Alloy nozzle surface treatment method, alloy nozzle and photoresist edge glue line removing device

Abstract

The invention provides a surface treatment method of an alloy nozzle, the alloy nozzle and a photoresist edge glue line removing device. The surface treatment method comprises the steps that the alloy nozzle is subjected to first treatment so that a micron-sized rough structure can be formed on the surface of the alloy nozzle, the first treatment comprises the steps that first wet etching and polishing treatment are conducted through a rough etching solution, the rough etching solution comprises nitric acid and ferric trichloride, and the alloy nozzle at least comprises iron, chromium and nickel; second treatment is carried out on the alloy nozzle so as to form nanoscale holes in the micron-sized rough structure, and the second treatment comprises the steps that second wet etching is carried out through the first fine etching solution and third wet etching is carried out through the second fine etching solution; according to the method, the alloy nozzle is subjected to low surface energy treatment by adopting the surface modifier, so that the super-hydrophobic surface is formed on the surface of the alloy nozzle, and the problem that the wafer surface has process defects due to the fact that liquid medicine drops and splashes easily at the nozzle in the moving process of the alloy nozzle is solved.

Description

Technical Field

[0001] This application relates to the field of semiconductor manufacturing technology, and more specifically, to a surface treatment method for an alloy nozzle, an alloy nozzle, and a photoresist edge line removal device. Background Technology

[0002] In semiconductor manufacturing, photolithography is a core process used to precisely replicate design patterns on silicon wafers. This process involves uniformly coating a layer of photoresist onto the silicon wafer, followed by pattern exposure using a mask and light source. After exposure, the photoresist undergoes development and etching to ultimately pattern the desired circuitry. However, common techniques have limitations in the edge-line removal (EBR) step after photoresist coating, directly impacting the quality and efficiency of subsequent processes.

[0003] Edge line removal (EBR) is a necessary step after photoresist coating, designed to remove excess photoresist from the wafer edges to prevent it from peeling off in subsequent processes and affecting product performance. EBR devices typically use an angled jet of remover solvent, acting directly on the wafer edges to effectively remove accumulated photoresist. However, during EBR operation, especially during the arm movement phase, there is a risk that the remover solvent may be flung or drip from the nozzle tip due to instantaneous acceleration. This can cause defects on the photoresist surface, severely impacting product quality and production yield.

[0004] The information disclosed above in the background section is only intended to enhance the understanding of the background art of the art described herein. Therefore, the background art may contain certain information that does not constitute prior art known to those skilled in the art in this country. Summary of the Invention

[0005] The main objective of this application is to provide a surface treatment method for an alloy nozzle, an alloy nozzle and a photoresist edge adhesive line removal device, in order to solve the problem in the prior art that the alloy nozzle is prone to dripping and splashing of the reagent during the movement of the nozzle, resulting in process defects on the wafer surface.

[0006] To achieve the above objectives, according to one aspect of this application, a surface treatment method for an alloy nozzle is provided, comprising: performing a first treatment on the alloy nozzle to form a micron-scale rough structure on the surface of the alloy nozzle, the first treatment comprising performing a first wet etching and polishing treatment with a coarse etching solution, the coarse etching solution comprising nitric acid and ferric chloride, the alloy nozzle comprising at least iron, chromium and nickel; performing a second treatment on the alloy nozzle to form nanoscale pores in the micron-scale rough structure, the second treatment comprising performing a second wet etching with a first fine etching solution and a third wet etching with a second fine etching solution, the first fine etching solution comprising sulfuric acid and nitric acid, the second fine etching solution comprising sodium carbonate; and performing a low surface energy treatment on the alloy nozzle with a surface modifier to form a superhydrophobic surface on the surface of the alloy nozzle.

[0007] Optionally, the coarse etching solution further includes hydrogen peroxide and hydrofluoric acid, and the surface treatment method further includes: preparing 65% concentrated nitric acid using the nitric acid and water; preparing the preliminary coarse etching solution using ferric chloride solid, the 65% concentrated nitric acid, and water, wherein the volume ratio of 65% concentrated nitric acid to water is 1:4 to 1:3, and the mass fraction of ferric chloride solid in the preliminary coarse etching solution is 35% to 45%; mixing the preliminary coarse etching solution with the hydrogen peroxide and the hydrofluoric acid to obtain the coarse etching solution, wherein the volume percentage of hydrogen peroxide in the coarse etching solution is 10% to 15%, and the volume percentage of hydrofluoric acid in the coarse etching solution is 15% to 30%.

[0008] Optionally, the step of performing the first treatment on the alloy nozzle to form the micron-level rough structure on the surface of the alloy nozzle includes: heating the coarse etching solution at a temperature of 30°C to 50°C; placing the alloy nozzle in the coarse etching solution for 1 min to 3 min; and performing the polishing treatment on the alloy nozzle to form the micron-level rough structure on the surface of the alloy nozzle.

