Method for removing SnO2 film from chamber

Abstract

A method for removing SnO2 residue from a processing chamber is provided as an embodiment. The method embodiment comprises introducing hydrocarbon gas and hydrogen gas into a plasma processing system at a ratio of 1% to 60%. The plasma generated by a plasma source is used to etch the SnO2 residue from the surface of the processing chamber. The SnH4 gas reacts with the hydrocarbon gas to generate a volatile organic tin compound. The method also provides evacuating the organic tin compound from the processing chamber. The hydrocarbon gas is introduced with the hydrogen gas at a ratio of 1% to 60% so that the rate at which the SnH4 gas decomposes into Sn powder is reduced.

Description

Technical Field

[0001] The presented embodiments relate to semiconductor substrate processing methods and equipment tools, and more particularly, to methods and systems for reducing tin oxide powder formation during plasma etch processes (eg, for cleaning plasma processing chambers). Background Art

[0002] The manufacture of integrated circuits (ICs) typically involves a plasma treatment step. During plasma treatment, a substrate (e.g., a semiconductor, dielectric, or metal substrate) is subjected to an etchant in the presence of plasma in a vacuum processing chamber. As a result, the substrate has material that is etched by the plasma, or has material deposited on an exposed surface of the substrate. Although most of the reactants and byproducts of the plasma treatment are discharged from the chamber by a vacuum pump, undesirable particles may remain in the chamber by attaching to the walls and components of the processing chamber. After multiple repetitions of the plasma treatment step, a film containing one or more byproducts of the plasma treatment may be formed. The presence of such a film may contaminate subsequent processing steps because particles of the film may sublimate and adversely affect the process chemistry. In addition, portions of the film may peel off from various surfaces and cause defects on the wafer substrate.

[0003] The implementation scheme of this article is produced in this context. Summary of the invention

[0004] Embodiments herein relate to methods for etching and removing tin (IV) oxide (SnO 2 , also known as stannic oxide) residues. It should be understood that the embodiments herein can be implemented in many ways, such as by a method, apparatus, system, device, or computer program on a computer readable medium. Several embodiments are described below.

[0005] In one embodiment, a method for removing SnO from a process chamber is provided. 2 The method comprises the steps of introducing hydrocarbon gas and hydrogen gas into a plasma processing system, wherein the ratio of the hydrocarbon gas flow rate to the hydrogen gas flow rate is between 1% and 60%. The method also provides: etching the SnO from the surface of the processing chamber using plasma generated by a plasma source of the plasma processing system; 2 Residues, using the hydrogen to etch the SnO 2 The residue produces stannane (SnH 4 ), the SnH 4The gas reacts with the hydrocarbon gas to generate a volatile organic tin compound. The method also provides: evacuating the organic tin compound from the processing chamber, wherein the hydrocarbon gas and the hydrogen gas are introduced together at a certain ratio so that SnH 4 The rate at which the gas decomposes into Sn powder is reduced.

[0006] In another embodiment, there is provided a SnO 2 A method for patterning a layer of SnO and simultaneously reducing the formation of tin (Sn) powder on a surface of a processing chamber of a plasma processing system. The method comprises: depositing SnO on a substrate; 2 layer, and applying an etching mask to the SnO 2 The method also provides: introducing hydrocarbon gas and hydrogen gas into the plasma processing system, wherein the ratio of hydrocarbon gas flow rate to hydrogen gas flow rate is between 1% and 60%. The method also provides: etching the SnO 2 The SnO 2 SnH 4 Gas, the SnH 4 The gas reacts with the hydrocarbon gas to form a volatile organic tin compound. In addition, the method includes: evacuating the organic tin compound from the processing chamber, wherein the hydrocarbon gas and the hydrogen gas are introduced together at a ratio between 1% and 60% so that SnH 4 The rate of decomposition into Sn powder is reduced.

[0007] In another embodiment, a plasma processing system is provided. The system includes: a hydrogen gas supply source and a hydrocarbon gas supply source; a processing chamber; a first mass flow controller and a second MFC, wherein the first mass flow controller is used to control the flow rate of hydrogen gas flowing into the processing chamber, and the second MFC is used to control the flow rate of hydrocarbon gas flowing into the processing chamber. The system also provides a plasma source, which is used to generate plasma in the processing chamber, and the plasma is used to etch SnO 2 In addition, the plasma processing system includes a controller for adjusting the first MFC and the second MFC so that the ratio of the hydrocarbon gas flow rate to the hydrogen gas flow rate flowing into the processing chamber is between 1% and 60%, so that when etching the SnO 2 SnH is generated during 4 When the SnH 4 In the reaction, it reacts with hydrocarbon gas to form a volatile organic tin compound, which is more 4The decomposition reaction into Sn powder is more kinetically favorable, wherein the formation of the organotin compound enables Sn to be extracted from the process chamber to prevent Sn powder from etching SnO. 2 During deposition on the surface of the processing chamber.

[0008] These and other advantages will be appreciated by those skilled in the art from a reading of the entire specification and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0009] The embodiments are best understood by referring to the following description taken in conjunction with the accompanying drawings.

[0010] Figure 1A According to one embodiment, a simplified processing chamber is shown, wherein SnO 2 The layers are deposited on a substrate.

[0011] Figure 1B According to one embodiment, a cleaning process is shown which involves plasma etching SnO from the interior surface of the process chamber. 2 membrane.

[0012] Figure 2A and 2B Showing etching and removal of SnO from the process chamber 2 Embodiment of a chemical process to reduce Sn powder formation during thin film.

[0013] Figure 3 A schematic diagram of a plasma processing system is shown according to one embodiment, wherein the plasma processing system undergoes a process of removing SnO from a processing chamber using a mixture of hydrogen and hydrocarbon gases. 2 Residue handling.

[0014] Figure 4 According to one embodiment, the SnO 2 Simplified schematic diagram of an inductively coupled plasma (ICP) processing system for a residue removal method.

[0015] Figure 5 A simplified schematic diagram of an ICP and CCP plasma processing system is shown according to one embodiment, wherein the system undergoes SnO removal from the interior walls of the processing chamber. 2 Residue handling.

[0016] Figure 6 A simplified schematic diagram of a plasma processing system is shown according to one embodiment, wherein the plasma processing system has a CCP configuration and is connected to a remote ICP source to remove SnO from a processing chamber. 2 Residue.

[0017] Figure 7A simplified schematic diagram of a plasma processing system for treating SnO in a stack is shown. 2 layer is etched.

[0018] Figures 8A-8D According to various embodiments, the use of hydrogen plasma chemistry to etch SnO 2 And the final result of forming Sn powder.

[0019] Figures 9A-9D The use of hydrogen and hydrocarbon plasma chemistries to etch SnO 2 And the experimental results of reducing Sn powder formation.

[0020] Fig.10 A reactor system is shown according to one embodiment that can be used to deposit films on a substrate, such as those formed in an atomic layer deposition (ALD) process.

