Interaction between shallow <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:msup> <mml:mrow> <mml:mi>NV</mml:mi> </mml:mrow> <mml:mo>−</mml:mo> </mml:msup> </mml:math> centers and spin-active azafullerenes on hydrogenated and fluorinat

The interaction between surface-lying nitrogen-substituted fullerenes (radical azafullerene, <a:math xmlns:a="http://www.w3.org/1998/Math/MathML"> <a:mrow> <a:msub> <a:mi mathvariant="normal">C</a:mi> <a:mn>59</a:mn> </a:msub> <a:msup> <a:mrow> <a:mi mathvariant="normal">N</a:mi> </a:mrow> <a:mo>•</a:mo> </a:msup> </a:mrow> </a:math> ) with subsurface negative nitrogen-vacancy complexes <d:math xmlns:d="http://www.w3.org/1998/Math/MathML"> <d:mo>(</d:mo> <d:msup> <d:mrow> <d:mi>NV</d:mi> </d:mrow> <d:mo>−</d:mo> </d:msup> <d:mo>)</d:mo> </d:math> in diamond is investigated using first-principles calculations. We consider <e:math xmlns:e="http://www.w3.org/1998/Math/MathML"> <e:mrow> <e:mo>(</e:mo> <e:mn>2</e:mn> <e:mo>×</e:mo> <e:mn>1</e:mn> <e:mo>)</e:mo> </e:mrow> </e:math> reconstructed (001) oriented diamond surfaces with both H- and F-surface termination. The charge stability of <f:math xmlns:f="http://www.w3.org/1998/Math/MathML"> <f:msup> <f:mrow> <f:mi>NV</f:mi> </f:mrow> <f:mo>−</f:mo> </f:msup> </f:math> when in close proximity to both the nearby surface and the spin active azafullerene is discussed, in the context of diamond band bending arising from surface-induced changes in electron affinity (EA). In the case of the hydrogenated surface, the system spin is quenched, yielding a negatively charged azafullerene <g:math xmlns:g="http://www.w3.org/1998/Math/MathML"> <g:mrow> <g:mo>(</g:mo> <g:msub> <g:mi mathvariant="normal">C</g:mi> <g:mn>59</g:mn> </g:msub> <g:msup> <g:mrow> <g:mi mathvariant="normal">N</g:mi> </g:mrow> <g:mo>−</g:mo> </g:msup> <g:mo>)</g:mo> </g:mrow> </g:math> and neutrally charged <j:math xmlns:j="http://www.w3.org/1998/Math/MathML"> <j:msup> <j:mrow> <j:mi>NV</j:mi> </j:mrow> <j:mn>0</j:mn> </j:msup> </j:math> as the most stable electronic configuration. In contrast, fluorinating the surface favors the negatively charged <k:math xmlns:k="http://www.w3.org/1998/Math/MathML"> <k:msup> <k:mrow> <k:mi>NV</k:mi> </k:mrow> <k:mo>−</k:mo> </k:msup> </k:math> and conserves the <l:math xmlns:l="http://www.w3.org/1998/Math/MathML"> <l:mrow> <l:msub> <l:mi mathvariant="normal">C</l:mi> <l:mn>59</l:mn> </l:msub> <l:msup> <l:mrow> <l:mi mathvariant="normal">N</l:mi> </l:mrow> <l:mo>•</l:mo> </l:msup> </l:mrow> </l:math> neutrality and stabilizes uncompensated free spins. This opposing behaviour is attributed to surface charge doping emerging from different band bending effects associated with the surface EA. This study is consistent with experimentally observed photoluminescence quenching, and shows that surface passivation by fluorination could efficiently tackle the problem of charge transfer between adsorbed molecules and shallow NV centers.