[0009] Optionally, the surface treatment method further includes: preparing 98% concentrated sulfuric acid and 65% concentrated nitric acid using the sulfuric acid, the nitric acid and water; preparing the first fine etching solution using the 98% concentrated sulfuric acid and the 65% concentrated nitric acid, wherein the volume fraction of the 98% concentrated sulfuric acid is 70%~80% and the volume fraction of the 65% concentrated nitric acid is 20%~30%.

[0010] Optionally, the step of performing the second treatment on the alloy nozzle to form the nanoscale pores in the micron-scale rough structure includes: heating the first fine etching solution at a constant temperature of 38°C to 42°C; placing the alloy nozzle in the first fine etching solution for 5 min to 15 min and subjecting the alloy nozzle to ultrasonic oscillation at an ultrasonic frequency of 30 Hz to 50 Hz and an ultrasonic power of 100 W to 200 W; and reacting the alloy nozzle in the second fine etching solution to neutralize the first fine etching solution remaining on the surface of the alloy nozzle, wherein the concentration of the second fine etching solution is 3% to 5% and the reaction time is 30 s to 60 s.

[0011] Optionally, the step of using the surface modifier to perform the low surface energy treatment on the alloy nozzle to form the superhydrophobic surface on the surface of the alloy nozzle includes: heating the surface modifier at a constant temperature of 100℃~110℃, wherein the surface modifier includes hexamethylsilanediamine; placing the alloy nozzle after the second treatment in the surface modifier for reaction, and subjecting the alloy nozzle to ultrasonic oscillation, wherein the ultrasonic oscillation frequency is 10Hz~20Hz, the ultrasonic power is 50W~100W, and the reaction time is 5min~10min.

[0012] Optionally, the surface treatment method further includes: polishing the surface of the alloy nozzle; immersing the alloy nozzle in an industrial cleaning agent and subjecting it to ultrasonic oscillation, wherein the ultrasonic oscillation frequency is 30Hz~50Hz, the ultrasonic power is 100W~200W, and the time is 3min~5min; and air-drying the surface of the alloy nozzle for 1min~2min.

[0013] Optionally, the polishing process includes polishing the surface of the alloy nozzle with sandpaper of 1500-2000 grit and a polishing stroke of 30-50 cm.

[0014] According to another aspect of this application, an alloy nozzle is provided, which is obtained by the surface treatment method of the alloy nozzle.

[0015] According to another aspect of this application, a photoresist edge line removal apparatus is provided, including the aforementioned alloy nozzle.

[0016] By applying the technical solution of this application, a superhydrophobic surface is formed by constructing a micron- and nano-scale composite rough structure on the nozzle surface and performing low surface energy treatment. This significantly enhances the liquid adhesion ability of the nozzle surface, effectively preventing the dripping and splashing of the liquid during movement, and improving the yield and efficiency of semiconductor manufacturing processes. Specifically, a coarse etching solution mainly composed of nitric acid and ferric chloride is used to etch the surface of the alloy nozzle. The mixture of ferric chloride and nitric acid acts on the alloy surface to form a micron-scale rough structure with a certain depth and width. After etching, the alloy nozzle is polished to remove irregular etching products, smooth the surface, and achieve a uniform micron-scale roughness. This initial roughening of the nozzle surface facilitates the formation of nano-scale pores in subsequent processing. A second etching is performed using a first fine etching solution (a mixture of sulfuric acid and nitric acid), with sulfuric acid providing... Nitric acid, acting as an oxidant, promotes metal dissolution and forms a dynamic passivation film, controlling the etching rate and preventing over-etching. Simultaneously, it creates nanoscale pores within the micron-level rough structure, increasing the surface's nanoscale complexity. A second fine etching solution (sodium carbonate solution) neutralizes residual acidic substances and further treats the surface, forming a stable nanoscale pore structure. This step provides a final cleaning and finishing of the nozzle surface, ensuring the clarity and stability of the pores. A low surface energy molecular film is formed on the micro / nano composite structure surface using a surface modifier. This film significantly reduces the surface's hydrophilicity, giving the nozzle surface superhydrophobic properties. This coating increases the surface tension of the nozzle, making droplets more likely to maintain a spherical shape, reducing the contact area between the droplets and the surface, enhancing droplet adhesion, and lowering the free energy of the droplets on the nozzle surface, making them less prone to detachment. This effectively suppresses the phenomenon of spontaneous droplet dripping, solving the problem in existing technologies where alloy nozzles easily generate liquid dripping and splashing during movement, leading to process defects on the wafer surface. Attached Figure Description

[0017] The accompanying drawings, which form part of this application, are used to provide a further understanding of this application. The illustrative embodiments and descriptions of this application are used to explain this application and do not constitute an undue limitation of this application. In the drawings:

[0018] Figure 1 A schematic flowchart of a surface treatment method for an alloy nozzle according to an embodiment of this application is shown.

