Electron-induced deposition using Fe(CO)4MA and Fe(CO)5 - effect of MA ligand and process conditions.

The electron-induced decomposition of Fe(CO)4MA (MA = methyl acrylate), which is a potential new precursor for focused electron beam-induced deposition (FEBID), was investigated by surface science experiments under UHV conditions. Auger electron spectroscopy was used to monitor deposit formation. The comparison between Fe(CO)4MA and Fe(CO)5 revealed the effect of the modified ligand architecture on the deposit formation in electron irradiation experiments that mimic FEBID and cryo-FEBID processes. Electron-stimulated desorption and post-irradiation thermal desorption spectrometry were used to obtain insight into the fate of the ligands upon electron irradiation. As a key finding, the deposits obtained from Fe(CO)4MA and Fe(CO)5 were surprisingly similar, and the relative amount of carbon in deposits prepared from Fe(CO)4MA was considerably less than the amount of carbon in the MA ligand. This demonstrates that electron irradiation efficiently cleaves the neutral MA ligand from the precursor. In addition to deposit formation by electron irradiation, the thermal decomposition of Fe(CO)4MA and Fe(CO)5 on an Fe seed layer prepared by EBID was compared. While Fe(CO)5 sustains autocatalytic growth of the deposit, the MA ligand hinders the thermal decomposition in the case of Fe(CO)4MA. The heteroleptic precursor Fe(CO)4MA, thus, offers the possibility to suppress contributions of thermal reactions, which can compromise control over the deposit shape and size in FEBID processes.

6-Phenylhexyl silane derivatized, sputtered silicon solid phase microextraction fiber for the parts-per-trillion detection of polyaromatic hydrocarbons in water and baby formula.

We report the fabrication of 6-phenylhexylsilane derivatized, sputtered silicon, solid phase microextraction fibers that show parts per trillion detection limits for polyaromatic hydrocarbons, and negligible carry over and phase bleed. Their fabrication involves sputtering silicon on silica fibers under various conditions. Six different fibers were evaluated by generating three different thicknesses of sputtered silicon at two different throw distances, which altered the morphologies of the silicon surfaces. All of the fibers were coated with similar thicknesses of 6-phenylhexylsilane (ca. 2 nm). These fibers were characterized with multiple analytical techniques. The optimum fiber configuration was then used to analyze polyaromatic hydrocarbons via direct immersion, gas chromatography mass spectrometry. Our best fiber for the extraction of low molecular weight polyaromatic hydrocarbons in water had similar performance to that of a commercial fiber. However, our fiber demonstrated ca. 3 times the extraction efficiency for higher molecular weight polyaromatic hydrocarbons. In addition, it outperformed the commercial fiber by showing better linearity, repeatability, and detection limits. A method for analyzing polyaromatic hydrocarbons in baby formula was developed, which showed very good linearity (0.5-125 ppb), repeatability (2-26%), detection limits (0.12-0.81 ppb), and recoveries (103-135%). In addition, our fiber showed much less (negligible) carry over and phase bleed than the commercially available fibers.

Cuprous or cupric? How substrate polarity can select for different phases of copper sulfide films in chemical bath deposition.

Copper sulfides have many applications from thermoelectrics to biotechnology. While the properties of different copper sulfide phases are well understood, controlling the deposited copper sulfide stoichiometry remains a significant challenge, especially in solution-phase synthesis techniques. In this work, we investigate the chemical bath deposition of CuxS on functionalized self-assembled monolayers (SAMs). Time-of-flight mass spectrometry, Raman spectroscopy, and x-ray photoelectron spectroscopy are employed to analyze the deposited films. We show that the use of thiourea as a sulfur source leads to the deposition of different copper sulfide phases and is controlled by the interaction of sulfur-containing ions in solution with the functionalized SAMs. For -COOH terminated SAMs, copper sulfide deposition is controlled by the surface polarity of the substrate. At the bath pH used in these experiments, the -COOH terminal groups are deprotonated. The resulting -COO- terminated SAM surface repels negatively charged sulfur-containing ions, leading to the deposition of Cu2S. For -CH3 terminated SAMs, which are non-polar, there is no specific interaction between the SAM terminal group and sulfur-containing ions and CuS is deposited. For -OH terminated SAMs, which have a polar terminal group, there are two competing effects: the repulsion of S-containing ions by the small negative charge of the terminal -OH group and the increase in the concentration of sulfur-containing ions in solution as the bath pH increases. This competition leads to the deposit stoichiometry changing from Cu2S at pH 9 to CuS at pH 12.

