We report our investigation of the atomic layer deposition (ALD) of HfO₂ on the MoS₂ surface. In contrast to previous reports of conformal growth on MoS₂ flakes, we find that ALD on MoS₂ bulk material is not uniform. No covalent bonding between the HfO₂ and MoS₂ is detected. We highlight that individual precursors do not permanently adsorb on the clean MoS₂ surface but that organic and solvent residues can dramatically change ALD nucleation behavior. We then posit that prior reports of conformal ALD deposition on MoS₂ flakes that had been exposed to such organics and solvents likely rely on contamination-mediated nucleation. These results highlight that surface functionalization will be required before controllable and low defect density high-κ/MoS₂ interfaces will be realized. The band structure of the HfO₂/MoS₂ system is experimentally derived with valence and conduction band offsets found to be 2.67 and 2.09 eV, respectively.