1. Introduction
In the semiconductor manufacturing process, dry etching of dielectric SiO
2 and cleaning processes have increased due to multi-level interface connections [
1]. Moreover, recently, as the incorporation of integrated circuits on wafers reaches its limit, three-dimensional vertical NAND (3D V NAND) technology, which stacks circuits in multi-layers, has been introduced and thereby the dry etching process is repeated many times in a chamber. As fluorocarbon plasma gases such as CF
4, CHF
3, and C
2F
6 are typically used in the process, the inner wall of the chamber is exposed to those corrosive gases [
2]. These fluorocarbon gases tend to etch the materials of the inner wall. As a result, many contamination particles are generated and the etching causes a process drift phenomenon [
3]. These phenomena cause fatal problems such as a decrease in yield during mass production and the reduced operating efficiency of machines [
4]. In order to prevent the etching phenomena, SiO
2 and Al
2O
3 are used as plasma-resistant materials of the inner wall of the chamber. However, they turn out to become vulnerable to the fluorocarbon plasma gases as the number of drying etching cycles increases [
1,
5,
6,
7,
8]. Recently, Y
2O
3, which is more chemically stable to the fluorocarbon plasma than Al
2O
3 and SiO
2, has been used as a plasma-resistant material [
9]. When Y
2O
3 coating is exposed to fluorocarbon plasma, a fluorinated layer forms on its surface [
9,
10]. The fluorinated layer acts as a protective layer which prevents the coating from reacting with the fluorocarbon plasma [
9]. Although Y
2O
3 is known to be more resistant to plasma than SiO
2 and Al
2O
3, it would not be the best plasma-resistant material because fluoride particles whose chemical composition is close to YF
3 are generated as contaminants in the process of the Y
2O
3 surface being converted to a Y
xO
yF
z layer, due to the reaction with plasma [
11,
12]. Nowadays, many researchers are paying attention to the Y
xO
yF
z (YOF) layer formed on the surface of the Y
2O
3. Since yttrium oxyfluoride (YOF) contains fluorine, it would not react with the fluorocarbon plasma gas. Shiba et al. [
9] reported that the surface crystallinity of YOF, which is a fluorine-based material, was not changed, while that of Y
2O
3 was changed by the penetration and reaction with fluorocarbon plasma gas. YOF has metal and oxide compositions which are chemically stable, so particle generation would also be suppressed [
9,
13]. Shiba et al. [
9] also reported that the resistance to erosion of YOF for various plasma gases was superior to that of Y
2O
3 through X-ray diffractometry (XRD) and X-ray photoelectron spectrum (XPS) analyses, although those materials were deposited by ion plating. Since atmospheric plasma spraying (APS) is more cost effective and suitable for coating large areas than ion plating, it is widely used in coating plasma resistant materials. Although APS can produce a thick coating on a large area with high efficiency, numerous cracks and pores tend to be formed in the coating and thereby the coating is vulnerable to plasma erosion. If suspension plasma spraying (SPS) is used, a dense coating free of cracks can be deposited. This is because relatively fine particles less than 5 μm in size can be dispersed in the suspension, and the splat size of the coating layer is sufficiently small. Considering that SPS is such a promising coating method, it is worth depositing the YOF coating by SPS and analyzing its plasma-resistant properties. However, there have only been a few reports about dense YOF coating deposited by SPS and its plasma-resistant properties. Recently, a dense YOF coating was successfully deposited by SPS by our group [
11]. Our previous paper focused on the optimum process conditions to deposit a dense coating by SPS. In this paper, the plasma-resistant properties of the YOF coatings were analyzed in comparison with those of Al
2O
3 bulk and Y
2O
3 coating. After exposing these materials to fluorocarbon plasma, the surface and internal compositions were analyzed by XPS, and the crystalline structures were analyzed by XRD.