[0021] Fig.11 A top view of a multi-station processing tool is shown according to one embodiment, wherein four processing stations are arranged.

[0022] Fig.12 A schematic diagram of an embodiment of a multi-station processing tool having an inbound load lock and an outbound load lock is shown according to one embodiment. DETAILED DESCRIPTION

[0023] Although the following detailed description contains many specific details for the purpose of illustration, it will be appreciated by those skilled in the art that many variations and modifications of the following details are within the scope of the present disclosure. Therefore, the aspects of the present disclosure described below are set forth without causing any loss of generality to the subsequent claims and without imposing limitations.

[0024] SnO 2 Layers (e.g., thin films) are considered for use in substrate processing for a variety of applications. Some of these applications include as an extreme ultraviolet (EUV) hard mask (HM), as spacers and mandrel cores for patterning, as a gap fill oxide, as a hard mask, and as an etch stop layer. SnO can be deposited on a substrate in several ways. 2 In a chemical vapor deposition (CVD) process, a substrate is exposed to a phase containing tin (e.g., Sn(CH 3 ) 4 SnCl 4 , Sn, etc.) to form SnO on the substrate 2 layer

[0025] SnO 2The deposition of SnO usually leads to the accumulation of residue films on the internal surfaces of the plasma chamber, including the chamber walls, showerheads, electrodes, substrate supports, chucks, etc. 2 When the film is formed on the inner surface of the plasma chamber, these SnO 2 Films tend to contaminate wafer substrates by peeling off from internal surfaces. Therefore, the processing chamber must be cleaned regularly to prevent wafer contamination.

[0026] It is conceivable that SnO can be removed from the processing chamber 2 One method is to use plasma to etch SnO 2 SnO 2 Easily reacts with a variety of chemicals (such as H 2 , Cl 2 , Br, HBr, BCl 3 , HI and I 2 However, since many of the processing chambers used are made of aluminum components, materials such as Cl 2 , Br, HBr, HI and I 2 Chemicals such as , as they cause degradation of aluminum components. Therefore, consider using H 2 Plasma chemistries to etch SnO from the interior walls and components of the processing chamber (such as those with aluminum components) 2 membrane

[0027] When using H 2 Chemicals to etch SnO 2 When the film is formed, the volatile SnH 4 However, in connection with the present invention, it has also been found that the use of H 2 Plasma chemicals for SnO 2 Etching of the film will form Sn residues in powder form. For example, in industrial reactors (such as those manufactured by Lam Research Corporation (Fremont, CA) Tin powder is subjected to SnH 4 Tin powder is formed in large quantities by decomposition. This is true whether the reactor is configured as a capacitively coupled plasma (CCP) or inductively coupled plasma (ICP) source. The formed tin powder is a source of contamination for subsequent processing steps and may cause defects in the processing operation.

[0028] The embodiments described herein enable the use of H 2 Plasma Chemicals Etch SnO 2, and at the same time reduce or nearly eliminate the formation of tin powder. In particular, various hydrocarbon gases have been tested for their ability to provide thermodynamically and kinetically superior SnH 4 The decomposition reaction into tin powder is more favorable for SnH 4 A number of hydrocarbon gases and their reaction with H have been proposed for this purpose. 2 to achieve the best effect in reducing tin powder formation.

[0029] With the above general understanding of various embodiments, exemplary details of the embodiments will now be described with reference to various drawings. Elements and / or components with similar reference numerals in one or more of the drawings are meant to generally have the same configuration and / or function. In addition, the drawings may not be drawn to scale, but are intended to illustrate and emphasize new concepts. Obviously, embodiments of the present invention can be implemented without some or all of these specific details. On the other hand, well-known processing operations are no longer described in detail herein to avoid unnecessarily obscuring embodiments of the present invention.

[0030] As used herein, a "favorable" reaction is used to refer to a kinetically favorable reaction and / or a thermodynamically favorable reaction under the conditions (e.g., pressure, temperature, reactant concentration, and presence of plasma) in which the reaction is expected to occur. A thermodynamically favorable reaction is a reaction in which the reaction product has a lower free energy than the reactant. A kinetically favorable reaction is a reaction in which the reaction activation energy is low enough so that the reaction can be carried out within a period commonly used in substrate processing operations. As used herein, when the reactant can be carried out via a first or second reaction, and the first reaction is more favorable than the second reaction, it generally means that the first reaction can be more thermodynamically favorable (e.g., having a Gibbs free energy that is more negative than the Gibbs free energy of the second reaction) and / or kinetically more favorable (e.g., the first reaction has a reaction rate greater than the reaction rate of the second reaction) than the second reaction. As used herein, a kinetically more favorable first reaction is a reaction caused by the conditions of the plasma processing chamber, which is carried out at a rate greater than the second reaction, so that the reactant is more likely to react via the first reaction than the second reaction.

[0031] Figure 1A According to one embodiment, a simplified processing chamber 100 is shown, wherein SnO 2 Layer 118 is deposited on the substrate. Processing chamber 100 includes wall 102, chuck 104, lower electrode 106, upper electrode 108, showerhead 110, drain 112, wafer 114, layer 116, and SnO formed by the deposition process. 2Layer 118. In certain embodiments, SnO can be deposited by chemical vapor deposition (CVD), atomic layer deposition (ALD), and other processes. 2 In an exemplary CVD process, a tin precursor (e.g., SnCl 4 ) is introduced into the processing chamber 100 via the showerhead 110. In this example, Sn reacts with the substrate and oxygen to form SnO 2 Byproducts (such as Cl 2 ) and unreacted tin precursor are discharged through the discharge portion 112.

[0032] SnO is deposited on 2 Layer 116 of layer 118 may include spin-on carbon (SOC), photoresist (PR), silicon layer, metal layer, glass, etc. 2 During the deposition of SnO 2 The film is formed on the inner surfaces of the process chamber 100, including the inner surfaces of the wall 102, the chuck 104, the lower electrode 106, the upper electrode 108, and the showerhead 110. 2 During the multiple repetitions of the deposition process, SnO 2 Films can grow and can become a source of contamination in subsequent plasma processing steps. Therefore, plasma etching is routinely performed in a cleaning step of the processing chamber.

[0033] Figure 1B According to one embodiment, a cleaning process is shown that involves plasma etching SnO from the interior surface of the processing chamber 100. 2 Film 120. SnO 2 Film 120 is shown adhered to wall 102, lower electrode 106, upper electrode 108, and the interior surfaces of showerhead 110. SnO 2 The film 120 may also be formed on components within a processing chamber (not shown).

