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Abstract Over the past decades, zinc oxide semiconductor and its derivatives have been extensively developed because of its optoelectronic properties. Since ZnO is an intrinsic n-type semiconductor, how to synthesize high-quality p-type ZnO semiconductors and investigate their optoelectronic properties and local chemical structures are important and necessary. In this article, two studies of synthesizing both undoped and phosphorus-doped ZnO nanostructures by hydrothermal method and chemical vapor deposition （CVD） technique are presented. Scanning electron microscopy （SEM） and laboratory X-ray diffraction （XRD） are used to track the surface morphology and the crystalline structure of both undoped and phosphorus doped ZnO nanostructures, respectively. X-ray absorption near edge structures （XANES）, X-ray emission spectroscopy （XES） and X-ray excited optical luminescence （XEOL） are also used to determine the local chemical information of both undoped and?phosphorus-doped ZnO nano/microstructures such as local symmetry and optical properties. It is found that the phosphorus is successfully doped into the surface of ZnO and substituted the Zn. The phosphorus-doped ZnO products have better crystallinity and less oxygen vacancies on the surface. These two are correlated as one leads to the other. The XEOL results suggest that the average bandgap for undoped and phosphorus doped ZnO is the same, 3.24?eV. The second derivative of the absorption-emission spectra yields the fundamental bandgap for undoped ZnO and phosphorus-doped ZnO is 3.25?eV. The implication of this observation is discussed.
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