[0019] Figure 2 A schematic flowchart of another surface treatment method for an alloy nozzle according to an embodiment of this application is shown;

[0020] Figure 3 A schematic diagram of the water droplet morphology on the surface of an alloy nozzle according to an embodiment of this application is shown;

[0021] Figure 4 A schematic diagram of a photoresist edge line removal apparatus according to an embodiment of this application is shown. Detailed Implementation

[0022] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0023] It should be noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the exemplary embodiments according to this application. As used herein, the singular form is intended to include the plural form as well, unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this specification, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0024] It should be noted that the terms "first," "second," etc., in the specification, claims, and accompanying drawings of this invention are used to distinguish similar objects and are not necessarily used to describe a specific order or sequence. It should be understood that such data can be interchanged where appropriate for the embodiments of the invention described herein. Furthermore, the terms "comprising" and "having," and any variations thereof, are intended to cover non-exclusive inclusion; for example, a process, method, system, product, or apparatus that comprises a series of steps or units is not necessarily limited to those steps or units explicitly listed, but may include other steps or units not explicitly listed or inherent to such processes, methods, products, or apparatus.

[0025] It should be understood that when an element (such as a layer, film, region, or substrate) is described as being "on" another element, the element may be directly on the other element, or there may be an intermediate element present. Furthermore, in the specification and claims, when an element is described as being "connected" to another element, the element may be "directly connected" to the other element, or "connected" to the other element via a third element.

[0026] As described in the background section, existing EBR devices typically employ an angled spraying method to directly apply photoresist remover to the wafer edge, effectively removing accumulated photoresist. However, during EBR operation, especially during the arm movement phase, there is a risk that the photoresist remover may be ejected or dripped from the nozzle tip due to instantaneous acceleration, potentially causing defects on the photoresist surface. To address the problem of easy dripping and splashing of the alloy nozzle during movement, leading to process defects on the wafer surface, embodiments of this application provide a surface treatment method for an alloy nozzle, an alloy nozzle, and a photoresist edge line removal device.

[0027] The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.

[0028] Figure 1 This is a flowchart of a surface treatment method for an alloy nozzle according to an embodiment of this application. Figure 1 As shown, the method includes the following steps:

[0029] Step S1: Perform a first treatment on the alloy nozzle to form a micron-level rough structure on the surface of the alloy nozzle. The first treatment includes a first wet etching and polishing treatment using a coarse etching solution. The coarse etching solution includes nitric acid and ferric chloride. The alloy nozzle contains at least iron, chromium and nickel.

[0030] Specifically, the alloy nozzle is immersed in a coarse etching solution containing nitric acid and ferric chloride. The solution concentration and temperature are set, and a first wet etching process is performed for a certain period to form a micron-scale rough structure. After etching, the nozzle surface is polished to ensure the uniformity and stability of the surface structure. The key to this step lies in the selection of nitric acid and ferric chloride, which can effectively etch the alloy surface to form the desired micron-scale rough structure without damaging the alloy's basic properties. The alloy nozzle contains at least iron, chromium, and nickel; for example, it can be a stainless steel nozzle. The micron-scale rough structure increases the contact angle between the liquid and the surface, thereby improving the liquid's adhesion and allowing it to form stable droplets on the nozzle surface, making it less susceptible to detachment due to external forces.

[0031] Step S2, the alloy nozzle is subjected to a second treatment to form nanoscale pores in the micron-scale rough structure. The second treatment includes a second wet etching using a first fine etching solution and a third wet etching using a second fine etching solution. The first fine etching solution includes sulfuric acid and nitric acid, and the second fine etching solution includes sodium carbonate.

[0032] Specifically, a second wet etching process is performed using a mixed solution of sulfuric acid and nitric acid. The temperature and ultrasonic frequency of the etching solution are set to further form nanoscale pores within the micron-scale rough structure. After etching, the nozzle is immersed in a sodium carbonate solution for neutralization to remove surface acid residue. It is then rinsed with deionized water and dried at high temperature, forming a surface combining the micron-scale rough structure and nanoscale pores. The nanoscale pores can adsorb more surface liquid molecules, maintaining liquid stability even under low backflow conditions through surface tension. This allows for more effective prevention of dripping or splashing onto the wafer surface during EBR (edge ​​line removal) processes equipped with alloy nozzles, even with lower solution viscosity, significantly reducing process defects and improving wafer production yield and efficiency.

