3.1 Microstructure of silicon coating
The surface and fracture morphologies of silicon coatings prepared with 4.7 L/min, 2.4 L/min and 0 L/min secondary gas flow are shown in Fig. 1(a) ~ 1(d), Fig. 1(e) ~ 1(h), Fig. 1(i) ~ 1(l), respectively. It can be seen that silicon coatings prepared with different secondary gas flow all show the typical lamellar morphology of plasma sprayed coating and the fractures of coatings are dense. The surfaces of all coatings are relatively flat and most of the silicon powders completely melt and spread out (Fig. 1(a), 1(e) and 1(i)). Some fragments appear on the surfaces of silicon lamellas (Fig. 1(c), 1(g) and 1(k)) and some pores can be seen at the nonoverlapping area of silicon lamellas (Fig. 1(a), 1(e) and 1(i)). The splashing particles approximately 10µm in diameter attach around the silicon lamellas, which can be seen from the surface and fracture of silicon coatings. The differences between coatings prepared with different secondary gas flow are the numbers of splashing particles and fragments. When secondary gas flow is 4.7 L/min, the number of splashing particles shown in the surface and fracture of silicon coating is the maximum. The number of fragments in coating prepared with 4.7 L/min secondary gas flow is also the maximum among these coatings. With the decrease of secondary gas flow, the numbers of splashing particles and fragments decrease. When the secondary gas flow is 0 L/min, there are scarcely splashing particles attaching around the well-spread lamellas and the surfaces of silicon lamellas are smooth without any fragments.
According to the analysis results from Fig. 1, we find that the secondary gas can deteriorate the quality of plasma sprayed silicon coating. The quality of silicon coating prepared without secondary gas is the best. The main gas and secondary gas used in plasma spraying are argon and helium. The heat conductivity of helium is much bigger than argon. When we provide helium secondary gas in plasma spraying process, it will transfer more heat to silicon powders than argon when main gas is ionized. With the help of secondary gas, the temperature of silicon droplets is higher than the temperature of droplets without the help of secondary gas. And the morphology of silicon coating is closely related with the temperature of silicon droplets. Because the higher the temperature of silicon droplets is, the smaller the surface tension and viscosity of silicon droplets are, the better the fluidity of silicon droplet is[23–25]. When providing secondary gas during plasma spraying, excessive heat leads to the excessive temperature of silicon droplets. When over-heated silicon droplets hit the substrate, small particles easily splash from the droplets due to lower viscosity and smaller surface tension. So as shown in Fig. 1(b) and 1(f) that some splashing powders attaching around the silicon lamellas when secondary gas flow is 2.4 L/min and 4.7 L/min. Besides, the melting point and boiling point of crystal silicon are only 1414℃ and 2900 ℃. The silicon powders smaller than 30 µm account for approximately 10% among the spraying silicon powders. When excessive heat is transferred to silicon powders during its in-flight process, small powders are much easier to evaporate. The increase of secondary gas flow will accelerate the flying velocity and shorten the flying time of silicon droplets in spraying gas. But the heat transferred by secondary gas is enough to get smaller silicon powders evaporate. When silicon droplets hit the substrate, the silicon vapor around the droplets will solidify on the surface of spread lamella in the form of fragments[26–28]. Both the numbers of splashing particles and fragments in coating prepared with 4.7 L/min secondary gas flow are slightly larger than that in coating prepared with 2.4 L/min secondary gas flow because of the higher temperature of silicon droplets. Without secondary gas, heat transferred by argon can just melt silicon powders. Silicon droplets spread well when they are deposited on the substrate, forming a smooth and dense coating. And there are rarely splashing particles and fragments on the surface of silicon coating prepared without secondary gas. Although small splashing particles and fragments have adverse influence on the surface quality of silicon coatings, the silicon coatings prepared with different secondary gas flow all show the dense fractures, which can also be attributed to the secondary gas flow. With the help of smaller surface tension and viscosity, the fluidity of over melted silicon droplets is good enough to penetrate intervals between splashing particles, successfully sealing the intervals. So, the fractures of all coatings are dense. According to the analysis results, we find that the secondary gas has an adverse influence on the quality of silicon coatings. And the quality of silicon coating prepared without secondary gas is the best.
