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Title

Metal‑Organic Coordination Network Thin Film by
Surface‑Induced Assembly

Author(s)Laokroekkiat, Salinthip; Hara, Mitsuo; Nagano,
Shusaku; Nagao, Yuki

Citation

Langmuir, 32(26): 6648‑6655

Issue Date

2016‑06‑21

Type

Journal Article

Text version

author

URL

http://hdl.handle.net/10119/14269

RightsSalinthip Laokroekkiat, Mitsuo Hara, Shusaku
Nagano, and Yuki Nagao, Langmuir, 2016, 32(26),pp.6648‑6655. This document is the unedited
author's version of a Submitted Work that was
subsequently accepted for publication in
Langmuir, copyright (c) American Chemical Society
after peer review. To access the final edited andpublished work, see
http://dx.doi.org/10.1021/acs.langmuir.6b01251

Description

Japan Advanced Institute of Science and Technology

Metal-Organic Coordination Network Thin Filmby Surface-Induced Assembly

Salinthip Laokroekkiata, Mitsuo Harab, Shusaku Naganoc, Yuki Nagaoa*aSchool of Materials Science, Japan Advanced Institute of Science and Technology,
1-1 Asahidai, Nomi, Ishikawa, 923-1292, Japanb

Department of Molecular Design & Engineering, Graduate School of Engineering,
Nagoya University, Furo-cho, Chikusa, Nagoya, 464-8603, Japanc

Nagoya University Venture Business Laboratory, Nagoya University, Furo-cho,
Chikusa, Nagoya, 464-8603, JapanKEYWORDS: Porphyrin, Self-assembly, Multilayer thin film, Surface-Induced Assembly(SIA), Organized structure1

ABSTRACTThe growth of metal-organic coordination network thin films on surfaces has been pursued
extensively and intensively to manipulate the molecular arrangement. For this study, theoriented multilayer thin films based on porphyrinic nano-architecture were synthesized
toward metal-organic coordination networks using surface-induced assembly (SIA).
Nanoscale molecular thin films were prepared at room temperature using cobalt(II) ion andporphyrin building blocks as precursors. Stepwise growth with a highly uniform layer wascharacterized using UV-Vis, AFM, IR, and XPS studies. The grazing incidence small angle
X-ray scattering (GI-SAXS) and X-ray reflectivity (XRR) results remarkably suggested aperiodic structure in in-plane (IP) direction with constant and high mass density (ca. 1.5
g/cm3) throughout the multilayer formation. We propose that orientation of the porphyrin
macrocycle plane with a hexagonal packed model by single anchoring mode was tilted
approximately 60° with respect to the surface substrate. It is noteworthy that the wellorganized structure of porphyrin-based macrocyclic framework on the amine-terminatedsurface substrate can be achieved efficiently using a simple SIA approach under mild
synthetic conditions. The synthesized thin film provides a different structure from thatobtained using bulk synthesis. This result suggests that the SIA technique can control not
only the film thickness, but also the structural arrangement on the surface. This report of ourresearch provides insight into the ordered porphyrin-based metal-organic coordination
network thin films, which opens up opportunities for exploration of unique thin film materials
for diverse applications.

