Photo-deprotection patterning of self-assembled monolayers

Photo-deprotectable self-assembled monolayers (SAMs) provide a versatile platform for creating functional patterned surfaces. In this study, we present nanoscale photo-patterning, multi-component patterning, and a method for producing molecular gradients using photo-deprotectable SAMs. Nanoscale patterning of photo-deprotectable SAMs was achieved by coupling a UV laser (365 nm) through a scanning near field probe to produce nanoscale lines of ～40 nm, i.e. λ/9. Multi-component patterning was achieved by a two-stage method combining both microcontact printing and soft-UV photo-patterning. The example demonstrated in this study produced a three-component patterned surface with regions of CF₃, CH₃ and COOH/CF₃ functionality. The versatility of these photocleavable SAMs is further demonstrated by creating linear molecular gradients of two functionalities along a distance of ～25 mm. The use of ‘soft’ UV gives several advantages including the ability to pattern SAMs with micron-scale features over large areas quickly, with greater control over the photochemical reactions, and compatibility with existing lithographic facilities thus offering an effective alternative to other patterning methods such microcontact-printing or deep UV patterning.     

钛金属薄膜上两种短链自组装分子膜的制备与摩擦特性

采用自组装技术在钛金属薄膜上制备了两种分子链长相同、官能团不同的自组装分子膜,并对其进行了不同时间的紫外照射,对钛金属薄膜和自组装分子膜进行了表征和摩擦特性测试,研究了紫外照射、官能团、滑动速度和载荷对自组装分子膜摩擦特性的影响,结果表明:通过紫外照射钛金属薄膜表面羟基化、自组装分子水解及自组装分子缩合可在钛金属薄膜上制备结构致密的自组装分子膜,制备的两种短链自组装分子膜可降低钛金属薄膜的摩擦特性,APS自组装分子膜的摩擦特性优于MPS自组装分子膜的摩擦特性,紫外照射5 min的自组装分子膜表面吸附的有机杂质被蒸发掉,对针尖的黏着力减小,从而导致针尖的变形减小,摩擦力最低,而紫外照射15 min的自组装分子膜致密的网状结构被破坏,减弱了自组装分子膜的润滑效应,两种自组装分子膜的摩擦力随着滑动速度的增加略呈上升趋势,随着载荷的增加略呈下降趋势,但是变化不大.     

Study on chemical vapor deposited copper films on cyano and carboxylic self-assembled monolayer diffusion barriers

Thin copper films were produced by chemical vapor deposition using the precursor Cu^IIbis-hexafluoroacetylacetonate on the SiO₂/Si substrate modified with cyano and carboxylic self-assembled monolayers (SAMs) as diffusion barriers. The characterizations of the deposited copper films were measured by various thin film analysis techniques, i.e., scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy and X-ray diffraction. The comparison between copper deposited on SiO₂ and on the SAM-modified SiO₂ substrates indicates that the copper films tend to be deposited onto the SAM-modified substrate, which is further proved by the calculation results of the interaction energies of copper and the SAMs with density functional theory method.     

Influence of an external magnetic field on the formation of self-assembled monolayers of dodecanethiol on polycrystalline gold electrode

This paper reports the preparation of dodecanethiol self-assembled monolayers (C₁₂SH-SAMs) on polycrystalline gold electrodes in a magnetic field. The qualities of C₁₂SH-SAMs were characterized by both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results show that highly dense and well-ordered SAMs could form in a relatively short time (3 h), indicating that the rate of SAMs formation increased under an external magnetic field compared with the natural self-assembly process. Moreover, the results of CV and EIS measurements also suggested that the presence of a magnetic field had influenced the qualities of the SAMs; the stronger magnetic intensity can help to obtain much denser and well-ordered SAMs.     

Synthesis of hydroxyapatite on titanium coated with organic self-assembled monolayers

The work focuses the formation of hydroxyapatite (HA) layers from simulated body fluids (SBF) onto titanium coated with NH₂-, SH-, and SO₃H-SAMs, respectively, at room temperature and 37 °C as well as pH values of SBF of 7.4, 8, and 8.4. At an upside up arrangement of the samples in the SBF, the formation of sufficient thick HA layers with a pillow like structure onto all SAMs were observed, which is believed to be caused by combined homogeneous and heterogeneous precipitation of HA from the SBF. These layers do not show sufficient adhesive strength. An upside down arrangement of the samples result in the formation of up to 5–10 μm thick flat HA layers with a much higher adhesive strength, which is believed to be due to formation of HA from the SBF only by heterogeneous precipitation. Also HA layers were obtained onto all studied SAMs, SH-SAM appears to favour the formation of HA resulting in a layer with a thickness of about 10 μm and an almost stoichiometric Ca/P-ratio of the layer of 1.72. All other layers exhibit much lower ratios.     