[0034] When the plasma 122 is energized in the processing chamber 100, the plasma 122 begins to react with SnO 2 The film 120 is etched 124. 2 In one embodiment of the plasma chemistry, the following reaction occurs in the presence of a plasma:

[0035] SnO 2 +H 2 →SnH 4 (1)

[0036] In the temperature and pressure ranges used to maintain the plasma 122, SnH 4 is a volatile compound. Therefore, the SnH generated by the etching 124 process4 Most of SnH is evacuated from the process chamber 100. However, 4 A portion of the gas will tend to decompose into tin powder which is described by the following reaction:

[0037] HkDJ 4 →Sn(powder)+H 2 (2)

[0038] It is observed for the present disclosure that SnH 4 The decomposition of SnH occurs at a higher rate in plasma treatment conditions with lower density of radicals and ions in the formed plasma. 4 The decomposition of SnO also occurs at a higher rate under processing conditions with higher pressures. The amount of Sn powder formed by the cleaning process varies, depending on the SnO 2 The amount or thickness of the film 120, and various other parameters related to the plasma processing conditions, such as temperature, pressure, frequency of radio frequency (RF) power, and whether the plasma is generated via CCP or ICP. The amount of Sn powder formed via the cleaning process may therefore vary from less than about 0.001 grams to more than about 10 grams. When Sn powder is formed, it cannot be discharged from the chamber, but is manually removed through a time-consuming cleaning process.

[0039] Therefore, improved plasma chemistry is considered to facilitate etching and cleaning of SnO from the interior surfaces of the processing chamber. 2 film, and at the same time reduce SnH 4 Decompose into Sn powder. Figure 2A In one embodiment shown in FIG. 1 , hydrocarbon gas is mixed with H 2 The hydrocarbon gas is expected to be SnH 4 Gases provide kinetically favorable reaction pathways to form volatile organotin compounds. For example, k 1 The expected reaction rate is k 2 From about 2 to about 10 12 times or about 10 2 to about 10 9 times, or about 10 3 to about 10 6 times, depending on various parameters and implementation. Organotin compounds are volatile and are vented from the process chamber. 4 Reaction with hydrocarbons, SnH 4 Decomposition into Sn powder was significantly reduced and in many cases undetectable.

[0040] In About Figure 2A In one embodiment, the hydrocarbon flow rate is H 2The ratio of the flow rate is between about 1% to about 60%, or between about 2% to about 10%, or between about 5% to about 8%. In one embodiment, the temperature of the processing chamber is maintained at about 65°C to about 300°C. In one embodiment, the RF power supplied is about 500W to about 5000W. In various embodiments, the frequency of the RF power is about 13.56MHz or about 27MHz. For various embodiments, 27MHz can be used for faster etching rates due to the higher hydrogen radical concentration. In various embodiments, the pressure of the chamber can be set at about 0.1Torr to about 10Torr. Higher pressures within this range are expected to have a greater effect when etching more centrally located chamber components (such as electrodes), while lower pressures within this range are expected to be more suitable for etching components located near the outer positions of the chamber. In addition, hydrocarbons and H 2 The plasma chemistry is effective in reducing Sn powder formation in both ICP and CCP configurations.

[0041] Figure 2B shows the etching and removal of SnO from the chamber 2 Another embodiment of the reaction to reduce the formation of tin powder during the processing of the thin film. Figure 2B In an embodiment of the present invention, CH 4 With H 2 When gaseous SnH 4 Through SnO 2 When the plasma etching of the film is generated from the inner surface of the chamber, CH 4 With SnH 4 The reaction produces Sn(CH 3 ) 4 .SnH 4 With CH 4 Formation of Sn(CH 3 ) 4 The reaction pathway is better than SnH 4 Decomposition into Sn powder is kinetically more favorable. For example, the reaction rate k 3 The expected reaction rate k 2 From about 2 to about 10 12 times or about 10 2 Up to 10 9 times, or about 10 3 Up to 10 6 times, depending on various parameters and implementation. Sn(CH 3 ) 4 It is volatile at the temperature and pressure maintained in the chamber and is easily evacuated from the chamber. 4 With H 2The plasma chemistry is expected to allow the plasma to etch and remove SnO from the chamber. 2 The amount of tin powder formed during processing of the film is reduced.

[0042] In About Figure 2B In one embodiment, CH 4 Flow ratio H 2 The ratio of the flow rate is between about 1% to about 60%, or between about 2% to about 10%, or between about 5% to about 8%. In one embodiment, the temperature of the processing chamber is maintained at about 65°C to about 300°C. In one embodiment, the RF power supplied is about 500W to about 5000W. In various embodiments, the frequency of the RF power is about 13.56MHz or about 27MHz. For various embodiments, 27MHz can be used for faster etching rates due to the higher concentration of hydrogen radicals. In various embodiments, the pressure of the chamber can be set at about 0.1Torr to about 10Torr. Higher pressures within this range are expected to have a greater effect when etching more centrally located chamber components (such as electrodes), while lower pressures within this range are expected to be more suitable for etching components located near the outer position of the chamber. In addition, CH 4 and H 2 The plasma chemistry is effective in reducing Sn powder formation in both ICP and CCP configurations.

[0043] Figure 3 A schematic diagram of a plasma processing system 300 is shown according to one embodiment, wherein the plasma processing system 300 undergoes a process of removing SnO from the processing chamber 100 using a mixture of hydrogen and hydrocarbon gases. 2 Residue 120 operation. 2 The hydrogen gas is supplied by the hydrogen supply source 302, and the hydrocarbon gas is supplied by the hydrocarbon gas supply source 304. 2 The flows of H and hydrocarbon gas are controlled by MFC306 and 308 respectively, and both MFC306 and 308 are controlled by controller 301. 2 Both H and hydrocarbon gases flow through respective lines to a gas supply manifold 310, which mixes the gases and feeds the resulting gas mixture to the showerhead 110. The showerhead 110 feeds H 2 and hydrocarbon gas is distributed into the processing chamber 100. RF power supply 312 and matching network 314 are shown supplying power to the lower electrode 106. The upper electrode 108 is positioned parallel to the bottom electrode and is grounded. The plasma 122 is ignited and maintained between the upper electrode 108 and the lower electrode 106. In other embodiments, the RF power supply 312 can supply power to the upper electrode 108, while the bottom electrode 106 is grounded.

[0044] SnO 2Residue 120 is shown adhering to and coating the surface of chamber 100. In the previous SnO 2 During the deposition process, SnO 2 The residue 120 may be formed as a crystalline layer, a matrix, a tube, or an amorphous shape on the surface of the processing chamber 100. The plasma 122 excites the hydrogen gas to react with the SnO 2 The residue 120 reacts to generate SnH 4 The plasma 122 also excites the hydrocarbon gas supply to react with SnH 4 The reaction generates volatile organic tin compounds, which are exhausted from the processing chamber 100 via the exhaust portion 112. In one embodiment, CH 4 Used as hydrocarbon gas. 4 When exposed to plasma 122, reactive ions and free radicals are generated, such as CH 4 +、CH 3 , CH 3 +、CH 2 +, CH+, C+, CH 5 +, etc. These ions and free radicals are important for SnH 4 , CH 4 , and are highly reactive with each other. One of the products is SnR 4 , where R is CH 3 , C 2 H 5 , C 2 H 3 , or other carbon substances. In addition, CH 4 Some of the free radicals and ions react with each other to form carbonaceous polymers, the rate of which varies with the amount of CH 4 As the molecular weight of these carbonaceous polymers increases, their tendency to vaporize decreases, which is attributed to many kinetic and intermolecular interaction factors.

