Self-assembled monolayers on magnesium alloy surfaces from carboxylate ions

Self-assembled monolayers (SAMs) of carboxylate salts (C_n−1H_2n−1COONa, n = 12, 16, 18) were successfully formed on Mg alloy substrate in ethanol solution and characterized by the contact angle measurement, ATR-FTIR, ellipsometry and XPS. The SAMs were regularly and densely anchored to the Mg alloy substrate via monodentate bonding with the tilting angles of about 40°, 33° and 27° for C12, C16 and C18 monolayers, respectively. Electrochemical impedance spectroscopy (EIS) proved the corrosion protection of SAMs for Mg alloy substrate with protective efficiency (PE) of even up to 98.5%.     

Conformational order of n-dodecanethiol and n-dodecaneselenol monolayers on polycrystalline copper investigated by PM-IRRAS and SFG spectroscopy

Self-assembled monolayers (SAMs) of n-dodecanethiol (C₁₂H₂₅SH) and n-dodecaneselenol (C₁₂H₂₅SeH) on polycrystalline copper have been elaborated with the purpose of achieving densely packed and crystalline-like assemblies. By combining the surface sensitivity of polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) and sum-frequency generation spectroscopy (SFG), the effect of the self-assembly time (15 min, 30 min, 1 h, 2 h and 24 h) on the formation of n-dodecanethiol and n-dodecaneselenol monolayers on untreated and electrochemically reduced polycrystalline copper has been investigated. On electrochemically reduced copper, PM-IRRAS spectroscopy shows that both molecules are able to form well organized layers. SFG spectroscopy indicates that the C₁₂H₂₅SeH SAMs are slightly better ordered than those achieved with C₁₂H₂₅SH. On untreated copper, the two molecules lead to different film organizations. Both PM-IRRAS and SFG indicate that C₁₂H₂₅SH SAMs are of the same film quality as those obtained on electrochemically reduced copper. On the contrary, C₁₂H₂₅SeH monolayers are invariably poorly organized at the molecular level.     

COOH-terminated SAMs on gold fabricated from an azobenzene derivative with a 1,2-dithiolane headgroup

Well-defined and homogeneous, contamination-free self-assembled monolayers (SAMs) were fabricated by the chemisorption of lip-NH-p-C₆H₄-NN-p-C₆H₄-COOH (lip = α-lipoyl) onto gold. This adsorbate species is composed of a 1,2-dithiolane-based headgroup, an azobenzene-based (and hence photochromic) spacer unit and a carboxylic acid functional group. The SAM constituents are covalently attached to the substrate by the bidentate thiolate anchor groups and exhibit a strongly tilted binding configuration.     

Characterization and protonation behavior of bipyridine thiol self-assembled monolayer on Au(1 1 1) studied using X-ray photoelectron spectroscopy and scanning tunneling microscopy

The adsorption process, molecular arrangement and protonation behavior of self-assembled monolayers (SAMs) of bipyridine thiol on Au(1 1 1) were investigated using X-ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM), with a view towards constructing a molecular ion sensor. When the bipyridine SAMs were immersed in a strong CF₃SO₃H solution for protonation of the bipyridine group, additional N(1s) XPS peaks were generated at higher binding peak positions where the origin of the peak was considered to be the N-H species. We further investigated the relationship between the immersion time for the SAMs and the probability of protonation. We observed a decrease in the probability of protonation with a longer immersion time for the SAMs. We consider that both the bipyridine molecular arrangements and the molecular density on the Au surface are crucial for controlling the probability of protonation based on the STM and XPS data.     