硅基双层复合自组装分子膜结构特性及其润湿行为的分子动力学模拟

用分子动力学方法模拟了单晶硅（Si）表面N-3-（三甲氧基硅烷基）丙基乙二胺（DA）-月桂酰氯（LA）（DA-LA）双层复合自组装分子膜（SAMs）的结构特性,得到膜层中DA和LA分子的最佳覆盖率及分布情况。进一步讨论了水滴在DA-LA双层复合SAMs表面的润湿过程,通过接触角和径向分布函数等参量对其润湿行为进行了分析。研究表明：DA分子在Si上覆盖率为50%、LA分子在DA自组装单分子膜（DA SAM）上接枝率为100%时,分子膜呈有序排布,体系能量最低,从分子角度揭示了Si表面覆盖致密SAMs的形成机制。当取最佳覆盖率体系进行润湿机制模拟时,DA-LA双层复合SAMs表面水滴接触角与实验值相似,表现出良好的疏水性。而DA SAM表面由于DA分子短而稀疏,暴露出底层更亲水的羟基分子,从而导致所得接触角较实验偏小;经测量及计算得出,羟基化Si表面自由能最高,表现出较强的亲水性;DA表面次之;DA-LA表面自由能最低,表现出良好的疏水性。进一步分析发现：羟基化Si表面、DA SAM表面与水滴间存在氢键,加强了表面的亲水性,而DA-LA双层复合SAMs表面与水滴间只存在弱范德华力,有利于表面呈现疏水性。     

Preparation and tribological properties of novel carbon nanotube self-assembled composite films

Carbon nanotube (CNT) composite thin films were prepared on a single-crystal silicon substrate by a self-assembling process from a specially formulated solution. Rare earth solution (RES) surface modification and appropriate acid-treatment methods were used to functionalise carbon nanotubes (CNTs). Silane coupling regent (3-mercaptopropyl trimethoxysilane (MPTS)) was prepared first. The terminal thiol groups (–SH) in the film was oxidised to sulphonic acid groups (–SO₃H) in situ to enhance the film with good chemisorption ability. Treated Caron nanotubes were deposited on the oxidised MPTS–SAM by means of chemisorption with the SO₃H group. The surface energy, chemical composition, phase transformation and surface morphology of the films were analysed using contact angle measurements, X-ray photoelectron spectroscopy (XPS), scanning electron microscope (SEM) and atomic force microscopy. As a result, a conclusion could be made that some lanthanum elements react with –SO₃H groups on the surface of the substrate by a chemical bond, which will improve the bonding strength between the films and the CNTs. Since the CNT thin films were well adhered to the silicon substrate, it might find promising application in the surface-modification of single-crystal Si and SiC in microelectromechanical systems (MEMS).     

Numerical ellipsometry: Advanced analysis of thin absorbing films in the n-k plane

A major challenge for those utilizing ellipsometry is numerical processing of the measured data. The transcendental, multivalued equations arising from the physics of simple reflection are problematic for the least-squares numerical methods in common use. Previously we have applied Complex Analysis in the n-k plane and this has led to a growing array of numerical research methods which achieve computational accuracy at a chosen limit (~ 10^− 14) rather than achieving only a mean square value of a large number of measurements, more than 14 orders of magnitude less accurate in this case. The work presented here is the mathematics for film stacks of an arbitrary number of layers required to apply numerical methods for use with absorbing films deposited on transparent and on absorbing substrates. The approach finds intersections of projections of three “twisted curves” resulting from a single light incidence angle and light wavelength measurement for three film thicknesses at a time. The approach employed here determines the thickness and optical properties of chromium films (between 10 and 25 nm nominal thickness) deposited onto silicon substrates. A simple single film model matched the measurements to a first order only. Improved agreement is obtained by the addition of interface layers above and below the main chromium film.     

官能团对自组装分子膜摩擦特性的影响

在原子力显微镜上,对分子链长相同、官能团不同的两种自组装分子膜的摩擦特性进行了研究,分析了载荷和滑动速度对自组装分子膜摩擦特性的影响.结果表明:自组装分子末端官能团的化学活性越强,形成的自组装分子膜的团簇特征越显著;对于两种短链自组装分子,摩擦力随着载荷的增大而增大,而滑动速度的影响在自组装分子末端官能团化学活性较大时才表现出来.形成结构稳定的自组装分子膜后,摩擦力比成膜初期的自组装分子膜显著降低,具有减摩效应.具有较强化学活性官能团的自组装分子膜,当载荷增加到一定值以后,会失去减摩效应,其化学活性越强,摩擦力越大.     

