TW505971B - New methodologies and apparatus of etching substrates in a chamber for reducing process sensitivity to the chamber condition - Google Patents

Abstract

A method and apparatus for reducing the sensitivity of semiconductor processing to chamber conditions is provided. Process repeatability of common processes are affected by changing surface conditions which alter the recombination rates of processing chemicals to the chamber surfaces. In one aspect of the invention, a composition of one or more etchants is selected to optimize the etch performance and reduce deposition on chamber surfaces. The one or more etchants are selected to minimize buildup on the chamber surfaces, thereby controlling the chamber surface condition to minimize changes in etch rates due to differing recombination rates of free radicals with different surface conditions and achieve etch repeatability. In another embodiment, the etchant chemistry is adjusted to reduce the change to internal surface conditions after a cleaning cycle. In another embodiment, a process recipe is selected to reduce the sensitivity of the etch process to the chamber conditions, in another embodiment, chamber surface materials are selected to minimize the differences in recombination rates of free radicals on the surface materials and the byproduct depositions formed on the materials during processing.

Description

B7 B7 5. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economics. Description of the invention () Inventive jaw area: The present invention relates to a plasma processing method and equipment. More specifically, the present invention relates to a method and apparatus for minimizing the sensitivity of a process to reaction chamber conditions during etching. BACKGROUND OF THE INVENTION: In the manufacture of integrated circuits and other electronic devices, multiple layers of conductive, semi-conductive and dielectric materials are deposited on a substrate and removed from the substrate during the manufacturing process. In device manufacturing, it is known that substrate etching methods and equipment are used to remove material from a substrate. Typical etching techniques include wet and dry etching. However, wet engraving is limited to the manufacture of components with a lateral dimension of one micron or greater. Solid-state devices and integrated circuits are now often manufactured in sub-micron or even nanometer sizes. Therefore, dry etching is now the preferred etching method. One of the commonly known methods of dry name engraving is plasma enhanced etching (" plasma etching "). But slurry etching is very suitable for the manufacture of nano-sized devices. A conventional plasma etching reactor includes a reaction chamber and equipment for generating a plasma in the reaction chamber. The plasma can be generated inductively by using an inductive RF coil or capacitively by using a parallel plate glow discharge reactor. Typically, the plasma is struck and held capacitively and inductively. Generally, plasma etching involves placing a mask on the surface of an upper substrate to define a bare portion of the substrate to be etched into the substrate, or the batch of substrates, and then placed on the substrate. Β in the reaction chamber and then the etching gas is introduced on page 3. The paper size is in accordance with Chinese National Standard (CNS) A4 (210 X 297 mm) 505971 A7 V. Description of the invention (In the reaction chamber, a plasma was fired. During processing, the active material in the plasma is etched by a metal material, a dielectric material, or a semiconductor material by contacting the exposed portion of the substrate. At the molecular level, the etching treatment is the activity in the plasma. The reaction between the substance and the bare surface layer of the substrate. The active substance includes free radicals, ions and other particles. Although the reaction between the substrate and free radicals is mainly chemical in nature, it However, it is significantly strengthened by ion bombardment. Ion bombardment contributes to the etching and provides activation energy to the surface reaction. The reaction between the plasma and the substrate generates an etching by-product, that is, a small amount of volatile molecules is caused by The surface is released and diffused into the reaction chamber. Most of the volatile by-products are pumped out of the reaction chamber. The etching of a single material layer usually includes two main steps:-the main etching process and an excessive etching process The main etching process removes a large amount of material from the surface of the exposed substrate to form the desired feature. The excessive etching process is required because the remaining material is removed from the substrate and at the same time Avoid undercutting (ie, isotropic etching) and selective loss of «V 3¾ degrees at interfacial layers such as polycrystalline silicon / oxide interface. Chemicals and processing parameters at each step are chosen to be W 4 In order to reach the non-Economic and Intellectual Property Bureau employee consumer cooperative printing (please read the —If page on the back page) and other directivity, stability, and high etching rate, uniformity, high selectivity, ^ King and repeatability. Successful Etching requires a controllable process to ensure a controlled uniform etch rate and a stable speed relative to each substrate. Changes in control will result in changes in the device shape and size. It is best to use the National Standard for Cattle (CNS) A4 for this specific paper size and the etch rate between each substrate. Page 4 Specifications (210 X 297 mm)

Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 505971 V. Description of Invention () The change is less than 10%. Processing stability can be implemented by several methods and techniques often used in this art. For example, a significant change in etch rate can be seen after a cleaning process. The cleaning process needs to be performed periodically to remove by-product deposits formed on the surface of the chamber during the treatment. Most of the volatile by-products formed during the etching are pumped out of the reaction chamber. However, these by-products usually react with different gas components used in etching silicon with helium plasma, such as oxygen additives, to form less volatile fields] products. In other cases, the by-product itself is less volatile, depending on the material being etched and the etch chemistry. These less volatile materials can deposit on the walls of the reaction chamber and other exposed surfaces in the chamber. After a period of time, the sediment will peel off the surface of the reaction chamber and become the main source of particulate contamination. Such particles often get stuck on the mask or on the surface of the substrate and cause device defects. As the size of the etched features becomes smaller, the effects of particles become more severe. Therefore, in order to control the accumulation of contaminants, the surface of the reaction chamber is periodically cleaned. One method of cleaning a reaction chamber, called dry cleaning, involves placing an unwanted substrate in the reaction chamber and firing a plasma. The plasma chemistry is selected to react chemically and physically simultaneously with the deposition on the reaction chamber, whereby the deposit is formed as a by-product β that can be pumped out of the reaction chamber. However, the reaction chamber is clean A problem with the method is that the etching rate of subsequent processes can be adversely affected. In a typical plasma etch, after the reaction chamber is cleaned, the etch rate may decrease by more than 33%. The change of the etching rate is unwelcome, because it will cause processing and recycling. Page 5 The paper size applies the Chinese National Standard (CNS) A4 specification < 210 X 297 mm) (Please read the precautions on the back before filling in this page)