Mixed self-assembled monolayers of Co-porphyrin and n-alkane phosphonates on gold

The present work focuses on the surface immobilization by self-assembly of pure and mixed Co-porphyrin (Co-Porph-PO₃H₂) and n-alkane phosphonic acids (n-C_nH_2n + 1PO₃H₂; n = 4, 5 and 10) from n-butanol solutions on gold substrates. The stability, amount, and packing of the phosphonic molecules attached to the Au (111) surface were investigated by electrochemical reductive desorption studies, and monolayers' thickness was estimated by ellipsometry. The morphological changes induced by the adsorption of n-decane phosphonic acid on gold were analysed by scanning tunnelling microscopy. The redox behavior of Co-Porph-PO₃H₂ SAMs was assessed in organic medium and compared that of Co-Porph-CO₂CH₃ precursor in solution, confirming the self-assembly of the metalloporphyrin molecules. With the purpose of reducing the electrostatic interactions between the porphyrin bulky terminal groups in the SAM, n-C₅H₁₁PO₃H₂ and n-C₁₀H₂₁PO₃H₂ were used to form mixed monolayers with Co-Porph-PO₃H₂ on gold. Intermediate electrochemical desorption potentials regarding those values of pure monolayers, as well as an increase of phosphonate surface density compared to that of Co-Porph-PO₃H₂ SAM, confirm the presence of two-component SAMs, which indicates that porphyrin moieties are diluted in the monolayer. The electrocatalytic activity of the immobilized molecules was demonstrated towards the reduction of molecular oxygen, in acidic medium.     

Effect of end groups on contact resistance of alkanethiol based metal-molecule-metal junctions using current sensing AFM

Tuning the charge transport through a metal-molecule-metal junction by changing the interface properties is widely studied and is of paramount importance for applications in molecular electronic devices. We used current sensing atomic force microscopy (CSAFM) as a tool to study the contact resistance of metal-molecule-metal (MmM) junctions formed by sandwiching self-assembled monolayers (SAMs) of alkanethiols with various end groups (-CH₃, -OH and -NH₂) between Au(1 1 1) substrates and Au coated AFM tips. The effect of interface chemistry on charge transport through such SAMs with varying end groups was studied in an inert, non-polar liquid (hexadecane) environment. We find that the contact resistances of these MmM junctions vary significantly based on the end group chemistry of the molecules.     

Rotational spectra of gauche perfluoro-n-butane, C4F10; perfluoro-iso-butane, (CF3)3CF; and tris(trifluoromethyl)methane, (CF3)3CH

The microwave spectra of the gauche conformer of perfluoro-n-butane, n-C₄F₁₀, of perfluoro-iso-butane, (CF₃)₃CF, and of tris(trifluoromethyl)methane, (CF₃)₃CH, have been observed and assigned. The rotational and centrifugal distortion constants for gauche n-C₄F₁₀ are: A = 1058.11750(7) MHz, B = 617.6832(1) MHz, C = 552.18794(1) MHz, Δ_J = 0.0257(5) kHz, δ_J = 0.0052(3) kHz. A C-C-C-C dihedral angle, ω, of ∼55° has been determined. These values agree well with those obtained from a coupled cluster (CCSD/cc-PVTZ) calculation. The rotational and centrifugal distortion constants for iso-C₄F₁₀ and iso-C₄HF₉ are: B_o = 816.4519(4) MHz, D_J = 0.023(2) kHz, and B_o = 903.6985(25) MHz, D_J = 0.043(4) kHz, respectively. The dipole moment of iso-C₄F₁₀ and iso-C₄HF₉ have been measured and found to be 0.0338(8) and 1.69(9) D, respectively.     

