氧化锆作为一种宽禁带半导体氧化物，由于其优异的力热光电性质以及化学稳定性，广泛应用于各种领域。在发光领域，氧化锆主要应用于荧光粉、发光二极管以及闪烁体等发光器件。近年来，基于具有微米空间分辨率的X射线成像技术在众多科学与工业应用领域蓬勃发展，氧化锆因具有高密度和高原子序数，可以高效吸收X射线，从而成为薄膜闪烁体探测器的优秀候选。了解氧化锆的发光机理对器件性能的提升具有十分重大意义。然而，目前针对氧化锆发光起源仍没有一个共识，一部分人认为发光起源于氧空位的电子转移过程，另一部分人认为发光起源于Ti³⁺杂质。

为对氧化锆发光起源进行进一步探究，尤其是氧空位对发光的影响，本文研究了不同退火温度以及不同退火气体条件下氧化锆的光致发光情况，并与未退火样品进行了对比。离子激发发光手段被用于研究未处理氧化锆的发光强度随辐照注量增加的实时变化趋势，这种趋势可以用来反映辐照过程中离子激发发光光谱强度与氧空位浓度的变化关系(定性分析)。电感耦合等离子体质谱(ICP-MS)与X射线衍射(XRD)实验分别被用来研究氧化锆样品的元素含量与晶相，为光致发光、离子激发发光与第一性原理的计算作铺垫。

在理论计算上，本文研究了Ti替位Zr、氧空位（Vo）以及Ti-Vo复杂缺陷的形成能与转变能，并结合位形图给出了一个合理的发光模型。本文的研究工作具体如下：

(1)研究了氧化锆样品的电感耦合等离子体质谱，获得了样品几个主要元素的含量分布，后续光谱的杂质峰可能就与这些元素有关。X射线衍射实验结果表明氧化锆样品为单斜相，为第一性原理的计算提供了模型依据。

(2)研究了200、500和800度空气中退火3小时的氧化锆的光致发光情况。发现三者均弱于未退火样品，并且随着温度升高发光强度越弱。

(3)研究了500度下氮气、氧气和空气中退火3小时的氧化锆的光致发光情况。发现氮气中退火样品发光强度高于未处理样品，而空气中退火的样品发光强度弱于未处理样品。氧气中退火的样品正反面结果差异很大。

(4)离子激发发光结果显示随着H⁺离子注量增加，氧化锆样品不仅整体的发光呈衰减趋势，500nm处的发光也呈现单一衰减规律。

(5)运用第一性原理计算了Ti³⁺，Vo以及Ti-Vo的形成能与转变能。结果表明了氧空位对Ti⁴⁺向Ti³⁺转变的有利影响。利用Vo和F_A的位形图得出了理论上的光学跃迁能级。

Zirconia, a wide band gap semiconductor oxide, has been widely used in various fields due to its excellent thermoelectric properties and chemical stability. In the field of light-emitting, mainly used in phosphors, light-emitting diodes and scintillators and other light-emitting devices. In recent years, X-ray imaging technology based on micron spatial resolution has developed rapidly in many scientific and industrial applications. Zirconia has become an excellent candidate for thin film scintillator detector because of its high density and high atomic number, which can absorb X-ray efficiently. Understanding the luminescence mechanism of zirconia is of great significance to improve the performance of devices. However, the origin of the luminescence of zirconia is controversial. Some people believe that the luminescence originates from the electron transfer process of oxygen vacancy, while others believe that the luminescence originates from Ti³⁺ impurity.

In order to further explore the origin of luminescence of zirconia, especially the influence of oxygen vacancy on luminescence, the photoluminescence of zirconia under different annealing temperature and different annealing gas conditions was studied, and compared with the samples without annealing. The real-time change trend of the luminescence intensity of untreated zirconia with the increase of irradiation fluence was studied by using the ion excited luminescence method. This trend can be used to reflect the relationship between the intensity of the ion excited luminescence spectrum and the oxygen vacancy concentration (qualitative analysis). Inductively coupled plasma mass spectrometry (ICP-MS) and X-ray diffraction (XRD) experiments were used to study the element content and crystal phase of zirconia samples, respectively, to pave the way for photoluminescence, ion excited luminescence and first principles calculation.

In this paper, the formation energy and transition energy of Ti substituted Zr, oxygen vacancy (V_O) and Ti-V_O complex defects are studied theoretically, and a reasonable luminescent model is given based on the configuration diagram. The work of this thesis is as follows：

(1) Inductively coupled plasma mass spectrometry (ICP-MS) of zirconia samples was studied. The content distributions of several main elements in the samples were obtained. The impurity peaks in the subsequent spectra may be related to these elements. The X-ray diffraction result indicate that the zirconia sample is monoclinic phase, which provides a model basis for the first principle calculation.

(2) The photoluminescence of zirconia annealed at 200, 500 and 800 ℃ for 3 hours was studied. It is found that all of them are weaker than those of the non-annealed samples, and the luminescence intensity decreases when the temperature increase.

(3) The photoluminescence of zirconia annealed in nitrogen, oxygen and air at 500 ℃ for 3 hours was studied. It is found that the luminescence intensity of annealed samples in nitrogen is higher than that of untreated samples, while that of annealed samples in air is lower than that of untreated samples. The results of the samples annealed in oxygen are very different.

(4) The results of ion stimulated luminescence show that with the increase of H⁺ ion fluence, not only the overall luminescence of zirconia sample decreases, but also the luminescence at 500 nm presents a single decay law.

(5) The formation and transformation energies of Ti³⁺, V_O and Ti-V_O are calculated by first principles. The results show that the oxygen vacancy has a favorable effect on the transformation of Ti⁴⁺ to Ti³⁺.The theoretical optical transition energy levels are obtained by using the configuration diagrams of V_O and F_A.