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505971 A7 _ B7 V. Description of the invention (), or loss of repeatability. Because the etch process is often timed according to a pre-planned 妤 formula, fluctuations in the etch rate can cause the substrate to be etched or under-etched. As a result, repeatability between substrates is sacrificed. In order to minimize the adverse effect of the change in etching rate after the cleaning process, a method is to use a seasoning cycle during which the reaction chamber is adjusted after a cleaning process. Seasoning refers to the operation of the reaction chamber to allow a film layer to be deposited on the surface of the reaction chamber. During a restoration, an adjustment coating is allowed to be formed on the reaction chamber surface by firing a plasma in the reaction chamber and depositing a flip on the exposed interior of the reaction chamber. The reaction chamber adjustment is continued until the pre-cleaning etching rate is completely restored. This recovery period is quite time consuming and unproductive because no substrate can be processed. As a result, the system's output rate will be severely reduced. Another problem associated with process stability occurs when high concentrations of corrosive chemicals are used. For example, in the case where fluorine is the main etchant, such as in planarization and recess etching, problems may occur. Fluorine is a highly corrosive etchant, which can attack the surface of the reaction chamber and cause surface topography changes and / or cause the deposition of a by-product, such as A1F x on the surface of the Al2O2 reaction chamber. Unlike non-invasive cleaning methods such as plasma cleaning to remove SiOx deposits, fluorine etching must be performed by opening the reaction chamber and refinishing the reaction chamber walls. Therefore, the output rate will be greatly affected. Page 6 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first ¾ fill out this page) I n I · n Mate Mmmmme mmee immmm ϋ · fll_ · · el n tme i-Printed by the Intellectual Property Office of the Ministry of Economic Affairs, Consumer Cooperatives, 505971 A7 V. Description of the invention (Impact. In addition, after the cleaning process, fluctuations in the etching rate will be observed, and This hinders the stability of the etching rate. The inventors of the present case also observed sensitivity to the conditions of the reaction chamber in other cases than post-cleaning treatments. For example, when the same _ 0 magnetic & * '' Tian 1 J 夂 应 到It is used to implement different applications involving chemical changes #, and the change in money rate can be observed. Therefore, the alternating treatment between fluorine-based chemicals and non-fluorine-based chemicals will be performed every cycle Etching rate changes between them. For example, a reaction chamber can first be used to treat several substrates during a fluorine-based process, such as a hard mask opening, to etch the recesses. Next, the reaction chamber is used ^ One that does not involve the use of fluorine Second treatment, such as capacitor etching. For reasons unknown until now, the etching rate under these conditions will fluctuate and cause the loss of process repeatability. Therefore, there is a reduction in the sensitivity of the process to the reaction chamber surface conditions Need for spring. Purpose and summary of the invention: The present invention generally provides a method and equipment that can minimize the sensitivity of the etching process to the conditions of the reaction chamber. The sensitivity of the etching process can be treated by including the variable etching chemical. The parameters and / or the material of the reaction chamber are controlled by different methods. In one aspect of the present invention, the composition of one or more etchant is selected to optimize the etching performance and reduce the surface of the reaction chamber. The one or more etchant is selected to minimize the deposition on the surface of the reaction chamber, thereby controlling the surface conditions of the reaction chamber and leading to free radicals and differences. Page 7 This paper applies Chinese national standards. CNS) A4 size (210 X 297 mm) (Please read the precautions on the back before filling this page)

m-44i ^ __ * · I ina— I nnn B nnnnnnn I Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 505971 A7 B7 V. Description of the invention (9 n ϋ n ^ sai λ— J— SI §m§ I wake up— (Please read the note on the back first to fill in this page) The different recombination rates caused by different surface conditions minimize the change in etching rate and achieve etching repeatability. In one embodiment, at least one etchant is introduced into the The reaction chamber and a plasma are fired to form at least a first radical density from the first etchant. The etchant is selected to react the radical density to produce a minimum rate of deposition on the surface of the reaction chamber. And where the recombination rate of free radical density and the deposit formed on the inner surface is different from the recombination rate of free radical density and the inner surface. In another embodiment, 'chlorine and bromine are first and second flows respectively. The rate is introduced into a reaction chamber; wherein the first flow rate is greater than the second flow rate. Preferably, the ratio of gas to bromine is greater than 3: 1. In another aspect of the present invention, a first and a first Two etchants flow into one etch In the chamber, the first etchant is used to clean the inner surface of the chamber and prevent by-products from being deposited thereon and simultaneously etch a substrate. A substantially consistent reaction is maintained until the surface profile is maintained to maintain a large The recombination rate of the plasma composition fixed on the surface of the reaction chamber. Preferably, the first etchant is a fluorine-containing fluid and the second etchant is a voxel, such as chlorine or bromine. Wisdom of the Ministry of Economy Printed by the Property Agency Consumer Cooperative. In another aspect of the invention, an etching chemical is selected to minimize corrosion in the reaction chamber β-a corrosive first etchant is applied with a second etchant Dilute, where the second etchant is preferably non-corrosive or less corrosive than the first etchant. The first etchant is a corrosive fluid that is corrosive when it comes in contact with the inner surface of the reaction chamber. The combination of the second nicking agent and the first etchant is used to reduce the corrosion effect of the first nicking agent on the surface of the reaction chamber. The resulting mixture is best. Page 8 505971 A7 B7 Ministry of Economic Affairs Printed by the Consumer Property Cooperative of the Intellectual Property Bureau. V. Invention Description () It shows the effect of reducing the corrosion on the surface of the reaction chamber and allows continuous processing of multiple substrates under approximately the same reaction chamber surface conditions. In one embodiment, the first etchant is a fluorine-containing fluid, such as CF4, SF6, or NF3. The second etchant is preferably a chlorine-containing fluid, such as Ch. In another aspect of the present invention, an The chamber pressure is controlled to reduce the sensitivity of an etch process to the surface conditions of the reaction chamber. The chamber pressure is controlled during an over-etch process to increase the ion-to-radical ratio, thereby increasing ion-assisted etching and reducing pure freedom In one embodiment, the pressure during the over-etching of a polycrystalline silicon layer is less than 30 mTorr. The etching treatment is most preferably a bromo or chloro group. In another aspect of the invention, the reaction chamber pressure and the oxygen concentration in the reaction chamber are controlled to reduce the sensitivity of an etching process to the surface conditions of the reaction chamber. The reaction chamber pressure is controlled during an over-etching process to increase the ratio of ionic radicals, thereby increasing ion-assisted etching and reducing pure radical etching. The oxygen concentration is controlled to reduce the oxidation of a substrate to be etched. In one embodiment, the pressure during an overetch of a polycrystalline silicon layer is preferably less than 30 mTorr and the oxygen concentration is preferably less than the reaction. 25% of the total fluid volume in the room. The etching treatment is preferably a bromo group or a chloro group. In another aspect of the present invention, the pressure in the reaction chamber, the oxygen concentration in the reaction chamber, and the source power are controlled to reduce the sensitivity of an etching process to the surface conditions of the reaction chamber. The process is controlled to increase the ratio of ionic radicals, thereby increasing the ion-assisted etching and reducing pure radical etching. Oxygen concentration is controlled Page 9 (please read I Γ l · -1..r ___ Please read the notes on the back to write this page) Order ·· This paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) 505971 A7 B7_____ 5. Description of the invention () The system is used to reduce the oxidation of a substrate to be etched. The source power delivered to an induction coil is adjusted to control the surface oxidation and engraving of the substrate. In one embodiment, the pressure during the over-etching of a polycrystalline silicon layer is preferably less than 3OmTorr and the oxygen concentration is preferably less than 25% of the total fluid volume in the reaction chamber and the source power is between 100-500 Between tiles. Preferably, the oxygen concentration and the source power are adjusted in the reverse direction so that when the oxygen concentration is increased, the source power is reduced and vice versa. The etching treatment is preferably a bromo group or a chloro group. In another aspect of the invention, the material of the reaction chamber is selected to reduce the sensitivity of an etching process to the surface conditions of the reaction chamber. The material is selected based on the recombination rate with free radicals. Preferably, the binding rate between the radical and the selected material is approximately equal to the recombination rate between the radical and the by-products that are formed on the surface of the reaction chamber during the etching process. In one embodiment, The reaction chamber components exposed in the processing environment of a silicon etching chamber, such as the reaction chamber body and the reaction chamber dome / cover, generally contain quartz. The reaction chamber components may be composed of or lined with quartz. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. In another embodiment of the present invention, the temperature of the reaction chamber is controlled to reduce the sensitivity of an etching process to the surface conditions of the reaction chamber. The temperature is preferably high enough to reduce deposition on the exposed reaction chamber surface. In one embodiment, a polycrystalline silicon layer is etched at a reaction chamber temperature of at least 200 ° C. Brief description of the drawings: A more specific description of the present invention can be made by referring to the embodiments shown in the drawings, so that the above features, advantages, and contents of the present invention are applicable to the country of China on page 10 Standard (CNS > A4 specification (210 X 297 public love) Printed by the Consumer Property Cooperative of the Intellectual Property Bureau of the Ministry of Economy 12 Body 505971 A7 _B7 V. The description of the invention () can be understood in detail. However, it should be noted that the The figure shows a typical embodiment of the present invention, so it should not be considered as a limitation of the scope of the present invention, because the present invention can have other equivalent embodiments. Figure 1 is a perspective view of an etching reaction chamber. Fig. 2 is a graph showing the deposition rate of the etchant as a function of oxygen. Fig. 3 is a graph showing the decrease in tf and the free radical density as a function of the pressure of HBr-based etching. Part 4 The figure is a graph showing the decrease in etch rate and free radical density as a function of the pressure of a Cl2-based etch. Figure 5 is a graph showing the etch rate decrease as a function of the oxygen in an HBr-based etch. Figure 6 shows a Table showing the etch rate as a function of oxygen for HBr-based etching. Figure 7 is a chart showing the etch rate as a function of oxygen for ci2-based etching. Figure 8 is a chart showing the etch rate as ci2-based. Function of etched oxygen. Figure 9 is a graph showing the etch rate as a function of the oxygen of the ci2-based etch at different source power levels. Figure 10 is a graph showing the etch rate as a function of source power. . Explanation of drawing number comparison: 10 reaction room page 11 This paper size is applicable to China National Standard (CNS) A4 (210 X 297 mm)

