It is crucial to make Si wafer surfaces ultraclean in order to realize such advanced processes as the low-temperature process and the high-selectivity in the ULSI production. The ultra clean wafer surface must be perfectly free from particles, organic materials, metallic impurities, native oxide, surface microroughness, and adsorbed molecule impurities. Since the metallic contamination on the wafer surface, which is one of the major contaminants to be overcome in order to come up with the ultra clean wafer surface, has the fatal effect on the device characteristics, the metallic impurities in the wafer surface must be suppressed at least below 1010 atoms/cm2. Meanwhile the current dry processes such as reactive ion etching or ion implantation, suffer the metallic contamination of 10121013 atoms/cm2. The wet process becomes increasingly important to remove the metallic impurities introduced in the dry process. Employing a new evaluation method, the metallic impurity segregations at the inrerface between the Si and liquid employed in the wet cleaning process of the Si surface such as ultrapure water and various clemicals were studied. This article clearly indicate that it is important to suppress the metallic impurities, such as Cu, which can exchange electrons with Si to be segregated, at least below the 10 ppt level in ultrapure water and liquid chemical such as HF, H2O2, which are employed in the final step of the wet cleaning. When the ultrapure water rinsing is performed in the ambience containing oxygen, the native oxide grows accompanying an inclusion of metals featuring lower electron negativity than Si. It is revealed that, in order to provent the metallic impurity precipitation, it is require not only to remove metallic impurities from ultrapure water but also to keep the cleaning ambience without oxygen, such as the nitrogen ambience, so as to suppress the native oxide formation.

The increase of surface microroughness on Si substrate degrades the electrical characteristics such as the dielectric breakdown field intensity (EBD) and charge to break-down (QBD) of thin oxide film. It has been found that the surface microroughness increases in the wet chemical process, particularly in NH4OH-H2O2-H2O cleaning (APM cleaning). It has been revealed that the surface microroughness does not increase at all if the NH4OH mixing ratio in NH4OH-H2O2-H2O solution is reduced from the conventional level of 1:1:5 to 0.05:1:5, and the room temperature ultrapure water rinsing is introduced right after the APM cleaning. At the same time, the APM cleaning with NH4OH-H2O2-H2O mixing ratio of 0.05:1:5 has been very effective to remove particles and metallic impurities from the Si surface. The surface microroughness dominating the electrical properties of very thin oxide films is strictly influenced by the wafer quality. The increase of surface microroughness due to the APM cleaning has varied among the wafer types such as Cz, FZ and epitaxial (EPI) wafers. The increase of surface microroughness in EPI wafer was very much limited, while the surface microroughness of FZ and Cz wafers gradually increase. As a result of investigating the amount of diffused phosphorus atoms into these wafers, the increase of the surface microroughness in APM cleaning has been confirmed to strongly depend on the silicon vacancy cluster concentration in wafer. The EPI wafer having low silicon vacancy concentration is essentially revealed superior for future sub-half-micron ULSI devices.