CN106894000B - Protection method of quartz tube - Google Patents

Protection method of quartz tube Download PDF

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Publication number
CN106894000B
CN106894000B CN201510960961.1A CN201510960961A CN106894000B CN 106894000 B CN106894000 B CN 106894000B CN 201510960961 A CN201510960961 A CN 201510960961A CN 106894000 B CN106894000 B CN 106894000B
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quartz tube
protecting
ammonia gas
silicon
silicon nitride
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CN106894000A (en
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沈建飞
范建国
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Semiconductor Manufacturing International Shanghai Corp
Semiconductor Manufacturing International Beijing Corp
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Semiconductor Manufacturing International Shanghai Corp
Semiconductor Manufacturing International Beijing Corp
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4404—Coatings or surface treatment on the inside of the reaction chamber or on parts thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/4401—Means for minimising impurities, e.g. dust, moisture or residual gas, in the reaction chamber
    • C23C16/4405—Cleaning of reactor or parts inside the reactor by using reactive gases

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  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)

Abstract

The invention provides a protection method of a quartz tube, which is used for deposition equipment adopting chlorine-containing substances as reactants, and comprises the following steps: removing hydroxyl in the quartz tube; and generating a reinforcement of bond energy within the quartz tube. In the method for protecting the quartz tube, the hydroxyl in the quartz tube is removed, so that the hydroxyl can be prevented from reacting with the chlorine-containing substance to generate a yellow reactant, and the generated bond energy reinforcement can prevent the oxygen element in the quartz material from reacting with the chlorine-containing substance to generate the yellow reactant, so that the maintenance of the quartz tube is facilitated after the deposition process is carried out, and the service life of the quartz tube is prolonged; and the surface characteristic of the quartz tube can be improved by the reinforcement of the bond energy, so that the quartz tube is not easily damaged by later-stage maintenance, and the reliability of a deposition process is ensured.

Description

Protection method of quartz tube
Technical Field
The invention relates to the technical field of integrated circuit manufacturing, in particular to a protection method of a quartz tube.
Background
In semiconductor manufacturing, silicon oxide formed by Thermal Oxidation (Thermal Oxidation) has the advantages of high quality and good flatness, and is therefore commonly used. However, thermal oxidation processes require higher temperatures (typically greater than 1000 ℃) and longer process times relative to Chemical vapor deposition processes (CVD for short).
In view of the above problem, one current alternative is to use a low pressure Chemical Vapor Deposition High Temperature Oxidation (LPCVD HTO) process. Typically, the LPCVD HTO process will be carried out at a relatively low temperature (typically less than 1000 ℃) and low pressure, so that the LPCVD HTO process will incur less thermal expense, while the LPCVD HTO process has very good step performance, which results in a higher quality, more planar silicon oxide.
Using the LPCVD HTO process for high temperature deposition of silicon oxide as an example, the reactant dichlorosilane (SiH) will be used2Cl2) And nitrous oxide (N)2O), the specific reaction is as follows:
SiH2Cl2+2N2O→SiO2+2N2+2HCl
the conventional LPCVD apparatus for performing the LPCVD HTO process is generally a quartz tube furnace, and as shown in fig. 1, the conventional LPCVD apparatus 100 includes a first quartz tube 110, a second quartz tube 120 and a vacuum pumping device 130, wherein the second quartz tube 120 is located inside the first quartz tube 110, an upper end of the first quartz tube 110 is of a closed structure, and an upper end of the second quartz tube 120 is of an open structure, so that the second quartz tube 120 is communicated with the first quartz tube 110 at the upper end thereof, and both can form a vacuum environment under the action of the vacuum pumping device 130 to perform the LPCVD HTO process.
