Preparation and Application of New Amorphous Materials in Non-chalcogenide System

在非硫系玻璃中发现了两种新的光敏非晶态材料：无掺杂铝酸钙玻璃和无定形红磷。铝酸钙玻璃对紫外光具有两种不同性质的光敏性质，即稳定的着色性(加热到200ﾟC可漂白)和光致变色性。外观不需要掺杂光学活性成分，如金、银或卤素，这与目前为止的光敏玻璃完全不同。只需改变熔融气氛，如氧化或还原，即可使化学成分相同的铝酸钙玻璃具有这些不敏感性。这些灵敏度归因于玻璃中氧相关点缺陷(氧过量类型或氧空位)的存在。利用射频溅射方法成功地制备了无定形红磷薄膜。这些薄膜表现出三种光诱导现象：光变暗和银的光掺杂，这是首次在非壳源体系中观察到的光漂白现象，这是迄今为止在壳源体系中尚未观察到的光漂白现象。结果表明，价带的顶端是由p西格纳轨道组成的，即带隙照明使P-P键解离。由此产生的P_2分子或P自由基重新排列或与氧分子反应，这取决于大气。没有观察到这种光诱导的键解离，因为孤立的一对轨道占据了CHAGENIES中价带的顶部。

Two new photosensitive amorphous materials were found in non- chalcogenide systems; dopant-free calcium aluminate glasses and amorphous red phosphorus.Binary calcium aluminate glasses show two types of photosensitivities with different nature to ultravioletradiation, stable coloring( bleachable by heating tip to 200ﾟC) and photochromism. No doping of optically active components such as Au, Ag or halogens is required for the appearance, which is totally differs from photosensitive glasses so far. These insensitivities can be imparted to calcium aluminate glasses with the same chemical compositions by only changing the melting atmosphere such as oxidizing or reducing. These sensitivities were attributed to the presence of oxygen-related point defects (oxygen-excess type or oxygen vacancy) in the glasses.Amorphous red phosphorus films were successfully prepared by rf sputtering method. These films were found to show three photoinduced phenomena, photodarkening, and photodoping of silver.These observation is the fist report in non-chacogenide systems.Further, photobleaching was found, which has been not observed in chacogenide systems so far. The results were explained by that the top of the valence band is composed of p sigina orbital,i.e.band gap illumination dissociates P-P bonds. The resulting P_2 molecule or P radicals rearrange or react with oxygen molecule, depending on the atmosphere. No such a photo-induced bond dissociation is observed because the lone pair orbitals occupy the top of the valence band in chacogenides.