Supplementary Information
Room temperature stable ﬁlm formation of -conjugated organic
molecules on 3d magnetic substrate
Eiichi Inami1,*, Mikio Shimasaki2, Hideki Yorimitsu3 & Toyo Kazu Yamada1,4,†1

Graduate School of Science and Engineering, Chiba University,
1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan,

2

Graduate School of Advanced Integration Science, Chiba University,
1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan,

3

Department of Chemistry, Graduate School of Science, Kyoto University,
Kitashirakawa, Oiwakecho, Sakyo-ku, Kyoto 606-8502, Japan,4Molecular Chirality Research Center, Chiba University,
1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan,*†

e_inami@chiba-u.jp
toyoyamada@faculty.chiba-u.jp
1Supplementary Figure 1. H2Pc film on Fe(001). STM topography image (55 nm × 55 nm, Vs= –2.0 V,
It = 500 pA) of H2Pc film on Fe(001) without drift compensation. To reduce the image distortion due to thethermal drift, the rectangular region was extracted and then stretched vertically, obtaining the image of Fig.
2(b) in the main manuscript.

Supplementary Figure 2. Sketch of the proposed molecular arrangement of H2Pc film. The
model was proposed under the assumption that the second-layer molecules are adsorbed with type A
configuration (see main manuscript). This model is not energetically favorable due to the repulsive H-Hinteractions between benzene groups of neighboring molecules. The model with type B configuration (seemain manuscript), which is energetically favorable, is shown in the main manuscript.
2Supplementary Figure 3. Sequential STM images of H2Pc molecules on Fe(001). (a)-(d)Sequential STM image of H2Pc single molecules on Fe(001) (20 nm × 20 nm, Vs= -1.0 V, It = 200 pA).
(e)-(g) Sequential STM image of H2Pc molecular films on Fe(001) (Vs= -2.0 V, It = 200 pA). The size of each
image is 100 nm × 100 nm, (e), 50 nm × 50 nm, (f)-(g), 83 nm × 83 nm, (h). The dashed circles in (e)-(h)mark the identical area.

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Supplementary Figure 4. Structural ball-stick model of the H2TPP molecule. (a) top view, (b)side view.

Supplementary Figure 5. STM images of H2TPP films on Au(111) surface. (a) STM topography
image of H2TPP monolayer films on Au(111) surface at 78 K (75 nm × 75 nm, Vs = 1.4 V, It = 30 pA).
Molecular films, labeled A, B, and C, are in three-fold symmetry. The inset shows the expanded scale imageof film A. (b) Expanded scale image of film B. (c) Topographic height profile along the blue line in (b).

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Supplementary Figure 6. Atom-resolved STM images of H2TPP film on Au(111) surface. (a)STM topography image of H2TPP monolayer films on Au(111) surface acquired at 78 K (20 nm × 10 nm, Vs= 1.3 V, It = 77.5 pA). (b) Expanded scale image of the rectangular area in (a), showing the atomicarrangement of Au(111) surface. (c) 2D fast Fourier transformed image of (b). Bright spots surrounded bycircles attribute to the hexagonal lattice of the Au(111) substrate.

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Supplementary Figure 7. Continuous STM images of H2TPP films on Au(111). (a)-(c) were a setof continuous images acquired at 78 K (22 nm × 15 nm, Vs= 1.4 V, It = 130 pA), while (d)-(f) were the otherset of images acquired at 300 K (15 nm × 11 nm, Vs = 1.3 V, It = 40 pA).

6Supplementary Figure 8. H2Pc distributions on Fe(001) simulated by kinetic Monte Carlomethod. Desorption probability D was set as follows: (a) Di (1st) = 15 %, Di (2nd) = 20 %, Di (3rd) = 25 %.
(b) Di (1st) = 10 %, Di (2nd) = 15 %, Di (3rd) = 20 %, (c) Di (1st) = 7 %, Di (2nd) = 12 %, Di (3rd) = 17 %, (d) Di(1st) = 5 %, Di (2nd) = 10 %, Di (3rd) = 15 %, (e) Di (1st) = 2 %, Di (2nd) = 7 %, Di (3rd) = 12 %. The otherparameters were set to be the same values as in Table I in Main manuscript.
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Supplementary Figure 9. H2Pc distributions on Fe(001) simulated by kinetic Monte Carlomethod. Hopping rate of the second layer molecules Wi = 1,2,3,4 were set as 10, (a), 20, (b), 30, (c), 40, (d), 50,(e). Hopping rate of the third layer molecules Wi = 1,2,3,…,8 were set as 30, (a), 40, (b), 50, (c), 60, (d), 70, (e).
The other parameters were set to be the same values as in Table I in Main manuscript.

