High-Purity Semiconducting Single-Walled Carbon Nanotubes: A Key Enabling Material in Emerging Electronics.

Semiconducting single-walled carbon nanotubes (sc-SWCNTs) are emerging as a promising material for high-performance, high-density devices as well as low-cost, large-area macroelectronics produced via additive manufacturing methods such as roll-to-roll printing. Proof-of-concept demonstrations have indicated the potential of sc-SWCNTs for digital electronics, radiofrequency circuits, radiation hard memory, improved sensors, and flexible, stretchable, conformable electronics. Advances toward commercial applications bring numerous opportunities in SWCNT materials development and characterization as well as fabrication processes and printing technologies. Commercialization in electronics will require large quantities of sc-SWCNTs, and the challenge for materials science is the development of scalable synthesis, purification, and enrichment methods. While a few synthesis routes have shown promising results in making near-monochiral SWCNTs, gram quantities are available only for small-diameter sc-SWCNTs, which underperform in transistors. Most synthesis routes yield mixtures of SWCNTs, typically 30% metallic and 70% semiconducting, necessitating the extraction of sc-SWCNTs from their metallic counterparts in high purity using scalable postsynthetic methods. Numerous routes to obtain high-purity sc-SWCNTs from raw soot have been developed, including density-gradient ultracentrifugation, chromatography, aqueous two-phase extraction, and selective DNA or polymer wrapping. By these methods (termed sorting or enrichment), >99% sc-SWCNT content can be achieved. Currently, all of these approaches have drawbacks and limitations with respect to electronics applications, such as excessive dilution, expensive consumables, and high ionic impurity content. Excess amount of dispersant is a common challenge that hinders direct inclusion of sc-SWCNTs into electronic devices. At present, conjugated polymer extraction may represent the most practical route to sc-SWCNTs. By the use of polymers with a π-conjugated backbone, sc-SWCNTs with >99.9% purity can be dispersed in organic solvents via a simple sonication and centrifugation process. With 1000 times less excipient and the flexibility to accommodate a broad range of solvents via diverse polymer constructs, inks are readily deployable in solution-based fabrication processes such as aerosol spray, inkjet, and gravure. Further gains in sc-SWCNT purity, among other attributes, are possible with a better understanding of the structure-property relationships that govern conjugated polymer extraction. This Account covers three interlinked topics in SWCNT electronics: metrology, enrichment, and SWCNT transistors fabricated via solution processes. First, we describe how spectroscopic techniques such as optical absorption, fluorescence, and Raman spectroscopy are applied for sc-SWCNT purity assessment. Stringent requirements for sc-SWCNTs in electronics are pushing the techniques to new levels while serving as an important driver toward the development of quantitative metrology. Next, we highlight recent progress in understanding the sc-SWCNT enrichment process using conjugated polymers, with special consideration given to the effect of doping on the mechanism. Finally, developments in sc-SWCNT-based electronics are described, with emphasis on the performance of transistors utilizing random networks of sc-SWCNTs as the semiconducting channel material. Challenges and advances associated with using polymer-based dielectrics in the unique context of sc-SWCNT transistors are presented. Such transistor packages have enabled the realization of fully printed transistors as well as transparent and even stretchable transistors as a result of the unique and excellent electrical and mechanical properties of sc-SWCNTs.

Determination of chemical purity and isotopic composition of natural and carbon-13-labeled arsenobetaine bromide standards by quantitative(1)H-NMR.

In this study, we report the characterization of three arsenobetaine-certified reference materials by quantitative NMR. We have synthesized an arsenobetaine bromide high-purity standard of natural isotopic composition (ABET-1) and two carbon-13-labeled isotopic standards (BBET-1 and CBET-1). Assignments of the chemical purity and isotopic composition are not trivial in the case of arsenobetaine, and in this study we utilized quantitative(1)H-NMR techniques for the determination of the mass fractions (chemical purity). The isotopic purity of all three standards was also assessed by NMR from the carbon-13 satellite signals. The standards are non-hygroscopic, high-purity (ca. 0.99 g/g), and the carbon-13 enrichment for both isotopic standards is x((13)C)≈0.99. These standards are designed for use as primary calibrators for mass spectrometric determination of arsenobetaine in environmental samples.

Strategic Design of Hemi-Isoindigo Polymer for a Highly Sensitive and Selective All-Printed Flexible Nitrogen Dioxide Chemiresistive Sensor.

