Abstract: Micro­Raman Spectroscopy Investigation of Hard Coatings Diamond, silicon carbide, and boron nitride have attracted great interest in the last years, due to their excellent material properties. Especially the extreme hardness and the high thermal con­ ductivity of these materials favour them as protective layers. The very large hardness gave these materials, deposited as films on various substrates, their name: hard coatings. In contrast to di­ amond, silicon carbide and boron nitride can be n­ as well as p­doped, making them promising candidates for high speed and high temperature electronic applications. Contrarily to the materials mentioned above, carbon nitride was obtained in crystalline form just very recently. Up to now the deposited films mainly consist of amorphous or nanocrystalline, carbon­rich material. For all these material systems inelastic light scattering (Raman spectroscopy) has been already applied for the material properties investigation. However, these investigations usually were restricted to only one of the various Raman spectroscopy tools, described in this work: Incident laser light energy varia­ tion, temperature variation, utilizing the selection rules, measurements at varying sample positions, two­dimensional mappings and one­dimensional scans in the conventional plane­view and the addi­ tional cross­sectional sample geometry. In contrast to this, this work demonstrates the improvement of the information about the investigated material and/or the sample heterostructure obtained by using the combination of all the above mentioned techniques. In the case of the diamond material system, films deposited on silicon substrates were investigated and an interfacial graphitic layer of 2nm thickness was found by scanning across the interface, which was obscured in the conven­ tional plane­view sample geometry. Similar to this an ultra­thin top layer and buried intermixed regions were identified in the silicon carbide material system utilizing the cross­sectional sample geometry. In addition to this, the temperature and the incident laser light energy dependences for 5 SiC polytypes (3C, 4H, 6H, 15R, and 21R) were measured. A resonance enhancement for the 3C and the 21R polytype was found corresponding to their fundamental bandgaps at 2.46eV and ß2.8eV, respectively. For the other polytypes no resonance enhancement was found, due to their larger fundamental bandgap. In the boron nitride material system the spatial correlation model for Raman lineshape analysis was applied for the first time and the values of the asymmetric broad­ ening and the frequency downshift for decreasing crystal sizes were evaluated. This was measured for single crystals of different size and for films deposited on silicon substrates. The correlation lengths in the ten nanometer region found for the deposited films corroborate the nanocrystalline nature of these films. Additionally incident laser light energy was measured, revealing the 488.0nm (Ar + ) and 482.5nm (Kr + ) laser lines as the optimum laser lines for the boron nitride investigation. Furthermore the dependence of the phonon feature parameters was investigated depending on the incident laser light power. A maximum power of 5­10mW for the micro­Raman spectroscopy setup was found to avoid any laser light induced heating of the investigated material. Two­dimensional mappings of the deposited boron nitride films were performed to improve the information about the material system. In the case of carbon nitride for the first time distinct phonon features were measured in a wide spectral range contrarily to most of the other investigations, which usually show only broad bands.

Abstract: Micro­Raman Spectroscopy Investigation of Hard Coatings Diamond, silicon carbide, and boron nitride have attracted great interest in the last years, due to their excellent material properties. Especially the extreme hardness and the high thermal con­ ductivity of these materials favour them as protective layers. The very large hardness gave these materials, deposited as films on various substrates, their name: hard coatings. In contrast to di­ amond, silicon carbide and boron nitride can be n­ as well as p­doped, making them promising candidates for high speed and high temperature electronic applications. Contrarily to the materials mentioned above, carbon nitride was obtained in crystalline form just very recently. Up to now the deposited films mainly consist of amorphous or nanocrystalline, carbon­rich material. For all these material systems inelastic light scattering (Raman spectroscopy) has been already applied for the material properties investigation. However, these investigations usually were restricted to only one of the various Raman spectroscopy tools, described in this work: Incident laser light energy varia­ tion, temperature variation, utilizing the selection rules, measurements at varying sample positions, two­dimensional mappings and one­dimensional scans in the conventional plane­view and the addi­ tional cross­sectional sample geometry. In contrast to this, this work demonstrates the improvement of the information about the investigated material and/or the sample heterostructure obtained by using the combination of all the above mentioned techniques. In the case of the diamond material system, films deposited on silicon substrates were investigated and an interfacial graphitic layer of 2nm thickness was found by scanning across the interface, which was obscured in the conven­ tional plane­view sample geometry. Similar to this an ultra­thin top layer and buried intermixed regions were identified in the silicon carbide material system utilizing the cross­sectional sample geometry. In addition to this, the temperature and the incident laser light energy dependences for 5 SiC polytypes (3C, 4H, 6H, 15R, and 21R) were measured. A resonance enhancement for the 3C and the 21R polytype was found corresponding to their fundamental bandgaps at 2.46eV and ß2.8eV, respectively. For the other polytypes no resonance enhancement was found, due to their larger fundamental bandgap. In the boron nitride material system the spatial correlation model for Raman lineshape analysis was applied for the first time and the values of the asymmetric broad­ ening and the frequency downshift for decreasing crystal sizes were evaluated. This was measured for single crystals of different size and for films deposited on silicon substrates. The correlation lengths in the ten nanometer region found for the deposited films corroborate the nanocrystalline nature of these films. Additionally incident laser light energy was measured, revealing the 488.0nm (Ar + ) and 482.5nm (Kr + ) laser lines as the optimum laser lines for the boron nitride investigation. Furthermore the dependence of the phonon feature parameters was investigated depending on the incident laser light power. A maximum power of 5­10mW for the micro­Raman spectroscopy setup was found to avoid any laser light induced heating of the investigated material. Two­dimensional mappings of the deposited boron nitride films were performed to improve the information about the material system. In the case of carbon nitride for the first time distinct phonon features were measured in a wide spectral range contrarily to most of the other investigations, which usually show only broad bands.