2. Experimental Procedures
Commercially available Y5O4F7 suspension (Nippon Yttrium Co., Ltd., Omuta, Fukuoka, Japan), which consists of Y5O4F7 particles with an average size of 3 µm dispersed in deionized water with a solid concentration of 10 wt.%, was used as a feedstock material. A YOF coating was prepared using a suspension plasma spraying (SPS) system, which had triple anodes and cathodes with coaxial feeding (Mettech’s Axial III, Northwest Mettech Corp., North Vancouver, BC, Canada). A plate of Al alloy 6061 (50 mm × 50 mm × 10 mm) was used as a substrate.
To improve the adhesion strength of the YOF coating, the substrate was sandblasted to have a surface roughness average (Ra) of ~2.8 µm by alumina particles less than 254 µm in size. The Al alloy substrate was preheated with the plasma flame before the SPS coating process. The temperature of the substrate was found to be ~380 K after the substrate was preheated, and was measured to be ~550 K by a pyrometer (568 IR thermometer, Fluke, Washington, USA) after SPS coating. During the SPS process, the substrate was cooled by an air gun at a distance of 100 cm to prevent the substrate from melting in the high-temperature plasma flame. The axial III SPS system with axial feeding has a higher coating efficiency than other SPS systems with radial feeding.
As shown in
Figure 1, the suspension flows directly through the plasma jet and thereby the heat generated from the plasma jet transfers efficiently to the suspension. The SPS coating was carried out under the following conditions; the flow rate of argon as a primary gas was set to 90 standard liters per minute (slm), and the flow rates of nitrogen and hydrogen as secondary gases were set to 54 and 36 slm, respectively, to induce the generation of a plasma arc with an arc current of 230 A. The role of gases is illustrated in our previous paper [
11]. The feeding rate of the suspension was 45 standard cubic centimeters per minute (sccm), and the flow rate of nitrogen atomizing gas was 30 sccm. The atomizing gas, which is injected to the feeding flow and splits the suspension droplets into small ones, turned out to affect the quality of the YOF coating because it made the droplet size of the suspension smaller and thus, the particles in the droplet melted more easily [
14,
15]. The transverse speed of the plasma gun was 1000 mm/s, and coating cycles were repeated 20 times during the entire spraying process. The stand-off distance was 50 mm, which refers to the distance between the plasma gun and Al substrate. The details of the processing parameters of the YOF coating are shown in
Table 1. The thickness of the YOF coating was about 55 µm, and the surface was polished to less than 0.1 µm of roughness for the test of fluorocarbon plasma etching. Polycrystalline Al
2O
3 bulk and Y
2O
3 coating deposited by SPS were prepared as a comparison group to investigate the etching behavior of the YOF coating and were polished to less than 0.1 µm surface roughness.
The plasma etching process was carried out by an inductively coupled plasma (ICP) etcher (Multiplex ICP, Surface Technology Systems (STS), Newport, UK) with the gases CHF
3 and Ar.
Figure 2 shows a schematic of the STS multiplex ICP system. The YOF coating, Y
2O
3 coating, and Al
2O
3 bulk specimens were placed on a silicon wafer and loaded into the ICP etching chamber to compare their etching behavior using fluorocarbon plasma. The mixture of CHF
3 and Ar gases was injected into the ICP etching chamber for plasma generation, and the gases were supplied at a 6:1 ratio of 50 and 8.3 sccm, respectively, through a gas inlet. Helium gas was used to cool the specimens on the wafer to prevent thermal damage during the etching process and was injected into the gas inlet under the electrostatic chuck (ESC). The RF source power and bias power were set to 2100 and 210 W, respectively, which were 70% of the maximum allowable values of the ICP etching chamber (3000, 300 W). Dry and turbo molecular pumps were utilized to prepare the vacuum. The working pressure in the plasma etching chamber was 20 mTorr. The specimens were exposed to CHF
3/Ar plasma for 60 min. The details of the plasma etching conditions are shown in
Table 2.
