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A surface chemical reaction in organic–inorganic materials using a new chemical evaporation system Seong Jun Kim, Sung Myung, Wooseok Song, Bok Ki Min, Seong-Jin Hong, Myungwoo Chung, Hyunjung Kim, Ki-Jeong Kong, Jongsun Lim, Taek-Mo Chung, and Ki-Seok An Chem. Mater., Just Accepted Manuscript • DOI: 10.1021/acs.chemmater.5b00377 • Publication Date (Web): 02 Jun 2015 Downloaded from http://pubs.acs.org on June 8, 2015

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Chemistry of Materials

A surface chemical reaction in organic–inorganic materials using a new chemical evaporation system Seong Jun Kim,†,‡,§ Sung Myung,†,§ Wooseok Song,† Bok Ki Min,† Seong-Jin Hong,† Myungwoo Chung,|| Hyunjung Kim,|| Ki-Jeong Kong,† Jongsun Lim,† Taek Mo Chung,† and Ki-Seok An*,†,⊥ †

Thin Film Materials Research Group, Korea Research Institute of Chemical Technology, Daejeon 305-343, Republic of Korea ‡

Nanomaterials Science and Engineering, University of Science and Technology, Daejeon 305-350, Republic of Korea ⊥

Chemical Convergence Materials, University of Science and Technology, Daejeon 305-350, Republic of Korea

||

Department of Physics, Sogang University, Seoul 121-742, Republic of Korea

ABSTRACT: We report the surface reaction that occurs in organic-inorganic thin films using a hybrid deposition system that combines thermal evaporation (TE) and metalation process. Growth of a smooth, uniform organic-inorganic hybrid thin film was demonstrated, and the occurrence of a self-limited surface reaction between the organic semiconductor and the inorganic metal atom during metalation process was confirmed with X-ray photoelectron spectroscopy (XPS) and Raman analysis. In this study, we utilized a hybrid deposition system that combined TE and vapor phase-metalation to create an organic-inorganic hybrid thin film. Experimental data and theoretical simulation of a model system are also provided to explain the barrierless reaction that occurs during synthesis of a zinc tetraphenyl porphyrin (ZnTPP) thin film. This process can be utilized to increase the flexibility for the advanced synthesis of organic-inorganic hybrid thin films.

INTRODUCTION Recently, there has been increased interest in various porphyrin-based materials because of their intensive absorption band in the long wavelength of the visible spectrum and a fluorescence characteristic caused by a number of π-conjugated electrons (22-π). In particular, porphyrin is able to exhibit a large variety of chemical and electrical properties by changing its central metal atoms, viz. Ni, Co, Cu, Zn, Pt, and Mn.1-5 For instance, various applications of porphyrin-related materials, such as the light-absorbing components in dye sensitized solar cells69 , active layers for organic thin film transistors10-11, and multi-functional sensors12-14, have been developed. Previous studies have been reported the porphyrin metalation involving the coordination with post- or pre-deposited metal atoms on well-defined metal or metal oxide substrate15-21 or vapor phase-metalation by atomic layer deposition process.22 In the former case, this synthesis is not appropriate for the preparation of multi-stacked metal-

loporphyrin thin films. In our metalation process of porphyrin, the metal precursor in the gas phase directly reacts with porphyrin on a solid substrate. Here, we controlled the thickness of metalloporphyrin by repeating porphyrin evaporation and metalation of porphyrin. In this respect, our hybrid process comprised of thermal evaporation (TE) and vapor phase-metalation23-26 is a more suitable synthetic method for making thin films of metalloporphyrin. Significantly, various types of metal atoms can be embedded in the center of the porphyrin molecule by repeating the hybrid process to produce new types of heterostructures such as a zinc tetraphenyl porphyrin (ZnTPP) monolayer stacked on a NiTPP monolayer. In this study, we demonstrate an alternative synthetic method, which consists of TE and vapor phase-metalation (Figure 1(a)), to make thin films of ZnTPP. Herein, tetraphenyl porphyrin (H2TPP) and diethyl zinc (DEZ) were employed as the organic and inorganic sources, respectively. The formation mechanism of ZnTPP thin films can be explained by a two-step reaction. In the first step,

