Properties of hybridized DNA arrays on single-crystalline undoped and boron-doped (100) diamonds studied by atomic force microscopy in electrolytes

Properties of hybridized deoxyribonucleic acid (DNA) arrays on single-crystalline undoped and boron-doped diamonds are studied at the microscopic level by atomic force microscopy (AFM) in buffered electrolytic solutions. DNA is linked to diamond via aminodecene molecules (TFAAD) that are attached to undoped diamonds by a photochemical reaction and via nitrophenyl-diazonium molecules attached electrochemically to boron-doped diamonds. Both H-terminated and oxidized diamond surfaces are used in this process. On H-terminated surfaces, AFM measurements detect compact DNA layers. By analyzing phase and height contrast in AFM, a DNA layer height of 76 angstrom is determined on the photochemically functionalized diamonds and a DNA layer height of up to 92 angstrom is determined on the electrochemically functionalized diamonds. Based on the layer thickness, the DNA chains are tilted under the angle of 31 degrees. The morphology of the DNA layers exhibits long-range (30-50 nm) undulations of 20 angstrom in height and a nanoroughness of 8 angstrom. Using Hertz's model for calculating the contact area of the AFM tip on a DNA layer and a geometrical model of DNA arrangement on diamond yields the DNA density on diamonds of 6 x 10(12) cm(-2) on both photochemically and electrochemically functionalized diamonds. The structure of these dense DNA layers is not significantly influenced by variations in buffer salinity of 1-300 mM NaCl. DNA molecules can be removed from the diamond surface by contact-mode AFM with forces >= 45 nN and >= 76 nN on photochemically and electrochemically functionalized diamonds, respectively, indicating that DNA is bonded covalently and stronger on diamond than on gold substrates. The DNA arrangement and bonding strength are similar on oxidized diamond surfaces when using an electrochemical process. On oxidized surfaces after photochemical processing, DNA is bonded noncovalently as deduced from the removal force < 6 nN. The presence of hybridized DNA as well as the selective removal of DNA by AFM scanning are corroborated by fluorescence microscopy.