Covalently modified silicon and diamond surfaces: resistance to nonspecific protein adsorption and optimization for biosensing

We report the direct covalent functionalization of silicon and diamond surfaces with short ethylene glycol (EG) oligomers via photochemical reaction of the hydrogen-terminated surfaces with terminal vinyl groups of the oligomers, and the use of these monolayers to control protein binding at surfaces. Photochemical modification of Si(111) and polycrystalline diamond surfaces produces EG monolayers linked via Si-C bond formation (silicon) or C-C bond formation (diamond). X-ray photoelectron spectroscopy was used to characterize the monolayer composition. Measurements using fluorescently labeled proteins show that the EG-functionalized surfaces effectively resist nonspecific adsorption of proteins. Additionally, we demonstrate the use of mixed monolayers on silicon and diamond and apply these surfaces to control specific versus nonspecific binding to optimize a model protein sensing assay.     

Direct photopatterning and SEM imaging of molecular monolayers on diamond surfaces: mechanistic insights into UV-initiated molecular grafting

We have used X-ray photoelectron spectroscopy (XPS), infrared reflection-absorption spectroscopy, and field-emission scanning electron microscopy (SEM) to investigate the formation of single- and two-component molecular patterns by direct photochemical grafting of alkenes onto hydrogen-terminated diamond surfaces using sub-band gap 254 nm ultraviolet light. Trifluoroacetamide-protected 1-aminodec-1-ene (TFAAD) and 1-dodecene were used as model systems for grafting. Illumination with sub-band gap light can induce several different kinds of excitations, including creation of mobile electrons and holes in the bulk and creation of radicals at the surface and in the adjacent fluid, which induce grafting of the alkenes to the surface. SEM images of patterned molecular layers on nanocrystalline diamond surfaces reveal sharp transitions between functionalized and nonfunctionalized regions consistent with diffraction-limited excitation. However, identical experiments on type IIb single-crystal diamond yield a significantly more extended transition region in the molecular pattern. These data imply that the spatial resolution of the direct molecular photopatterning is affected by diffusion of charge carriers in the bulk of the diamond samples. The molecular contrast between surfaces with different terminations is consistent with the expected trends in molecular electron affinity. These results provide new mechanistic insights into the direct patterning and imaging of molecular monolayers on surfaces.     

Alkene/diamond liquid/solid interface characterization using internal photoemission spectroscopy

The photochemical attachment of 10-amino-dec-1-ene molecules protected with a trifluoroacetic acid group (TFAAD) on hydrogen-terminated single-crystalline chemical vapor deposited (CVD) diamond is characterized by total photoyield spectroscopy (TPYS), conductivity, Hall-effect, spectrally resolved photoconductivity (SPC), optical transmission experiments, and, for the first time, by in situ internal photoemission (IPE) spectroscopy applied in the spectral regime from 4 to 6 eV on the alkene/diamond (liquid/solid) heterostructures. These experiments are performed on undoped, (100) oriented, single-crystalline CVD diamond films, which contain no grain boundaries and have negligible bulk and surface defect densities. X-ray photoelectron spectroscopy (XPS) is used to investigate the chemical bonding of alkene molecules to diamond. The spectroscopic set of data shows that the photochemical reaction window of H-terminated diamond is shifted below the optical gap of diamond because of the negative electron affinity. In situ IPE experiments reveal electron emission between 4.5 and 5.2 eV. A model is introduced and discussed in which valence-band electrons are optically excited into empty hydrogen-induced surface states of diamond from where they tunnel into empty pi states of alkene molecules. We theoretically discuss the fastest attachment time to achieve a saturated TFAAD layer of about 2 x 10(14) cm(-)(2) on diamond, which is experimentally detected to be 7 h. In the case of direct optical electron excitations from diamond, the bonding efficiency will be one TFAAD molecule attachment arising from about 1600 emitted electrons.     

Thermally induced alkylation of diamond

We present an approach for the thermally activated formation of alkene-derived self-assembled monolayers on oxygen-terminated single and polycrystalline diamond surfaces. Chemical modification of the oxygen and hydrogen plasma-treated samples was achieved by heating in 1-octadecene. The resulting layers were characterized using X-ray photoelectron spectroscopy, thermal desorption spectroscopy, atomic force microscopy, Fourier transform infrared spectroscopy, and water contact angle measurements. This investigation reveals that alkenes selectively attach to the oxygen-terminated sites via covalent C-O-C bonds. The hydrophilic oxygen-terminated diamond is rendered strongly hydrophobic following this reaction. The nature of the process limits the organic layer growth to a single monolayer, and FTIR measurements reveal that such monolayers are dense and well ordered. In contrast, hydrogen-terminated diamond sites remain unaffected by this process. This method is thus complementary to the UV-initiated reaction of alkenes with diamond, which exhibits the opposite reactivity contrast. Thermal alkylation increases the range of available diamond functionalization strategies and provides a means of straightforwardly forming single organic layers in order to engineer the surface properties of diamond.     