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H2TPP molecules were physisorbed on a solid substrate via TE, and a purging sequence was also carried out to remove excess molecules (Figure S1). Next, DEZ was chemically absorbed onto the H2TPP on the substrate during the metalation process (H2TPP + Zn(CH2CH3)2 → ZnTPP + 2C2H6 ↑). Thereafter, the thickness of the ZnTPP thin film can be controlled by repeating this two-step reaction. We also established systematically optimized conditions for the uniform deposition of ZnTPP layers and confirmed the self-limited surface reactions between DEZ and H2TPP using N 1s core spectra obtained by X-ray photoelectron spectroscopy (XPS). We also carried out theoretical simulations in order to calculate the activation energy. The experimental results and the first principle calculation showed that the reaction for the two-step process was nearly barrierless at room temperature. This approach provides a facile, easily controlled synthetic method to generate organic-inorganic thin films for use in future electronic applications such as solar cells, organic thin film transistors, and multi-functional sensors.

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TE were maintained at ~0.05 Å/s and ~10-6 Torr, respectively. Since the top and bottom chambers in our hybrid deposition system can be isolated by the main gate between chambers, ZnTPP hybrid thin films were formed onto the H2TPP TPP film by introducing DEZ at 2.8×10-1 Torr via metalation process by rotating the sample upward. Eventually, a purging process was conducted with liquid nitrogen gas for 30s. ZnTPP hybrid thin films were formed by repeating this deposition cycle. ZnTPP thin films were also synthesized under various DEZ exposure conditions (exposure times of 5, 10, 20, 30, 40, 50, and 70s) using the hybrid system at room temperature. XPS was used for chemical identification of the ZnTPP thin films. XPS spectra were acquired with a normal emission geometry using conventional monochromatic Al Kα radiation (hν = 1486.6 eV). The pass energy was 20.0 eV, and the spectra were deconvoluted by a standard nonlinear-leastsquares fitting procedure using Voigt functions. The layer thicknesses of the ZnTPP thin films were measured using scanning electron microscopy (SEM) and Xray reflectometry (XRR). The structural and optical properties of ZnTPP films were verified by Raman spectroscopy and ultraviolet (UV)-visible spectroscopy. The surface topology and roughness of the films were also observed by atomic force microscopy (AFM).

RESULTS AND DISCUSSION

Figure 1. Schematics for the (a) formation mechanism and (b) hybrid deposition system for ZnTPP thin films.

EXPERIMENTAL DETAILS ZnTPP hybrid thin films were formed by a hybrid synthetic system combining TE and vapor phase-metalation, as depicted in Figure 1(b). Initially, a highly p-doped Si(100) substrate with 300 nm-thick SiO2 was placed onto the rotatable sample holder in the top chamber. Next, the H2TPP film (0.35 nm thick) was deposited on the SiO2 surface by opening the main gate valve and facing the sample downward. The growth rate and pressure during

XPS is utilized to analyze the surface reaction during ZnTPP fabrication. Figure 2(a) shows the N 1s core level spectra obtained from ZnTPP thin films formed at different DEZ precursor exposure times. For the H2TPP thin film, two prominent peaks at binding energies (EB) = 397.8 and 399.9 eV, which correspond to iminic nitrogen (=N-) and pyrrolic nitrogen (-NH-),17 respectively, are observed (Figure 2(a, i)). The N 1s peak of pyrrolic nitrogen is usually found at a higher binding energy than that of iminic nitrogen.17-20 Here, the peak shift of pyrrolic nitrogen was not occurred, and the peak of C 1s of H2TPP thin film was not changed comparing that with the peak of bulk H2TPP (Figure S2). This result showed that there is no chemical reaction between H2TPP molecules and SiO2 substrate in the first step. As the exposure time to the DEZ precursor increased, the pyrrolic and iminic nitrogen peaks of the N 1s spectra for the ZnTPP hybrid films decreased significantly. Also, the metalloporphyrincomplex-related single peak at EB = 398.3 eV appeared (Figure 2(a, iii-vii)). The peak area of the iminic/pyrrolic nitrogen and -Zn-N- bonding became saturated at an exposure time of about 40s. When DEZ was introduced onto the surface of the H2TPP monolayer in the gas phase, the pyrrolic and iminic nitrogen in the H2TPP molecules interacted with Zn in DEZ.