The study has developed two hemi-isoindigo (HID)-based polymers for printed flexible resistor-type nitrogen oxide (NO2 ) sensors: poly[2-ethylhexyl 3-((3'",4'-bis(dodecyloxy)-3,4-dimethoxy-[2,2':5',2'"-terthiophen]-5-yl)methylene)-2-oxoindoline-1-carboxylate] (P1) and poly[2-ethylhexyl 2-oxo-3-((3,3'",4,4'-tetrakis(dodecyloxy)-[2,2':5',2'"-terthiophen]-5-yl)methylene)indoline-1-carboxylate] (P2). These polymers feature thermally removable carbamate side chains on the HID units, providing solubility and creating molecular cavities after thermal annealing. These cavities enhance NO2 diffusion, and the liberated unsubstituted amide ─C(═O)NH─ groups readily form robust double hydrogen bonds (DHB), as demonstrated by computer simulations. Furthermore, both polymers possess elevated highest occupied molecular orbital (HOMO) energy levels of -4.74 and -4.77 eV, making them highly susceptible to p-doping by NO2 . Gas sensors fabricated from P1 and P2 films, anneal under optimized conditions to partially remove carbamate side chains, exhibit remarkable sensitivities of +1400% ppm-1 and +3844% ppm-1 , and low detection limit (LOD) values of 514 ppb and 38.9 ppb toward NO2 , respectively. These sensors also demonstrate excellent selectivity for NO2 over other gases.

Novel ethyl-derivatization approach for the determination of fluoride by headspace gas chromatography/mass spectrometry.

We report a novel derivatization chemistry for determination of fluoride based on the batch reaction of fluoride ions with triethyloxonium tetrachloroferrate(III) in a closed vessel to yield fluoroethane. Gaseous fluoroethane was readily separated from the matrix, sampled from the headspace, and determined by gas chromatography/mass spectrometry. The method was validated using rainwater certified reference material (IRMM CA408) and subsequently applied to the determination of fluoride in various matrixes, including tap water, seawater, and urine. An instrumental limit of detection of 3.2 µg/L with a linear range up to 50 mg/L was achieved. The proposed derivatization is a one-step reaction, requires no organic solvents, and is safe, as the derivatizing agent is nonvolatile. Determination of fluoride is affected by common fluoride-complexing agents, such as Al(III) and Fe(III). The effect of large amounts of these interferences was studied, and the adverse effect of these ions was eliminated by use of the method of standard additions.

Silver Nanoparticles Anchored on Single-Walled Carbon Nanotubes via a Conjugated Polymer for Enhanced Sensing Applications.

Single-walled carbon nanotubes (SWCNTs) are candidate matrices for loading metal nanoparticles (NPs) for sensor and catalytic applications owing to their high electron conductivity and mechanical strength, larger surface area, excellent chemical stability, and ease of surface modification. The performance of the formed NP/SWCNT composites is dependent on the NP size, the physical and chemical interactions between the components, and the charge transfer capabilities. Anchoring metal complexes onto the surface of SWCNTs through noncovalent interactions is a viable strategy for achieving high-level metal dispersion and high charge transfer capacities between metal NPs and SWCNTs. However, traditional metal complexes have small molecular sizes, and their noncovalent interactions with SWCNTs are limited to provide excellent sensing and catalytic capability with restricted efficiency and durability. Here, we selected poly(9,9-di-n-dodecylfluorenyl-2,7-diyl-alt-2,2'-bipyridine-5,5') (PFBPy) to increase the noncovalent interactions between silver nanoparticles (AgNPs) and SWCNTs. A silver triflate (Ag-OTf) solution was added into a PFBPy-wrapped SWCNT solution to form Ag-PFBPy complexes on the nanotube surface, after which Ag+ was photoreduced to AgNPs to form a Ag-PFBPy/SWCNT composite in the solution. In various feeding molar ratios of Ag-OTf over the BPy unit (0.4-50), the size of the formed AgNPs may be well-controlled at sub-nm levels to provide them with an energy level comparable to that of the SWCNTs. Additionally, the 2,2'-bipyridine (BPy) unit of the polymer provided a coordinating interaction with Ag+ and the formed AgNPs as well. The 5,5'-linage of BPy with the fluorene unit in PFBPy ensured a straight main chain structure to retain strong π-π interactions with nanotubes before and after Ag+ chelation. All of these factors confirmed a tight contact between the formed AgNPs and SWCNTs, promoting the charge transfer between them and enhancing the sensing capabilities with a 5-fold increase in humidity sensing sensitivity.