Photochemical grafting of n-alkenes onto carbon surfaces: the role of photoelectron ejection

The grafting of molecular layers to carbon-based materials provides a way to combine the high chemical and thermal stability of these materials with surface properties such as chemical recognition or reactivity. The functionalization of surfaces with ultraviolet light has emerged as a way to modify difficult-to-functionalize materials, such as diamond. We have performed a combined experimental and computational investigation of the photochemical reaction of terminal alkenes with hydrogen-terminated carbon surfaces. 1-Alkenes carrying various terminal functional groups (-NHCOCF3, -NHCOO(tert-butyl), -COOCH3, -CH3) were grafted from the neat liquids using 254 nm light. These layers were characterized using X-ray Photoelectron Spectroscopy and Infrared Reflectance Absorption Spectroscopy. Pronounced differences in reactivity were observed between the molecules: trifluoroacetamide-terminated alkenes grafted the fastest and yielded self-terminating layers after approximately 4 h. Ultraviolet photoelectron spectroscopy and photocurrent measurements show that the grafting reaction involves photoemission of electrons into the liquid. Density functional calculations show that the reactivities of the four molecules are correlated with their electron affinities, with the trifluoroacetamide group acting as the best electron acceptor and having the highest reactivity. Our results demonstrate that photoejection of electrons from the solid into the acceptor levels of the alkenes initiates the functionalization reaction and controls the overall rate. Finally, marginally reactive n-alkenes were induced to react and form dense monolayers by seeding the carbon surface with small amounts of a good electron acceptor, such as the trifluoroacetamide moiety. This study provides important new mechanistic insights into the use of ultraviolet light to initiate grafting of alkenes onto surfaces.     

Chemical functionalization of diamond surfaces by reaction with diaryl carbenes

A rapid route to the chemical functionalization of hydrogen-terminated diamond surfaces deposited by chemical vapor deposition involving their reaction with substituted diaryl carbenes has been investigated. To avoid difficulties in the handling of highly reactive compounds, the carbene is generated in situ from the thermal decomposition at 400 K of a thin film of the corresponding diaryl diazomethane precursor deposited at the diamond interface. X-ray photoelectron spectroscopy (XPS) has been used to verify that surface functionalization using two starting compounds, bis(4-iodophenyl) diazomethane and bis(4-nitrophenyl) diazomethane, can be achieved using this approach in agreement with recent theoretical studies. The surface grafting density is measured to be around 10(14) cm(-2) in each case. The chemistry observed is found to be insensitive to the detailed properties of the diamond film and to the presence of oxygen contamination at the hydrogen-terminated diamond surface. We further demonstrate the utility of the approach, in the case of the bound nitrophenyl compound, by its reduction to the corresponding primary amine followed by reaction with fluorescein isothiocyanate to achieve fluorescent tagging of the diamond interface.     

Surface Modification of Boron-Doped Diamond with Microcrystalline Copper Phthalocyanine: Oxygen Reduction Catalysis

Surface modification of boron-doped diamond (BDD) with copper phthalocyanine was achieved using a simple and convenient dropcast deposition, giving rise to a microcrystalline structure. Both unmodified and modified BDD electrodes of different surface terminations (namely hydrogen and oxygen) were compared via the electrochemical reduction of oxygen in aqueous solution. A significant lowering of the cathodic overpotential by about 500 mV was observed after modification of hydrogen-terminated (hydrophobic) diamond, while no voltammetric peak was seen on modified oxidised (hydrophilic) diamond, signifying greater interaction between copper phthalocyanine and the hydrogen-terminated BDD. Oxygen reduction was found to undergo a two-electron process on the modified hydrogen-terminated diamond, which was shown to be also active for the reduction of hydrogen peroxide. The lack of a further conversion of the peroxide was attributed to its rapid diffusion away from the triple phase boundary at which the reaction is expected to exclusively occur.     