[0033] Step S3: Apply a surface modifier to the alloy nozzle to perform low surface energy treatment in order to form a superhydrophobic surface on the surface of the alloy nozzle.

[0034] Specifically, the superhydrophobic surface formed greatly enhances the hydrophobicity of the nozzle surface. This is because the low surface energy treatment effectively reduces the contact area between the liquid and the alloy surface. By increasing the surface tension, the liquid is less likely to spread on the surface and form independent droplets. As a result, the liquid can still adhere stably to the surface and will not fall off when the nozzle moves or vibrates slightly.

[0035] In this embodiment, a coarse etching solution primarily composed of nitric acid and ferric chloride can be used to etch the surface of an alloy nozzle. The mixture of ferric chloride and nitric acid works synergistically on the alloy surface, forming a micron-scale rough structure with a certain depth and width. After etching, the alloy nozzle is polished to remove irregular etching products, smoothing and leveling the surface to achieve a uniform micron-scale roughness. This initial roughening of the nozzle surface facilitates the formation of nanoscale pores in subsequent processing. A second etching is then performed using a first fine etching solution (a mixture of sulfuric acid and nitric acid), with sulfuric acid providing... Nitric acid, acting as an oxidant, promotes metal dissolution and forms a dynamic passivation film, controlling the etching rate and preventing over-etching. Simultaneously, it creates nanoscale pores within the micron-level rough structure, increasing the surface's nanoscale complexity. A second fine etching solution (sodium carbonate solution) neutralizes residual acidic substances and further treats the surface, forming a stable nanoscale pore structure. This step provides a final cleaning and finishing of the nozzle surface, ensuring the clarity and stability of the pores. A low surface energy molecular film is formed on the micro / nano composite structure surface using a surface modifier. This film significantly reduces the surface's hydrophilicity, giving the nozzle surface superhydrophobic properties. This coating increases the surface tension of the nozzle, making droplets more likely to maintain a spherical shape, reducing the contact area between the droplets and the surface, enhancing droplet adhesion, and lowering the free energy of the droplets on the nozzle surface, making them less prone to detachment. This effectively suppresses the phenomenon of spontaneous droplet dripping, solving the problem in existing technologies where alloy nozzles easily generate liquid dripping and splashing during movement, leading to process defects on the wafer surface.

[0036] In some alternative embodiments, the coarse etching solution further includes hydrogen peroxide and hydrofluoric acid, and the surface treatment method further includes:

[0037] 65% concentrated nitric acid was prepared using nitric acid and water; a preliminary rough etching solution was prepared using ferric chloride solid, 65% concentrated nitric acid, and water, with a volume ratio of 65% concentrated nitric acid to water of 1:4 to 1:3, and the mass fraction of ferric chloride solid in the preliminary rough etching solution of 35% to 45%.

[0038] Specifically, a preliminary coarse etching solution is prepared using solid ferric chloride, the aforementioned 65% concentrated nitric acid, and water. The volume ratio of concentrated nitric acid to water is set between 1:4 and 1:3, and the mass fraction of solid ferric chloride in the solution is controlled between 35% and 45%. Ferric chloride, as an iron salt, possesses strong oxidizing and corrosive properties, playing a decisive role in the micron-level etching of stainless steel surfaces. Setting the concentration and ratio of the ferric chloride solution within the aforementioned range balances the etching rate and surface roughness, ensuring that the desired micron-level rough structure is effectively etched during the coarse etching process without over-etching and causing material damage.

[0039] The initial coarse etching solution is mixed with hydrogen peroxide and hydrofluoric acid to obtain a coarse etching solution. The volume percentage of hydrogen peroxide in the coarse etching solution is 10%~15%, and the volume percentage of hydrofluoric acid in the coarse etching solution is 15%~30%.

[0040] Specifically, hydrogen peroxide, as a strong oxidant, can accelerate the oxidation reaction of ferric chloride, promoting the etching process on the stainless steel surface. Hydrofluoric acid can complex metal ions, preventing iron ions generated during etching from depositing on the surface and disrupting the uniformity of the micron-level rough structure. It also acts as a corrosion accelerater, ensuring that the etching depth and width meet the requirements of subsequent processes. The appropriate ratio of these components can significantly improve the efficiency and effectiveness of alloy nozzle surface modification.

[0041] In the specific implementation process, step S1 above, which involves performing a first treatment on the alloy nozzle to form a micron-level rough structure on the surface of the alloy nozzle, can be achieved through the following steps:

[0042] The coarse etching solution is heated to a temperature of 30℃~50℃; the alloy nozzle is placed in the coarse etching solution for 1min~3min.