3.2 Oxygen content of silicon coating
The oxygen contents of silicon powders and coatings are shown in Fig. 2. The oxygen contents in SP and CSP are 0.089%, 0.101%. And the oxygen contents in coatings prepared with 4.7 L/min, 2.4 L/min, 0 L/min secondary gas flow are 0.489%, 0.35%, 0.387%, respectively. According to the calculation results, the oxygen content of SP is 11.88% less than oxygen content of CSP. The oxygen content of silicon coating prepared with 4.7 L/min is 39.7%, 26.36% higher than that in coatings prepared with 2.4 L/min and 0 L/min secondary gas flow. By the comparison above, we could think that the incidence of aqua regia to oxygen content of silicon coatings is negligible compared with the incidence of secondary gas flow. Decreasing the secondary gas flow can significantly reduce the oxygen content in silicon coating.
As presented in Fig. 2 that oxygen contents in coatings are much higher than that in silicon powders because oxidation between silicon sprayed powders and oxygen is inevitable during plasma spraying process. Although silicon powders are melted in inert atmosphere, some silicon powders still be blown out from inert atmosphere. The high-speed plasma gases will incur air entrainment[29]. Besides, helium has a very high viscosity compared to argon which will aggravate the air entrainment. The reasons above-mentioned enhance the contacting likelihood of silicon droplets and oxygen, leading to the oxidation of silicon droplets. Besides, the higher secondary gas flow will transfer more heat to silicon powders when plasma gas is ionized. The higher the temperature of silicon droplets is, the severer oxidation happens in plasma spraying process. So, the oxygen content in silicon coating prepared with 4.7 L/min secondary gas flow is higher than that in coatings prepared in other two situations.
3.3 Component of silicon lamella
Figure 3(a) and 3(b) show the XPS spectra of silicon coating tested at the same location under room temperature and 400℃. The sample used in XPS is as-sprayed silicon coating prepared without secondary gas. According to the XPS results shown in Fig. 3(a) and 3(b), both Si 2p spectra are deconvoluted into four bases of 99.6 eV, 100.2 eV, 102.5 eV and 103.6 eV. The BE peaks at 99.6 eV and 100.2 eV are assigned to Si 2p3/2 and 2p1/2 with a spin-orbit split of 0.6 eV. The BE peak at 102.5 eV corresponds to Si-O bond in SiOx (1 < x < 1.5). SiOx is formed by alternant arrangement of SiO and Si2O3 tetrahedrons. The BE peak at 103.6eV is associated with Si-O bond in SiO2. Both O 1s fine spectra in Fig. 3(a) and 3(b) are deconvoluted into two bases of 532.8 eV and 533.9 eV. The BE peaks at 532.8 eV and 533.9 eV are attributed to O-Si bonds in SiOx and SiO2, which are consistent with the results from Si 2p spectra. The differences between the analysis results from Fig. 3(a) and 3(b) are the proportions of atoms and components. Atomic percentage of oxygen detected at room temperature and 400℃ are 59.25% and 54.99% respectively. At room temperature and 400℃, the proportions of Si, SiOx, SiO2 contained on the surface of silicon lamella are 46.11%, 5.87%, 48.02% and 44.43%, 18.00%, 37.57% (as shown in Table 3). It is obvious that with the increase of temperature, the proportion of SiO2 detected on the surface of silicon lamella decreases and the proportion of SiOx increases, which can be can be attributed to the weakly bonded O-Si bond in SiO2. With the increase of temperature, weakly bonded O-Si bond break, leading to the decrease of oxygen element. So, the changing tendencies of the proportion of SiOx and SiO2 are opposite. 9
Table 3
Components proportions of silicon lamellaa on different conditions
Component
|
Room temperature
|
400℃
|
0 nm
|
60 nm
|
120 nm
|
180 nm
|
Si
|
46.11%
|
44.43%
|
67.97%
|
68.64%
|
90.80%
|
100.00%
|
Si2O
|
—
|
—
|
—
|
23.78%
|
—
|
—
|
SiOx
|
5.87%
|
18.00%
|
—
|
—
|
9.20%
|
—
|
SiO2
|
48.02%
|
37.57%
|
32.03%
|
7.58%
|
—
|
—
|
aThe Chosen lamella was prepared without argon secondary gas. |
