Semiconductor barrier structures are essential elements of modern integrated electronics. The band theory explains properties of barrier structures using deep levels in the semiconductor band gap. The relentless interest in studying the characteristics of deep levels is due to practical needs, ambiguous interpretations and scatters of experimental results obtained by different researchers. In order to increase the accuracy of the measurements, a modified capacitive deep-level transient spectroscopy technic of has been developed. A mathematical model of the hardware transformations of the barrier structure capacitance transient signal is developed and provided in this article. The model considers the nonexponentiality of the capacitance transient and the spectrometer hardware transformations nonlinearity. There are the results of the deep levels experimental studies in silicon diodes and the model parametric identification. The technic makes it possible to reduce by five or more times the six-sigma confidence interval for the discrete deep level activation energy determining in comparison with the round robin test results of ASTM F978-02.