Supporting Information

Controlled deposition number of organic molecules
using quartz crystal microbalance evaluated by STM
single molecule counting
Eiichi Inami,*,†,‡ Masataka Yamaguchi,† Takayuki Yamaguchi,†Mikio Shimasaki,† and Toyo Kazu Yamada*,†,¶†Department of Materials Science, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba
263-8522, Japan‡School of Systems Engineering, Kochi University of Technology, 185 Miyanokuchi,
Tosayamada, Kami, Kochi 782-8502, Japan¶Molecular Chirality Research Center, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba
263-8522, JapanAUTHOR INFORMATION
Corresponding Author*E-mail: inami.eiichi@kochi-tech.ac.jp; toyoyamada@faculty.chiba-u.jp

Contents
Molecules used for QCM performance check……………………………………………………….………S-2
Monitoring QCM resonant frequency during molecular sublimation……………………………….………S-2

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Molecules used for QCM performance check
The performance of our home-build molecular evaporator and QCM were experimentally confirmed. In theexperiment, two different phthalocyanine molecules [metal-free phthalocyanine (H2Pc), and ironphthalocyanine (FePc)] and six different porphyrin molecules [metal-free tetraphenylporphyrin (H2TPP),
tetrakis(pentafluorophenyl)porphyrin (H2TPFPP), tetrakis (di-tert-butylphenyl)porphyrin (H2TTBPP),
tetraphenylporphyrin iron(III) chloride (FeTPPCl), tetrakis(pentafluorophenyl)porphyrin iron(III) chloride(FeTPFPPCl), and tetrakis(di-tert-butylphenyl)porphyrin iron(III) chloride (FeTTBPPCl)] were sublimatedwith several crucible temperature, and measured their evaporation rates using QCM. Figure S1 shows thechemical structures of the molecules we used in the experiments. H2Pc, H2TPP, H2TPFPP, and H2TTBPP aremetal-free molecules, while FePc, FeTPPCl, FeTPFPPCl, and FeTTBPPCl include Fe atom at the core.

Figure S1: Chemical structures of the two different phthalocyanine (H2Pc, and FePc) and porphyrin(H2TPP, H2TPFPP, H2TTBPP, FeTPPCl, FeTPFPPCl, and FeTTBPPCl) molecules we used in theexperiment.

Monitoring QCM resonant frequency during molecular sublimation
Figure S2(a) presents typical result, showing time dependence of QCM resonant frequency ( f ) measured
during the sublimation of H2TPFPP molecules. The crucible temperature was increased by about every 10min. At each temperature, f was decreased linearly with time under the equilibrium conditions [indicated byarrows in Fig. S2(a)]. One can see that the decrement rate of f becomes larger with crucible temperature. Bytaking slopes of f, df / dt as a function of crucible temperature was evaluated as shown in the upper panel ofFig. S2(b), where the results for the other molecules are also presented. Further, by using Eq. (2) in the main
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text, the rate of the adsorbed molecule number onto the quartz plate per unit area dnQCM/dt were alsoevaluated, as shown in the lower panel of Fig. S2(b). It can be seen that, for each molecules, dnQCM/dt
increases exponentially with the crucible temperature. We confirmed that, for all molecules, the obtained
dnQCM/dt values can be fit by the equation based on the Arrhenius relation as,dnQCMdt ΔH  N 0v exp   RT (1)where N0 is the number of surface molecules,  the attempt frequency, H the enthalpy of sublimation, R thegas constant. The result guarantees that the crucible temperature in our home-build molecular evaporator canbe precisely controlled, and the resulting evaporation rate can be accurately monitored by the QCM.

Figure S2: (a) f variation as a function of time during sublimation of H2TPFPP molecules. (b) Dependenceof the logarithm of df/dt (lower panel) and dnQCM/dt (lower panel) on the inverse of the crucibletemperature. The solid lines in lower panel show fits of the data by Arrhenius equation.

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