[0043] Specifically, a rough etching solution containing 65% concentrated nitric acid, ferric chloride, hydrogen peroxide, and hydrofluoric acid is placed in a constant-temperature water bath, with the heating temperature controlled between 30°C and 50°C. The purpose of this step is to accelerate the chemical reaction rate, especially the reaction rate between ferric chloride and the alloy surface, by increasing the solution temperature, thereby promoting the surface etching process. The increased temperature reduces the viscosity of the solution, making it easier for the reactants to approach the target surface and improving etching efficiency. Simultaneously, the temperature effect also promotes the decomposition of hydrogen peroxide, releasing more oxygen and further enhancing the oxidation effect, making the etching process more thorough and rapid. A suitable etching time ensures that the formation of micron-scale rough structures is both sufficient and appropriate, providing ideal surface conditions for the subsequent formation of nanoscale pores.

[0044] The alloy nozzle is polished to create a micron-level rough structure on its surface.

[0045] Specifically, the etched alloy nozzles then need to be polished. Polishing can eliminate protrusions or depressions that may be formed during the rough etching process, making the surface rough structure more uniform and consistent, which is beneficial to the uniform distribution of subsequent nanoscale pores.

[0046] The polishing process in step S1 includes polishing the surface of the alloy nozzle with sandpaper of 1500-2000 grit for a stroke of 30-50 cm. The purpose of this process is to smooth out any unevenness or over-etched areas that may have occurred on the surface after etching, ensuring a uniform distribution of the micron-level rough structure. Subsequently, the nozzle is ultrasonically vibrated in an industrial cleaning agent, such as acetone solution, for 3-5 minutes until the acetone has completely evaporated, resulting in the micron-level rough structure on the alloy nozzle surface.

[0047] In some optional embodiments, the surface treatment method further includes:

[0048] 98% concentrated sulfuric acid and 65% concentrated nitric acid were prepared using sulfuric acid, nitric acid and water. The first fine etching solution was prepared using 98% concentrated sulfuric acid and 65% concentrated nitric acid, with the volume fraction of 98% concentrated sulfuric acid being 70%~80% and the volume fraction of 65% concentrated nitric acid being 20%~30%.

[0049] Specifically, the selected slow-speed fine etching solution consists of 98% concentrated sulfuric acid and 65% concentrated nitric acid, with the concentrated sulfuric acid providing H₂. + Nitric acid promotes metal dissolution, while nitric acid acts as an oxidant to form a dynamic passivation film, inhibiting over-etching. Concentrated sulfuric acid, acting as a proton donor, accelerates metal dissolution, while concentrated nitric acid acts as an oxidant, forming a passivation film of the metal oxide, controlling the metal dissolution rate and preventing over-etching. A mixture of 70% to 80% concentrated sulfuric acid and 20% to 30% concentrated nitric acid can precisely control the etching depth while ensuring etching efficiency, forming the desired nanoscale pores without damaging the micron-scale rough structure. This micro-nano composite structure is key to improving surface hydrophobicity.

[0050] The step S2 described above in this application, which involves a second treatment of the alloy nozzle to form nanoscale pores in a micron-scale rough structure, can be achieved through the following steps:

[0051] The first fine etching solution is heated at a constant temperature of 38℃~42℃; the alloy nozzle is placed in the first fine etching solution for 5min~15min and subjected to ultrasonic oscillation at an ultrasonic frequency of 30Hz~50Hz and an ultrasonic power of 100W~200W.

[0052] Specifically, the etching solution is placed in a constant-temperature water bath at 38℃~42℃. This heating temperature activates the chemical reactions in the solution, especially the reactions of sulfuric acid and nitric acid with the alloy surface, without causing overheating, thus avoiding unnecessary side reactions or damage to the alloy material structure. At this temperature, the solution has high activity, effectively promoting the formation of nanoscale pores while maintaining solution stability, preventing excessive bubble formation or solution decomposition, and ensuring the uniformity and controllability of the etching process. Ultrasonic oscillation at the aforementioned frequency is used for auxiliary stirring to remove surface reaction bubbles and reaction products, ensuring uniform etching solution concentration in the etched area. The ultrasonic frequency is set to 30Hz-50Hz, and the ultrasonic power to 100W-200W. The stainless steel sample with micron-level rough structure obtained in step 2.3 is placed in the solution and reacted for 5min-15min.

[0053] The alloy nozzle is placed in a second fine etching solution to neutralize the first fine etching solution remaining on the surface of the alloy nozzle. The concentration of the second fine etching solution is 3% to 5%, and the reaction time is 30 to 60 seconds.

