Oliver Seitz

Copper-metal deposition on self assembled monolayer for making top contacts in molecular electronic devices.

Molecular electronics is an attractive option for low-cost devices because it involves highly uniform self-assembly of molecules with a variety of possible functional groups. However, the potential of molecular electronics can only be turned into practical applications if reliable contacts can be established without damaging the organic layer or contaminating its interfaces. Here, a method is described to prepare tightly packed carboxyl-terminated alkyl self-assembled monolayers (SAMs) that are covalently attached to silicon surfaces and to deposit thin metallic copper top contact electrodes without damage to this layer. This method is based on a two-step procedure for SAM preparation and the implementation of atomic layer deposition (ALD) using copper di-sec-butylacetamidinate [Cu(sBu-amd)](2). In situ and ex situ infrared spectroscopy (IRS), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and electrical measurements are used to characterize the chemical modification of the Si/SAM interface, the perturbation of the SAM layer itself, and the metal homogeneity and interaction with the SAM headgroups. This work shows that (i) carboxyl-terminated alkyl monolayers can be prepared with the same high density and quality as those achieved for less versatile methyl-terminated alkyl monolayers, as evidenced by electrical properties that are not dominated by interface defects; (ii) Cu is deposited with ALD, forming a bidentate complexation between the Cu and the COOH groups during the first half cycle of the ALD reaction; and (iii) the Si/SAM interface remains chemically intact after metal deposition. The nondamaging thin Cu film deposited by ALD protects the SAM layer, making it possible to deposit a thicker metal top contact leading ultimately to a controlled preparation of molecular electronic devices.

Infrared characterization of interfacial Si-O bond formation on silanized flat SiO2/Si Surfaces

Chemical functionalization of silicon oxide (SiO(2)) surfaces with silane molecules is an important technique for a variety of device and sensor applications. Quality control of self-assembled monolayers (SAMs) is difficult to achieve because of the lack of a direct measure for newly formed interfacial Si-O bonds. Herein we report a sensitive measure of the bonding interface between the SAM and SiO(2), whereby the longitudinal optical (LO) phonon mode of SiO(2) provides a high level of selectivity for the characterization of newly formed interfacial bonds. The intensity and spectral position of the LO peak, observed upon silanization of a variety of silane molecules, are shown to be reliable fingerprints of formation of interfacial bonds that effectively extend the Si-O network after SAM formation. While the IR absorption intensities of functional groups (e.g., >C=O, CH(2)/CH(3)) depend on the nature of the films, the blue-shift and intensity increase of the LO phonon mode are common to all silane molecules investigated and their magnitude is associated with the creation of interfacial bonds only. Moreover, results from this study demonstrate the ability of the LO phonon mode to analyze the silanization kinetics of SiO(2) surfaces, which provides mechanistic insights on the self-assembly process to help achieve a stable and high quality SAM.

Chemical properties of oxidized silicon carbide surfaces upon etching in hydrofluoric acid.

Hydrogen termination of oxidized silicon in hydrofluoric acid results from an etching process that is now well understood and accepted. This surface has become a standard for studies of surface science and an important component in silicon device processing for microelectronics, energy, and sensor applications. The present work shows that HF etching of oxidized silicon carbide (SiC) leads to a very different surface termination, whether the surface is carbon or silicon terminated. Specifically, the silicon carbide surfaces are hydrophilic with hydroxyl termination, resulting from the inability of HF to remove the last oxygen layer at the oxide/SiC interface. The final surface chemistry and stability critically depend on the crystal face and surface stoichiometry. These surface properties affect the ability to chemically functionalize the surface and therefore impact how SiC can be used for biomedical applications.

Control and stability of self-assembled monolayers under biosensing conditions

The ability to stabilize and control the attachment of cells on the surfaces of a variety of inorganic materials is important for the development of biomedical devices and sensors. An important intermediate step is the functionalization of semiconducting surfaces with a self-assembled monolayer (SAM) with an appropriate surface termination to interact with proteins. The stability of such SAMs is critical to withstanding subsequent processing and measurement conditions (e.g. long exposure to a buffer solution) to avoid artifacts resulting from such deterioration during electrical measurements. This work highlights the importance of surface cleaning and SAM chain length by comparing two commonly used short alkyl chains, aminopropyltriethoxysilane (APTES) or 3-(trimethoxysilyl)propyl aldehyde (C4-ald) molecules, with their long-chain counterparts, amino-undecilenyltriethoxysilane (AUTES) and 11-(triethoxysilyl)undecanal (C11-ald). Using IR spectroscopy, spectroscopic ellipsometry, and electrical measurements, a cleaning method is developed, based on a short room temperature (RT) SC-1 treatment, to remove photoresist without degrading device performance as is the case with currently used oxygen plasma methods. The spectroscopic and electrical measurements also show that short-chain SAMs, typically used for pH- or bio-sensing, do not have the stability suitable for biosensor environments. In contrast, long-chain SAMs display much higher stability and can be reproducibly grafted. These findings are the basis for a reliable preparation and robust operation of biosensors.