Bulk heterojunction solar cells using thieno[3,4-c]pyrrole-4,6-dione and dithieno[3,2-b:2',3'-d]silole copolymer with a power conversion efficiency of 7.3%.

A new alternating copolymer of dithienosilole and thienopyrrole-4,6-dione (PDTSTPD) possesses both a low optical bandgap (1.73 eV) and a deep highest occupied molecular orbital energy level (5.57 eV). The introduction of branched alkyl chains to the dithienosilole unit was found to be critical for the improvement of the polymer solubility. When blended with PC(71)BM, PDTSTPD exhibited a power conversion efficiency of 7.3% on the photovoltaic devices with an active area of 1 cm(2).

Determination of arsenobetaine in fish tissue by species specific isotope dilution LC-LTQ-Orbitrap-MS and standard addition LC-ICPMS.

An accurate and precise method for the determination of arsenobetaine (AsB, (CH(3))(3)(+)AsCH(2)COO(-)) in fish samples using exact matching species specific isotope dilution (ID) liquid chromatography LTQ-Orbitrap mass spectrometry (LC-LTQ-Orbitrap-MS) and standard addition LC inductively coupled plasma mass spectrometry (LC-ICPMS) is described. Samples were extracted by sonication for 30 min with high purity deionized water. An in-house synthesized (13)C enriched AsB spike was used for species specific ID analysis whereas natural abundance AsB, synthesized and characterized by quantitative (1)H NMR (nuclear magnetic resonance spectroscopy), was used for reverse ID and standard addition LC-ICPMS. With the LTQ-Orbitrap-MS instrument in scan mode (m/z 170-190) and resolution set at 7500, the intensities of [M + H](+) ions at m/z of 179.0053 and 180.0087 were used to calculate the 179.0053/180.0087 ion ratio for quantification of AsB in fish tissues. To circumvent potential difficulty in mass bias correction, an exact matching approach was applied. A quantitatively prepared mixture of the natural abundance AsB standard and the enriched spike to give a ratio near one was used for mass bias correction. Concentrations of 9.65 ± 0.24 and 11.39 ± 0.39 mg kg(-1) (expanded uncertainty, k = 2) for AsB in two fish samples of fish1 and fish2, respectively, were obtained by ID LC-LTQ-Orbitrap-MS. These results are in good agreement with those obtained by standard addition LC-ICPMS, 9.56 ± 0.32 and 11.26 ± 0.44 mg kg(-1) (expanded uncertainty, k = 2), respectively. Fish CRM DORM-2 was used for method validation and measured results of 37.9 ± 1.8 and 38.7 ± 0.66 mg kg(-1) (expanded uncertainty, k = 2) for AsB obtained by standard addition LC-ICPMS and ID LC-LTQ-Orbitrap-MS, respectively, are in good agreement with the certified value of 39.0 ± 2.6 mg kg(-1) (expanded uncertainty, k = 2). Detection limits of 0.011 and 0.033 mg kg(-1) for AsB with LC-ICPMS and ID LC-LTQ-Orbitrap-MS, respectively, were obtained demonstrating that the technique is well suited to the determination AsB in fish samples. To the best of our knowledge, this is first application of species specific isotope dilution for the accurate and precise determination of AsB in biological tissues.

Development of a new s-tetrazine-based copolymer for efficient solar cells.

A new s-tetrazine-based low-bandgap semiconducting polymer, PCPDTTTz, was designed and synthesized. This is the first solution-processable conjugated polymer with tetrazine in the main chain. This polymer shows good thermal stability and broad absorption covering 450-700 nm. The HOMO and LUMO energy levels were estimated to be -5.34 and -3.48 eV, with an electrochemical bandgap of 1.86 eV. Simple polymer solar cells based on PCPDTTTz and PC(71)BM exhibit a calibrated power conversion efficiency of 5.4%.

Enrichment of Semiconducting Single-Walled Carbon Nanotubes with Indigo-Fluorene-Based Copolymers and Their Use in Printed Thin-Film Transistors and Carbon Dioxide Gas Sensors.

