| Copper indium gallium selenide (Cu(In,Ga)Se2 or CIGS) has become a significant topic of research and development for photovoltaic application. CIGS photovoltaic devices have demonstrated record conversion efficiencies however are still below the maximum solar conversion efficiency. Losses in performance have been attributed structural defects including vacancies, doping, grain boundaries, and compositional non-uniformity that are poorly understood and controlled.;The cadmium sulfide (CdS) buffer layer plays a critical role in high-performance CIGS photovoltaic devices, serving as the n-type component of the p-n junction formed with the p-type CIGS absorber layer. Cadmium diffusion into the CIGS surface during CdS deposition creates a buried p-n homojunction in addition to the CIGS/CdS p-n heterojunction. CdS is believed to assist in reducing carrier recombination at the CIGS/CdS interface, an important attribute of high-efficiency solar cells. In the present work, cadmium diffusion mechanisms in CIGS are experimentally investigated via secondary ion mass spectroscopy (SIMS) and Auger electron spectroscopy (AES). Two cadmium diffusion profiles with distinct Arrhenius diffusion kinetics within a single depth profile of the CIGS thin film are observed with SIMS and AES: an intense first-stage diffusion profile directly below the CIGS/CdS interface and a long-range, second-stage diffusion profile that extends deep into the thin film. Cadmium grain boundary diffusion is also detected in fine-grain CIGS samples. These multiple diffusion processes are quantified in the present work, and the two-stage cadmium diffusion profiles suggest distinctive lattice diffusion mechanisms.;Calculations and modeling of general impurity diffusion via interstitial sites in CIGS are also conducted via numerical including cadmium, iron, and zinc. In the numerical simulations, the standard diffusion-reaction kinetics theory is extended to vacancy-rich materials like CIGS that contain 1 at. % copper vacancies. With rapid impurity interstitial diffusion in vacancy-rich materials, annihilation of vacancies in vacancy-rich materials occurs via the interstitial-vacancy recombination, introducing non-equilibrium vacancy concentration profiles. A semi-Fickian effective diffusion coefficient that is inversely proportional to the vacancy concentration is derived from the calculations despite the annihilation of excess vacancies. Additional simulations also show that semi-Fickian diffusion profiles can still be obtained even if impurity incorporation via the interstitial diffusion mechanism raises the vacancy concentration of the material, a behavior that may be relevant in CIGS-related materials. |