However, when the LPCVD HTO process is performed, it is found during maintenance of the LPCVD apparatus 100 that: the surfaces of the first quartz tube 110 and the second quartz tube 120 both showed a lot of yellow reactants after the LPCVD HTO process. The inventors have long studied and found that these yellow reactants are the result of the reaction of dichlorosilane gas and the quartz tube wall. Specifically, on the one hand, since the quartz tube is manufactured by the oxyhydrogen flame fusion method, a large amount of hydroxyl groups remain in the quartz tube, and these hydroxyl groups react with dichlorosilane at high temperature to generate a yellow reactant (chlorine-containing compound), and on the other hand, oxygen in the quartz tube also reacts with dichlorosilane to generate a yellow reactant (chlorine-containing compound).
In order to remove the yellow reactant, hydrofluoric acid is usually used to repeatedly acid-wash the quartz tube, which not only results in poor cleaning efficiency, but also damages the quartz tube wall and affects the manufacturing process. At present, in order to avoid influencing the manufacturing process, the quartz tube is usually directly replaced after a maintenance period (generally 3 months), so that the service life of the quartz tube is greatly shortened, and the production cost is increased.
Disclosure of Invention
The invention aims to provide a protection method of a quartz tube, which aims to solve the problems that the quartz tube on deposition equipment adopting chlorine-containing substances as reactants in the prior art is difficult to clean and short in service life.
In order to solve the above technical problems, the present invention provides a method for protecting a quartz tube used in a deposition apparatus using a chlorine-containing substance as a reactant, wherein the method for protecting a quartz tube comprises:
removing hydroxyl in the quartz tube; and
a reinforcement of bond energy is generated within the quartz tube.
Optionally, in the method for protecting a quartz tube, the step of removing hydroxyl groups in the quartz tube includes:
performing first removal treatment of hydroxyl on the quartz tube; and
and carrying out second removal treatment on the hydroxyl on the quartz tube.
Optionally, in the method for protecting a quartz tube, a first surface chemical treatment is performed on the quartz tube to generate a reinforcement of bond energy in the quartz tube.
Optionally, in the method for protecting a quartz tube, after the first surface chemical treatment is performed on the quartz tube, the method further includes: the quartz tube is subjected to a second surface chemical treatment to regrow the reinforcement of bond energy.
Optionally, in the method for protecting a quartz tube, the first removal treatment and the first surface chemical treatment are performed simultaneously, and then the second removal treatment is performed, and finally the second surface chemical treatment is performed.
Optionally, in the protection method for the quartz tube, ammonia gas is used to perform a first removal treatment on hydroxyl groups of the quartz tube, wherein the time for introducing the ammonia gas is 30 minutes to 120 minutes, and the reaction temperature of the ammonia gas is 600 ℃ to 800 ℃.
Optionally, in the protection method for the quartz tube, hydrogen or deuterium is used to perform a second removal treatment of hydroxyl groups on the quartz tube, wherein the time for introducing the hydrogen or deuterium is 30 to 120 minutes, and the reaction temperature of the hydrogen or deuterium is 700 to 1000 ℃.
Optionally, in the protection method for the quartz tube, ammonia gas is used to perform the first surface chemical treatment on the quartz tube, wherein the time for introducing the ammonia gas is 30 minutes to 120 minutes, and the reaction temperature of the ammonia gas is 600 ℃ to 800 ℃. .
Optionally, in the protection method for the quartz tube, the reinforcement of the bond energy is silicon nitride, and the growth thickness of the silicon nitride is 10 nm angstrom-50 nm.
Optionally, in the protection method for the quartz tube, dichlorosilane and ammonia gas are used for the second surface chemical treatment, wherein the growth temperature of the silicon nitride is 650 ℃ to 800 ℃, and the growth pressure of the silicon nitride is 26.66Pa to 133.3 Pa.
Optionally, in the method for protecting a quartz tube, after the step of generating a reinforcement of bond energy in the quartz tube, the method further includes: and arranging a protective layer on the quartz tube.
Optionally, in the protection method for the quartz tube, the protective layer is a silicon dioxide layer, and the growth thickness of the silicon dioxide is 10 nm to 50 nm.
