Applied Science and Convergence Technology 2019; 28(3): 60-65
Published online May 31, 2019
Copyright © The Korean Vacuum Society.
Soo Ho Choia, Chang Seok Ohb, Stephen Boandohb, Woochul Yanga, Soo Min Kimc, and Ki Kang Kimb,*
aDepartment of Physics, Dongguk University, Seoul 04620, Republic of Korea, bDepartment of Energy and Materials Engineering, Dongguk University, Seoul 04620, Republic of Korea, cInstitute of Advanced Composite Materials, Korea Institute of Science and Technology (KIST), Jeonbuk 55324, Republic of Korea
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We introduce liquid ammonium sulfide as a reliable and carbon-free sulfur precursor for synthesizing large-area transition metal disulfides (TMdS) in chemical vapor deposition. The flux of sulfur during TMdS growth is precisely controlled by passing a known amount of carrier gas through a bubbling system containing liquid ammonium sulfide. However, controlling the flux of sulfur through the conventional evaporation of sulfur powder using a heating belt remains a challenge. By achieving controllability of sulfur flux, we study growth kinetics such as nucleation density and growth rate. Furthermore, the continuous supply of the sulfur precursor results in the growth of a large-area monolayer and a few layers of MoS2 film. In addition, we present the feasibility of ammonium sulfide as an effective and clean precursor for the growth of a wide range of TMdS, thus enabling it to serve as a universal sulfur precursor.
Keywords: Two-dimensional materials, Transition metal dichalcogenides, Chemical vapor deposition, Precursor, Ammonium sulfide
Since the discovery of graphene in 2004 , two dimensional (2D) materials have been highlighted due to their unique physical and chemical properties such as exceptional high carrier mobility, gigantic magnet-oresistance, and thickness-dependent electronic structural changes [2–8], which were not observed in bulk materials. These unique properties allow the developing of unprecedented electronic devices and new functionality of conventional devices with integrated 2D materials [9,10]. Theoretical calculation predicts that 350 monolayer 2D materials are stable at room temperature under ambient atmosphere . The electronic structures of various 2D materials strongly depend on the constituent elements in 2D layer and their thickness . For instance, while graphene consists of carbon atoms in hexagonal lattice and exhibits semi-metallic property, hexagonal boron nitride (hBN) composed of boron and nitrogen atoms in hexagonal lattice is an insulator with energy band gap of ~ 6 eV. In addition, transition metal dichalcogenides (TMdCs) which consists of transition metal and chalcogen atoms exhibits metallic or semiconducting properties. Furthermore, the energy band gaps of TMdCs varies with thickness due to the orbital interaction between layers .
To apply these 2D materials in numerous devices, large-area and high-quality 2D materials are highly necessary. Chemical vapor deposition (CVD) is one of the promising methods in terms of high throughput, low cost and high crystallinity for the growth of wafer-scale 2D materials [14,15]. This is evident in the number of research conducted over the past decade to grow 2D materials via CVD [16–20]. Recently, wafer-scale single-crystal graphene and hBN have been successfully synthesized via “epitaxial growth” and “self-collimated growth” on single crystal Cu (111) and liquid Au substrates, respectively. These growths were made possible due to the presence of reliable vapor and liquid phase precursors, which allowed precise controlling of the precursors [21,22]. By contrast, the precursors for growth of TMdCs are quite limited to solid-phase precursors due to the absence of vapor or liquid phase alternatives [17–19]. Typically, solid phase precursors such as metal oxides MoO3 and WO3 and chalcogen powders such as S, Se and Te are supplied by evaporating with local heating, restricting the continuous and simultaneous supply of precursors. This limits the reproducible and reliable growth of TMdCs. To overcome this problem, volatile metal carbonyls such as Mo(CO)6 and W(CO)6 and liquid organochalcogen compounds such C2H6S2 and C2H6Se2 as alternative precursors have been developed for the growth of TMdCs in metal-organic CVD (MOCVD) [23,24]. Large-area monolayer molybdenum disulfide (MoS2) and tungsten disulfide (WS2) film are readily grown via the proposed MOCVD, but the presence of carbon in the precursors hinders the growth of high quality TMdCs. Therefore, it is still highly necessitated to develop new precursors which do not generate carbon radicals during growth, while ensuring a constant and simultaneous supply of precursors.
