Label–free DNA detection is of crucial role to when developing point-of-care biochips to be used in personalized therapy. Capacitance detection is a promising technology for label-free DNA detection. However, data published in literature often show evident time drift, large standard deviation, scattered data points, and poor reproducibility. To solve these problems, alkanethiol molecules such as mercapto-hexanol are usually considered as blocking agents. The aim of the present paper is to investigate new blocking agents to further improve DNA probe surfaces. Data from AFM, SPR, florescence microscopy, and capacitance measurements are used to demonstrate the new lipoates molecules. Moreover precursor layers obtained by using Ethylene-glycol alkanethiols offer further improvements in terms of diminished detection errors. Film structure is investigated at the nano-scale to justify the detection improvements in terms of probe surface quality. This study demonstrates the superiority of lipoate and Ethylene-glycol molecules as blocking candidates when immobilizing molecular probes onto spot surfaces in labelfree DNA biochip.