Chemical Bath Deposition of Copper Sulfide on Functionalized SAMs: An Unusual Selectivity Mechanism.

We have investigated the chemical bath deposition (CBD) of CuS using thioacetamide on functionalized self-assembled monolayers (SAMs) using scanning electron and optical microscopies, X-ray photoelectron spectroscopy, and time-of-flight secondary ion mass spectrometry. For all SAMs studied, the amount of CuS deposited is strongly dependent on the bath pH and can be attributed to the interaction of the SAM terminal groups with the chalcogenide ions present in solution. For -CH3-terminated SAMs, there is a steady increase in the amount of CuS deposited with an increase in the bath pH because there is an increase in the concentration of chalcogenide ion. However, for -OH- and -COOH-terminated SAMs, we observe that the maximum amount of CuS is deposited at pH 10. We attribute this behavior to a competition between the repulsion of the chalcogenide ions by the negatively charged SAM terminal groups and an increase in the chalcogenide ion concentration with an increase in the bath pH. Using the interaction of the chalcogenide ions with the different SAM terminal functional groups, we demonstrate that CuS can be selectively deposited on the -CH3-terminated areas of patterned -OH/-CH3- and -COOH/-CH3-terminated SAMs.

Modulating the Electronic Properties of Au-MoS2 Interfaces Using Functionalized Self-Assembled Monolayers.

Molybdenum disulfide (MoS2) is a transition-metal dichalcogenide with many applications including in electronic devices and sensors. A critical issue in the development of these devices is the high resistance between the metal contact and the molybdenum disulfide layer. In this study, we employ Raman spectroscopy and X-ray photoelectron spectroscopy to investigate the modification of Au-MoS2 contact properties using functionalized alkanethiolate self-assembled monolayers (SAMs). We demonstrate that both 2H and 1T MoS2 strongly interact with the underlying Au substrate. The electronic properties of the interface are mediated by the dipole moment of the alkanethiolate SAM, which have a -CH3, -CO2C6F5, -OH, or -COOH terminal group. Finally, we demonstrate the site-selective deposition of 2H and 1T MoS2 on micropatterned SAMs to form conducting-semiconducting patterned MoS2 films.

Polytype control of MoS2 using chemical bath deposition.

Molybdenum disulfide (MoS2) has a wide range of applications from electronics to catalysis. While the properties of single-layer and multilayer MoS2 films are well understood, controlling the deposited MoS2 polytype remains a significant challenge. In this work, we employ chemical bath deposition, an aqueous deposition technique, to deposit large area MoS2 thin films at room temperature. Using Raman spectroscopy and x-ray photoelectron spectroscopy, we show that the deposited MoS2 polytype can be changed from semiconducting 2H MoS2 on hydrophobic -CH3 and -CO2C6F5 terminated self-assembled monolayers (SAMs) to semimetallic 1T MoS2 on hydrophilic -OH and -COOH terminated SAMs. The data suggest that the deposition of MoS2 polytypes is controlled by the substrate surface energy. High surface energy substrates stabilize 1T MoS2 films, while 2H MoS2 is deposited on lower surface energy substrates. This effect appears to be general enabling the deposition of different MoS2 polytypes on a wide range of substrates.

Law and Disorder: Special Stacking Units-Building the Intergrowth Ce6Co5Ge16.

A new structure type of composition Ce6Co5Ge16 was grown out of a molten Sn flux. Ce6Co5Ge16 crystallizes in the orthorhombic space group Cmcm, with highly anisotropic lattice parameters of a = 4.3293(5) Å, b = 55.438(8) Å, and c = 4.3104(4) Å. The resulting single crystals were characterized by X-ray diffraction, and the magnetic and transport properties are presented. The Sn-stabilized structure of Ce6Co5Ge16 is based on the stacking of disordered Ce cuboctahedra and is an intergrowth of existing structure types including AlB2, BaNiSn3, and AuCu3. The stacking of structural subunits has previously been shown to be significant in the fields of superconductivity, quantum materials, and optical materials. Herein, we present the synthesis, characterization, and complex magnetic behavior of Ce6Co5Ge16 at low temperature, including three distinct magnetic transitions.

Femtosecond laser desorption ionization mass spectrometry imaging and multivariate analysis of lipids in pancreatic tissue.

Femtosecond laser desorption ionization mass spectrometry was used to obtain mass spectrometric (MS) images of lipids in human pancreatic tissue. The resulting MS images were analyzed using multivariate analysis, specifically principal component analysis and maximum a posteriori (MAP) reconstruction. Both analysis methods showed that the MS images can be separated into lipid and non-lipid areas. MAP analysis further indicated that the lipid areas are composed of phosphatidylcholines and fatty acids. However, definitive identification of the lipids cannot be made because none of the intact parent ions of phosphatidylcholine, sphingomyelins, and/or other lipids were observed. The MAP analysis also revealed that the non-lipid areas could be separated into components that are due to the sample chemical treatment and topography.