High-purity semiconducting single-walled carbon nanotubes (sc-SWCNTs) are promising for portable and high-sensitivity gas sensors because of their excellent physical and electrical properties. Here, we describe the synthesis of a novel indigo-fluorene-based copolymer (PFIDBoc) that has been designed to selectively enrich sc-SWCNTs with excellent purity (>99.9%) yet contain a latent function in the form of a tert-butoxy (t-BOC)-protected amine that can be later revealed and exploited for carbon dioxide (CO2) gas sensing. SWCNTs wrapped with the PFIDBoc polymer can be easily converted via an on-chip thermal process to reveal a vinylogous amide moiety with a secondary amine nitrogen within the indigo building block of the copolymer which is perfectly suited for CO2 recognition. Thin-film transistors and sensors were inkjet-printed onto rigid and flexible substrates, demonstrating the versatility of enriched PFIDBoc-derived sc-SWCNT dispersions. The printed transistors exhibited a mobility up to 9 cm2 V-1 s-1 and on/off current ratios >105. We further demonstrate herein a CO2 sensor for indoor air quality monitoring even in low humidity environments, possessing a linear response with up to ∼5.4% sensitivity and a dynamic range between 400 and 2000 ppm in air with a relative humidity of ∼ 40%.

Hybrid silica/polymer long period gratings for wavelength filtering and power distribution.

We report long period grating (LPG) devices based on a hybrid architecture incorporating photopatternable fluorinated poly(aryl ether ketone) and silica layers for applications in wavelength filtering and power distribution. The grating structure was implemented using a periodic corrugation on a thermally oxidized silica lower cladding layer, a photopatterned fluorinated polymer ridge waveguide, and a similar polymer top cladding. In this design, the corrugated silica layer allows a highly stable grating structure, while the fluorinated polymer offers a low propagation loss and easy processability. Strong rejection bands have been demonstrated in the C+L wavelength band, in good agreement with theoretical calculations. The fabricated LPG devices show a thermal dependence of 1.5 nm/ degrees C. Based on this design, an array of waveguides incorporating LPGs has also been fabricated. Distribution of light at the resonance wavelength across all the channels from a single input has been demonstrated. These results are promising for power distribution in photonic network applications or on-chip sensors.

Polymer Encapsulants for Threshold Voltage Control in Carbon Nanotube Transistors.

Although carbon nanotube transistors present outstanding performances based on key metrics, large-scale uniformity and repeatability required in printable electronics depend greatly on proper control of the electrostatic environment. Through a survey of polymer dielectric encapsulants compatible with printing processes, a simple correlation is found between the measured interfacial charge density and the onset of conduction in a transistor, providing a rational route to control the electrical characteristics of carbon nanotube transistors. Smooth and continuous balancing of the properties between unipolar p-type and n-type transport is achieved using a molar fraction series of poly(styrene-co-2-vinylpyridine) statistical copolymers combined with an electron-donating molecule. We further demonstrate the easy fabrication of a p-n diode which shows a modest rectification of 8:1.

Probing Ca2+-induced conformational change of calmodulin with gold nanoparticle-decorated single-walled carbon nanotube field-effect transistors.

Nanomaterials are ideal for electrochemical biosensors, with their nanoscale dimensions enabling the sensitive probing of biomolecular interactions. In this study, we compare field-effect transistors (FET) comprised of unsorted (un-) and semiconducting-enriched (sc-) single-walled carbon nanotubes (SWCNTs). un-SWCNTs have both metallic and semiconducting SWCNTs in the ensemble, while sc-SWCNTs have a >99.9% purity of semiconducting nanotubes. Both SWCNT FET devices were decorated with gold nanoparticles (AuNPs) and were then employed in investigating the Ca2+-induced conformational change of calmodulin (CaM) - a vital process in calcium signal transduction in the human body. Different biosensing behavior was observed from FET characteristics of the two types of SWCNTs, with sc-SWCNT FET devices displaying better sensing performance with a dynamic range from 10-15 M to 10-13 M Ca2+, and a lower limit of detection at 10-15 M Ca2+.

Crystalline low band-gap alternating indolocarbazole and benzothiadiazole-cored oligothiophene copolymer for organic solar cell applications.