Here, we introduce liquid ammonium sulfide ((NH4)2S) as a new reliable and carbon-free sulfur precursor for the growth of transition metal dichalcogenides (TMdS) family. The sulfur flux is precisely controlled by the flow rate of Ar carrier gas through a bubbling system containing the liquid ammonium sulfide. The nucleation density and domain size of MoS2 can be controlled by the flow rate of Ar carrier gas. Furthermore, the continuous supply of ammonium sulfide enables the growth of large-area MoS2 film. Lastly, the growth of WS2 and ReS2 are demonstrated, indicating that ammonium sulfide can be regarded as a universal sulfur precursor for the growth of diverse range of TMdS.
MoS2 grains and films were grown using a furnace equipped with a 2-inch quartz tube. As sulfur precursor, a bubbler containing ammonium sulfide solution ((NH4)2S, 40–48 wt% in H2O, Sigma Aldrich) was connected with high purity (99.9999 %) argon gas and to the inlet of the quartz tube. 0.02 M sodium molyb-date dihydrate (Na2MoO4 · 2H2O, ≥99.5 %, Sigma Aldrich) aqueous solution was prepared as the molybdenum precursor. The molybdenum precursor solution was spun onto hydrophilic SiO2/Si substrate with 2500 rpm for 1 min. The molybdenum precursor coated substrate was placed in the center of the quartz tube. To remove residual gas, the quartz tube was purged with 350 sccm argon for 10 min. The temperature of the quartz tube was then elevated to 850 °C in 15 min (~55 °C/min). For growth to commence, 2–20 sccm of argon carrier gas was introduced into the bubbler for 5–20 min. After growth, the supply of (NH4)2S was stopped by a mass flow controller. The quartz tube was rapidly cooled down (−50 °C/min) by taking out the quartz tube from the furnace. The entire growth process was carried out in atmospheric pressure. In the case of the growth of WS2 and ReS2, sodium tung-state dihydrate (Na2WO4 · 2H2O, ≥99 %, Sigma Aldrich) and sodium perrhenate (NaReO4, 99.99 %, Sigma Aldrich) aqueous solutions were used as transition metal precursors. The growth temperatures for WS2 and ReS2 grains were 850 and 600 °C, respectively. For the growth of ReS2, cleaved mica was used as a growth substrate.
To analyze the lateral size, the number of nucleation and the coverage of MoS2 grains and films, optical microscopy (Eclipse LV150, Nikon) and field emission scanning electron microscopy (FE-SEM, JSM-7100F, JEOL) were used. The thickness and the crystallinity of MoS2 were confirmed via atomic force microscopy (AFM, N8-NEOS, Bruker), micro-Raman spectroscopy and photoluminescence (PL, XperRAM 100, Nanobase) measurements. Silicon probes (Tap 190-G, BudgetSensors) were used for the non-contact mode AFM measurement. During the Raman and PL measurements, 532-nm laser was used with ≤0.1 mW laser power to avoid damages to TMdS.
Figure 1(a) shows the schematic illustration of a CVD system equipped with an (NH4)2S bubbler. The (NH4)2S solution constitutes NH4+ and S2− ions required for the growth of TMdS. The amount of (NH4)2S supplied is controlled by the flow rate of argon gas injected into the (NH4)2S bubbler, and the (NH4)2S molecules are thermally decomposed to NH3 and H2S molecules . Therefore, decomposed H2S molecules act as sulfur precursors during the growth of MoS2. According to our previously reported paper, MoS2 grains and films are grown through the sulfurization of Na2MoO4 coated on SiO2/Si substrate . Figure 1(b) shows a photograph of bare SiO2/Si substrate and as-grown MoS2 film. The color of the bare SiO2/Si substrate is changed to uniform blue-green after growth. Due to the Fresnel effect, the optical color contrast difference between the SiO2/Si substrate and MoS2 grains can clearly be distinguished as shown in Fig. 1(c) . Similar color contrast is observed for all MoS2 grains, indicating a uniform thickness of MoS2 grains is attained. To identify the thickness of grown MoS2 grains, AFM measurement is carried out. Figure 1(d) is an AFM topography image of transferred MoS2 grain indicated by the white-dashed box in [Fig. 1(c)]. The thickness of MoS2 grain is ~0.9 nm, which is well matched with reported value of monolayer MoS2 . Spectroscopic analyses are generally used to investigate the crystallinity of synthetic material. In the case of MoS2, the vibrational energy difference between two MoS2 Raman modes (E12g and A1g), provides information on the thickness of MoS2 as well as its crystallinity. Figure 1(e) shows the Raman intensity mapping image corresponding to the E12g mode of MoS2. Uniform Raman intensity distribution implies uniform thickness of the MoS2 grain. Figure 1(f) displays the representative Raman spectrum extracted from the intensity map. The vibration energy difference (Δ
One of the great advantages of the liquid precursor is controllability. Based on the controllability of the liquid (NH4)2S precursor, the growth kinetics of MoS2 is studied by controlling of the flow rate of (NH4)2S. Figures 2(a)–(d) present the optical microscopy images of as-grown MoS2 grains with different (NH4)2S supply of 2, 5, 10, and 20 sccm, respectively. With 2 sccm of (NH4)2S flow rate, various sizes of MoS2 grains are observed, indicating that the nucleation of MoS2 grains occurs at different stages with continuous supply of (NH4)2S. On the contrary, more uniform lateral size is observed at 20 sccm, implying that the nucleation of MoS2 grains occurs at similar time. This might be attributed to the fast supersaturation of precursor molecules originated from the higher precursor concentration. Figure 2(e) displays the grain size and the nucleation density variations of MoS2 grains as a function of the flow rate of (NH4)2S from 2 to 20 sccm. While average lateral size of MoS2 grains grown with increasing flow rate of (NH4)S2 is decreased from ~123 to 54 μm, the number of MoS2 grains per unit area (10,000 μm2) is increased from 0.87 to 4.01. This is attributed to the increment of the concentration of precursor, which was typically observed in the growth of 2D materials such as graphene and hBN [30,31]. These results further prove that the supply of (NH4)2S is successfully controlled by the bubbler system.