Effect of Ethanolamines on the Electroless Deposition of Copper on Functionalized Organic Surfaces.

Electroless deposition (ELD) is widely used in industry to deposit metals because it is inexpensive and compatible with organic materials. The deposition rate and deposited film properties critically depend on the reducing agent, complexing agent, and bath pH and temperature as well as bath additives. We have investigated the role of ethanolamine additives in the ELD of copper using the reducing agent dimethylamine borane on -CH3- and -OH-terminated self-assembled monolayers (SAMs) adsorbed on gold. Three additives were studied: ethanolamine (EOA), diethanolamine (DEOA), and triethanolamine (TEOA). Both the chemical identity and concentration of the ethanolamine significantly affect the deposition process. We show that the Cu deposition rate is faster on -CH3-terminated surfaces than on -OH-terminated SAMs because of the stronger interaction of the ethanolamines with the hydroxyl terminal group. In contrast to physical vapor deposition and other ELD processes, Cu deposits atop methyl-terminated SAMs using TEOA. However, using EOA and DEOA, copper penetrates through -CH3-terminated SAMs to the Au/S interface. For -OH-terminated SAMs, copper is observed to penetrate through the SAM for all ethanolamines investigated. The amount of copper penetration through the SAM to the Au/S interface increases with ethanolamine concentration. These effects are attributed to an adsorption-inhibition mechanism and differences in the chelation of Cu2+ in the deposition bath.

Application of visible-light photosensitization to form alkyl-radical-derived thin films on gold.

Visible-light irradiation of phthalimide esters in the presence of the photosensitizer [Ru(bpy)3]2+ and the stoichiometric reducing agent benzyl nicotinamide results in the formation of alkyl radicals under mild conditions. This approach to radical generation has proven useful for the synthesis of small organic molecules. Herein, we demonstrate for the first time the visible-light photosensitized deposition of robust alkyl thin films on Au surfaces using phthalimide esters as the alkyl radical precursors. In particular, we combine visible-light photosensitization with particle lithography to produce nanostructured thin films, the thickness of which can be measured easily using AFM cursor profiles. Analysis with AFM demonstrated that the films are robust and resistant to mechanical force while contact angle goniometry suggests a multilayered and disordered film structure. Analysis with IRRAS, XPS, and TOF SIMS provides further insights.

Correction: Facile synthesis of stable, water soluble, dendron-coated gold nanoparticles.

Correction for 'Facile synthesis of stable, water soluble, dendron-coated gold nanoparticles' by Alan E. Enciso, et al., Nanoscale, 2017, 9, 3128-3132.

Role of the Reducing Agent in the Electroless Deposition of Copper on Functionalized SAMs.

Metallized organic layer constructs have a wide range of technological applications. Electroless deposition is an attractive technique by which to deposit metal overlayers because it is inexpensive and can be performed at low temperatures, compatible with organic materials. Amine borane reducing agents are versatile and are capable of depositing metals, semiconductors, and even insulators. We have investigated the role of amine borane reducing agents in the electroless deposition of copper on -CH3-, -OH-, and -COOH-terminated SAMs adsorbed on gold using time-of-flight secondary ion mass spectrometry, optical microscopy, and complementary MP2 calculations. Three reducing agents were studied: amine borane, dimethylamine borane, and trimethylamine borane. At pH >9, -COOH-terminated SAMs form copper-carboxylate complexes, which serve as nucleation sites for subsequent copper deposition. The rate of copper deposition is dependent on the strength of the B-N bond of the amine borane reducing agent. Similarly, if the terminal group is nonpolar such as a -CH3 functionality, then the rate of copper deposition is dependent on the amine borane B-N bond strength. However, in contrast to -COOH-terminated SAMs, copper deposition does not begin immediately. If the terminal group contains polar bonds, such as the C-OH bond of -OH-terminated SAMs, deposition is dominated by the interaction of the reducing agent with the terminal group rather than the relative bond strengths of the amine borane reducing agents.

Photochemical CVD of Ru on functionalized self-assembled monolayers from organometallic precursors.