[0045] Therefore, the expected range of hydrocarbon gas flow rate relative to hydrogen flow rate is designed so that a sufficient concentration of CH 4 Free radicals and ions can react with SnH 4 Reaction to prevent SnH 4 On the other hand, the ratio of the hydrocarbon gas flow rate to the hydrogen gas flow rate is also designed to be low enough to ensure that carbonaceous polymers do not form to the extent that these carbonaceous polymers are used to etch SnO 2 The residue is no longer in a gaseous state at a temperature and pressure range. As determined empirically, this range has been found to be between about 1% to about 60%, or between about 2% to about 10% hydrocarbon flow to hydrogen flow, or about 7%.

[0046] Certain embodiments may have a hydrocarbon flow ratio H greater than 60%, such as up to 100% (e.g., containing only hydrocarbons). 2 However, as the proportion of hydrocarbon increases, the possibility of forming carbonaceous polymers and their subsequent deposition or condensation also increases. On the other hand, a small flow rate of hydrocarbon gas can be used, so that the ratio of hydrocarbon gas flow rate to hydrogen flow rate is less than 1%. However, it has been found that when the ratio of hydrocarbon gas flow rate to hydrogen flow rate is less than about 1%, the hydrocarbon reactant is insufficient, resulting in a certain amount of SnH 4 decomposes into Sn powder. In addition, once SnH 4 The Sn powder decomposes into Sn powder, which is no longer reactive towards hydrocarbon gas under the expected plasma conditions. Therefore, the Sn powder must be removed from the process chamber manually, and the Sn powder cannot be volatilized under the typical temperature and pressure range used in the process chamber.

[0047] Figure 4 According to one embodiment, the SnO 2 A simplified schematic diagram of an inductively coupled plasma (ICP) processing system 400 for a residue removal method. The ICP processing system 400 is shown to include an ICP source 401 and a processing chamber 100 separated by a wall 408. The ICP source 401 is formed by a chamber wall 406 and a dielectric window 404. A gas inlet (not shown) introduces a mixture of hydrogen and hydrocarbon gases into the chamber of the ICP source 401. The ICP source 401 also includes an induction source 402, which in some embodiments takes the form of a coil, which is located at the dielectric window 404. The induction source 402 is powered by an RF power source 403 and generates a time-varying magnetic field that excites the gas present in the chamber of the ICP source 401 into a plasma 122. The ICP source 401 can be generally cylindrical in shape, dome-like in shape, conical in shape, or some other shape that enables the induction source 402 to induce and maintain a plasma in the chamber of the ICP source 401. In some embodiments, chamber wall 406 is grounded (as shown), while in other embodiments, a portion of inductive source 402 is grounded.

[0048] The plasma 122 generates hydrogen and hydrocarbon radicals and ions. In some configurations, the plasma generates H, H+, and H- from hydrogen. If CH 4 As hydrocarbon gas, the plasma makes CH 4 +、CH 3 , CH 3 +、CH 2 +, CH+, C+, CH 5 + and other free radicals and ions are generated. These free radicals and ions are introduced into the processing chamber 100 through the opening 410 in the wall 408. The hydrogen-containing free radicals and ions diffuse around in the processing chamber 100 and react with SnO2 The residue 120 reacts to generate SnH 4 , its macroscopic effect is on SnO 2 The residue 120 is etched 124. Once SnH is generated during the etching 124 4 The carbon-containing radicals and ions in the processing chamber 100 react with SnH 4 react to form organotin compounds such as Sn(CH 3 ) 4 , or Sn 2 (CH 3 ) 6 , or SnH 4 , wherein R is hydrogen or alkyl.

[0049] Organotins with simple alkyl groups (e.g., methyl, ethyl, etc.) remain volatile and do not deposit at the temperature and pressure of the process chamber 100 used for etching 124. However, when the alkyl group of the organotin compound reaches a certain length, molecular weight, and branching, the organotin compound becomes less volatile. Therefore, it is found that a flow rate of hydrocarbon between about 1% and about 60% of the flow rate of hydrogen is effective in reducing the deposition of the organotin compound, while supplying enough hydrocarbon to react with SnH 4 The reaction is carried out. In addition, it has been found that for the embodiments herein, an effective ICP configuration has a temperature range of about 40°C to about 500°C, or about 100°C to about 400°C, or about 150°C to about 180°C, or about 160°C; a pressure range of about 0.1 Torr to about 10 Torr, or about 1 Torr to about 8 Torr, or about 7 Torr; and a power of about 50W to about 5000W, or about 100W to about 4000W, or about 250W to about 1000W at about 13.56, 27, or 35MHz.

[0050] Although Figure 4 The embodiment shown in FIG. 4 has the ICP source 401 connected to the processing chamber 100 via a plurality of openings 410, but other embodiments are contemplated in which the ICP source 401 is capable of feeding hydrogen and hydrocarbon radicals and ions into the processing chamber 100 via one or more interconnecting channels. In other embodiments, the ICP source 401 is considered a remote plasma source and is not necessarily connected to the processing chamber 100. Figure 4 The embodiment is generally adjacent to the processing chamber 100.

[0051] Figure 5 A simplified schematic diagram of a hybrid ICP and CCP plasma processing system 500 is shown that undergoes SnO removal from the interior wall 102 of the processing chamber 100 according to one embodiment. 210. The operation of the residue 120. Hydrogen and hydrocarbon gases are supplied by a hydrogen supply source 302 and a hydrocarbon gas supply source 304 via MFCs 306 and 308 and a gas supply manifold 310. In this embodiment, both CCP and ICP configurations are used to generate plasma 122. An RF power supply 312 supplies power to the lower electrode 106, while the upper electrode 108 is grounded. An electric field is thereby generated between the lower electrode 106 and the upper electrode 108, which excites the hydrocarbon and hydrogen gases to form plasma 122. The plasma 122 is additionally excited by a magnetic field provided by an induction source 402, which assists in maintaining and controlling the density and position of the plasma 122. In the configuration shown, the induction source 402 has the shape of a coil and is grounded at one or both ends of the coil.

[0052] Figure 6 A simplified schematic diagram of a plasma processing system 600 is shown having a CCP configuration and connected to a remote ICP source 601 to remove SnO from a processing chamber 100 according to one embodiment. 2 The hydrogen gas is provided to the remote ICP source 601 where it is excited via a magnetic field. Once excited, free radicals and ions flow into the processing chamber 100 to react with SnO 2 The residue is etched 124. A hydrocarbon gas is provided into the processing chamber and excited into a plasma 122, which is combined with the etching of SnO 2 The residue 120 produces SnH 4 As a result, the SnO 2 Residue 120 is removed from chamber 100 without Sn powder formation (eg, or effectively reducing such formation). In certain embodiments, remote ICP source 601 may be used to activate (eg, excite, ionize, dissociate, generate free radicals, etc.) hydrocarbon gas, while CCP may be used to activate hydrogen gas.