Tuning the electron affinity and secondary electron emission of diamond (100) surfaces by Diels-Alder reaction

The tuning of electron affinity and secondary electron emission on diamond (100) surfaces due to cycloaddition with 1,3-butadiene is investigated by photoemission experiments and density functional theory (DFT) calculations. A significant reduction in electron affinity up to 0.7 eV and enhancement of secondary electron emission were observed after 1,3-butadiene adsorption. The lowering of vacuum level via 1,3-butadiene adsorption is supported by DFT calculations. The C-H bonds in the covalently bonded organics on diamond contribute to the enhanced secondary electron emission and reduced electron affinity in a mechanism similar to that of C-H bonds on hydrogenated diamond surfaces. This combination of strong secondary emission and low electron affinity by the organic functionalization of diamond has potential applications in diamond-based molecular electronic devices.     

Dehydrative cyclocondensation reactions on hydrogen-terminated Si(100) and Si(111): an ex situ tool for the modification of semiconductor surfaces

Dehydrative cyclocondensation processes for semiconductor surface modification can be generally suggested on the basis of well-known condensation schemes; however, in practice this approach for organic functionalization of semiconductors has never been investigated. Here we report the modification of hydrogen-terminated silicon surfaces by cyclocondensation. The cyclocondensation reactions of nitrobenzene with hydrogen-terminated Si(100) and Si(111) surfaces are investigated and paralleled with selected cycloaddition reactions of nitro- and nitrosobenzene with Si(100)-2x1. Infrared spectroscopy is used to confirm the reactions and verify an intact phenyl ring and C-N bond in the reaction products as well as the depletion of surface hydrogen. High resolution N 1s X-ray photoelectron spectroscopy (XPS) suggests that the major product for both cyclocondensation reactions investigated is a nitrosobenzene adduct that can only be formed following water elimination. Both IR and XPS are augmented by density functional theory (DFT) calculations that are also used to investigate the feasibility of several surface reaction pathways, which are insightful in understanding the relative distribution of products found experimentally. This novel surface modification approach will be generally applicable for semiconductor functionalization in a highly selective and easily controlled manner.     

Electrical properties of diamond surfaces functionalized with molecular monolayers

Recent studies have shown that semiconductor surfaces such as silicon and diamond can be functionalized with organic monolayers, and that these monolayer films can be used to tether biomolecules such as DNA to the surfaces. Electrical measurements of these interfaces show a change in response to DNA hybridization and other biological binding processes, but the fundamental nature of the electrical signal transduction has remained unclear. We have explored the electrical impedance of polycrystalline and single-crystal diamond surfaces modified with an organic monolayer produced by photochemical reaction of diamond with 1-dodecene. Our results show that, by measuring the impedance as a function of frequency and potential, it is possible to dissect the complex interfacial structure into frequency ranges where the total impedance is controlled by the molecular monolayer, by the diamond space-charge region, and by the electrolyte. The results have implications for understanding the ability to use molecularly modified semiconductor surfaces for applications such as chemical and biological sensing.     

Hydrogenated polycrystalline diamond films: Elastic and inelastic electron reflectivity

The microstructure and properties of carbon-based thin films depend on the deposition process and conditions used, including pressure, gas phase composition, and substrate temperature, as well as the energy of the reactive species (atoms or ions). For instance concerning diamond films, each method results in different type of films which may differ in terms of diamond grain size (from nano to micro), grain boundary nature, hydrogen content, defect density, amorphous or graphitic components, morphological properties and different chemical and physical properties. Among them, the well-known negative electron affinity, very attractive for the detection and emission of electrons, and high conductivity of diamond surfaces are properties of fully hydrogenated diamond surfaces. Similarly, diamond grain size may influence the electronic and optical properties of the films. More generally the chemical and physical characterization of the uppermost surface atomic layer of diamond films presents a great challenge.In this review we present results on hydrogen bonding configuration in hydrogenated polycrystalline diamond films of varying size (few nanometers up to micrometers) obtained by high resolution electron energy loss spectroscopy (HREELS). More precisely we will present energy loss spectra extended up to 800 meV, as well as elastic and inelastic reflectivity curves (associated to different vibrational modes of hydrogenated diamond surfaces), measured over the 3–18 eV electron energy range. We will show in particular that due to the specific features of diamond bulk electronic band structure, which is maintained up to the surface in the case of fully hydrogenated diamond, it is possible to extract from these data valuable information about the surface properties and composition such as diamond or graphitic like nature of the films, surface versus lattice nature of the vibrational modes.     