Chemical vapor deposition (CVD) is an attractive technique for the metallization of organic thin films because it is selective and the thickness of the deposited film can easily be controlled. However, thermal CVD processes often require high temperatures which are generally incompatible with organic films. In this paper, we perform proof-of-concept studies of photochemical CVD to metallize organic thin films. In this method, a precursor undergoes photolytic decomposition to generate thermally labile intermediates prior to adsorption on the sample. Three readily available Ru precursors, CpRu(CO)2Me, (η3-allyl)Ru(CO)3Br, and (COT)Ru(CO)3, were employed to investigate the role of precursor quantum yield, ligand chemistry, and the Ru oxidation state on the deposition. To investigate the role of the substrate chemistry on deposition, carboxylic acid-, hydroxyl-, and methyl-terminated self-assembled monolayers were used. The data indicate that moderate quantum yields for ligand loss (φ ≥ 0.4) are required for ruthenium deposition, and the deposition is wavelength dependent. Second, anionic polyhapto ligands such as cyclopentadienyl and allyl are more difficult to remove than carbonyls, halides, and alkyls. Third, in contrast to the atomic layer deposition, acid-base reactions between the precursor and the substrate are more effective for deposition than nucleophilic reactions. Finally, the data suggest that selective deposition can be achieved on organic thin films by judicious choice of precursor and functional groups present on the substrate. These studies thus provide guidelines for the rational design of new precursors specifically for selective photochemical CVD on organic substrates.

Facile synthesis of stable, water soluble, dendron-coated gold nanoparticles.

Upon reduction with sodium borohydride, diazonium tetrachloroaurate salts of triazine dendrons yield dendron-coated gold nanoparticles connected by a gold-carbon bond. These robust nanoparticles are stable in water and toluene solutions for longer than one year and present surface groups that can be reacted to change surface chemistry and manipulate solubility. Molecular modeling was used to provide insight on the hydration of the nanoparticles and their observed solubilties.

From Nanowires to Nanopores: A Versatile Method for Electroless Deposition of Nanostructures on Micropatterned Organic Substrates.

We demonstrate a fast, flexible, parallel, and highly controllable method by which to synthesize a variety of nanoscale and mesoscale structures. This method addresses one of the most significant challenges in nanoscience: the in situ parallel placement and synthesis of nano-objects over the mesoscale. The method is based on electroless nanowire deposition on micropatterned substrates (ENDOM). In ENDOM nanostructures are produced at the boundary between two unlike materials if two conditions are met: (a) deposition is kinetically preferred on one of the materials while (b) transport of reactants is favored on the other. In this study, copper structures were deposited on patterned -OH/-CH3-terminated alkanethiolate self-assembled monolayers (SAMs) by exploiting the different reaction rates of electroless deposition on these using the reducing agent dimethylamine borane (DMAB). We demonstrate production of nanowires (width < 100 nm), mesowires (100 nm < width < ∼3000 nm), nanorings, nanopores, and nanochannels. We show that a variety of experimental conditions can be employed, making this method compatible with many substrates. We have also studied the nucleation and growth kinetics of the ENDOM process. The width of the deposit grows exponentially with deposition time and can be modeled using classical nucleation theory. Although the deposit width increases, the height and grain size of the copper deposit is constant (to within experimental uncertainty) with deposition time. These observations indicate that the minimum deposit width is controlled by the nanoparticle dimensions and so can be controlled using the reaction conditions.

Emergence of Magnetic States in Pr2Fe(4-x)Co(x)Sb5 (1 < x < 2.5).

Single crystals of Pr2Fe(4-x)Co(x)Sb5 (1 < x < 2.5) were grown from a Bi flux and characterized by X-ray diffraction. The compounds adopt the La2Fe4Sb5 structure type (I4/mmm). The structure of Pr2Fe(4-x)Co(x)Sb5 (1 < x < 2.5) contains a network of transition metals forming isosceles triangles. The x ∼ 1 analogue is metallic and exhibits a magnetic transition at T1 ≈ 25 K. The magnetic moment obtained from the Curie-Weiss fit is 11.49(4) µ(B), which is larger than the spin-only Pr(3+) moment. The x ∼ 2 analogue orders magnetically at T1 ≈ 80 and T2 ≈ 45 K. This is the first case of the substitution of Co into the La2Fe4Sb5 structure type, evidenced by the increased concentration of dopant with decreased lattice parameters coupled with a change in the transition temperature with a change in the cobalt concentration. The added complexity in the magnetic behavior of the x ∼ 1 and 2 analogues indicates that the increased concentration of Co invokes an additional magnetic contribution of the transition metal in the sublattice. Furthermore, X-ray photoelectron spectroscopy measurements support the change in the oxidation states of transition metals with increasing cobalt concentration.

Chemical bath deposition of ZnO on functionalized self-assembled monolayers: selective deposition and control of deposit morphology.