21. INTRODUCTION
Nanostructural materials have been developed continuously because of their higher efficiency
than that of conventional materials.1 The engineering of nanomaterials onto the surface ispromoted more progressively via the concept of coordination chemistry and surface science.2
However, the control of structural arrangement at a nanoscale level is a crucially importantand highly challenging aspect of these materials.
Metal-Organic Frameworks (MOFs)3, 4 are hybrid porous materials composed of a metalcluster connecting with organic linkers. The potential of MOFs is exploited in widely diverse
applications including gas adsorption and separation, sensing, optoelectronic, biomedical andcatalysis.5 Thin film assembly techniques for MOFs are necessary to apply to various devices
with these applications. The fabrication of MOF thin films on the surface is described using
various methods including Layer-by-Layer (LbL) (also Liquid Phase Epitaxy, LPE)6,
Langmuir-Blodgett (LB), microwave, colloidal, electrochemical deposition, inkjet, spraycoating5 and spin coating.7 Among these methods, LbL is a widely used solution-based
fabrication process for control of the generation of the multilayer nanostructure on a surface
substrate.8, 9 Wöll, Fischer and co-workers introduced the LbL method to generate MOF films
on surface.10, 11 The particular MOF thin films in multilayer fashion with nanometer range arerecently referred to surface-attached Metal-Organic Frameworks (SURMOFs). The
SURMOFs are particularly beneficial because of their highly oriented structure,homogeneous morphology with a smooth surface, precisely controllable thickness via
deposition cycle, and less defective framework than bulk synthesis.12
Porphyrin is a fascinating candidate for use as a linker backbone in molecular networks.
The various functional properties of porphyrin-based materials have been reported, including
photosensitizing, optoelectronic, magnetic, molecular recognition, selective gas sorption, andcatalytic properties.13, 14 Numerous bulk porphyrin-based MOFs have been studied, while the3thin films have been less explored.15 Recently, porphyrin-based MOFs thin films on substrate
have been more investigated by Kitagawa and Hupp groups.16, 17
Molecular ordering and the alignment direction in the thin film play significant role for thematerial performance. For example, the edge-on orientation of molecular binding on thesurface is preferred for FET devices, whereas the face-on orientation is desirable forphotovoltaic devices such as solar cells. Consequently, the determination of molecularalignment is necessary to clarify the appropriate application. The strategy to control thearchitectures is extremely important. At this point, Surface-Induced Assembly (SIA) is
considered for this achievement. Sequential immobilization between metal ion and organic
building units on the surface can promote variation of the coordination network structures ina controllable manner. This stepwise growth phenomenon is dissimilar to that of bulk, forwhich the coordination is simultaneously driven. From this aspect, novel structures on thesurface can be discovered using this approach. Synergistic concern between the structuralarrangement and the material properties presents a challenging issue for breakthrough in therequired utilizations.
In this work, we demonstrated that sequential coordination from a surface substrate createsa new molecular assembly structure. The structure differs greatly from bulk system. We
fabricated metal-organic coordination network multilayer from metal ions (Co2+) anddeprotonated free-base porphyrin (H 2 TCPP4-) using the sequential coordination from theamine-modified surface substrate. Systematic characterization of the multilayered film using
optical spectroscopy and X-ray photoelectron spectroscopy (XPS) revealed ideally sequential
growth of the coordination network structure. Moreover, the coordination network structureof the multilayered film produced by sequential surface growth was characterized using Xray scattering. It was completely dissimilar to the bulk structure obtained from conventional
synthesis.

42. EXPERIMENTAL
2.1 Materials
Silicon wafer (100, p-type) substrates were purchased from Electronics and Materials Corp.
Ltd. Quartz substrates were purchased from Sendai Sekiei Glass Seisakusho Y.K.. Bothsubstrates were used for SIA deposition. 3-Aminopropyltrimethoxysilane (APTMS, >96%)
was purchased from Tokyo Chemical Industry Co. Ltd. (TCI). 5,10,15,20-Tetrakis(4carboxyphenyl)-porphyrin (H 2 TCPP) (purity 98%) was purchased from Strem Chemical Inc.,
USA. Cobalt(II) acetate tetrahydrate (Co(OAc) 2 .4H 2 O) was purchased from Wako Pure
Chemical Industries Ltd. HPLC and AR grade of 2-propanol and ethanol were used forsurface modification. Chloroform (CHCl 3 ), methanol and 2-propanol as super dehydrated
solvents (low water content; (≤ 0.001% or 10 ppm)) were used with a syringe to prepare
solutions for SIA deposition. All solvents were purchased from Wako Pure Chemical
Industries Ltd. All chemicals were used as received without further purification.
2.2 Modification of Surface Substrate with Silane Coupling Agent (APTMS)
Before use, silicon wafer substrates (40×25 mm2) and quartz plate substrates (25×15 mm2)
were cleaned using 2-propanol two times with sonication for 10 minutes. Then they weredried immediately and kept on a clean bench. To obtain the amine-functionalized substrates,allcleanedsubstrates

wereimmersed

in

10

mM

ethanolsolutionof3-aminopropyltrimethoxysilane (APTMS) at room temperature for 1 hour under argon
atmosphere with mild shaking. Then, all substrates were washed respectively with ethanol (2times), 2-propanol (2 times), and dried. All APTMS-modified substrates were kept in argon
atmosphere until use.
2.3 Fabrication of Multilayer Porphyrin-based Coordination Networks on AmineFunctionalized Substrate5