[0053] In another embodiment with a remote ICP source coupled to a process chamber, it is contemplated that Ar and / or He gas is introduced into the ICP source, while hydrocarbon and hydrogen gas is introduced into the process chamber. When a plasma is generated from the Ar and / or He gas in the remote ICP source, Ar and He ions are fed into the process chamber to excite the hydrocarbon and hydrogen gas. The Ar and He ions are highly reactive and once in the process chamber, hydrocarbon ions and free radicals are generated with hydrogen ions and free radicals. The hydrogen ions and free radicals react with SnO 2 The residue is reacted to form SnH 4 , while hydrocarbon radicals and ions react with SnH 4reacts to form volatile organotin compounds that will be purged from the system. Thus, there are contemplated embodiments where hydrogen and hydrocarbon gases can be utilized to etch and remove SnO from the system. 2 residues without having to form a plasma from hydrogen and hydrocarbon gases.

[0054] Figure 7 A simplified schematic diagram of a plasma processing system 700 is shown for treating SnO in a stack 701. 2 The stack 701 is shown as including a substrate (e.g., a wafer), one or more layers, which may include photoresist, spin-on carbon, silicon dioxide, a metal layer, an organometallic layer, or some other material. The stack 701 is also shown as including the etched SnO 2 layer and a photoresist for blocking etching 702. When SnO 2 When etched by the plasma 122, SnH 4 , SnH 4 may decompose into Sn powder and deposit on the substrate and other surfaces of the process chamber 100. 4 Decompose to form Sn powder, it is possible that SnO 2 However, since hydrocarbon gas is also supplied to the process chamber 100, SnH 4 It reacts with hydrocarbon ions and free radicals to form volatile organotin compounds that are vented from the process chamber. As a result, SnH 4 The decomposition into Sn powder is reduced. Therefore, it is also contemplated that the SnO 2 The formation of Sn powder is reduced in situ during the layering.

[0055] Figures 8A-8D According to various embodiments, the use of hydrogen plasma chemistry to etch SnO 2 And the final result of Sn powder formation. For example, Fig. 8A The SnO 2 A wafer placed in a process chamber during film etching. The right side of the wafer shows that Sn powder has accumulated, while the left side of the wafer shows the wafer after the Sn powder has been wiped off. Figure 8B It is also shown that when using a remote ICP source and hydrogen chemistry to etch SnO 2 Sn powder is formed when the film is formed. Figure 8C The same wafer is shown after being wiped. Fig.8D Shows Figure 8BX-ray scans of the wafers of FIG. 1 and FIG. 2 show that Sn powder is formed for the range of 0.5 Torr to 6 Torr for the plasma processing chamber. In addition, it is found that the following conditions lead to Sn powder formation: SnO is treated in the plasma processing chamber within its specified pressure range of 200 mTorr to 10 Torr and temperature range of 40°C to 400°C. 2 Etching is performed.

[0056] Figures 9A-9D The use of hydrogen and hydrocarbon plasma chemistries to etch SnO 2 And the experimental results of reducing Sn powder formation. Fig. 9A In the experiment, CCP plasma was used with hydrogen and CH 4 Chemicals to etch input SnO with 400 angstroms 2 The wafer was etched to a thickness of about 40 angstroms. The right side of the wafer is after etching, while the left side of the wafer is after wiping, showing the effects of using hydrogen and CH 4 Chemicals are used to reduce the formation of Sn powder so that no observable Sn powder is formed on the wafer. Fig. 9B shows the use of hydrogen and CH 4 X-ray scans of the wafer before and after etching with the chemical confirm that SnO 2 The thickness is uniform and no Sn powder is formed.

[0057] Fig. 9C shows the use of a remote ICP source with hydrogen and CH 4 Wafer after 360 seconds of etching with the chemical. Similar to Fig. 9A The etched wafer shown in FIG. 1 was etched using hydrogen and CH 4 The ICP mode of etching with the chemical also did not form observable Sn powder after 360 seconds of treatment. Fig.9D X-ray scans of the thickness of the etched wafer after 0, 5, 60, 180, and 360 seconds are shown. Before etching, the wafer had a thickness of SnO of about 250 angstroms. 2 After 360 seconds of treatment, SnO 2 is etched away without leaving observable Sn powder. In some embodiments, the 4 The ratio of the flow rate to the hydrogen flow rate is optimized, and the CH 4 The flow rates of ions and radicals and hydrogen ions and radicals are optimized, as well as the temperature and pressure range of the process chamber to achieve processing times of less than 360 seconds using a higher density plasma from a remote ICP source.

[0058] It should be noted that Figures 8A-8C, 9A and 9B have vertical white marks due to reflections from ceiling lights. These white marks do not represent any structure of the wafer shown.

[0059] Fig.10 A reactor system 1000 is shown that can be used to deposit films on a substrate, such as those formed in an atomic layer deposition (ALD) process. These reactors can use two or more heaters, and a common terminal configuration can be used in this exemplary reactor to control temperature to achieve uniformity or custom settings. Specifically, Fig.10 A substrate processing system 1000 for processing a wafer 1001 is shown. The system includes a chamber 1002 having a lower chamber portion 1002b and an upper chamber portion 1002a. A central column is configured to support a pedestal 1040, which in one embodiment is a powered electrode. In one embodiment, the pedestal 1040 is electrically coupled to a power source 1004 via a matching network 1006. The power source is controlled by a control module 1010 (e.g., a controller). The control module 1010 is configured to operate the substrate processing system 1000 by executing a process input and control device 1008. The process input and control device 1008 may include a process recipe (e.g., power level, timing parameters, process gases, mechanical movement of the wafer 1001, etc.) to, for example, deposit or form a film on the wafer 1001.

[0060] The central column also includes lift pins (not shown), each of which is actuated by a corresponding lift pin actuation ring 1020 controlled by a lift pin control device 1022. The lift pins are used to lift the wafer 1001 from the pedestal 1040 so that the end effector can pick up the wafer and lower it after the end effector places the wafer 1001. The substrate processing system 1000 also includes a gas supply manifold 1012 connected to a process gas 1014 (e.g., a gas chemical supply source from a factory). Depending on the process being performed, the control module 1010 controls the delivery of the process gas 1014 through the gas supply manifold 1012. The selected gas is then flowed into the showerhead 1050 and distributed in the spatial volume defined between the face of the showerhead 1050 facing the wafer 1001 and the wafer 1001 disposed on the pedestal 1040. In the ALD process, the gas can be a reactant selected for adsorption or a reactant that reacts with the adsorbed reactant.