Optionally, in the protection method for the quartz tube, dichlorosilane and nitrous oxide are used to form the protection layer, wherein the growth temperature of silicon dioxide is 700 ℃ to 900 ℃, and the growth pressure of silicon dioxide is 26.66Pa to 133.3 Pa.
Optionally, in the method for protecting a quartz tube, the deposition apparatus is a deposition apparatus for performing an LPCVD HTO process.
Optionally, in the method for protecting a quartz tube, the chlorine-containing substance is dichlorosilane.
Optionally, in the method for protecting a quartz tube, the deposition apparatus is used for depositing silicon oxide or silicon nitride.
In summary, in the protection method for a quartz tube provided by the present invention, on one hand, hydroxyl groups in the quartz tube are removed, so that the surface of the quartz tube does not have hydroxyl groups, thereby avoiding the reaction between chlorine-containing substances and hydroxyl groups during a deposition process, and then, a reinforcement of bond energy is generated in the quartz tube, so as to prevent oxygen in the quartz material from reacting with the chlorine-containing substances to generate yellow reactants (chlorine-containing), and thus, by the above two treatments, the hydroxyl groups and oxygen in the quartz tube are finally prevented from reacting with the chlorine-containing substances during the deposition process, and the formation of yellow reactants is avoided, thereby facilitating the maintenance and repair of the quartz tube, and further improving the service life of the quartz tube; and the generation of the reinforcement of the bond energy also improves the surface characteristic of the quartz tube, so that the quartz tube is not easily damaged by later maintenance, particles of deposition equipment are reduced, and the reliability of a deposition process is ensured.
Drawings
FIG. 1 is a schematic view of a prior art LPCVD apparatus;
FIG. 2 is a flow chart illustrating a method for protecting a quartz tube according to an embodiment of the present invention;
FIG. 3 is a sub-flowchart illustrating the removal of hydroxyl radicals from the quartz tube according to an embodiment of the present invention.
Detailed Description
According to the background art, in the LPCVD HTO process in the prior art, many yellow reactants appear on the surface of the quartz tube, and the yellow reactants need to be removed by repeated pickling with hydrofluoric acid, however, the repeated pickling increases the roughness of the quartz tube wall, which easily causes the high particle height of the deposition process.
As a result of intensive studies on the process for producing a quartz tube according to the prior art, the inventors have found that, on the one hand, a quartz tube is produced by melting a quartz tube with an oxyhydrogen flame so that a large number of hydroxyl groups remain on the quartz tube, and the remaining hydroxyl groups react with dichlorosilane at a high temperature to produce the above-mentioned yellow reactant (chlorine-containing compound), and on the other hand, oxygen in the quartz tube also reacts with dichlorosilane to produce a yellow reactant (chlorine-containing compound). The inventor further researches and discovers that yellow reactants appear on the wall of the quartz tube after the deposition process is carried out by adopting the deposition equipment with chlorine-containing substances as reactants.
Based on this, the inventor proposes a method for protecting a quartz tube, which can remove hydroxyl groups in the quartz tube in advance to avoid the reaction between chlorine-containing substances and hydroxyl groups during the deposition process, and then generate a reinforcement of bond energy in the quartz tube, so as to prevent the reaction between oxygen in the quartz material and chlorine-containing substances because the reinforcement of bond energy breaks the bond energy (silicon-silicon bond and silicon-oxygen bond) originally existing in the quartz material. Therefore, through the two treatments, the hydroxyl and the oxygen in the quartz tube can not react with chlorine-containing substances in the deposition process, so that the adhesion of yellow reactants on the wall of the quartz tube is avoided, the maintenance difficulty of the quartz tube is reduced, and the service life of the quartz tube is prolonged; and moreover, the surface characteristics of the quartz tube are improved simultaneously by the generation of the reinforcement of the bond energy, so that the quartz tube is not easily damaged by later maintenance, particles of deposition equipment are reduced, and the reliability of a deposition process is ensured.
In order to make the objects, advantages and features of the present invention clearer, the following describes the protection method of the quartz tube proposed by the present invention in further detail with reference to fig. 2 to 3. It is to be noted that the drawings are in a very simplified form and are not to precise scale, which is merely for the purpose of facilitating and distinctly claiming the embodiments of the present invention.