Figure 3(c) ~ 3(f) show the XPS outcomes detected at the same location but different depths of one silicon lamella. The testing location here is different from the testing location depicted in Fig. 3(a) and 3(b). And the testing depths shown in Fig. 3(c) ~ 3(f) are the surface of silicon lamella and 60 nm, 120 nm, 180 nm below the surface of lamella, respectively. It can be obviously seen from Fig. 3(c) ~ 3(f) that the categories and proportions of silicon oxides tested in different depths are different. As shown in Fig. 3(c), SiO2 can be detected on the surface of silicon lamella except to Si, which is different from the results obtained from Fig. 3(a). The difference in components at different positions can be attributed to the inhomogeneous distribution of oxygen element on lamella surface. The results from Fig. 3(d) indicate Si, Si2O and SiO2 existing beneath 60 nm of lamella surface. The analysis results of XPS spectra in Fig. 3(e) and 3(f) are basically same. Both Si and SiOx can be detected 120 nm and 180 nm below the surface of silicon lamella. But the proportion of SiOx in 180 nm depth is less than that in 120 nm depths. As shown in Table 4, the intensity ratio of Si 2p peaks and O 1s peaks detected on the surface and 60 nm, 120 nm, 180 nm beneath surface of silicon lamella are 0.47, 2.72, 4.14 and 5.14, respectively. According to the intensity ratios of Si 2p peaks and O 1s peaks and analysis results obtained from Si 2p spectra in Fig. 3(f), we could think only Si exists beneath 180 nm of silicon lamella. From the surface to the 180 nm below the surface of silicon lamella, the total proportions of silicon oxides decrease, and the proportions of Si increase from 67.97–100% as shown in Table 3.
Table 4
Parameters of Si 2p and O 1s XPS peaks tested in different depths
Depth (nm)
|
Element
|
Binding energy (eV)
|
Peak intensity (counts s− 1)
|
Intensity ratio
ISi/IO
|
0
|
O
|
532.18
|
44507.24
|
0.47
|
Si
|
98.98
|
20885.11
|
60
|
O
|
532.88
|
13873.57
|
2.72
|
Si
|
99.68
|
37742.96
|
120
|
O
|
533.08
|
9746.38
|
4.14
|
Si
|
99.78
|
40368.81
|
180
|
O
|
532.58
|
8010.6
|
5.14
|
Si
|
99.88
|
41213.53
|
Combining the analysis results above, we can find that oxygen atoms concentrate on the outermost layer of silicon lamella, existing in the form of different silicon oxides. The thickness of OEA is about 180 nm. The components from surface to inner of OEA change as following order: Si + SiOx+SiO2→Si + Si2O + SiO2→Si + SiOx→Si (1༜x༜1.5). The reason why silicon oxides distribute as above will be discussed in Sect. 3.4.
3.4 Microstructure and element distribution of silicon coating
Figure 4(a) reveals the microscopic features of as-sprayed silicon coating prepared without secondary gas. A and B represent the two silicon lamellas deposited in succession. Lamella A is deposited first, followed by lamella B. There is an obvious boundary between lamella A and B. A nanocrystal zone of 100 nm in thickness can be observed in the lamella A. The nanocrystal zone closely next to the interface. The columnar grains above nanocrystal zone are perpendicular to the interface of silicon lamellas. Relatively big equiaxed crystals, as shown in lamella B in Fig. 4(a), appear near the upper surface of silicon lamella. The difference in size and morphology of grains can be attributed to the cooling rate and stress on different locations. In the process of plasma spraying, melted silicon droplets obtain a great amount of kinetic energy. When droplet A hits the as-deposited and solidified lamella B, the stress is generated at the bottom of solidified lamella A due to kinetic energy. The temperature gradient at interface between lamella A and B is higher than that in the interior of silicon lamella. The comprehensive effect of temperature gradient and stress causes the formation of nanocrystal. The high-resolution transaction electron micrography (HRTEM) image in nanocrystal zone shown in Fig. 4(j) further illustrates the existence of nanocrystals. Due to the high cooling rate, grains near nanocrystal zone grow in the form of columnar crystals, silicon atoms nearing the nanocrystals arrange in complete disorder, as shown in Fig. 4(k). Equiaxed grains are formed near the upper surface of silicon lamella affected by a medium temperature gradient. As shown in Fig. 4(i), the silicon atoms orderly arrange and the interplanar spacing of (111) is 0.32 nm.