[0054] Specifically, by reacting with sodium carbonate solution, residual acidic substances (such as concentrated sulfuric acid and concentrated nitric acid) on the nozzle surface are neutralized, preventing the surface modifier in subsequent low surface energy treatment from reacting with the acidic substances. This ensures that the surface modifier can be effectively adsorbed onto the alloy nozzle surface, forming a superhydrophobic layer. Simultaneously, the neutralization treatment also eliminates residual metal ions on the surface, preventing them from forming an oxide layer during subsequent drying that would affect surface properties. After the neutralization reaction, the alloy nozzle is rinsed with deionized water for 1-3 minutes, and finally dried in an oven at 100-120°C for 5-10 minutes to remove residual water stains in the etched micropores. This process etches nanoscale micropores into the micron-scale rough structure, resulting in a micro-nano composite alloy nozzle.

[0055] The step S3 above, which involves treating the alloy nozzle with a surface modifier to form a superhydrophobic surface, can also be achieved through other methods:

[0056] The surface modifier is heated at a constant temperature of 100℃~110℃. The surface modifier includes hexamethylsilanediamine.

[0057] Specifically, using silicone oil as the heating medium, HMDS (hexamethylsilanediamine) is added to a constant-temperature water bath. At the aforementioned heating temperature, HMDS can effectively undergo a modification reaction on the surface of the alloy nozzle, forming a modified layer with low surface energy properties. This temperature range can activate the activity of HMDS, causing it to chemically bond with the micro-nano composite structure on the nozzle surface, forming a superhydrophobic surface.

[0058] The alloy nozzle after the second treatment is placed in a surface modifier for reaction, and the alloy nozzle is subjected to ultrasonic oscillation. The ultrasonic oscillation frequency is 10Hz~20Hz, the ultrasonic power is 50W~100W, and the reaction time is 5min~10min.

[0059] Specifically, the alloy nozzle is placed in HMDS and sealed for ultrasonic oscillation. Ultrasonic oscillation helps remove residual air and microbubbles from the surface, ensuring that the HMDS solution can uniformly cover the nozzle surface, especially inside the micron-scale rough structures and nano-scale pores formed after the second treatment. Furthermore, ultrasonic oscillation promotes deeper contact between HMDS and the alloy surface, accelerating its adsorption and chemical bonding, forming a more stable surface-modified layer.

[0060] In the above embodiments, the alloy nozzle can be dried in a high-temperature oven at 90°C to 100°C for 10 to 15 minutes to further complete the low surface energy treatment and obtain a high-viscosity superhydrophobic surface with better quality.

[0061] The high viscosity hydrophobicity of the surface treated by this metal surface treatment method may be lost after long-term use or after being exposed to liquid residues with hydrophilic groups. The high viscosity hydrophobicity can be restored by simply immersing the surface in anhydrous ethanol and ultrasonically cleaning it for 10-15 minutes and then repeating step S3.

[0062] In some optional embodiments, the surface treatment method further includes:

[0063] Polish the surface of the alloy nozzle; immerse the alloy nozzle in an industrial cleaning agent and subject it to ultrasonic oscillation at a frequency of 30Hz~50Hz, an ultrasonic power of 100W~200W, and a duration of 3min~5min; then air dry the surface of the alloy nozzle for 1min~2min.

[0064] Specifically, the surface of the alloy nozzle is polished to remove the oxide layer, and then immersed in an industrial cleaning agent, such as a solution containing acetone. Ultrasonic cleaning utilizes the energy generated by high-frequency vibrations to form tiny vacuum bubbles in the liquid. When these bubbles burst, they generate strong local shear forces and shock waves, effectively removing fine particles and oil stains from the surface of the alloy nozzle and its micro / nanostructure. A dry spray gun can then be used to blow away any remaining industrial cleaning agent from the alloy nozzle, resulting in a clean metal surface. Setting the ultrasonic power and time within the specified range achieves optimal cleaning results without damaging the alloy material, ensuring thorough cleaning of all surface areas while avoiding surface corrosion that may result from prolonged exposure to the cleaning agent.

[0065] like Figure 2 As shown, taking a stainless steel nozzle as an example, the surface treatment method for the alloy nozzle in this application includes:

[0066] The specific steps for surface pretreatment of stainless steel nozzles are as follows:

[0067] The inner wall of the stainless steel nozzle is polished with sandpaper to remove the surface oxide layer; the resulting stainless steel nozzle is immersed in acetone and ultrasonically vibrated for 5 minutes to remove the debris and residual grease generated during polishing; the resulting stainless steel nozzle is then sprayed with a dry spray gun for 1 minute to evaporate the residual acetone on the surface, resulting in a clean stainless steel nozzle.