The microstructures and surface morphologies were observed by field emission scanning electron microscopy (FE-SEM, SU-70, Hitachi, Tokyo, Japan) to analyze erosion behavior after fluorocarbon plasma etching. The crystal structure of the YOF coating by the SPS process was analyzed by high-resolution X-ray diffractometry (HR-XRD, SmartLab, Rigaku, Austin, TX, USA). In order to analyze the porosity of the cross-section of the YOF coating, an image analyzing program (ImageJ software (version 1.51k)) was used [
16]. The hardness of the YOF coating was measured by a Vickers hardness tester (Duramin-40, Struers, Cleveland, USA) under a load of 200 gf. The etching depth of the specimens was measured by a noncontact three-dimensional surface profiler (NanoView-E1000, NanoSystem, Daejeon, Korea). High-resolution X-ray photoelectron spectrum (HR-XPS, AXIS SUPRA, Kratos, Manchester, UK) analysis was carried out by a monochromatic Al Kα X-ray source at a passing energy of 20 eV with a 700 µm × 400 µm spot size. The deconvolution of the photoelectron spectrum was performed by using a fitting program (Fitt-win software (version 1.3)) to analyze the spectrum of the core energy levels of the Y3
d and Al2
p states from the surface of YOF and Al
2O
3 after exposure to fluorocarbon plasma. In order to investigate the chemical compositions, depth profiling was performed with focused Ar
+ ions for sputtering of the etched surface of the Al
2O
3 bulk, Y
2O
3 coating, and YOF coating.
3. Results and Discussion
Figure 3 shows FE-SEM images of the surface and cross-section microstructures of the YOF coating deposited under the SPS conditions in
Table 1. The FE-SEM image of the as-coated YOF surface morphology in
Figure 3a shows both smooth and rough areas. After the solvent of the droplets coming out from the torch outlet is evaporated, the remaining particles will be melted by the plasma flame. The completely melted particles will be spread out onto a growing surface and produce smooth areas called splats [
17]. The partially or incompletely melted particles produce rough areas.
The pores observed on the cross-section in
Figure 3b came from partial or incomplete melting [
15]. The porosity was 0.15% ± 0.01%, which was calculated by the image analyzing program and determined by averaging five randomly selected areas from the entire area of coating. The thickness of the YOF coating in
Figure 3b was 55 ± 3.2 µm and the coating rate was ~9.2 µm/min. The porosity of the YOF coating affects its hardness. The Vickers hardness of the YOF coating in
Figure 3 was 553 ± 60 HV, which is much higher than 290 ± 30 HV for the YOF coating deposited by atmospheric plasma spraying (APS) reported recently by Lin et al. [
18] and 69.34 ± 4 HV (0.68 ± 0.04 GPa) for the YOF coating fabricated by hot pressing reported by Tsunoura et al. [
10].
Figure 4 shows the XRD peaks of the YOF coating. The major peaks indicated by the reverse triangles in
Figure 4 represent the crystalline structure of trigonal YOF. The minor peaks indicated by squares and rhombuses represent, respectively, the crystalline phases of cubic and monoclinic Y
2O
3. Although cubic and monoclinic Y
2O
3 are unwanted phases, their formation was unavoidable to a certain extent. A possible scenario for the formation of Y
2O
3 would be as follows. First, Y
5O
4F
7 particles in suspension would be transformed into YOF particles, while Y
5O
4F
7 particles volatilize in the form of YF
3 in the plasma jet region [
19]. Then, some of the YOF would be transformed into Y
2O
3, while the YOF is mainly volatilized in the form of YF
3 by sufficient heat energy in the plasma jet region [
20]. The detailed mechanism is explained in our previous paper [
11].
Figure 5 shows the FE-SEM images of the surface microstructure of the Al
2O
3 bulk, Y
2O
3 coating, and YOF coating before and after exposure to the CHF
3/Ar plasma for 60 min. The Al
2O
3, Y
2O
3 coating, and YOF coating were polished to less than 0.1 µm of roughness, respectively. Furthermore, as shown in
Figure 5a,c,e, they had a smooth surface before plasma exposure. After exposure to the fluorocarbon plasma, the erosion on the surface of the Al
2O
3 bulk was much more severe than that of the Y
2O
3 coating and the YOF coating. As shown in
Figure 5b, large and small crater-like erosion sites were generated and contamination particles, which are shown as tiny dots in the figure, were observed on the Al
2O
3 surface after exposure to fluorocarbon plasma. As shown in
Figure 5d, although the Y
2O
3 coating showed much less erosion than the Al
2O
3 bulk, it had more cavities and deeper erosion than the YOF coating.