Referring to fig. 2, fig. 2 is a flowchart illustrating a method for protecting a quartz tube according to an embodiment of the invention.
As shown in fig. 2, step S1 is performed to remove hydroxyl groups in the quartz tube to eliminate hydroxyl groups carried on the surface of the quartz tube, so as to avoid the reaction between the hydroxyl groups and chlorine-containing substances when performing a deposition process using chlorine-containing substances as reactants, so that yellow reactants (mainly chlorine-containing elements) are attached to the wall of the quartz tube.
In this example, the quartz tube was used in a deposition apparatus using a chlorine-containing substance as a reactant. The chlorine-containing substance is, for example, dichlorosilane (SiH)2Cl2) And the like. Silicon oxide and silicon nitride may be deposited using a deposition apparatus that employs dichlorosilane as a reactant.
Wherein the content of the first and second substances,the silicon oxide deposition can be carried out by a low pressure chemical vapor deposition high temperature oxidation (LPCVD HTO) process using reaction gases of dichlorosilane and nitrous oxide (N)2O), the reaction process of the two is as follows:
SiH2Cl2+2N2O→SiO2+2N2+2HCl (1)
in the formula (1), SiO2Thus obtaining the prepared silicon oxide film material. The high temperature oxidation deposition temperature is typically around 900 ℃ and is performed at low pressure.
In addition, the deposition of silicon nitride may be accomplished by a Low Pressure Chemical Vapor Deposition (LPCVD) process using dichlorosilane and ammonia (NH) as reactant gases3) The specific reaction process is as follows:
3SiH2Cl2+4NH3→Si3N4+6H2+6HCL (2)
in the formula (2, Si3N4Thus obtaining the prepared silicon nitride film material. The low pressure deposition temperature is typically 700 ℃ to 800 ℃.
With continued reference to fig. 2, step S2 is performed to generate a reinforcement of bond energy in the quartz tube to break the silicon-silicon bond and silicon-oxygen bond in the quartz material and regenerate other substances (such as nitride) with bond energy larger than the silicon-silicon bond and silicon-oxygen bond, so as to prevent the oxygen element in the quartz material from reacting with the chlorine-containing substance in the subsequent deposition process, and to prevent the yellow reactant (mainly chlorine-containing element) from adhering to the wall of the quartz tube.
After the quartz tube is processed in the steps S1 and S2, the reaction between the hydroxyl and oxygen carried by the quartz tube and chlorine-containing substances in the deposition process can be avoided, so that the generation of yellow reactants is prevented, the maintenance difficulty of the quartz tube is reduced, and the service life of the quartz tube is prolonged.
Specifically, in step S2, the generation of the reinforcement of bond energy may be performed by a first surface chemical treatment for ease of implementation.
Of course, the person skilled in the art knows that: surface chemical treatment is a process capable of improving the surface properties of a material, and is, for example, carburization (i.e., carbonization), nitridation (i.e., nitridation), carbonitriding (i.e., cyanidation), or the like. The surface chemical treatment can change the chemical components and the organization structure of the surface layer of the material so as to enhance the surface characteristics of the material, such as wear resistance, corrosion resistance, chemical stability and the like.
Specifically, after the first surface chemical treatment, the quartz tube has enhanced surface properties such as wear resistance, corrosion resistance, chemical stability, etc. due to the formation of other silicon bonds, such as silicon-nitrogen bonds, having a bond energy greater than that of silicon-silicon bonds and silicon-oxygen bonds. The improvement of chemical stability can ensure that the quartz tube wall is not easy to react with chlorine-containing substances in the deposition process. And the improvement of wear resistance, corrosion resistance and the like, so that the quartz tube wall is not easy to be damaged by acid washing and the like during later maintenance, thereby reducing particles of deposition equipment and improving the reliability of a deposition process.