[0068] The specific steps for constructing the micron-level roughened structure on the surface of a stainless steel nozzle are as follows:

[0069] A rapid rough etching apparatus was selected to heat the rough etching solution (including ferric chloride (FeCl3), hydrogen peroxide (H2O2), and hydrofluoric acid (HF) in a water bath. The resulting rough etching solution and its container were placed in a water bath heating pot, and the water bath heating temperature was set to 40°C. Subsequently, a stainless steel nozzle was immersed in the etching solution for 3 minutes to prepare a micron-level rough structure. Ferric chloride acts as an etchant, accounting for 65% of the volume in the rough etching solution. The ferric chloride solution is composed of solid ferric chloride, concentrated nitric acid, and water, with a volume ratio of 65% concentrated nitric acid to water of 1:4, and a ferric chloride mass fraction of 40%. Hydrogen peroxide acts as an oxidant, accounting for 10% of the volume in the rough etching solution, and the concentration of the hydrogen peroxide solution is 10% (volume fraction). Hydrofluoric acid acts as a complexing agent for metal ions, promoting the reaction, and accounts for 25% of the volume in the rough etching solution, and the concentration of the hydrofluoric acid solution is 25% (volume fraction).

[0070] After rinsing the obtained stainless steel nozzle with deionized water for 60 seconds, it was then polished with 2000-grit sandpaper under a 3N load for 50 cm to make the surface of the stainless steel nozzle smooth. Subsequently, it was ultrasonically vibrated in acetone solution for 5 minutes. After the acetone evaporated, a micron-level rough structure was obtained on the surface of the stainless steel nozzle.

[0071] The specific steps for constructing the nanoscale roughened structure on the surface of a stainless steel nozzle are as follows:

[0072] A slow-speed fine etching apparatus was used to heat the fine etching solution (including 98% concentrated sulfuric acid (H₂SO₄) and 65% concentrated nitric acid (HNO₃) in a water bath and to perform ultrasonic oscillation. The ultrasonic frequency was set to 40 Hz and the ultrasonic power to 150 W. The 98% concentrated sulfuric acid provided the H₂SO₄. + To promote metal dissolution, 65% concentrated nitric acid is used as an oxidant to form a dynamic passivation film, inhibiting excessive etching. The volume fraction of 98% concentrated sulfuric acid is 75%, and the volume fraction of 65% concentrated nitric acid is 25%. The resulting stainless steel nozzle with a micron-level rough structure is placed in a fine etching solution and reacted for 15 minutes.

[0073] The obtained stainless steel nozzle was immersed in a 5% sodium carbonate solution for 60 seconds to neutralize the residual acid on the sample surface. Then it was rinsed with deionized water for 1 minute and finally dried in an oven at 120°C for 5 minutes to remove residual water stains in the etched micropores. Nanoscale fine pores were etched in the micron-level rough structure to obtain a stainless steel nozzle with a micro-nano composite structure.

[0074] The specific steps for performing low surface energy treatment on stainless steel nozzles are as follows:

[0075] Using silicone oil as a heating medium, HMDS (hexamethylsilanediamine) surface modifier was added to a constant temperature water bath. The constant temperature was set to 110℃. The resulting stainless steel nozzle was placed in HMDS and sealed. The ultrasonic frequency was set to 20Hz, the ultrasonic power to 100W, and the reaction time was 10min.

[0076] The obtained stainless steel nozzle was dried in a drying oven at 100°C for 10 minutes to complete the low surface energy treatment and obtain a high viscosity superhydrophobic stainless steel nozzle. The stainless steel surface can effectively adhere to droplets and inhibit their natural dripping.

[0077] According to another aspect of this application, an alloy nozzle is provided, which is obtained by the surface treatment method of the alloy nozzle described above.

[0078] After a superhydrophobic surface is formed on the surface of the alloy nozzle, the droplet morphology of being suspended and not dripping is as follows: Figure 3 As shown in (a), the superhydrophobic properties of the horizontally placed surface are as follows: Figure 3 As shown in (b).

[0079] According to another aspect of this application, a photoresist edge line removal apparatus is provided, including the aforementioned alloy nozzle. Figure 4 As shown, the photoresist edge line removal device includes a coating nozzle, an EBR nozzle (the alloy nozzle of this application: a high-viscosity ultra-water stainless steel nozzle), a backwash nozzle, and an exhaust port. The alloy nozzle, in conjunction with the back suction effect of the existing pipeline, can effectively suppress the dripping and splashing of the removal solvent at the nozzle. Even when the back suction is weak, surface tension can still adhere the droplets to the nozzle, achieving good engineering results.