A low band-gap alternating copolymer of indolocarbazole and benzothiadiazole-cored oligothiophene demonstrated balanced crystallinity and solubility; a solar cell combining this polymer with PC(61)BM in a preliminary test demonstrated power conversion efficiencies of 3.6%.

Dopant-Modulated Conjugated Polymer Enrichment of Semiconducting SWCNTs.

Conjugated polymer extraction (CPE) is a low-cost, scalable process that can enrich single-walled carbon nanotube (SWCNT) materials in organic media. For other separation methods in aqueous phases, redox chemistry and/or pH control dramatically affect the sorting process of the SWCNTs. We have previously determined that the CPE process can be fine-tuned by adjusting the pH on the tube surface. Here, we systematically studied the effect of redox chemistry on the CPE process by adding organic p-/n-dopants. At a very strong p-/n-doping level, static repulsions dominated the interactions between the tubes and the CPE lost selectivity. When the doping level changed from a medium p-doping to a neutral state, the yield of CPE increased and the selectivity was compromised. We also observed chiral selectivity when a weak p-dopant was used. A photoluminescence excitation mapping under different titration conditions provided more insight into the doping level of the tubes relative to their diameters, chiralities, and redox potentials. We proposed a mechanism for the CPE process. The semiconducting and metallic tubes are separated because of their different solubilities, which are determined by the bundling energy between the tubes and are related to their doping level in polymer solutions.

Sorting of Semiconducting Single-Walled Carbon Nanotubes in Polar Solvents with an Amphiphilic Conjugated Polymer Provides General Guidelines for Enrichment.

Conjugated polymer extraction (CPE) has been shown to be a highly effective method to isolate high-purity semiconducting single-walled carbon nanotubes (sc-SWCNTs). In both literature reports and industrial manufacturing, this method has enabled enrichment of sc-SWCNTs with high purity (≥99.9%). High selectivity is typically obtained in nonpolar aromatic solvents, yet polar solvents may provide process improvements in terms of yield, purity and efficiency. Using an amphiphilic fluorene-alt-pyridine conjugated copolymer with hydrophilic side chains, we have investigated the enrichment of sc-SWCNTs in polar solvents. Various conditions such as polymer/SWCNT ratio, solvent polarity, solvent dielectric constant as well as polymer solubility and SWCNT dispersibility were explored in order to optimize the purity and yield of the enriched product. Herein, we provide insights on CPE by demonstrating that a conjugated polymer having a hydrophobic backbone and hydrophilic oligo(ethylene oxide) side chains provides near full recovery (95%) of sc-SWCNTs using a multiextraction protocol. High purity is also obtained, and differences in chiral selectivity compared to analogous hydrophobic systems were confirmed by optical absorption and Raman spectroscopy as well as photoluminescence excitation mapping. Taking into consideration the solvent dielectric constant, polarity index as well as polymer solubility and SWCNT dispersibility provides a better understanding of structure-property effects on sc-SWCNT enrichment. The resulting hydrophilic SWCNT dispersions demonstrate long-term colloidal stability, making them suitable for ink formulation and high-performance thin-film transistors fabrication.

Determination of cyanocobalamin by isotope dilution LC-MS/MS.

Cyanocobalamin (CNCbl) is an active form of vitamin B12, commonly employed for the preparation of multivitamin supplements and fortified food. In this study, we present a novel analytical method for its determination based on stable isotope dilution liquid chromatography electrospray tandem mass spectrometry (ID LC-MS/MS). Isotopically enriched 13C15NCbl was synthesized in-house and used as internal standard. The method was validated using NIST SRM 3280 multivitamin reference material and by comparison with an independent methodology based on LC-ICPMS. The proposed method provided a detection limit of 57 pg/g and could be applied for the determination of trace level of CNCbl in multivitamin supplements with a relative standard uncertainty better than 3%. The novel ID LC-MS/MS is a primary ratio method that could become a reference for CNCbl determination in multivitamins and food supplements. The method was applied for the characterization of two NRC multivitamin tablet Certified Reference Material (CRM) candidates, VITA-1 and VITB-1 whose CNCbl levels were quantified as 2.64 ± 0.09 and 1.75 ± 0.12 µg/g, respectively.

Interaction Potency of Single-Walled Carbon Nanotubes with DNAs: A Novel Assay for Assessment of Hazard Risk.

