Phosphonic Acid Monolayers Research Articles

Self-assembled monolayers of cyclohexyl-terminated phosphonic acids as a general dielectric surface for high-performance organic thin-film transistors.

A novel self-assembled monolayer (SAM) on AlOy /TiOx is terminated with cyclohexyl groups, an unprecedented terminal group for all kinds of SAMs. The SAM-modified AlOy /TiOx functions as a general dielectric, enabling organic thin-film transistors with a field-effect mobility higher than 5 cm(2) V(-1) s(-1) for both holes and electrons, good air stability with low operating voltage, and general applicability to solution-processed and vacuum-deposited n-type and p-type organic semiconductors.

Contact‐Induced Mechanisms in Organic Photovoltaics: A Steady‐State and Transient Study

The role of the contacts in thin‐film, blended heterojunctions (<100 nm thick) organic photovoltaics is explored, specifically considering concepts of carrier selectivity, injection, and extraction efficiency, relative to recombination. Contact effects are investigated by comparing two hole‐collecting interlayers: a phosphonic acid monolayer on indium tin oxide (ITO) and a nickel oxide thin film. The interlayers have equivalent work functions (≈5.4 eV) but widely variant energy band offsets relative to the lowest unoccupied molecular orbital of the acceptor (electron blocking versus not), which are coupled to large differences in carrier density. Trends in open‐circuit voltages (VOC) as a function of light intensity and temperature are compared and it is concluded that the dominant mechanism limiting VOC for high density of states contacts is free carrier injection, not surface recombination or extraction barriers. Transient photocurrent decay measurements confirm excess reinjected carriers decrease the extraction efficiency via increased recombination and decrease free carrier lifetime, even at high internal electric fields, due to space charge accumulation. These results demonstrate that the energetics and injection dynamics of the interface between interlayers and high carrier density electrodes (typically ITO and metals) must be considered with fabrication and processing of interlayers, in addition to possible carrier selectivity and the interface with the active layer.

Impedance Spectroscopy Study of Nanopore Arrays for Biosensing Applications

Molecular or ion transport through a single nanopore or nanopore array is a key process in a number of applications including: molecular separation, biosensing, energy storage, nanofluidics and nanoelectronics. In this study, the electrochemical and electrical properties of nanopore arrays were investigated by electrochemical impedance spectroscopy (EIS), to explore their capability towards the development of improved nanopore biosensing devices. Anodic aluminum oxide (AAO) nanopore arrays with square patterns were fabricated by a photolithographic technique for use as a biosensing platform. To demonstrate the potential capability of these nanoporous arrays for biosensing applications, their internal surfaces were functionalized with a self-assembled monolayer of phosphonic acid; followed by covalent bonding with the model binding molecule streptavidin. The sensing performance of the prepared sensing device was characterized by EIS using different concentrations of biotin as probe molecule. The changes in impedance signal in response to the specific binding of biotin molecules to the streptavidin inside nanopores were monitored and explored depending on pore morphology. The results obtained for this system exhibit a high level of sensitivity and selectivity, which could provide the basis for the development of superior biosensing devices.

Modification of the Gallium‐Doped Zinc Oxide Surface with Self‐Assembled Monolayers of Phosphonic Acids: A Joint Theoretical and Experimental Study

Gallium‐doped zinc oxide (GZO) surfaces, both bare and modified with chemisorbed phosphonic acid (PA) molecules, are studied using a combination of density functional theory calculations and ultraviolet and X‐ray photoelectron spectroscopy measurements. Excellent agreement between theory and experiment is obtained, which leads to an understanding of: i) the core‐level binding energy shifts of the various oxygen atoms belonging to different surface sites and to the phosphonic acid molecules; ii) the GZO work‐function change upon surface modification, and; iii) the energy level alignments of the frontier molecular orbitals of the PA molecules with respect to the valence band edge and Fermi level of the GZO surface. Importantly, both density of states calculations and experimental measurements of the valence band features demonstrate an increase in the density of states and changes in the characteristics of the valence band edge of GZO upon deposition of the phosphonic acid molecules. The new valence band features are associated with contributions from surface oxygen atoms near a defect site on the oxide surface and from the highest occupied molecular orbitals of the phosphonic acid molecules.

