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Surface Treatment Effect on Si (111) Substrate for Carbon Deposition using DC Unbalanced Magnetron Sputtering

A. S. Aji*, M. F. Sahdan, I. B. Hendra, P. Dinari, Y. Darma
Quantum Semiconductor and Devices Lab., Physics of Material Electronics Research Division Department of Physics, Institut Teknologi Bandung *Email:
Abstract. In this work, we studied the effect of different surface treatment in silicon (111) substrate deposited with carbon. We focused on surface treatment of silicon substrate that utilizes fluoride acid to remove contaminants and native oxides on silicon (111) substrate. The effect of HF treatment is investigated by SEM, EDAX, and Raman spectroscopy. The SEM EDAX results show that the carbon islands grow not uniformly on the surface of substrate which uses the surface treatment than another one. Those results are clarified by Raman spectroscopy. But, the Raman spectroscopy intensity of sample treated by HF is lower than sample without treatment. Moreover, we also investigate the thermal stability of these samples by thermal annealed to 600 ºC and 900 ºC.

PACS: 81.15Fg, 81.15.Cd, 81.65.-b, 81.05.UKeyword: film deposition, sputtering, surface treatments, carbon based materials.

Nowadays, carbon-based materials are on the trending for material research, from carbon nanotube to graphene. Graphene is the latest structure of carbonbased materials known recently. Graphene and carbon nanotube have many promising utilities from solar cell to electronic devices. Usually that carbon-based material will be grown on a silicon substrate in order to be used [1]. As we know that surface treatment is one of many important things before depositing material on silicon substrate. Carbon layer on silicon substrate has been done from several groups by using CVD [2]. This method resulted great outcome. In this paper, we deposited the carbon layer on the silicon substrate by using DC unbalanced magnetron sputtering. Before growing the carbon layer, we perform the surface treatment on the substrate by dipping and cleaning in a HF solution. In this paper, we will discuss the HF treatment on the surface of silicon (111) substrate for carbon growth. HF dip has several advantages, for example it can remove organic contaminant, native oxides, and increase surface contact angle up to 70º. Furthermore, we also investigate the effect of annealing on this material from 600 ºC to 900 ºC. The results can be seen on SEM images and Raman spectroscopy.

HF treatment is one of the wafer-cleaning techniques alongside RCA solutions that have been used from the 1970s [3]. RCA solution is divided into two types depend on its pH value. SC-1 (standard cleaning 1) has high pH value. SC-1 has the ability to remove organic contaminant and particle. Furthermore, SC-2 (standard cleaning 2) has low pH value. SC-2 has the ability to desorb metal contaminant by forming a soluble complex. Silicon wafer substrate that has been cleaned by both SC solutions still has a problem that the native oxide, organic, and metal contaminant are still remain. Native oxide is hard to be removed using RCA solutions. Native oxide is a very shallow layer (10 Å to 1 nm) on top of silicon substrate that formed when silicon substrate is exposed in the air. Native oxides arise from several causes and their main source is emerging from the air in the room growing on the silicon wafer itself, and they also emerge from DI water [4][5]. Organic contaminant usually arises from organic vapor in the ambient and wafer storage containers while metal contaminant usually arises from ion in chemical solutions. Organic contaminant usually arises from organic vapor in the ambient and wafer storage containers while metal contaminant usually arises from ion in chemical solutions. HF dipping is just a way to remove the native oxide from silicon substrate.