As shown in
Figure 5f, there was no noticeable difference in the surface of the YOF coating before and after exposure to the fluorocarbon plasma in comparison with those of the Al
2O
3 bulk and Y
2O
3 coating. Contamination particles were not observed. Although both the Y
2O
3 and YOF coatings were deposited by the SPS process under the same conditions, the YOF coating showed less erosion, which means that YOF is chemically more stable than Y
2O
3 against fluoride etching species, which is in agreement with the previous report by Yoshinobu et al. [
5].
On the other hand, the plasma resistance of the YOF coating is closely related to its densification because the internal pores within the grains or at grain boundaries tend to be intensively eroded from their edges, forming crater-like erosion sites [
21]. The crater-like erosion sites formed from internal pores were barely observed in
Figure 5f, which would be due to the low porosity of 0.15% ± 0.01% of the YOF coating deposited by SPS with a uniaxial feeding system. Hence, in addition to the chemical stability of the YOF coating, it is further necessary to reduce the porosity of the YOF coating to improve its plasma resistance. The SPS process is suitable for reducing the porosity of the YOF coating.
Figure 6 shows the etched depth of the Al
2O
3, Y
2O
3, and YOF surfaces with the plasma exposure time. The etched depth was measured in nine areas of their surfaces and the average value was calculated. The etched depth of the Al
2O
3 surface steeply increased after 30 min in comparison with that of the Y
2O
3 and YOF surfaces and became more than 1025 nm after 60 min. As plasma etching progressed, crater-like erosion sites were formed. Once they were formed, the erosion seemed to be accelerated, spreading from the erosion sites as shown in
Figure 6. On the other hand, the etched depths of the Y
2O
3 and YOF surfaces were, respectively, 289 and 142 nm after 60 min of plasma exposure and increased almost linearly with the plasma exposure time. Considering that the Al
2O
3, Y
2O
3, and YOF surfaces were equally bombarded by ions of Ar plasma in the presence of highly corrosive fluorocarbon [
13], the difference in the etched depth of the three samples in
Figure 6 means that the YOF coating is more resistant to the CHF
3 plasma than the Y
2O
3 coating, which is more resistant than the Al
2O
3 bulk.
Figure 7 shows the XPS spectra of the Al
2O
3, Y
2O
3, and YOF surfaces after 60 min of CHF
3/Ar plasma etching. The peak separation of XPS spectra of the three samples indicated that their surfaces were obviously fluorinated. The XPS spectra of the fluorinated surfaces, which are shown by the dotted lines in
Figure 7, were fitted to two doublets, which are shown by the dashed and long dashed lines.
In
Figure 7a of Al
2O
3 bulk, the two doublets of Al atoms from Al
2O
3 are Al2
p3/2 and Al2
p1/2 peaks, which represent 3/2 and 1/2 spins of the 2
p orbital, respectively. It is reported in the handbook of XPS standards [
22] that the peaks have an intensity ratio of 2:1 and peak position spacing in the binding energy of 0.4 eV. The two peaks of Al2
p3/2 were located at 75.0 and 76.2 eV. The peak of lower binding energy of 75.0 eV would be for Al–O bonding of pure Al
2O
3 [
23,
24]. The peak at the higher binding energy of 76.2 eV would be for Al–F bonding, which was also confirmed by the peak of F1
s located at 686.2 eV in the XPS spectrum of fluorine bonding [
22].
