In a method of forming an insulation structure, at least one oxide layer is formed on an object by at least one oxidation process, and then at least one nitride layer is formed from the oxide layer by at least one nitration process. An edge portion of the insulation structure may have a thickness substantially the same as that of a central portion of the insulation structure so that the insulation structure may have a uniform thickness and improved insulation characteristics. When the insulation structure is employed as a tunnel insulation layer of a semiconductor device, the semiconductor device may have enhanced endurance and improved electrical characteristics because a threshold voltage distribution of cells in the semiconductor device may become uniform.