Increasing use of single-walled carbon nanotubes (SWCNTs) necessitates a novel method for hazard risk assessment. In this work, we investigated the interaction of several types of commercial SWCNTs with single-stranded (ss) and double-stranded (ds) DNA oligonucleotides (20-mer and 20 bp). Based on the results achieved, we proposed a novel assay that employed the DNA interaction potency to assess the hazard risk of SWCNTs. It was found that SWCNTs in different sizes or different batches of the same product number of SWCNTs showed dramatically different potency of interaction with DNAs. In addition, the same SWCNTs also exerted strikingly different interaction potency with ss- versus ds- DNAs. The interaction rates of SWCNTs with DNAs were investigated, which could be utilized as the indicator of potential hazard for acute exposure. Compared to solid SWCNTs, the SWCNTs dispersed in liquid medium (2% sodium cholate solution) exhibited dramatically different interaction potency with DNAs. This indicates that the exposure medium may greatly influence the subsequent toxicity and hazard risk produced by SWCNTs. Based on the findings of dose-dependences and time-dependences from the interactions between SWCNTs and DNAs, a new chemistry based assay for hazard risk assessment of nanomaterials including SWCNTs has been presented.

A hybrid enrichment process combining conjugated polymer extraction and silica gel adsorption for high purity semiconducting single-walled carbon nanotubes (SWCNT).

A novel purification process for the enrichment of sc-SWCNTs that combines selective conjugated polymer extraction (CPE) with selective adsorption using silica gel, termed hybrid-CPE (h-CPE), has been developed, providing a high purity sc-SWCNT material with a significant improvement in process efficiency and yield. Using the h-CPE protocol, a greater than 5 fold improvement in yield can be obtained compared to traditional CPE while obtaining sc-SWCNT with a purity >99.9% as assessed by absorption spectroscopy and Raman mapping. Thin film transistor devices using the h-CPE derived sc-SWCNTs as the semiconductor possess mobility values ranging from 10-30 cm(2) V(-1) s(-1) and current ON/OFF ratio of 10(4)-10(5) for channel lengths between 2.5 and 20 µm.

Preparation and Properties of Nanoporous Triblock Copolymer Membranes.

"Unplug those pores!" could be a slogan common to cosmetologists and polymer chemists. Membranes with nanochannels can be obtained by first forming a film by casting a solution of a triblock and homopolymer mixture, then selectively cross-linking domains in the film by photolysis, and finally forming nanochannels through removal of the homopolymer by solvent extraction. Such membranes are not liquid permeable but have gas-permeability constants about six orders of magnitude higher than that of low-density polyethylene films.

Superhydrophobic stability of nanotube array surfaces under impact and static forces.

The surfaces of nanotube arrays were coated with poly(methyl methacrylate) (PMMA) using an imprinting method with an anodized alumina membrane as the template. The prepared nanotube array surfaces then either remained untreated or were coated with NH2(CH2)3Si(OCH3)3(PDNS) or CF3(CF2)7CH2CH2Si(OC2H5)3 (PFO). Thus, nanotube arrays with three different surfaces, PDNS, PMMA (without coating), and PFO, were obtained. All three surfaces (PDNS, PMMA, and PFO) exhibited superhydrophobic properties with contact angles (CA) of 155, 166, and 168°, respectively, and their intrinsic water contact angles were 30, 79, and 118°, respectively. The superhydrophobic stabilities of these three surfaces were examined under dynamic impact and static pressures in terms of the transition from the Cassie-Baxter mode to the Wenzel mode. This transition was determined by the maximum pressure (p(max)), which is dependent on the intrinsic contact angle and the nanotube density of the surface. A p(max) greater than 10 kPa, which is sufficiently large to maintain stable superhydrophobicity under extreme weather conditions, such as in heavy rain, was expected from the PFO surface. Interestingly, the PDNS surface, with an intrinsic CA of only 30°, also displayed superhydrophobicity, with a CA of 155°. This property was partially maintained under the dynamic impact and static pressure tests. However, under an extremely high pressure (0.5 MPa), all three surfaces transitioned from the Cassie-Baxter mode to the Wenzel mode. Furthermore, the lost superhydrophobicity could not be recovered by simply relieving the pressure. This result indicates that the best way to maintain superhydrophobicity is to increase the p(max) of the surface to a value higher than the applied external pressure by using low surface energy materials and having high-density binary nano-/microstructures on the surface.