Phynox Improved Corrosion Resistance with MPC Initiated from Mixed Monolayers of Phosphonic Acids

This work investigated the grafting of 11-(2-bromoisobutyrate)-undecyl-1-phosphonic acid (BUPA) and 1-dodecylphosphonic acid (C12PA) to form (mixed) monolayers with different proportions of BUPA and C12PA on Phynox. The role and impact of these grafted molecules have been evaluated in terms of the corrosion resistance and the feasibility to act as a suitable platform for surface initiated atom transfer radical polymerization (ATRP) of 2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate (MPC). It appeared that both molecules play an important role: BUPA to initiate the ATRP polymerization of MPC and C12PA to increase the resistance to corrosion of Phynox substrates. Moreover, the presence of C12PA in the mixed monolayer beneath the poly-2-(methacryloyloxy)ethyl 2-(trimethylammonio)ethyl phosphate (PMPC) layer has a beneficial impact in terms of corrosion resistance.

X-ray and neutron investigation of self-assembled lipid layers on a titanium surface

Titanium is the most widely preferred metal material for bone reconstruction in orthopedics and dentistry. To improve its biological performance, various coatings can be applied. In this investigation, a biomimetic coating on a model implant surface was studied in X-ray and neutron reflectivity experiments to probe the quality of this coating, which is only few nanometers thick. Titanium was deposited on polished silicon surfaces using a magnetron sputtering technique. To improve the lipid coating's stability, a stronger van der Waals interaction was first created between the implant surface and the biomimetic coating by adding a phosphonic acid (n-octadecylphosphonic acid - OPA) monolayer onto the surfaces. Then, three monolayers of POPE (phospholipid 1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-ethanolamine) were transferred using the Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) techniques. The analysis of X-ray and neutron specular reflectivity data shows that OPA molecules cover the model implant surface completely and that approximately 50% coverage of POPE can be achieved by LB and LS transfer.

Competing Effects of Fluorination on the Orientation of Aromatic and Aliphatic Phosphonic Acid Monolayers on Indium Tin Oxide

Transparent conductive oxides such as indium tin oxide (ITO) are common substrates for optoelectronic devices, including organic light-emitting diodes and organic solar cells. Tailoring the interface between the oxide and the active layer by adjusting the work function or wettability of the oxide can improve the performance of these devices in both emissive and photovoltaic applications. The use of carefully designed surface modifiers that form self-assembled monolayers (SAMs) can allow the tuning of the surface of one oxide material to optimize its properties for use with a variety of different organic semiconductors or for different applications. Fluorinated phosphonic-acid-based SAMs can affect the interface dipole and the work function of a metal oxide. Fluorination may also affect the molecular packing and the orientation of the SAM once bound to the surface. We utilize angle-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to determine the molecular orientations of octylphosphonic acid, phenylphosphonic acid, and fluorinated derivatives on ITO and correlate the molecular orientations derived from these studies with predictions from density functional theory (DFT). We account quantitatively for the effect of surface roughness on the measured orientations. We observe that fluorination of the octylphosphonic acid SAM results in a more upright orientation, an effect we attribute to intermolecular forces and increased steric bulk. In contrast, fluorination of the phenylphosphonic acid SAM leads to a less upright orientation that we associate with changes in binding mode.

Dynamic, in situ study of self-assembling organic phosphonic acid monolayers from ethanolic solutions on aluminium oxides by means of odd random phase multisine electrochemical impedance spectroscopy