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Figure 2. (a) XPS spectra of N 1s core level for (i) H2TPP ; (iivii) ZnTPP thin films formed by introducing DEZ precursor for 5, 10, 20, 30, 40, and 50s; and (viii) thin film of commercially available ZnTPP powder. (b) Plots of the atomic ratio of Zn 2p to N 1s peaks and -NH- peak area extracted from survey and N 1s core level spectra as a function of DEZ exposure time. (c) The growth rate of ZnTPP hybrid films as a function of the DEZ precursor exposure time (5, 20, 40, and 50s) extracted from cross-sectional SEM images (blue circles) and XRR analysis (black triangles). (d) The layer thickness of ZnTPP hybrid films formed by 75, 100, 150, and 300 cycles measured from cross-sectional SEM images (blue circles) and XRR analysis (black triangles).

As H2TPP molecules became coordinated with the Zn atoms in DEZ, the new peak position, corresponding to Zn-N- in ZnTPP, appeared at a lower binding energy than that of the pyrrolic nitrogen of H2TPP. Namely, the -ZnN- bonding force is weaker than that of the pyrrolic nitrogen of H2TPP. Moreover, iminic nitrogen combined with Zn-N- in ZnTPP via coordinate bonding; this additional bonding energy between Zn in -Zn-N- and iminic nitrogen led to a shift in the XPS peak position to a higher binding energy. To compare these results with ZnTPP prepared by the conventional synthetic method, a conventional ZnTPP thin film was prepared on a solid substrate via TE. The N 1s spectrum for this ZnTPP thin film was obtained. Comparing the thin film of pre-synthesized ZnTPP powder (Figure 2(a, viii)) with our ZnTPP thin film (Figure 2(a, vi)), the both thin films have almost identical values for the iminic/pyrrolic nitrogen ratio and -Zn-Nbonding in their N 1s spectra. Figure 2(b) shows the atomic concentration ratio of Zn 2p to N 1s (blue line) and the normalized -NH- peak area (red line) as a function of DEZ exposure time. The atomic ratio of Zn 2p to N 1s increased significantly with increasing DEZ exposure times up to 40s. The atomic ratio by using the longer exposure time than 40s was unchanged, which is similar result to the

case of the -NH- peak area and Zn 2p peak area (Figure S3). In addition, the quantitative analysis of Zn as a function of the DEZ exposure time by using X-ray fluorescence (XRF) corresponds with the results of XPS analysis (Figure S4). Here, the spot size and energy of X-radition in XRF analysis was fixed. Since the thickness of nanometer-scale ZnTPP thin film is very small comparing with skin depth of X-ray, the exact area density of Zn atom was able to be calculated. These results can be explained by the self-limited surface chemical reaction between H2TPP and DEZ during the vapor phase-metalation process. In previous works, it has been reported that the stacking distance between neighboring porphyrin ligands in single crystals of H2TPP and the interlayer spacing in metalloporphyrin thin films are about 0.3 - 0.35 nm and 0.31 0.35 nm, respectively.17, 20, 27-29 Significantly, the growth rate of ZnTPP obtained in our experiment was 0.34 ± 0.015 nm, and this value was independent on DEZ exposure time (Figure 2(c)). Presumably, it is because Zn atoms of the DEZ molecules were being put into the center of the H2TPP molecules. The change in ZnTPP film thickness as a function of the number of reaction cycles is also shown in Figure 2(d). Cross-sectional SEM images (blue circles) and XRR (black triangles) were used to analyze the layer thickness of ZnTPP thin films. This result confirmed that ZnTPP thickness per cycle via the surface chemical reaction is about 0.34 nm, when we utilized DEZ exposing time of 40s.

Figure 3. (a) Raman spectra obtained with an excitation wavelength at 514 nm and (b) UV-visible absorption spectra for H2TPP thin film, ZnTPP films using our hybrid synthesis system with various DEZ exposure times (5, 10, 20, 30, 40, 50, and 70s), and ZnTPP thin film using ZnTPP powder.

