In this letter, we demonstrate the control of dipole alignment of monolayer chloroaluminum phthalocyanine (ClAlPc) molecules via the strain in Au (111) substrates. Local ordering of ClAlPc dipole comprising alternate Cl-up and Cl-down configurations is found on the tensile-strained Au(111)/mica as a result of strain-enhanced absorption of Cl-down ClAlPc's and the dipole-dipole interaction. In contrast, the strain-released single crystal Au(111) substrate shows negligible coupling to Cl-down ClAlPc, therefore, facilitating the formation of unidirectionally aligned Cl-up ClAlPc dipole array. The dipole-dipole interaction becomes less prominent at low ClAlPc coverage where ClAlPc molecules can find their favorable absorption sites more easily according to their inherent dipole orientation. Our results emphasize the superior role of molecule-substrate interaction in functional molecular engineering on metal surface hence provide fundamental insight into the potential applications in molecular nanodevices with tunable and controllable properties. V C 2015 AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4918989]Manipulating the two-dimensional (2D) arrangement of functional molecules on a substrate at atomic scale represents one of the most challenging aspects of molecular nanodevice fabrication. 1-4 By tuning the intermolecular, 5-9 molecule-substrate interfacial, 10-13 or substrate-mediated intermolecular interactions, 14,15 one is able to engineer the local ordering of 2D molecular assemblies. Dipolar phthalocyanine molecules, such as chlorogallium phthalocyanine (ClGaPc), 16,17 chloroaluminum phthalocyanine (ClAlPc), 18 vanadyl phthalocyanine (VOPc), 19 titanyl phthalocyanine (TiOPc), 20 and tin phthalocyanine (SnPc), 21 a class of large p-conjugated molecules with intrinsic dipole moment perpendicular to the p-plane, 22 have attracted intensive attention for their prospective applications in molecular nanoelectronics and organic electronics. 23-25 For instance, unidirectionally aligned molecular dipoles can effectively modify the substrate work function and stimulate the charge injection or collection at the molecule-electrode interface. 26,27 Reversible molecular switching (i.e., dipole-up versus dipole-down orientation) has been realized in monolayer ClAlPc, VOPc on graphite, 28,29 VOPc in hydrogen-bonded networks on graphite, 30 and SnPc on Cu(111), 31 which might fuel ultrahigh density information storage eventually. 32 To further expand their applications in molecular nanodevice, it is necessary to develop novel interfacial engineering techniques to manipulate the molecular dipoles on a solid surface. In this letter, the strain mediated dipole alignment of nonplanar ClAlPc on the tensile-strained Au(111)/mica and the strain-released single crystal Au(111) was investigated in situ by low-temperature scanning tunneling microscopy (LT-STM). The tensile strain in Au(111)/mica shifts the metal d bands towards the Fermi level and adjusts the interfacial coupling between ClAlPc and gold. Local ordering of dipole al...