Preparation of novel photoreactive polycarbazole‐based microparticles: Reactivity features

Four types of innovative benzophenone (BPh)‐ or aryl azide (ArAz)‐containing photoreactive polycarbazole (polyCbz)‐based microparticles (MPs) were prepared using an oxidative liquid phase polymerization system. Their photochemical reactivity was evaluated by their reaction with highly inert poly(2‐chloro‐paraxylelene) (Parylene C) films. Possible mechanisms for the photochemical reaction of those MPs with Parylene C were discussed. The highly photoreactive BPh was found to react more inside the particle causing internal cross‐linking of MP polyCbz chains, fusion between adjoining particles and deformation of their spherical structure. In contrast, the less reactive but more selective ArAz‐containing MPs were found to react much more with Parylene C. The strong reactivity of such photoreactive MPs toward Parylene C films emphasizes a general method for the functionalization of stable nonfunctional polymeric coatings. This paves the way to simple and solvent‐free functionalization of nonfunctional coatings and materials by light. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Direct electrochemistry of cytochrome C at nanocrystalline boron-doped diamond

Direct electron transfer of horse heart cytochrome c is measured at a nanocrystalline boron-doped diamond thin-film electrode. A quasi-reversible, diffusion-controlled cyclic voltammetric response is observed for untreated diamond. The peak currents change linearly with the concentration, and importantly, there is no electrode fouling. The results, observed for a hydrogen-terminated and uncharged surface, (i.e., no ionizable carbon-oxygen functional groups), raise interesting questions about the necessary surface interactions of cytochrome c for relatively rapid electrode kinetics.     

HREELS investigation of the surfaces of nanocrystalline diamond films oxidized by different processes

This article reports on the use of high-resolution electron energy loss spectroscopy (HREELS) for the investigation of as-grown (hydrogen-terminated) and oxidized nanocrystalline diamond films (NCD) using chemical, physical, and electrochemical approaches. The results indicate that the nature and number of oxygen-related chemical groups generated on the NCD surface depend strongly on the oxidation process. A high concentration of C-O functions has been obtained on the NCD surface oxidized by rf (radio frequency) oxygen plasma, whereas the highest C═O/C-O ratio has been achieved by electrochemical oxidation. The NCD surface oxidized by rf plasma was totally free of C═O groups. Traces of surface hydroxyl groups (C-OH) have been detected upon annealing in air or through UV/ozone oxidation.     

Covalent photochemical functionalization of amorphous carbon thin films for integrated real-time biosensing

Recent studies have demonstrated that carbon, in the form of diamond, can be functionalized with molecular and/or biomolecular species to yield interfaces exhibiting extremely high stability and selectivity in binding to target biomolecules in solution. However, diamond and most other crystalline forms of carbon involve high-temperature deposition or processing steps that restrict their ability to be integrated with other materials. Here, we demonstrate that photochemical functionalization of amorphous carbon films followed by covalent immobilization of DNA yields highly stable surfaces with excellent biomolecular recognition properties that can be used for real-time biological detection. Carbon films deposited onto substrates at 300 K were functionalized with organic alkenes bearing protected amine groups and characterized using X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. The functionalized carbon surfaces were covalently linked to DNA oligonucleotides. Measurements show very high selectivity for binding to the complementary sequence, and a high density of hybridizing DNA molecules. Samples repeatedly hybridized and denatured 25 times showed no significant degradation. The ability to use amorphous carbon films as a basis for real-time biosensing is demonstrated by coating quartz crystal microbalance (QCM) crystals with a thin carbon film and using this for covalent modification with DNA. Measurements of the resonance frequency show the ability to detect DNA hybridization in real time with a detection limit of <3% of a monolayer, with a high degree of reversibility. These results demonstrate that functionalized films of amorphous carbon can be used as a chemically stable platform for integrated biosensing using only room-temperature processing steps.     

Detailed structural examinations of covalently immobilized gold nanoparticles onto hydrogen-terminated silicon surfaces

The modification of flat semiconductor surfaces with nanoscale materials has been the subject of considerable interest. This paper provides detailed structural examinations of gold nanoparticles covalently immobilized onto hydrogen-terminated silicon surfaces by a convenient thermal hydrosilylation to form Si-C bonds. Gold nanoparticles stabilized by omega-alkene-1-thiols with different alkyl chain lengths (C3, C6, and C11), with average diameters of 2-3 nm and a narrow size distribution were used. The thermal hydrosilylation reactions of these nanoparticles with hydrogen-terminated Si(111) surfaces were carried out in toluene at various conditions under N2. The obtained modified surfaces were observed by high-resolution scanning electron microscopy (HR-SEM). The obtained images indicate considerable changes in morphology with reaction time, reaction temperature, as well as the length of the stabilizing omega-alkene-1-thiol molecules. These surfaces are stable and can be stored under ambient conditions for several weeks without measurable decomposition. It was also found that the aggregation of immobilized particles on a silicon surface occurred at high temperature (> 100 degrees C). Precise XPS measurements of modified surfaces were carried out by using a Au-S ligand-exchange technique. The spectrum clearly showed the existence of Si-C bonds. Cross-sectional HR-TEM images also directly indicate that the particles were covalently attached to the silicon surface through Si-C bonds.     