Figure 4(b) is the HAADF image of region marked with blue box in Fig. 4(a). There is an obvious dark irregular strip between lamellas A and B. Figure 4(c) and 4(d) are enlarged views of regions C and D marked with blue boxes in Fig. 4(b). According to the line scanning results shown in Fig. 4(e), there is an obvious vibration of elements proportions along the dotted line in Fig. 4(d). Oxygen proportion obviously increases in dark irregular strip region, but silicon proportion decreases at the same position. This opposite changing tendency means dark irregular strip is OEA. As illustrated in Fig. 4(f) and 4(g), the mapping results of region shown in Fig. 4(c) also prove that the dark strip made up by white dotted line is the OEA. Furthermore, the contrast of OEA is high. The light gray area and dark gray area exist at the same time in OEA. Light gray area corresponds to silicon oxides with less oxygen, and the oxygen proportion in dark gray is higher, corresponding the silicon oxygen with more oxygen. This also demonstrates oxygen heterogeneously distribute in OEA of silicon lamellas.
The results obtained from EDS mapping images in Fig. 4 and XPS spectra in Sect. 3.3 both illustrate that oxygen atoms concentrate at the outermost layer of silicon lamellas. But the thickness of OEA depicted in Fig. 4 and Sect. 3.3 are greatly different. According to the XPS analysis results, we could find that the thickness of OEA is about 180 nm, but the maximum thickness of OEA depicted in EDS mapping images is only 30 nm. And this 30 nm thick OEA belongs to two adjacent lamellas. We know that the silicon coating is formed by lamellas piling one atop another. And the difference in thickness of OEA is attributed to the location of silicon lamellas. The results obtained from XPS spectra in Sect. 3.3 reflect the information of silicon lamellas at the top layer of coating. But EDS mapping images reveal the information about lamellas in inner coating. During the plasma spraying process, silicon powders are heated in inert gas flow. The high-speed inert gas flow incurs air entrainment as shown in Fig. 5. The silicon atoms at the surface of silicon droplets react with entrained oxygen, forming the silicon oxides. When hit the substrate, the solidification of silicon droplets always accompanies with the oxidation. Both in-flight and solidification are moments every silicon powder goes through in coating formation process. So OEA can be detected at any lamella, both on the top of coating and inside coating. But for lamellas on the top of silicon coating, they contact with oxygen not only in the process of plasma spraying, but also in the cooling process after removing the spraying gun[30, 31]. The in-flight time of silicon powders only lasts several microseconds, but the cooling time of top lamellas continues for several seconds. The longer contacting time between oxygen and lamellas leads to the thicker OEA of lamellas. So, the OEA in lamellas on the top layer of silicon coating is much thicker than that in lamellas inside the coating. Besides, oxygen heterogeneously distribute at the OEA of silicon lamellas due to the different oxygen permeability in different components[32]. When silicon atoms directly contacting with oxygen, SiO2 is formed covering the surface of silicon lamellas. With the penetration of oxygen in lamella, the SiO2 layer gets thicker. But the oxygen permeability in SiO2 is worse than that in Si. Oxygen partial pressure in inner lamella is not enough to generate SiO2, so less-oxygen oxides such as Si2O and SiOx forms inside the OEA. As depicted in Fig. 5 that Si and silicon oxides distribute from outside to inner OEA are Si + SiOx+SiO2→Si + Si2O + SiO2→Si + SiOx→Si (1<x<1.5).