Optionally, the first surface chemical treatment in this embodiment is a nitriding treatment. After the nitriding treatment, nitrides (such as silicon nitride) can be generated in the quartz tube, and the chemical stability of the nitrides is superior to that of the oxides, so that the quartz tube has more excellent surface characteristics and better chemical stability, and is not easy to react with chlorine-containing substances.
More optionally, the nitriding treatment is carried out using ammonia gas. Specifically, the principle of the nitriding treatment by ammonia gas is as follows: the active nitrogen atoms decomposed by ammonia gas under a certain temperature can permeate and diffuse to the surface layer of the quartz tube to form silicon nitride (not limited to a specific chemical structure), namely the decomposed active nitrogen atoms break the inside of the quartz tube material (SiO)2) The silicon-silicon bond and the silicon-oxygen bond of (a) form a silicon-nitrogen bond again.
With continued reference to fig. 2, after the first surface chemical treatment is performed on the quartz tube, the method preferably further includes:
step S3: the quartz tube is subjected to a second surface chemical treatment to regrow the reinforcement of bond energy.
Specifically, in step S2, when the generated reinforcement of bond energy is silicon nitride, it is preferable to perform the second surface chemical treatment with dichlorosilane and ammonia gas, that is, to perform the growth of the silicon nitride by introducing dichlorosilane and ammonia gas, wherein the reaction process of dichlorosilane and ammonia gas can be referred to formula (2).
Silicon nitride (Si) formed in the formula (2)3N4) The performance is more stable, and the bonding energy of the silicon nitride generated after the first surface chemical treatment is further improved, so that the surface characteristic of the quartz tube is more stable.
Optionally, when dichlorosilane and ammonia gas are introduced for regeneration of the silicon nitride, the silicon nitride (Si) is obtained3N4) The growth temperature of the silicon nitride (Si) is controlled to be 650-800 DEG C3N4) The growth pressure of (A) is controlled to be 26.66Pa to 133.3 Pa. The growth thickness of the silicon nitride is preferably 10 nm to 50 nm, so as to avoid influencing the thickness of the product of the deposition process.
Referring to fig. 3, fig. 3 is a sub-flowchart of the method for removing hydroxyl radicals in a quartz tube according to an embodiment of the present invention.
As shown in fig. 3, the step S1 of removing hydroxyl groups in the quartz tube preferably includes:
step S11: performing first removal treatment of hydroxyl on the quartz tube; and
step S12: and carrying out second removal treatment on the hydroxyl on the quartz tube.
By removing the hydroxyl groups twice, the surface of the quartz tube can be effectively ensured to have no residual hydroxyl groups.
Preferably, ammonia gas is adopted to carry out first removal treatment on hydroxyl groups of the quartz tube, the time for introducing the ammonia gas is 30-120 minutes, and the reaction temperature of the ammonia gas is controlled to be 600-800 ℃ so as to ensure that the ammonia gas and the hydroxyl groups are fully reacted and the hydroxyl groups are effectively removed.
The ammonia gas (NH)3) And Hydroxyl (OH)-) The reaction process comprises the following steps:
OH-+NH3→NH2+H2O (3)
in the formula (3), NH2And H2O is all generated reaction by-products.
And, when the thin film material deposited by the subsequent deposition process is silicon nitride, the Nitride (NH) generated in the above formula (3)2) Corresponding to the deposited silicon nitride film, thereby avoiding the generated reaction by-products from polluting the deposition equipment and ensuring the reliability of the deposition process. Of course, both the reaction by-products generated after the hydroxyl radical removal treatment and the bond energy enhancers generated are preferably compatible with the thin film materials deposited by the deposition process, thereby preventing the products from contaminating the deposition equipment and affecting the deposition process.
Obviously, ammonia gas may perform the first removal treatment of hydroxyl groups or the nitriding treatment (i.e., the first surface chemical treatment) on the quartz tube. Therefore, the ammonia gas can simultaneously perform the first removal treatment of the hydroxyl groups and the nitriding treatment of the quartz tube. Accordingly, when the first removal treatment and the nitriding treatment are performed simultaneously, the time for introducing the ammonia gas is preferably 30 to 120 minutes, and the reaction temperature of the ammonia gas is preferably controlled to 600 to 800 ℃, so as to ensure effective aminolysis of hydroxyl groups.
