Wolfgang Geyer

Electron-induced crosslinking of aromatic self-assembled monolayers: Negative resists for nanolithography

We have explored the interaction of self-assembled monolayers of 1,1′-biphenyl-4-thiol (BPT) with low energy electrons. X-ray photoelectron, infrared, and near edge x-ray absorption fine structure spectroscopy showed that BPT forms well-ordered monolayers with the phenyl rings tilted ∼15° from the surface normal. The films were exposed to 50 eV electrons and changes were monitored in situ. Even after high (∼10 mC/cm2) exposures, the molecules maintain their preferred orientation and remain bonded on the gold substrate. An increased etching resistance and changes in the infrared spectra imply a crosslinking between neighboring phenyl groups, which suggests that BPT can be utilized as an ultrathin negative resist. This is demonstrated by the generation of patterns in the underlying gold.

Nanoscale patterning of self-assembled monolayers with electrons

We show the fabrication of gold nanostructures using self-assembled monolayers of aliphatic and aromatic thiols as positive and negative electron beam resists. We applied a simple and versatile proximity printing technique using focused ion beam structured stencil masks and low energy (300 eV) electrons. We also used conventional e-beam lithography with a beam energy of 2.5 keV and doses from 3500 to 80 000 μC/cm2. Gold patterns were generated by wet etching in KCN/KOH and characterized by atomic force microscopy and scanning electron microscopy. The width of the finest lines is ∼20 nm; their edge definition is limited by the isotropic etching process in the polycrystalline gold.

Nanostructuring of silicon by electron-beam lithography of self-assembled hydroxybiphenyl monolayers

We report the fabrication of silicon nanostructures using aromatic hydroxybiphenyl self-assembled monolayers as ultrathin (1.1 nm) negative tone electron-beam resist. The formation of the monolayer and the electron-induced crosslinking have been characterized by x-ray photoelectron spectroscopy. Nanometer size patterns were defined by electron-beam lithography in the molecular layer and transferred into silicon by wet chemical etching with potassium hydroxide. We demonstrate the fabrication of silicon line gratings with a resolution of ∼20 nm and of isolated silicon lines with linewidths down to ∼10 nm.

Modification of alkanethiolate monolayers on Au-substrate by low energy electron irradiation: Alkyl chains and the S/Au interface

Low-energy electron irradiation damage in alkanethiol (AT) self-assembled monolayers (SAM) has been studied by using hexadecanethiolate [HDT: CH3–(CH2)15–S-] film on Au-substrate as a model system. The induced changes were monitored by insitu photoelectron spectroscopy and angle resolved near edge X-ray absorption fine structure spectroscopy. AT SAMs are found to be very sensitive to low-energy electron irradiation. Both the alkyl chains and the S/Au interface are affected simultaneously through the electron-induced dissociation of C–H, C–C, C–S, and Au–thiolate bonds. The most noticeable processes are the loss of the orientational and conformational order, partial dehydrogenation and desorption of the film, and the appearance of new sulfur species. The latter process can be related to the formation of disulfide at the S/Au interface or an incorporation of the thiolate (or the corresponding radical) into the alkyl matrix via bonding to irradiation-induced carbon radicals in the adjacent aliphatic chains. The most essential damage in the AT films occurs in the early stages of irradiation. Irradiation with a dose of 1000 µC cm-2 (about 13 electrons per HDT chain) at the primary electron energy of 50 eV results in almost complete breakdown of the orientational order in the initially well-ordered HDT film, a decrease of its thickness by about 25%, and a destruction of ≈40% of the original Au–thiolate bonds. The film becomes a disordered structure comprising both saturated and unsaturated hydrocarbons. Further irradiation of the residual film is accompanied by a continuous C–C bond cleavage and the desorption of the remaining hydrogen, which merely leads to increasing cross-linking and the transformation of saturated hydrocarbons into unsaturated ones through C2C double bond formation.

Electrode modification by electron-induced patterning of aromatic self-assembled monolayers

Self-assembled monolayers of ω-(4′-methyl-biphenyl-4-yl)-dodecyl thiol [CH3–C6H4-C6H4–(CH2)12–SH,BP12] on gold were patterned via exposure to 300 eV electrons. Subsequent copper deposition in an electrochemical cell revealed behavior opposite to that of electron beam patterned monolayers of alkanethiols. Whereas alkanethiols act as a positive resist and lead to copper deposition only on irradiated parts, the biphenyl based thiol acts as a negative resist. At the irradiated areas the layer exhibits blocking behavior and copper deposition is observed only on the nonirradiated parts.

Electron induced chemical nanolithography with self-assembled monolayers

We demonstrate a simple scheme to generate chemical surface nanostructures. Electron-beam writing is used to locally modify the terminal nitro functionality in self-assembled monolayers of 4′-nitro-1,1′-biphenyl-4-thiol to amino groups, while the underlying aromatic layer is dehydrogenated and cross linked. Using low energy electron proximity printing and conventional electron-beam lithography with a beam energy of 2.5 keV and doses from 2500 to 50 000 μC/cm2, templates of reactive amino sites with lateral dimensions down to ∼20 nm could be fabricated. The templates were used for the surface immobilization of fluorinated carboxylic acid anhydrides and rhodamine dyes. The molecular structures were then imaged and analyzed by atomic force and scanning confocal fluorescence microscopy.

Nanoscale patterning of self-assembled monolayers by e-beam lithography

Abstract The resolution of e-beam lithography in standard resists is limited by the size of the molecules in the resist. High resolution e-beam resists therefore should not only show a specific sensitivity to electrons but also be thin and composed of small subunits. Self-assembled monolayers (SAMs) fulfil these criteria because they are homogeneous, highly ordered films of amphiphilic molecules with a typical thickness of 1–2 nm and an intermolecular spacing of 1–0.5 nm. We demonstrate that gold nanostructures can be fabricated using aliphatic and aromatic thiol self-assembled monolayers as positive and negative electron beam resists.

Electron-beam lithography with aromatic self-assembled monolayers on silicon surfaces

Aromatic self-assembled monolayers are formed via the coupling of hydroxy head groups to hydrogen-terminated silicon surfaces. We first investigate the application of 4-hydroxy-1,1′-biphenyl as an ultrathin negative tone electron-beam (e-beam) resist using conventional e-beam lithography with a beam energy of 3 keV. We demonstrate the fabrication of nanometer silicon patterns that are transferred using the modified monolayer as a resist mask for a wet chemical etching process in potassium hydroxide. The necessary dose for complete cross linking was determined to be 20 mC/cm2. Using this approach, isolated silicon structures with lateral dimensions down to ∼10 nm and periodic structures with a resolution of ∼20 nm were fabricated. On the other hand, 4′-nitro-4-hydroxy-1,1′-biphenyl has been found not to form monolayers suitable for chemical lithography on hydrogenated silicon surfaces. Upon adsorption, the nitro groups are partially reduced to amino groups by the hydrogenated surface and some of the molecu...