Sebastian W. Schmidt

Dynamic Strength of the Silicon-Carbon Bond Observed over Three Decades of Force-Loading Rates

The mechanical strength of individual Si-C bonds was determined as a function of the applied force-loading rate by dynamic single-molecule force spectroscopy, using an atomic force microscope. The applied force-loading rates ranged from 0.5 to 267 nN/s, spanning 3 orders of magnitude. As predicted by Arrhenius kinetics models, a logarithmic increase of the bond rupture force with increasing force-loading rate was observed, with average rupture forces ranging from 1.1 nN for 0.5 nN/s to 1.8 nN for 267 nN/s. Three different theoretical models, all based on Arrhenius kinetics and analytic forms of the binding potential, were used to analyze the experimental data and to extract the parameters fmax and D(e) of the binding potential, together with the Arrhenius A-factor. All three models well reproduced the experimental data, including statistical scattering; nevertheless, the three free parameters allow so much flexibility that they cannot be extracted unambiguously from the experimental data. Successful fits with a Morse potential were achieved with fmax = 2.0-4.8 nN and D(e) = 76-87 kJ/mol, with the Arrhenius A-factor covering 2.45 x 10(-10)-3 x 10(-5) s(-1), respectively. The Morse potential parameters and A-factor taken from gas-phase density functional calculations, on the other hand, did not reproduce the experimental forces and force-loading rate dependence.

Mechanically activated rupture of single covalent bonds: evidence of force induced bond hydrolysis.

We have used temperature-dependent single molecule force spectroscopy to stretch covalently anchored carboxymethylated amylose (CMA) polymers attached to an amino-functionalized AFM cantilever. Using an Arrhenius kinetics model based on a Morse potential as a one-dimensional representation of covalent bonds, we have extracted kinetic and structural parameters of the bond rupture process. With 35.5 kJ mol(-1), we found a significantly smaller dissociation energy and with 9.0 × 10(2) s(-1) to 3.6 × 10(3) s(-1) also smaller Arrhenius pre-factors than expected for homolytic bond scission. One possible explanation for the severely reduced dissociation energy and Arrhenius pre-factors is the mechanically activated hydrolysis of covalent bonds. Both the carboxylic acid amide and the siloxane bond in the amino-silane surface linker are in principle prone to bond hydrolysis. Scattering, slope and curvature of the scattered data plots indicate that in fact two competing rupture mechanisms are observed.

Simple Coupling Chemistry Linking Carboxyl-Containing Organic Molecules to Silicon Oxide Surfaces under Acidic Conditions

The coupling chemistry of carboxymethylated amylose with organo-silanized silicon oxide surfaces at pH 7.4 and 2.0 was investigated using atomic force microscopy (AFM) based single-molecule force spectroscopy. At close to neutral pH, carbodiimide activation of a carboxylic acid affords formation of an amide bond with an amino surface linker. At pH 2.0, no activation with carbodiimide was required to anchor carboxymethylated amylose between an AFM tip and a glass substrate. At the same time, the mean bond rupture force f(r) dropped from 1.65 ± 0.37 nN at pH 7.4 to 1.39 ± 0.30 nN at pH 2.0 without carbodiimide, indicating that a different link to the surface can be formed at low pH. The coupling mechanism at pH 2.0 was elucidated by a series of experiments, in which the surface was functionalized with four different organosilanes, each containing characteristic functional groups. The results are rationalized with an acid-catalyzed ester condensation between a carboxyl group and a free, unreacted silanol group in the surface anchor or on the surface.