However, if the product does not correspond to the thin film material deposited by the deposition process, as shown in fig. 2, after the strengthening substance of the bond energy is generated in the quartz tube (S2), the method further includes:
step S4: and arranging a protective layer on the quartz tube. Step S4 of the present embodiment is preferably performed after step S3.
Wherein the protective layer can completely cover the reaction product (including the reaction byproduct generated when removing hydroxyl group and the reinforcement of bonding energy, but mainly the reinforcement of bonding energy), such as nitride, so as to prevent the product from affecting the product thickness of the deposition process, and also prevent the product from affecting the product particles of the deposition process. Moreover, the protective layer can well adsorb the deposited film and can prevent the particles from falling off.
Specifically, if the thin film material deposited by the deposition process is an oxide, and the oxide is silicon dioxide, the protective layer is preferably a silicon dioxide layer. The silicon dioxide of the present embodiment may cover the nitride (e.g., silicon nitride) generated in the steps S1 and S2, so that the nitride does not directly contact the oxide in the deposition process, thereby avoiding affecting the thickness of the oxide film.
The protective layer of this embodiment is a silicon dioxide layer, preferably formed by dichlorosilane and nitrous oxide (N)2O) forming the silicon dioxide layer. Specifically, dichlorosilane and nitrous oxide are introduced to carry out growth of silicon dioxide, so that a silicon dioxide layer is formed. Wherein dichlorosilane (SiH)2Cl2) And nitrous oxide (N)2O) the reaction process is as follows:
SiH2Cl2+2N2O→SiO2+2N2+2HCl (4)
in the formula (4), SiO2Is silicon dioxide generated after reaction.
Preferably, the growth temperature of the silicon dioxide is controlled to be 700-900 ℃, and meanwhile, the growth pressure is set to be 26.66-133.3 Pa. And the growth thickness of the silicon dioxide is controlled to be 10-50 nanometers, so that the thickness of a product in a subsequent deposition process is prevented from being influenced.
In this embodiment, hydrogen (H) may be optionally used2) Or deuterium gas (D)2) And carrying out second removal treatment on the hydroxyl on the quartz tube. Wherein, the time of introducing the hydrogen or deuterium is preferably 30-120 minutes, and the reaction temperature of the hydrogen or deuterium is controlled to be 700-1000 ℃, so that residual hydroxyl and other dangling bonds can be effectively removed.
As a preferred embodiment, the first removal treatment and the first surface chemical treatment are performed simultaneously, so as to simplify the process and reduce the protection cost of the quartz tube. Subsequently, the second removal treatment is performed after the first surface chemical treatment, and finally, the second surface chemical treatment is performed. By adopting the protection flow, the protection effect of the quartz tube is good.
In summary, in the protection method for a quartz tube provided by the present invention, on one hand, hydroxyl groups in the quartz tube are removed, so that the surface of the quartz tube does not have hydroxyl groups, thereby avoiding the reaction between chlorine-containing substances and hydroxyl groups during a deposition process, and then, a reinforcement of bond energy is generated in the quartz tube, so as to prevent oxygen in the quartz material from reacting with the chlorine-containing substances to generate yellow reactants (chlorine-containing), and thus, by the above two treatments, the hydroxyl groups and oxygen in the quartz tube are finally prevented from reacting with the chlorine-containing substances during the deposition process, and the formation of yellow reactants is avoided, thereby facilitating the maintenance and repair of the quartz tube, and further improving the service life of the quartz tube; and the generation of the reinforcement of the bond energy also improves the surface characteristic of the quartz tube, so that the quartz tube is not easily damaged by later maintenance, particles of deposition equipment are reduced, and the reliability of a deposition process is ensured.