Another advantage of the liquid precursor is the sustainable supply of the precursor molecules. Therefore, time-dependent growth is performed to confirm the continuous supply of (NH4)2S precursor. Figures 3(a)–(d) show optical microscopy images of as-grown MoS2 grains and films for 5, 10, 15, and 20 min, respectively. The lateral size of MoS2 grains grown for 5 min is ~40 μm, indicating that the growth rate at the initial stage is very high (~160 μm2/min). At 10 min, the grain size increases to ~60 μm, while the number of MoS2 grains is maintained. It implies that the continuous supply of (NH4)2S precursor contributes to the increase in size of the grown MoS2 grains instead of forming new nucleation sites. With further supply of (NH4)2S precursor, monolayer MoS2 film is successfully grown within 15 min. In addition, the growth of bilayer and few-layer MoS2 grains occurs at the grain boundary of monolayer MoS2 film, similar to our previous reports [23,26]. This might be attributed to the aggregation of Na2MoO4 precursor on the grain boundary of the monolayer MoS2 film. For 20 min, further growths of bilayer and few-layer MoS2 grains are observed. Figure 3(e) shows the statistics of monolayer (1L), bilayer (2L), and few-layer (FL) MoS2 coverage as a function of the growth time. With high growth rate at the initial growth stage, the coverage of 1L MoS2 is already ~70 %, and linearly increased to 100 % in 15 min. The coverage of both 2L and FL MoS2 grains increase with increasing of the growth time. To analyze the grown MoS2 film, Raman and PL measurements are carried out. Figure 3(f) shows a Raman intensity mapping image at E12g mode corresponding to the red box in [Fig. 3(d)]. Due to the different thickness of MoS2, stronger Raman intensity is observed at 2L and FL MoS2 grains than that of 1L MoS2. Figures 3(g) and 3(h) present three Raman and PL spectra extracted from different regions (A–C) in the mapping image. Different Δ
In order to confirm the versatility of (NH4)2S precursor, the growth of tungsten disulfide (WS2) is demonstrated. Na2WO4 · 2H2O aqueous solution is used as tungsten precursor instead of the use of Na2MoO4 · 2H2O solution. Figure 4(a) shows an optical microscopy image of as-grown WS2 grains. Equilateral triangular shaped WS2 grains are grown with uniform grain size (~10 μm). Two representative WS2 phonon modes (2LA (M) mode at 349.2 cm−1 and A1g mode at 415.3 cm−1) are clearly observed in the Raman spectrum as shown in Fig. 4(b). The Δ
In summary, we report the use of liquid (NH4)2S solution as a universal sulfur precursor for CVD growth of TMdS. Based on the advantage of the liquid precursor, the growth kinetics are studied by controlling of the precursor flow rate and the growth time. The lateral size and the number of nucleation sites of MoS2 grains are controlled by the flow rate of (NH4)2S precursor. With increasing of the growth time to 15 min, centimeter-scaled MoS2 film is successfully grown. After further supply of (NH4)2S precursor, the growth of MoS2 is governed by the Stranski-Krastanov model. Furthermore, the growth of WS2 and ReS2 using (NH4)2S precursor are also demonstrated. We believe that our approach not only open a facile way for the high quality reliable growth of TMdS but also helps the commercialization of TMdS in the near future.
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science, ICT & Future Planning (2018R1A2B2002302).