[0061] In addition, the gases may be premixed, or not. Appropriate valve control and mass flow control mechanisms may be employed to ensure that the appropriate gases are delivered during the deposition and plasma treatment phases of the process. The process gases leave the chamber via an outlet. A vacuum pump (e.g., a one- or two-stage mechanical dry pump and / or a turbomolecular pump) draws the process gases out and maintains a suitably low pressure within the reactor through a closed-loop controlled flow restriction (e.g., a throttle valve, or a pendulum valve).

[0062] Also shown is a carrier ring 1200 surrounding an outer region of the pedestal 1040. The carrier ring 1200 is configured to sit on a carrier ring support area that is a step down from a wafer support area in the center of the pedestal 1040. The carrier ring includes an outer edge side (e.g., an outer radius) of its dish-shaped structure and a wafer edge side (e.g., an inner radius) of its dish-shaped structure that is closest to where the wafer 1001 is disposed. The wafer edge side of the carrier ring includes a plurality of contact support structures that are configured to lift the wafer 1001 when the carrier ring 1200 is lifted by the spider forks 1080. The carrier ring 1200 is thus lifted along with the wafer 1001 and can be transferred to another station (e.g., in a multi-station system). In other embodiments, the chamber is a single-station chamber.

[0063] Fig.11 A top view of a multi-station processing tool is shown, wherein four processing stations are provided. The top view is of a lower chamber portion 1002b (e.g., with the top chamber portion 1002a removed for illustration), wherein the four processing stations are accessed by crosses 1226. Each cross or fork includes first and second arms, each of which surrounds a portion of each side of the susceptor 1040. In this figure, the crosses 1226 are depicted with dashed lines to convey that they are located below the carrier ring 1200. The crosses 1226 using the engagement and rotation mechanism 1220 are configured to simultaneously lift and raise the carrier ring 1200 from the processing station (i.e., from the lower surface of the carrier ring 1200), and then rotate at least one or more stations to the next position before lowering the carrier ring 1200 (where at least one carrier ring supports a wafer 1001) so that further plasma processing, treatment and / or film deposition can be performed on the corresponding wafer 1001.

[0064] Fig.12A schematic diagram of an embodiment of a multi-station processing tool 1300 having an inbound load lock 1302 and an outbound load lock 1304 is shown. A robot 1306 at atmospheric pressure is configured to move substrates from a cassette loaded via a pod 1308 into the inbound load lock 1302 via an atmospheric port 1310. The inbound load lock 1302 is coupled to a vacuum source (not shown) so that the inbound load lock 1302 can be evacuated when the atmospheric port 1310 is closed. The inbound load lock 1302 also includes a chamber transfer port 1316 connected to the processing chamber 1002b. Thus, when the chamber transfer port 1316 is opened, another robot (not shown) can move the substrate from the inbound load lock 1302 to the pedestal 1040 of the first processing station for processing.

[0065] The depicted processing chamber 1002b includes four processing stations, which are Fig.12 In the illustrated embodiment, the processing chamber 1002b can be configured to maintain a low pressure environment so that substrates can be transported between processing stations using the carrier ring 1200 without experiencing a vacuum break and / or exposure to air. Fig.12 Each of the processing stations includes a processing station substrate holder (shown at 1318 for processing station 1) and a process gas delivery line inlet.

[0066] Fig.12 Also depicted is a cross 1226 for transferring substrates within the processing chamber 1002b. The cross 1226 rotates the wafer and can transfer the wafer from one station to another. The transfer can be performed by causing the cross 1226 to lift the carrier ring 1200 from the outer lower surface to lift the wafer and transfer the wafer and carrier together to the next station. In one configuration, the cross 1226 is made of a ceramic material to withstand high levels of heat during processing.

[0067] The computer program for controlling the delivery of process gases may be written in, for example, any conventional computer readable programming language: assembly language, C, C++, Pascal, Fortran or others. The compiled object code or script is executed by the processor to perform the tasks identified in the program.

[0068] System software can be designed or configured in many different ways. For example, various chamber subroutines or control objects can be written to control the operation of chamber components necessary to perform flow control processes.

[0069] In view of the above embodiments, it should be understood that these embodiments can adopt many computer-implemented operations, which involve data stored in a computer system. These operations are operations that require the physical manipulation of physical quantities. Any operation that constitutes a part of the embodiments described herein is a useful machine operation. Some of these embodiments also relate to devices or equipment that perform these operations. The device can be built specifically for the desired purpose, such as a special-purpose computer. When defined as a special-purpose computer, the computer can also perform other processing, program execution or routines of non-special-purpose parts, and still have the ability to operate for special purposes. Alternatively, the general-purpose computer that can be selectively enabled or configured by one or more computer programs stored in a computer memory, a cache, or obtained via a network can process the operations. When data is obtained through a network, other computers on a computer network (e.g., a cloud of computing resources) can be used to process the data.

[0070] One or more embodiments may also be compiled as computer readable code on a computer readable medium. A computer readable medium is any data storage device that can store data that can thereafter be read by a computer system. Examples of computer readable media include hard disks, network attached storage (NAS), read-only memory, random access memory, CD-ROMs, CD-Rs, CD-RWs, magnetic tapes, and other optical and non-optical data storage devices. Computer readable media may include computer readable tangible media distributed across a network coupled computer system such that computer readable code is stored and executed in a distributed manner.

[0071] Although these method operations are described in a particular order, it should be understood that other housekeeping operations may be performed between multiple operations, or the operations may be coordinated so that the operations occur at slightly different times, or the operations may be distributed in a system that allows multiple processing operations to occur at many intervals related to the processing, as long as the processing of overlapping operations is performed in the desired manner.

[0072] Although the foregoing embodiments have been described in considerable detail for the purpose of clarity of understanding, it should be understood that certain changes and modifications may be made within the scope of the disclosed embodiments. It should be noted that there are many alternative ways of implementing the processes, systems and apparatus of the presented embodiments. Therefore, the present embodiments should be considered illustrative rather than restrictive, and the embodiments should not be limited to the details provided herein.

Claims

1. A method for removing SnO2 residue from a processing chamber, comprising: introducing hydrocarbon gas and hydrogen gas into the plasma processing system; etching the SnO2 residue in crystalline form from a surface of the processing chamber using plasma generated by a plasma source of the plasma processing system, etching the SnO2 residue using the hydrogen gas to generate SnH4 gas, the SnH4 gas reacting with the hydrocarbon gas to generate a volatile organotin compound, wherein generating the organotin compound from the SnH4 gas reduces the amount of SnH4 gas available for decomposition into Sn powder; and evacuating the organotin compound from the process chamber, wherein the ratio of the flow rate of the hydrocarbon gas to the flow rate of the hydrogen gas is at least 1% hydrocarbon gas to hydrogen gas and is less than 60% hydrocarbon gas to hydrogen gas, The hydrocarbon gas and the hydrogen gas are introduced into the process chamber to generate plasma through a CCP source, and introduced into an ICP source to generate plasma through the ICP source, wherein free radicals generated by the CCP source and the ICP source are used for the etching.