Resonant Raman spectroscopy is a well-established method that can be used to provide structural information about porphyrins and related molecules.30 Figure 3(a) exhibits the resonant Raman spectra of ZnTPP thin films at various DEZ exposure times using an excitation wave-

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length at 514 nm. In the case of the H2TPP thin film, only the peak associated with the -NH- bonding state was observed (at 1492 cm-1); this is similar to what has been seen previously.31 For the ZnTPP hybrid thin films formed via surface reaction, a prominent C-N vibrational A1g mode at 1352 cm-1 is observed; however, the -NH- bonding state is no longer visible.32 When compared with the ZnTPP layer of the pre-synthesized ZnTPP powder, we can confirm that our ZnTPP thin films have been converted from H2TPP via surface reaction during the vapor phasemetalation process. The UV-visible absorption spectra of H2TPP, ZnTPP thin films, and the thin layer made from pre-synthesized ZnTPP powder are shown in Figure 3(b). In general, the absorption spectrum of a typical H2TPP consists of a strong electronic transition to the second excited state (S0 → S2) at ~400 nm (the Soret band) and a weak transition to the first excited state (S0 → S1) at ~550 nm (the Q-band).33,34 For H2TPP thin films, four wellseparated Q-bands at 528, 554, 594, and 660 nm are unambiguously observed. An intense Soret band at about 400 nm was also measured. These results are similar to those in previous work.33 However, in the case of ZnTPP, we observed a noticeable change in the relative intensities and the positions of the Q-bands. There are two interesting features that arise as the DEZ exposure time to the H2TPP thin layer is increased: the two Q-bands at 528 and 660 nm disappear, and the other Q-band peaks at 554 and 594 nm become significantly blue-shifted.34 This is indicative of the formation of ZnTPP hybrid thin films.

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topology (Figure 4). AFM images of ZnTPP hybrid thin films showed that the grain size and root mean square (RMS) roughness of the films increased monotonically as the DEZ exposure time was increased and showed a constant value after a DEZ exposure time of 40s. The saturated RMS roughness obtained from ZnTPP hybrid thin films was ~1.72 nm. In this synthesis, since the thickness of ZnTPP on the surface of H2TPP layer was controlled in the metalation process, we were able to fabricate ZnTPP layer-embedded on the specific H2TPP layer by carrying out the sequential TE of H2TPP. In addition, other metallic atoms can be coordinated on the center of H2TPP using a same method, and a new hybrid layer consisting ZnTPP and other metalloporphyrins such as AlTPP and NiTPP also can be demonstrated. To optimize synthesis method for various porphyrin-based thin films and to apply this layer to organic transistors or photodetectors is currently under investigation. Therefore, this synthesis method may pave the way toward the nanoscale production of porphyrinebased thin film for practical applications.

Figure 5. (a) Plot of the normalized peak area ratio (ρt/ρ0) of pyrrolic nitrogen versus DEZ exposure time at different substrate temperatures. (b) Logarithmic chart of the data in Figure 5(a). (c) Arrhenius plot of the rate constants, KT, obtained from the slopes of Figure 5(b). (d) Energy profile for the proposed reaction of Zn insertion into porphyrin.

Figure 4. AFM images for (a) H2TPP thin film, ZnTPP hybrid thin films formed with introducing DEZ precursor for (b) 5, (c) 10, (d) 20, (e) 30, (f) 40, (g) 50, and (h) 70s and (i) RMS roughness of ZnTPP hybrid films as a function DEZ exposure time.

AFM measurements on 5×5 µm2 areas were also performed in order to obtain information regarding thin film

In order to analyze the activation energy barrier, we examined the normalized peak area ratio in the pyrrolic nitrogen (ρt/ρ0 where ρt is the pyrrolic nitrogen peak area (exposure time to DEZ = 3, 5, 10, and, 20s) and ρ0 is the pyrrolic nitrogen peak area of H2TPP (exposure time to DEZ = zero). As shown in Figure 5(a), a decrease in the normalized peak area ratio in the pyrrolic nitrogen with increasing DEZ exposure time was observed. As the substrate temperature increased, the number of Zn atoms coordinated with H2TPP decreased. We believe that this is caused by the fact that the desorption reaction velocity is larger than the chemisorption reaction of Zn to the cen-

