CAJ | 학술논문

最近研究表明:丙酮能与半导体si(100)表面发生[2+2]环加成和α-H裂解反应形成相应的Si-C键或Si-O键,在半导体材料的合成方面具有重要意义.为进一步弄清不同羰基化合物在Si(100)表面的反应机理,本文应用密度泛函理论方法在B3LYP/6-311 ++G(d,p)//6-31G(d)水平上较为系统地研究了一系列羰基化合物CH3COR (R=CH3,H,C2H5,C8H5)与Si(100)表面的反应.研究结果表明:不论是[2+2]环加成反应还是α-H裂解反应都对应较低的反应势垒(小于25 kJ·mol-1);环加成反应的势垒比α-H裂解反应的势垒略高;羰基上的取代基对反应势垒的影响较少;α-H裂解反应产物为动力学和热力学控制产物;对丁酮来说,1-位和3-位H原子的裂解反应都比较容易,势垒相差很小,这些结果表明羰基化合物与Si(100)表面的反应将得到多种产物.
최근연구표명:병동능여반도체si(100)표면발생[2+2]배가성화α-H렬해반응형성상응적Si-C건혹Si-O건,재반도체재료적합성방면구유중요의의.위진일보롱청불동탄기화합물재Si(100)표면적반응궤리,본문응용밀도범함이론방법재B3LYP/6-311 ++G(d,p)//6-31G(d)수평상교위계통지연구료일계렬탄기화합물CH3COR (R=CH3,H,C2H5,C8H5)여Si(100)표면적반응.연구결과표명:불론시[2+2]배가성반응환시α-H렬해반응도대응교저적반응세루(소우25 kJ·mol-1);배가성반응적세루비α-H렬해반응적세루략고;탄기상적취대기대반응세루적영향교소;α-H렬해반응산물위동역학화열역학공제산물;대정동래설,1-위화3-위H원자적렬해반응도비교용역,세루상차흔소,저사결과표명탄기화합물여Si(100)표면적반응장득도다충산물.
Recent studies have demonstrated that a simple ketone [acetone,(CH3)2C=O)] reacts with the Si(100) surface in a [2+2] C=O cycloaddition or by α-H cleavage to form Si-C and/or Si-O σ-bonds.To understand the reactivity of carbonyl compounds bearing different substitutes,the [2 + 2] C=O cycloaddition and α-H cleavage of carbonyl compounds CH3COR (R=CH3,H,C2H5,C8H5) on Si(100) surface have been investigated using density functional theory at the B3LYP/6-311 ++ G(d,p)//6-31G(d) level.Our calculation results reveal that:(1) both cycloaddition and α-H cleavage corresponds to very low energy barriers (lower than 25 kJ-mol-1),and the energy barrier for cycloaddition is slightly higher than α-H cleavage; (2) the substituents on the carbonyl compound [CH3COR] has only a minor influence on the energy barrier; (3) the α-H cleavage reactions are thermodynamically and kinetically more favorable than cycloadditions; (4) for the α-H cleavage of butanone,reactions at C1 and C3 positions are competitive.These findings suggest that the reactions of ketone derivatives with Si(100) surface will generate multiple products.