Efficient radiative and nonradiative energy transfer from proximal CdSe/ZnS nanocrystals into silicon nanomembranes

We demonstrate efficient excitonic sensitization of crystalline Si nanomembranes via combined effects of radiative (RET) and nonradiative (NRET) energy transfer from a proximal monolayer of colloidal semiconductor nanocrystals. Ultrathin, 25-300 nm Si films are prepared on top of insulating SiO(2) substrates and grafted with a monolayer of CdSe/ZnS nanocrystals via carboxy-alkyl chain linkers. The wet chemical preparation ensures that Si surfaces are fully passivated with a negligible number of nonradiative surface state defects and that the separation between nanocrystals and Si is tightly controlled. Time-resolved photoluminescence measurements combined with theoretical modeling allow us to quantify individual contributions from RET and NRET. Overall efficiency of ET into Si is estimated to exceed 85% for a short distance of about 4 nm from nanocrystals to the Si surface. Effective and longer-range radiative coupling of nanocrystals emission to waveguiding modes of Si films is clearly revealed. This demonstration supports the feasibility of an advanced thin-film hybrid solar cell concept that relies on energy transfer between strong light absorbers and adjacent high-mobility Si layers.

Spectroscopic evidence for nonradiative energy transfer between colloidal CdSe/ZnS nanocrystals and functionalized silicon substrates

We present the fabrication and properties of hybrid structures consisting of a monolayer of colloidal CdSe nanocrystals grafted on hydrogenated Si surfaces via amine modified carboxy-alkyl chain linkers. The wet chemical preparation ensures that Si surfaces are fully passivated with a negligible number of nonradiative surface state defects and that the separation between nanocrystals and Si is tightly controlled. An eightfold decrease in photoluminescence lifetime of nanocrystals on Si is observed as compared to glass. A quantitative analysis reveals that the nonradiative transfer from nanocrystals to Si is 65% efficient, demonstrating the potential of such hybrids for practical photovoltaic devices.

Visible to near-infrared sensitization of silicon substrates via energy transfer from proximal nanocrystals: further insights for hybrid photovoltaics.

We provide a unified spectroscopic evidence of efficient energy transfer (ET) from optically excited colloidal nanocrystal quantum dots (NQDs) into Si substrates in a broad range of wavelengths: from visible (545 nm) to near-infrared (800 nm). Chemical grafting of nanocrystals on hydrogenated Si surfaces is achieved via amine-modified carboxy-alkyl chain linkers, thus ensuring complete surface passivation and accurate NQD positioning. Time-resolved photoluminescence (PL) has been measured for a set of CdSe/ZnS and CdSeTe/ZnS NQDs of various sizes and compositions grafted on Si and SiO2 substrates. The measured acceleration of the PL decays on Si substrates is in good agreement with theoretical expectations based on the frequency-dependent dielectric properties of Si and NQD-Si separation distances. A comparative analysis reveals separate contributions to ET coming from the nonradiative (NRET) and radiative (RET) channels: NRET is a dominant mechanism for proximal NQDs in the middle of the visible range and becomes comparable with RET toward near-infrared wavelengths. The broad range over which the ET efficiency is estimated to be at the level of ∼90% further supports the concept that hybrid nanocrystal/silicon thin-film photovoltaic devices could efficiently harvest solar energy across the entire spectrum of wavelengths.

One-step selective chemistry for silicon-on-insulator sensor geometries.

A one-step functionalization process has been developed for oxide-free channels of field effect transistor structures, enabling a self-selective grafting of receptor molecules on the device active area, while protecting the nonactive part from nonspecific attachment of target molecules. Characterization of the self-organized chemical process is performed on both Si(100) and SiO(2) surfaces by infrared and X-ray photoelectron spectroscopy, atomic force microscopy, and electrical measurements. This selective functionalization leads to structures with better chemical stability, reproducibility, and reliability than current SiO(2)-based devices using silane molecules.

Optimizing non-radiative energy transfer in hybrid colloidal-nanocrystal/silicon structures by controlled nanopillar architectures for future photovoltaic cells

To optimize colloidal nanocrystals/Si hybrid structures, nanopillars are prepared and organized via microparticle patterning and Si etching. A monolayer of CdSe nanocrystals is then grafted on the passivated oxide-free nanopillar surfaces, functionalized with carboxy-alkyl chain linkers. This process results to a negligible number of non-radiative surface state defects with a tightly controlled separation between the nanocrystals and Si. Steady-state and time-resolved photoluminescence measurements confirm the close-packing nanocrystal arrangement and the dominance of non-radiative energy transfer from nanocrystals to Si. We suggest that radially doped p-n junction devices based on energy transfer offer a viable approach for thin film photovoltaic devices.

1 ∕ f γ tunnel current noise through Si-bound alkyl monolayers

We report low frequency tunnel current noise characteristics of an organic monolayer tunnel junction. The measured devices, n-Si/alkyl chain (C18H37)/Al junctions, exhibit a clear 1/ f γ power spectrum noise with 1 0.4 V, with an amplitude varying from device to device. We attribute this effect to an energy-dependent trap-induced tunnel current. We find that the background noise, SI, scales with . A model is proposed showing qualitative agreements with our experimental data.