Cossaro Albano, Terreni Silvana, Cavalleri Ornella, Prato Mirko, Cvetko Dean, Morgante Alberto, Floreano Luca, Canepa Maurizio
CNR-INFM Laboratorio Nazionale TASC, Basovizza SS-14, Km 163.5, I-34012 Trieste, Italy.
Langmuir. 2006 Dec 19;22(26):11193-8. doi: 10.1021/la061833r.
We have studied the vapor-phase deposition of L-cysteine on the Au(110) surface by means of synchrotron-based techniques. Relying on a comparison with previous X-ray photoemission analysis, we have assigned the fine structure of the C K-shell X-ray absorption spectra to the nonequivalent carbon bonds within the molecule. In particular, the C1s --> sigma* transition, where the sigma* state is mainly localized on the C-S bond, is shifted well below the ionization threshold, at approximately -5 eV from the characteristic pi* transition line related to carboxylic group. From the polarization dependence of the absorption spectra in the monolayer coverage range, the molecules are found to lay flat on the surface with both the C-S bond and the carboxylic group almost parallel to the surface. We performed in situ complementary surface X-ray diffraction, SXRD, measurements to probe the rearrangement of the Au atoms beneath the L-cysteine molecules. Since the early stage of deposition, L-cysteine domains are formed which display an intermediate fourfold symmetry along [001]. The self-assembly of molecules into paired rows, extending along the [1(-)10] direction, is fully compatible with our observations, as has been reported for the case of D-cysteine molecules grown on Au(110) [Kühnle, A. et al. Phys. Rev. Lett. 2004, 93, 086101.]
我们借助基于同步加速器的技术研究了L-半胱氨酸在Au(110)表面的气相沉积。通过与之前的X射线光电子能谱分析结果进行比较,我们将C K壳层X射线吸收光谱的精细结构归因于分子内不等价的碳键。特别是,C1s→σ跃迁(其中σ态主要定域在C-S键上)的能量明显低于电离阈值,相对于与羧基相关的特征π*跃迁线大约低5 eV。从单层覆盖范围内吸收光谱的偏振依赖性可知,分子在表面平躺,C-S键和羧基几乎都与表面平行。我们进行了原位互补表面X射线衍射(SXRD)测量,以探测L-半胱氨酸分子下方Au原子的重排情况。从沉积初期开始,就形成了L-半胱氨酸畴,这些畴沿[001]方向呈现出中间四重对称性。分子自组装成沿[1(-)10]方向延伸的成对行,这与我们的观察结果完全相符,正如在Au(110)上生长的D-半胱氨酸分子的情况所报道的那样[库恩勒,A.等人,《物理评论快报》,2004年,93卷,086101] 。