To fabricate the multilayer porphyrin-based coordination networks on modified substrates,
the SIA method was used via an LbL automated machine. The APTMS-modified substrates
were used for all SIA experiments with the following procedures under argon atmosphere: (i)the modified substrates were immersed into 10 mM Co(OAc) 2 .4H 2 O in the mixture solventof super dehydrated methanol and chloroform (1:9, v/v) for 10 minutes and were then rinsed
with four separated containers of the same ratio mixture solvent as those described above foreach 1 minute washing to remove leftover reactants from the surface and were dried byblowing. (ii) then, the metal-terminated substrates were immersed into 0.11 mM H 2 TCPP in
2-propanol for 10 minute following the same washing procedure in 2-propanol. The firstlayer of coordination networks has been generated. The further growth of the multilayer wascontrolled by repeating the above procedure (Scheme 1). The desired number of layers
according to the alternate deposition of metal ion (Co(II)) and organic linker (H 2 TCPP)
solution is shown as the “N” layers, denoted as (Co/ H 2 TCPP) N .

6

Scheme 1.

Schematic representation of the surface-induced assembly (SIA) process tofabricate porphyrin-based metal-organic coordination network thin films

2.4 Characterization Techniques
UV-Visible absorption spectra of the multilayer film on quartz substrates were measured as afunction of number of layers in absorption mode using a spectrophotometer (V-630; Jasco
Corp.) at room temperature. The APTMS-modified quartz was used as a background to
subtract from each spectrum.
X-ray reflectivity (XRR) was use to ascertain the film thickness, roughness and massdensity of the thin film using a high-resolution X-ray diffractometer (ATX-G; Rigaku Corp.).
The diffractometer was equipped with a Cu Kα radiation source (λ= 0.1542 nm). The X-rays
were generated from a Cu rotating anode (50 kV, 300 mA). The reflective oscillation spectrafrom the experiment were fitted using software (GXRR; Rigaku Corp.). The fitting curve7was varied from 0.2° to 3°. The difference of the fringe between SAM layer (APTMS) and Si
wafer could not be observed (Figure S5). Essentially, the thickness of the SAM layer had
little effect on the overall thickness of thin films. Therefore, the thickness of APTMS and thinfilm has been estimated as a single layer model.
An atomic force microscope (AFM) with tapping mode was utilized to investigate thesurface morphology and roughness of thin film. AFM images were collected using a digital
AFM system (Nanoscope IIIa; Veeco Instruments). Silicon cantilevers (SI-DF3FM;
Nanosensors Corp.) with a spring constant between 2.8 N/m and 4.4 N/m and a resonancefrequency of 79-89 kHz were used. The measurement was proceeded under air atmospherewith a scan rate of 0.4 Hz and scanned area of 1×1 µm2.
The thickness measurement was conducted using AFM (VN-8000; Keyence Co.) with
DFM/SS mode cantilever (OP-75041; Keyence Co.). Prior to measurement, the thin film on
Si wafer substrate was removed by sharp blaze without damaging the hard substrate surface.
The analysis was done across the scratched line in at least five different positions to estimate
the average film thickness.
Fourier-transform infrared attenuated total reflectance (FTIR-ATR) was handled to obtainthe molecular vibration of chemical bond in chemical precursors and the bulk sample. The IR
spectrum was acquired using an FT-IR spectrometer (Nicolet 6700; Thermo-Fisher
Scientific) equipped with a deuterated triglycine sulfate (DTGS) detector. All spectra wererecorded with 64 scans and 4 cm-1 resolution. Infrared p-polarized multiple angle incidence
resolution spectroscopy (p-MAIRS)18, 19 was used to clarify the molecular vibration ofchemical bond in both of in-plane (2×IP) and out-of-plane (OP) orientation of thin film
sample. The p-MAIRS measurements were conducted on a FT-IR spectrometer (Nicolet
6700; Thermo-Fisher Scientific) equipped with a mercury-cadmium-telluride (MCT) detector.
Single-beam spectra were collected from 38° to 8° by means of 6° steps in a range of angle of8