Electrical bias dependent photochemical functionalization of diamond surfaces

Diamond is an excellent substrate for many sensing and electronic applications because of its outstanding stability in biological and aqueous environments. When the diamond surface is H-terminated, it can be covalently modified with organic alkenes using wet photochemical methods that are surface-mediated and initiated by the ejection of electrons from the diamond. To develop a better understanding of the photochemical reaction mechanism, we examine the effect of applying an electrical bias to the diamond samples during the photochemical reaction. Applying a 1 V potential between two diamond electrodes significantly increases the rate of functionalization of the negative electrode. Cyclic voltammetry and electrochemical impedance measurements show that the 1 V potential induces strong downward band-bending within the diamond film of the negative electrode. At higher voltages a Faradaic current is observed, with no further acceleration of the functionalization rate. We attribute the bias-dependent changes in rate to a field effect, in which the applied potential induces a strong downward band-bending on the negative electrode and facilitates the ejection of electrons into the adjacent fluid of reactant organic alkenes. We also demonstrate the ability to directly photopattern the surface with reactant molecules on length scales of <25 microm, the smallest we have measured, using simple photomasking techniques.     

Reaction of alkenes with hydrogen-terminated and photooxidized silicon surfaces. A comparison of thermal and photochemical processes

Reagentless micropatterning of hydrogen-terminated Si(111) via UV irradiation through a photomask has proven to be a convenient strategy for the preparation of ordered bicomponent monolayers. The success of this technique relies upon the differential rate of reaction of an alkene with the hydrogen-terminated and photooxidized regions of the surface. Monolayer formation can be accomplished under either thermal or photochemical conditions. It was observed that, after 3 h, reaction in neat alkene solution irradiation (Rayonet, 300 nm) afforded the expected patterned surface, while thermal conditions (150 degrees C) resulted in a partial loss of pattern fidelity. Monolayer properties and formation were studied on oxidized and hydrogen-terminated silicon under thermal and photochemical initiation, by contact angle, ellipsometry, Fourier transform infrared spectroscopy, high-resolution electron energy loss spectroscopy, and X-ray photoelectron spectroscopy. Results show that alkenes add to silanol groups on the silica surface in a manner consistent with acid catalysis: once attached to the surface, the silica oxidized the hydrocarbon.     

On the photocatalytic properties of nano-TiO<Subscript>2</Subscript> with dual-phase structure for aqueous methyl-red dye degradation

Heterogeneous photocatalytic removal of methyl-red (MR) dye from liquid phase was done using mixed-phase nanocrystalline TiO₂ for enhancement its photochemical decomposition capabilities. The mixed-phase nanocrystalline TiO₂ was characterized using various techniques to investigate its physicochemical properties. The photocatalytic efficiency of mixed-phase nanocrystalline titania was explored by monitoring the photochemical decay of aqueous MR dye. The results showed that the as-prepared mixed-phase nanocrystalline TiO₂ was excellent for degradation of MR molecule, and the impurity of rutile form increases the photochemical activity by a by a factor of 3. The reaction mechanism was proposed and the results demonstrate that the photocatalytic oxidation reaction followed a pseudo-first-order kinetics.     

Dépôt de revêtements peu rugueux de diamant sur un alliage de titane

Deposition of smooth diamond coatings on titanium alloy. A new process has been perfected to deposit smooth diamond coatings, at 600 °C, on titanium alloys. Scanning electron microscopy, X-ray diffraction, visible and UV Raman spectroscopy show that these coatings are smooth and mainly composed of crystalline diamond with a fine-grained morphology. The results are compared here to those obtained with classical rough polycrystalline coatings. Optical emission spectroscopy reveals important differences between the plasma species produced for the deposition of these smooth coatings and the plasma species produced for the deposition of both polycrystalline diamond and nanocrystalline films. © 2000 Académie des sciences / Éditions scientifiques et médicales Elsevier SASdiamond / coating / titanium alloy / plasma / roughness / Raman spectroscopy / emission spectroscopy