The reactivity evaluation of copper is performed using ethylenediamine, aminoethanol, and piperidine to apply organic chelators to copper etching. It is revealed that piperidine, which is a ring-type chelator, has the lowest reactivity on copper and copper oxide and ethylenediamine, which is a chain-type chelator, has the highest reactivity via inductively coupled plasma-mass spectroscopy (ICP-MS). Furthermore, it is confirmed that the stable complex of copper-ethylenediamine can be formed during the reaction between copper and ethylenediamine using nuclear magnetic resonance (NMR) and radio-thin layer chromatography. As a final evaluation, the copper reactivity is evaluated by wet etching using each solution. Scanning electron micrographs reveal that the degree of copper reaction in ethylenediamine is stronger than that in any other chelator. This result is in good agreement with the evaluation results obtained by ICP-MS and NMR. It is concluded that ethylenediamine is a prospective etch gas for the dry etching of the copper.

Dry etching of copper thin films is performed using high density plasma of ethylenediamine (EDA)/ hexafluoroisopropanol (HFIP)/Ar gas mixture. The etch rates, etch selectivities and etch profiles of the copper thin films are improved by adding HFIP to EDA/Ar gas. As the EDA/HFIP concentration in EDA/HFIP/Ar increases, the etch rate of copper thin films decreases, whereas the etch profile is improved. In the EDA/HFIP/Ar gas mixture, the optimal ratio of EDA to HFIP is investigated. In addition, the etch parameters including ICP source power, dc-bias voltage, process pressure are varied to examine the etch characteristics. Optical emission spectroscopy results show that among all species, [CH], [CN] and [H] are the main species in the EDA/HFIP/Ar plasma. The X-ray photoelectron spectroscopy results indicate the formation of CuCN compound and C-N-H-containing polymers during the etching process, leading to a good etch profile. Finally, anisotropic etch profiles of the copper thin films patterned with 150 nm scale are obtained in EDA/HFIP/Ar gas mixture.