Structural and electrical properties of high-k HfO2 films modified by CHF3 and C4F8/O2 plasmas

As-deposited HfO2 films were modified by CHF3, C4F8, and mixed C4F8/O-2 plasmas in a dual-frequency capacitively coupled plasma chamber driven by radio frequency generators of 60 MHz as the high frequency (HF) source and 2 MHz as the low frequency source (60/2 MHz). The influences of various surface plasma treatments under CHF3, C4F8, and C4F8/O-2 were investigated in order to understand the chemical and structural changes in thin-film systems, as well as their influence on the electrical properties. Fluorine atoms were incorporated into the HfO2 films by either CHF3 or C4F8 plasma treatment; meanwhile, the C/F films were formed on the surface of the HfO2 films. The formation of C/F layers decreased the k value of the gate stacks because of its low dielectric constant. However, the addition of O-2 gas in the discharge gases suppressed the formation of C/F layers. After thermal annealing, tetragonal HfO2 phase was investigated in both samples treated with CHF3 and C4F8 plasmas. However, the samples treated with O-rich plasmas showed monoclinic phase, which indicated that the addition of O plasmas could influence the Hf/O ratio of the HfO2 films. The mechanism of the t-HfO2 formation was attributed to oxygen insufficiency generated by the incorporation of F atoms. The capacitors treated with C4F8/O-2 plasmas displayed the highest k value, which ascribed that the C/F layers were suppressed and the tetragonal phase of HfO2 was formed. Good electrical properties, especially on the hysteresis voltage and frequency dispersion, were obtained because the bulk traps were passivated by the incorporation of F atoms. However, the H-related traps were generated during the CHF3 plasma treatments, which caused the performance degradation. All the treated samples showed lower leakage current density than the asdeposited HfO2 films at negative bias due to the reduced trap-assisted tunneling by the incorporation of F to block the electrons transferring from metal electrode to the trap level.