Diluting thiol-derivatized oligonucleotide monolayers on Au(1 1 1) by mercaptohexanol replacement reaction

Surface replacement reaction of thiol-derivatized, single-stranded oligonucleotide (HS-ssDNA) by mercaptohexanol (MCH) is investigated in order to reduce surface density of the HS-ssDNA adsorbed to Au(1 1 1) surface. Cyclic voltammograms (CVs) and scanning tunneling microscopy (STM) are employed to assess the composition and state of these mixed monolayers. It is found that each CV of mixed self-assembled monolayers (SAMs) only shows a single reductive desorption peak, which suggests that the resulted, mixed SAMs do not form discernable phase-separated domains. The peak potential gradually shifts to negative direction and the peak area increases step by step over the whole replacement process. By analyzing these peak areas, it is concluded that two MCH molecules will replace one HS-ssDNA molecule and relative coverage can also be estimated as a function of exposing time. The possible mechanism of the replacement reaction is also proposed. The DNA surface density exponentially reduces with the exposing time increasing, in other words, the replacement reaction is very fast in the first several hours and then gradually slows down. Moreover, the morphological change in the process is also followed by STM.     

Two-photon resonance in optical second harmonic generation from quantum well states in ultra-thin Ag films grown on Si(1 1 1) surfaces

We studied optical second harmonic generation (SHG) oscillations during the growth of Ag films on Si(1 1 1) 7 × 7 clean and H-terminated surfaces. In the growth on the 7 × 7 surfaces at room temperature, the second and third peaks of the oscillation shift towards the thinner side with an increase in pump photon energy. Our analysis revealed that these peaks are caused by two-photon resonant transitions from the n = 1 and 2 occupied quantum well states (QWSs) in the Ag film to the Ag/Si interface at 1.9 eV above the Fermi level (E_f). In Ag growth on the hydrogen-terminated surfaces, the SHG oscillation was similar to that on the 7 × 7 surfaces at room temperature. However, the QWS-related peak was suppressed in the growth at 300 °C. This is attributed to an inhibited intrusion of the interface state into the Ag layers.     

Primary ion fluence dependence in time-of-flight SIMS of self-assembled monolayer of alkyl thiol molecules on Au(1 1 1)—Discussion of static limit

The nondestructive nature of static secondary ion mass spectrometry (SIMS) in the context of studies of self-assembled monolayers (SAMs) of organic molecules has been examined by measuring the primary ion fluence dependence of secondary ion signals with two well-known SAMs, C₁₈H₃₇SH on Au(1 1 1) and C₁₈H₃₇PO₃H₂ on freshly cleaved mica. This SIMS analysis is challenging because the bonding nature is delicate and the areal molecular density is less than 10¹⁵ cm⁻². In SIMS, it is prevalently assumed that if the primary ion fluence is confined to not more than 1 × 10¹² cm⁻², all secondary ion signals should not change by more than 10% and the practically defined static condition is satisfied. Our results from time-of-flight SIMS with the common primary ions of Bi₃⁺, Bi⁺ and Ar⁺, indicate that this prevalent static assumption fails for both model SAMs. The SIMS results from the phosphyl case, which have been recently published, consistently display the evidence of bombardment-induced damage. In comparison, the thiol case presented here shows much more complex primary ion fluence dependence of SIMS signals. It is therefore concluded that practical static analysis should use primary ion fluence not more than 1 × 10¹¹ cm⁻² or should simply record and report the effects of primary ion fluence.     

Molecular dynamics study of interfacial bonding strength of self-assembled monolayer-coated Au-epoxy and Au-Au systems