[0080] The technical features of the above embodiments can be combined in any way. For the sake of brevity, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0081] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A surface treatment method for an alloy nozzle, characterized by, The surface treatment method comprises the following steps: a first treatment is performed on the alloy nozzle to form a microscale rough structure on the surface of the alloy nozzle, the first treatment comprising a first wet etching using a coarse etching solution and a polishing treatment, the coarse etching solution comprising nitric acid and ferric chloride, the alloy nozzle comprising at least iron, chromium and nickel; a second treatment is performed on the alloy nozzle to form nanoscale holes in the microscale rough structure, the second treatment comprising a second wet etching using a first fine etching solution and a third wet etching using a second fine etching solution, the first fine etching solution comprising sulfuric acid and nitric acid, the second fine etching solution comprising sodium carbonate; a low surface energy treatment is performed on the alloy nozzle using a surface modifier to form a super-hydrophobic surface on the surface of the alloy nozzle.

2. The surface treatment method according to claim 1, characterized by, The coarse etching solution further comprises hydrogen peroxide and hydrofluoric acid, and the surface treatment method further comprises: 65% concentrated nitric acid is prepared using the nitric acid and water; a preliminary coarse etching solution is prepared using ferric chloride solid, the 65% concentrated nitric acid and water, the volume ratio of the 65% concentrated nitric acid to water being 1:4 to 1:3, and the mass fraction of the ferric chloride solid in the preliminary coarse etching solution being 35% to 45%; the preliminary coarse etching solution is mixed with the hydrogen peroxide and the hydrofluoric acid to obtain the coarse etching solution, the volume ratio of the hydrogen peroxide in the coarse etching solution being 10% to 15%, and the volume ratio of the hydrofluoric acid in the coarse etching solution being 15% to 30%.

3. The surface treatment method according to claim 1, characterized by, The step of performing the first treatment on the alloy nozzle to form the microscale rough structure on the surface of the alloy nozzle comprises: the coarse etching solution is heated, and the heating temperature is 30°C to 50°C; the alloy nozzle is placed in the coarse etching solution for 1 minute to 3 minutes; the alloy nozzle is subjected to the polishing treatment to form the microscale rough structure on the surface of the alloy nozzle.

4. The surface treatment method according to claim 1, characterized by, The surface treatment method further comprises: 98% concentrated sulfuric acid and 65% concentrated nitric acid are prepared using the sulfuric acid, the nitric acid and water; the first fine etching solution is prepared using the 98% concentrated sulfuric acid and the 65% concentrated nitric acid, the volume fraction of the 98% concentrated sulfuric acid being 70% to 80%, and the volume fraction of the 65% concentrated nitric acid being 20% to 30%.

5. The surface treatment method according to claim 1, characterized by, The step of performing the second treatment on the alloy nozzle to form the nanoscale holes in the microscale rough structure comprises: the first fine etching solution is subjected to constant temperature heating, and the heating temperature is 38°C to 42°C; the alloy nozzle is placed in the first fine etching solution for 5 minutes to 15 minutes, and the alloy nozzle is subjected to ultrasonic oscillation, the ultrasonic frequency of the ultrasonic oscillation being 30Hz to 50Hz, and the ultrasonic power being 100W to 200W; the alloy nozzle is placed in the second fine etching solution to react to neutralize the first fine etching solution remaining on the surface of the alloy nozzle, the concentration of the second fine etching solution being 3% to 5%, and the reaction time being 30 seconds to 60 seconds.

6. The surface treatment method according to claim 1, characterized by, The step of performing the low surface energy treatment on the alloy nozzle using the surface modifier to form the superhydrophobic surface on the surface of the alloy nozzle includes: The surface modifier is subjected to constant temperature heating at a temperature of 100℃~110℃, and the surface modifier includes hexamethylsilanediamine; The alloy nozzle after the second treatment is placed in the surface modifier for reaction, and the alloy nozzle is subjected to ultrasonic oscillation. The ultrasonic oscillation frequency is 10Hz~20Hz, the ultrasonic power is 50W~100W, and the reaction time is 5min~10min.

7. The surface treatment method according to claim 1, characterized by, The surface treatment method further includes: The surface of the alloy nozzle is polished. The alloy nozzle is immersed in an industrial cleaning agent and subjected to ultrasonic oscillation. The ultrasonic oscillation frequency is 30Hz~50Hz, the ultrasonic power is 100W~200W, and the time is 3min~5min. The surface of the alloy nozzle is air-dried for 1 to 2 minutes.

8. The surface treatment method according to claim 1, characterized by, The polishing process includes the following steps: The surface of the alloy nozzle is polished using sandpaper of 1500-2000 grit, with a polishing stroke of 30-50 cm.

9. An alloy nozzle characterized by, It is obtained by the surface treatment method of the alloy nozzle according to any one of claims 1 to 8.

10. A photoresist edge bead line removal apparatus, characterized by, Includes the alloy nozzle as described in claim 9.

Images