incidence with 64 scans and 4 cm-1 resolution. The aperture was fully opened (size of 150). A
metal plate with small pores was placed in the light path of the incident beam to prevent
saturation. A ZnSe polarizer was used to obtain the p-polarized light. The APTMS-modified
silicon wafer substrate was used as a background in p-MAIRS measurement. All p-MAIRS
measurements were done under N 2 atmosphere at room temperature.
X-ray photoelectron spectroscopy (XPS) was used to determine the elemental compositionof thin film on Si wafer and bulk sample on carbon tape. The XPS experiment was conductedusing a spectrometer (Axis-Ultra DLD; Kratos Analytical Ltd.) with an Al Kα radiation
source (1486.6 eV). The binding energies were calibrated using C1s peak at 284.5 eV as astandard. Curve fitting was performed by processing software (Vision) using a Gaussianenvelope with Shirley background correction.
Powder X-ray diffraction (PXRD) was used to investigate the crystalline properties of asynthesized bulk sample. Measurement was carried using a high-resolution X-ray
diffractometer (ATX-G; Rigaku Corp.) equipped with a Cu Kα radiation source (λ= 0.1542
nm.) at the step size of 0.02°.
Grazing incidence small angle X-ray scattering (GI-SAXS) measurement was performed toobserve the thin film interior structure. Measurement was taken using X-ray diffractometer(FR-E; Rigaku Corp.) with two-dimensional (2D) detector (R-AXIS IV; Rigaku Corp.). The
sample stage included the goniometer and a vertical stage (ATS-C316-EM/ALV-300-HM;
Chuo Precision Industrial Co. Ltd.). The Cu Kα radiation source (λ= 0.1542 nm.) with beam
size of approx. 300 µm  300 µm and camera length of 300 mm was used. The angle ofincidence was varied from 0.21° to 0.22°. The diffraction patterns of in-plane and out-ofplane directions were obtained.

3. RESULTS AND DISCUSSION

9

3.1 Investigation of Step-by-Step Multilayer Growth
Porphyrinic compounds exhibit characteristic absorption in the UV-Vis region as known as
soret band (B-band) and Q-bands, which are useful to follow the multilayer growth of thinfilm using UV-Vis spectroscopy.20 The UV-Vis absorption spectra on the transparent quartz
substrate displayed the typical intense soret band at 418 nm along with four weak Q-bands at
500-700 nm (Figure 1a). The absorbance increased linearly with the number of depositedlayers, which was ascribed to the sequential growth of the multilayer film20 (Figure 1b).
Figure 2 shows the film thickness by XRR and AFM measurements along with the layer
growth.21, 22 Both results are well consistent. Thickness exhibited a linear increase with layer
growth. The average thickness per layer was ca.1 nm. Figure 3 shows that the topological thinfilm exhibited smooth and homogeneous morphology. These results demonstrate to theadvantage of the controllable film growth by SIA.

a)b)

Figure 1. (a) UV-Vis absorption spectra of multilayer thin films as a number of depositedlayers (Co/H 2 TCPP) 1-15 on the APTMS-modified transparent quartz substrate. (b) The UV-

10Vis absorption intensity of the soret band at 418 nm and Q 1 -band at 526 nm as a number ofdeposited layers.

a)b)

Figure 2. (a) XRR profiles of multilayer films (Co/H 2 TCPP) 5 , (Co/H 2 TCPP) 10 , and(Co/H 2 TCPP) 15 on the APTMS-modified Si-wafer substrates. Experimental and fitted data
are shown respectively as dashed line and solid line. (b) Thickness of multilayer film
comparing between XRR and AFM study with the error bar.

11

a)

b)

c)

Figure 3. (a) 2D, (b) 3D AFM height image, and (c) section analysis of (Co/H 2 TCPP) 5 ,(Co/H 2 TCPP) 10 and (Co/H 2 TCPP) 15 on the APTMS-modified Si wafer substrate
respectively; Scan size = 1µm × 1µm ; Data scale 20 nm.