Furthermore. After the top silicon layer is removed by dip the silicon substrate to HF solution. (a) (b) EXPERIMENTAL SETUP Samples used were prepared from silicon (111) substrate. This technique actually scrapes the top from silicon that has a native oxide and other contaminants.(a) (b) (c) 1μm 1μm (d) 1μm 1μm Figure 1. After rinsing with HF solution.7]. A surface with a contact angle of 0° is completely hydrophilic. We create two samples with varying sample preparation techniques using and without using HF dip on wet cleaning technique on Figure 2. the native oxide along other contaminants and a small silicon layer will be lifted and detached from substrate. (a) no surface treatment at x10000 magnification. while a contact angle of equal to or greater than 90° (H2O which is beading on the surface can have an angle greater than 90°) defines a completely hydrophobic surface. In this work. (c) no surface treatment at x25000 magnification. (b) HF surface treatment at x10000 magnification. Contact angle of silicon substrate with H2O after dipped on HF solution is 66º-85º [6. it will form a silicon surface that has a large contact angle. (d) HF surface treatment at x25000 magnification. SEM images for no treatment and HF treatment on silicon substrate preparation and annealed at 900 ºC. AFM Images of HF treated surface (a) and nontreated surface (b) . HF dipping also makes the silicon substrate become hydrophobic. The sample was cut to 1x1 cm2. we focused on substrate preparation using wet cleaning technique. silicon (111) substrate.

Samples measured by EDAX are all composed of carbon and silicon 100%.86 93. Second. First. The highest peaks from the figure 1 lies on 500 – 550 cm-1 Raman shift. we also see the energy dispersion to emphasize the results obtained. carbon on it than another one. Sample without HF dip treated substrate is given on figure 1(a) and 1(c). Before the sample is dipped on HF solution. Furthermore.77 86.Figure 3. The carbon itself is shown on figure 1(a) and 1(c) by the white and black island on silicon surface. Pressure and temperature given is 2x10 -2 mbar and 300 ºC for 1 hour. we annealed the samples on 600 ºC for 30 minutes and 900 ºC for 1 hour. The SEM images are also taken to see the surface of this sample. The difference is on the second sample we did not using HF solution after ultrasonic cleaning process. Silicon (111) peak on 550 Raman shift is removed to see the difference silicon-carbon and carbon-carbon peak between HF treated surface and non treated surface. From the AFM images in figure 2. EDAX values obtained shown on tabel 1 also confirm the presence of carbon in both samples. Table 1. We used Ar gas for sputtered the target and accelerated the Ar gas with 500 V from power supply. The EDAX results from two samples with HF treatment and without HF treatment. Raman spectroscopy for no treatment and HF treatment on silicon substrate. The HF completely removes the Si-H bond on surface and providing silicon arms to the place of carbon to be grown. Next. the resulting sample is completely clean from oxides and impurities. There are two possibilities which can be deduced from these results.13 17.46 Si 91. That peaks is resulted from the silicon on the substrate. the small area measured by EDAX are consist only that two materials. This is caused performed by the HF treatment on silicon (111) substrate. Samples without . After the carbon is grown with DC unbalanced magnetron sputtering. Characterization of these samples is performed by Raman Spectra to see the bound between silicon and carbon. it can be clearly seen that the substrate treated by HF has more Figure 4 shows the difference of Raman spectroscopy results from two samples. The Raman spectroscopy in figure 3 emphasizes the AFM images that the carbon-silicon and carbon-carbon peak has higher intensity. but there is the possibility of oxides and other impurities on other area. HF treatment Non HF treatment Element Mass (%) Atom (%) Mass (%) Atom (%) C 8. the samples have been cleaned using H2O2 1% and ultrasonic cleaned around 70 ºC sample. After the substrate preparation is done. the carbon is grown using DC unbalanced magnetron sputtering system.54 Total 100 100 100 100 RESULTS AND DISCUSSION SEM images of two samples are given on figure 1. so there is no percentage other than carbon and silicon. The figure clearly shows the carbon island is completely spread. There are 3 peaks on figure 4(a) that indicated silicon and carbon bound.23 13.14 6.87 82. Although amount of carbon on HF treated substrate less than non HF treated substrate. The target that used is Fe:C from BATAN. Figure 1(a) and 1(c) clearly demonstrate the presence of polluter (white part) that cannot be removed without HF dip treatment. but the SEM images shows that the carbon layer more uniform on HF treated substrate. Silicon substrate that penetrated is about 100 nanometers. The first sample is dipped using HF 1% diluted on DI water. figure 1(b) and 1(d) show the result of HF dip treated substrate. The peaks became the highest peak than other two because of penetration depth of laser that used for Raman spectroscopy.

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