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对于深能级杂质,通常的有效质量近似已不再成立。本文由Bloch波函数出发,应用赝势的概念,证明了杂质波函数及能级满足一等效的薛定谔方程。其中除包含通常的长程库仑位势外,还有一短程位势,后者随不同杂质原子而异。对浅能级杂质,它引起谷-轨道分裂,但对深能级杂质,它已不能看成微扰项了。我们讨论了这部分短程位势对杂质束缚能级的影响。只有当等效势阱深到足以单独地引起电子的共振散射或束缚态时,它对杂质束缚能级才有很明显的影响,束缚能级随此势阱加深而迅速增加。此外可以证明,短程作用的带间矩阵元可以近似用一等价带内排斥势来代替,当束缚能接近禁带宽度时,带间作用影响很大。我们指出,带间作用可以解释为什么杂质能够同时俘获电子和空穴。通过一个简单的例子,我们进行了具体的数值计算,并进一步分析了短程作用的影响。最后我们利用这个简单模型讨论了Cu,Ag,Au在Ge中的能级。It was well known that the effective mass approximation cannot be used to calculate the deep impurity levels in semiconductors. Starting from the band wave functions and making use of the idea of pseudo-potential, we proved that, the impurity states are the approximate solutions of an equivalent Schr?dinger equation, which contains not only the usual term of the long range Coulomb potential, but also a short range one. For the shallow level impurities this short range force gives rise to the so called "valley-orbit" splitting, while for deep level impurities it cannot be taken as perturbation. It is essentially different for different impurities.The effect of this short range force on the bond states was discussed. It was shown that, when this part is so strong that it alone can give rise to resonance scattering or bond state of electron, the bond energy does strongly depend on it, and rapidly increases as it increases. At the same time the wave function also shrinks largely. It was proved that the matrix elements between valence and conduction bands of this part of potential can be replaced approximately by an equivalent intraband repulsive interaction and the influence of interband interaction is important when the bond energy is nearly equal to the forbidden band width. It also may be the cause of the fact that many impurities can capture electron and hole simultaneously.Furthermore, we carried out numerical calculation for a simple model and analysed in detail all the above mentioned effects. Finally the energy levels of Cu, Ag, Au in Ge were discussed with the help of this simple model.
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