3.2 Determination of Coordination Networks
p-MAIRS was used to investigate the molecular vibration of chemical bonds in both IP and
OP vibrational modes in thin film.18, 19 The p-MAIR spectra are shown in Figure 4a and 4cwith corresponding to the number of layers. The intense peaks at 1600 and 1400 cm-1 were
attributed respectively to asymmetric and symmetric stretching of carboxylate (O−C=O) inthin film.17, 23, 24 These observations provided the clear evidence for the deprotonation of12carboxylic group (COOH) upon assembly with cobalt ion. These results supported thecoordination networks by SIA. Furthermore, the absorbance increased linearly with thenumber of deposited layers in both IP and OP spectra, which implied the well-growth
behavior along with multilayer formation (Figure 4b and 4d).
a)

c)

b)

d)

13

Figure 4. p-MAIR spectra of multilayer film as a number of deposited layers (Co/H 2 TCPP) 5 ,(Co/H 2 TCPP) 10 and (Co/H 2 TCPP) 15 on the APTMS-modified Si wafer substrates in (a) Inplane (2×IP) and (c) Out-of-plane (OP).

Figure S7 shows that the XPS survey scans of multilayer film have been primarily
examined. The systematic analysis of XPS results was considered with respect to themultilayer film formation. The attenuation trends of Si2p and O1s peak intensities fromsubstrate signal and the increment of N1s, C1s, and Co2p after layer deposition indicated thegrowth of coordination networks on the substrate. Figure 5 and S8 show the fine scan spectrawith deconvolution.

Figure 5. Deconvolution of Co2p spectra of (Co/H 2 TCPP) 10 .

For C1s spectra, the fitted peak result showed the presence of COO- species at 288.1 eV,
while the COOH species at 289.4 eV was less observed (Figure S8c).25, 26 This result shows
good agreement with the carboxylate feature from IR spectra. The peaks of Co2p 3/2 and14

Co2p 1/2 were located at 781.1 and 796.9 eV, respectively27, 28 along with the presence of thetwo strong satellite peaks of cobalt at 784.9 and 802.2 eV, representing the oxidation state ofcobalt ion as +2 (Figure 5).29, 30, 31 Furthermore, no difference in Co2p spectra was observed,
indicating that the cobalt oxidation number was not changed during fabrication process. The
results show the coordination network between cobalt ion and H 2 TCPP.

3.3 Structural Alignment of Coordination Networks by SIA
Figure 6a and Table S10 respectively present the PXRD and d-value of three peaks in thebulk sample ((Co/H 2 TCPP) Bulk-2 ). These results suggest that not only the crystalline phase(sharp peaks), but also the amorphous phase (broad peaks) are obtainable in this bulk system.
The GI-SAXS profiles and d-value of thin film were taken32 as shown in Figure 6 and Table
S7, respectively. The peak positions of the thin films were completely different from that of
the bulk, probably because of the dissimilarity in growth mechanisms or moleculararrangements during network formation on the surface by SIA. In the IP direction, the firstweak diffraction peak with a d-value of around 1.9 nm was observed in all thin films.
However, the broad and weak peaks indicate the presence of the low degree of molecularordering. The improvement of molecular ordering in thin films occurred with increasing
number of layers. The growth behavior in multilayer films represented high reproducibility
with anisotropic properties. We systematically considered the possible structure of thin filmon the surface using XRR, AFM, and GI-SAXS results. Particular attention was devoted tofour para-carboxyphenyl structures of porphyrin, as shown in Figure 7. It was highly possible
to bind at the surface with one or two carboxyl groups33, 34, whereas the four binding points(parallel or face-on; Figure 7(a)) were less possible because of the difficulties of coordinationgeometry between cobalt ion and four para-carboxyl groups. Consequently, the single anddouble anchoring modes can be proposed (Figure 7 (b), (c), (d) and (e)). We further

15

considered the molecular packing of porphyrin. The double-anchor binding mode (Figure7(c) and (e)) provides more fixable binding geometry on the surface. This geometry mightengender more random arrangement than that provided by the well-organized structure. In
contrast, the single-anchor binding mode can freely rotate on the surface, suggesting thepossibility for hexagonal packing (Figure S9). Base on the above proposal, we proved thisconcept by calculation through considering of the porphyrin dimension with cobalt binding
moiety that the diameter for its rotation is expected to be ca. 2.2-2.3 nm. Figure S9(c) showsthat this proposed model was well supported by the IP diffraction peak of GI-SAXS with a dvalue of 1.9 nm. The perpendicular (or edge-on) arrangement of single-anchor configuration(2.3 nm) (Figure 7(b)) was discarded because of the higher repeating length of porphyrin unit
than the experimental thickness per layer (1 nm) from XRR and AFM analysis (Table S8).
Therefore, the tilting growth with respect to the surface may dominate the structure (Figure7(d)). The tilting angle can be calculated based on thickness from XRR approximately 60°
with respect to the surface normal (Table S9 and Figure S10(a)). This result agrees well withsome reported tilted porphyrin arrays of thin films.21, 35-38