We have developed a method by which to selectively and reproducibly deposit ZnO films on functionalized self-assembled monolayers (SAMs) using chemical bath deposition (CBD). The deposition bath is composed of zinc acetate and ethylenediamine. The deposition reaction pathways are shown to be similar to those observed for sulfides and selenides, even though ethylenediamine acts as both an oxygen source and a complexing agent. On -COOH terminated SAMs, Zn-carboxylate surface complexes act as nucleation sites for ion-by-ion growth, leading to the formation of adherent ZnO nanocrystallites. Cluster-by-cluster growth is also observed, which produces weakly adherent micrometer-sized ZnO crystallites. On -CH3 and -OH terminated SAMs, only micrometer-sized ZnO crystallites are observed because Zn(2+) does not complex with the SAM terminal group, preventing nucleation of the nanocrystalline phase. The application of either ultrasound ("sonication-assisted CBD") or stirring promotes ion-by-ion ZnO growth on -COOH terminated SAMs. Stirring produces smoother but less reproducible ZnO films than sonication-assisted CBD.

Partially fluorinated oxo-alkoxide tungsten(VI) complexes as precursors for deposition of WOx nanomaterials.

The partially fluorinated oxo-alkoxide tungsten(VI) complexes WO(OR)4 [4; R = C(CH3)2CF3, 5; R = C(CH3)(CF3)2] have been synthesized as precursors for chemical vapour deposition (CVD) of WOx nanocrystalline material. Complexes 4 and 5 were prepared by salt metathesis between sodium salts of the fluoroalkoxides and WOCl4. Crystallographic structure analysis allows comparison of the bonding in 4 and 5 as the fluorine content of the fluoroalkoxide ligands is varied. Screening of as a CVD precursor by mass spectrometry and thermogravimetric analysis was followed by deposition of WOx nanorods.

Morphological control of PbS grown on functionalized self-assembled monolayers by chemical bath deposition.

We have investigated the chemical bath deposition (CBD) of PbS on functionalized alkanethiolate self-assembled monolayers (SAMs) using time-of-flight secondary ion mass spectrometry (SIMS), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy. The deposition mechanism involves both cluster-by-cluster and ion-by-ion growth. The dominant reaction pathway and the chemical composition and morphology of the deposited layer are dependent on both the SAM terminal group and the experimental conditions. On -COOH-terminated SAMs, three types of crystallites are observed: nanocrystals formed by heterogeneous ion-by-ion growth, larger needle-like particles, and ~2 µm particles deposited by homogeneous cluster-by-cluster deposition. The nanocrystals nucleate at Pb(2+)-carboxylate surface complexes, and so strongly adhere to the substrate. On -OH- and -CH3-terminated SAMs, only the micrometer-sized particles are formed by a cluster-by-cluster deposition mechanism. These particles do not adhere strongly to the SAM surface and can be easily removed. SIMS and XPS analyses indicate that the larger needle-like crystals and micrometer-sized particles are composed of oxidized lead sulfide and lead oxides, while the nanocrystals are composed of ≥85% PbS. Using sonication-assisted CBD, we demonstrate that PbS is deposited by ion-by-ion growth alone on -COOH-terminated SAMs. The deposited film is more compact with a smaller grain size and is >90% PbS.

Towards the rational design of ionic liquid matrices for secondary ion mass spectrometry: role of the anion.

The role of the ionic liquid (IL) anion structure on analyte signal enhancements has been systematically investigated in secondary ion mass spectrometry (SIMS) using a variety of samples, including lipids, sterols, polymers, and peptides. Twenty-four ILs were synthesized. The 12 matrix acids were cinnamic acid derivatives. Two bases were employed: 1-methylimidazole and tripropylamine. Three matrices, methylimmidazolium o-coumarate, tripropylammonium o-coumarate, and tripropylammonium 3,4,5-trimethoxycinnamate, were "universal" matrices enhancing all analytes tested. The pKa of the matrix acid does not appear to have a strong effect on analyte ion intensities. Rather, it is observed that a single hydroxyl group on the anion aromatic ring leads to significantly increased molecular ion intensities. No analyte signal enhancements were observed for -CH3, -CF3 and -OCH3 groups present on the aromatic ring. The position of the -OH group on the aromatic ring also alters molecular ion intensity enhancements. As well as the chemical identity and position of substituents, the number of moieties on the aromatic ring may affect the analyte signal enhancements observed. These observations suggest that the activation of the IL anion aromatic ring is important for optimizing analyte signal intensities. The implications for SIMS imaging of complex structures, such as biological samples, are discussed.