505971 A7 B7 V. Description of the invention (13. Dome 16 Support 22 Gas distributor 2 7 Coil power supply 30 Emission system 14 20 26 28 32 Plasma area substrate Inductive coil electrode power supply Throttle valve invention detailed description : The present invention is generally related to a method for sensitivity of a low-etching process to a reaction chamber condition. The sensitivity of the etching process can be varied by changing the etching chemistry and / or processing parameters and changing the reaction chamber material. For the sake of clarity and ease of description, the following description mainly refers to a silicon etching system and the processes implemented therein, including polycrystalline silicon etching. However, the present invention can also be applied to the use of chemicals Other types of treatments for depositing materials on a substrate or materials etched on a substrate, these treatments will respond to changes in surface conditions. For example, chemical vapor deposition (CVD) treatments can be obtained using the present invention Improvement. (Please read the notes on the back before filling this page)

" n n n n ^ eJββι · J A reaction chamber 10 which can be used in the present invention is schematically shown in the figure

V Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The reaction chamber 10 includes a body 12 preferably made of a metal, such as anodized aluminum, and a dome 13 preferably made of a dielectric, such as ceramic. The reaction chamber 10 defines a plasma region 14 in which a support 16 is provided. The support 16 may be a mechanical chuck with a groove or an electrostatic chuck. The groove contains a cooling gas, such as helium. Used to control the temperature of the substrate on the support 16 during processing. The paper size of the support 16 to page 12 applies to the Chinese National Standard (CNS) A4 specification (210 X 297 mm 505971 A7 B7) 5. Description of the invention (a small part is conductive and used as a treated cathode. Support 16 Cooperate with the body 12 which is electrically grounded as an anode to form a processing electrode in the plasma area 14. Please read the note on the back first that the processing gas passes through a gas distributor 22 provided around the support 16 It is introduced into the reaction chamber 10. By using a plasma generator, a plasma is generated from the processing gas, and the plasma generator couples an electrical asset into the plasma area 14. The plasma generation The device includes an inductive coil 26 disposed adjacent to the dome 13 of the reaction chamber 10. Preferably, the inductive coil 26 is wound around the dome 13 and is charged by a coil power supply 27 An inductive electricity can be formed in the reaction chamber.

In addition to the inductance coil 26, the support member 16 is powered by an electrode power supply 28 to generate a capacitive electric field in the reaction chamber 10. Typically, a radio frequency (RF) voltage is applied to the support 16 when the body 12 is grounded. The capacitor is perpendicular to the plane of the support member 16 and accelerates the plasma material that is formed inductively toward the substrate 20 to provide etching of the substrate 20 in a more non-isotropic direction. Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs The exhausted processing gas and etching by-products are discharged from the reaction chamber 10 through a placement system 30. A throttle valve 32 is provided in a discharge hole 34 to control the pressure in the reaction chamber 10. Moreover, an optical endpoint measurement technique that measures the change in light emission at a specific wavelength corresponding to a detectable gaseous substance can be used to determine whether the etching of a particular layer is complete or not. A sudden lowering or raising of the material represents the completion of the etching of a specific layer and the beginning of another layer. "The process described below is the 13th paper in a reaction chamber as shown in the figure. Standards are applicable to China National Standard (CNS) A4 specifications (210 X 297 mm) 505971 A7 B7 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 5. Implementation of the invention (). However, the processing reaction chamber used in the present invention is not limited to this specific processing reaction chamber. Other reaction chambers can also be used. As described above, the stability of the process during the etching is desired to ensure the repeatability of the etching results. In addition, as mentioned above, many common treatments in the etching reaction chamber, such as cleaning the reaction chamber, will cause unacceptable changes in the etching rate. The conditions of the reaction chamber are changed, such as the surface conditions of the reaction chamber wall. Usually, these reaction chamber conditions are changed without knowing the effect on subsequent etching processes. The inventor of the present case assumes that at least one of the reasons for the fluctuation of the etching rate is the result of the different rates of no longer binding of reactive radicals on the surfaces of different reaction chambers. For example, in the case of silicon etching, a by-product of a SiOx (x = 1-2) compound is deposited on the surface of the inner reaction chamber. After a cleaning cycle, the by-products were removed and the surface of the reaction chamber underneath was exposed again. If the recombination rate of free radicals and by-products is lower than the recombination rate of free radicals and typical reaction chamber materials, such as ceramics and anodized aluminum, when the surface of the reaction chamber is covered by by-products, the plasma The density of free radicals will increase. Therefore, when there is no deposit on the surface of the reaction chamber, such as immediately after the cleaning cycle, the 'radicals are recombined with the surface of the reaction chamber at the first ratio. After a period of time, a layer of by-products is formed on the surface of the reaction chamber, and a second recombination ratio of free radicals to the surface of the reaction chamber is obtained, wherein the second ratio is smaller than the first ratio. When the thickness of the by-product deposition exceeds an acceptable level, the reaction chamber is cleaned to expose the surface of the underlying reaction chamber again, so that the subsequent treatment can have the first recombination of the free radicals. (Please read the notes on the back before filling out this page) Binding ------- Γ

