Supplementary Information
Growth of Transition-Metal Cobalt Nanoclusters on 2D Covalent
Organic Frameworks
Toyo Kazu Yamada1, 2*, Shingo Kanazawa1,3, Keisuke Fukutani3, and Satoshi Kera3
1. Department of Materials Science, Chiba University, 1-33 Yayoi-Cho, Inage-ku, Chiba 263-8522, Japan.
2. Molecular Chirality Research Centre, Chiba University, 1-33 Yayoi-cho, Inage-ku, Chiba 263-8522, Japan.
3. Institute for Molecular Science, Myodaiji, Okazaki 444-8585 Japan

Author Information,Corresponding Author: Toyo Kazu Yamada *E-mail: toyoyamada@faculty.chiba-u.jp

S1

Figure S1

Cleaning conditions
Sputter gun

Ar+ sputter
0.8 KV
Anneal880 K~0.2 nm

LEED spots beam energy: 178.9 eVSample

Ar+de

Figure S1. STM/LEED/ARUPS results on a cleaned Cu(111) substrate. (a) STM topographic image (100 ×100 nm2, Vs = -1 V, I = 100 pA) with a height profile along the arrow. (b) Cleaning setup model inside theUHV preparation chamber. A Cu(111) single crystal fixed onto the Mo sample holder with Ta sheet springs
was set into the heating stage inside the preparation chamber. The sputter gun (Ulvac, FIG-5) pointed to thesample surface accelerated Ar ions to the Cu(111) surface and sputtered the surface. After the sputtering,
hot electrons accelerated from the filament located behind the sample holder to the Mo sample plate, which
temperature was monitored using a pyrometer (Japan sensor, FTZ6-P300-10522, spectral range of 0.8-1.6μm, emissivity 0.42). (c) LEED spots with a beam energy (BE) of 178.9 eV/ (d) UPS spectrum. (e) ARUPSspectrum.

S2

Figure S2TBB/Au(001)
2D-SAM film
10 nm2D-SAM film

From TBB to COFs/Au(001)

3 nm

5 nm

COFs

Au(001)anneal
2D-SAM
SAMisland

COFs

Figure S2. .STM imaging on the TBB SAM film growth on Au(001) before and after the thermal annealing.
STM topographic images from left to right: 100 × 100 nm2, Vs = -1.9 V, I = 10 pA; 30 × 30 nm2, Vs = -1.4
V, I = 10 pA; 50 × 50 nm2, Vs = -2 V, I = 10 pA.

S3

Figure S3

Cobalt evaporation conditions

STM image

Ifil =2.50 A
HV: 870 V
Iemi =10 mA
Iflux =10.5 nA
time: 120 sec

LEED ImageUPS Spectrum

XPS Spectrum
Co 2pCo 3d
0.35 eV

2p3/2hν= 1486.6 eV

2p1/2hν= 40.81 eV

777.9 eVFigure S3. Cobalt (Co) deposition process in UHV preparation chamber. (a) sketch of the electronbombardment type Co evaporator. (b) STM topographic image (50 × 50 nm2, Vs = -1 V, I = 1 nA.) of
triangular-shaped Co bilayer islands grown Cu(111). (c) Height profile along the arrow in (b). (d) LEED
spots obtained on the Co deposition on Cu(111). (e) UPS and (f) XPS spectra obtained on the Co deposition
on Cu(111).

S4

Figure S4

Molecule deposition
conditions
Filament: 1.10 A、1.20 V
Rate: 0.155 nm/min
Thickness: 0.131 nm
Crucible temp. T = 391 K
Cu substrate: 300 K

Intro/C

Substrate

Molecule Evaporator

W filament(φ = 0.3)

Quart crucible~10 cmTBB

Thermocouple (type K)

Intermediate state

Final stateBr
Cu atomC

Anneal420 K

HFigure S4. TBB precursor deposition on Cu(111). Molecules were deposited in the UHV introduction
chamber. We used a home-built molecular evaporator using a W wire and a quartz tube. Lower panels denote
Ullmann reaction models of the TBB precursors from the intermediate to the final state.

S5

Figure S5bBE: 27.1 eVRing

7 nm

Spot

8 nm

Figure S5. STM topographic images and LEED spots on COFs / Cu(111) before and after the post-annealing
to 430 K. Left side: STM image: 35 × 35 nm2, Vs = 2 V, I = 10 pA. Right side: STM image: 40 × 40 nm2, Vs= 2 V, I = 10 pA.

S6

Figure S6-1.5-1.0-0.5

0.0-1.5-1.0

0.0

-0.5

-1.5

-1.0

-0.5

0.0

Wave number (Å-1)

Figure S6. Angle-resolved UPS maps, from left to right, obtained on the bare Cu(111), COFs / Cu(111)
before and after the post-annealing. Insets denote LEED spots.

S7

Figure S7()g

TBB HOMO
2.2 eV

(Å-1)

(Å-1)

(Å-1)

Figure S7. Angle-resolved UPS maps in differential mode, from left to right, obtained on the bare Cu(111),
COFs / Cu(111) before and after the post-annealing. Insets denote LEED spots.

S8

Figure S8Carbon 1s

Intensity (arb. units)

Co deposition

Co / TBB (0.4 nm)
Annealed TBB (1.6 nm)
TBB (1.6 nm)
Annealed TBB (0.8 nm)
TBB (0.8 nm)
TBB (0.4 nm)

Binding energy (eV)Figure S8. XPS spectra for the C 1s peak obtained at the molecular thicknesses of 0.4 nm (purple and bluelines), 0.8 nm (green and light-green lines), and 1.6 nm (red and pink lines). The spectra for “as grown”(red., blue, green), “annealed” (light-green and pink), and Co deposition on TBB samples are shown. The
vertical lines are shown to indicate the approximate positions of each of the peaks. The intermediate state
before the annealing includes C-Cu-C bonding, but the final state consists of C-C covalent bonding.

S9