Study of the formation of chromate conversion coatings on Alclad 2024 aluminum alloy using spectroscopic ellipsometry

The influence of pH of a chromate bath on the morphological and chemical properties of a chromate conversion coating, formed on Alclad 2024-T3 aluminum alloy, has been investigated by variable angle spectroscopic ellipsometry in the visible and infra-red regions. Other techniques such as glow discharge optical emission spectroscopy, transmission and scanning electron microscopy, atomic force microscopy and Auger electron spectroscopy have been used in order to confirm and sustain the results obtained with this technique. The combination of different analytical methods showed a decrease in thickness together with changes in the morphology and chemical composition of the chromate film when the pH is increased from 1.2 to 2.4. Although the complexity of the chromate system and the pronounced roughness of commercial rolled aluminum limit the accuracy of spectroscopic ellipsometry, it is demonstrated that this technique can be usefully applied to the study of thin chromate films formed on industrially relevant aluminum products.     

Optical properties of an octadecylphosphonic acid self-assembled monolayer on a silicon wafer

We report a study of a full-coverage octadecylphosphonic acid (OPA or ODPA) self-assembled monolayer (SAM) spin-coated on the native oxide layer (SiO₂) of a single crystalline silicon (c-Si) wafer using spectroscopic ellipsometry (SE) and reflectometry (SR). The OPA SAM showed characteristics of being a dielectric film in visible range and becoming absorbing in deep-UV range. By assuming an optical stack model of OPA/SiO₂/c-Si for the OPA monolayer system and adopting the parameterized Tauc-Lorentz dispersion model, we obtained an excellent fit of the model to the SE and SR data, from which dispersion of optical functions as well as thickness of the OPA film were deduced. The OPA film thickness measured by atomic force microscopy (AFM) on partial coverage OPA samples was used as the initial trial film thickness in the fitting processes. The deduced OPA film thickness from SE and SR data fitting was in good agreement with that obtained by AFM.     

A vapor phase deposition of self-assembled monolayers: Vinyl-terminated films of volatile silanes on silicon oxide substrates

Vinyl-terminated self-assembled monolayers (SAMs) offer significant flexibility for further chemical modification and can serve as a versatile starting point for a tailoring of surface properties. A vapor phase deposition of such films would offer advantages in cases where the preparation from solution is not an option or not desired, for example in connection with silicon microstructures such as micro-electromechanical systems. We show that SAMs of 9-decenyltrichlorosilane (CH₂CH(CH₂)₈SiCl₃), 10-undecenyltrichlorosilane (CH₂CH(CH₂)₉SiCl₃), 14-pentadecenyltrichlorosilane (CH₂CH(CH₂)₁₃SiCl₃), decyltrichlorosilane (CH₃(CH₂)₉SiCl₃), and octadecanetrichlorosilane (CH₃(CH₂)₁₇SiCl₃) can be prepared both from solution and from the vapor phase. The resulting layers were compared by static contact angle measurements, ellipsometry, X-ray photoelectron spectroscopy, and atomic force microscopy to determine their surface wettability, the film thickness, the smoothness and homogeneity of the respective films, and their chemical composition and each method gave films of comparable quality. Deposition of functionalized SAMs from the vapor phase is rare. Here we report the parameters for the preparation of well-ordered vinyl-terminated SAMs from the vapor phase.     

Evaluation of the real-time protein adsorption kinetics on albumin-binding surfaces by dynamic in situ spectroscopic ellipsometry

Functionalized surfaces with an affinity for albumin over competing serum proteins were prepared by immobilizing linear peptides or a small chemical ligand (SCL) with albumin-binding properties on silanized silicon surfaces. The real time adsorption of human serum albumin from single- and multi-component systems was monitored by dynamic ellipsometry. The experimentally obtained time-dependent adsorption data were analyzed by two models: a) a pseudo-first-order model and b) a biphasic kinetic model that accounted for the formation of tightly and loosely bound complexes. The biphasic kinetic model better fit the experimental data, and the binding constants were determined by non-linear regression analyses. The net forward rate constant for the tightly bound complex formation was distinctively higher for surfaces functionalized with peptides (~ 0.014 min^− 1) when compared to surfaces functionalized with SCL (~ 10^− 3 min^− 1).     