The study of self-assembling monolayers on various oxide substrates is a scientific field still in full development. One of the challenges in this type of work is to probe the interactions in situ and dynamically. In this study a novel approach to investigate the adsorption of n-octylphosphonic acid on aluminium oxide from an ethanolic solution through odd random phase electrochemical impedance spectroscopy is presented. A model is proposed to describe the system and its validity is statistically established. It is observed that molecules adsorb on the surface. It is proven that the acid–base condensation reaction expels water which stays nearby the hydrophilic surface. Furthermore, it is shown that the phosphonic molecules bind ionically with the oxide surface. The work in this manuscript clearly shows that ethanol as a solvent is not suited to form stable organic acid layers on the surface. Due to the fact that water diffuses slowly in the bulk solvent, hazardous local environments are created at the oxide surface. During adsorption, the oxide is at the same time attacked. In this work, it is shown that odd random phase multisine electrochemical impedance spectroscopy is the ideal technique to not only investigate in situ dynamically the adsorbing behaviour of very thin films, but also to comprehend what happens with the buried substrate. Moreover, complex models can be used to fit the datasets obtained as it is possible with this analysis technique to prove statistically that they are correct.

Self‐Assembled Monolayers of Phosphonic Acids with Enhanced Surface Energy for High‐Performance Solution‐Processed N‐Channel Organic Thin‐Film Transistors

Add an O: A new strategy for preparing solution-processed organic thin-film transistors (OTFTs) is based on enhancing the surface energy of self-assembled monolayers (SAMs) by inserting polar oxygen atoms into the long alkyl chain of phosphonic acids. SAMs of these phosphonic acids on a high-k metal oxide layer lead to solution-processed n-channel OTFTs with average field effect mobilities of up to 2.5 cm2 V−1 s−1 and low operational voltages.

Self‐Assembled Monolayers of Phosphonic Acids with Enhanced Surface Energy for High‐Performance Solution‐Processed N‐Channel Organic Thin‐Film Transistors

Man füge ein O hinzu: Eine neue Strategie für die Herstellung organischer Dünnfilmtransistoren (OTFTs) nutzt die Erhöhung der Oberflächenenergie selbstorganisierter Monoschichten (SAMs) durch polare Sauerstoffatome in den langen Alkylketten von Phosphonsäuren. SAMs dieser Phosphonsäuren auf einem Hoch-k-Metalloxid ergeben lösungsprozessierte n-Kanal-OTFTs mit mittleren Feldeffektbeweglichkeiten bis zu 2.5 cm2 V−1 s−1 bei niedriger Betriebsspannung. As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re-organized for online delivery, but are not copy-edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Orientation of Phenylphosphonic Acid Self-Assembled Monolayers on a Transparent Conductive Oxide: A Combined NEXAFS, PM-IRRAS, and DFT Study

Self-assembled monolayers (SAMs) of dipolar phosphonic acids can tailor the interface between organic semiconductors and transparent conductive oxides. When used in optoelectronic devices such as organic light emitting diodes and solar cells, these SAMs can increase current density and photovoltaic performance. The molecular ordering and conformation adopted by the SAMs determine properties such as work function and wettability at these critical interfaces. We combine angle-dependent near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and polarization modulation infrared reflection absorption spectroscopy (PM-IRRAS) to determine the molecular orientations of a model phenylphosphonic acid on indium zinc oxide, and correlate the resulting values with density functional theory (DFT). We find that the SAMs are surprisingly well-oriented, with the phenyl ring adopting a well-defined tilt angle of 12-16° from the surface normal. We find quantitative agreement between the two experimental techniques and density functional theory calculations. These results not only provide a detailed picture of the molecular structure of a technologically important class of SAMs, but also resolve a long-standing ambiguity regarding the vibrational-mode assignments for phosphonic acids on oxide surfaces, thus improving the utility of PM-IRRAS for future studies.

Adsorption and stability of self-assembled organophosphonic acid monolayers on plasma modified Zn–Mg–Al alloy surfaces

The adsorption and stability of adhesion promoting organophosphonic acid monolayers on plasma modified Zn–Mg–Al alloy surfaces were investigated by means of microscopic and spectroscopic techniques. A strip hollow cathode (SHC) was chosen for the plasma surface modification. The chemical composition of the plasma treated surfaces and the influence of reducing and oxidizing plasma modifications on the corrosion properties of Zn–Mg–Al alloy surfaces were analyzed by means of X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry, respectively. The adsorption and stability of phosphonic acid monolayers were comparatively studied on plasma modified and non-plasma modified Zn–Mg–Al alloy surfaces. Self-organization of monofunctional monolayers was confirmed by means of polarization modulated infrared reflection absorption spectroscopy (PM-IRRAS) and XPS. Contact angle measurements were performed to prove the stability of the octadecylphosphonic acid (ODPA) monolayer on the native and different plasma treated surfaces in aqueous media. Plasma modification and ODPA adsorption resulted in a synergistic inhibition of the redox current densities of the alloy surface. The strongest inhibition was observed for an Ar/H2 plasma+O2 plasma treatment followed by octadecylphosphonic acid self-assembled monolayer adsorption.

