为了探究在只有阴离子不同的情况下铜颗粒的沉积差异，将第二组硅片平均分为

In order to explore the difference in the deposition of copper particles when only the anions are different, the second group of silicon wafers is divided into 3 small piles, 4 pieces in each pile, and deposited in the nitric acid system, sulfuric acid system and chloride ion system for 5s, 10s. , Take it out after 30s and 60s, and observe the change of copper deposition state by SEM. Figures 2a~d show the copper deposition in the copper nitrate deposition system. In the first 10s of the reaction, a large number of copper ions capture electrons to form small copper particles. On the silicon surface, the copper is spread over the entire silicon wafer. As the deposition time increases, a large number of copper particles gather along the cut lines to form larger round copper particles. For the copper sulfate system, as shown in Figure 2e~h, the reaction just started , A dense copper film is quickly formed on the surface of the silicon wafer, and the size of the copper particles is small. When it is deposited to 60s, a small amount of agglomerated copper particles appear on the surface of the copper film, indicating that in the copper sulfate system, the copper is dispersed and small in size. The morphology of the dense copper film is deposited, and agglomeration is not easy to occur. In the chloride ion system, as shown in Figure 2I~l, the morphology at the beginning of the reaction is similar to copper nitrate, and the agglomeration phenomenon is obvious after 10s of deposition. After 30s, A large number of agglomerated rod-shaped copper particles appeared along the cut lines on the surface of the silicon wafer; Figure 2m~o shows the quality change of the silicon wafer before and after the deposition of the silicon wafer. It can be seen that after 60s of deposition, the copper sulfate and copper chloride systems before and after the deposition of silicon The mass loss of the flakes is within 0.002g, which can basically be considered that the quality has not changed. In the copper nitrate system, the mass loss reaches 0.007g, which is caused by the oxidation of the silicon surface by nitrate. Figure 2p uses Q to characterize the relative deposition of copper particles. Size and copper deposition rate, where mCU=m2-m1, it can be seen that the copper nitrate deposition rate is the fastest in the first 30s, and then due to the oxidation of nitrate, a small amount of copper particles are oxidized into copper ions, which makes the copper particles The amount of copper increases basically at a uniform rate, while the copper particles in the copper sulfate system increase rapidly, causing the copper deposition amount to exceed the copper particles in the copper nitrate system after 60s, and the copper deposition in the copper sulfate system is not restricted, making copper easier and faster Obtain electrons and spread the silicon surface in the form of a dense film instead of agglomerating together. Due to the polarization of the chloride ions in the copper chloride solution, the force between the chloride ions and the copper ions in the solution is strengthened, making the copper It is difficult for ions to capture electrons on the surface of silicon wafers and deposit them into copper particles, resulting in a slower copper deposition rate than the former two. It can be seen that the chemical properties of anions greatly affect the deposition of copper ions, and the deposition of copper greatly affects the etching rate, etching morphology, and reflectivity of the silicon wafer surface.