磁头表面含氟三氯硅烷自组装膜的生长机理

在磁头表面制备了1H,1H,2H,2H-四氢全氟辛烷基三氯硅烷（FOTS）自组装膜,采用X射线光电子能谱仪（XPS）、时间飞行二次离子质谱仪（TOF-SIMS）、接触角测量仪和原子力显微镜（AFM）对FOTS自组装膜进行表征,研究了自组装膜的生长机理．结果表明,FOTS自组装膜的生长经过了亚单层膜的低等覆盖,亚单层膜的中等覆盖、团聚和聚结四个阶段．其中第一层和第二层自组装膜的亚单层膜形态和生长方式不同,第一层的亚单层膜呈岛状,岛的生长是自身向外扩展;第二层的亚单层膜呈簇状,簇通过效量增加来实现生长．超薄完整的单层FOTS自组装膜（膜厚为0．8nm、Ra为0．125nm）能使磁头表面的接触角值增加,疏水性能提高．     

Detection of various self-assembled monolayers by AlN-based film bulk acoustic resonator

Various self-assembled monolayers such as carcinoembryonic antigen (CEA), beta actin, and bovine serum albumin (BSA) were detected using an AlN-based film bulk acoustic resonator (FBAR). AlN thin film was deposited by reactive RF magnetron sputtering, on a substrate of Mo (100 nm)/Ti (34 nm)/SiO₂ (480 nm)/Si (300 μm)/Si₃N₄ (300 nm). The film showed a strongly c-axis preferred orientation with a main (0 0 2) peak, as well as a good full width at half maximum (FWHM) of 2.50° in XRD and rocking curve results. The AlN-based FBAR was confirmed to have a resonant frequency of 2.477 GHz and a sensitivity of 3514 Hz cm²/ng. In beta actin, BSA, and CEA, the frequency properties showed variation values of 472.142, 932.573, and 685.421 kHz and mass sensitivities of 3530, 3506, and 3514 Hz-cm²/ng, respectively. The FBAR sensor was confirmed to be very useful for detecting target antigens through the binding of an antigen and an anti-body.     

Investigation of hexadecanethiol self-assembled monolayers on cadmium tin oxide thin films

This study reports the use of variable angle reflectance Fourier transform infrared spectroscopy and X-ray photoelectron spectroscopy to investigate the formation of a 1-hexadecanethiol adlayer on cadmium tin oxide (CTO) thin film surfaces. These adlayers appear to be robust, ordered monolayers. The optical and electronic properties of CTO thin films chemically vapor deposited onto glass substrates were also investigated. The reflectance of the CTO films was dependent upon the incident angle of the impinging radiation and revealed a reflectance decrease indicative of a plasma frequency in the mid-IR using p-polarized radiation.     

Preparation of BiFeO3 thin film by the liquid phase deposition (LPD) method on functionalized organic self-assembled monolayers (SAMs)

BiFeO₃ thin films were prepared for the first time on the functionalized self-assembled monolayers (SAMs) by the liquid phase deposition (LPD) method. The measurement of contact angle showed that after the substrate was immersed into octadecyl trichlorosilane (OTS) solution for 30 min, the surface of the substrate was covered with a layer of hydrophobe. The hydrophobe on the substrate was changed into hydrophile after UV irradiation. It was found that the octadecyl trichlorosilane self-assembled monolayers (OTS-SAMs) as chemical templates played an active role in controlling nucleation and growth of BiFeO₃ thin film. The study on the effect of different soaking times showed that the BiFeO₃ thin film was a layer growth model and the optimum deposition time was 12 h.     

Molecular layer deposition of ZrO2-based organic-inorganic nanohybrid thin films for organic thin film transistors

Molecular layer deposition (MLD) technique can be used for preparation of various organic-inorganic nanohybrid superlattices at a gas-phase. The MLD method is a self-controlled layer-by-layer growth process under vacuum conditions, and is perfectly compatible with the atomic layer deposition (ALD) method. In this paper, we fabricated a new type organic-inorganic nanohybrid thin film using MLD method combined with ALD. A self-assembled organic layer (SAOL) was formed at 170 °C using MLD with repeated sequential adsorptions of CC terminated alkylsilane and zirconium hydroxyl with ozone activation. A ZrO₂ inorganic nanolayer was deposited at the same temperature using ALD with alternating surface-saturating reactions of Zr(OC(CH₃)₃)₄ and H₂O. The prepared SAOL-ZrO₂ organic-inorganic nanohybrid films exhibited good mechanical stability, excellent insulating properties, and relatively high dielectric constant k (~ 16). They were then used as a 23 nm-thick dielectric for low voltage pentacene-based thin film transistors, which showed a maximum field effect mobility of 0.63 cm²/V s, operating at − 1 V with an on/off current ratio of ~ 10³.