This paper size applies to the national standard of the bracelet <CNS) A4 specification (21 × 297 mm) 505971 A7 V. Description of the invention (Ratio .. By using optical photometry, the inventor of this case observed a clean After cycling, the free radical density decreases by 50% to 70% in gas-based and stream-based etching. Changes in the recombination rate lead to fluctuations in the degree of self-contact and etching rate in the electropolymerization of the substrate. Time changes as a function of the composition and conditions of the reaction chamber surface. Generally, for polycrystalline chip etching, the etch rate increases when a deposit, such as Sioxoc ^ aw, is formed on the surface of the reaction chamber. However, it will The etch rate, which has a significant effect on the consistency and repeatability of the etching process, is considered to be deleterious. The effect of changing the density of free radicals involves processes that are dominated by the concentration of free radicals, such as an over-etching process. Etching is particularly harmful in the case. As mentioned above, the over-etching process is a process in which residual material from the substrate is selectively removed to form features of a substrate under extremely controlled conditions. In one embodiment of the present invention, the etching chemicals are adjusted to deposit the free radicals on the surface of the chamber when the recombination rate of the radicals with the substance deposited on the chamber surface is different from the recombination rate with the material of the chamber surface. By-products are minimized. A primary etchant is selected based on the potential for the etchant to deposit by-products on the chamber surface. The primary etchant is defined as relative to each of the chemical mixture flowing into the reaction chamber. A component has the largest volume flow and in some instances it is the only etchant used. Preferably, the primary etchant is selected to reduce the by-products deposited on the chamber surface. At least. An example of the present invention is shown in Table I and Table π. Table Ϊ shows a traditional &quot; baseline of a silicon main etching process and over-etching process. Page 15 This paper applies Chinese national standards (CNS ) A4 size (210 X 297 mm) Please read the note on the back first

Two things: I installed this page I I I I I I Order Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs Employee Cooperatives 505971 A7 ______B7 —______ V. Description of the invention (baseline) &quot; Processing formula. The main etch process includes a chromogen, such as a mixture of chlorine and brook, which has a higher proportion of bromine content. This over-etching is made of &gt; odor-based chemicals and is performed at a higher pressure than the main etching process. The main etching process and the over-etching process use a bromine-containing plasma to provide highly selective anisotropic polycrystalline silicon etching. Compared to chlorine, bromine was found to increase the selectivity of polycrystalline silicon: oxides and more control over the shape of the etch. The parameters in Table I are typically used for polycrystalline shredded layers inscribed on a substrate.

Table I Parameters_Main Etching Excessive Etching

Composition: Cl2? HBr (lCl: 2Br) 3 HBr 〇2 (&lt; 5% volume), 〇2 (&lt; 3% volume) Flow rate: 200sccm 155-160sccm Coil power: 500W 500-1000W Bias power: 80W 100-1 50W Pressure: 4mTorr SOmTorr Temperature: 50 ° C 50 ° C Printed by the Consumers' Cooperative of Intellectual Property Bureau of the Ministry of Economic Affairs The inventor believes that contrary to the trend and general expectations, a high proportion of chlorine will change the surface conditions of the reaction chamber The adverse effects of ZnO are minimized, as the change in ratio in overetching is dominated by free radicals. The figure below is a comparison chart showing a deposition curve of HBr etching of a 3000A thick polycrystalline silicon etch and a deposition curve of Cl2 etching. These curves are drawn to change the oxygen concentration. The paper size is applicable to the Chinese National Standard &lt; CNS) A4 specification (210 X 297 mm) 505971 A7. Printed by the Consumers ’Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The deposition thickness of SiOx (x = 1-2) on the surface of a chamber at degrees. The parameters of the two curves are approximately the same and the β-chloro groups listed below are: 50 ° C, 100 sccm (chlorine and oxygen), 3mToirr, 400W (coil), 60W (bias). Base group: 5 (rc, 100 sccm (HBr and oxygen), 6 mTorr, 400 W (coil), 60 W (bias). Figure 2 shows the deposits obtained with the use of chlorine-based chemicals such as chlorine. In comparison, a higher degree of deposits can be obtained in the reaction chamber using a bromine-based chemical such as HBr. This result is due to the SiCl and SiBr compounds that can be found during polycrystalline hard names. SiCl is volatile and can be The reaction chamber is pulled out. However, SiBr is less volatile and reacts with oxygen to produce SiOx compounds which are deposited on the surface of the chamber. As mentioned above, the density of free radicals in the plasma and the surface conditions of the reaction chamber Directly related. Because the recombination rate of free radicals and SiOx is lower than the recombination rate of free radicals and typical reaction chamber materials, such as ceramic or anodized aluminum, the density of free radicals in the plasma follows the surface of the reaction chamber. It is covered by Si〇x 1¾ ^ Therefore, when the surface conditions of the chamber change with time, the etching rate also changes. In particular, because free radicals contribute to the polysilicon engraving, the etching will change with On the surface of the reaction chamber The increase in the increase in the amount of material. This change in the etching rate is undesirable because it will sacrifice the repeatability of the etching. The radical density is essentially a chemical treatment, such as over-etching, and traditionally relies on high concentrations The treatment of free radicals to maintain an important etch rate is particularly important. Changes in the density of free radicals will cause changes in excessive etch rates and lose repeatability. Therefore, successful etching requires etching The rate is controlled and approximately constant at any time. 0 Page 17 This paper size applies the Chinese National Standard (CNS) A4 (210 X 297 mm) ^ ~-(Please read the precautions on the back to write this page) K equipment la ·

505971 A7 ____B7 ___-_ V. Description of the invention (). The inventor of this case found that the etching chemical contained a relatively high proportion of chlorine relative to bromine to reduce the deposition of SiOx compounds on the surface of the reaction chamber during etching. Minimizing the accumulation of deposits on the chamber surface allows the free radical density in the etching plasma to be kept approximately constant, so a substantially constant etching rate can be obtained.

