is due ...

Surface Properties of Synthesized Nanoporous Carbon and Silica Matrices

In this work, we report the synthesis and characterization of ordered nanoporous carbon material (also called ordered mesoporous carbon material [OMC]) with a 4.6 nm pore size, and ordered silica porous matrix, SBA-15, with a 5.3 nm pore size. This work describes the surface properties of nanoporous molecular sieves, their wettability, and the melting behavior of D2O confined in the differently ordered porous materials with similar pore sizes. For this purpose, OMC and SBA-15 with highly ordered nanoporous structures are synthesized via impregnation of the silica matrix by applying a carbon precursor and by the sol-gel method, respectively. The porous structure of investigated systems is characterized by an N2 adsorption-desorption analysis at 77 K. To determine the electrochemical character of the surface of synthesized materials, potentiometric titration measurements are conducted; the obtained results for OMC shows a significant pHpzc shift toward the higher values of pH, relative to SBA-15. This suggests that investigated OMC has surface properties related to oxygen-based functional groups. To describe the surface properties of the materials, the contact angles of liquids penetrating the studied porous beds are also determined. The capillary rise method has confirmed the increased wettability of the silica walls relative to the carbon walls and an influence of the pore roughness on the fluid/wall interactions, which is much more pronounced for silica than for carbon mesopores. We have also studied the melting behavior of D2O confined in OMC and SBA-15 by applying the dielectric method. The results show that the depression of the melting temperature of D2O in the pores of OMC is about 15 K higher relative to the depression of the melting temperature in SBA-15 pores with a comparable 5 nm size. This is caused by the influence of adsorbate/adsorbent interactions of the studied matrices.

Here we report the synthesis and characterization of ordered nanoporous carbon (with a 4.6 nm pore size) and SBA-15 (with a 5.3 nm pore size). The work describes the surface and textural properties of nanoporous molecular sieves, their wettability, and the melting behavior of D2O confined in the materials.

In this work, we report the synthesis and characterization of ordered nanoporous carbon material (also called ordered mesoporous carbon material [OMC]) ...

Microparticle Manipulation by Standing Surface Acoustic Waves with Dual-frequency Excitations

We demonstrate a method for increasing the tuning ability of a standing surface acoustic wave (SSAW) for microparticles manipulation in a lab-on-a-chip (LOC) system. The simultaneous excitation of the fundamental frequency and its third harmonic, which is termed as dual-frequency excitation, to a pair of interdigital transducers (IDTs) could generate a new type of standing acoustic waves in a microfluidic channel. Varying the power and the phase in the dual-frequency excitation signals results in a reconfigurable field of the acoustic radiation force applied to the microparticles across the microchannel (e.g., the number and location of the pressure nodes and the microparticle concentrations at the corresponding pressure nodes). This article demonstrates that the motion time of the microparticle to only one pressure node can be reduced ~2-fold at the power ratio of the fundamental frequency greater than ~90%. In contrast, there are three pressure nodes in the microchannel if less than this threshold. Furthermore, adjusting the initial phase between the fundamental frequency and the third harmonic results in different motion rates of the three SSAW pressure nodes, as well as in the percentage of microparticles at each pressure node in the microchannel. There is a good agreement between the experimental observation and the numerical predictions. This novel excitation method can easily and non-invasively integrate into the LOC system, with a wide tenability and only a few changes to the experimental set-up.

A protocol for manipulating the microparticles in a microfluidic channel with a dual-frequency excitation is presented.

We demonstrate a method for increasing the tuning ability of a standing surface acoustic wave (SSAW) for microparticles manipulation in a lab-on-a-chip ...

Multiscale Structures Aggregated by Imprinted Nanofibers for Functional Surfaces

Multiscale surface structures have attracted increasing interest owing to several potential applications in surface devices. However, an existing challenge in the field is the fabrication of hybrid micro-nano structures using a facile, cost-effective, and high-throughput method. To overcome these challenges, this paper proposes a protocol to fabricate multiscale structures using only an imprint process with an anodic aluminum oxide (AAO) filter and an evaporative self-aggregation process of nanofibers. Unlike previous attempts that have aimed to straighten nanofibers, we demonstrate a unique fabrication method for multiscale aggregated nanofibers with high aspect ratios. Furthermore, the surface morphology and wettability of these structures on various liquids were investigated to facilitate their use in multifunctional surfaces.

Presented is an easy method to fabricate nano-micro multiscale structures, for functional surfaces, by aggregating nanofibers fabricated using an anodic aluminum oxide filter.

Multiscale surface structures have attracted increasing interest owing to several potential applications in surface devices. However, an existing ...

Proof-of-Concept for Gas-Entrapping Membranes Derived from Water-Loving SiO2/Si/SiO2 Wafers for Green Desalination

Desalination through direct contact membrane distillation (DCMD) exploits water-repellent membranes to robustly separate counterflowing streams of hot and salty seawater from cold and pure water, thus allowing only pure water vapor to pass through. To achieve this feat, commercial DCMD membranes are derived from or coated with water-repellent perfluorocarbons such as polytetrafluoroethylene (PTFE) and polyvinylidene difluoride (PVDF). However, the use of perfluorocarbons is limiting due to their high cost, non-biodegradability, and vulnerability to harsh operational conditions. Unveiled here is a new class of membranes referred to as gas-entrapping membranes (GEMs) that can robustly entrap air upon immersion in water. GEMs achieve this function by their microstructure rather than their chemical make-up. This work demonstrates a proof-of-concept for GEMs using intrinsically wetting SiO2/Si/SiO2 wafers as the model system; the contact angle of water on SiO2 is &#952;o &#8776; 40&#176;. Silica-GEMs had 300 &#956;m-long cylindrical pores whose diameters at the (2 &#956;m-long) inlet and outlet regions were significantly smaller; this geometrically discontinuous structure, with 90&#176; turns at the inlets and outlets, is known as the &#34;reentrant microtexture&#34;. The microfabrication protocol for silica-GEMs entails designing, photolithography, chrome sputtering, and isotropic and anisotropic etching. Despite the water loving nature of silica, water does not intrude silica-GEMs on submersion. In fact, they robustly entrap air underwater and keep it intact even after six weeks (&#62;106 seconds). On the other hand, silica membranes with simple cylindrical pores spontaneously imbibe water (&#60; 1 s). These findings highlight the potential of the GEMs architecture for separation processes. While the choice of SiO2/Si/SiO2 wafers for GEMs is limited to demonstrating the proof-of-concept, it is expected that the protocols and concepts presented here will advance the rational design of scalable GEMs using inexpensive common materials for desalination and beyond.

Proof-of-Concept for Gas-Entrapping Membranes Derived from Water-Loving SiO2/Si/SiO2 Wafers for Green Desalination

Presented here is a stepwise protocol for realizing gas-entrapping membranes (GEMs) from SiO2/Si wafers using integrated circuit microfabrication technology. When silica-GEMs are immersed in water, the intrusion of water is prevented, despite the water-loving composition of silica.

Desalination through direct contact membrane distillation (DCMD) exploits water-repellent membranes to robustly separate counterflowing streams of hot and ...

Rendering SiO₂/Si Surfaces Omniphobic by Carving Gas-Entrapping Microtextures Comprising Reentrant and Doubly Reentrant Cavities or Pillars

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