An energy conservation approach to adsorbate-induced surface stress and the extraction of binding energy using nanomechanics

Surface stress induced by molecular adsorption in three different binding processes has been studied experimentally using a microcantilever sensor. A comprehensive free-energy analysis based on an energy conservation approach is proposed to explain the experimental observations. We show that when guest molecules bind to atoms/molecules on a microcantilever surface, the released binding energy is retained in the host surface, leading to a metastable state where the excess energy on the surface is manifested as an increase in surface stress leading to the bending of the microcantilever. The released binding energy appears to be almost exclusively channeled to the surface energy, and energy distribution to other channels, including heat, appears to be inactive for this micromechanical system. When this excess surface energy is released, the microcantilever relaxes back to the original state, and the relaxation time depends on the particular binding process involved. Such vapor phase experiments were conducted for three binding processes: physisorption, hydrogen bonding, and chemisorption. Binding energies for these three processes were also estimated.

[1]  James K. Gimzewski,et al.  Observation of a chemical reaction using a micromechanical sensor , 1994 .

[2]  W. Haiss,et al.  Surface stress of clean and adsorbate-covered solids , 2001 .

[3]  M. Linford,et al.  Determination of the bonding of alkyl monolayers to the Si(111) surface using chemical-shift, scanned-energy photoelectron diffraction , 1997 .

[4]  R. Needs,et al.  Application of the Frenkel-Kontorova model to surface reconstructions , 1990 .

[5]  Thomas Thundat,et al.  Determination of adsorption-induced variation in the spring constant of a microcantilever , 2002 .

[6]  F. Allen,et al.  Hydrogen‐Bond Acceptor Properties of Nitro‐O Atoms: A Combined Crystallographic Database and Ab Initio Molecular Orbital Study , 1997 .

[7]  Anthony C Gehl,et al.  Quantitative analysis of ternary vapor mixtures using a microcantilever-based electronic nose , 2007 .

[8]  Matthew R. Linford,et al.  Alkyl monolayers covalently bonded to silicon surfaces , 1993 .

[9]  A. Saúl,et al.  Elastic effects on surface physics , 2004 .

[10]  Hans-Jürgen Butt,et al.  A Sensitive Method to Measure Changes in the Surface Stress of Solids , 1996 .

[11]  Jillian M Buriak,et al.  Organometallic chemistry on silicon and germanium surfaces. , 2002, Chemical reviews.

[12]  Anja Boisen,et al.  Adsorption kinetics and mechanical properties of thiol-modified DNA-oligos on gold investigated by microcantilever sensors. , 2002, Ultramicroscopy.

[13]  G. Stoney The Tension of Metallic Films Deposited by Electrolysis , 1909 .

[14]  T. Thundat,et al.  Detection of trinitrotoluene via deflagration on a microcantilever , 2004 .

[15]  R. Koch,et al.  On the influence of thermal effects on internal stress measurements during and after deposition of silver, gold and copper films , 1985 .

[16]  R Shuttleworth,et al.  The Surface Tension of Solids , 1950 .

[17]  Wolf Should all surfaces be reconstructed? , 1993, Physical review letters.

[18]  R. A. McGill,et al.  Detection of 2,4-dinitrotoluene using microcantilever sensors , 2004 .

[19]  Anja Boisen,et al.  Miniature sensor suitable for electronic nose applications. , 2007, The Review of scientific instruments.

[20]  U. Harms,et al.  Influence of stress in thin film modulus measurements by the vibrating reed technique , 1998 .

[21]  W. Erley,et al.  ADSORBATE-INDUCED SURFACE STRESS MEASUREMENTS: A NEW METHOD FOR MONITORING IN-SITU SURFACE REACTIONS , 1995 .

[22]  M. Sepaniak,et al.  Cantilever transducers as a platform for chemical and biological sensors , 2004 .

[23]  Y. Chu,et al.  Bright-field imaging of lattice distortions using x rays , 2006 .

[24]  B. Rogers,et al.  Explosives: A microsensor for trinitrotoluene vapour , 2003, Nature.

[25]  T. Thundat,et al.  Photochemical hydrosilylation of 11-undecenyltriethylammonium bromide with hydrogen-terminated Si surfaces for the development of robust microcantilever sensors for Cr(VI). , 2005, Langmuir : the ACS journal of surfaces and colloids.

[26]  T. Thundat,et al.  Sensitive detection of plastic explosives with self-assembled monolayer-coated microcantilevers , 2003 .

[27]  Thomas Thundat,et al.  Adsorption-induced surface stress and its effects on resonance frequency of microcantilevers , 1995 .

[28]  Gerber,et al.  Atomic force microscope. , 1986, Physical review letters.

[29]  Tae Song Kim,et al.  Effect of mass and stress on resonant frequency shift of functionalized Pb(Zr0.52Ti0.48)O3 thin film microcantilever for the detection of C-reactive protein , 2004 .