Table II

Parameter Main etching over-etching components: Ch, HBr (4Cl: lBr), HBr 〇2 (&lt; 5% volume), 〇2 (&lt; 3% volume) Flow rate: 100-200sccm 1 00-200sccm Coil power: 300 -500W 300-500W Bias power: 80W 100W Pressure: 4mTorr SOmTorr Temperature: 10-30 ° C 10-30 ° C Comparing Table I and Table II, we can find a significant difference from the traditional formula. The treatment formulation of the present invention preferably includes a Cl: Br ratio between 3: 1 and 5: 1 (preferably, the Cl: Br ratio is 4: 1 as shown in Table Π). The treatment according to Table I will cause a considerable amount of deposits to accumulate on the surface of the reaction chamber in a short time. The deposition rate of the SiOx compound is 50-100 A / min. In contrast, the treatment formula of 'Table II achieved a deposition rate of only 10-30 A / min. The reduced deposition rate is due to the higher Cl relative to Br. Page 18 This paper applies Chinese National Standards &lt; CNS) A4 (210 X 297 public love) • 71 ^ — ^ &lt; Please read the note on the back first Matters written on this page) II an I 一 δ * &quot; · ϋ n II ai ϋ i

Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs 'employee consumer cooperative 505971 A7 Printed by the Intellectual Property Bureau of the Ministry of Economic Affairs' employee consumer cooperative. V. The ratio of invention description The deposition of by-products obtained on the surface of the chamber is negligible. The excessive etching process removes the residual material from the features of the device formed during the main etching process. Therefore, the unwanted deposition of the reaction chamber surface only requires It is formed during the main etching process, and over-etching will only form a negligible amount of deposits on the surface of the reaction chamber. However, C1 and Br-based etching is only one of many processes that can be profitable by the present invention. The present invention can be applied to any plasma treatment that deposits byproducts on the surface of the reaction chamber that can affect the recombination rate of free radicals. These treatments include plasma-enhanced chemical vapor deposition. In addition, although the above description with reference to Tables Ϊ and „takes the effect that silicon is mainly etched on an excessive etch as an example, the present invention can be applied to Used in any step that changes the surface conditions of the reaction chamber. In addition to the etch chemistry, processing parameters such as pressure will also respond to the etch rate. Furthermore, referring to Table I, the processing pressure in the baseline overetch formula is 50mT0rr. Traditionally, the processing pressure in the overetching process is 50mT0rr or higher because higher pressures provide higher polycrystalline silicon: oxide selectivity. At pressures of 50mTorr or higher Etching is actually more chemical in nature, because the ratio of free radicals to ions is higher compared to lower pressures. When the pressure is reduced, the ratio of free radicals to ions is also reduced, resulting in an ion Bombardment or ion-assisted etching ° Ion-assisted etching means that the etching is done by free radicals, of which ion bombardment is the activation energy that provides surface reactions. "Ion-assisted etching can be reduced on page 19. This paper applies Chinese national standards ) A4 size (21〇X 297mm T 1 · -H ϋ nn ϋ I ^ yinn el · -1 ii βϋ II _ (Please read the precautions on the back # (Fill this page) • Install 50597 1 A7 B7 V. Description of the invention () The sensitivity of low etching treatment to the density of free radicals, thereby reducing the sensitivity of etching to the fluctuation of free radical density as the surface conditions of the reaction chamber change. Figure 3 shows the over-etching rate and freedom. The base density decreases as a function of the pressure of the Br-based etch. The etch rate / density reduction is calculated as a percentage of the excess etch rate / density after a dry cleaning process relative to the excess etch / density before the dry cleaning process, The reaction chamber has accumulated deposits on the surface. The over-etching treatment formula in Figure 3 is as follows: 150sccm of HBr and 10SCCm of He02, 5 (TC, 1000W (source rate), 100W (section Pressure power). Under the pressure of 4mTorr, the corresponding reduction of the etching rate is only about 1% and the density of Br decreases by about 50%. ^ When the pressure increases, the etching rate decreases and the density decreases. Under a pressure of about 50 mTorr, the etching rate decreased by about 33% and the radical density decreased by about 58%. Figure 4 shows a decrease in the etch rate and a function of the radical density ci2 and the pressure of the etch. Again, when the pressure is increased, both the decrease in the etch rate and the decrease in density increase with the increase in pressure, because the etching becomes more and more dependent on free radicals. The inventors of the present case assume that the substantial decrease in the etching rate under higher pressure is due to the relationship between the radicals and the recombination rate on the surface of the reaction chamber. After a cleaning process, the recombination rate of free radicals to the surface of the reaction chamber is higher than the recombination rate during the pre-cleaning process where the reaction chamber surface is still covered by deposits. As a result of the cleaning process, the surface of the reaction chamber underneath was exposed. Because the recombination rate of free radicals to the surface of the reaction chamber below is higher than the recombination rate of free radicals and deposits, the density of free radicals in the plasma is reduced, leading to etching in processing steps that rely on high free radical concentrations Rate, such as page 20, this paper size applies the Chinese National Standard (CNS) A4 specification (210 X 297 mm) (Please read the precautions on the back and fill out this page first) Binding · ^ ---------- Ministry of Economic Affairs Wisdom Printed by the Consumer Affairs Cooperative of the Property Bureau 505971 A7 B7 V. Description of invention () Excessive etching, followed by decline. However, at lower pressures, the etching becomes ion bombardment and chemical etching due to the decrease in free radicals. Reducing the pressure can reduce the specific force of free radicals relative to ions, thereby increasing ion etching and reducing free radical etching. As a result, the etching process is less dependent on the free radical density. Therefore, the effect of cleaning a reaction chamber on excessive etching can be mitigated in accordance with the low-pressure treatment of the present invention. In a preferred embodiment, the polycrystalline over-etched formulation contains a pressure of less than 30 mTorr and preferably a pressure of about 10 mTorr. Enli can be optimized for a specific etching chemistry and processing parameters. Preferably, the change in the etching rate after a cleaning process is less than 10%. Therefore, in contrast to conventional formulations, the present invention provides a low-pressure method of over-etching to minimize the effects of reaction chamber wall conditions. This solution is the opposite of intuitive thinking, because selectivity is sacrificed when stress is reduced. However, the selectivity at the low pressure of the present invention can be improved by controlling other processing parameters. For example, the bias power can be reduced to reduce the rate at which the substrate is etched by the ions. Furthermore, the oxygen flow rate can be increased to promote oxidation of the surface of the substrate, thereby reducing the etching rate. In another embodiment, the result of low-pressure over-etching is further improved by optimizing the oxygen concentration, wherein the oxygen concentration is an etching chemical additive used to achieve higher selectivity. Figures 5 and 6 show the decrease in the overetch rate and the overetch rate of the Cl2-based etch, respectively. Both ΗΒγ-based and Ch-based etching are adversely affected by increasing the oxygen concentration due to the oxidation of the substrate surface. After a dry cleaning process, free radical etchants, such as C1 and Br, page 21 This paper is sized to the Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first to complete this Page) Binding ------- l .. Printed by the Employees 'Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 505971 A7 B7 Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Go up high. This oxygen will oxidize the surface of the substrate 'to prevent the reaction between the etchant and the surface of the substrate from occurring. Therefore, the etching rate is reduced. Although a small amount of oxygen is necessary to achieve greater selectivity, the oxygen concentration must be controlled to avoid adversely affecting the rate of money due to excessive oxidation of the substrate surface. As shown in Figures 5 and 7v ', the preferred oxygen concentration is also related to the etch chemistry used. For HBr-based etching as shown in Fig. 6, the oxygen concentration is preferably between 0% and 5%. For Ch-based etching as shown in item 8, the oxygen concentration is preferably between 0% and 15%. However, the maximum oxygen concentration also varies with other processing parameters and must be adjusted. For example, 'the preferred oxygen concentration is related to the source power, that is, the power of the induction coil supplied to the induction coil, such as coil 26 in Fig. 1. Number 9 shows two curves of eh-based etching, in which the flow rate of ci2 is about 50 sccm, the bias power applied to the support is about 40w ', and the reaction standing pressure is about 3mTorr. The first curve 50 shows the effect of the oxygen concentration on the excessive etching of the 200W power and the curve 52 shows the effect of the oxygen concentration on the excessive excess of the 400w power. Curve 50 shows a peak etch rate at an oxygen concentration of about 10% and a source power of 400W. Curve 52 shows a peak etch rate at an oxygen concentration of about 15% and a source power of 200W. Although both curves show that the etch rate decreases with increasing oxygen concentration after key points 54 and 56, curve 52 still maintains a higher etch rate at higher oxygen concentrations. Therefore, at an oxygen concentration of about 25%, curve 50 shows an etch rate of about 800 A / min, and curve 52 shows an etch rate of about 2000 A / min. Therefore, according to the present invention, the oxygen concentration and source Page 22 (Please read the precautions on the back first, fill out this page)