16

a)

c)

b)

d)

Figure 6. (a) PXRD pattern of bulk ((Co/H 2 TCPP) Bulk-2 ), (b) 2D GI-SAXS profile ofmultilayer film (Co/H 2 TCPP) 5 , (Co/H 2 TCPP) 10 and (Co/H 2 TCPP) 15 on the APTMS-

17

modified Si wafer substrates. (c) and (d) 1D GI-SAXS profiles in in-plane (IP) and out-ofplane (OP), respectively.

Figure 7. The different molecular models aligned on surface with repeating length (nm) of
porphyrin unit with cobalt coordination as denoted as (a) parallel, (b) perpendicular withsingle-anchor (trans-), (c) perpendicular with double-anchor (cis-), (d) tilt with single-anchor(trans-) and (e) tilt with double-anchor (cis-). The cobalt atom has been omitted from thescheme for the clarity.

In this coordination network system, the well-organized structure and unique thin film on
the surface can be effectively achieved using SIA approach even in room temperature
conditions. Results suggested that the SIA technique has a powerful ability to control not
only the film thickness, but also the structural arrangement on the surface. The structuraldissimilarity between the bulk and thin film occurs because of the contribution from SIA
method. The step-by-step growth between organic building unit and metal ion on the surface
can provide controllable structures. These phenomena are distinct from the bulk situation, forwhich the coordination architecture between organic molecule and metal ion can occur
concurrently. The SIA approach can contribute efficiently to building up of the variety of18

molecular conformations. Consequently, novel structures on the surface can be expected andexplored using this assembly technology. The design of metal-organic coordination network
thin film with controllable growth behavior persists as an important challenge that must be
addressed to promote these solid state phenomena for nanoscale device. The interior
perspective for the molecular growth manner is highly necessary to elucidate the growthmechanisms along with the development of material properties for specific applications.

4. CONCLUSIONS
The aligned porphyrin-based multilayer film on the substrate can be afforded efficiently
through the metal-organic coordination networks using cobalt ion and porphyrin precursors.
The thin film growth was controllable using a potential bottom-up approach such as SIA atroom temperature with no catalyst. Stepwise growth with compact packing and homogeneous
surface was effectively feasible. The mass density of film was almost constant throughout themultilayer structure along with the presence of periodic structure, indicating a well-organizedstructure of film growth. The alignment of the porphyrin macrocycle plane of the frameworkhas been proposed as a hexagonal packed model using single-anchor binding with tilting ofapproximately 60° relative to the surface substrate. The structure of the synthesized thin film
was distinct from the bulk synthesis, which suggests a significant role of the surface for thecoordination network formation. This technique of nanostructure fabrication on the surface
provides high probability to promote the unique structure and develop the material properties
for the desirable applications.

19

ASSOCIATED CONTENTS
Supporting Information.
Supporting information provides additional details including those related to the following:
UV-Vis, XRR, AFM, FTIR, XPS, GI-SAXS, structural alignment on surface, the reported
porphyrin network, and synthesis and characterization of bulk samples ((Co/H 2 TCPP) bulk ).
These materials are available free of charge via the internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author* E-mail: ynagao@jaist.ac.jp Phone: +81-761-51-1541.
Notes
The authors have no conflict of interest, financial or otherwise, in relation to this study.
ACKNOWLEDGMENTS
This work was financially supported by the Japan Society for the Promotion of Science(JSPS) through the Funding Program (GR060) for Next Generation World-Leading
Researchers (NEXT Program), initiated by the Council for Science and Technology Policy(CSTP). This work was partially supported by research funds from The Murata Science
Foundation and The Foundation Hattori-Hokokai. We would like to thank Prof. Kenneth S.
Suslick for sending cif file data of PIZA-1, Assoc. Prof. Masashi Akabori for guidance in
AFM measurement, and Mr. Ryosuke Goto for PXRD measurement.

20

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Table of contents (TOC).

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