The decreasing feature sizes in complementary metal-oxide semiconductor (CMOS) transistor technology will require the replacement of SiO2 with gate dielectrics that have a high dielectric constant (high-k) because as the SiO2 gate thickness is reduced below 1.4 nm, electron tunnelling effects and high leakage currents occur in SiO2, which present serious obstacles to future device reliability.In recent years significant progress has been made on the screening and selection of high-k gate dielectrics, understanding their physical properties, and their integration into CMOS technology.Now the family of hafnium oxide-based materials has emerged as the leading candidate for high-k gate dielectrics due to their excellent physical properties.It is also realized that the high-k oxides must be implemented in conjunction with metal gate electrodes to get sufficient potential for CMOS continue scaling.In the advanced nanoscale Si-based CMOS devices, the composition and thickness of interfacial layers in the gate stacks determine the critical performance of devices.Therefore, detailed atomicscale understandings of the microstructures and interfacial structures built in the advanced CMOS gate stacks,are highly required.In this paper, several high-resolution electron, ion, and photon-based techniques currently used to characterize the high-k gate dielectrics and interfaces at atomic-scale, are reviewed.Particularly, we critically review the research progress on the characterization of interface behavior and structural evolution in the high-k gate dielectrics by high-resolution transmission electron microscopy (HRTEM) and the related techniques based on scanning transmission electron microscopy (STEM), including high-angle annular darkfield (HAADF) imaging (also known as Z-contrast imaging), electron energy-loss spectroscopy (EELS), and energy dispersive X-ray spectroscopy (EDS), due to that HRTEM and STEM have become essential metrology tools for characterizing the dielectric gate stacks in the present and future generations of CMOS devices.In Section 1 of this review, the working principles of each technique are briefly introduced and their key features are outlined. In Section 2, microstructural characterizations of high-k gate dielectrics at atomic-scale by electron microscopy are critically reviewed by citing some recent results reported on high-k gate dielectrics.In Section 3, metal gate electrodes and the interfacial structures between high-k dielectrics and metal gates are discussed.The electron beam damage effects in high-k gate stacks are also evaluated, and their origins and prevention are described in Section 4.Finally, we end this review with personal perspectives towards the future challenges of atomic-scale material characterization in advanced CMOS gate stacks.