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ter of the H2TPP molecule as the substrate temperature increases. We obtained the rate constants, KT, of the metalation reaction at each temperature by calculating the slopes of the plots in Figure 5(b). Then, using the Arrhenius equation (ln(KT) = −Ea/RT + ln(A)), we determined the activation energy from the slope of ln(KT) versus 1000/T (Figure 5(c)).35 The activation energy is -6.11×10-2 eV, which indicates that the synthesis of ZnTPP is barrierless. The formation mechanism of ZnTPP was further investigated with first-principles electronic structure calculations using the DMol3 density functional theory (DFT) code.36 We first calculated the total energies and atomic geometries of the reactant, intermediate, and product. We chose optimized H2TPP and DEZ molecules as the reactant and an optimized ZnTPP monomer and a pair of ethanes as the product. The intermediate structure was composed of monoethyl zinc bonded with pyrrolic nitrogen in H2TPP; a mono hydrogen atom was detached to form ethane when combined with ethyl from DEZ. The optimized molecular structures are shown in Figure 5(d). The spin-unrestricted generalized gradient approximation (GGA) functional with Perdew–Burke–Ernzerhof (PBE) exchange-correlation,37 along with an all-electron treatment and double numeric polarized basis set including the p-polarization function (DNP), was used for all geometry optimizations. The van der Waals interaction was included with a semi-empirical approach: the DFT-D method parameterized by Grimme.38 The atomic coordinates were relaxed until the Hellman-Feynman forces were less than 0.002 Ha (Hartree)/Å, and the energy change between relaxation steps was less than 1×10-5 Ha. A self-consistent-field (SCF) convergence threshold value of 1×10-6 Ha was also specified. Next, we studied the reaction pathway and the activation barrier for ZnTPP formation. The transition state (TS), the saddle point on the potential energy surface (PES), is a transient structure along the reaction pathway. The activation barrier between the TS and the reactant is a crucial criterion for chemical reaction. While searching for the TS, synchronous transit methods were used to interpolate a reaction pathway and find a transition state starting from the reactant and product structures. Calculations were performed using the complete linear and quadratic synchronous transit (LST/QST) scheme.39 This begins by performing the LST optimization calculation; the TS approximation obtained in this way was then used to perform the QST maximization. Then, a further conjugate gradient minimization was performed. We repeated this cycle until either a stationary point was located within the number of allowed QST steps or the allowed number of QST steps was exhausted. To enhance the SCF convergence efficiency during the transition state search, a thermal smearing of 0.005 eV was applied when calculating the occupancy of electronic states. All transition structure geometries

exhibit only a single imaginary frequency in the reaction coordinate. The Zn metal insertion reaction pathways, along with the energy changes of the ZnTPP species, are shown in Figure 5(d). ZnTPP formation is an exothermic reaction with an energy gain of 60.65 kcal/mol. The reaction energy barrier for the overall reaction is 0.28 eV (6.46 kcal/mol). Along the reaction pathways, there exists an intermediate that is spontaneously formed from the reactant. The intermediate structure is more stable than the reactant by 26.52 kcal/mol. The atomic charge of Zn, as calculated by Mulliken analysis, changes from +0.17 e (DEZ) to +0.45 e (ZnTPP) via the intermediate (+0.32 e). The Mulliken charges of nitrogen in the reactant (H2TPP) show two values: −0.34 e (pyrrolic) and −0.48 e (iminic). Alternatively, the Mulliken charges of nitrogen in the ZnTPP are mono-valued (−0.45 e). This change in atomic charge is in agreement with the experimental findings depicted by the evolution of the N 1s peaks in our XPS spectra.

CONCLUSIONS We developed a novel synthesis method to create metalloporphyrin thin films via a surface chemical reaction using a hybrid deposition system that combines TE and metalation process. ZnTPP films with smooth and uniform surfaces were achieved via a surface reaction, and the self-limited surface reaction between the organic semiconductor (H2TPP) and the metal atom (Zn) during metalation process was confirmed by XPS and Raman analyses. In addition, experimental data and theoretical simulation of a model system were provided to explain the barrierless reaction for the ZnTPP in our hybrid deposition system. This work takes advantage of the flexible properties of our hybrid deposi-tion system and allows for the possibility to synthesize new types of organic/inorganic hybrid thin films.

ASSOCIATED CONTENT Supporting Information. Quantitative analysis of ZnTPP hybrid thin films using XPS and XRF. This material is available free of charge via the Internet at http://pubs.acs.org.

AUTHOR INFORMATION Corresponding Author *E-mail: [email protected] Author Contributions §

These authors contributed equally to this work.

ACKNOWLEDGMENT This research was supported by a grant (2011-0031636) from the Center for Advanced Soft Electronics under the Global

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Frontier Research Program of the Ministry of Science, ICT and Future Planning, Korea.

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Figure_TOC 147x87mm (300 x 300 DPI)


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