On the other hand, the XPS spectra of Y atoms from the Y
2O
3 and YOF coatings with two doublets in
Figure 7b,c consist of Y3
d5/2 and Y3
d3/2 peaks, respectively. The two peaks have an intensity ratio of 3:2 and peak position spacing in the binding energy of 2.05 eV [
25]. The peaks of the lower binding energies of Y3
d5/2 and Y3
d3/2 from Y
2O
3 coating were located at 157.10 and 159.15 eV, and those of the higher binding energies of Y3
d5/2 and Y3
d3/2 were located at 159.40 and 161.45 eV in
Figure 7b. The peaks at the lower binding energies at 157.10 and 159.15 eV correspond to the Y–O bonding, and those at the higher binding energies at 159.40 and 161.45 eV correspond to the Y–F bonding.
In
Figure 7c of the YOF coating, the peaks at the lower binding energies of Y3
d5/2 and Y3
d3/2 at 158.35 and 160.40 eV correspond to the Y–O bonding, and those peaks at the higher binding energies of Y3
d5/2 and Y3
d3/2 at 159.55 and 161.60 eV correspond to the Y–F bonding. Fluorination was also confirmed at the peak of F1
s located at 685.1 eV in the XPS spectrum of fluorine bonding. The peak position of the YOF coating was changed less than those of the Al
2O
3 bulk and Y
2O
3 coating after the plasma etching. The shift of the peaks of fluorine bonding to higher binding energy than those of oxygen bonding was attributed to the replacement of oxygen atoms by fluorine atoms around the cations during the etching process [
26]. Fluorine bonding being stronger than oxygen bonding comes from the higher electronegativity of fluorine—3.98 as compared to 3.44 for oxygen [
26].
The relative intensity ratio of the Al–F to Al–O peaks on the Al2O3 surface was 0.19 and that of the Y–F to Y–O peaks on the Y2O3 coating was 2.70, whereas that of the Y–F to Y–O peaks on the YOF coating surface was 4.79. These values indicate that the YOF coating formed much stronger fluorination on the surface, which would be related with the excellent intrinsic chemical stability and strong erosion resistance, suppressing the generation of fluorine contamination particles after exposure to fluorocarbon plasma.
Figure 8 shows the XPS depth profiles of compositions as a function of the Ar
+ sputtering time from the surface of the Al
2O
3, Y
2O
3, and YOF samples after exposure to CHF
3/Ar plasma for 60 min. Fluorination was confirmed on all the surfaces of the Al
2O
3, Y
2O
3, and YOF, while the fluorine content on the fluorinated layer of the YOF coating was higher than those of the Al
2O
3 and Y
2O
3. The percentages of F atoms reached the maximum values of 58.97% on the fluorinated layer of the Y
2O
3 coating (
Figure 8b) and 17.76% on the Al
2O
3 bulk (
Figure 8a), while the percentage reached the highest value of 67.75% on the YOF coating surface (
Figure 8c). Furthermore, the percentage of F atoms started to decrease from the maximum value to the original composition with sputtering time. Given that the fluorine content decreased from 17.76% and approached 0% with sputtering time in
Figure 8a, the Al
2O
3 bulk surface appeared to be barely fluorinated. In addition, the fluorine content on the Y
2O
3 coating surface was rapidly decreased compared to that on the YOF coating surface (
Figure 8b,c). These results indicated that the fluorination layer of the YOF coating was much thicker than that of the Y
2O
3 coating. This fluorination layer, with a higher concentration of fluorine on the surface, plays an important role in preventing erosion from fluorocarbon plasma and would not easily vaporize because of its chemical stability during the etching process [
1,
27].
On the other hand, the carbon content sharply decreased from the surface to the depth direction with the sputtering time in all of the Al
2O
3, Y
2O
3, and YOF samples, which indicated that the fluorocarbon layer is very thin, as shown in
Figure 8. The thin fluorocarbon layer formed on the surface of the samples was previously reported in Si-based materials etched after exposure to fluorocarbon plasma [
28]. From these results, we could confirm that the fluorination layer of the YOF coating was much thicker than those of the Al
2O
3 and Y
2O
3 samples. This would be why the YOF coating exhibits excellent plasma-resistance to CHF
3/Ar plasma etching.