Interfacial adhesion between metals and organic polymers plays a crucial role in the mechanical properties and reliability performance of multiplayer thin film structures. To improve their interfacial bonding strength and so the reliability, the self-assembled monolayer (SAM) method is considered as an effective means. The present study is devoted to studying the effects of SAM coating on the interfacial bonding strength of the Au-epoxy and the Au-Au bonding structures through molecular dynamics (MD) simulation. Three different types of functionalized alkanethiol SAMs (SH(CH₂)_nX, X = CH₃, OH, NH₂) chemisorbed onto two different Au crystal planes, i.e., (1 0 0) and (1 1 1), are considered. The study starts from the characterization of the interfacial bonding strength of both the SAM-coated Au-epoxy and Au-Au systems, followed by the investigation of the dependence of the interfacial bonding strength on the chain lengths and tail groups of the n-alkanethiolates. A comparative study of the effects of the crystal orientation of Au substrate on the bonding strength is reported, and the elastic moduli of these SAMs through uniaxial tensile simulation are also examined. The calculated results are compared with the published experimental data, and also with each other to identify the optimal SAM candidate.Results show that the interfacial bonding strength of the SAM-coated Au-epoxy and Au-Au systems exhibits a strong dependency on the crystal orientation of Au substrate and also on the chain length of the monolayer where it tends to increase with an increasing SAM chain length. In specific, the interfacial bonding strength of the SH(CH₂)_nCH₃ SAM-coated Au-Au joint would reach a maximal value at the chain length n = 8 while that of the SAM/epoxy interface in the SH(CH₂)_nCH₃ SAM-coated Au-epoxy system attains a minimal value at n = 4 and becomes the maximum at n = 10, regardless of the crystal orientation of the Au substrates. Besides, the Au substrate with (1 1 1) crystal orientation would outperform the Au(1 0 0) substrate in the SAM/epoxy interfacial bonding strength of the SAM-coated Au-epoxy system while there is a totally opposite result for that of the SAM-coated Au-Au joint.     

Control of surface properties of self-assembled monolayers by tuning the degree of molecular asymmetry

We have studied self-assembled monolayers (SAMs) of asymmetric dialkyldisulfide derivatives of the form CH₃-(CH₂)_11+m-S-S-(CH₂)₁₁-OH with m = −4, −3, 0, +2 and +4 on gold. Sub-nanoscale changes in the length of the CH₃-terminated alkylchain have been used to selectively protrude one particular end group in the resulting film. The alteration of the chain length in only two methylene units already results in changes of surface properties, which have been detected with local (chemical force microscopy) and macroscopic (contact angle) techniques. In particular, advancing contact angles can be adjusted between 40° and 80°. The adhesion between a hydrophobic tip and these SAMs in water is determined by the chemical nature of the protruding end group. Chemical force microscopy, X-ray photoelectron spectroscopy and infrared reflection absorption spectroscopy have shown that these SAMs are composed of mixed, well-packed CH₃- and OH-alkylthiolate branches. The surface composition ratio is close to 1:1 for all investigated SAMs.     

Molecular self-assembly and passivation of GaAs (0 0 1) with alkanethiol monolayers: A view towards bio-functionalization

Properties of as prepared or nanoengineered III-V semiconductor surfaces provide attractive means for photonic detection of different adsorbants from surrounding gaseous or liquid environments. To be practical, this approach requires that the surface is made selectively sensitive (functionalized) to targeted species. In addition, such surface has also to stay stable over extended period of time to make it available for rapid testing. Numerous reports demonstrate attractive properties of GaAs for sensing applications. One of the most fundamental issues relevant to these applications concerns the ability to functionalize chemically, or biologically, the surface of GaAs. The most studied method of GaAs surface functionalization is based on formation of self-assembled monolayers (SAMs) of various n-alkanethiols, HS-(CH₂)_n-T (T = CH₃, COOH, NH₂, etc.). In spite of multi-year research concerning this issue, it has only been recently that a comprehensive picture of SAMs formation on GaAs and an understanding of the natural limitation of the SAM-GaAs interface in some bio-chemical sensing architectures has begun to emerge.     

Integrity of functional self-assembled monolayers on hydrogen-terminated silicon-on-insulator wafers

Silicon-on-insulator (SOI) wafers are commonly used to design microelectronics, energy conversion, and sensing devices. Thin solid films on the surfaces of SOI wafers have been a subject of numerous studies. However, SOI wafers modified by self-assembled monolayers (SAMs) that can also be used as functional device platforms have been investigated to a much lesser extent. In the present work, tert-butoxycarbonyl (t-boc, (CH₃)₃-C-O-C(O)-)-protected 1-amino-10-undecene monolayers were covalently attached to a H-terminated SOI (1 0 0) surface. The modified wafers were characterized by X-ray photoelectron spectroscopy to confirm the stability of the SAM/Si interface and the integrity of the secondary amine in the SAM. The transmission electron microscopy investigation suggested that this t-boc-protected 1-amino-10-undecene SAM produces atomically flat interface with the 2 μm single crystalline silicon of the SOI wafer, that the SiO_x and both available Si/SiO_x interfaces are preserved, and that the organic monolayers are stable, with apparent thickness of 1.7 nm, which is consistent with the result of the density functional theory modeling of the molecular features within a SAM.     