In addition, when the deposited film material is different from reaction products (including reaction byproducts generated during hydroxyl removal and generated energetic reinforcement) generated during the protection of the quartz tube, the protective layer is further arranged on the quartz tube, so that the influence of the reaction products on the product thickness of the deposition process can be avoided, and the precision of the deposition process is ensured.
Particularly, in the actual production process, after the protection method of the quartz tube provided by the invention is implemented, yellow reactants are not attached to the surface of the quartz tube after the LPCVD HTO process, and the service life of the quartz tube is prolonged by more than 10 times, so that the protection effect is good.
The above description is only for the purpose of describing the preferred embodiments of the present invention, and is not intended to limit the scope of the present invention, and any variations and modifications made by those skilled in the art based on the above disclosure are within the scope of the appended claims.

Claims (13)

1. A method of protecting a quartz tube used for a deposition apparatus using a chlorine-containing substance as a reactant, comprising:
performing first removal treatment of hydroxyl groups and first surface chemical treatment on the quartz tube by using ammonia gas at the same time, so as to generate a silicon nitride reinforcement with bond energy larger than silicon-silicon bonds and silicon-oxygen bonds in the quartz tube while removing the hydroxyl groups;
performing second removal treatment of hydroxyl on the quartz tube by using hydrogen or deuterium to remove the residual hydroxyl and other dangling bonds;
and carrying out second surface chemical treatment on the quartz tube by adopting dichlorosilane and ammonia gas so as to regrow the silicon nitride reinforcement.
2. The method for protecting a quartz tube according to claim 1, wherein the first removal treatment is performed simultaneously with the first surface chemical treatment, followed by the second removal treatment, and finally the second surface chemical treatment.
3. The method for protecting a quartz tube according to claim 2, wherein the quartz tube is subjected to the first removal treatment of hydroxyl groups with ammonia gas, wherein the time for introducing the ammonia gas is 30 minutes to 120 minutes, and the reaction temperature of the ammonia gas is 600 ℃ to 800 ℃.
4. The method for protecting a quartz tube as claimed in claim 2, wherein the quartz tube is subjected to the second removal treatment of hydroxyl groups using hydrogen or deuterium, wherein the time for introducing the hydrogen or deuterium is 30 to 120 minutes, and the reaction temperature of the hydrogen or deuterium is 700 to 1000 ℃.
5. The method for protecting a quartz tube according to claim 2, wherein the first surface chemical treatment is performed on the quartz tube using ammonia gas, wherein the ammonia gas is introduced for 30 to 120 minutes, and the reaction temperature of the ammonia gas is 600 to 800 ℃.
6. The method for protecting a quartz tube as claimed in claim 5, wherein the silicon nitride is grown to a thickness of 10 nm to 50 nm.
7. The method for protecting a quartz tube as claimed in claim 6, wherein the second surface chemical treatment is performed using dichlorosilane and ammonia gas, wherein the growth temperature of the silicon nitride is 650 ℃ to 800 ℃, and the growth pressure of the silicon nitride is 26.66Pa to 133.3 Pa.
8. The method of shielding a quartz tube as recited in claim 1, further comprising, after generating a silicon nitride reinforcement of bond energy within the quartz tube:
and arranging a protective layer on the quartz tube.
9. The method for protecting a quartz tube as claimed in claim 8, wherein the protective layer is a silicon dioxide layer, and the growth thickness of the silicon dioxide is 10 nm to 50 nm.
10. The method for protecting a quartz tube as claimed in claim 9, wherein the protective layer is formed using dichlorosilane and nitrous oxide, and wherein the growth temperature of silicon dioxide is 700 ℃ to 900 ℃ and the growth pressure of silicon dioxide is 26.66Pa to 133.3 Pa.
11. The method for protecting a quartz tube as claimed in claim 1, wherein the deposition apparatus is a deposition apparatus performing LPCVDHTO process.
12. The method of claim 11, wherein the chlorine-containing species is dichlorosilane.
13. The method of claim 12, wherein the deposition apparatus is used to deposit silicon oxide or silicon nitride.
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