M F1 pack --- order i This paper size applies Chinese National Standard (CNS) A4 specification (210 X 297 public love) 505971 V. Description of the invention () The pole power is adjusted to optimize the etching rate. When a higher oxygen concentration is required, the source power is reduced to obtain the best etch rate. In contrast, when a low oxygen concentration is preferred, a higher source power can be used to obtain a better etch rate. Although not shown in Figure 9, ΗΒγ and other etchant exhibit similar responses to changes in source power in the presence of oxygen. However, at the upper limit, the source power will cause a decrease in the etch rate, as shown by the points on the curves 50 and 52 that slope down the lane after the key points 54 and 56. This decrease in etching rate is a result of accelerated surface oxidation at high source power. Fig. 10-The etching rate of the HBr-based etching process having an oxygen concentration of about 4% is decreased. At a source power of about 600W, the etch rate decreases rapidly, which is a result of excessive oxidation of the substrate surface. Therefore, the optimal treatment formulation is achieved by controlling both the oxygen concentration and source power. Examples of two low pressure over-etching treatments in the presence of oxygen are shown in Table III. In one embodiment, a C1-based chemical is used. In another embodiment, Br-based chemicals are used. (Please read the precautions on the back and fill out this page first) * 丨 |! Packing-printed by the Intellectual Property Bureau of the Ministry of Economic Affairs and the Ministry of Economic Affairs's Consumer Cooperatives Page 23 505971 A7 B7 V. Description of the invention (

Parameter Br-based overetching composition: C12, HBr 〇2 (&lt; 15% volume), 〇2 (&lt; 5% volume) Flow rate: 5 Osccm 1 OOsccm Coil power: 100-200W 300-500W Bias power: 30 -50W 50-100W Pressure: 3 -5mTorr 1 0-3 OmTorr Temperature: 0-10 ° C 30-50 ° C

Table III C1-based over-etching (please read the precautions on the back first! Write this page) Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs. Although Table III only shows C1-based and Br-based chemicals for silicon etching. The invention can be applied to other processes traditionally done in the high pressure range and sensitive to surface conditions. The optimal parameters for a known etching chemistry are determined based on the correlation between pressure, oxygen concentration, and source power. Another embodiment of the invention includes the use of a cleaner during etching. The term "detergent" refers to highly volatile gases commonly used to periodically clean the surfaces of reaction chambers. "The present invention uses these gases during the etching process. Therefore, 'cleaners provide two functions, etching and At the same time maintain a clean reaction chamber surface. One of the cleaner bodies that can be used during the main neodymium engraving process is fluorine. Table IV and Table V provide the preferred processing formulas of the present invention. This paper is applicable in the National Standard (CNS) A4 size (210 X 297 mm) Printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs 505971 A7 B7

Description of the invention () Table IV Parameters Main etching: C1-based components: Chlorine-containing etchant: Cl2; and fluorine-containing chemicals: CF4 (&lt; 50% by volume), SF6 (&lt; 20% by volume) or NF3 (&lt; 20 % Volume) Flow rate: 200sccm Coil power: 300-500W Bias power: 50-100W Pressure: 4mTorr Temperature: 30-50 ° C Table V Parameters Main etching: HBr-based and / or HC1-based composition: Etchant: HBr and / Or HC1; and fluorine-containing chemicals: CF4 (&lt; 20% by volume), NF3 (&lt; 20% by volume) or CF4 and 〇2 (&lt; 50% by volume, where CF4: 〇2 = 4: 1) Flow rate: 200sccm Coil power: 300-500W Bias power: 50-100W Pressure: 4mTorr Temperature: 30 ^ 50 ° C Table IV provides a better formula using Cl-based etching chemicals. 'Table V provides preferred formulations using HBir-based and / or HC1-based # engraving chemicals. Both Page 25 This paper size is in accordance with China National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back first to write this page)