2. A method for removing SnO2 residue from a processing chamber, comprising: introducing hydrocarbon gas and hydrogen gas into the plasma processing system; etching the SnO2 residue in crystalline form from a surface of the processing chamber using plasma generated by a plasma source of the plasma processing system, etching the SnO2 residue using the hydrogen gas to generate SnH4 gas, the SnH4 gas reacting with the hydrocarbon gas to generate a volatile organotin compound, wherein generating the organotin compound from the SnH4 gas reduces the amount of SnH4 gas available for decomposition into Sn powder; and evacuating the organotin compound from the process chamber, wherein the ratio of the flow rate of the hydrocarbon gas to the flow rate of the hydrogen gas is at least 1% hydrocarbon gas to hydrogen gas and is less than 60% hydrocarbon gas to hydrogen gas, wherein the hydrocarbon gas is introduced into the processing chamber to generate plasma through a CCP source, and the free radicals generated by the CCP source react with the SnH4 gas to generate the organic tin compound, and wherein the hydrogen gas is introduced into an ICP source away from the processing chamber to generate plasma, and the free radicals generated by the ICP source are transported to the processing chamber for etching the SnO2 residue.

3. A method for removing SnO2 residue from a processing chamber, comprising: introducing hydrocarbon gas and hydrogen gas into the plasma processing system; etching the SnO2 residue in crystalline form from the surface of the processing chamber using plasma generated by a plasma source of the plasma processing system, etching the SnO2 residue using the hydrogen gas to generate SnH4 gas, the SnH4 gas reacting with the hydrocarbon gas to generate a volatile organotin compound, wherein generating the organotin compound from the SnH4 gas reduces the amount of SnH4 gas available for decomposition into Sn powder; as well as evacuating the organotin compound from the process chamber, wherein the ratio of the flow rate of the hydrocarbon gas to the flow rate of the hydrogen gas is at least 1% hydrocarbon gas to hydrogen gas and is less than 60% hydrocarbon gas to hydrogen gas, wherein the hydrocarbon gas and the hydrogen gas are introduced into the process chamber, the method further comprising: introducing hydrogen or helium into the ICP source to generate a plasma, which generates free radicals; as well as The free radicals are delivered into the process chamber to ionize the hydrocarbon gas and the hydrogen gas for etching the SnO2 residue.

4. The method of any one of claims 1-3, wherein the hydrocarbon gas is configured to provide a reaction pathway for SnH4 gas to generate the organotin compound, the reaction pathway being more kinetically favorable than a reaction in which the SnH4 gas decomposes into Sn powder, wherein generating the organotin compound enables the organotin compound to be pumped out of the process chamber to prevent Sn powder from being deposited on the surfaces of the process chamber during etching of the SnO2 residue.

5. The method of any one of claims 1-3, wherein the temperature of the process chamber is maintained between 65°C and 300°C to enable the organotin compound to volatilize and the volatilized organotin compound to be extracted from the process chamber.

6. The method according to any one of claims 1 to 3, wherein the pressure of the process chamber is maintained between 0.1 Torr and 10 Torr to enable SnH4 to react with the hydrocarbon gas to generate the organic tin compound.

7. The method according to any one of claims 1 to 3, wherein: The hydrocarbon gas to hydrogen ratio of at least 1% enables the hydrocarbon gas to react with the SnH4 gas to reduce the SnH4 gas available for decomposition into the Sn powder, and wherein the hydrocarbon gas to hydrogen ratio of less than 60% reduces the formation of carbonaceous polymers and their deposition on the surface of the processing chamber.

8. The method according to any one of claims 1-3, wherein the hydrocarbon gas is selected from the group consisting of: CH4, CH3OH, C2H5OH, HCOOH, or a mixture of NH3+CH4.

9. A method for patterning a SnO2 layer and simultaneously reducing Sn powder formation on a surface of a processing chamber of a plasma processing system, comprising: Depositing a SnO2 layer in crystalline form on a substrate and applying an etching mask to the SnO2 layer; introducing hydrocarbon gas and hydrogen gas into the plasma processing system; Etching the SnO2 layer at a portion exposed by the etching mask using plasma generated by a plasma source, wherein the etching of the SnO2 layer generates SnH4 gas, and the SnH4 gas reacts with the hydrocarbon gas to generate a volatile organic tin compound, wherein the generation of the organic tin compound from the SnH4 gas reduces the amount of the SnH4 gas that can be used to decompose into Sn powder; as well as evacuating the organotin compound from the process chamber, wherein the ratio of the flow rate of the hydrocarbon gas to the flow rate of the hydrogen gas is at least 1% hydrocarbon gas to hydrogen gas and is less than 60% hydrocarbon gas to hydrogen gas, The hydrocarbon gas and the hydrogen gas are introduced into the process chamber to generate plasma through a CCP source, and introduced into an ICP source to generate plasma through the ICP source, wherein free radicals generated by the CCP source and the ICP source are used for the etching.

10. A method for patterning a SnO2 layer and simultaneously reducing Sn powder formation on a surface of a processing chamber of a plasma processing system, comprising: Depositing a SnO2 layer in crystalline form on a substrate and applying an etching mask to the SnO2 layer; introducing hydrocarbon gas and hydrogen gas into the plasma processing system; Etching the SnO2 layer at a portion exposed by the etching mask using plasma generated by a plasma source, wherein the etching of the SnO2 layer generates SnH4 gas, and the SnH4 gas reacts with the hydrocarbon gas to generate a volatile organic tin compound, wherein the generation of the organic tin compound from the SnH4 gas reduces the amount of the SnH4 gas that can be used to decompose into Sn powder; as well as evacuating the organotin compound from the process chamber, wherein the ratio of the flow rate of the hydrocarbon gas to the flow rate of the hydrogen gas is at least 1% hydrocarbon gas to hydrogen gas and is less than 60% hydrocarbon gas to hydrogen gas, wherein the hydrocarbon gas is introduced into the processing chamber to generate plasma through a CCP source, and the free radicals generated by the CCP source react with the SnH4 gas to generate the organic tin compound, and wherein the hydrogen gas is introduced into an ICP source away from the processing chamber to generate plasma, and the free radicals generated by the ICP source are transported to the processing chamber for etching the SnO2 residue.