In order to explore the sedimentation differences of copper particles with different anions, the second group of silicon wafers was divided into 3 small piles of 4 pieces each, which were deposited in nitric acid systems, sulphuric acid systems and chloride ion systems in 5s, 10s, 30s and 60s. After removal, SEM was used to observe the change of copper deposition status, Figure 2a-d shows the deposition of copper in the copper nitrate deposition system, the reaction began in 10s, a large number of copper ion capture electrons to form small copper particles deposited on the silicon surface, so that copper covered the entire silicon wafer, With the extension of deposition time, a large number of copper particles along the cutting pattern gathered to form a larger round copper particles, copper sulfate system, as shown in Figure 2e to h, the reaction began, the silicon surface will quickly form a dense copper film, and copper particle size is small, deposited to 6 At 0s, a small amount of reunited copper particles appear on the surface of the copper film, indicating that in the copper sulfate system, copper is deposited in the form of a dispersed, small-size dense copper film, and it is not easy to reunite, while in the chloride ion system, as shown in Figure 2I to l, The initial form of the reaction is similar to copper nitrate, the deposition of 10s will obviously appear reunion phenomenon, 30s, the surface of the silicon wafer along the cutting pattern appeared a large number of reuniting rod copper particles; Before and after deposition in the copper chloride system silicon chip quality loss is within 0.002g, it can be basically considered that the quality has not changed, and in the copper nitrate system, the mass loss reached 0.007g, caused by nitric acid root oxidation of the silicon surface, Figure 2p Q shows the relative size of the deposition of copper particles and the deposition rate of copper, wherein mCU is m2-m1, it can be seen that in the first 30s, copper nitrate deposition rate is the fastest, and then due to the oxidation of nitric acid, a small amount of copper particles oxidized into copper ions, The amount of copper particles is increased at a basic uniform rate, while the copper particles in the copper sulfate system increase rapidly, resulting in copper deposits after 60s exceeding the copper particles in the copper nitrate system, and the deposition of copper in the copper sulfate system is unrestricted, making it easier for copper to obtain electrons quickly. So that the form of dense film covered the silicon surface, rather than reuniting together, and because of the polarization of chloride ions in the copper chloride solution, the force between chlorine ions and copper ions in the solution is strengthened, making it difficult for copper ions to capture the silicon surface electron deposition into copper particles. , resulting in a slower rate of copper deposition than the first two. It can be learned that the chemical properties of anions greatly affect the deposition of copper ions, while the deposition of copper greatly affects the rate of etching, etching, the reflectivity of the surface of silicon wafers.

In order to explore the deposition difference of copper particles with only different anions, the second group of silicon wafers were divided into three small stacks with four pieces in each pile, which were deposited in nitric acid system, sulfuric acid system and chloride ion system for 5S and 10s respectively, After 30s and 60s, the change of copper deposition state was observed by SEM. Fig. 2A ~ d shows the deposition of copper in the copper nitrate deposition system. In the first 10 seconds of the reaction, a large number of copper ions capture electrons to form small copper particles and deposit on the silicon surface, so that copper covers the whole silicon chip. With the deposition time prolonging, a large number of copper particles gather along the cutting lines to form large round copper particles In copper system, as shown in Fig. 2E ~ h, at the beginning of reaction, a layer of dense copper film is rapidly formed on the surface of silicon wafer, and the size of copper particles is small. When the copper particles are deposited to 60s, a small amount of agglomerated copper particles appear on the surface of the copper film, which indicates that in the copper sulfate system, copper is deposited in the form of dispersed and small-sized dense copper film, which is not easy to agglomerate; in the chloride ion system, as shown in Fig. 2I ~ 1 It is shown that the morphology of the reaction is similar to that of cupric nitrate at the beginning of the reaction. After 10s of deposition, a large number of rod-shaped copper particles appear on the surface of the silicon wafer along the cutting grain after 30s. Figure 2m ~ o shows the quality change of silicon wafer before and after deposition. It can be seen that after 60s of deposition, the mass loss of silicon wafer in copper sulfate and copper chloride system before and after deposition is less than 0.002g, which is basically acceptable It is considered that the mass loss of 0.007g in copper nitrate system is caused by the oxidation of silicon surface by nitrate. In Fig. 2p, q is used to characterize the relative size of copper particles deposition and the deposition rate of copper, where MCU = m2-m1. It can be seen that the deposition rate of copper nitrate is the fastest in the first 30 seconds, and then a small amount of copper particles are oxidized to copper ions due to the oxidation of nitrate The results show that the amount of copper particles increases at a constant rate, while the copper particles in the copper sulfate system increase rapidly, which leads to the copper deposition more than that in the copper nitrate system after 60 s. moreover, the copper deposition in the copper sulfate system is not limited, which makes it easier for copper to obtain electrons quickly, so that the dense film forms on the silicon surface instead of agglomerating together Because of the polarization of the ions, the interaction between chloride ions and copper ions in the solution is strengthened, which makes it difficult for copper ions to capture electrons on the surface of silicon wafers and deposit them into copper particles, resulting in slower deposition rate of copper than the former two. It can be seen that the chemical properties of anions greatly affect the deposition of copper ions, while the deposition of copper greatly affects the etching rate, etching morphology and reflectivity of silicon surface.