505971 Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs A7 B7 _________ V. Description of Invention () All the formulas are mainly etching treatment formulas. The use of the volatile cleaner according to the present invention is very suitable for the main etching process for removing a large amount of substances from the characteristics of the device because of the high etching rate. Subsequent over-etching treatments that require higher selectivity can be performed according to any conventional recipe or a recipe according to the present invention. During operation, the surface of the reaction chamber is exposed to a cleaning agent, such as a fluorine-based fluid. Under the condition, the cleaning agent reacts with by-products generated during the main etching process and the deposits formed on the surface of the reaction chamber and etches at the same time. A predetermined area of the substrate. The fluorine-based fluid and by-products form volatile compounds which are pumped away from the reaction chamber. Therefore, the deposition on the reaction chamber surface is minimized and the reaction chamber surface maintains a substantially fixed composition. As a result of maintaining the surface conditions of the reaction chamber fixed, the recombination rate between free radicals and the deposits on the surface of the reaction chamber remains approximately constant after a long period of time that cannot be achieved by a conventional etching method. Because the reaction chamber does not need to be cleaned periodically, the yield of the etching system can be improved. Although adding a small amount of fluorine-containing gas to a process that generates a considerable amount of by-products can prevent by-products from depositing on the surface of the reaction chamber However, in the case of fluorine as the main etchant, such as planarization and recess etching, there will be problems. Fluorine is a highly corrosive etchant which will attack the surface of the reaction chamber. Changes in the surface of the reaction chamber include the formation of by-products due to corrosion, which can cause radicals to exhibit a recombination rate different from the recombination rate on a clean reaction chamber surface. In addition, changes in the surface of the reaction chamber also include changes in the reaction Changes in the structure of the indoor surface will increase the exposed surface area. Therefore, it is provided on page 26. The paper size applies the Chinese National Standard (CNS) A4 specification (21 × 297 mm). (Please read the precautions on the back first ^^ (Write this page)

505971 A7 B7 V. Description of the invention After a period of time, the reaction chamber surface must be adjusted, or in extreme cases, the reaction chamber components, such as the body and the dome, must be discarded and replaced. Otherwise, the etching results will change as the surface conditions change. The inventors have discovered that the etching chemistry can be altered to reduce the corrosive effect of the fluorine-based etchant on the surface of the reaction chamber. In one embodiment, C1 is added to the etching chemistry. Table VI shows the preferred formulations of the present invention involving silicon etching.

Table VI _Parameters Main etching components for silicon etching: Chlorine-containing etchant: ci2: and fluorine-containing chemicals: CF4, SF6, NF3, (&lt; 50% volume) Flow rate: 200sccm Coil power: 500-1000W Bias power ： 0-50W Pressure ： 4-20mTorr Temperature ： _5Q ° C_ —_____ Generally speaking, the ratio of C1 to F, that is ChF, is preferably between i: 2 to 2: 1 and the best is about 1 : 1 ° C1 Added to fluorine-based chemicals was found to reduce the corrosion of the reaction chamber surface by gas. Therefore, the conditions of the reaction chamber can remain approximately constant for a long period of time that cannot be achieved with the conventional method. As a result, free radicals are still in the air ~ you will be on the surface for a long time. Page 27 (Please read the precautions on the back first ί__ 良 i I • Item write this page)

I Order I I Printed by the Intellectual Property Office of the Ministry of Economic Affairs / Consumer Affairs Co., Ltd. / 丄 A7 '—______ B7 V. Description of the invention () The rate of the composition is kept substantially constant during the processing of the substrate and between each substrate. In another embodiment of the present invention, the reaction chamber wall temperature is adjusted to reduce the deposition of by-products on the surface of the reaction chamber. Currently, the reaction chamber wall temperature is maintained at about 60-80 ° C. The inventors of the present case found that the deposition of by-products on the surface of the reaction chamber decreases with increasing temperature. Therefore, the temperature can be controlled to reduce the amount of by-products deposited on the surface of the reaction chamber during processing. Preferably, the reaction chamber wall temperature is higher than 200 ° C to minimize the accumulation of deposits on the reaction chamber surface, thereby preventing the reaction chamber surface profile from changing during processing. In another embodiment of the invention, the material of the etching reaction chamber is selected to reduce the sensitivity of the etching process to surface conditions. One of the causes of the fluctuation of the etching rate after cleaning of a reaction chamber as described above is the radical recombination rate of the etchant on different surfaces. Therefore, when the radical has a first recombination rate on the surface of the reaction chamber containing the first material, such as aluminum or ceramic, the free substrate processing by-product will have a second recombination rate. Deposited on the surface of the reaction chamber during processing. After a period of time, the surface material of the reaction chamber is covered by deposits of by-products, thus changing the composition of the surface exposed to the etchant, resulting in a change in the etching rate. Traditionally, the effect of changes in free radical recombination rate can be minimized or eliminated by a seasoning cycle, in which a thin film containing by-products formed during etching is deposited on the surface of the reaction chamber To cover the surface of the reaction chamber. However, this adjustment cycle is quite time consuming and will apply the Chinese National Standard (CNS) A4 size (210 X 297 mm) on page 28. 11 ^ — rhlrx— Μ (Please read the cautionary note on the back first Page) Β— .1 I n, I ΛΜββ n Is I ai_i _ Printed by Intellectual Property Bureau of the Ministry of Economy X Consumer Cooperatives 505971 A7 B7 V. Description of the invention (to reduce the output rate of the system because the entire manufacturing must be stopped. The present invention The sufficient method and equipment involve the selection of the reaction chamber material according to the reaction chamber material and the free radical binding rate. Preferably, the radical recombination rate with the reaction chamber material is approximately equal to the deposition of by-products formed on the surface of the reaction chamber. The free radical recombination rate of the product. Therefore, a substantially constant etching rate can be maintained during changing the surface conditions of the reaction chamber. Preferably, the selected material contains at least 80% of the surface of the reaction chamber. In one embodiment, A polycrystalline silicon etching reaction chamber contains an inner surface made of one or more whole materials, such as quartz. However, the selected material is different depending on the etching chemistry. In each case The material is selected so that the free radical recombination rate thereon is substantially equal to the recombination rate of the deposits formed on the chamber surface. Referring to the figure, the selected material is preferably used to form the reaction chamber. The inner surface of the body 12 and / or the dome 13. The foregoing embodiments are presented separately for the sake of clarity. However, the present invention can apply one or more of the above embodiments in combination to make the etching rate, repeatability and Selective optimization. The example of Mingfa published in the relationship statement is a step by step. And it is published under the template, but the basis of Mingfa is not exemplified. The Ministry of Economic Affairs, Intellectual Property Bureau, Employee Consumer Cooperatives, printed the development industry to Calai Fanli, and the reason for the request is the Mingfa version of Fanfa. 9 第 The 2nd paper standard applies Chinese National Standards (CNS) A4 size (210 X 297 mm)

Claims (1)

