Alain Schumacher

• Boron nitride films were deposited by controlled plasma assisted chemical vapor deposition (PACVD) on the basis of borane-ammonia (BH3NH3) as B- and N- supplier. Having a high vapor pressure, this white crystalline solid of less toxicity in comparision to generally used boron precursors can easily be transferred into the gas phase by moderate heating. Together with argon as working gas the BH3NH3-vapor is led into a two-circuit plasma source utilizing the electron cyclotron wave resonance technique (ECWR) for ionization and dissoziation of the gas mixture by electron impact in the low pressure range (~10 microbar). For a precise adjustment of the energy of the ionic plasma species arriving at the growing film, an r.f.-diode circuit is superimposed to the discharge. Since for a controlled film deposition by PACVD a stationary plasma composition is mandatory, the evaporation characteristics of the reactant source was determined primarily. Therefore the evolution of the plasma and the vapor composition in dependence of evaporation time and temperature was investigated by optical emission spectroscopy (OES) and by mass spectrometric measurements respectively. By these investigations it was shown that stationary plasma conditions are established in a temperature range of 120 - 160°C. This behavior can be explained by a change in the chemical composition of the reactant during the evaporation process. In the following thin boron nitride films were deposited onto Si(100)-substrates for fixed partial pressures of BH3NH3 (2,9 mbar) and argon (9,3 microbar, FAr=5 sccm). For all experiments the plasma power as well as the substrate temperature was kept at 200 W (B0=34 G) and 380°C, respectively. By a defined tuning of the r.f.-amplitude in the diode circuit it was demonstrated that the energy of the ionic species arriving at the growing film is an essential process parameter for c-BN growth. For these experiments c-BN growth took place in a small energy window with a width of about 25 eV. The maximum c-BN content was achieved at 107 eV. The fraction of h-BN and c-BN phases were determined by Fourier Transform Infrared Spectroscopy (FTIR). At a film thickness of 61 nm the volume fraction of c-BN, derived from the IR-absorption peak areas of h-BN at 1385 cm -1 and c-BN at 1081 cm -1 , already achieved 68 vol%. This is due to an early starting point of c-BN growth, which was confirmed by cross sectional high resolution transmission electron microscopy measurements (HRTEM). Furthermore these investigations confirmed the growth of a thin amorphous BN-layer followed by a (0002)-textured h-BN-film primarily to the c-BN-nucleation step as commonly observed in literature. After the c-BN-nucleation step has finished the growth of a nearly pure c-BN-phase is achieved. This was emphasized by auger electron spectroscopy. By means of secondary ion mass spectrometry in the MCs + -mode (MCs + -SIMS) it was shown that the c-BN-films contain a certain amount of hydrogen, which can be estimated to be around 10 - 15 at%. Since in FTIR no perceptible amount on B-H- or N-H-bindings in the c-BN- films could be detected, it must be concluded that the hydrogen is located as H2-molecules in the c-BN-network. Finally the elastic properties of a c-BN-film were estimated by calculations, based on Brillouin light scattering (BLS) results.