Single-Molecule Force-Clamp Experiments Reveal Kinetics of Mechanically Activated Silyl Ester Hydrolysis

We have investigated the strength of silyl ester bonds formed between carboxymethylated amylose (CMA) molecules and silane-functionalized silicon oxide surfaces using AFM-based single-molecule force spectroscopy in the force-clamp mode. Single tethered CMA molecules were picked up, and bond lifetimes were determined at constant clamp forces of 0.8, 1.0, and 1.2 nN at seven temperatures between 295 and 320 K at pH 2.0. The results reveal biexponential rupture kinetics. To obtain the reaction rate constants for each force and temperature individually, the results were analyzed with a biexponential kinetic model using the maximum likelihood estimation (MLE) method. The force-independent kinetic and structural parameters of the underlying bond rupture mechanisms were extracted by fitting the entire data set with a parallel MLE fit procedure using the Zhurkov/Bell model and, alternatively, an Arrhenius kinetics model combined with a Morse potential as an analytic representation of the binding potential. With activation energies between 37 and 40 kJ mol(-1), and with Arrhenius prefactors between 5 × 10(4) and 2 × 10(6) s(-1), the results point to the hydrolysis of the silyl ester bond.

A density functional theory model of mechanically activated silyl ester hydrolysis

To elucidate the mechanism of the mechanically activated dissociation of chemical bonds between carboxymethylated amylose (CMA) and silane functionalized silicon dioxide, we have investigated the dissociation kinetics of the bonds connecting CMA to silicon oxide surfaces with density functional calculations including the effects of force, solvent polarizability, and pH. We have determined the activation energies, the pre-exponential factors, and the reaction rate constants of candidate reactions. The weakest bond was found to be the silyl ester bond between the silicon and the alkoxy oxygen atom. Under acidic conditions, spontaneous proton addition occurs close to the silyl ester such that neutral reactions become insignificant. Upon proton addition at the most favored position, the activation energy for bond hydrolysis becomes 31 kJ mol(-1), which agrees very well with experimental observation. Heterolytic bond scission in the protonated molecule has a much higher activation energy. The experimentally observed bi-exponential rupture kinetics can be explained by different side groups attached to the silicon atom of the silyl ester. The fact that different side groups lead to different dissociation kinetics provides an opportunity to deliberately modify and tune the kinetic parameters of mechanically activated bond dissociation of silyl esters.

Tip characterization method using multi-feature characterizer for CD-AFM.

In atomic force microscopy (AFM) metrology, the tip is a key source of uncertainty. Images taken with an AFM show a change in feature width and shape that depends on tip geometry. This geometric dilation is more pronounced when measuring features with high aspect ratios, and makes it difficult to obtain absolute dimensions. In order to accurately measure nanoscale features using an AFM, the tip dimensions should be known with a high degree of precision. We evaluate a new AFM tip characterizer, and apply it to critical dimension AFM (CD-AFM) tips used for high aspect ratio features. The characterizer is made up of comb-shaped lines and spaces, and includes a series of gratings that could be used as an integrated nanoscale length reference. We also demonstrate a simulation method that could be used to specify what range of tip sizes and shapes the characterizer can measure. Our experiments show that for non re-entrant features, the results obtained with this characterizer are consistent to 1nm with the results obtained by using widely accepted but slower methods that are common practice in CD-AFM metrology. A validation of the integrated length standard using displacement interferometry indicates a uniformity of better than 0.75%, suggesting that the sample could be used as highly accurate and SI traceable lateral scale for the whole evaluation process.

Manufacturing and advanced characterization of sub-25nm diameter CD-AFM probes with sub-10nm tip edges radius