Selective MOCVD of titanium oxide and zirconium oxide thin films using single molecular precursors on Si(1 0 0) substrates

Titanium oxide (TiO₂) and zirconium oxide (ZrO₂) thin films have been deposited on modified Si(1 0 0) substrates selectively by metal-organic chemical vapor deposition (MOCVD) method using new single molecular precursor of [M(OⁱPr)₂(tbaoac)₂] (M=Ti, Zr; tbaoac=tertiarybutyl-acetoacetate). For changing the characteristic of the Si(1 0 0) surface, micro-contact printing (μCP) method was adapted to make self-assembled monolayers (SAMs) using an octadecyltrichlorosilane (OTS) organic molecule which has -CH₃ terminal group. The single molecular precursors were prepared using metal (Ti, Zr) isopropoxide and tert-butylacetoacetate (tbaoacH) by modifying standard synthetic procedures. Selective depositions of TiO₂ and ZrO₂ were achieved in a home-built horizontal MOCVD reactor in the temperature range of 300-500 °C and deposition pressure of 1×10⁻³-3×10⁻² Torr. N₂ gas (5 sccm) was used as a carrier gas during film depositions. TiO₂ and ZrO₂ thin films were able to deposit on the hydrophilic area selectively. The difference in surface characteristics (hydrophobic/hydrophilic) between the OTS SAMs area and the SiO₂ or Si-OH layer on the Si(1 0 0) substrate led to the site-selectivity of oxide thin film growth.     

Hydrogen desorption kinetics and band bending for 6H-SiC(0 0 0 1) surfaces

The desorption kinetics of hydrogen from polished 6H-SiC(0 0 0 1) surfaces exposed to various sources of hydrogen have been determined using temperature programmed desorption (TPD). For (3 × 3) 6H-SiC(0 0 0 1) surfaces prepared via annealing and cooling in SiH₄, desorption of 0.2 ± 0.05 monolayer of molecular hydrogen was observed to occur at ≈590 °C. This β₁ H₂ desorption peak exhibited second order kinetics with an activation energy of 2.4 ± 0.2 eV. For (3 × 3) 6H-SiC surfaces exposed to atomic hydrogen generated via either a hot rhenium filament or remote hydrogen plasma, low energy electron diffraction patterns showed an eventual conversion back to (1 × 1) symmetry. Spectra acquired using Auger electron and X-ray photoelectron spectroscopies revealed that the atomic hydrogen exposure removed the excess Si. Photoelectron spectroscopy results also showed a 0.5 eV increase in binding energy for the Si2p and C1s core levels after removal of the Si-Si bilayer that is indicative of a decrease in band bending at the SiC surface. TPD from the (3 × 3) 6H-SiC(0 0 0 1) surfaces exposed to atomic hydrogen showed substantially more molecular hydrogen desorption (1-2 ML) through the appearance of a new desorption peak (β_2,3) that started at ≈200 °C. The β_2,3 peak exhibited second order desorption kinetics and a much lower activation energy of 0.6 ± 0.2 eV. A third smaller hydrogen desorption state was also detected in the 650-850 °C range. This last feature could be resolved into two separate desorption peaks (α₁ and α₂) both of which exhibited second order kinetics with activation energies of 4.15 ± 0.15 and 4.3 ± 0.15 eV, respectively. Based on comparisons to hydrogen desorption from Si and diamond surfaces, the β and α desorption peaks were assigned to hydrogen desorption from Si and C sites, respectively.     