505971 Sixth, the ancient method of patent application scope, wherein the reaction chamber has 1. A substrate etched in a reaction chamber has a common inner surface, the method includes at least The sword is introduced into the reaction chamber; and eg «庐 / plasma to cause the solution of the first etchant (b) in the 1¾ reaction 击 hit I, 丄 ^ in order to let the separation on the inner surface, where the The first etchant is added, and the deposition of the dissociated substance on the continuous substance is reduced to a minimum, and the T is the dissociated etch on the inner surface of the j5p reading. The first recombination rate of the agent is different from the second recombination rate of the etchant in the coating. 2. The method as described in the scope of patent application $ 1 ', wherein the deposition rate of the shell on the inner surface is less than 30 / min. 3. The method according to item 1 of the scope of patent application, further enclosing (c) cleaning the inner surface before step (a). 4 · The method as described in item 1 of the scope of patent application, wherein the first etching "contains chlorine. 5 · The method as described in item 4 of the scope of patent application, further comprising: (c) from a silicon-containing substrate One or more layers are etched on top 6. A method of etching a substrate in a reaction chamber, wherein the reaction main body has an inner surface, the method includes at least: (a) at least a first etchant and a second Etchant flows into the reaction page 30 This paper size applies Chinese National Standard (CNS) A4 (210 X 297 mm) (Please read the precautions on the back before filling this page) Order ----- Intellectual Property of the Ministry of Economic Affairs Bureau of Consumer Cooperatives printed 505971 ABCD patent application room, in which a volume flow of the first etchant is greater than the volume flow of the second etchant; and (Please read the precautions on the back before filling this page) (b ) Firing a plasma in the reaction chamber to cause dissociation of the first etchant and the second etchant, wherein the dissociated first etchant deposits a substance at a first rate on the inner surface and the dissociated The second etchant is A second rate deposit material is less than the first rate on the inner surface. 7. The method as described in item 6 of the patent application range, wherein the first etchant contains chlorine. 8. As described in item 6 of the patent application range. The method, wherein the second etchant comprises bromine. 9. The method according to item 6 of the scope of patent application, wherein the first etchant comprises chlorine and the second etchant comprises bromine. 1 〇. As applied The method described in item 6 of the patent scope, further comprising: (c) etching one or more layers from the substrate, wherein the one or more layers include printed pieces printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs. The method described in item 6 of the patent scope, further comprising cleaning the inner surface before step (a). Page 31 This paper size applies the Chinese National Standard (CNS) A4 specification (210X297 mm) 505971 ABCD Six Ministry of Economy wisdom The property bureau employee consumer cooperative prints the scope of patent application 12. The method as described in item 6 of the scope of patent application, further comprising flowing oxygen into the reaction chamber. 1 3. As the scope of patent application scope 12 The method, wherein the first etchant comprises chlorine and the second etchant comprises bromine. 14. A substrate that can be etched in a reaction chamber having an inner surface and the inner surface condition can be etched for an etching. A method for minimizing the impact of processing, the method comprising at least: 0) etching a first substrate in the reaction chamber under a first pressure according to a main recipe; and (b) according to a An overetch formula overetches the first substrate in the reaction chamber at a second pressure below 30 mToη *. 15. The method as described in item 14 of the patent application scope, wherein the substrate comprises A polycrystalline layer disposed thereon and the over-etching formulation include flowing one or more of a bromine-containing fluid, a chlorine-containing fluid, or a combination thereof into the reaction chamber. 16. The method according to item 14 of the scope of patent application, wherein (b) comprises flowing a chemical mixture containing a bromine-containing fluid and an oxygen-containing fluid into the reaction chamber, wherein the oxygen-containing fluid accounts for the volume flow of the chemical mixture 10% or less. Page 32 This paper size applies to China National Standard (CNS) A4 (210X297 mm) ......... «........., but ... (Please read the Please note this page before filling in this page) 505971 A BCD patent application scope (please read the notes on the back before filling this page) 17. The method described in item 14 of the patent application scope, where (b) includes A chemical mixture of a fluid and an oxygen-containing fluid flows into the reaction chamber, wherein the oxygen-containing fluid accounts for 25% or less of the volumetric flow rate of the chemical mixture. 1 8. A method of etching a substrate, comprising at least: (a) placing the substrate in a reaction chamber having an inner surface; (b) flowing a chemical mixture into the reaction chamber; (c) ) Firing a plasma from the chemical mixture in the reaction chamber to form one or more plasma compositions, and (d) depositing a thin film on the inner surface; wherein the one or more plasma compositions and the inner surface A first recombination rate of is approximately equal to a second recombination rate of the one or more plasma compositions and the film. 19. The method of claim 18, wherein the substrate comprises polycrystalline silicon and the inner surface thereof comprises quartz. 2 0. The method according to item 19 of the scope of patent application, wherein the inner surface is printed by the Consumer Cooperative of the Intellectual Property Bureau of the Ministry of Economic Affairs and includes a lining disposed on a reaction chamber body. 2 1. A method of etching a substrate, which at least comprises: (a) placing the substrate in a reaction chamber; (b) flowing a chemical mixture into the reaction chamber, the chemical mixture on page 33 Paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 505971 ABCD patent application scope includes:-(Please read the precautions on the back before filling this page) (i) A bromine-containing fluid and a chlorine-containing fluid And (ii) a fluorine-containing fluid; wherein the volume flow of one or more of the bromine-containing fluid and a chlorine-containing fluid is at least 50% of the chemical mixture; and (c) firing a plasma. 22. The method of claim 21, wherein the fluorine-containing fluid comprises one or more of SF6, NF3, and combinations thereof and the volume flow rate of the fluorine-containing fluid is less than 20% of the chemical mixture. 2 3. The method according to item 21 of the scope of patent application, wherein the fluorine-containing fluid contains CF4 and 02 and the volume flow rate of the fluorine-containing fluid is less than 50% and the volume flow ratio of CF4 to 02 is 4: 1 . 24. The method according to item 21 of the scope of patent application, wherein the fluorine-containing fluid comprises CF4 and CF4 in a volume flow rate of less than 50% of the chemical mixture. Printed by the Consumer Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs 25. The method described in item 21 of the scope of patent application, wherein the bromine-containing fluid contains HBr and the chlorine-containing fluid contains HC1. 26. The method of claim 21, further comprising: (c) etching one or more layers from the substrate, wherein the one or more layers include sentences. Page 34 This paper size applies Chinese National Standard (CNS) A4 specification (210X 297 mm) 505971 A8 B8 C8 D8 VI. Application for patent scope 2 7. —A device for etching a substrate, which at least contains: ( Please read the precautions on the back before filling out this page) (a) —Processing reaction chamber, which includes a reaction chamber body with an inner surface; (b) One or more surnames connected to the processing reaction chamber One or more sources; and (c) at least one coil disposed adjacent to the processing reaction chamber for firing a plasma in the processing reaction chamber to dissociate the one or more etchant, wherein the A first reaction rate of the dissociated one or more etchant and the inner surface is substantially equal to a second reaction rate of the dissociated one or more etchant and a substance formed on the inner surface during processing. 28. The device of claim 27, wherein the substrate comprises polycrystalline silicon and the inner surface comprises quartz. 29. The device according to item 27 of the scope of patent application, wherein the inner surface includes a lining provided on the body of the reaction chamber. Printed by the Employees' Cooperatives of the Intellectual Property Bureau of the Ministry of Economic Affairs Page 35 This paper size applies to China National Standard (CNS) A4 (210X297 mm)