8Supplementary Figure 10. H2Pc distributions on Fe(001) simulated by kinetic Monte Carlomethod. Hopping rate of the second layer molecules Wi = 1,2,3,4 and the third layer molecules Wi = 1,2,3,…,8 wereset as 30 and 50, respectively. Wi = 5,6,7,8 of the second layer molecules were set as 1, (a), 2, (b), 3, (c), 4, (d), 5,(e). The other parameters were set to be the same values as in Table I in Main manuscript.

9Supplementary Method 1: Extracting Consecutive STM images at the same area
Due to the lateral thermal drift, the consecutive STM imaging results in the shift of the imaging area. Toaddress this issue, we carried out the following procedures. First, during the STM imaging, we estimatedroughly the directions of the lateral thermal drift, that is, we checked which directions the image area shifts
at every imaging. Based on the obtained information on the lateral drift direction, we could intentionallychange the imaging area to reduce the effect of the image shift. By this procedure, the particular morphologyof the single molecules or the molecular films can be traced (see Supplementary Figure 3). Second, based on
the obtained STM images, the overlap regions (indicated by the rectangular areas in Supplementary Figure 3)
have been analytically evaluated, and then, extracted from the images. The extracted areas of initial images[Supplementary Figure 3(a) and (e)] and final images [Supplementary Figure 3(d) and (h)] were highlightedin Fig. 3 of the main manuscript.

Supplementary Method 2: Preparation of H2TPP film on Au(111)
A single crystalline Au(111) substrate was subjected to several cycles of Ne+-ion sputtering (+1.0 kV, 10min) and subsequent annealing (800 K, 10 min) in the sample preparation chamber, by which cleaned andatomically-flat surface was obtained. The H2TPP powder (see Supplementary Figure 4) located in a crucible
was first degassed at 443 K for 5 min, and then, deposited onto the clean Au(111) surface. During thedeposition process, the temperature of the crucible and the Au(111) substrate was maintained at 443 K and at
300 K, respectively. No annealing of the substrate was performed after deposition.

Supplementary Method 3: STM measurements
The H2TPP film on Au(111) was characterized by STM measurements at 78 K and 300 K. The imaging wasperformed in the constant current mode. Electrochemically etched W-tips (= 0.3 nm, purity 99.99 %) were
carefully cleaned up by annealing in the load-lock chamber prior to use. Bias voltage was applied to thesample with respect to the tip being held at virtual ground potential. Tunneling current was detected from thetip.

Supplementary Note 1: STM characterization of H2TPP film on Au(111) at 78 K
A low-temperature (78 K) STM measurement first confirmed that the H2TPP molecules organize 2D orderedsquare lattice on bare Au(111) surface where the herringbone reconstruction was clearly resolved [seeSupplementary Figure 5(b)]. The H2TPP monolayer films were rotated by 120 deg. with respect to each otherowing to the threefold symmetry of the Au(111) surface [see Supplementary Figure 5(a)]. The matrix
notation of the molecular superstructure was obtained as10 6  2 2 6 with respect to the Au(111) unit cell (see Supplementary Figure 6). The image analysis also revealed that theH2TPP monolayer height from the Au(111) surface was approximately 0.22 nm [see Supplementary Figure5(c)], which is almost equal to the case of the H2Pc/Ag(001) system [1]. These features indicate that theH2TPP molecules are physisorbed on the Au(111) substrate, which enables diffusion and the following filmformations.

Supplementary Note 2: Thermal stability of H2TPP film on Au(111) substrate
To check the stability of the H2TPP monolayer film on Au(111) substrate, we performed the continuous STM
imaging, in the same manner as that of H2Pc film (Fig. 3 in the body of the manuscript or SupplementaryMethod 1). Supplementary Figure 7 shows the sequential STM images of the H2TPP monolayer film on theAu(111) substrate acquired at 78 K, (a)-(c), and 300 K, (d)-(f), respectively. At 78 K, the H2TPP film
maintained the molecular arrangement and the edge feature. At 300 K, however, the edge changed
remarkably with time. Furthermore, we observed considerable noise at the Au(111) terrace, which is anindication for interactions between the tip and the moving molecules [2]. This result clearly indicate that themobility of the molecule on this surface is enough large at RT, where adsorption and desorption of themolecules at the film edges, i.e. film growths and collapses, are steadily induced. These results clearlyindicate that the H2TPP film cannot exist stably on Au(111) surface at RT.

Supplementary References
1.

Yamada, T. K., Yamagishi, Y., Nakashima, S., Kitaoka, Y. & Nakamura, K. Role of -d hybridization in
300-K organic-magnetic interface: metal-free phthalocyanine single molecules on bcc Fe(001)-whisker.
Phys. Rev. B 94, 195437 (2016).

2.

Naitoh, Y., Matsumoto, T., Sugiura, K., Sakata, Y. & Kawai, T. Self-assembled stripe structure of zinc–phthalocyanine on graphite surfaces. Surf. Sci. 487, L534–L540 (2001).

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