Pastes based on copper (Cu) nanoparticles (NPs) are promising electronic-packaging materials for the attachment of high-power devices. However, the rapid oxidation of nanostructured Cu requires the use of reducing agents during processing, which makes it less suitable for attaching large-area dies (> 4 mm2). Recently, the functionalization of Cu-NP surfaces with a mixture of amines prevented oxidation, allowing for sintering without the need for reducing agents. Here we investigate the sintering mechanisms involved during die attachment using pastes of passivated Cu NPs, with particular focus on the critical role of the carrier solvents. Using 1-nonanol or 1-decanol as solvents, we first demonstrate the absence of Cu-oxide phases in the pastes after fabrication and the stability of the resulting nanostructured copper for as much as 30 min in air. By measuring the evolution of the electrical characteristics of the paste during drying and sintering, we show that electrically conductive agglomerates form among the NPs between 141°C and 144°C, independent of the carrier solvent used. The carrier solvent was found to affect mainly the densification temperature of the copper agglomerates. Because they lead to uniform sintering of the material, Cu pastes based on solvents with a low boiling point and high vapor pressure are preferable for attaching dies with area greater than 25 mm2. We show that dies with an area as large as 100 mm2 can be attached using a Cu paste based on 1-nonanol. These pastes enables the formation of temperature-resistant bonding for high-power devices using a simple and cost-effective approach.