Crystal structure and ferromagnetism of (n-C3H7)4N[CoFe(dto)3] (dto=C2O2S2)

Recently, we have discovered a new type of first order phase transition around 120 K for (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] (dto=C₂O₂S₂), where the charge transfer transition between Fe^II and Fe^III occurs reversibly. In order to elucidate the origin of this peculiar first order phase transition. Detailed information about the crystal structure is indispensable. We have synthesized the single crystal of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃] whose crystal structure is isomorphous to that of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃], and determined its detailed crystal structure. Crystal data: space group P6₃, a=b=10.044(2) Å, c=15.960(6) Å, α=β=90°, γ=120°, Z=2 (C₁₈H₂₈NS₆O₆FeCo). In this complex, we found a ferromagnetic transition at T_c=3.5 K. Moreover, on the basis of the crystal data of (n-C₃H₇)₄N[Co^IIFe^III(dto)₃], we determined the crystal structure of (n-C₃H₇)₄N[Fe^IIFe^III(dto)₃] by simulation of powder X-ray diffraction results.     

Characterisation of alkyl-functionalised Si(1 1 1) using reflectometry and AC impedance spectroscopy

The past few years have seen a dramatic increase in the study of organic thin-film systems that are based on silicon-carbon covalent bonds for bio-passivation or bio-sensing applications. This approach to functionalizing Si wafers is in contrast to gold-thiol or siloxane chemistries and has been shown to lead to densely packed alkyl monolayers. In this study, a series of alkyl monolayers [CH₃(CH₂)_nCH=CH₂; n = 7, 9, 11, 13, 15] were directly covalent-linked to Si(1 1 1) wafers. The structures of these monolayers were studied using X-ray reflectometry (XRR) and AC impedance spectroscopy. Both techniques are sensitive to the variation in thickness with each addition of a CH₂ unit and thus provide a useful means for monitoring molecular-scale events. The combination of these techniques is able to probe not only the thickness, but also the interfacial roughness and capacitance of the layer at the immobilized surface with atomic resolution. Fundamental physical properties of these films such as chain canting angles were also determined.     

Laser desorption of NO from a thick C60 film

The desorption of NO molecules from a thick C₆₀ film is reported. A thermal desorption spectrum indicates two adsorption sites with binding energies of E_b = 0.30 eV and 0.55 eV. For laser desorption the fullerene surface is exposed to NO and excited by 7 ns UV laser pulses. Desorbing NO molecules are recorded state selectively as well as time resolved. The time-of-flight measurement indicates three different desorption pathways. A fast channel shows rovibronic temperatures of T_rot(v″ = 0) = 370 K, T_rot(v″ = 1) = 390 K and T_vib = 610 K as well as strong rotational-translational coupling. The desorption yield for the fast channel increases linearly with pulse energy with a desorption cross section of σ = (5.1 ± 0.9) × 10⁻¹⁷ cm². Dominating the signal for small J″ values is a slow channel with low rotational and translational temperatures of about 110 K. We assign this peak to a laser-induced thermal desorption. For large pump-probe delays the data deviate from the Maxwellian flux distribution and a third channel appears with extremely late arrival times.     

Electron affinity study of adamantane on Si(1 1 1)

Recently, tetramantane, a member of diamondoid series (C_4n+6H_4n+12), has shown to exhibit negative-electron-affinity effect which has a potential use for efficient electron emitting devices. Here, we explore the electronic property of adamantane (C₁₀H₁₆), the smallest member of the series. We prepare adamantane films on Si(1 1 1) substrates and then study their electronic structure with photoemission spectroscopy. Photoelectron spectra of adamantane on Si(1 1 1) have shown a peak at low-kinetic energy which could be a generic property of diamondoids. The possibility of the negative-electron-affinity effect in adamantane is further discussed.