11. A method for patterning a SnO2 layer and simultaneously reducing Sn powder formation on a surface of a processing chamber of a plasma processing system, comprising: Depositing a SnO2 layer in crystalline form on a substrate and applying an etching mask to the SnO2 layer; introducing hydrocarbon gas and hydrogen gas into the plasma processing system; Etching the SnO2 layer at a portion exposed by the etching mask using plasma generated by a plasma source, wherein the etching of the SnO2 layer generates SnH4 gas, and the SnH4 gas reacts with the hydrocarbon gas to generate a volatile organic tin compound, wherein the generation of the organic tin compound from the SnH4 gas reduces the amount of the SnH4 gas that can be used to decompose into Sn powder; as well as evacuating the organotin compound from the process chamber, wherein the ratio of the flow rate of the hydrocarbon gas to the flow rate of the hydrogen gas is at least 1% hydrocarbon gas to hydrogen gas and is less than 60% hydrocarbon gas to hydrogen gas, wherein the hydrocarbon gas and the hydrogen gas are introduced into the process chamber, the method further comprising: introducing hydrogen or helium into the ICP source to generate a plasma, which generates free radicals; as well as The free radicals are delivered into the process chamber to ionize the hydrocarbon gas and the hydrogen gas for etching the SnO2 residue.

12. The method of any one of claims 9-11, wherein the hydrocarbon gas is configured to provide a reaction pathway for SnH4 gas to generate the organotin compound, the reaction pathway being more kinetically favorable than a reaction in which SnH4 gas decomposes into Sn powder, wherein generating the organotin compound enables the organotin compound to be pumped out of the process chamber to prevent tin powder from being deposited on the surface of the process chamber during etching of the SnO2 layer.

13. The method according to any one of claims 9 to 11, wherein: The hydrocarbon gas to hydrogen ratio of at least 1% enables the hydrocarbon gas to react with the SnH4 gas to reduce the SnH4 gas available for decomposition into the Sn powder, and wherein the hydrocarbon gas to hydrogen ratio of less than 60% reduces the formation of carbonaceous polymers and their deposition on the surface of the processing chamber.

14. The method according to any one of claims 9-11, wherein the hydrocarbon gas is selected from the group consisting of: CH4, CH3OH, C2H5OH, HCOOH, or a mixture of NH3+CH4.

15. A plasma processing system comprising: a hydrogen gas supply source and a hydrocarbon gas supply source; Processing room; a first mass flow controller and a second mass flow controller, the first mass flow controller being used to control a flow rate of hydrogen gas flowing into the process chamber, and the second mass flow controller being used to control a flow rate of hydrocarbon gas flowing into the process chamber; A plasma source, which is used to generate plasma in the processing chamber, and the plasma is used to etch SnO2; as well as a controller for adjusting the first mass flow controller and the second mass flow controller so that the ratio of the hydrocarbon gas flow rate to the hydrogen gas flow rate into the process chamber is between 1% and 60%, so that when SnH4 is generated during the etching of SnO2, the SnH4 reacts with the hydrocarbon gas in a reaction to generate a volatile organotin compound, the reaction being kinetically more favorable than the reaction in which the SnH4 decomposes into Sn powder, wherein the generation of the organotin compound enables Sn to be drawn out of the process chamber to prevent Sn powder from being deposited on surfaces of the process chamber during the etching of SnO2, The hydrocarbon gas and the hydrogen gas are introduced into the process chamber to generate plasma through a CCP source, and introduced into an ICP source to generate plasma through the ICP source, wherein free radicals generated by the CCP source and the ICP source are used for the etching.

16. A plasma processing system comprising: a hydrogen gas supply source and a hydrocarbon gas supply source; Processing room; a first mass flow controller (MFC) and a second mass flow controller, the first mass flow controller being used to control the flow of hydrogen gas flowing into the process chamber, and the second mass flow controller being used to control the flow of hydrocarbon gas flowing into the process chamber; a plasma source for generating plasma in the processing chamber, wherein the plasma is used to etch SnO2; and a controller for adjusting the first mass flow controller and the second mass flow controller so that the ratio of the hydrocarbon gas flow rate to the hydrogen gas flow rate into the process chamber is between 1% and 60%, so that when SnH4 is generated during the etching of SnO2, the SnH4 reacts with the hydrocarbon gas in a reaction to generate a volatile organotin compound, the reaction being kinetically more favorable than the reaction in which the SnH4 decomposes into Sn powder, wherein the generation of the organotin compound enables Sn to be drawn out of the process chamber to prevent Sn powder from being deposited on surfaces of the process chamber during the etching of SnO2, wherein the hydrocarbon gas is introduced into the processing chamber to generate plasma through a CCP source, and the free radicals generated by the CCP source react with the SnH4 gas to generate the organic tin compound, and wherein the hydrogen gas is introduced into an ICP source away from the processing chamber to generate plasma, and the free radicals generated by the ICP source are transported to the processing chamber for etching the SnO2 residue.

17. A plasma processing system comprising: a hydrogen gas supply source and a hydrocarbon gas supply source; Processing room; a first mass flow controller (MFC) and a second mass flow controller, the first mass flow controller being used to control the flow of hydrogen gas flowing into the process chamber, and the second mass flow controller being used to control the flow of hydrocarbon gas flowing into the process chamber; A plasma source, which is used to generate plasma in the processing chamber, and the plasma is used to etch SnO2; as well as a controller for adjusting the first mass flow controller and the second mass flow controller so that the ratio of the hydrocarbon gas flow rate to the hydrogen gas flow rate into the process chamber is between 1% and 60%, so that when SnH4 is generated during the etching of SnO2, the SnH4 reacts with the hydrocarbon gas in a reaction to generate a volatile organotin compound, the reaction being kinetically more favorable than the reaction in which the SnH4 decomposes into Sn powder, wherein the generation of the organotin compound enables Sn to be drawn out of the process chamber to prevent Sn powder from being deposited on surfaces of the process chamber during the etching of SnO2, wherein the hydrocarbon gas and the hydrogen gas are introduced into the process chamber, introducing hydrogen or helium into the ICP source to generate a plasma, which generates free radicals; as well as The free radicals are delivered into the process chamber to ionize the hydrocarbon gas and the hydrogen gas for etching the SnO2 residue.

18. The plasma processing system according to any one of claims 15 to 17, wherein: A ratio of the hydrocarbon gas flow rate to the hydrogen gas flow rate of 1% or more enables SnH4 to react with the hydrocarbon gas while reducing the decomposition of SnH4 into Sn powder, and wherein a ratio of the hydrocarbon gas flow rate to the hydrogen gas flow rate of 60% or less enables sufficient hydrocarbon gas to react with SnH4 while preventing the formation of carbonaceous polymers and their deposition on the surface of the processing chamber.

19. The plasma processing system of any one of claims 15-17, further comprising: a heating element for maintaining the temperature of the processing chamber controlled by the controller; and a vacuum unit for maintaining a low pressure in the processing chamber controlled by the controller; The controller is configured to adjust the heating element to maintain a temperature between 65° C. and 300° C., so that the organotin compound can volatilize and the volatilized organotin compound can be extracted from the process chamber, and the controller is configured to adjust the vacuum unit to maintain a pressure of the process chamber between 1 Torr and 10 Torr, so that SnH4 can react with the hydrocarbon gas to generate the organotin compound.

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