Polyelectrolyte Multilayer Deposition on Nickel Modified with Self-Assembled Monolayers of Organophosphonic Acids for Biomaterials: Electrochemical and Spectroscopic Evaluation

Layer-by-layer assembly of polyelectrolytes is an efficient method for the formation of functional thin films with the prospect of biomedical applications. Polyethyleneimine (PEI) is commonly used as an adhesion promoter but has been shown to be potentially cytotoxic and therefore could not be suitable for biomedical applications besides providing no or little corrosion protection to the underlying substrate. In the present work, we report on the use of a self-assembled phosphonic acid monolayer as a corrosion inhibitor and adhesion promoter for polyelectrolyte multilayer (PEM) formation on nickel substrates. The interest in using a phosphonic acid monolayer as an adhesion promoter for the deposition of polyelectrolyte multilayers lies in the robust grafting of the PEM adhesion promoter to the modified surface and the corrosion inhibition provided by this monolayer. This protection is crucial when considering the biodegradability of many polyelectrolytes used for biomedical applications. Nickel surfaces have thus been modified with an 11-methylundecanoatephosphonic acid monolayer. This monolayer has been shown to significantly improve the nickel corrosion resistance. Hydrolysis of the ester terminal function of this monolayer allowed the formation of negative charges on the modified nickel surfaces and therefore the successive deposition of chitosan and alginate layers.

Microrough Cobalt–Chromium Alloy Surfaces for Paclitaxel Delivery: Preparation, Characterization, andIn VitroDrug Release Studies

Cobalt-chromium (Co-Cr) alloys have extensive biomedical applications including drug-eluting stents (DES). This study investigates the use of eight different microrough Co-Cr alloy surfaces for delivering paclitaxel (PAT) for potential use in DES. The eight different surfaces include four bare microrough and four self-assembled monolayer (SAM) coated microrough surfaces. The bare microrough surfaces were prepared by grit blasting Co-Cr with glass beads (50 and 100 μm in size) and Al(2)O(3) (50 and 110 μm). The SAM coated surfaces were prepared by depositing a -COOH terminated phosphonic acid monolayer on the different microrough surfaces. PAT was then deposited on all the bare and SAM coated microrough surfaces. The surfaces were characterized using scanning electron microscopy (SEM), 3D optical profilometry, and Fourier transform infrared spectroscopy (FTIR). SEM showed the different morphologies of microrough surfaces without and with PAT coating. An optical profiler showed the 3D topography of the different surfaces and the changes in surface roughness and surface area after SAM and PAT deposition. FTIR showed ordered SAMs were formed on glass bead grit blasted surfaces, while the molecules were disordered on Al(2)O(3) grit blasted surfaces. Also, FTIR showed the successful deposition of PAT on these surfaces. The PAT release was investigated for up to two weeks using high performance liquid chromatography. Al(2)O(3) grit blasted bare microrough surfaces showed sustained release profiles, while the glass bead grit blasted surfaces showed burst release profiles. All SAM coated surfaces showed biphasic drug release profiles, which is an initial burst release followed by a slow and sustained release. SAM coated Al(2)O(3) grit blasted surfaces prolonged the sustained release of PAT in a significant amount during the second week of drug elution studies, while this behavior was not observed for any other surfaces used in this study. Thus, this study demonstrates the use of different microrough Co-Cr alloy surfaces for delivering PAT for potential applications in DES and other medical devices.

