Development of ALD Precursors for Semiconductor Devices

Abstract

Two novel precursors, tetrakis(2-methyl-3-butene-2-oxy) hafnium (HMBO) and tetrakis(2-methyl-3-butene-2-oxy) zirconium (ZMBO), are synthesized for the deposition of hafnium dioxide (HfO 2 ) and zirconium dioxide (ZrO 2 ), respectively. HMBO and ZMBO have carbon-carbon double bond in their molecule, for ozone reactivity is added to themselves. Thermal stabilities of HMBO and ZMBO are more stabilized than those of TEMAH and TEMAZ. The effect of carbon-carbon double bond for the improvement of the O 3 reactivity with HMBO and ZMBO is confirmed by thermogravimetric analysis (TG) under O 3 atmosphere.

Recent Development of ALD Precursors for Semiconductor Devices

“…In Figure 6, weight of Zr(DMAMP) 4 decreases with a huge exothermal peak of DTA under 100 o C, which shows that the oxidation reaction with O 3 is violently occurred on Zr(DMAMP) 4 at such a low temperature. Reactivity of Zr(DMAMP) 4 with ozone is obviously higher than that of ZMBO [11] and is similar to first reaction of TEMAZ with ECS Transactions, 25 (4) 209-216 (2009) ozone(Figure 7). In previous report [11], ZMBO reacts with ozone at two temperature regions around 150 and 200 o C. In the case of TEMAZ (Figure 7), intensive exothermal peaks of DTA are appeared around 50 o C and 100 o C with the weight decrease of TEMAZ by TG spectrum, which apparently shows that the reaction of TEMAZ with O 3 is occurred by two steps.…”

“…Reactivity of Zr(DMAMP) 4 with ozone is obviously higher than that of ZMBO [11] and is similar to first reaction of TEMAZ with ECS Transactions, 25 (4) 209-216 (2009) ozone(Figure 7). In previous report [11], ZMBO reacts with ozone at two temperature regions around 150 and 200 o C. In the case of TEMAZ (Figure 7), intensive exothermal peaks of DTA are appeared around 50 o C and 100 o C with the weight decrease of TEMAZ by TG spectrum, which apparently shows that the reaction of TEMAZ with O 3 is occurred by two steps. In the case of ZTTB [11], only vaporization was observed and there was no reaction with ozone.…”

“…In previous report [11], ZMBO reacts with ozone at two temperature regions around 150 and 200 o C. In the case of TEMAZ (Figure 7), intensive exothermal peaks of DTA are appeared around 50 o C and 100 o C with the weight decrease of TEMAZ by TG spectrum, which apparently shows that the reaction of TEMAZ with O 3 is occurred by two steps. In the case of ZTTB [11], only vaporization was observed and there was no reaction with ozone. To judge from the result of TG-DTA analysis under ozone atmosphere, the order of the reactivity of precursors with ozone is TEMAZ > Zr(DMAMP) 4 > ZMBO > ZTTB.…”

“…Previously we reported tetrakis(2-methyl-3-butene-2-oxy) hafnium (HMBO) and tetrakis(2-methyl-3-butene-2-oxy) zirconium (ZMBO) as new precursors for HfO 2 and ZrO 2 deposition [11]. They embedded carbon-carbon double bond in their molecules as the reaction point with ozone.…”