In this work, several scientific problems related to high pressure–high temperature (HP–HT) synthesis of new materials using fullerite as a precursor were studied: first, the mechanism of the transformation of C₆₀ crystal into a nano-clustered graphene phase (NGP) at a pressure of 8 GPa; and second, the effect of disorder introduced into C₆₀ crystals by ball milling prior to HP–HT synthesis on the structure and properties of the NGP. A separate set of experiments was devoted to compression of C₆₀ precursor at unexplored before pressure of 25 GPa and elevated temperatures in search for new type of disordered carbon-based materials.

In the first study, Raman spectroscopy, HRSTEM-EELS, and indentation hardness demonstrate that, under pressure, C₆₀ exhibits a path of transformation from polymerized C₆₀ to NGP. This phase exhibits a short-range order and preferential orientation of nano-clusters of graphene assembled in a highly disordered carbon matrix. In our studies, we observe that the mechanism of C₆₀ transformation into NGP could be understood in terms of nucleation and growth mechanism as opposed to the pseudomartensitic mechanism. Changes in Raman intensity of the Ag(2) C₆₀ mode monitored in polished incompletely transformed carbon particles reveal different steps of transformation. Moreover, the polishing reveals the distribution of shear bands resulting from plastic deformation of the C₆₀ monomer and following the direction of the <110> slip planes in FCC system.

HRSTEM analysis reveals the presence of disorder as an intermediate state between the parent C60 and the nano-graphene units. EELS spectra show that C₆₀ molecules in such state are present as monomers, and the intermediate phase is an sp²–sp³ disordered phase, in which the sp² fraction is by up to 20% lower than that of graphene nanoclusters. The findings suggest that, after the collapse, the polymer structure breaks down with the formation of a disordered (sp²–sp³) carbon phase containing some fraction of residual C₆₀ molecules. The graphene nanoclusters further nucleate and grow in the intermediate disordered phase. Thus, a nucleation and growth mechanism is proposed for the formation of NGP phase from C₆₀ upon HP-HT action.

For the second problem, highly disordered systems were obtained from ball-milled C₆₀ through HP–HT demonstrating a promising technique to create hard (hardness > 30 GPa) disordered carbons at relatively low pressure (up to 8 GPa).

The nanoarchitecture of NGP and disordered systems was studied using multi-wavelength Raman spectroscopy, HRSTEM, and indentation techniques. The Raman data treatment was carefully studied following the three-stage amorphization trajectory of amorphous carbon. The Raman model consists of G and D bands and data from semi-empirical models that include peak position, FWHM, and intensity ratio. A new approach proposed by the research team includes the presence of carbon pentagons (F band) and carbon heptagons as defects in the graphene clusters and are eventually present in the disordered carbon matrix as well. A peak deconvolution considering the G, D, F and heptagon bands is the model that allows building an empirical correlation between the Raman spectra features and hardness. Using peak deconvolution model based on G, D, F heptagon and sp³ carbon-derived bands allowed us to build an empirical correlation that can be used for a semi-quantitative estimation/prediction of hardness of an arbitrary disordered sp² carbon-based system based on their spectroscopic (Raman) data.

Finally, experiments on compressed C₆₀ at 25 GPa, previously unexplored pressure, produce superhard 3D-C₆₀ polymers at temperatures below 600 ^oC. As the temperature increases, sp³ carbon starts dominating the disordered structures. The synthesized materials are semiconductors exhibiting ultra-high hardness that in a particular case exceeds that of single crystalline diamond. UV-Raman spectroscopy reveals a high intensity of T band and a G band position typically observed in tetrahedral amorphous carbon (ta-C)-based thin films. The phase has a residual fraction of sp² carbons, mainly linear chains and fused aromatic rings.

In summary, the results demonstrate that a whole class of novel materials with outstanding physical properties - superelastic-hard and ultrahard semiconducting carbons - can be produced for demanding technological applications at HP-HT by using C₆₀ as a precursor and tuning its microstructure.