Epitaxial two dimensional aluminum films on silicon (111) by ultra-fast thermal deposition

Aluminum thin films are known for their extremely rough surface, which is detrimental for applications such as molecular electronics and photonics, where protrusions cause electrical shorts or strong scattering. We achieved atomically flat Al films using a highly non-equilibrium approach. Ultra-fast thermal deposition (UFTD), at rates >10 nm/s, yields RMS roughness of 0.4 to 0.8 nm for 30–50 nm thick Al films on variety of substrates. For UFTD on Si(111) substrates, the top surface follows closely the substrate topography (etch pits), indicating a 2D, layer-by-layer growth. The Al film is a mixture of (100) and (111) grains, where the latter are commensurate with the in-plane orientation of the underlying Si (epitaxy). We show the use of these ultra-smooth Al films for highly reproducible charge-transport measurements across a monolayer of alkyl phosphonic acid as well as for plasmonics applications by directly patterning them by focused ion beam to form a long-range ordered array of holes. UFTD is a one-step process, with no need for annealing, peeling, or primer layers. It is conceptually opposite to high quality deposition methods, such as MBE or ALD, which are slow and near-equilibrium processes. For Al, though, we find that limited diffusion length (and good wetting) is critical for achieving ultra-smooth thin films.

Environment-Controlled Tethering by Aggregation and Growth of Phosphonic Acid Monolayers on Silicon Oxide

Phosphonic acid monolayers are being considered as versatile surface modification agents due to their unique ability to attach to surfaces in different configurations, including mono-, bi-, or even tridentate arrangements. Tethering by aggregation and growth (T-BAG) of octadecylphosphonic acid (ODPA) on silicon oxide surfaces has proven to be a robust method to establish a strong chemical bond. However, it requires a long processing time (> 48 h) that is a substantial drawback for industrial applications. We demonstrate here that the humidity level during processing is the most important parameter controlling the reaction. Using in situ Fourier Transform Infrared Spectroscopy (FTIR), we first show that the initially physisorbed layer obtained upon immersion in ODPA is composed of well-ordered bilayers and only reacts with the SiO(2) surface at 140 °C. Importantly, we show that the presence of water at the interface (determined by the humidity level) greatly influences the reaction time and completion. In humid environments (relative humidity, RH > 40%), there is no reaction, while in dry environments (RH < 16%), the reaction is essentially instantaneous at 140 °C. Ab initio calculations and modeling confirm that the degree of chemical reaction with the surface OH groups depends on the chemical potential (i.e., concentration) of interfacial water molecules. These findings provide a workable modification of the traditional T-BAG method consistent with many industrial applications.

Electron-Transfer Processes in Zinc Phthalocyanine-Phosphonic Acid Monolayers on ITO: Characterization of Orientation and Charge-Transfer Kinetics by Waveguide Spectroelectrochemistry.

Using a monolayer of zinc phthalocyanine (ZnPcPA) tethered to indium tin oxide (ITO) as a model for the donor/transparent conducting oxide (TCO) interface in organic photovoltaics (OPVs), we demonstrate the relationship between molecular orientation and charge-transfer rates using spectroscopic, electrochemical, and spectroelectrochemical methods. Both monomeric and aggregated forms of the phthalocyanine (Pc) are observed in ZnPcPA monolayers. Potential-modulated attenuated total reflectance (PM-ATR) measurements show that the monomeric subpopulation undergoes oxidation/reduction with ks,app = 2 × 10(2) s(-1), independent of Pc orientation. For the aggregated ZnPcPA, faster orientation-dependent charge-transfer rates are observed. For in-plane-oriented Pc aggregates, ks,app = 2 × 10(3) s(-1), whereas for upright Pc aggregates, ks,app = 7 × 10(2) s(-1). The rates for the aggregates are comparable to those required for redox-active interlayer films at the hole-collection contact in organic solar cells.