Atomic force microscopy (AFM) is increasingly used in the semiconductor industry as a versatile monitoring tool for highly critical lithography and etching process steps. Applications range from the inspection of the surface roughness of new materials, over accurate depth measurements to the determination of critical dimension structures. The aim to address the rapidly growing demands on measurement uncertainty and throughput more and more shifts the focus of attention to the AFM tip, which represents the crucial link between AFM tool and the sample to be monitored. Consequently, in order to reach the AFM tool’s full potential, the performance of the AFM tip has to be considered as a determining parameter. Currently available AFM tips made from silicon are generally limited by their diameter, radius, and sharpness, considerably restricting the AFM measurement capabilities on sub-30nm spaces. In addition to that, there’s lack of adequate characterization structures to accurately characterize sub-25nm tip diameters. Here, we present and discuss a recently introduced AFM tip design (T-shape like design) with precise tip diameters down to 15nm and tip radii down to 5nm fabricated from amorphous, high density diamond-like carbon (HDC/DLC) using electron beam induced processing (EBIP). In addition to that advanced design, we propose a new characterizer structure, which allows for accurate characterization and design control of sub-25nm tip diameters and sub-10nm tip edges radii. We demonstrate the potential advantages of combining a small tip shape design, i.e. tip diameter and tip edge radius, and an advanced tip characterizer for the semiconductor industry by the measurement of advanced lithography patterns.

Controlled fabrication of advanced functional structures on the nanoscale by means of electron beam-induced processing

The controlled deposition of materials by means of electron beam induced processing (EBIP) is a well-established patterning method, which allows for the fabrication of nanostructures with high spatial resolution in a highly precise and flexible manner. Applications range from the production of ultrathin coatings and nanoscaled conductivity probes to super sharp atomic force microscopy (AFM) tips, to name but a few. The latter are typically deposited at the very end of silicon or silicon-nitride tips, which are fabricated with MEMS technologies. EBIP therefore provides the unique ability to converge MEMS to NEMS in a highly controllable way, and thus represents an encouraging opportunity to refine or even develop further MEMS-based features with advanced functionality and applicability. In this paper, we will present and discuss exemplary application solutions, where we successfully applied EBIP to overcome dimensional and/or functional limitations. We therefore show the fabrication stability and accuracy of “T-like-shaped” AFM tips made from high density, diamond-like carbon (HDC/DLC) for the investigation of undercut structures on the base of CDR30-EBD tips. Such aggressive CD-AFM tip dimensions are mandatory to fulfill ITRS requirements for the inspection of sub-28nm nodes, but are unattainable with state-of-art Si-based MEMS technologies today. In addition to that, we demonstrate the ability of EBIP to realize field enhancement in sensor applications and the fabrication of cold field emitters (CFE). For example: applying the EBIP approach allows for the production of CFEs, which are characterized by considerably enhanced imaging resolution compared to standard thermal field emitters and stable operation properties at room temperature without the need for periodic cathode flashing – unlike typical CFEs. Based on these examples, we outline the strong capabilities of the EBIP approach to further downscale functional structures in order to meet future demands in the semiconductor industry, and demonstrate its promising potential for the development of advanced functionalities in the field of NEMS.

In-line metrology for atomic resolution local height variation

We demonstrated fully automated in-line atomic force microscopy (AFM) for local height variation monitoring solution. Two use cases, which are local variation of SADP Fin height and oxide recess height in Fin reveal process and that of Cu nail protrusion and Cu pad recess height in wafer-to-wafer hybrid bonding process were evaluated in order to evaluate in-line AFM capability as a metrology solution for process development and in-line process monitoring. In-line AFM provides not only visual information of nanotopography, which could lead to quick decision making, but also to quantitative information of local height variation where other metrology solutions could not have provided. In-line AFM could provide many advantages, which are nondestructive measurement, sub-nanometer accuracy and long term reliability. Those advantages help learning cycle and process quality to enhance.

Atomic Resolution Quality Control for Fin Oxide Recess by Atomic Resolution Profiler

A non-destructive metrology technique for critical dimension of Fin structure is important for better device characterization and development for improving yield. Due to extremely small dimension with high complexity in FinFET a new metrology solution needs to be evaluated. In-line atomic resolution profiler was performed to provide a suitable metrology for oxide recess metrology in Fin process. The technique could measure accurately the height and CD of Fin structures, which has the space with of 25 nm and the height of 60 nm. The uniformity of recess height could be measured, which could be interpreted by loading effect of etch process. High long term repeatability of the technique was achieved for process monitoring purpose.