Ion-enhanced chemical etching of HfO2 for integration in metal–oxide–semiconductor field effect transistors

High-density chlorine plasmas were used to chemically etch HfO2, a promising high dielectric constant material, where the etch rate scaled up linearly with the square root of ion energy at energies above 50 eV. Higher etch rates were obtained at lower pressures and high microwave powers, where the electron temperature and ion densities were high. Optical emission spectroscopy and quadrupole mass spectrometry were used to identify the etching products, which are mainly highly chlorinated hafnium (HfCl3 and HfCl4) and ClO. Surface chlorination was confirmed after etching was confirmed by x-ray photoelectron spectroscopy. The addition of BCl3 in the Cl2 plasmas was found to significantly enhance the HfO2 etch rate and improve the etching selectivity to Si from ∼0.01 in a pure Cl2 plasma to ∼0.9 in a pure BCl3 plasma at an ion energy of 75 eV. The etching selectivity was improved to 4 as the ion energies reduced towards the etching threshold energy in a pure BCl3 plasma. BCl3 plasmas were found effective in p...

[1]  R. Wallace,et al.  Wet chemical etching studies of Zr and Hf-silicate gate dielectrics , 2002 .

[2]  Jane P. Chang,et al.  Dielectric property and thermal stability of HfO2 on silicon , 2002 .

[3]  Jane P. Chang,et al.  Ion-enhanced chemical etching of ZrO2 in a chlorine discharge , 2002 .

[4]  Howard R. Huff,et al.  Experimental observations of the thermal stability of high-k gate dielectric materials on silicon , 2002 .

[5]  David P. Norton,et al.  Etch characteristics of HfO2 films on Si substrates , 2002 .

[6]  Jane P. Chang,et al.  Tuning the electrical properties of zirconium oxide thin films , 2002 .

[7]  Eray S. Aydil,et al.  Effect of chamber wall conditions on Cl and Cl2 concentrations in an inductively coupled plasma reactor , 2002 .

[8]  Jane P. Chang,et al.  Ultrathin zirconium oxide films as alternative gate dielectrics , 2001 .

[9]  Jane P. Chang,et al.  Rapid thermal chemical vapor deposition of zirconium oxide for metal-oxide-semiconductor field effect transistor application , 2001 .

[10]  V. M. Donnelly,et al.  Etching of high-k dielectric Zr1−xAlxOy films in chlorine-containing plasmas , 2001 .

[11]  Robert M. Wallace,et al.  Stable zirconium silicate gate dielectrics deposited directly on silicon , 2000 .

[12]  M. V. Malyshev,et al.  Ultrahigh frequency versus inductively coupled chlorine plasmas: Comparisons of Cl and Cl2 concentrations and electron temperatures measured by trace rare gases optical emission spectroscopy , 1998 .

[13]  B. Shore,et al.  Etch‐stop characteristics of Sc2O3 and HfO2 films for multilayer dielectric grating applications , 1996 .

[14]  V. M. Donnelly Mass spectrometric measurements of neutral reactant and product densities during Si etching in a high‐density helical resonator Cl2 plasma , 1996 .

[15]  V. M. Donnelly A simple optical emission method for measuring percent dissociations of feed gases in plasmas: Application to Cl2 in a high‐density helical resonator plasma , 1996 .

[16]  R. C. King,et al.  Handbook of X Ray Photoelectron Spectroscopy: A Reference Book of Standard Spectra for Identification and Interpretation of Xps Data , 1995 .

[17]  C. Steinbrüchel Universal energy dependence of physical and ion-enhanced chemical etch yields at low ion energy , 1989 .

[18]  S. Peyerimhoff,et al.  Electronically excited and ionized states of the chlorine molecule , 1981 .

[19]  R. Wallace,et al.  Hafnium and zirconium silicates for advanced gate dielectrics , 2000 .

[20]  H. W. Lehmann,et al.  Mechanism of Dry Etching of Silicon Dioxide A Case of Direct Reactive Ion Etching , 1985 .