Light-directed nanosynthesis: near-field optical approaches to integration of the top-down and bottom-up fabrication paradigms

The integration of top-down (lithographic) and bottom-up (synthetic chemical) methodologies remains a major goal in nanoscience. At larger length scales, light-directed chemical synthesis, first reported two decades ago, provides a model for this integration, by combining the spatial selectivity of photolithography with the synthetic utility of photochemistry. This review describes attempts to realise a similar integration at the nanoscale, by employing near-field optical probes to initiate selective chemical transformations in regions a few tens of nm in size. A combination of near-field exposure and an ultra-thin resist yields exceptional performance: in self-assembled monolayers, an ultimate resolution of 9 nm (ca. λ/30) has been achieved. A wide range of methodologies, based on monolayers of thiols, silanes and phosphonic acids, and thin films of nanoparticles and polymers, have been developed for use on metal and oxide surfaces, enabling the fabrication of metal nanowires, nanostructured polymers and nanopatterned oligonucleotides and proteins. Recently parallel lithography approaches have demonstrated the capacity to pattern macroscopic areas, and the ability to function under fluid, suggesting exciting possibilities for surface chemistry at the nanoscale.

Tuning the Molecular Order of C60 Functionalized Phosphonic Acid Monolayers

Mixed self-assembled monolayers (SAM) of alkyl phosphonic acids and C(60) functionalized octadecyl phosphonic acids (C(60)C(18)-PA) are deposited on alumina substrates from solution and are shown to form well-ordered structures with an insulating layer of alkyl chains and a semiconducting layer that comprises mainly C(60). Such an ordered structure is a necessity for the application of SAMs in organic transistors but is difficult to obtain since C(60)C(18)-PA without additional support do self-assemble in dense packaging but not in a well-ordered fashion. To avoid disordering of the SAM and to gain a better control of the interfacial properties we have investigated the stabilizing effects of fluorinated dodecyl phosphonic acids (FC(12)-PA) on the C(60)C(18)-PA monolayer. Vibrational sum-frequency (SFG) spectroscopy, ellipsometry, X-ray photoelectron spectroscopy, and electrical measurements were applied to study the mixed monolayers. Here, we make use of the differently labeled PA to determine surface coverages and molecular properties of the two species independently. Adsorption of FC(12)-PA gives rise to vibrational bands at 1344 cm(-1) and 1376 cm(-1) in SFG spectra, while a pronounced vibrational band centered at 1465 cm(-1) is attributable to C(60) vibrations. The coexistence of the bands is indicative for the presence of a mixed monolayer that is composed of both molecular species. Furthermore, a pronounced maximum in SFG intensity of the C(60) band is observed for SAMs, which are deposited from solutions with ~75% C(60)C(18)-PA and ~25% FC(12)-PA. The intensity maximum originates from successful stabilization of C(60) modified C(60)C(18)-PA by FC(12)-PA and a significantly improved molecular order. Conclusions from SFG spectra are corroborated by electric measurements that show best performance at these concentrations. Our results provide new information on the morphology and composition of C(60) modified SAMs and establish a route to fabricate well-defined layers for molecular scale organic electronics.

Interface Engineering in High-Performance Low-Voltage Organic Thin-Film Transistors Based on 2,7-Dialkyl-[1]benzothieno[3,2-b][1]benzothiophenes

We investigated two different (2,7-dialkyl-[1]benzothieno[3,2-b][1]benzothiophenes; C(n)-BTBT-C(n), where n = 12 or 13) semiconductors in low-voltage operating thin-film transistors. By choosing functional molecules in nanoscaled hybrid dielectric layers, we were able to tune the surface energy and improve device characteristics, such as leakage current and hysteresis. The dipolar nature of the self-assembled molecules led to a shift in the threshold voltage. All devices exhibited high charge carrier mobilities of 0.6-7.0 cm(2) V(-1) s(-1). The thin-film morphology of BTBT was studied by means of atomic force microscopy (AFM), presented a dependency upon the surface energy of the self-assembled monolayer (SAM) hybrid dielectrics but not upon the device performance. The use of C(13)-BTBT-C(13) on hybrid dielectrics of AlO(x) and a F(15)C(18)-phosphonic acid monolayer led to devices with a hole mobility of 1.9 cm(2) V(-1) s(-1) at 3 V, on/off ratio of 10(5), small device-device variation of mobility, and a threshold voltage of only -0.9 V, thus providing excellent characteristics for further integration.